EP1099748A2 - Compositions détèrgentes contenant des tensioactifs - Google Patents

Compositions détèrgentes contenant des tensioactifs Download PDF

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Publication number
EP1099748A2
EP1099748A2 EP00124048A EP00124048A EP1099748A2 EP 1099748 A2 EP1099748 A2 EP 1099748A2 EP 00124048 A EP00124048 A EP 00124048A EP 00124048 A EP00124048 A EP 00124048A EP 1099748 A2 EP1099748 A2 EP 1099748A2
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EP
European Patent Office
Prior art keywords
weight
acid
alcohols
surfactant
surfactants
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EP00124048A
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German (de)
English (en)
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EP1099748A3 (fr
Inventor
Wilfried Dr. Rähse
Ansgar Dr. Behler
Peter Dr. Sandkühler
Kathleen Dr. Paatz
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Henkel AG and Co KGaA
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Henkel AG and Co KGaA
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Publication of EP1099748A2 publication Critical patent/EP1099748A2/fr
Publication of EP1099748A3 publication Critical patent/EP1099748A3/fr
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    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D17/00Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/0008Detergent materials or soaps characterised by their shape or physical properties aqueous liquid non soap compositions
    • C11D17/003Colloidal solutions, e.g. gels; Thixotropic solutions or pastes
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66Non-ionic compounds
    • C11D1/74Carboxylates or sulfonates esters of polyoxyalkylene glycols
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D17/00Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/06Powder; Flakes; Free-flowing mixtures; Sheets

Definitions

  • the present invention relates to solid or liquid to gel-like washing and Detergents containing surfactants and other detergent ingredients, the Use of these agents for cleaning hard surfaces and for washing Textiles.
  • the surfactants are one of the most important ingredients in detergents and cleaning agents.
  • a variety of synthetic surfactants were also used developed a wide variety of physical properties, such as ionic, non-ionic or non-thermal surfactants. These surfactants differ in their "Physical states" at processing and storage temperature in their solubility in Water and its affinity for the substrates to be cleaned.
  • Anionic surfactants show a good affinity for the substrates to be cleaned and one excellent washing and cleaning effect, which indicates the interactions between the negatively charged anionic surfactant and the positively charged Soiling is attributable.
  • the disadvantage is that sensitive substrates, especially textiles, damage with frequent washing with anionic surfactants can take.
  • the nonionic surfactants known as "mild surfactants” are usually as Liquids before.
  • the liquid nonionic surfactants are excellent as Solvents in liquids, however, they pose problems when used in solids Means should be incorporated, as they lead to a deterioration in pourability of these funds can lead.
  • the nonionic surfactants are soluble in water, form gel phases on contact with water, which make dissolving difficult. Further is however, the affinity because of its uncharged hydrophilic part to be cleaned Substrate or soiling less than that of the anionic surfactants.
  • the present invention had for its object to find surfactants that quickly are soluble and do not form a gel phase when dissolved and have a good affinity for them have cleaning substrates.
  • esters of di-, tri- and Polycarboxylic acids with alkoxylated fatty alcohols are anionic surfactants, which are a have good affinity for the substrate, but is delayed in the washing process hydrolyze alkoxylated fatty alcohol and a di- or polycarboxylic acid, in other words to a nonionic surfactant and to compounds that have cobuilder properties demonstrate.
  • These esters are liquids that work very well in solid media to let.
  • the present invention accordingly relates to solid or liquid to gel-form detergents and cleaning agents containing surfactants and other detergent components, characterized in that at least one surfactant from the group of di-, tri- and polycarboxylic acid esters with alkoxylated C 8-22 alcohols is contained .
  • esters of di-, tri- and polycarboxylic acids used according to the invention are Compounds which are known from the acids with the corresponding alcohols can be obtained.
  • Examples of the di-, tri- and polycarboxylic acids used as starting compounds for Preparation of the esters used according to the invention can be used all aliphatic and aromatic carboxylic acids with at least two acid groups and optionally at least one hydroxy group in the molecule.
  • examples for aliphatic di-, tri- and polycarboxylic acids are malic acid, tartaric acid, citric acid, Propane tricarboxylic acid, maleic acid, fumaric acid, succinic acid, etc.
  • suitable aromatic carboxylic acids are phthalic acid, terephthalic acid, Trimellitic acid, pyromellitic acid and mellitic acid.
  • Citric acid will particularly preferably used because citric acid or its salts Have cobuilder properties and the surfactant used according to the invention in in this case a nonionic surfactant and a cobuilder, i.e. two active washing components, hydrolyzed.
  • the alcohols used are alkoxylated C 8-22 alcohols, which are also known as nonionic surfactants and are referred to as fatty alcohol alkoxylates .
  • Alkoxylated, advantageously ethoxylated, in particular primary alcohols with preferably 8 to 18 carbon atoms and an average of 1 to 12 moles of ethylene oxide (EO) per mole of alcohol in which the alcohol radical can be linear or preferably methyl-branched in the 2-position or linear are particularly suitable and may contain methyl-branched radicals in the mixture, as are usually present in oxo alcohols.
  • EO ethylene oxide
  • alcohol ethoxylates with linear residues of alcohols of native origin with 12 to 18 carbon atoms for example from coconut, palm, tallow fat or oleyl alcohol, and an average of 2 to 8 EO per mole of alcohol are particularly preferred.
  • the preferred ethoxylated alcohols include, for example, C 12 -C 14 alcohols with 3 EO or 4 EO, C 9 -C 11 alcohols with 7 EO, C 13 -C 15 alcohols with 3 EO, 5 EO, 7 EO or 8 EO, C 12 -C 18 alcohols with 3 EO to 7 EO and mixtures thereof, such as mixtures of C 12 -C 14 alcohol with 3 EO and C 12 -C 18 alcohol with 7EO.
  • 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 of these are (tallow) fatty alcohols with 14 EO, 16 EO, 20 EO, 25 EO, 30 EO or 40 EO.
  • the agents according to the invention can all usually be used in detergents and cleaning agents substances contained, such as other surfactants, in particular anionic surfactants, and builder substances, inorganic salts, bleaching agents, Bleach activators, enzymes, enzyme stabilizers, graying inhibitors, Foam inhibitors, silicone oils, soil release compounds, color transfer inhibitors, Salts of polyphosphonic acids, optical brighteners, fluorescent agents, fragrances, Dyes, antistatic agents, ironing aids, phobing and impregnating agents, swelling and Anti-slip agents, UV absorbers or mixtures thereof are included.
  • surfactants in particular anionic surfactants, and builder substances
  • inorganic salts such as other surfactants, in particular anionic surfactants, and builder substances, inorganic salts, bleaching agents, Bleach activators, enzymes, enzyme stabilizers, graying inhibitors, Foam inhibitors, silicone oils, soil release compounds, color transfer inhibitors, Salts of polyphosphonic acids, optical brighteners, fluorescent agents, fragrances, D
  • the agents according to the invention can the esters from the di-, tri- and polycarboxylic acids with alkoxylated C 8-22 alcohols in an amount of 0.5 to 60% by weight, preferably 3 to 15% by weight, based on the finished funds included.
  • compositions can include further agents Surfactants selected from the non-ionic, anionic, cationic and amphoteric Contain surfactants.
  • nonionic surfactants are non-esterified alkoxylated fatty alcohols, Sugar surfactants, especially dialkyl and alkenyl oligogliycosides and Polyhydroxy fatty acid amides, alkoxylated fatty acid methyl esters, and amine oxides in Consideration.
  • sugar surfactants that can be used in process step A come especially the alkyl and alkenyl oliglycosides and polyhydroxy fatty acid amides in Consideration.
  • the alkyl and alkenyl oliglycosides have the general formula R 1 O (G) x in which R 1 is a primary straight-chain or methyl-branched, in particular in the 2-position methyl-branched alkyl or alkenyl radical having 8 to 22, preferably 12 to 18, carbon atoms and G is the symbol which represents a glycose unit having 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.
  • Polyhydroxy fatty acid amides which can be used are those having the formula (II). in the R 2 CO for an aliphatic acyl radical having 6 to 22 carbon atoms, R 3 for hydrogen, an alkyl or hydroxyalkyl radical with 1 to 4 carbon atoms and [Z] for a linear or branched polyhydroxyalkyl radical with 3 to 10 carbon atoms and 3 to 10 hydroxyl groups stands.
  • the polyhydroxy fatty acid amides are known substances that usually 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 can be obtained can.
  • 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 can be obtained can.
  • the derive Polyhydroxy fatty acid amides of reducing sugars with 5 or 6 carbon atoms, especially on the glucose is preferred.
  • the sugar surfactants can be in the form of aqueous solutions, such as those from the Manufacturing processes are obtained, used. Other forms of use are Granules or steam-dried products.
  • Anionic surfactants used are, for example, those of the sulfonate and sulfate type.
  • the surfactants of the sulfonate type are preferably C 9-13- alkylbenzenesulfonates, olefin sulfonates, ie mixtures of alkene and hydroxyalkanesulfonates and disulfonates, such as are obtained, for example, from C 12-18 monoolefins with a terminal or internal double bond by sulfonation with gaseous sulfur trioxide and subsequent alkaline or acidic hydrolysis of the sulfonation products is considered.
  • alkanesulfonates obtained from C 12-18 alkanes, for example by sulfochlorination or sulfoxidation with subsequent hydrolysis or neutralization.
  • the esters of ⁇ -sulfofatty acids for example the ⁇ -sulfonated methyl esters of hydrogenated coconut, palm kernel or tallow fatty acids, are also suitable.
  • Suitable anionic surfactants are sulfonated fatty acid glycerol esters.
  • Fatty acid glycerol esters are the mono-, di- and triesters as well as their mixtures understand how they are produced by esterification of a monoglycerin with 1 up to 3 moles of fatty acid or in the transesterification of triglycerides with 0.3 to 2 moles of glycerin be preserved.
  • Preferred sulfonated fatty acid glycerol esters are the sulfonation products of saturated fatty acids with 6 to 22 carbon atoms, for example the 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 18 fatty alcohols, for example from coconut oil 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 prepared on a petrochemical basis and which have a degradation behavior analogous to that of the adequate compounds based on oleochemical raw materials.
  • C 12 -C 16 alkyl sulfates and C 12 -C 15 alkyl sulfates as well as C 14 -C 15 alkyl sulfates are preferred from the point of view of washing technology.
  • 2,3-Alkyl sulfates are also suitable anionic surfactants.
  • the sulfuric acid monoesters of the straight-chain or branched C 7-21 alcohols ethoxylated with 1 to 6 mol of ethylene oxide such as 2-methyl-branched C 9-11 alcohols with an average of 3.5 mol 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 in particular ethoxylated fatty alcohols.
  • alcohols preferably fatty alcohols and in particular ethoxylated fatty alcohols.
  • Preferred sulfosuccinates contain C 8-18 fatty alcohol residues or mixtures 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).
  • alk (en) ylsuccinic acid with preferably 8 to 18 carbon atoms in the alk (en) yl chain or salts thereof.
  • Soaps are particularly suitable as further anionic surfactants.
  • saturated fatty acid soaps such as the salts of lauric acid, myristic acid, palmitic acid, Stearic acid, hydrogenated erucic acid and behenic acid and in particular from natural Fatty acids, e.g. Coconut, palm kernel or tallow fatty acids, derived soap mixtures.
  • the anionic surfactants including the soaps can be in the form of their sodium, potassium or ammonium salts and as soluble salts of organic bases, such as mono-, di- or triethanolamine.
  • the anionic surfactants are preferably in the form their sodium or potassium salts, especially in the form of the sodium salts.
  • Suitable crystalline, layered sodium silicates have the general formula NaMSi x O 2x + 1 .H 2 O, 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.
  • Preferred crystalline layered silicates of the formula given are those in which M represents sodium and x assumes the values 2 or 3. In particular, both ⁇ - and ⁇ -sodium disilicates Na 2 Si 2 O 5 .yH 2 O are preferred.
  • the delay in dissolution compared to conventional amorphous sodium silicates can be caused in various ways, for example by surface treatment, compounding, compacting / compression 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 deliver 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.
  • 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 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.
  • Commercially available and can preferably be used in the context of the present invention for example a co-crystallizate of zeolite X and zeolite A (approx ), which is sold by CONDEA Augusta SpA under the brand name VEGOBOND AX® and by the formula n Na 2 O (1-n) K 2 O Al 2 O 3 (2 - 2.5) SiO 2 (3.5 - 5.5) H 2 O can be described.
  • 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.
  • 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 (HPO 3 ) n and orthophosphoric acid H 3 PO 4 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 tissues and also contribute to cleaning performance.
  • Sodium dihydrogen phosphate, NaH 2 PO 4 exists as a dihydrate (density 1.91 gcm -3 , melting point 60 °) and as a monohydrate (density 2.04 gcm -3 ). Both salts are white, water-soluble powders, which lose water of crystallization when heated and at 200 ° C into the weakly acidic diphosphate (disodium hydrogen diphosphate, Na 2 H 2 P 2 O 7 ), at higher temperature in sodium trimetaphosphate (Na 3 P 3 O 9 ) and Maddrell's salt (see below).
  • NaH 2 PO 4 is acidic; it occurs 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 PO 4 , is a white salt with a density of 2.33 gcm -3 , has a melting point of 253 ° [decomposition to form potassium polyphosphate (KPO 3 ) x ] and is light soluble in water.
  • Disodium hydrogen phosphate (secondary sodium phosphate), Na 2 HPO 4 , is a colorless, very easily water-soluble crystalline salt. It exists without water and with 2 mol. (Density 2.066 gcm -3 , water loss at 95 °), 7 mol. (Density 1.68 gcm -3 , melting point 48 ° with loss of 5 H 2 O) and 12 mol. Water (density 1.52 gcm -3 , melting point 35 ° with loss of 5 H 2 O), becomes anhydrous at 100 ° and changes to diphosphate Na 4 P 2 O 7 when heated more. Disodium hydrogen phosphate is prepared by neutralizing phosphoric acid with soda solution using phenolphthalein as an indicator. Dipotassium hydrogen phosphate (secondary or dibasic potassium phosphate), K 2 HPO 4 , is an amorphous, white salt that is easily soluble in water.
  • Trisodium phosphate, tertiary sodium phosphate, Na 3 PO 4 are colorless crystals which, as dodecahydrate, have a density of 1.62 gcm -3 and a melting point of 73-76 ° C (decomposition), as decahydrate (corresponding to 19-20% P 2 O 5 ) have a melting point of 100 ° C and in anhydrous form (corresponding to 39-40% P 2 O 5 ) have a density of 2.536 gcm -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 triphase potassium phosphate), K 3 PO 4 , is a white, deliquescent, granular powder with a density of 2.56 gcm -3 , has a melting point of 1340 ° and is easily soluble in water with an alkaline reaction. It arises, for example, when heating Thomas slag with coal and potassium sulfate. Despite the higher price, the more easily soluble, therefore highly effective, potassium phosphates are often preferred over corresponding sodium compounds in the cleaning agent industry.
  • Tetrasodium diphosphate (sodium pyrophosphate), Na 4 P 2 O 7 , exists in anhydrous form (density 2.534 gcm -3 , melting point 988 °, also given 880 °) and as decahydrate (density 1.815-1.836 gcm -3 , melting point 94 ° with loss of water) .
  • Substances are colorless crystals that are soluble in water with an alkaline reaction.
  • Na 4 P 2 O 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 O 7 exists in the form of the trihydrate and is a colorless, hygroscopic powder with a density of 2.33 gcm -3 , which is soluble in water, the pH value being 1% Solution at 25 ° is 10.4.
  • 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. A large number of terms are used in particular for the latter: 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)
  • sodium tripolyphosphate sodium tripolyphosphate
  • n 3
  • Approx. 17 g of the salt free from water of crystallization dissolve in 100 g of water at room temperature, approx. 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% strength by weight solution (> 23% P 2 O 5 , 25% K 2 O). The potassium polyphosphates are widely used in the detergent and cleaning agent industry.
  • sodium potassium tripolyphosphates which can also be used in the context of the present invention. These occur, for example, when hydrolyzing sodium trimetaphosphate with KOH: (NaPO 3 ) 3 + 2 KOH ⁇ Na 3 K 2 P 3 O 10 + H 2 O
  • these are exactly like sodium tripolyphosphate, potassium tripolyphosphate or mixtures of these two can be used; also 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 be used according to the invention.
  • organic cobuilders in the washing and Detergent tablets in particular polycarboxylates / polycarboxylic acids, polymeric polycarboxylates, aspartic acid, polyacetals, dextrins, other organic Cobuilder (see below) and phosphonates are used. These substance classes are described below.
  • Usable organic builders are, for example, those in the form of their Polycarboxylic acids that can be used are sodium salts, with polycarboxylic acids being such Carboxylic acids are understood that carry more than one acid function.
  • these are 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 for ecological reasons objectionable, 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 have besides theirs Builder effect typically also the property of an acidifying component and thus also serve to set a lower and milder pH value of Detergents or cleaning agents.
  • Polymeric polycarboxylates are also suitable as builders, for example those Alkali metal salts of polyacrylic acid or polymethacrylic acid, for example those with a 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), using a UV detector. The measurement was made 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 molecular weights measured against polystyrene sulfonic acids are generally significantly higher than the molecular weights given in this document.
  • Suitable polymers are in particular polyacrylates, which preferably have a molecular weight have from 2000 to 20,000 g / mol. Because of their superior solubility, can this group in turn the short-chain polyacrylates, the molecular weights from 2000 to 10000 g / mol, and particularly preferably from 3000 to 5000 g / mol, preferably his.
  • copolymeric polycarboxylates especially those of Acrylic acid with methacrylic acid and acrylic acid or methacrylic acid with maleic acid.
  • Copolymers of acrylic acid with maleic acid have proven particularly suitable proven that 50 to 90 wt .-% acrylic acid and 50 to 10 wt .-% maleic acid contain.
  • Their relative molecular weight, based on free acids, is in general 2000 to 70,000 g / mol, preferably 20,000 to 50,000 g / mol and in particular 30,000 up to 40,000 g / mol.
  • the (co) polymeric polycarboxylates can either be as a powder or as an aqueous Solution are used.
  • the content of the agents in (co) polymeric polycarboxylates is preferably 0.5 to 20% by weight, in particular 3 to 10% by weight.
  • the polymers can also contain allylsulfonic acids, such as allyloxybenzenesulfonic acid and methallylsulfonic acid, as a monomer contain.
  • allylsulfonic acids such as allyloxybenzenesulfonic acid and methallylsulfonic acid
  • Biodegradable polymers of more than two are also particularly preferred various monomer units, for example those which are salts of the monomers Acrylic acid and maleic acid as well as vinyl alcohol or vinyl alcohol derivatives or the as monomers, salts of acrylic acid and 2-alkylallylsulfonic acid and sugar derivatives contain.
  • copolymers are those which preferably contain acrolein as monomers and acrylic acid / acrylic acid salts or acrolein and vinyl acetate.
  • Polymeric aminodicarboxylic acids are also further preferred builder substances. to name their salts or their precursors. Are particularly preferred Polyaspartic acids or their salts and derivatives.
  • polyacetals which are obtained by converting Dialdehydes with polyol carboxylic acids, which have 5 to 7 carbon atoms and at least 3 Have hydroxyl groups can be obtained.
  • Preferred polyacetals will be from dialdehydes such as glyoxal, glutaraldehyde, terephthalaldehyde and mixtures thereof and obtained from polyol carboxylic acids such as gluconic acid and / or glucoheptonic acid.
  • Suitable organic builder substances are dextrins, for example Oligomers or polymers of carbohydrates by partial hydrolysis of starches can be obtained.
  • the hydrolysis can be carried out according to conventional methods, for example acid or enzyme-catalyzed processes are carried out. It is preferably Hydrolysis products with average molecular weights in the range of 400 to 500000 g / mol.
  • a polysaccharide with a dextrose equivalent (DE) in the range from 0.5 to 40, particularly preferred from 2 to 30, DE being a common measure of the reducing effect of a polysaccharide compared to dextrose, which a DE out of 100.
  • DE dextrose equivalent
  • 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.
  • An oxidized oligosaccharide is also suitable, a product oxidized at the C 6 of the saccharide ring being particularly advantageous.
  • Ethylene diamine disuccinate are other suitable cobuilders. This is ethylenediamine-N, N'-disuccinate (EDDS) preferred in the form of its sodium or magnesium salts used. Also preferred in this context Glycerol disuccinates and glycerol trisuccinates. Suitable amounts are in Zeolite-containing and / or silicate-containing formulations at 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 have at least 4 carbon atoms and at least one Contain hydroxy group and a maximum of two acid groups.
  • phosphonates are, in particular, hydroxyalkane or aminoalkane phosphonates.
  • hydroxyalkane phosphonates is 1-hydroxyethane-1,1-diphosphonate (HEDP) of particular importance as a cobuilder.
  • HEDP 1-hydroxyethane-1,1-diphosphonate
  • Preferred aminoalkane phosphonates are ethylenediaminetetramethylenephosphonate (EDTMP), diethylene triamine pentamethylene phosphonate (DTPMP) and their higher homologues in question. They are preferably in the form of neutral reacting sodium salts, e.g.
  • the Class of phosphonates preferably uses HEDP.
  • the aminoalkane phosphonates also have a strong ability to bind heavy metals. Accordingly, it is preferred, especially if the agents also contain bleach, Aminoalkanephosphonate, especially DTPMP to use, or mixtures of the to use the named phosphonates.
  • bleaching agents are, for example, sodium percarbonate, peroxypyrophosphates, citrate perhydrates and H 2 O 2 -producing peracidic salts or peracids, such as perbenzoates, peroxophthalates, diperazelaic acid, diperdodecanedioic acid or phthaloiminoperacids such as phthaliminopercaproic acid.
  • Organic peracids, alkali perborates and / or alkali percarbonates are preferably used in amounts of 0.1 to 40% by weight, preferably 3 to 30% by weight, in particular 5 to 25% by weight.
  • bleach activators can be compounds that are under perhydrolysis conditions
  • Peroxocarboxylic acids with preferably 1 to 10 carbon atoms, in particular 2 to 4 carbon atoms and / or optionally substituted perbenzoic acid are used become.
  • Suitable substances are the O- and / or N-acyl groups of the named C number of carbon atoms and / or optionally substituted benzoyl groups.
  • Preferred bleach activators are sodium 4- (octanoyloxy) benzene sulfonate, Undecenoyloxybenzenesulfonate (UDOBS), sodium dodecanoyloxybenzenesulfonate (DOBS), Decanoyloxybenzoic acid (DOBA, OBC 10) and / or dodecanoyloxybenzenesulfonate (OBS 12) and N-methylmorpholinum acetonitrile (MMA).
  • Such bleach activators are in the usual range of 0.01 to 20 wt .-%, preferably in amounts of 0.1 to 15% by weight, in particular 1% by weight to 10% by weight, based on the total Means included.
  • the bleach activator can be coated with coating substances in a known manner or if necessary, using auxiliaries, in particular methyl celluloses and / or Carboxymethyl celluloses, granulated or extruded / pelleted and if desired, contain further additives, for example dye, the Dye has no coloring effect on the textiles to be washed.
  • auxiliaries in particular methyl celluloses and / or Carboxymethyl celluloses
  • the Dye has no coloring effect on the textiles to be washed.
  • a bleach activator is preferably used, the under Washing conditions forms peracetic acid.
  • transition metal compounds in question include in particular those known from German patent application DE-A-195 29 905 Manganese, iron, cobalt, ruthenium or molybdenum salt complexes and their from German patent application DE-A-196 20 267 known N-analog compounds which German patent application DE-A-195 36 082 known manganese, iron, cobalt, Ruthenium or molybdenum carbonyl complexes described in the German patent application DE-A-196 05 688 described manganese, iron, cobalt, ruthenium, molybdenum, Titanium, vanadium and copper complexes with nitrogen-containing tripod ligands, which German patent application DE-A-196 20 411 known cobalt, iron, copper and ruthenium-amine complexes, which are described in German patent application DE 4416 438 Manganese, copper and cobalt complexes described in the European Patent application EP-A-0 272 030 described cobalt complexes, which come from the European Patent application EP-A-0
  • Combinations of bleach activators and transition metal bleach catalysts are for example from the German patent application DE-A-196 13 103 and the international patent application WO-A-95/27775.
  • Bleach-enhancing transition metal complexes especially with the central atoms Mn, Fe, Co, Cu, Mo, V, Ti and / or Ru are used in conventional amounts, preferably in one Amount up to 1 wt .-%, in particular from 0.0025 wt .-% to 0.25 wt .-% and particularly preferably from 0.01% by weight to 0.1% by weight, in each case based on the total Means used.
  • hydrolase class such as Proteases, esterases, lipases or lipolytically active enzymes, amylases, cellulases or other glycosyl hydrolases and mixtures of the enzymes mentioned. All these hydrolases help to remove stains, such as protein, greasy or starchy stains, and graying. Cellulases and others Glycosyl hydrolases can be removed by removing pilling and microf
  • Enzymes obtained from bacterial strains or fungi such as Bacillus subtilis, Bacillus licheniformis, Streptomyces griseus and Humicola insolens are particularly suitable.
  • Proteases of the subtilisin type and in particular proteases which are 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, in particular, however, mixtures containing protease and / or lipase 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 ⁇ -amylases, iso-amylases, pullulanases and pectinases.
  • Cellobiohydrolases, endoglucanases and ⁇ -glucosidases, which are also called cellobiases, or mixtures thereof, are preferably used as ceilulases. Since the 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 and / or embedded in coating substances to protect them against premature decomposition.
  • the proportion of enzymes, enzyme mixtures or enzyme granules can, for example, about 0.1 to 5% by weight, preferably 0.1 to about 3% by weight.
  • the detergents and cleaning agents according to the invention can be both in solid and are in liquid to gel form.
  • the fixed funds include e.g. Powder, Granules and also pressed products, such as moldings, e.g. B. tablets, each do not have to represent uniform products, but from individual components, so-called compounds. You can in a manner known per se getting produced.
  • the agents according to the invention are in liquid to gel form, it can these are aqueous or non-aqueous systems.
  • the production of Liquid to gel preparations can be carried out continuously or batchwise simple mixing of the components, if necessary at elevated temperature.
  • Solvents used in the liquid to gel compositions can come, for example, from the group of mono- or polyvalent Alcohols, alkanolamines or glycol ethers, provided they are specified in the Concentration range are miscible with water.
  • the Solvents selected from ethanol, n- or i-propanol, butanols, Ethylene glycol methyl ether, ethylene glycol ethyl ether, ethylene glycol propyl ether, Ethylene glycol mono-n-butyl ether, diethylene glycol methyl ether, diethylene glycol ethyl ether, Propylene glycol methyl, ethyl or propyl ether, dipropylene glycol monomethyl, or - ethyl ether, di-isopropylene glycol monomethyl or ethyl ether, methoxy, ethoxy or Butoxytriglycol, 1-butoxyethoxy-2-propanol, 3-methyl-3-methoxybut
  • composition according to the invention can be used to adjust the viscosity or several thickeners or thickening systems can be added.
  • the viscosity of the Compositions according to the invention can be prepared using customary standard methods (e.g. Brookfield RVD-VII viscometer at 20 rpm and 20 ° C, spindle 3) be measured and is preferably in the range of 100 to 5000 mPas.
  • Preferred compositions have viscosities of 200 to 4000 mPas, where Values between 400 and 2000 mPas are particularly preferred.
  • Suitable thickeners are inorganic or polymeric organic compounds. This mostly organic high molecular substances, which are also called swelling agents, usually absorb the liquids and swell them, eventually turning into viscous to pass real or colloidal solutions.
  • the inorganic thickeners include, for example, polysilicic acids, Clay minerals like montmorillonie, zeolites, silicic acids and bentonites.
  • the organic thickeners come from the groups of natural polymers, the modified natural polymers and the fully synthetic polymers.
  • Natural polymers that are used as thickeners for example agar agar, carrageenan, tragacanth, gum arabic, alginates, pectins, Polyoses, guar flour, locust bean gum, starch, dextrins, gelatin and Casein.
  • Modified natural products mainly come from the group of modified starches and celluloses, for example carboxymethyl cellulose and others Cellulose ether, hydroxyethyl and propyl cellulose as well as core meal ether called.
  • a large group of thickeners that are widely used in the Find the most diverse fields of application are the fully synthetic polymers such as polyacrylic and polymethacrylic compounds, vinyl polymers, polycarboxylic acids, Polyethers, polyimines, polyamides and polyurethanes.
  • the thickeners can be present in an amount of up to 5% by weight, preferably from 0.05 to 2% % By weight, and particularly preferably from 0.1 to 1.5% by weight, based on the finished product Composition.
  • the washing and cleaning agents according to the invention are suitable both for cleaning hard surfaces including dishes and for washing textiles.
  • Another object of the present invention is accordingly an agent for cleaning hard surfaces containing surfactants and other detergent components, characterized in that at least one surfactant from the group of di-, tri- and polycarboxylic acid esters with alkoxylated C 8-22 alcohols is contained .
  • Cleaning hard surfaces in the sense of the present invention excludes this Cleaning all surfaces in the household and in the commercial area including floors, wall and cabinet surfaces and windows. Likewise is includes cleaning dishes.
  • the cleaning process also includes steps for Pre- and post-treatment, like a rinsing process.
  • an agent according to the invention for cleaning hard surfaces contains 0.5 to 15% by weight of the surfactant from the group of di-, tri- and polycarboxylic acid esters with alkoxylated C 8-22 alcohols , from 0.5 to 10 % By weight of further surfactants, up to 10% by weight of organic solvent (hydrophilizing agent), optionally complexing agent and water.
  • Another object of the present invention is accordingly a textile detergent containing surfactants and other detergent components, which is characterized in that at least one surfactant from the group of di-, tri- and polycarboxylic acid esters with alkoxylated C 8-22 alcohols is contained.
  • the textile detergents can be used depending on their special recipe Pre-treatment of laundry, for washing and post-treatment, i.e. as a fabric softener, etc. are used.
  • a textile detergent according to the invention which is in solid form, contains 3 to 15% by weight of a surfactant from the group of di-, tri- and polycarboxylic acid esters with alkoxylated C 8-22 alcohols , 2.5% by weight. % to 20% by weight of anionic surfactant, 1% by weight to 20% by weight of further nonionic surfactant, 30% by weight to 55% by weight of water-insoluble inorganic builder, up to 25% by weight, in particular 1 %
  • By weight to 15% by weight of bleach up to 8% by weight, in particular 0.5% by weight to 6% by weight of bleach activator and up to 20% by weight, in particular 0.1% by weight. % to 15% by weight of inorganic salts, in particular alkali carbonate, sulfate and / or silicate, and up to 2% by weight, in particular 0.4% to 1.2% by weight of enzyme.
  • a textile detergent according to the invention which is in liquid form contains 3 to 60% by weight of a surfactant from the group of di-, tri- and polycarboxylic acid esters with alkoxylated C 8-22 alcohols , up to 15% by weight.
  • % in particular 3% by weight to 10% by weight, of anionic surfactants, up to 15% by weight, in particular 3% by weight to 10% by weight, of further nonionic surfactants, up to 18% by weight, in particular 4% by weight to 16% by weight of soap, 0.5% by weight, up to 20% by weight of water-soluble organic builder, up to 20% by weight, in particular 0.1% by weight to 5 %
  • water-insoluble inorganic builders and up to 60% by weight, in particular 10% by weight to 50% by weight of water and / or water-miscible solvent, enzyme and up to 10% by weight, in particular 0.01 % By weight to 7.5% by weight of enzyme stabilizer system.
  • Example 1 (invent.) [% By weight]
  • Example 2 (comp.) [% By weight]
  • Tower powder (see Table 2) 66 66 Sodium perborate monohydrate 20th 20th PEG 4000 7 7 C 12/18 -FA x 7 EO - 7 Citric acid C 12/18 FA x 7 EO ester 7 - L test (residue%) 7.8 18th Tower powder component Amount [% by weight] Zeolite A 46.25 Sokalan CP 5 3 8.75 Phosponate 0.5 C 9-13 alkyl benzene sulfonate 31.25 Soap 2.5 water 10.75
  • the test results show that the agent according to the invention is significantly better Has solubility as the agent from the comparative example.

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  • Engineering & Computer Science (AREA)
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  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Dispersion Chemistry (AREA)
  • Detergent Compositions (AREA)
EP00124048A 1999-11-13 2000-11-04 Compositions détèrgentes contenant des tensioactifs Withdrawn EP1099748A3 (fr)

Applications Claiming Priority (2)

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DE1999154831 DE19954831A1 (de) 1999-11-13 1999-11-13 Tensid-haltige Wasch- und Reinigungsmittel

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Cited By (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7268103B2 (en) * 2004-11-05 2007-09-11 Cognis Ip Management Gmbh Use of alkoxylated hydroxycarboxylic acid esters for solubilizing perfume oils in water
WO2011120799A1 (fr) 2010-04-01 2011-10-06 Unilever Plc Procédé de structuration de liquides détergents à l'aide d'huile de ricin hydrogénée
EP2476743A1 (fr) 2011-04-04 2012-07-18 Unilever Plc, A Company Registered In England And Wales under company no. 41424 of Unilever House Procédé de lavage du linge
EP2495300A1 (fr) 2011-03-04 2012-09-05 Unilever Plc, A Company Registered In England And Wales under company no. 41424 of Unilever House Structuration de liquides détergents avec de l'huile de ricin hydrogénée
WO2013139702A1 (fr) 2012-03-21 2013-09-26 Unilever Plc Particules de détergent à lessive
WO2016155993A1 (fr) 2015-04-02 2016-10-06 Unilever Plc Composition
WO2017133879A1 (fr) 2016-02-04 2017-08-10 Unilever Plc Liquide détergent
WO2017211700A1 (fr) 2016-06-09 2017-12-14 Unilever Plc Produits de blanchisserie
WO2017211697A1 (fr) 2016-06-09 2017-12-14 Unilever Plc Produits de lessive
WO2018127390A1 (fr) 2017-01-06 2018-07-12 Unilever N.V. Composition d'élimination de taches
WO2018224379A1 (fr) 2017-06-09 2018-12-13 Unilever Plc Système de distribution de lessive liquide
WO2019038187A1 (fr) 2017-08-24 2019-02-28 Unilever Plc Perfectionnements se rapportant au nettoyage de tissus
WO2019038186A1 (fr) 2017-08-24 2019-02-28 Unilever Plc Perfectionnements se rapportant au nettoyage de tissus
WO2019063402A1 (fr) 2017-09-29 2019-04-04 Unilever Plc Produits de lessive
WO2019068473A1 (fr) 2017-10-05 2019-04-11 Unilever Plc Produits de lessive

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US3948976A (en) * 1974-03-29 1976-04-06 American Cyanamid Company Partial esters of hydroxy polycarboxylic acids
FR2562556A1 (fr) * 1984-04-09 1985-10-11 Colgate Palmolive Co Composition detergente liquide de blanchissage contenant un acide polyether-carboxylique et hemy-ester correspondant
US4622173A (en) * 1984-12-31 1986-11-11 Colgate-Palmolive Co. Non-aqueous liquid laundry detergents containing three surfactants including a polycarboxylic acid ester of a non-ionic
US4772413A (en) * 1986-08-28 1988-09-20 Colgate-Palmolive Company Nonaqueous liquid nonbuilt laundry detergent bleach booster composition containing diacetyl methyl amine and method of use
DE4225136A1 (de) * 1992-07-30 1994-02-03 Henkel Kgaa Verfahren zur Herstellung von nichtionischen Tensiden
WO1994025562A1 (fr) * 1993-05-04 1994-11-10 Unilever N.V. Composition detergente liquide

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3948976A (en) * 1974-03-29 1976-04-06 American Cyanamid Company Partial esters of hydroxy polycarboxylic acids
FR2562556A1 (fr) * 1984-04-09 1985-10-11 Colgate Palmolive Co Composition detergente liquide de blanchissage contenant un acide polyether-carboxylique et hemy-ester correspondant
US4622173A (en) * 1984-12-31 1986-11-11 Colgate-Palmolive Co. Non-aqueous liquid laundry detergents containing three surfactants including a polycarboxylic acid ester of a non-ionic
US4772413A (en) * 1986-08-28 1988-09-20 Colgate-Palmolive Company Nonaqueous liquid nonbuilt laundry detergent bleach booster composition containing diacetyl methyl amine and method of use
DE4225136A1 (de) * 1992-07-30 1994-02-03 Henkel Kgaa Verfahren zur Herstellung von nichtionischen Tensiden
WO1994025562A1 (fr) * 1993-05-04 1994-11-10 Unilever N.V. Composition detergente liquide

Cited By (17)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7268103B2 (en) * 2004-11-05 2007-09-11 Cognis Ip Management Gmbh Use of alkoxylated hydroxycarboxylic acid esters for solubilizing perfume oils in water
WO2011120799A1 (fr) 2010-04-01 2011-10-06 Unilever Plc Procédé de structuration de liquides détergents à l'aide d'huile de ricin hydrogénée
EP2495300A1 (fr) 2011-03-04 2012-09-05 Unilever Plc, A Company Registered In England And Wales under company no. 41424 of Unilever House Structuration de liquides détergents avec de l'huile de ricin hydrogénée
EP2476743A1 (fr) 2011-04-04 2012-07-18 Unilever Plc, A Company Registered In England And Wales under company no. 41424 of Unilever House Procédé de lavage du linge
WO2012136427A1 (fr) 2011-04-04 2012-10-11 Unilever Plc Procédé de lavage d'un tissu
WO2013139702A1 (fr) 2012-03-21 2013-09-26 Unilever Plc Particules de détergent à lessive
WO2016155993A1 (fr) 2015-04-02 2016-10-06 Unilever Plc Composition
WO2017133879A1 (fr) 2016-02-04 2017-08-10 Unilever Plc Liquide détergent
WO2017211700A1 (fr) 2016-06-09 2017-12-14 Unilever Plc Produits de blanchisserie
WO2017211697A1 (fr) 2016-06-09 2017-12-14 Unilever Plc Produits de lessive
WO2018127390A1 (fr) 2017-01-06 2018-07-12 Unilever N.V. Composition d'élimination de taches
WO2018224379A1 (fr) 2017-06-09 2018-12-13 Unilever Plc Système de distribution de lessive liquide
WO2019038187A1 (fr) 2017-08-24 2019-02-28 Unilever Plc Perfectionnements se rapportant au nettoyage de tissus
WO2019038186A1 (fr) 2017-08-24 2019-02-28 Unilever Plc Perfectionnements se rapportant au nettoyage de tissus
WO2019063402A1 (fr) 2017-09-29 2019-04-04 Unilever Plc Produits de lessive
WO2019068473A1 (fr) 2017-10-05 2019-04-11 Unilever Plc Produits de lessive
DE212018000292U1 (de) 2017-10-05 2020-04-15 Unilever N.V. Waschmittelprodukte

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