EP0802965B1 - Detergent seche par pulverisation ou constituant pour celui-ci - Google Patents

Detergent seche par pulverisation ou constituant pour celui-ci Download PDF

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Publication number
EP0802965B1
EP0802965B1 EP95942725A EP95942725A EP0802965B1 EP 0802965 B1 EP0802965 B1 EP 0802965B1 EP 95942725 A EP95942725 A EP 95942725A EP 95942725 A EP95942725 A EP 95942725A EP 0802965 B1 EP0802965 B1 EP 0802965B1
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EP
European Patent Office
Prior art keywords
weight
detergent
spray
dried
sodium
Prior art date
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Revoked
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EP95942725A
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German (de)
English (en)
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EP0802965A1 (fr
Inventor
Fred Schambil
Wolfram Linke
Hubert Freese
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Henkel AG and Co KGaA
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Henkel AG and Co KGaA
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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
    • C11D3/02—Inorganic compounds ; Elemental compounds
    • C11D3/12—Water-insoluble compounds
    • C11D3/124—Silicon containing, e.g. silica, silex, quartz or glass beads
    • C11D3/1246—Silicates, e.g. diatomaceous earth
    • C11D3/128—Aluminium silicates, e.g. zeolites
    • 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
    • C11D11/00—Special methods for preparing compositions containing mixtures of detergents
    • C11D11/0082—Special methods for preparing compositions containing mixtures of detergents one or more of the detergent ingredients being in a liquefied state, e.g. slurry, paste or melt, and the process resulting in solid detergent particles such as granules, powders or beads
    • C11D11/0088—Special methods for preparing compositions containing mixtures of detergents one or more of the detergent ingredients being in a liquefied state, e.g. slurry, paste or melt, and the process resulting in solid detergent particles such as granules, powders or beads the liquefied ingredients being sprayed or adsorbed onto solid particles
    • 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
    • C11D11/00—Special methods for preparing compositions containing mixtures of detergents
    • C11D11/02—Preparation in the form of powder by spray drying
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/02—Inorganic compounds ; Elemental compounds
    • C11D3/04—Water-soluble compounds
    • C11D3/08—Silicates
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/02—Inorganic compounds ; Elemental compounds
    • C11D3/04—Water-soluble compounds
    • C11D3/10—Carbonates ; Bicarbonates

Definitions

  • the invention relates to a spray-dried detergent or a component for this, the spray-dried detergent or the component both good washing-in behavior and good dissolving behavior having.
  • the invention also relates to a washing process, wherein the spray-dried detergent into a commercial washing machine is washed in.
  • nonionic surfactants have a very high cleaning ability, what they are especially for use at washing temperatures of 60 ° C. and makes it suitable below.
  • non-ionic surfactants can only be spray-dried in certain Process quantities, otherwise there is excessive smoke formation in the Exhaust air from the spray towers and the poor flowability of the spray powder is coming. They also increase when incorporated into the slurry simultaneous presence of anionic surfactants whose viscosity is undesirable Wise. Methods have therefore been developed in which the liquid or melted nonionic surfactant on the previously spray dried Grain is mixed or sprayed onto a carrier.
  • EP-A-0 360 330 known mixtures of nonionic surfactants and fatty acids on a spray-dried base powder to spray, the spray-dried Base powder contained phosphates, and this treated spray-dried Process grain with substances such as carbonate.
  • Spray-dried carrier grains which are treated with nonionic surfactants were, for example, from the European patent application EP-A-0 149 264 and German patent applications DE-A-34 44 960, DE-A-35 45 947 and DE-A-39 36 405 are known.
  • the object of the invention was therefore a spray-dried Provide detergent that has both good wash-in behavior also has good dissolving behavior.
  • the quantities a) to e) relate to that which has not been aftertreated spray-dried grain unless otherwise stated in the text.
  • spray-dried products are used Detergent or components claimed for this, in which the Weight ratio of the spray-dried grain to the nonionic Surfactant is 10: 1 to 25: 1 and in particular 12: 1 to 20: 1.
  • the Agents as inorganic builder substances c) at least one silicate Builders, especially aluminosilicates and / or amorphous sodium and / or potassium silicates.
  • the agents advantageously contain at least one silicate builder in combination with sodium and / or Potassium carbonate.
  • aluminosilicates are fine-crystalline, synthetic and bound water-containing zeolites, such as zeolite A in detergent quality.
  • zeolite X and zeolite P and mixtures of zeolite A, X and / or P are also suitable.
  • the zeolite can be used as a spray-dried powder or as an undried stabilized suspension which is still moist from its production.
  • the zeolite in the event that the zeolite is used as a suspension, it can contain small additions of nonionic surfactants as stabilizers, for example 1 to 3% by weight, based on the zeolite, of ethoxylated C 12 -C 18 fatty alcohols with 2 to 5 Ethylene oxide groups, C 12 -C 14 fatty alcohols with 4 to 5 ethylene oxide groups or ethoxylated isotridecanols.
  • Suitable powdered 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.
  • sodium silicates with a Na 2 O: SiO 2 molar ratio of 1: 1 to 1: 4.5, preferably 1: 2 to 1: 3.5, are particularly suitable.
  • the content of the spray-dried grain in alkali carbonates and / or hydrogen carbonates, in particular in sodium carbonates and / or sodium bicarbonates, is preferably 3 to 25% by weight and in particular 10 to 25% by weight, while amorphous silicates, in particular sodium silicates with a Na 2 O: SiO 2 ratio of 1: 2 to 1: 3.5 is advantageously contained in amounts of 0.5 to 7.5% by weight, based on the spray-dried grain.
  • zeolite can vary widely in the spray dried grain vary. Both embodiments are preferred, which are more than 30% by weight and in particular at least 35% by weight of zeolite (based on contain anhydrous active substance) as well as such embodiments, the maximum 30% by weight of zeolite (based on anhydrous active substance) exhibit. In the latter cases, it is preferred that in the preparation for the aftertreated with nonionic surfactants spray-dried grain further builder substances can be added.
  • the spray-dried grain is treated with non-ionic surfactants, this aftertreatment by spraying on the nonionic surfactants or an aqueous solution or dispersion of nonionic surfactants on the spray-dried grain.
  • the spraying can, for example on conveyor belts once, several times or continuously.
  • a procedure in which nonionic surfactants are preferred is preferred mixed with the spray-dried grain in a mixer or the nonionic surfactants in a mixer on the spray dried grain be sprayed on.
  • compression can occur in this mixer of the grain take place, which causes an increase in bulk density.
  • the non-ionic surfactants used in the aftertreatment are preferably alkoxylated, advantageously ethoxylated, in particular primary alcohols having preferably 8 to 18 carbon atoms and an average of 1 to 12 moles of ethylene oxide (EO) per mole of alcohol, in which the alcohol radical is linear or preferably in the 2-position methyl may be branched or may contain linear and methyl-branched radicals in the mixture, as are usually present in oxo alcohol radicals.
  • 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, 5 EO or 7 EO and mixtures thereof, such as mixtures of C 12 -C 14 alcohol with 3 EO and C 12 -C 18 alcohol with 5 EO.
  • the degrees of ethoxylation given represent statistical averages, which can be an integer or a fraction for a specific product.
  • Preferred alcohol ethoxylates have a narrow homolog distribution (narrow range ethoxylates, NRE).
  • 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 can also be used as further nonionic surfactants, in which R is a primary straight-chain or methyl-branched, in particular methyl-branched aliphatic radical having 8 to 22, preferably 12 to 18, carbon atoms means and G is the symbol that stands for a glycose unit with 5 or 6 carbon atoms, preferably for glucose.
  • the degree of oligomization x which indicates the distribution of monoglycosides and oligoglycosides, is any number between 1 and 10 and is preferably 1.1 to 1.4.
  • nonionic surfactants of the amine oxide type for example N-cocoalkyl-N, N-dimethylamine oxide and N-tallow alkyl-N, N-dihydroxyethylamine oxide, and the fatty acid alkanolamides may be suitable.
  • the amount of this nonionic Surfactants are preferably no more than that of the ethoxylated ones Alcohols, especially not more than half of them.
  • Suitable surfactants are polyhydroxy fatty acid amides, which are 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.
  • the spray-dried grain itself should not amount to more than 2% by weight Have nonionic surfactants.
  • the spray-dried grain preferably contains aftertreatment even a maximum of 1% by weight of nonionic surfactants. It is even preferred that these nonionic surfactants are added to the slurry not added, but only via raw materials used, in which they e.g. B. are used as stabilizers in the spray-dried slurry.
  • non-ionic surfactants come here again primarily the alkoxylated, preferably ethoxylated alcohols and fatty alcohols as well as alkyl glycosides and Polyhydroxy fatty acid amides into consideration.
  • the grain to be spray-dried contains anionic surfactants in amounts of 3 to 20% by weight, with amounts of 5 to 15% by weight being preferred.
  • anionic surfactants are C 9 -C 13 alkylbenzenesulfonates, olefin sulfonates, ie mixtures of alkene and hydroxyalkanesulfonates, and also disulfonates such as are obtained, for example, from C 12 -C 18 -onoolefins with a terminal or internal double bond by sulfonating with gaseous Sulfur trioxide and subsequent alkaline or acidic hydrolysis of the sulfonation products is considered.
  • alkanesulfonates obtained from C 12 -C 18 alkanes, for example by sulfochlorination or sulfoxidation with subsequent hydrolysis or neutralization
  • esters of ⁇ -sulfofatty acids are also suitable, e.g. ⁇ -sulfonated methyl esters of hydrogenated coconut, palm kernel or tallow fatty acids, as well as those obtainable from these by ester cleavage ⁇ -sulfo fatty acids or their di-salts.
  • Suitable anionic surfactants are sulfonated fatty acid glycerol esters.
  • Fatty acid glycerol esters are the mono-, di- and triesters as well as their To understand mixtures as they are produced by esterification of a monoglycerin with 1 to 3 moles of fatty acid or in the transesterification of Triglycerides with 0.3 to 2 moles of glycerin can be obtained.
  • Preferred sulfated 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. If you start from fats and Oils, i.e. natural mixtures of different fatty acid glycerol esters off, it is necessary to in the feed products before sulfonation to saturate itself with hydrogen in a known manner.
  • Suitable feedstocks are palm oil, palm kernel oil, palm stearin, Olive oil, rapeseed oil, corander oil, sunflower oil, cottonseed oil, peanut oil, Linseed oil, lard oil or lard.
  • the sulfonation products represent a complex Mixture represents that mono-, di- and triglyceride sulfonates with ⁇ -standing and / or internal sulfonic acid grouping.
  • sulfonated fatty acid salts glyceride sulfates, Glycerin sulfates, glycerin and soaps. If you go from the sulfation of saturated Fatty acids or hardened fatty acid glycerol ester mixtures, the proportion of ⁇ -sulfonated fatty acid disalts can vary depending on the procedure can be up to about 60% by weight.
  • Suitable surfactants of the sulfate type are the sulfuric acid monoesters from primary alcohols of natural and synthetic origin.
  • 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.
  • 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 16 -C 18 alk (en) yl sulfates are particularly preferred from the point of view of washing technology. It can also be particularly advantageous and particularly advantageous for machine-wash detergents to use C 16 -C 18 -alk (en) yl sulfates in combination with lower melting anionic surfactants and in particular with those anionic surfactants which have a lower force point and at relatively low washing temperatures of for example, room temperature to 40 ° C show a lower tendency to crystallize.
  • the compositions therefore contain mixtures of short-chain and long-chain fatty alkyl sulfates, preferably mixtures of C 12 -C 14 fatty alkyl sulfates or C 12 -C 18 fatty alkyl sulfates with C 16 -C 18 fatty alkyl sulfates and in particular C 12 -C 16 -Fatty alkyl sulfates with C 16 -C 18 fatty alkyl sulfates.
  • not only saturated alkyl sulfates but also unsaturated alkyl sulfates with an alkenyl chain length of preferably C 16 to C 22 are used.
  • the sulfuric acid monoesters of the straight-chain or branched C 7 -C 21 alcohols ethoxylated with 1 to 6 mol ethylene oxide such as 2-methyl-branched C 9 -C 11 alcohols with an average of 3.5 mol EO or C 12 -C 18 - Fatty alcohols with 1 to 4 EO are suitable. Because of their high foaming behavior, they are used in detergents only in relatively small amounts, for example in amounts of 1 to 5% by weight.
  • Preferred anionic surfactants are also the salts of alkylsulfosuccinic acid, which are also referred to as sulfosuccinates or as sulfosuccinic acid esters and which represent monoesters and / or diesters of sulfosuccinic acid with alcohols, preferably fatty alcohols and in particular ethoxylated fatty alcohols.
  • Preferred sulfosuccinates contain C 8 to C 18 fatty alcohol residues or mixtures thereof.
  • Particularly preferred sulfosuccinates contain a fatty alcohol residue which is derived from fatty alcohols which, viewed in isolation, are nonionic surfactants.
  • alk (en) ylsuccinic acid with preferably 8 to 18 carbon atoms in the alk (en) yl chain or salts thereof.
  • Preferred anionic surfactant mixtures contain combinations with alk (en) yl sulfates, in particular combinations of alk (en) yl sulfates and alkylbenzenesulfonates.
  • the anionic surfactants can be in the form of their sodium, potassium or ammonium salts as well as soluble salts of organic bases, such as mono-, di- or Triethanolamine.
  • the anionic surfactants are preferably in Form of their sodium or potassium salts, especially in the form of the sodium salts in front.
  • the agents can also contain soaps, preferably in amounts of at most 5% by weight, in particular in amounts of Contain 0.5 to 3 wt .-%.
  • Saturated fatty acid soaps are particularly 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 soaps lie like the anionic surfactants preferably in the form of their sodium or potassium salts, in particular in the form the sodium salts.
  • the preferred salts used are the sodium sulfates and / or potassium sulfates, which are known to be used in spray drying processes is advantageous. These neutral salts are preferred and in particular sodium sulfate in amounts of 5 to 25% by weight.
  • the aftertreated spray-dried components can be used as further components
  • Means also contain organic builder substances.
  • organic builder substances include, for example Polycarboxylic acids or their salts, such as citric acid, adipic acid, Succinic acid, glutaric acid, tartaric acid, sugar acids, aminocarboxylic acids, Nitrilotriacetic acid (NTA), provided such use ecological reasons are not objectionable, as well as mixtures of these.
  • NTA Nitrilotriacetic acid
  • sugar acids can reduce the Slurry viscosity and lead to an increase in bulk density.
  • Suitable polymeric polycarboxylates are, for example, the sodium salts polyacrylic acid or polymethacrylic acid, for example those with a relative molecular weight of 800 to 150,000 (based on acid).
  • Suitable copolymeric polycarboxylates are, in particular, those of acrylic acid with methacrylic acid and acrylic acid or methacrylic acid with maleic acid. Copolymers of acrylic acid have been found to be particularly suitable Maleic acid proven to be 50 to 90% by weight acrylic acid and 50 to 10% by weight Contain maleic acid.
  • Their relative molecular mass, based on free acids is generally 5,000 to 200,000, preferably 10,000 to 120,000 and in particular 50,000 to 100,000.
  • Terpolymers for example those described in DE-A-43 00 772 as monomers Salts of acrylic acid and maleic acid as well as vinyl alcohol or Vinyl alcohol derivatives or according to DE-C-42 21 381 as monomer salts of Acrylic acid and 2-alkylallylsulfonic acid as well as sugar derivatives.
  • Other preferred copolymers are those described in the German patent applications DE 43 03 320 and P 44 17 734.8 are described and as Monomers preferably acrolein and acrylic acid or acrylic acid salts or Have vinyl acetate.
  • Suitable builder systems are oxidation products from carboxyl-containing polyglucosans and / or their water-soluble Salts such as those used in the international patent application WO-A-93/08251 are described or their production, for example, in of international patent application WO-A-93/16110.
  • More suitable Builder substances are polyacetals, which are produced by the implementation of Dialdehydes with polyol carboxylic acids, which have 5 to 7 carbon atoms and at least 3 have hydroxyl groups, for example as in the European patent application EP-A-0 280 223 can be obtained.
  • Preferred Polyacetals are made from dialdehydes such as glyoxal, glutaraldehyde, Terephthalaldehyde and mixtures thereof and from polyol carboxylic acids such as Obtain gluconic acid and / or glucoheptonic acid.
  • the content of the spray-dried agents in organic builder substances is generally between 0.5 and 10% by weight, preferably between 2 and 8% by weight.
  • the agents can also contain components which and grease washability from textiles positively. This effect becomes particularly clear when a textile that is already soiled is soiled previously several times with a detergent according to the invention that this oil and contains fat-dissolving component, is washed.
  • nonionic cellulose ethers such as methyl cellulose and methyl hydroxypropyl cellulose with a proportion on methoxyl groups from 15 to 30% by weight and on hydroxypropoxyl groups from 1 to 15% by weight, based in each case on the nonionic Cellulose ether, as well as the polymers known from the prior art Phthalic acid and / or terephthalic acid or their derivatives, in particular Polymers made from ethylene terephthalates and / or polyethylene glycol terephthalates or anionically and / or nonionically modified derivatives of these.
  • the agents can also contain components which have solubility improve.
  • Such components are, for example, polyethylene glycols with a relative molecular mass between 200 and 4000, preferably up to 2000, but also fatty alcohols with 20 to 80 moles of EO per mole of fatty alcohol, for example tallow fatty alcohol with 30 EO and tallow fatty alcohol with 40 EO, but also the fatty alcohol already mentioned for the non-ionic surfactants with 14 EO.
  • the spray-dried agents can include conventional foam inhibitors. These include, for example, soaps of natural or synthetic origin, which have a high proportion of C 18 -C 24 fatty acids.
  • Suitable non-surfactant-like foam inhibitors are, for example, organopolysiloxanes and their mixtures with microfine, optionally silanized silica, and paraffins, waxes, microcrystalline waxes and their mixtures with silanized silica or bistearylethylenediamide. Mixtures of various foam inhibitors are also used with advantages, for example those made of silicones, paraffins or waxes.
  • the salts of polyphosphonic acids are preferably the neutral ones Sodium salts of, for example, 1-hydroxyethane-1,1-diphosphonate, Diethylenetriaminepentamethylenephosphonate or ethylenediaminetetramethylenephosphonate used in amounts of 0.1 to 1.5 wt .-%.
  • Further constituents can be graying inhibitors, for example, which have the task of removing the dirt detached from the fiber in the To keep the fleet suspended and thus prevent graying.
  • water-soluble colloids mostly organic in nature, for example the water-soluble salts of polymeric carboxylic acids, glue, gelatin, Salts of ether carboxylic acids or ether sulfonic acids of starch or Cellulose or salts of acidic sulfuric acid esters of cellulose or Strength.
  • Water-soluble polyamides containing acidic groups are also suitable for suitable for this purpose. Soluble starch preparations and use starch products other than the above, e.g. degraded Starch, aldehyde starches, etc. Polyvinylpyrrolidone can also be used.
  • cellulose ethers such as carboxymethyl cellulose (sodium salt), Methyl cellulose, hydroxyalkyl cellulose and mixed ethers, such as methyl hydroxyethyl cellulose, Methyl hydroxypropyl cellulose, methyl carboxymethyl cellulose and their mixtures, as well as polyvinylpyrrolidone, for example in Amounts of 0.1 to 5 wt .-% used.
  • the agents can also contain optical brighteners, for example derivatives contain the diaminostilbenedisulfonic acid or its alkali metal salts. Suitable are e.g. Salts of 4,4'-bis (2-anilino-4-morpholino-1,3,5-triazinyl-6-amino) stilbene-2,2'-disulfonic acid or similarly constructed Compounds that have a diethanolamino group instead of the morpholino group, a methylamino group, an anilino group or a 2-methoxyethylamino group wear. Brighteners of the substituted type can also be used Diphenyl styrenes may be present, e.g.
  • the content of the spray-dried granules in these components is e) preferably less than 30% by weight and in particular less than 25 % By weight.
  • the aftertreated spray-dried agents are characterized by an excellent Dishwashing behavior as well as an excellent dissolving behavior out.
  • Conditions are simulated to determine the induction behavior, that of a induction device operated under critical conditions correspond to a household washing machine.
  • 100 g of product are given, after one 1 minute rest time becomes 10 1 tap water within 80 seconds fed.
  • the amount of residue that remains after that is for post-treated spray-dried agents preferably less than 5 g and especially less than 2 g.
  • the aftertreated spray-dried agents are preferably given notes judged less than 4.
  • the hand wash as well as that for the washing process simulates the important dissolving speed of a detergent in the washing machine.
  • the aftertreated spray-dried agents preferably have Residues less than 10% and especially less than 5% on.
  • the aftertreated are spray-dried grains with other components of detergents processed. It is particularly preferred here that the treatment only a maximum of 5% by weight, based on the finished detergent other nonionic surfactants can be introduced.
  • the other ingredients, which are spray dried afterwards Grain are added, especially those that are temperature and / or are sensitive to water and are therefore not without decomposition atomize.
  • the blended components include bleaches such as Peroxy bleaches and bleach activators, enzymes and enzyme stabilizers, Dyes and fragrances, opacifiers and pearlescent agents, if appropriate but also foam inhibitors, especially those containing silicone and / or paraffin Foam inhibitors that adhere to a granular, water-soluble or dispersible carrier are bound.
  • bleaches such as Peroxy bleaches and bleach activators, enzymes and enzyme stabilizers, Dyes and fragrances, opacifiers and pearlescent agents, if appropriate but also foam inhibitors, especially those containing silicone and / or paraffin Foam inhibitors that adhere to a granular, water-soluble or dispersible carrier are bound.
  • bleaching agents are, for example, sodium percarbonate, peroxypyrophosphates, citrate perhydrates and H 2 O 2 -producing peracid salts or peracids, such as perbenzoates, peroxophthalates, diperazelaic acid or diperdodecanedioic acid.
  • the bleach content of the detergents is preferably 5 to 25% by weight and in particular 10 to 20% by weight, based in each case on the finished detergent.
  • bleach activators can be incorporated into the preparations.
  • these are N-acyl or 0-acyl compounds which form organic peracids with H 2 O 2 , preferably N, N'-tetraacylated diamines, p- (alkanoyloxy) benzenesulfonates, furthermore carboxylic anhydrides and esters of polyols such as glucose pentaacetate.
  • Other known bleach activators are acetylated mixtures of sorbitol and mannitol, as described, for example, in European patent application EP-A-0 525 239.
  • the bleach activators contain bleach activators in the usual range, preferably between 1 and 10% by weight and in particular between 3 and 8% by weight, again each based on the finished detergent.
  • Particularly preferred bleach activators are N, N, N ', N'-tetraacetylethylene diamine (TAED), 1,5-diacetyl-2,4-dioxo-hexahydro-1,3,5-triazine (DADHT) and acetylated sorbitol-mannitol mixtures (SORMAN).
  • Enzymes come from the class of proteases, lipases or lipolytic acting enzymes, for example cutinases, amylases, cellulases or their mixtures in question.
  • Bacterial strains are particularly suitable or mushrooms, such as Bacillus subtilis, Bacillus licheniformis, Streptomyces griseus and Humicola insolens enzymatic active ingredients obtained.
  • Proteases of the subtilisin type and in particular are preferred Proteases obtained from Bacillus lentus are used.
  • Enzyme mixtures for example from protease and amylase or protease and Lipase or lipolytic enzymes or protease and cellulase or from cellulase and lipase or lipolytic enzymes or from protease, Amylase and lipase or lipolytic enzymes or protease, Lipase or lipolytic enzymes and cellulase, in particular however, protease and / or lipase-containing mixtures or mixtures with lipolytic enzymes of particular interest.
  • Peroxidases too or oxidases can be used.
  • the enzymes can on carriers adsorbed and / or embedded in enveloping substances to protect them against premature To protect decomposition.
  • the proportion of enzymes, enzyme mixtures or enzyme granules can, for example, about 0.1 to 5 wt .-%, preferably 0.1 to about 2% by weight, based in each case on the finished detergent, be.
  • the stabilizers come in particular for per-compounds and enzymes salts of polyphosphonic acids already mentioned. Is possible also the use of proteases with soluble calcium salts and a Calcium content of preferably about 1.2% by weight, based on the enzyme, are stabilized.
  • ingredients in detergents that can be used to prepare the post-treated spray-dried component also include other builder substances.
  • these additional builder substances are free of zeolite.
  • the preferred further builder substances include inorganic silicates such as crystalline layered silicates, amorphous silicates or compounds composed of amorphous silicates and carbonates, but also organic builder substances such as citric acid / citrate or Sokalan DCS (R) .
  • Preferred crystalline layered sodium silicates are those of the general formula NaMSi x O 2x + 1 .yH 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.
  • Such crystalline layered silicates are described, for example, in European patent application EP-AO 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.
  • the amorphous silicates or silicate-containing compounds can have been produced by spray drying, granulation and / or compacting, for example by roller compaction. Some of these silicates and granates containing carbonate and silicate are available as commercial products. Reference is made here, for example, to the commercial products Britesil (R) from Akzo & Nobel, Nabion 15 (R) from Rhönen-Poulenc, Gransil ( R) from Colin Stewart or Dizzil (R) G from Akzo & Nobel.
  • These other builder substances are preferably used in amounts of 5 to 20 wt .-%, based on the total detergent used.
  • the content of the post-treated spray-dried component in such a way processed detergent is at least 55 wt .-% of Total detergent.
  • the detergents according to the invention can because of their physical Properties both for example directly via a dosing aid into the washing drum as well as via the induction unit from commercial washing machines can be dosed. Since it is in the inventive Detergents are those that are both excellent A flushing behavior as well as a dissolving behavior is another Embodiment of the invention a method for washing white and / or colored textiles preferred, a detergent according to the invention or a component for this via a in a commercial washing machine intended induction device is dosed.
  • Agent M1 according to the invention was obtained by aftertreatment of 69.8 parts by weight of a spray-dried product P1 of the composition given below with 4.5 parts by weight of a C 12 -C 18 fatty alcohol with 7 EO.
  • an agent V1 with the same composition as M1 but containing 64.5 parts by weight of a spray-dried and untreated product in admixture with 9.8 parts by weight of a premix of 83% by weight sodium carbonate and 17% by weight.
  • % C 12 -C 18 fatty alcohol with 7 EO (the remaining nonionic surfactant was contained in the spray-dried product), and an agent V2 likewise with the same composition as M1, but containing 54.6 parts by weight of a spray-dried and untreated product in Mixture with 19.7 parts by weight of a carrier grain impregnated with C 12 -C 18 fatty alcohol with 7 EO, which consists of 54.6% by weight zeolite A (anhydrous active substance), 1.5% by weight tallow fatty alcohol with 5 EO (as stabilizer), 2% by weight of a C 12 -C 18 sodium fatty acid soap, 3.25% by weight of a copolymeric salt of acrylic acid and maleic acid, 22.8% by weight of C 12 -C 18 fatty alcohol 7 EO and rest of the water was made.
  • the total amount of C 12 -C 18 fatty alcohol with 7 EO was accordingly 6% by weight in M1 and in V1 and V2.
  • composition of P1 in% by weight C 9 -C 13 alkylbenzenesulfonate (sodium salt) 5.35 C 16 -C 18 tallow fatty alcohol sulfate (sodium salt) 5.35 C 12 -C 18 fatty acid soap (sodium salt) 2.15 sodium 11.45 Sodium sulfate 9.05 Zeolite (anhydrous active substance) 41.1 Copolymer of acrylic acid and maleic acid (sodium salt) 4.3 amorphous sodium disilicate 3.15 Phosphonate 0.5 water 14.45 Salts from solutions rest Induction behavior Residue behavior medium Residue in g in tub washing machine note in hand wash test in% M1 0.1 3.5 1.5 V1 3.3 4.0 15 V2 17.5 2.9 5.1 V3 18.5 5.8 3.3 V4 5.1 3.4 14.9
  • Two detergents M2 and M3 were prepared, which contained the spray-dried components P2 and P3, 57.5 parts by weight of P2 and P3 initially containing 3.8 parts by weight of C 12 -C 18 fatty alcohol with 7 EO and C 12 -C 18 fatty alcohol were post-treated with 5 EO and then with 14.2 parts by weight of Nabion 15 (R) (commercial product from Rhönen-Poulenc) or a spray-dried soda-silicate compound of 20 wt. Parts of perborate tetrahydrate, 3 parts by weight of bleach activator (TAED), 1 part by weight of enzyme granulate and 0.5 part by weight of a granular foam inhibitor based on silicone oil.
  • R Nabion 15
  • TAED bleach activator
  • compositions P2 and P3 in% by weight C 9 -C 13 alkylbenzenesulfonate (sodium salt) 6.95 6.95 C 16 -C 18 tallow fatty alcohol sulfate (sodium salt) 6.95 6.95 C 12 -C 18 fatty acid soap (sodium salt) 2.6 2.6 sodium 12.2 12.2 Sodium sulfate 16.1 22.45 Zeolite (anhydrous active substance) 28.35 28.35 Copolymer of acrylic acid and maleic acid (sodium salt) 6.9 6.9 amorphous sodium silicate (Na 2 O: SiO 2 1: 3.3) 5.2 --- Phosphonate 1.0 1.0 water 11.4 10.2 Salts from solutions rest rest rest
  • the bulk density of the compositions M1 to M3 and V1 to V2 was between 450 and 550 g / l.
  • Induction behavior Residue behavior medium Residue in g in tub washing machine note in hand wash test in% M2 --- 2.6 2.1 M3 0.1 2.9 2.9

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Claims (12)

  1. Détergent séché par pulvérisation ou composant pour celui-ci, contenant des agents tensioactifs anioniques, des substances adjuvantes inorganiques, ainsi que d'autres constituants de détergent,
    caractérisé en ce qu'
    il contient sous forme de granulés séchés par pulvérisation :
    a) de 3 à 20 % en poids d'agents tensioactifs anioniques,
    b) de 0 à 2 % en poids d'agents tensioactifs non ioniques,
    c) de 20 à 65 % en poids de substances adjuvantes inorganiques (par rapport à la matière active anhydre) du groupe des carbonates, carbonates acides et substances adjuvantes silicatées,
    d) de 0 à 25 % en poids de sels neutres,
    e) d'autres constituants habituels, sous réserve que le grain séché par pulvérisation est traité ultérieurement avec des agents tensioactifs non ioniques.
  2. Agent selon la revendication 1,
    caractérisé en ce que
    le rapport pondéral du granulé séché par pulvérisation à l'agent tensioactif non ionique se situe entre 10:1 et 25:1 et de préférence entre 12:1 et 20:1.
  3. Agent selon la revendication 1 ou 2,
    caractérisé en ce qu'
    il contient au moins un adjuvant silicaté, de préférence une zéolithe et/ou des silicates de sodium et/ou de potassium amorphes et en particulier une combinaison d'au moins un adjuvant silicaté et d'un carbonate de sodium et/ou de potassium.
  4. Agent selon l'une des revendication 1 à 3,
    caractérisé en ce qu'
    il contient de 3 à 25 % en poids, de préférence de 10 à 25 % en poids, de carbonate de métal alcalin et/ou de carbonate acide de métal alcalin, de préférence de carbonate de sodium et/ou de carbonate acide de sodium.
  5. Agent selon l'une des revendications 1 à 4,
    caractérisé en ce qu'
    il contient des silicates amorphes, en particulier des silicates de sodium ayant un rapport Na2SiO2 de 1:2 à 1:3,5, à des quantités de 0,5 à 7,5 % en poids.
  6. Agent selon l'une des revendications 1 à 5,
    caractérisé en ce qu'
    il contient plus de 30 % en poids de zéolithe (par rapport à la matière active anhydre) et de préférence au moins 35 % en poids de zéolithe (par rapport à la matière active anhydre).
  7. Agent selon l'une des revendications 1 à 5,
    caractérisé en ce qu'
    il contient au maximum 30 % en poids de zéolithe (par rapport à la matière active anhydre.
  8. Agent selon l'une des revendications 1 à 8,
    caractérisé en ce qu'
    il contient du sulfate de sodium et/ou du sulfate de potassium à des quantités de 5 à 25 % en poids.
  9. Détergent contenant un composant séché par pulvérisation et post-traité selon l'une des revendications 1 à 8,
    caractérisé en ce que
    ce composant est préparé avec d'autres constituants de détergents, qui en particulier introduisent au maximum au moins 5 % en poids, par rapport au détergent prêt à l'emploi, d'autres agents tensioactifs non ioniques.
  10. Détergent selon la revendication 9,
    caractérisé en ce que
    le composé séché par pulvérisation et post-traité constitue au moins 55 % en poids du produit détergent.
  11. Détergent selon la revendication 9 ou 10,
    caractérisé en ce que
    le composant séché par pulvérisation et post-traité est préparé avec d'autres substances adjuvantes, qui sont de préférence dépourvues de zéolithe, ces autres substances adjuvantes étant en particulier contenues à des quantités de 5 à 20 % en poids, par rapport à l'ensemble du détergent.
  12. Procédé de lavage de textiles blancs et/ou colorés,
    caractérisé en ce qu'
    un détergent séché par pulvérisation ou un composant pour celui-ci, contenant des agents tensioactifs anioniques, des substances adjuvantes inorganiques ainsi que d'autres constituants de détergents, dans lequel le granulé séché par pulvérisation contient :
    a) de 3 à 20 % en poids d'agents tensioactifs anioniques,
    b) de 0 à 2 % en poids d'agents tensioactifs non ioniques,
    c) de 20 à 65 % en poids de substances adjuvantes inorganiques (par rapport à la matière active anhydre) du groupe des carbonates, carbonates acides et substances adjuvantes silicatées,
    d) de 0 à 25 % en poids de sels neutres,
    e) d'autres constituants habituels, sous réserve que le grain séché par pulvérisation est traité ultérieurement avec des agents tensioactifs non ioniques,
    et dans lequel le granulé séché par pulvérisation subit un post-traitement avec des agents tensioactifs non ioniques, est dosé par un dispositif d'introduction prévu à cet effet dans une machine à laver habituelle du commerce.
EP95942725A 1995-01-12 1995-12-22 Detergent seche par pulverisation ou constituant pour celui-ci Revoked EP0802965B1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE19500644A DE19500644B4 (de) 1995-01-12 1995-01-12 Sprühgetrocknetes Waschmittel oder Komponente hierfür
DE19500644 1995-01-12
PCT/EP1995/005092 WO1996021713A1 (fr) 1995-01-12 1995-12-22 Detergent seche par pulverisation ou constituant pour celui-ci

Publications (2)

Publication Number Publication Date
EP0802965A1 EP0802965A1 (fr) 1997-10-29
EP0802965B1 true EP0802965B1 (fr) 2000-04-12

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US (1) US5948747A (fr)
EP (1) EP0802965B1 (fr)
JP (1) JP3841431B2 (fr)
AT (1) ATE191742T1 (fr)
DE (2) DE19500644B4 (fr)
ES (1) ES2146796T3 (fr)
WO (1) WO1996021713A1 (fr)

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US20030203832A1 (en) * 2002-04-26 2003-10-30 The Procter & Gamble Company Low organic spray drying process and composition formed thereby
US8246986B2 (en) 2003-09-26 2012-08-21 Alza Corporation Drug coating providing high drug loading
MXPA06003454A (es) * 2003-09-26 2006-08-31 Johnson & Johnson Formulaciones de liberacion controlada de analgesicos opioides y no opiodes.
US20070259033A1 (en) * 2003-09-26 2007-11-08 Evangeline Cruz Controlled release formulations exhibiting an ascending rate of release
US8541026B2 (en) 2004-09-24 2013-09-24 Abbvie Inc. Sustained release formulations of opioid and nonopioid analgesics
EP2123742A1 (fr) * 2008-05-14 2009-11-25 The Procter and Gamble Company Compositions de détergent solide pour lessive comprenant du sel de silicate à faible densité
MY187405A (en) 2014-09-29 2021-09-22 Malaysian Palm Oil Board Powder form of methyl ester sulphonates (mes) and process for producing the same

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WO1996021713A1 (fr) 1996-07-18
JPH10512007A (ja) 1998-11-17
EP0802965A1 (fr) 1997-10-29
ATE191742T1 (de) 2000-04-15
DE19500644B4 (de) 2010-09-09
ES2146796T3 (es) 2000-08-16
DE19500644A1 (de) 1996-07-18
JP3841431B2 (ja) 2006-11-01
DE59508178D1 (de) 2000-05-18
US5948747A (en) 1999-09-07

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