EP0802965B1 - Spray-dried washing agent or component therefor - Google Patents

Abstract

PCT No. PCT/EP95/05092 Sec. 371 Date Aug. 11, 1997 Sec. 102(e) Date Aug. 11, 1997 PCT Filed Dec. 22, 1995 PCT Pub. No. WO96/21713 PCT Pub. Date Jul. 18, 1996A spray-dried particulate detergent composition containing a) 3% to 20% by weight of anionic surfactant, b) 0 to 2% by weight of nonionic surfactant, c) 20% to 65% by weight of inorganic builders, based on water-free active substance, selected from carbonates, hydrogen carbonates and silicate-based builders, and d) 0 to 25% by weight of neutral salts, based on the weight of the spray-dried composition, wherein the spray-dried composition has been aftertreated with nonionic surfactant. The composition has favorable dispensing and solubility properties.

Description

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.

As is well known, 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. Depending on their hydrophilicity However, 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. For example, from European patent application 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.

However, the process variants described lead to powders that either good washing behavior or good dissolving properties or neither good dissolving properties and good wash-in behavior.

The object of the invention was therefore a spray-dried Provide detergent that has both good wash-in behavior also has good dissolving behavior.

a) 3 bis 20 Gew.-% Aniontenside,

b) 0 bis 2 Gew.-% nichtionische Tenside,

c) 20 bis 65 Gew.-% anorganische Buildersubstanzen (bezogen auf wasserfreie Aktivsubstanz) aus der Gruppe der Carbonate, Hydrogencarbonate und silikatischen Buildersubstanzen,

d) 0 bis 25 Gew.-% Neutralsalze,

e) weitere übliche Bestandteile

mit der Maßgabe enthält, daß das sprühgetrocknete Korn mit nichtionischen Tensiden nachbehandelt ist.Accordingly, the invention relates in a first embodiment to a spray-dried detergent or a component therefor, comprising anionic surfactants, inorganic builder substances and other ingredients of detergents, the agent being in the spray-dried grain

a) 3 to 20% by weight of anionic surfactants,

b) 0 to 2% by weight of nonionic surfactants,

c) 20 to 65% by weight of inorganic builder substances (based on anhydrous active substance) from the group of the carbonates, bicarbonates and silicate builder substances,

d) 0 to 25% by weight of neutral salts,

e) other common ingredients

with the proviso that the spray-dried grain is treated with nonionic surfactants.

The quantities a) to e) relate to that which has not been aftertreated spray-dried grain unless otherwise stated in the text.

Surprisingly, excellent flushing and dissolving properties obtained for such spray-dried components, although they only with nonionic surfactants and not - as described in EP-A-0 360 330 - With mixtures of non-ionic surfactants and fatty acids were treated.

In a special embodiment of the invention, 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.

In a further preferred embodiment of the invention, 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.

Particularly suitable aluminosilicates are fine-crystalline, synthetic and bound water-containing zeolites, such as zeolite A in detergent quality. However, 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. 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 μm (volume distribution; measurement method: Coulter Counter) and preferably contain 18 to 22% by weight, in particular 20 to 22% by weight, of bound water.

Of the amorphous silicate class, 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.

The amounts of 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. However, 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. At the same time, 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. However, 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). In addition to these nonionic surfactants, 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.

In addition, 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.

Also 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.

Other 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. Preferably the derive Polyhydroxy fatty acid amides of reducing sugars with 5 or 6 carbon atoms, especially on the glucose.

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. As 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. In particular, those of the sulfonate and sulfate type are used as anionic surfactants. Preferred surfactants of the sulfonate type 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. Also suitable are alkanesulfonates obtained from C ₁₂ -C ₁₈ alkanes, for example by sulfochlorination or sulfoxidation with subsequent hydrolysis or neutralization.

The esters of α-sulfofatty acids (ester sulfonates) are also suitable, e.g. α-sulfonated methyl esters of hydrogenated coconut, palm kernel or tallow fatty acids, as well as those obtainable from these by ester cleavage α-sulfo fatty acids or their di-salts.

Other suitable anionic surfactants are sulfonated fatty acid glycerol esters. Under 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. Typical Examples of 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 α-standing and / or internal sulfonic acid grouping. As by-products 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 α-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. 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 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. In a preferred embodiment of the invention, 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. In a further preferred embodiment of the invention, however, not only saturated alkyl sulfates but also unsaturated alkyl sulfates with an alkenyl chain length of preferably C ₁₆ to C ₂₂ are used. Mixtures of saturated sulfated fatty alcohols predominantly consisting of C ₁₆ and unsaturated sulfated fatty alcohols predominantly consisting of C ₁₈ are particularly preferred, for example those derived from solid or liquid HD-0cenol ^(R) fatty alcohol mixtures (commercial product of the applicant) . Weight ratios of alkyl sulfates to alkenyl sulfates from 10: 1 to 1: 2 and in particular from about 5: 1 to 1: 1 are preferred.

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. Again, sulfosuccinates whose fatty alcohol residues are derived from ethoxylated fatty alcohols with a narrow homolog distribution are particularly preferred. It is also possible to use 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.

In addition to the anionic surfactants, 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. These 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. In particular, the use of 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. Particularly preferred are also 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.

Other 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.

Also known are the other preferred builder substances To name polyaspartic acids or their salts and derivatives. 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.

In addition, 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. Among the preferred oil and fat-dissolving components include, for example, 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.

In addition, 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. For this are 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. Prefers however, 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 alkali salts of 4,4'-bis (2-sulfostyryl) diphenyl, 4,4'-bis (4-chloro-3-sulfostyryl) diphenyl, or 4- (4-chlorostyryl) -4 '- (2-sulfostyryl) diphenyl. Mixtures of the aforementioned brighteners can be used.

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. In the experimental device (Zanussi induction channel) 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.

Note 1:

einwandfrei, keine erkennbaren Rückstände;

Note 2:

tolerierbare, vereinzelte, noch nicht störende Rückstände;

Note 3:

erkennbare, bei kritischer Beurteilung bereits störende Rückstände;

ab Note 4:

deutlich erkennbare und störende Rückstände in steigender Anzahl und Menge.

To determine the dissolving behavior, residues on dark textiles are simulated in two different tests. In the first test, 30 l of tap water are first introduced into a tub washing machine (Arcelik type or comparable type), then 5.4 g / l of the agent are added and dissolved by stirring. The laundry, consisting of various dark-colored, easy-care delicate items made of wool, cotton, polyamide and polyacrylonitrile, is then inserted and the machine is heated to a temperature of 30 ° C. After this temperature has been reached, the laundry is washed for 10 minutes by actuating the agitator, then the washing liquor is drained off, rinsed three times with 30 l of water each time and the laundry is spun for 15 seconds. The laundry is dried with an infrared heater and graded by 5 trained people according to the following scheme (averaging):

Note 1:

flawless, no recognizable residues;

Grade 2:

tolerable, isolated, not yet disturbing residues;

Note 3:

recognizable residues that are already annoying in the event of a critical assessment;

from grade 4:

clearly recognizable and annoying residues in increasing number and quantity.

The aftertreated spray-dried agents are preferably given notes judged less than 4.

In a second test, the hand wash as well as that for the washing process simulates the important dissolving speed of a detergent in the washing machine.

8 g of the detergent to be tested are placed in a 2 1 beaker with stirring (800 rpm with laboratory stirrer / propeller stirring head 1.5 cm from Beaker bottom centered) sprinkled. The trial is in tap water performed at 16 ° d. The wash liquor is then passed through poured a sieve. The beaker is covered with very little cold water rinsed out the sieve. There is a double determination. The sieves are in the Drying cabinet at 40 ° C ± 2 ° C dried to constant weight. The Detergent residue is balanced. The backlog is called the mean given in percent from the two individual determinations. In the event of deviations from the Individual results by more than 20% from each other are further attempts carried out. The aftertreated spray-dried agents preferably have Residues less than 10% and especially less than 5% on.

In a particularly preferred embodiment of the invention, therefore post-treated spray-dried detergents or components therefor, what residues in the described wash-in test of less than 2 g, preferably even less than 1 g, a residue behavior in the Vat washing machine with a grade less than 4 and in the hand washing test of have less than 5%.

In a preferred embodiment of the invention, 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.

In particular, 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.

Among the compounds which serve as bleaching agents and supply H ₂ O ₂ in water, sodium perborate tetrahydrate and sodium perborate monohydrate are of particular importance. Further 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.

In order to achieve an improved bleaching effect when washing at temperatures of 60 ° C and below, bleach activators can be incorporated into the preparations. Examples of 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. Are there 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.

Other ingredients in detergents that can be used to prepare the post-treated spray-dried component also include other builder substances. In a preferred embodiment of the invention, however, 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 induction behavior as well as the dissolving behavior or the residue behavior the processed detergent is in the same preferred ranges, as specified for the post-treated spray-dried component were.

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.

Examples Example 1:

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. For comparison, 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.

As stated in the description, the rinsing-in behavior as well as the dissolving behavior and the residue test of all 3 agents were measured both in the tub washing machine and in the simulated hand washing test. Comparative examples V3 and V4 were commercial products from competitors (see Table 1). 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

Example 2:

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.

Again, both the washing-in behavior and the residue behavior were measured in the tub washing machine and in the hand washing test for the agents M2 and M3 according to the invention (see Table 2). The agent M2 left no residue in the induction channel. The amount of detergent used was already completely washed in after 8 l of the water flowing through. 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

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

Claims (12)

1. A spray-dried detergent or a component therefor containing anionic surfactants, inorganic builders and other ingredients of detergents, the detergent containing

   a) 3 to 20% by weight of anionic surfactants,

   b) 0 to 2% by weight of nonionic surfactants,

   c) 20 to 65% by weight of inorganic builders (based on water-free active substance) from the group of carbonates, hydrogen carbonates and silicate-based builders,

   d) 0 to 25% by weight of neutral salts, and

   e) other typical ingredients

   in the spray-dried particles, with the proviso that the spray-dried particles are aftertreated with nonionic surfactants.
2. A detergent as claimed in claim 1, characterized in that the ratio by weight of the spray-dried particles to nonionic surfactant is 10:1 to 25:1 and preferably 12:1 to 20:1.
3. A detergent as claimed in claim 1 or 2, characterized in that it contains at least one silicate-based builder, preferably zeolite and/or amorphous sodium and/or potassium silicates and, more particularly, a combination of at least one silicate-based builder and sodium and/or potassium carbonate.
4. A detergent as claimed in any of claims 1 to 3, characterized in that it contains 3 to 25% by weight and preferably 10 to 25% by weight of alkali metal carbonate and/or alkali metal hydrogen carbonate, preferably sodium carbonate and/or sodium hydrogen carbonate.
5. A detergent as claimed in any of claims 1 to 4, characterized in that it contains amorphous silicates, more particularly sodium silicates with an Na₂O to SiO₂ ratio of 1:2 to 1:3.5, in quantities of 0.5 to 7.5% by weight.
6. A detergent as claimed in any of claims 1 to 5, characterized in that it contains more than 30% by weight of zeolite (based on water-free active substance) and preferably at least 35% by weight of zeolite (based on water-free active substance).
7. A detergent as claimed in any of claims 1 to 5, characterized in that it contains at most 30% by weight of zeolite (based on water-free active substance).
8. A detergent as claimed in any of claims 1 to 7, characterized in that it contains sodium and/or potassium sulfate in quantities of 5 to 25% by weight.
9. A detergent containing an aftertreated spray-dried component as claimed in any of claims 1 to 8, characterized in that this component is compounded with other detergent ingredients which introduce only at most 5% by weight, based on the final detergent, of other nonionic surfactants.
10. A detergent as claimed in claim 9, characterized in that the aftertreated spray-dried component makes up at least 55% by weight of the detergent.
11. A detergent as claimed in claim 9 or 10, characterized in that the aftertreated spray-dried component is blended with other builders which are preferably zeolite-free, these other builders being present in particular in quantities of 5 to 20% by weight, based on the detergent as a whole.
12. A process for washing white and/or colored textiles, characterized in that a spray-dried detergent or a component therefor containing anionic surfactants, inorganic builders and other ingredients of detergents, the detergent containing

    a) 3 to 20% by weight of anionic surfactants,

    b) 0 to 2% by weight of nonionic surfactants,

    c) 20 to 65% by weight of inorganic builders (based on water-free active substance) from the group of carbonates and silicate-based builders,

    d) 0 to 25% by weight of neutral salts, and

    e) other typical ingredients of detergents,

    being present in the spray-dried particles, and the spray-dried particles having been aftertreated with nonionic surfactants,
    is introduced via a dispenser provided for this purpose in a commercial washing machine.