EP0802965A1

EP0802965A1 - Spray-dried washing agent or component therefor

Info

Publication number: EP0802965A1
Application number: EP95942725A
Authority: EP
Inventors: Fred Schambil; Wolfram Linke; Hubert Freese
Original assignee: Henkel AG and Co KGaA
Current assignee: Henkel AG and Co KGaA
Priority date: 1995-01-12
Filing date: 1995-12-22
Publication date: 1997-10-29
Anticipated expiration: 2015-12-22
Also published as: ES2146796T3; EP0802965B1; JPH10512007A; JP3841431B2; WO1996021713A1; DE19500644A1; DE59508178D1; DE19500644B4; ATE191742T1; US5948747A

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

"Spray-dried detergent or component therefor"

The invention relates to a spray-dried detergent or a component therefor, the spray-dried detergent or the component therefor having both good washing-in behavior and good dissolving behavior. The invention also relates to a washing method, in which the spray-dried detergent is washed into a commercially available washing machine via a washing-in chamber.

As is known, nonionic surfactants have a very high cleaning power, which makes them particularly suitable for use at washing temperatures of 60 ° C. and below. Depending on their hydrophilicity, however, nonionic surfactants can only be processed by spray drying in certain quantities, since otherwise there is excessive smoke formation in the exhaust air from the spray towers and poor sprayability of the spray powder. In addition, when incorporated into the slurry in the presence of anionic surfactants, they undesirably increase its viscosity. Processes have therefore been developed in which the liquid or melted nonionic surfactant is mixed onto the previously spray-dried grain or sprayed onto a carrier substance. For example, it is known from European patent application EP-A-0 360 330 to spray mixtures of nonionic surfactants and fatty acids onto a spray-dried base powder, the spray-dried base powder containing phosphates, and to treat the treated spray-dried grain with substances such as carbonate.

Spray-dried carrier grains which have been after-treated with nonionic surfactants are known, for example, from European patent application EP-A-0 149264 and German patent applications DE-A-3444960, DE-A-3545947 and DE-A-3936405.

However, the process variants described lead to powders which either have good washing-in behavior or good dissolving properties or neither good dissolving properties nor good washing-in behavior. The object of the invention was therefore to provide a spray-dried detergent which has both good wash-in behavior and good dissolving behavior.

Accordingly, the invention relates in a first embodiment to a spray-dried detergent or a component therefor, comprising anionic surfactants, inorganic fluoride substances and other constituents of detergents, the agent in the spray-dried particle a) 3 to 20% by weight 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 carbonates, bicarbonates and silicate builder substances, d) 0 to 25% by weight .-% neutral salts, e) contains other conventional ingredients with the proviso that the spray-dried grain is aftertreated with nonionic surfactants.

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

Surprisingly, excellent washing-in and dissolving properties were obtained for such spray-dried components, although they were only aftertreated with nonionic surfactants and not - as described in EP-A-0360330 - with mixtures of nonionic surfactants and fatty acids.

In a particular embodiment of the invention, spray-dried detergents or components therefor are claimed 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 contain, as inorganic builder substances c), at least one silicate builder, in particular 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 may contain small additions of nonionic surfactants as stabilizers, for example 1 to 3% by weight, based on the zeolite, of ethoxylated Ci2-Ci8-fatty alcohols with 2 to 5 ethylene oxide. Groups, Ci2-Ci4 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 class of amorphous silicates, sodium silicates with a molar ratio Na2θ: Siθ2 of 1: 1 to 1: 4.5, preferably of 1: 2 to 1: 3.5, are particularly suitable.

The content of the spray-dried grain of alkali carbonates and / or hydrogen carbonates, in particular sodium carbonates and / or sodium hydrogen carbonates, is preferably 3 to 25% by weight and in particular 10 to 25% by weight, while amorphous silicates, in particular sodium silicates, contain one Na2θ: Siθ2 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. Embodiments which contain more than 30% by weight and in particular at least 35% by weight of zeolite (based on anhydrous active substance) are preferred, as are embodiments which contain a maximum of 30% by weight zeolite (based on anhydrous active substance) exhibit. In the latter cases, it is preferred that additional builders are added to the spray-dried grain aftertreated with nonionic surfactants.

The spray-dried grain is post-treated with nonionic surfactants, this post-treatment being carried out by spraying the nonionic surfactants or an aqueous solution or dispersion of nonionic surfactants onto the spray-dried grain. Spraying can be carried out once, several times or continuously, for example on conveyor belts. However, preference is given to a procedure in which nonionic surfactants are mixed with the spray-dried grain in a mixer or the nonionic surfactants in a mixer onto the spray-dried grain be sprayed on. At the same time, the grain can be compacted in this mixer, which causes an increase in the bulk density.

The non-ionic surfactants used in the aftertreatment are preferably 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 is linear or preferably in the 2-position May be methyl-branched or line-are and may contain methyl-branched radicals in the mixture, such 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 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, Ci2-Ci4 alcohols with 3 EO or 4 EO, Cg-Cn alcohols with 7 EO, Ci3-Ci5 alcohols with 3 EO, 5 EO, 7 EO or 8 EO, Ci2-Ci8- Alcohols with 3 EO, 5 EO or 7 EO and mixtures of these, such as mixtures of Ci2-Ci4 alcohol with 3 EO and Ci2-Ci8 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 of this are tallow fatty alcohol with 14 EO, 25 EO, 30 EO or 40 EO. In addition, alkyl glycosides of the general formula R0 (G) _x can also be used as further nonionic surfactants, in which R is a primary straight-chain or methyl-branched aliphatic radical with 8 to 22, preferably 12 to, methyl-branched radicals 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-coconut alkyl-N, N-dimethylamine oxide and N-tallow alkyl-N, N-dihydroxyethylamine oxide, and the fatty acid alkanolamides can also be suitable. The amount of these non-ionic surfactants is preferably not more than that of the ethoxylated alcohols, in particular not more than half of them.

Other suitable surfactants are polyhydroxy fatty acid amides, which can usually be obtained by reductive amination of a reducing sugar with ammonia, an alkylamine or an alkanol and subsequent acylation with a fatty acid, a fatty acid alkyl ester or a fatty acid chloride. The polyhydroxy fatty acid amides are preferably derived from reducing sugars with 5 or 6 carbon atoms, in particular from glucose.

The spray-dried grain itself should not contain more than 2% by weight of nonionic surfactants. The spray-dried grain preferably contains only a maximum of 1% by weight of nonionic surfactants before its aftertreatment. It is even preferred that these nonionic surfactants are not added to the slurry, but only via raw materials used, in which they contain e.g. B. are used as stabilizers, are introduced into the spray-dried slurry. The non-ionic surfactants here in turn are primarily the alkoxylated, preferably ethoxylated alcohols and fatty alcohols, and also alkyl glycosides and polyhydroxy fatty acid amides. 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. The anionic surfactants used are, in particular, those of the sulfonate and sulfate type. Preferred surfactants of the sulfonate type are Cg-C ^ alkylbenzenesulfonates, olefin sulfonates, ie mixtures of alkene and hydroxyalkanesulfonates and disulfonates such as are obtained, for example, from C 2 -C 8 -monoolefins with a terminal or internal double bond by sulfo- kidneys with gaseous sulfur trioxide and subsequent alkaline or acid hydrolysis of the sulfonation products. Also suitable are alkanesulfonates which are obtained from Ci2-Ci8-alkanes, for example by sulfochlorination or sulfoxidation with subsequent hydrolysis or neutralization.

Also suitable are the esters of α-sulfofatty acids (ester sulfonates), for example oc-sulfonated methyl esters of hydrogenated coconut, palm kernel or tallow fatty acids, and the α-sulfofatty acids or their di-salts obtainable from these by ester cleavage.

Other suitable anionic surfactants are sulfonated fatty acid glycerol esters. Fatty acid glycerol esters are to be understood as the mono-, di- and triesters and their mixtures as obtained in the production by esterification of a monoglycerol with 1 to 3 moles of fatty acid or in the transesterification of triglycerides with 0.3 to 2 moles of glycerol become. Preferred sulfated fatty acid glycerol esters are the sulfonation products of saturated fatty acids having 6 to 22 carbon atoms, for example caproic acid, caprylic acid, capric acid, myristic acid, lauric acid, palmitic acid, stearic acid or behenic acid. If one starts from fats and oils, that is to say natural mixtures of different fatty acid glycerol esters, it is necessary to largely saturate the starting products with hydrogen in a manner known per se before the sulfonation. Typical examples of suitable feedstocks are palm oil, palm kernel oil, palm stearin, olive oil, rapeseed oil, korea oil, sunflower oil, cottonseed oil, peanut oil, linseed oil, lard oil or lard. The sulfonation products are a complex mixture that contains mono-, di- and triglyceride sulfonates with an α-and / or internal-sulfonic acid grouping. As by-products, sulfonated fatty acid salts, glyceride sulfates, Glycerin sulfates, glycerin and soaps. If one starts from the sulfonation of saturated fatty acids or hardened fatty acid glycerol ester mixtures, the proportion of the α-sulfonated fatty acid disalts can, depending on the procedure, be up to about 60% by weight.

Suitable sulfate-type surfactants are the sulfuric acid monoesters from primary alcohols of natural and synthetic origin. As alk (en) yl sulfates, the alkali and especially the sodium salts of the sulfuric acid half esters of the Ci2-Ci8 fatty alcohols, for example from coconut oil alcohol, tallow fatty alcohol, lauryl, myristyl, cetyl or stearyl alcohol or the Cιo-C2θ ^_ 0xoalcohols 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. Ciss-CJβ-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 washing agents, to use Ci6-Ci8-alk (en) yl sulfates in combination with lower melting anionic surfactants and in particular with those anionic surfactants which have a lower point of action 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 Ci2-Ci4-fatty alkyl sulfates or Cχ2-Ci8-fatty alkyl sulfates with Ci6-Ci8-fatty alkyl sulfates and in particular Ci2-Ci6-fatty alkyl sulfates with Ciβ-Ciβ -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 Ciö to C22 are used. Mixtures of saturated sulfated fatty alcohols consisting predominantly of Cχ6 and unsaturated sulfated fatty alcohols consisting predominantly of Ciβ are particularly preferred, for example those derived from solid or liquid fatty alcohol mixtures of the type HD-0cenol ( ^R ) (commercial product of the applicant) . Weight ratios of alkyl sulfates are too Alkenyl sulfates of 10: 1 to 1: 2 and in particular of about 5: 1 to 1: 1 are preferred.

The sulfuric acid monoesters of the straight-chain or branched C7-C2i alcohols ethoxylated with 1 to 6 mol of ethylene oxide, such as 2-methyl-branched Cg-Cn alcohols with an average of 3.5 mol of EO or Ci2-Ci8 fat 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 are monoesters and / or diesters of sulfosuccinic acid with alcohols, preferably fatty alcohols and in particular ethoxylated fatty alcohols. Preferred sulfosuccinates contain CQ to Ci8 ~ 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, the fatty alcohol residues of which are derived from ethoxylated fatty alcohols with a narrow homolog distribution, are particularly preferred. It is also possible to use alk (en) 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 present 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 of their sodium or potassium salts, in particular in the form of the sodium salts.

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 .-%. Particularly suitable are 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 soap mixtures derived from natural fatty acids, for example coconut, palm kernel or tallow fatty acids. Like the anionic surfactants, the soaps are preferably in the form of their sodium or potassium salts, in particular in the form of the sodium salts.

The preferred neutral salts include sodium sulfates and / or potassium sulfates, which are known to be advantageous in spray drying processes. These neutral salts and in particular sodium sulfate are preferably used in amounts of 5 to 25% by weight.

The aftertreated spray-dried agents can also contain organic builder substances as further constituents. 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 that such use is not objectionable for ecological reasons, and mixtures of these ¬ sen. In particular, the use of sugar acids can reduce the slurry viscosity and increase the bulk density.

Suitable poly ere polycarboxylates are, for example, the sodium salts of 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 of acrylic acid or methacrylic acid with maleic acid. Copolymers of acrylic acid with maleic acid which contain 50 to 90% by weight of acrylic acid and 50 to 10% by weight of maleic acid have proven to be particularly suitable. Their relative molecular weight, based on free acids, is generally 5,000 to 200,000, preferably 10,000 to 120,000 and in particular 50,000 to 100,000. Terpolymers are also particularly preferred, for example those which, according to DE-A-4300772, are monomers Salts of acrylic acid and maleic acid as well as vinyl alcohol or vinyl alcohol derivatives or according to DE-C-4221 381 as mono ere salts of Acrylic acid and 2-alkylallylsulfonic acid and sugar derivatives are included. Further preferred copolymers are those which are described in German patent applications DE 4303 320 and P 44 17734.8 and preferably contain acrolein and acrylic acid or acrylic acid salts or vinyl acetate as monomers .

Further suitable builder systems are oxidation products of carboxyl group-containing polyglucosans and / or their water-soluble salts, as are described, for example, in international patent application WO-A-93/08251 or whose preparation is described, for example, in international patent application WO-A-93/16110.

The known polyaspartic acids or their salts and derivatives are also to be mentioned as further preferred builder substances. Further suitable builder substances are polyacetals, which can be obtained by reacting dialdehydes with polyolcarboxylic acids which have 5 to 7 carbon atoms and at least 3 hydroxyl groups, for example as described in European patent application EP-A-0 280 223. Preferred polyacetals are obtained from dialdehydes such as glyoxal, glutaraldehyde, terephthalaldehyde and their mixtures and from polyol carboxylic acids such as gluconic acid and / or glucoheptonic acid.

The content of the organic dried substances in the spray-dried agents 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 have a positive influence on the oil and fat washability from textiles. This effect is particularly evident when a textile is soiled that has already been washed several times beforehand with a detergent according to the invention which contains this oil and fat-dissolving component. The preferred oil and fat-dissolving components include, for example, nonionic cellulose ethers such as methyl cellulose and methyl hydroxypropyl cellulose with a proportion of methoxyl groups of 15 to 30% by weight and hydroxypropoxyl groups of 1 to 15% by weight, in each case based on the nonionic cellulose ether, and the polymers known from the prior art Phthalic acid and / or terephthalic acid or its derivatives, in particular polymers made from ethylene terephthalates and / or polyethylene glycol terephthalates or anionically and / or nonionically modified derivatives thereof.

The agents can also contain components that improve solubility. Such constituents 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 mol E0 per mol fatty alcohol, for example taig fatty alcohol with 30 E0 and taig fatty alcohol with 40 E0, but also those with the nonionic surfactants called fatty alcohol with 14 E0.

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 Ci8 ~ C24 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 different foam inhibitors are also used with advantages, e.g. those made of silicone, paraffins or waxes.

The salts of polyphosphonic acids which are preferably used are the neutral reacting sodium salts of, for example, l-hydroxyethane-l, l-diphosphonate, diethylenetriaminepentamethylenephosphonate or ethylenediaminetetramethylenephosphonate in amounts of 0.1 to 1.5% by weight.

Further constituents can be graying inhibitors, for example, which have the task of keeping the dirt detached from the fiber suspended in the liquor and thus preventing graying. For this purpose, water-soluble colloids of mostly organic nature are suitable, 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 starch. Water-soluble polyamides containing acidic groups are also suitable for suitable for this purpose. Soluble starch preparations and starch products other than those mentioned above can also be used, for example degraded starch, aldehyde starches, etc. Polyvinylpyrrolidone can also be used. However, preference is given to cellulose ethers such as carboxyethyl cellulose (sodium salt), methyl cellulose, hydroxyalkyl cellulose and mixed ethers such as methyl hydroxyethyl cellulose, methyl hydroxypropyl cellulose, methyl carboxymethyl cellulose and mixtures thereof, and also polyvinylpyrrolidone, for example in amounts of 0.1 to 5% by weight. % used.

The agents can also contain optical brighteners, for example containing derivatives of diastostilbenedisulfonic acid or its alkali metal salts. Salts of 4,4'-bis (2-anilino-4-morpholino-l, 3,5-triazinyl-6-amino) stilbene-2,2'-disulfonic acid or compounds of similar structure which, instead of the morpholino group, contain a diethanolamino - wear a group, a methylamino group, an anilino group or a 2-methoxyethylaio group. Brighteners of the substituted diphenylstyryl type may also 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) diphenyls. Mixtures of the aforementioned brighteners can also be used.

The content of the spray-dried granules in these components e) is preferably less than 30% by weight and in particular less than 25% by weight.

The aftertreated spray-dried compositions are notable for excellent washing-in behavior and also for excellent dissolving behavior. To determine the washing-in behavior, conditions are simulated which correspond to a washing-in device of a household washing machine operated under critical conditions. 100 g of product are added to the test device (Zanussi induction channel). After a rest period of 1 minute, 10 liters of tap water are fed in within 80 seconds. The amount of the residue remaining afterwards is preferably less than 5 g and in particular less than 2 g for the aftertreated spray-dried compositions. To determine the dissolving behavior, residues on dark textiles are simulated in two different tests. In the first test, 30 liters of tap water are first introduced into a tub washing machine (type Arcelik 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, the washing liquor is then 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):

Grade 1: flawless, no discernible residues;

Grade 2: tolerable, isolated, not yet disturbing residues;

Grade 3: recognizable residues which are already disturbing in the case of a critical assessment; from grade 4: clearly recognizable and disruptive residues in increasing numbers and quantities.

The aftertreated spray-dried agents are preferably assessed with grades less than 4.

In a second test, hand washing and the reading speed of a detergent, which is important for the washing process in the washing machine, are simulated.

For this purpose, 8 g of the detergent to be tested are sprinkled into a 2 liter beaker while stirring (800 rpm with a laboratory stirrer / propeller stirring head 1.5 cm from the beaker bottom). The test is carried out in tap water at 16 ° d. The wash liquor is then poured off through a sieve. The beaker is rinsed out with very little cold water over the sieve. There is a double determination. The sieves are dried in a drying cabinet at 40 ^β C i 2 ° C to constant weight. The detergent residue is weighed out. The backlog is called the mean given in percent from the two individual determinations. If the individual results deviate from each other by more than 20%, further tests are carried out. The aftertreated spray-dried compositions preferably have residues of less than 10% and in particular less than 5%.

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

In a preferred embodiment of the invention, the post-treated spray-dried grains are processed with further components of detergents. It is particularly preferred here that the processing brings in only a maximum of 5% by weight, based on the finished detergent, of further nonionic surfactants. The further ingredients which are subsequently added to the aftertreated spray-dried grain are, in particular, those which are sensitive to temperature and / or water and therefore cannot be atomized without decomposition.

In particular, the admixed components include bleaching agents such as peroxy bleaching agents and bleach activators, enzymes and enzyme stabilizers, colorants and fragrances, opacifiers and pearlescent agents, but also, if appropriate, foam inhibitors, in particular foam inhibitors containing silicone and / or paraffin, which adhere to a granular, are soluble or dispersible carrier substance bound in water.

Among the compounds which serve as bleaching agents and supply H2O2 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 H2O2-delivering peracidic salts or peracids, such as perbenzoates, peroxophthalates, diperazelaic acid or diperdodecanedioic acid. The content of funds Bleaching agent is preferably 5 to 25 wt .-% and in particular 10 to 20 wt .-%, each based 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 include N-acyl or O-acyl compounds which form organic peracids with H2O2, preferably N, N'-tetraacylated diamines, p- (alkanoyloxy) benzenesulfonates, furthermore carboxylic acid anhydrides and esters of polyols such as glucose pentaacetate. Further known bleach activators are acetylated mixtures of sorbitol and mannitol, as are described, for example, in European patent application EP-A-0525239. The bleach activator content of the bleach-containing agents is in the usual range, preferably between 1 and 10% by weight and in particular between 3 and 8% by weight, again in each case based on the finished detergent. Particularly preferred bleach activators are N, N, N ', N'-tetraacetylethylenediamine (TAED), 1,5-diacetyl-2,4-dioxo-hexahydro-1,5,5-triazine (DADHT) and acetylated sorbitol-mannitol mixtures (SORMAN).

Suitable enzymes are those from the class of proteases, lipases or lipolytically active enzymes, for example cutinases, amylases, cellulases or mixtures thereof. Enzymatic substances 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 are, for example, from protease and amylase or protease and lipase or lipolitically acting enzymes or protease and cellulase or from cellulase and lipase or lipolitically acting enzymes or from protease, amylase and lipase or lipolitically acting enzymes or proteases , Lipase or lipolytic enzymes and cellulase, but especially protease- and / or lipase-containing mixtures or mixtures with lipolitic enzymes of particular interest. Peroxidases or oxidases can also be used. The enzymes can be adsorbed on carrier substances and / or embedded in Hü11 substances in order to protect them against premature decomposition. The proportion of enzymes, enzyme mixtures or enzyme granules can be, for example, about 0.1 to 5% by weight, preferably 0.1 to about 2% by weight, in each case based on the finished detergent.

The salts of polyphosphonic acids already mentioned come into consideration as stabilizers, in particular for per-compounds and enzymes. It is also possible to use proteases which are stabilized with soluble calcium salts and a calcium content of preferably about 1.2% by weight, based on the enzyme.

The other ingredients of detergents with which the post-treated spray-dried component can be processed also include other builder substances. In a preferred embodiment of the invention, these further builder substances are, however, 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 θ2χ ₊ i'-yH2θ, 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-A-0 164 514. Preferred crystalline sheet silicates of the given formula 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 lδ ( ^R ) from Rhönen-Poulenc, Gransil ( ^R ) from Colin Stewart or Dizzil ( ^R ) G from Akzo & Nobel. These further builder substances are preferably used in amounts of 5 to 20% by weight, based on the total detergent.

However, the content of the aftertreated spray-dried component in a detergent prepared in this way is at least 55% by weight of the total detergent.

The rinsing behavior and the dissolving behavior or the residue behavior of the processed detergents are in the same preferred ranges as were given for the aftertreated spray-dried component.

Due to their physical properties, the detergents according to the invention can be dosed, for example, via a dosing aid directly for use in the washing drum, or via the induction device of commercially available washing machines. Since the detergents according to the invention are those which have both excellent washing-in behavior and dissolving behavior, in a further embodiment of the invention a method for washing white and / or colored textiles is preferred, a detergent according to the invention or a component for this purpose, metering is carried out via a washing-in device provided for this purpose in a commercially available washing machine.

Examples

Example 1 :

Agent M1 according to the invention was prepared 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 with 7 EO. For comparison, an agent VI with the same composition as Ml but containing 64.5 parts by weight of a spray-dried and untreated product in admixture with 9.8 parts by weight of a pre-mixture of 83 was obtained % By weight of sodium carbonate and 17% by weight of C12-Ci8-fatty alcohol with 7 EO (the remaining nonionic surfactant was contained in the spray-dried product), and also an agent V2 likewise with the same composition as Ml, but containing 54.6% by weight Parts of a spray-dried and untreated product mixed with 19.7 parts by weight of a carrier grain impregnated with Ci2-Ci8 ~ fatty alcohol with 7 EO, which consists of 54.6% by weight of zeolite A (anhydrous active substance), 1.5% by weight .-% tallow fatty alcohol with 5 EO (as stabilizer), 2% by weight of a Ci2-Ci8 sodium fatty acid soap, 3.25% by weight of a copolymeric salt of acrylic acid and maleic acid, 22.8% by weight of Ci2-Ci8 -Fatty alcohol with 7 EO and the rest water, herge¬ manufactured. The total amount of Cχ2-Ci8 fatty alcohol with 7 EO was accordingly in Ml as well as in VI and V2 each 6% by weight.

As stated in the description, the rinsing behavior and the dissolving behavior or 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 Pl in% by weight:

Cg-Ci3-Alkylbenzenesulfonate (sodium salt) 5.35

Ci6 ~ Ci8 tallow fatty alcohol sulfate (sodium salt) 5.35

Ci2-Ci8 fatty acid soap (sodium salt) 2.15

Sodium carbonate 11.45

Sodium sulfate 9.05

Zeolite (anhydrous active substance) 41.1

Copolymer of acrylic acid and maleic acid 4.3

(Sodium salt) amorphous sodium disilicate 3.15 phosphonate 0.5 water 14.45 salts from solutions rest

Table 1:

Washing-in behavior residue behavior

Medium residue in vat washing machine in hand washing test in g grade in%

Ml 0.1 3.5 1.5

VI 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 produced, 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 Ci2-Ci8 fatty alcohol with 7 EO and C12-C18 fatty alcohol were post-treated with 5 EO and then with 14.2 parts by weight of Nabion lδ ( ^R ) (commercial product from Rhδne-Poulenc) or a spray-dried soda-silicate compound of 20 parts by weight 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 were prepared.

Again, the detergent behavior and also the residue behavior were measured in the tub washing machine and in the hand washing test for 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 completely washed in after 8 l of the water flowing through.

Compositions P P22 and PP33 in% wt%:

Cg-Ci3-alkylbenzenesulfonate (sodium salt) 6.95 6.95

Ci6-Ci8 tallow fatty alcohol sulfate (sodium salt) 6.95 6.95

Ci2-Ci8 ~ fatty acid soap (sodium salt) 2.6 2.6

Sodium carbonate 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 6.9 6.9

(Sodium salt) amorphous sodium silicate (Na2θ: Siθ2 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 agents Ml to M3 and VI to V2 was between 450 and 550 g / 1.

Table 2:

Detergent behavior Residue behavior

Medium residue in vat washing machine in hand washing test in g grade in%

M2 2.6 2.1 M3 0.1 2.9 2.9

Claims

Patent claims

1. Spray-dried detergent or component therefor, containing anionic surfactants, inorganic builder substances and other ingredients of detergents, characterized in that it contains a) 3 to 20% by weight of anionic surfactants in the spray-dried grain, b) 0 to 2% by weight. % non-ionic surfactants, c) 20 to 65% by weight of inorganic builder substances (based on water-free active substance) from the group of the carbonates, bicarbonates and silicone builders d) 0 to 25% by weight of neutral salts and e) other conventional constituents with the proviso that the spray-dried grain is aftertreated with nonionic surfactants.

2. Composition according to claim 1, characterized in that the ratio by weight of the spray-dried grain to nonionic surfactant is 10: 1 to 25: 1 and preferably 12: 1 to 20: 1.

3. Composition according to claim 1 or 2, characterized in that there is at least one silicate builder, preferably zeolite and / or amorphous sodium and / or potassium silicates and in particular a combination of at least one silicate builder and sodium and / or Contains potassium carbonate.

4. Composition according to one of claims 1 to 3, characterized in that it contains 3 to 25 wt .-%, preferably 10 to 25 wt .-%, alkali carbonate and / or alkali bicarbonate, preferably sodium carbonate and / or sodium bicarbonate.

5. Composition according to one of claims 1 to 4, characterized in that it is amorphous silicates, in particular sodium silicates with a Na2θ: Siθ2 ratio of 1: 2 to 1: 3.5 in amounts of 0.5 to 7.5% by weight. % contains.

6. Composition according to one of claims 1 to 5, characterized in that it contains more than 30 wt .-% zeolite (based on anhydrous active substance) and preferably at least 35 wt .-% zeolite (based on anhydrous active substance).

7. Composition according to one of claims 1 to 5, characterized in that it contains a maximum of 30 wt .-% zeolite (based on anhydrous active substance).

8. Composition according to one of claims 1 to 7, characterized in that it contains sodium and / or potassium sulfate in amounts of 5 to 25 wt .-% ent.

9. Detergent containing a post-treated spray-dried component according to one of claims 1 to 8, characterized in that this component with further constituents of detergents, but in particular a maximum of 5% by weight, based on the finished detergent introduce further nonionic surfactants, is prepared.

10. Detergent according to claim 9, characterized in that the after-treated spray-dried component makes up at least 55% by weight of the detergent.

11. Detergent according to claim 9 or 10, characterized in that the aftertreated spray-dried component is prepared with further buildersub¬ substances, which are preferably zeolite-free, these further builders substances in particular in amounts of 5 to 20 wt .-%, based on all detergents.

12. A process for washing white and / or colored textiles, characterized in that a spray-dried detergent or a component therefor, comprising anionic surfactants, inorganic builder substances and other ingredients of detergents, 3 to 20% by weight in the spray-dried grain a). % Anionic surfactants, b) 0 to 2% by weight of nonionic surfactants, c) 20 to 65% by weight of inorganic builder substances (based on water-free active substance) from the group of the carbonates and silicate builder substances, d) 0 to 25% by weight % Neutral salts and e) further conventional constituents of detergents are contained and the spray-dried grain is post-treated with nonionic surfactants, is metered in via a washing device provided for this purpose in a commercially available washing machine.