EP0961823B1 - Ph-controlled release of detergent components - Google Patents

Abstract

A process for washing textiles is presented involving the delayed release of ingredients from a detergent composition. The process involves first dissolving the detergent in water resulting in a pH below pH 8, slowly dissolving the coating on a coated alkalizing agent to raise the pH to above pH to above pH 8.5, and above pH 8.5 the polymeric acid coating on a detergent ingredient dissolves, releasing the ingredient into the wash water. Also presented is a detergent composition for delayed bleaching of 1 to 40 percent by weight of a coated bleaching agent having a coating which dissolves slowly in water irrespective of the pH value, 0.5 to 15 percent by weight of a bleach activator coated with a polymeric acid, and 0.1 to 40 percent by weight of an acidifying agent. The process results in a delayed release of bleaching in the wash cycle.

Description

The invention relates to coated solid detergent components and detergent compositions, containing these coated components. Specifically affects the Invention detergent compositions that delay one of their ingredients and Dispense controlled to the wash liquor, controlling the release via the pH the washing liquor takes place.

The controlled release of individual detergent components at certain times the washing process is advantageous from an economic and ecological point of view and accordingly subject to intensive research. While basically every single one Detergent component by suitable physical and / or chemical measures can be released at a certain time is this controlled release especially in the context of the interplay of bleaching and enzymatic cleaning of of outstanding importance. Most publications therefore deal with the Solving the problem of separating bleaching and enzymatic cleaning from one another in time, since the aggressive bleaching agents inactivate or even destroy the enzymes. Here are in principle two ways conceivable: Delayed release of the bleach, so that the enzymatic Cleaning is complete before the bleach is released in the wash liquor, or delayed release of the enzymes when the bleaching process is already close is completed. Because the bleach destroys excess enzyme and so does that To prevent remaining on the laundry (odor formation), the first way is usually chosen. On Another advantage that results from the coating of the bleach particles is the increased Storage stability, since uncoated bleaching agents stick to longer storage moist air can be hydrolyzed quickly and so the detergent compositions Lose washing power.

Numerous agents are available for coating the detergent ingredients. in this connection can, depending on the medium, a wide variety of factors such as temperature or Hydrolysis of the shell material can be used for release. A melt coating that the Sheath can only be permeable from a certain temperature is because of today preferred low washing temperatures difficult to achieve because at low Softening temperatures Problems such as clumping occur. Envelope materials that hydrolyzing through sheer moisture also have disadvantages in terms of Storage stability of funds. So you have to look for a wrapping material that On the one hand, under certain conditions in the wash liquor, quickly and without impairment the washing process is soluble, but on the other hand is so stable that storage is no problem is possible.

Detergent and bleaching compositions comprising a source of hydrogen peroxide and a Contain peroxyacid bleach precursors (bleach activator) and one in the wash liquor Provide initial pH in alkaline (pH 10-11), as well as the delayed release of Acid in the wash liquor in order to achieve a reduced pH in the liquor described in the prior art and for example in the European Patent applications EP-A-0 290 081 (Unilever) and EP-A-0 396 287 (Clorox) published.

The delayed release of individual components in detergent compositions containing bleach is mentioned in a number of patents. The international Patent applications WO95 / 28454 (Procter & Gamble) and the series from WO95 / 28464 to WO95 / 28469 (all Procter & Gamble) and WO95 / 28473 (Procter & Gamble) disclose detergent compositions containing bleach containing a hydrogen peroxide precursor and contain a peroxyacid precursor, the delivery of the peroxyacid being so controlled that 50% of the peroxyacid concentration (so-called T50 test) between 180 and 480 seconds is reached. The controlled delivery of the components is through Coating of individual components, defined particle sizes, compacting as well mechanical or manual addition achieved. The vary in the individual registrations In each case coated ingredients: So in WO95 / 28464 is the release of the peracid against the delivery of a complexing agent delayed, in WO95 / 28465 the release of the peracid is compared to the release of a builder is delayed and in WO95 / 28467 there is a before the release of the peracid Enzyme released. WO95 / 28466 describes the delayed release of an enzyme in comparison for dispensing a surfactant and describe WO95 / 28468 and WO95 / 28469 Detergent compositions in which the delivery of an enzyme versus the delivery a complexing agent for heavy metal ions or against a water-soluble builder is delayed. The systematic controlled release of individual ingredients through control the pH value is not described in any patent application of this series.

The coating of bleaching agents or bleach activators is also state of the art well known. U.S. Patent No. 5,000,869 (Safe Aid Products) describes detergent compositions which is a coated and pH-controlled released halogenated glycoluril compound contain. The bleach is coated with a polymer that is above pH 6, preferably between pH 7.2 to 11.

WO94 / 15010 (Procter & Gamble) discloses coating TAED with water-soluble acidic polymers, the coating being in the form of a melt, by spraying or can be applied in the form of solutions and dispersions, and also describes the simultaneous use of percarbonate, which is preferably also coated. The sour Polymer has a solubility of at least 5 g / l at 20 ° C.

EP-A-0 651 053 (Procter & Gamble) describes detergent compositions containing a alkali metal percarbonate coated with alkali metal sulfate and carbonate, a bleach activator and contain a sustained release (coated) acidifying agent so that the pH of the wash liquor (1% solution at 20 ° C) is initially 9.5 to 13 while it after complete release of the acidifying agent is 7 to 9.3. The time to complete release of the acidifying agent is in the range of 30 seconds up to 10 minutes. Only when a pH threshold is undershot is the coating on the Percarbonate attacked and dissolved, so that the bleaching effect occurs.

FR-A-2 180 864 discloses ― a washing and cleaning agent which, among others Ingredients has a coated pH regulator and coated enzymes, so that the pH regulator can set the optimal pH value for the enzyme. The release pH regulator and enzyme occur simultaneously or with a short time delay.

Coated bleaching agents that are only at a rising pH in the wash liquor released are not described in the prior art.

The invention is based on the object of developing a system which is pH-controlled Release of detergent ingredients, especially bleach, allows and the release takes place in an alkaline medium.

The invention accordingly relates to a washing method for washing textiles Fabrics using a solid, particulate detergent composition, wherein the pH of the wash liquor after dissolving the agent is below 8 and as it progresses the washing process by dissolving a coated alkalizing agent to values rises above 8.5, which is a release of a specially coated ingredient and a enable a delayed effect of this ingredient.

In a particular embodiment of the invention, an alkalizing agent is used Bleach, preferably sodium percarbonate, used while as special coated ingredient a bleach activator, preferably tetraacetylethylenediamine (TAED), is used.

a) 1 bis 40 Gew.-% eines beschichteten Bleichmittels,

b) 0,5 bis 15 Gew.-% eines Bleichaktivators,

c) 0,1 bis 40 Gew.-% eines Acidifizierungsmittels,

wobei das Bleichmittel mit einem Hüllmaterial beschichtet ist, welches sich unabhängig vom pH-Wert langsam in Wasser löst, der Bleichaktivator mit einer polymeren Säure beschichtet ist und das Acidifizierungsmittel ohne Beschichtung eingesetzt wird. The invention furthermore relates to a solid, particulate detergent composition comprising

a) 1 to 40% by weight of a coated bleaching agent,

b) 0.5 to 15% by weight of a bleach activator,

c) 0.1 to 40% by weight of an acidifying agent,

the bleaching agent being coated with a coating material which slowly dissolves in water regardless of the pH, the bleaching activator is coated with a polymeric acid and the acidifying agent is used without a coating.

Due to the acidifying agent, the pH in the wash liquor when adding the Detergent composition comparatively low, i.e. it is below 8. Subsequently solves the bleaching agent coating slowly builds up and increases alkaline bleach free, which increases the pH of the wash liquor. exceeds the pH of the liquor has a value of approx. 8.5, the coating of the Dissolve bleach activator and thereby releases the bleach activator. With a temporal Delay now starts the full bleaching effect in the wash liquor. The period up to the beginning of the bleaching action, on the one hand, the amount of added Acidifying agent, on the other hand about the thickness and permeability of the coatings be determined on the bleach and the bleach activator. Depending on the recipe and Washing conditions can range from one to twenty minutes, within which, for example, enzymatic purification can take place without the largest Part of the bleach is present. The detergent composition is through the Coating of both the bleach and the bleach activator have excellent storage stability and shows no loss in bleaching activity even in humid air.

Sodium perborate tetrahydrate and sodium perborate monohydrate are particularly important as coated bleaching agents (component a) which supply H ₂ O ₂ in water. Other usable bleaching agents are, for example, sodium percarbonate, peroxypyrophosphates, citrate perhydrates and salts and salts of peracids which provide H ₂ O ₂ , such as perbenzoic acid, peroxophthalic acid, diperazelaic acid, phthaloiminoperacid or diperdodecanedioic acid. The content of the agents in the coated bleaching agents is 1 to 40% by weight and in particular 10 to 20% by weight, advantageously using perborate monohydrate or percarbonate.

The coating materials for the bleaching agent particles are water-soluble Substances in question that slowly dissolve in the wash liquor, not one abrupt release of the coated bleach and lead to their dissolving properties have no strong pH dependence. In addition, fabrics are preferred, which in turn are used for Do not change the pH of the wash liquor. Preferred as covering materials Fatty alcohols, which can optionally be mixed with other coating materials. exemplary a mixture of fatty alcohols and aluminum stearate should be mentioned here. Other wrapping materials, that have already been used to coat bleach particles, are summarized below in key words: magnesium sulfate and sodium hexaphosphate (BE 857 017, Solvay Interox), dihydrogen phosphate or pyrophosphate (EP 024201, Clorox), phosphonic acids (EP 295 384, Degussa), sodium metaborate and silicate (DE 28 10 379, Degussa), water glass and sodium polyphosphate (DE 27 12 138, Degussa), Sodium sulfate, sodium carbonate and silicate (DE 26 22 610, Solvay Interox), or sodium bicarbonate (DE 24 17 572, Solvay Interox), borax and magnesium sulfate (DE 33 21 082, Kao), Boric acid (DE 28 00 916 Solvay-Interox), but also some organic components such as Fat derivatives, paraffins and waxes (EP 030 759, Solvay Interox, melting temperature of the compounds between 25 and 90 ° C), polyethylene glycols and fatty acid esters thereof with a Molecular weight from 300 to 1,700 (DE 23 37 338, Solvay Interox), combinations with Magnesium oxide (US 4 131 879, Gretay AG and US 4 120 812 and 4 131 562, both FMC Corp.), vinyl chloride-ethylene copolymer emulsions (DE 24 02 393, Solvay Interox) or Vinyl chloride-ethylene-methacrylate copolymer emulsions (DE 24 02 392, Solvay Interox).

The coating materials can be applied from the melt or from solutions or dispersions take place, the solvent or emulsifier being removed by evaporation application as a fine powder, for example by electrostatic techniques possible, although this method leads to irregular and poorly adhering coatings leads. The casing materials can be placed on the in agitators, mixers and granulators Bleach particles are applied. However, application of the wrapping materials is preferred in a fluidized bed, with a simultaneous size classification of the particles can. Under certain circumstances the wrapping materials should turn into sticky products lead, it can be useful to additionally coat the bleach particles with fine particles To apply substances ("powdering"). All fine particles come as powdering agents Substances in question, but also other detergent ingredients such as builder substances can be used. Preferred additional pudding agents are zeolites, silicates, polymeric polycarboxylates, carbonates, citrates, starch, etc. are used. Also a part of the acidifying agent can be used for powdering.

As coated bleach activators (component b) can be compounds that under Perhydrolysis conditions aliphatic peroxocarboxylic acids with preferably 1 to 10 carbon atoms, in particular 2 to 4 carbon atoms, and / or optionally substituted Perbenzoic acid result, are used. Substances containing O- and / or N-acyl groups are suitable the number of carbon atoms mentioned and / or optionally substituted Wear benzoyl groups. Multi-acylated alkylenediamines are preferred, in particular Tetraacetylethylenediamine (TAED), acylated triazine derivatives, especially 1,5-diacetyl-2,4-dioxohexahydro-1,3,5-triazine (DADHT), acylated glycolurils, in particular Tetraacetylglycoluril (TAGU), N-acylimides, especially N-nonanoylsuccinimide (NOSI), acylated phenol sulfonates, especially n-nonanoyl or isononanoyloxybenzenesulfonate (n- or. iso-NOBS), carboxylic anhydrides, especially phthalic anhydride, acylated polyhydric alcohols, especially triacetin, ethylene glycol diacetate, 2,5-diacetoxy-2,5-dihydrofuran and acetylated sorbitol and mannitol or their in the European patent application EP 0 525 239 (Ausimont SPA) (SORMAN), acylated sugar derivatives, in particular pentaacetylglucose (PAG), pentaacetylfructose, Tetraacetylxylose and Octaacetyllactose as well as acetylated, optionally N-alkylated Glucamine and gluconolactone, and / or N-acylated lactams, for example N-benzoylcaprolactam, from international patent applications WO 94/27970, WO 94/28102, WO 94/28103, WO 95/00626 (all Procter & Gamble), WO 95/14759 (Warwick) and WO 95/17498 (Procter & Gamble) are known. The international one Patent application WO 95/14075 (Degussa) also describes acyl lactams preferably used. Also from the German patent application DE 44 43 177 (Henkel) known combinations of conventional bleach activators can be used. Coated bleach activators of this type are present in amounts of 0.5% by weight to 15% by weight, based on total mean.

The bleach activator is coated with polymeric acids, which only change at pH values resolve above 8.5. At pH values below 8, the coated Bleach activator particles in aqueous solution are stirred for hours without being in solution go. Examples of these are polymeric acids which are particularly suitable for coating Called polyacrylates, which are dependent on the required solubilities from the pH value on the one hand and good processability on the other. Other polymeric acids that can be used as coating materials are copolymers from an unsaturated polycarboxylic acid such as maleic acid, citraconic acid, itaconic acid and mesaconic acid with an unsaturated monocarboxylic acid such as acrylic acid or α-alkyl substituted Acrylic acids.

The coating of the bleach activators can basically be done in the same way as that Bleaching agents are coated. A method is preferred in which the polymeric Acids are applied to the bleach activators via a dispersion.

The wrapping materials for both the bleach and the bleach activator are in such quantities used that an optimal interaction of the individual components and thus a precisely controlled release is made possible. Depending on the period, within whose release should not take place and depending on the size of the coated particles you will measure the amount of wrapping material. Use preferred embodiments less than 20% by weight of shell material, based on the mass of the coated particles, in particular less than 10% by weight of wrapping materials are preferred.

The acidifying agent used as the third component is used in amounts of 0.1 to 40 preferably from 1 to 25% by weight, based on the finished composition. As an acidifying agent all water-soluble substances can be used, which are suitable, the pH value to lower an aqueous solution below 8. In interaction with the In this way, other components of the agents according to the invention have a starting pH reached, which is slowly increased as the washing process progresses (release of the Bleach), which eventually releases the pH at 8.5 in the wash liquor Bleach activator and thus leads to the onset of the bleaching effect.

Preferred acidifying agents are inorganic and organic acids, for example the solid mono-, oligo- and polycarboxylic acids such as citric, tartaric and succinic acid, Polycarboxylic acids such as polyacrylic acid, but also acids such as malonic acid, adipic acid, maleic acid, Fumaric acid, oxalic acid, boric acid or amidosulfonic acid and mixtures of the mentioned acids. Acidic salts such as hydrogen sulfates or carbonates can also be used as acidifying agents are used, again in turn only on compliance with the pH conditions must be respected. In order to solve the agents according to the invention as possible Acidifiers are a quick way to get a wash liquor with a pH below 8 to be chosen so that they dissolve quickly and the pH quickly to the desired values bring. A coating that would cause a release delay is for the acidifiers unsuitable for the purposes of the present invention.

From the point of view of application technology, the requirement for the acidifying agent (s) is to be met make sure that they are not volatile. From this point of view, solid acidifiers are which have a low tendency to sublimation and a high melting point with a good one Agree on water solubility, clearly preferred. Liquid or pasty acidifying agents can only in minor amounts below 5 wt .-% of the total composition packaging measures must be taken when they are used to ensure the storage stability even with increased air humidity. liquid and volatile acids or those that cannot be handled in powder detergents, such as hydrochloric acid, Nitrate or sulfuric acid are therefore automatically forbidden the selection of the acidifying agent (s) also ensure that the resulting Washing liquor does not harm textiles or human skin.

The agents according to the invention contain, in addition to the coated components and uncoated Excipients that have a pH-controlled release of the coated ingredients enable other common ingredients for detergents, especially anionic and non-ionic surfactants, builder substances and other auxiliary substances such as soil repellents, Foam inhibitors, salts of polyphosphonic acids, optical brighteners, enzymes, enzyme stabilizers, small amounts of neutral filling salts as well as colors and fragrances, opacifiers or pearlescent agents.

Anionic surfactants used are, for example, those of the sulfonate and sulfate type. Preferred surfactants of the sulfonate type are olefin sulfonates, ie mixtures of alkene and hydroxyalkanesulfonates and disulfonates, such as are obtained, for example, from C _12-18 monoolefins with terminal or internal double bonds by sulfonation with gaseous sulfur trioxide and subsequent alkaline or acid hydrolysis of the Receives sulfonation products. Also suitable are alkanesulfonates which are obtained from C _12-18 alkanes, for example by sulfochlorination or sulfoxidation with subsequent hydrolysis or neutralization: Likewise, the esters of α-sulfofatty acids (ester sulfonates), for example the α-sulfonated methyl esters of the hydrogenated coconut , Palm kernel or tallow fatty acids are suitable.

Other suitable anionic surfactants are sulfonated fatty acid glycerol esters. Among fatty acid glycerol esters the mono-, di- and triesters and their mixtures are to be understood as they are in the Manufactured by esterification of a monoglycerin with 1 to 3 moles of fatty acid or the transesterification of triglycerides with 0.3 to 2 mol of glycerol can be obtained. preferred sulfated fatty acid glycerol esters are the sulfonation products of saturated fatty acids with 6 up to 22 carbon atoms, for example caproic acid, caprylic acid, capric acid, myristic acid, Lauric acid, palmitic acid, stearic acid or behenic acid.

Suitable surfactants of the sulfate type are the sulfuric acid monoesters from primary alcohols of natural and synthetic origin. The alk (en) yl sulfates are the alkali and in particular the sodium salts of the sulfuric acid half esters of C _12-18 fatty alcohols, for example from coconut fatty alcohol, tallow fatty alcohol, lauryl, myristyl, cetyl or stearyl alcohol or the C _10-20 oxo alcohols and those half esters 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 _16-18 alk (en) yl sulfates are particularly preferred for reasons of washing technology. It can also be particularly advantageous, and particularly advantageous for machine washing agents, 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 Krafft point and relatively low ones Washing temperatures of, for example, room temperature to 40 ° C. show a low 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 C _12-18 fatty alkyl sulfates or mixtures of C _12-14 fatty alkyl sulfates or C _12-18 fatty alkyl sulfates with C _16-18 fatty alkyl sulfates and in particular C _12-16 fatty alkyl sulfates with C _16-18 fatty alkyl sulfates. In a further preferred embodiment of the invention, however, not only saturated alkyl sulfates but also unsaturated alkenyl 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 fatty alcohol mixtures of the HD-Ocenol® type (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. 2,3-Alkyl sulfates, which can be prepared, for example, by addition of sulfuric acid to α-oletein, are also suitable.

The sulfuric acid monoesters of the straight-chain or branched C _7-21 alcohols ethoxylated with 1 to 6 mol of ethylene oxide, such as 2-methyl-branched C _9-11 alcohols with an average of 3.5 mol of ethylene oxide (EO) or C _12-18 - Fatty alcohols with 1 to 4 EO are suitable. Because of their high foaming behavior, they are used in cleaning agents only in relatively small amounts, for example in amounts of 1 to 5% by weight.

Other suitable anionic surfactants are also the salts of alkylsulfosuccinic acid, which are also referred to as sulfosuccinates or as sulfosuccinic acid esters and which are monoesters and / or diesters of sulfosuccinic acid with alcohols, preferably fatty alcohols and especially ethoxylated fatty alcohols. Preferred sulfosuccinates contain C _{8 18} fatty alcohol radicals or mixtures thereof. Particularly preferred sulfosuccinates contain a fatty alcohol residue which is derived from ethoxylated fatty alcohols, which in themselves are nonionic surfactants (description see below). 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.

Soaps are particularly suitable as further anionic surfactants. 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. In particular, those soap mixtures are preferred which are composed of 50 to .100% by weight of saturated C _12-24 fatty acid soaps and 0 to 50% by weight of oleic acid soap.

The anionic surfactants including the soaps can be in the form of their sodium, potassium or Ammonium salts and as soluble salts of organic bases, such as mono-, di- or triethanolamine, available. The anionic surfactants are preferably in the form of their sodium or Potassium salts, especially in the form of the sodium salts.

In addition to anionic surfactants, non-ionic, cationic, zwitterionic or amphoteric surfactants can be used. Here are particularly preferred nonionic surfactants.

The nonionic surfactants used are preferably alkoxylated, advantageously ethoxylated, in particular primary alcohols having preferably 8 to 18 carbon atoms and an average of 1 to 12 moles of ethylene oxide (EO) per mole of alcohol, in which the alcohol radical can be linear or preferably methyl-branched in the 2-position or may contain linear and methyl-branched radicals in the mixture, as are usually present in oxo alcohol radicals. 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 _12-14 alcohols with 3 EO or 4 EO, C _9-11 alcohol with 7 EO, C _13-15 alcohols with 3 EO, 5 EO, 7 EO or 8 EO, C _12-18 alcohols with 3 EO, 5 EO or 7 EO and mixtures thereof, such as mixtures of C _12-14 alcohol with 3 EO and C _12-18 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 denotes a primary straight-chain or methyl-branched, in particular methyl-branched aliphatic radical having 8 to 22, preferably 12 to 18, C atoms and G is the symbol which stands for a glycose unit with 5 or 6 carbon atoms, preferably for glucose. The degree of oligomerization x, which indicates the distribution of monoglycosides and oligoglycosides, is any number between 1 and 10; x is preferably 1.2 to 1.4.

Another class of preferred nonionic surfactants, either as the sole nonionic surfactant or used in combination with other nonionic surfactants are alkoxylated, preferably ethoxylated or ethoxylated and propoxylated, fatty acid alkyl esters, preferably with 1 to 4 carbon atoms in the alkyl chain, in particular Fatty acid methyl esters, as described, for example, in Japanese patent application JP 58/217598 or which are preferably described in the international patent application WO-A-90/13533 (Henkel) can be prepared.

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 can be suitable. The amount of these nonionic surfactants is preferably not more than that of the ethoxylated fatty alcohols, especially not more than half of them.

in der RCO für einen aliphatischen Acylrest mit 6 bis 22 Kohlenstoffatomen, R¹ für Wasserstoff, einen Alkyl- oder Hydroxyalkylrest mit 1 bis 4 Kohlenstoffatomen und [Z] für einen linearen oder verzweigten Polyhydroxyalkylrest mit 3 bis 10 Kohlenstoffatomen und 3 bis 10 Hydroxylgruppen steht. Bei den Polyhydroxyfettsäureamiden handelt es sich um bekannte Stoffe, die üblicherweise durch reduktive Aminierung eines reduzierenden Zuckers mit Ammoniak, einem Alkylamin oder einem Alkanolamin und nachfolgende Acylierung mit einer Fettsäure, einem Fettsäurealkylester oder einem Fettsäurechlorid erhalten werden können.Other suitable surfactants are polyhydroxy fatty acid amides of the formula (I),

in which RCO stands for an aliphatic acyl radical with 6 to 22 carbon atoms, R ¹ for hydrogen, an alkyl or hydroxyalkyl radical with 1 to 4 carbon atoms and [Z] for a linear or branched polyhydroxyalkyl radical with 3 to 10 carbon atoms and 3 to 10 hydroxyl groups. The polyhydroxy fatty acid amides are known substances which can usually be obtained by reductive amination of a reducing sugar with ammonia, an alkylamine or an alkanolamine and subsequent acylation with a fatty acid, a fatty acid alkyl ester or a fatty acid chloride.

in der R für einen linearen oder verzweigten Alkyl- oder Alkenylrest mit 7 bis 12 Kohlenstoffatomen, R¹ für einen linearen, verzweigten oder cyclischen Alkylrest oder einen Arylrest mit 2 bis 8 Kohlenstoffatomen und R² für einen linearen, verzweigten oder cyclischen Alkylrest oder einen Arylrest oder einen Oxy-Alkylrest mit 1 bis 8 Kohlenstoffatomen steht, wobei C_1-4-Alkyl- oder Phenylreste bevorzugt sind und [Z] für einen linearen Polyhydroxyalkylrest steht, dessen Alkylkette mit mindestens zwei Hydroxylgruppen substituiert ist, oder alkoxylierte, vorzugsweise ethoxylierte oder Propxylierte Derivate dieses Restes.The group of polyhydroxy fatty acid amides also includes compounds of the formula (II)

in which R represents a linear or branched alkyl or alkenyl radical having 7 to 12 carbon atoms, R ^{1 represents} a linear, branched or cyclic alkyl radical or an aryl radical having 2 to 8 carbon atoms and R ^{2 represents} a linear, branched or cyclic alkyl radical or an aryl radical or an oxyalkyl radical having 1 to 8 carbon atoms, C _1-4 -alkyl or phenyl radicals being preferred and [Z] being a linear polyhydroxyalkyl radical whose alkyl chain is substituted by at least two hydroxyl groups, or alkoxylated, preferably ethoxylated or propylated Derivatives of this rest.

[Z] is preferably obtained by reductive amination of a reduced sugar, for example Glucose, fructose, maltose, lactose, galactose, mannose or xylose. The N-alkoxy or N-aryloxy-substituted compounds can then, for example, according to the Teaching of international application WO-A-95/07331 (Procter & Gamble) by implementation with fatty acid methyl esters in the presence of an alkoxide as catalyst in the desired Polyhydroxy fatty acid amides are transferred.

In addition to the surfactant components, the detergent granules can also contain builder substances and other ingredients of detergents.

In addition to silicates, other builders and cobuilder substances can be used as builders in the Detergent compositions are used. These include in particular zeolites, Citrates and polymeric polycarboxylates.

Suitable crystalline, layered sodium silicates have 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-A-0 164 514. Preferred crystalline layered silicates of the formula given are those in which M represents sodium and x assumes the values 2 or 3. In particular, both β- and δ-sodium disilicate Na ₂ Si ₂ O ₅ .yH ₂ O are preferred, wherein β-sodium disilicate can be obtained, for example, by the method described in international patent application WO-A-91/08171 (Henkel) is.

Amorphous sodium silicates with a modulus Na ₂ O: SiO ₂ of 1: 2 to 1: 3.3, preferably from 1: 2 to 1: 2.8 and in particular from 1: 2 to 1: 2.6, can also be used are delayed in dissolving and have secondary washing properties. The delay in dissolution compared to conventional amorphous sodium silicates can be caused in various ways, for example by surface treatment, compounding, compacting / compression or by overdrying. In the context of this invention, the term “amorphous” is also understood to mean “X-ray amorphous”. This means that the silicates in X-ray diffraction experiments do not provide sharp X-ray reflections, as are typical for crystalline substances, but at most one or more maxima of the scattered X-rays, which have a width of several degree units of the diffraction angle. However, it can very well lead to particularly good builder properties if the silicate particles deliver washed-out or even sharp diffraction maxima in electron diffraction experiments. This is to be interpreted as meaning that the products have microcrystalline areas of size 10 to a few hundred nm, values up to max. 50 nm and in particular up to max. 20 nm are preferred. Such so-called X-ray amorphous silicates, which also have a delay in dissolution compared to conventional water glasses, are described, for example, in German patent application DE-A-44 00 024 (Henkel). Compacted / compacted amorphous silicates, compounded amorphous silicates and over-dried X-ray amorphous silicates are particularly preferred.

The finely crystalline, synthetic and bound water-containing zeolite used is preferably zeolite A and / or P. As zeolite P, zeolite MAP® (commercial product from Crosfield) is particularly preferred. However, zeolite X and mixtures of 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 minor additions of nonionic surfactants as stabilizers, for example 1 to 3% by weight, based on 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 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.

It goes without saying that the generally known phosphates are also used as builder substances possible if such use is not avoided for ecological reasons should be. The sodium salts of orthophosphates, pyrophosphates, are particularly suitable and especially the tripolyphosphates. Their salary is generally not more than 25 wt .-%, preferably not more than 20 wt .-%, each based on the finished Medium. In some cases it has been shown that tripolyphosphates in particular are already in small amounts up to a maximum of 10% by weight, based on the finished agent, in combination with other builder substances to a synergistic improvement of the secondary washing ability to lead.

Other suitable organic builder substances are dextrins, for example oligomers or polymers of carbohydrates, which can be obtained by partial hydrolysis of starches. The hydrolysis can be carried out by customary processes, for example acid-catalyzed or enzyme-catalyzed. They are preferably hydrolysis products with average molecular weights in the range from 400 to 500,000. A polysaccharide with a dextrose equivalent (DE) in the range from 0.5 to 40, in particular from 2 to 30, is preferred, DE being a customary measure for is the reducing effect of a polysaccharide compared to dextrose, which has a DE of 100. Both maltodextrins with a DE between 3 and 20 and dry glucose syrups with a DE between 20 and 37 as well as so-called yellow dextrins and white dextrins with higher molar masses in the range from 2000 to 30000 can be used. A preferred dextrin is described in British patent application 94 19 091 (Cerestar) described. The oxidized derivatives of such dextrins are their reaction products with oxidizing agents which are capable of oxidizing at least one alcohol function of the saccharide ring to the carboxylic acid function. Such oxidized dextrins and processes for their preparation are known, for example, from European patent applications EP-A-0 232 202 (Roquette Freres), EP-A-0 427 349 (Natural Science Institute NL), EP-A-0 472 042 (Fertec Ferruzzi) and EP-A-0 542 496 (Procter & Gamble) and international patent applications WO-A-92/18542 (Novamont), WO-A-93/08251 (Henkel), WO-A-94/28030 (Henkel), WO -A-95/07303 (Natural Science Institute NL), WO-A-95/12619 (Agricultural Institute NL) and WO-A-95/20608 (Henkel). A product oxidized at C _{6 of} the saccharide ring can be particularly advantageous.

Further suitable cobuilders are, preferably, oxydisuccinates and other derivatives of disuccinates Ethylenediamine. Are particularly preferred in this context also glycerol disuccinates and glycerol trisuccinates, such as those found in the United States Patents US 4,524,009, US 4,639,325 (both Staley), in European Patent application EP-A-0 150 930 (Staley) and Japanese patent application JP 93/339896 can be described. Suitable amounts are those containing zeolite and / or formulations containing silicate at 3 to 15% by weight.

Other useful organic cobuilders are, for example, acetylated hydroxycarboxylic acids or their salts, which may also be in lactone form and which at least 4 carbon atoms and at least one hydroxyl group and a maximum of two Acid groups included. Such cobuilders are used, for example, in the international Patent application WO-A-95/20029 (Henkel).

In addition to surfactants, bleaches and builders, detergents can contain a large number of compounds are used, for example foam inhibitors, phosphonates, Enzymes and optical brighteners called.

When used in machine washing processes, it can be advantageous to add conventional foam inhibitors to the agents. Suitable foam inhibitors are, 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 foam inhibitors, in particular silicone or paraffin-containing foam inhibitors, are preferably bound to a granular, water-soluble or dispersible carrier substance. Mixtures of paraffins and bistearylethylenediamides are particularly preferred.

The salts of polyphosphonic acids are preferably the neutral sodium salts for example 1-hydroxyethane-1,1-diphosphonate, diethylenetriaminepentamethylenephosphonate or ethylene diamine tetramethylene phosphonate in amounts from 0.1 to 1.5% by weight.

Enzymes come from the class of proteases, lipases, amylases, cellulases or their mixtures in question. From bacterial strains or fungi, such as Bacillus subtilis, Bacillus licheniformis and Streptomyces griseus Agents. Proteases of the subtilisin type and in particular are preferred Proteases obtained from Bacillus lentus are used. Here are enzyme mixtures, for example from protease and amylase or protease and lipase or protease and Cellulase or from cellulase and lipase or from protease, amylase and lipase or protease, Lipase and cellulase, but especially cellulase-containing mixtures of particular Interest. Peroxidases or oxidases have also proven to be suitable in some cases. The enzymes can be adsorbed on carriers and / or embedded in coating substances to protect them against premature decomposition. The proportion of enzymes, enzyme mixtures or enzyme granules can, for example, about 0.1 to 5 wt .-%, preferably 0.1 to about 2 wt .-%.

The agents according to the invention can be derivatives of diaminostilbenedisulfonic acid as optical brighteners or their 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 which instead of the morpholino group a diethanolamino group, a Carry a methylamino group, an anilino group or a 2-methoxyethylamino group. In addition, brighteners of the substituted diphenylstyryl type 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 invention described above should in principle not apply to the coating of Bleaches and bleach activators may be limited. Rather, everyone should Detergent ingredient coated according to the invention and thus controlled pH-controlled can be released. The parameters to be observed are generally those Coating the pH-controlled ingredient to be released with polymeric acids Coating an alkalizing agent with a shell that is slowly soluble in water dissolves regardless of the pH of the wash liquor, as well as the use of an uncoated Acidifying agent that enables a low starting pH in the wash liquor. By slowly dissolving the water-soluble shell, the wash liquor at Release of the alkalizing agent becomes increasingly alkaline until at pH values above 8.5, the shell finally begins to detach from the polymeric acids and thereby releases the pH-controlled ingredient to the wash liquor. So are For example, variants are also conceivable in which acid bleaching takes place and then a Is released that destroys the bleach. About the respective thickness of the A further delay can be achieved, so that the time of coating Release can be determined well.

Examples Coating the bleach activator:

Crystalline tetraacetylethylenediamine (TAED) was 5: 1 with a 32% Polyacrylate dispersion mixed, granulated and dried at 45 ° C. That way Granules obtained show a high stability and can be in a pH neutral to weakly acidic The surfactant solution should be stirred for several hours without going into solution. In alkaline Solution (pH> 8.5) the granules disintegrate in 1 to 2 minutes.

Bleach coating:

Commercial sodium percarbonate was made from a mixture at 15% by weight of its weight Fatty alcohols and aluminum stearate (2: 1) coated. Here the hell material in Form of a melt applied, which does not penetrate deep into the particles and so a relative forms a homogeneous covering layer so that the particles dissolve within a narrow period of time. The coated bleach particles were used to obtain good free-flowing granules additionally powdered with rice starch.

Production of the detergent:

A bleach and enzyme-free detergent composition comprising surfactants, builders and auxiliaries (for composition, see Table 1) was mixed with the coated bleach particles, the coated bleach activator particles and with crystalline citric acid in the amounts given in Table 2. Ingredients of the detergent composition (% by weight). Soap 5.42 Sodium C _12-14 alkyl benzene sulfonate 22.67 Sodium C _14-16 fatty alcohol sulfate 4.59 C _12-18 fatty alcohol-5 EO 0.81 sodium 4.55 Zeolite A 29.86 sodium silicate 8.00 Acrylic acid-maleic acid copolymer 16.16 opt. brighteners 0.45 phosphonate 2.30 NaOH, 50% 0.63 water 3.88 other salts 0.68 Ingredients of the detergent composition according to the invention (% by weight) detergent composition 59.5% by weight coated bleach (Na percarbonate) 23.3% by weight coated bleach activator (TAED) 7% by weight Citric acid monohydrate 10.2% by weight

The detergent obtained in this way was dissolved in water (30 ° C, 16 ° d, dosage: 6 g / l) and the release of the TAED as peracetic acid was determined iodometrically. Right after Dissolution of the detergent dropped the pH to around 6.5, then within four Minutes to rise to values above 8.5 (pH = 9.2 after 5 min. Constant). The release of the Peracetic acid only started after 4 minutes, i.e. only at pH values of the wash liquor above 8.5.

Claims (8)

1. A washing process for washing textiles using a solid particulate detergent composition, the pH value of the wash liquor being below 8 when the detergent is added and rising to values above pH 8.5 through the dissolution of a coated alkalizing agent as the washing process progresses, the pH values above 8.5 enabling an ingredient coated with polymeric acids to be released and allowing that ingredient to develop its effect with delay.
2. A washing process as claimed in claim 1, characterized in that the coated alkalizing agent is a bleaching agent of which an aqueous solution shows an alkaline reaction, preferably sodium percarbonate.
3. A washing process as claimed in claim 1 or 2, characterized in that the specially coated ingredient is a bleach activator, preferably tetraacetyl ethylenediamine (TAED).
4. A solid particulate detergent composition containing

   a) 1 to 40% by weight of a coated bleaching agent of which an aqueous solution shows an alkaline reaction,

   b) 0.5 to 15% by weight of a bleach activator,

   c) 0.1 to 40% by weight of an acidifying agent,

   characterized in that the bleaching agent is coated with a membrane material which dissolves slowly in water irrespective of the pH value, the bleach activator is coated with a polymeric acid and the acidifying agent is used without any coating.
5. A detergent composition as claimed in claim 4, characterized in that it contains fatty alcohols, preferably in admixture with other coating materials, as the coating material for the bleaching agent.
6. A detergent composition as claimed in claim 4 or 5, characterized in that it contains sodium percarbonate as the bleaching agent.
7. A detergent composition as claimed in any of claims 4 to 6, characterized in that it contains tetraacetyl ethylenediamine (TAED) as the bleach activator.
8. A detergent composition as claimed in any of claims 4 to 7, characterized in that it contains polycarboxylic acids as the acidifying agent.