DE10242221B4 - Process for bleaching anionic surfactant acids - Google Patents

Abstract

Process for bleaching water-poor anionic surfactant acids by reaction with one or more bleach (s), characterized in that in addition to the bleaching agent, an amount of the stabilizers water and phosphonic acid is added to the reaction mixture such that the resulting reaction mixture has a phosphonic acid content above 6 relative to its total weight % By weight.

Description

The The present invention relates to a process for bleaching anionic surfactant acids. Especially The invention relates to a process for bleaching anionic surfactant acids which the bleaching result achieved by adding the stabilizers Water and phosphonic acid is preserved.

The term "anionic surfactants" is taken to mean surface-active compounds which consist of an optionally substituted hydrocarbon skeleton with one or more anionic head groups which dissociate in aqueous solution. Examples of anionic surfactants are soaps (anionic head group: -COONa), alkylbenzenesulfonates, alkanesulfonates, methyl ester sulfonates and α-olefinsulfonates (anionic head group: -SO ₃ Na), alkyl sulfates and alkyl ether sulfates (anionic head group: -OSO ₃ Na). Due to their amphiphilic (bifunctional) structure with at least one hydrophobic and one hydrophilic moiety, anionic surfactants lower the interfacial tension in multiphase material systems and are therefore of great economic importance, in particular in the field of detergents or cleaners.

While the anionic surfactants in the form of pure substances are usually colorless or nearly colorless compounds, color changes and discoloration can occur in large-scale production, depending on the particular preparation process but also in the storage of the process products, for example due to side reactions of excess SO ₃ are based on the sulfonation. In particular, for the use of anionic surfactants in detergents or cleaning agents such discolorations are not acceptable. Although the cleaning-active activity of the surfactants is not diminished by the said discoloration, but the incorporation of discolored surfactants in detergents and cleaners results in a very disadvantageous product appearance, which is incompatible with the use of these agents for washing and cleaning, for example, textiles.

to Avoiding such problems and eliminating discoloration in the case of anionic surfactants subjected them to bleaching prior to further processing become. To carry out Such bleaching will be apparent to those skilled in the art in addition to the chlorine-releasing bleaching agents like sodium hypochlorite especially chlorine-free, active oxygen releasing bleaching agents such as hydrogen peroxide used. Even though Sodium hypochlorite is an easy-to-use and effective bleach, can when used by unwanted side reactions sensitizing substances are formed, which are the use exclude the reaction products, for example in laundry detergents.

At the Bleaching of anionic surfactants with oxygen or chlorine releasing agents Bleaching agents additionally results the problem of the temporary stability of the bleaching results obtained; that is, once bleached substance mixtures darken after some time, in particular at higher Temperatures, after; the bleaching process must be repeated. The repeated Repeating the bleaching process, however, is costly. moreover reduces the low color constancy and storage stability bleached Aniontenside the number of procedural degrees of freedom during their processing, for example in detergents or cleaners.

at an attempt to solve the above problems and an improved bleaching process for anionic surfactants to provide was now surprising found that yourself the bleaching effect of bleaching agents by adding certain amounts preserved by stabilizers; the bleaching effect remains even at elevated Temperatures above longer time get the acid does not darken anymore.

One The first subject of the present application is therefore a method for bleaching water-poor anionic surfactant acids by reaction with a or more bleach (s), characterized in that the reaction mixture in addition to de bleach continues to contain such an amount of water stabilizers and phosphonic acid is added that the resulting reaction mixture based on its total weight one phosphonic acid above 6 wt .-%. In preferred embodiments of the method according to the invention are added to the reaction mixture to the bleaching agent, such an amount of stabilizers continues added that the resulting reaction mixture has a phosphonic acid content above 7% by weight, preferably in the range of 7 to 12 wt .-% and in particular in the range between 8 and 11 wt .-%, each based on the total weight the resulting mixture.

to execution the method according to the invention All anionic surfactant acids known to those skilled in the art are suitable.

Preferred anionic surfactants in acid form are one or more substances from the group of carboxylic acids, sulfuric acid half esters and sulfonic acids, preferably from the group of fatty acids, fatty alkyl sulfuric acids and alkylaryl sulfonic acids. In order to have sufficient surface-active properties, the compounds mentioned should have longer-chain hydrocarbon radicals, ie at least 6 C atoms in the alkyl or alkenyl radical sen. Usually, the C chain distributions of the anionic surfactants are in the range of 6 to 40, preferably 8 to 30 and especially 12 to 22 carbon atoms.

Carboxylic acids, which are used in the form of their alkali metal salts as soaps in detergents and cleaners, are obtained industrially, for the most part, from native fats and oils by hydrolysis. While the alkaline saponification already carried out in the past century led directly to the alkali salts (soaps), today only large amounts of water are used for cleavage, which cleaves the fats into glycerol and the free fatty acids. Examples of industrially applied processes are the autoclave cleavage or continuous high pressure cleavage. For example, hexanoic acid (caproic acid), heptanoic acid (enanthic acid), octanoic acid (caprylic acid), nonanoic acid (pelargonic acid), decanoic acid (capric acid), undecanoic acid, etc. are preferred in the context of the present invention Use of fatty acids such as dodecanoic acid (lauric acid), tetradecanoic acid (myristic acid), hexadecanoic acid (palmitic acid), octadecanoic acid (stearic acid), eicosanoic acid (arachidic acid), docosanoic acid (behenic acid), tetracosanic acid (lignoceric acid), hexacosanoic acid (cerotic acid), triacotanoic acid (melissic acid) and unsaturated secies 9c-hexadecenoic acid (palmitoleic acid), 6c-octadecenoic acid (petroselinic acid), 6t-octadecenoic acid (petroselaidic acid), 9c-octadecenoic acid (oleic acid), 9t-octadecenoic acid ((elaidic acid), 9c, 12c-octadecadienoic acid (linoleic acid), 9t, 12t Octadecadienoic acid (linolaidic acid) and 9c, 12c, 15c-octadecatenic acid ( For reasons of cost, it is preferred not to use the pure species, but technical mixtures of the individual acids, as they are accessible from lipolysis. Such mixtures are for example coconut oil (about 6 wt .-% C ₈ , 6 wt .-% C ₁₀ , 48 wt .-% C ₁₂ , 18 wt .-% C ₁₄ , 10 wt .-% C ₁₆ , 2 wt % C ₁₈ , 8% by weight C _{18 '} , 1% by weight C _{18 "} ), palm kernel oil fatty acid (about 4% by weight C ₈ , 5% by weight C ₁₀ , 50% by weight). % C ₁₂ , 15 wt .-% C ₁₄ , 7 wt .-% C ₁₆ , 2 wt .-% C ₁₈ , 15 wt .-% C _{18 '} , 1 wt .-% C _18'' ), tallow fatty acid ( about 3 wt .-% C ₁₄ , 26 wt .-% C ₁₆ , 2 wt .-% C _{16 '} , 2 wt .-% C ₁₇ , 17 wt .-% C ₁₈ , 44 wt .-% C _{18 '} , 3 wt .-% C _18'' , 1 wt .-% C _18''' ), hardened tallow fatty acid (about 2 wt .-% C ₁₄ , 28 wt .-% C ₁₆ , 2 wt .-% C ₁₇ , 63 wt .-% C ₁₈ , 1 wt .-% C _{18 '} ), technical oleic acid (about 1 wt .-% C ₁₂ , 3 wt .-% C ₁₄ , 5 wt .-% C ₁₆ , 6% by weight C _{16 '} , 1% by weight C ₁₇ , 2% by weight C ₁₈ , 70% by weight C _18' , 10% by weight C _{18 "} , 0.5% by weight % C _{18 '''} ), technical palmitic / stearic acid (about 1 wt .-% C ₁₂ , 2 wt .-% C ₁₄ , 45 wt .-% C ₁₆ , 2 wt .-% C ₁₇ , 47 wt. % C ₁₈ , 1% by weight C _{18 '} ) and soybean oil fatty acid (about 2% by weight C ₁₄ , 15 wt .-% C ₁₆ , 5 wt .-% C ₁₈ , 25 wt .-% C _{18 '} , 45 wt .-% C _18'' , 7 wt .-% C _18''' ).

Sulfuric acid semi-esters of longer-chain alcohols are also anionic surfactants in their acid form and can be used in the context of the present invention. Their alkali metal salts, in particular sodium salts, the fatty alcohol sulfates are industrially available from fatty alcohols, which are reacted with sulfuric acid, chlorosulfonic acid, sulfamic acid or sulfur trioxide to the respective alkyl sulfuric acids and subsequently neutralized. The fatty alcohols are thereby obtained from the relevant fatty acids or fatty acid mixtures by high-pressure hydrogenation of fatty acid methyl esters. The quantitatively most important industrial process for the production of fatty alkylsulfuric acids is the sulfation of the alcohols with SO ₃ / air mixtures in special cascade, falling film or tube bundle reactors.

A another class of anionic surfactant acids, the used according to the invention are the alkyl ether sulfuric acids, their salts, the alkyl ether sulfates, compared to the alkyl sulfates by a higher water solubility and lower sensitivity to water hardness (solubility of Ca salts). Alkyl ether sulfuric acids are like the alkyl sulfuric acids from fatty alcohols synthesized, which with ethylene oxide to the relevant Be implemented fatty alcohol ethoxylates. Instead of ethylene oxide can also be used propylene oxide. The subsequent sulfonation with gaseous Sulfur trioxide in short-term sulfonation reactors yields over 98% on the relevant alkyl ether sulfuric acids.

Also alkanesulfonic and olefinsulfonic acids are in the context of the present invention as anionic surfactants in acid form used. alkanesulfonic can the sulfonic acid group terminal bound (primary alkane sulfonic acids) or along the C chain (secondary alkanesulfonic acids), wherein only the secondary alkanesulfonic have commercial significance. These are made by sulfochlorination or sulfoxidation of linear hydrocarbons. at Reed's sulfochlorination becomes n-paraffins with sulfur dioxide and chlorine upon irradiation with UV light to the corresponding sulfochlorides reacted directly with the alkalis on hydrolysis with the alkanesulfonates, when reacted with water, the alkanesulfonic provide. As in the sulfochlorination Di- and Polysulfochloride and chlorinated hydrocarbons as by-products The radical reaction can occur, the reaction is usually only up to implementation levels of 30% performed and then canceled.

Another process for producing alkanesulfonic acids is sulfoxidation in which n-paraffins are reacted with sulfur dioxide and oxygen under UV light irradiation. At this Radical reaction arise successive Alkylsulfonylradikale that react further with oxygen to the Alkylpersulfonylradiaklen. The reaction with unreacted paraffin provides an alkyl radical and the alkylpersulfonic acid which decomposes into an alkyl peroxysulfonyl radical and a hydroxyl radical. The reaction of the two radicals with unreacted paraffin provides the alkylsulfonic acids or water, which reacts with alkylpersulfonic acid and sulfur dioxide to form sulfuric acid. In order to keep the yield of the two end products alkyl sulfonic acid and sulfuric acid as high as possible and to suppress side reactions, this reaction is usually carried out only up to degrees of conversion of 1% and then terminated.

olefin be technically by reaction of α-olefins with sulfur trioxide produced. Intermediate zwitterions, which form Cyclize to so-called sultones. Under suitable conditions (alkaline or acidic hydrolysis), these sultones react to form Hydroxylalkansulfonsäuren or alkene sulfonic acids, which both can also be used as anionic surfactant acids.

Alkylbenzenesulfonic acids as High performance anionic surfactants have been around since the thirties known in our century. At that time were by monochlorination of kogasin fractions and subsequent Friedel-Crafts alkylation Alkylbenzenes prepared, which were sulfonated with oleum.

Beginning the fifties Years was for the production of alkylbenzenesulfonic propylene to branched α-dodecylene tetramerized and the product over a Friedel-Crafts reaction using aluminum trichloride or hydrogen fluoride is converted to tetrapropylene benzene, the following was sulfonated. This economic possibility the production of tetrapropylene benzene sulfonic acids (TPS) led to Breakthrough of this class of surfactants, which are the soaps as main surfactant in Washing and cleaning agents displaced.

by virtue of The lack of biodegradability of TPS made it necessary to new alkylbenzenesulfonic acids which are characterized by an improved ecological behavior. These requirements are met by linear alkyl benzene sulfonic acids which today almost exclusively produced alkylbenzenesulfonic acids are and the abbreviation ABSS.

linear alkylbenzenesulfonic are made from linear alkylbenzenes, which in turn accessible to linear olefins are. For this purpose are industrially Petroleum fractions with molecular sieves in the n-paraffins of the desired Purity separated and dehydrogenated to the n-olefins, both α- and i-olefins result. The resulting olefins are then in the presence reacted with benzene to the alkylbenzenes acid catalysts, the choice of the Friedel-Crafts catalyst has an influence on the Isomer distribution of the resulting linear alkylbenzenes has: bei Use of aluminum trichloride is the content of the 2-phenyl isomers in the mixture with the 3-, 4-, 5- and other isomers at ca. 30 wt .-%, however, hydrogen fluoride is used as catalyst, can the Lower the content of 2-phenyl isomer to about 20% by weight. The sulfonation of the linear Finally, alkylbenzenes succeeds today on an industrial scale with oleum, sulfuric acid or gaseous Sulfur trioxide, the latter having by far the greatest importance. For sulfonation special film or tube bundle reactors are used, the as a product, a 97 wt .-% alkylbenzenesulfonic acid (ABSS) provide, in the Preferred as the anionic surfactant according to the present invention is used.

Especially preferred alkyl benzene sulfonic acids in the present invention have a linear C ₈ -C ₁₈ -, preferably a C ₈ -, C ₉ -, C ₁₀ -, C ₁₁ -, C ₁₂ - or C ₁₃ -alkyl radical. Particular preference is given to mixtures of linear alkylbenzenesulfonic acids with the abovementioned C ₈ , C ₉ , C ₁₀ , C ₁₁ , C ₁₂ or C ₁₃ -alkyl radicals.

Alk (en) ylsulfates are the sulfuric monoesters of C ₁₂ -C ₁₈ fatty alcohols, for example coconut fatty alcohol, tallow fatty alcohol, lauryl, myristyl, cetyl or stearyl alcohol or C ₁₀ -C ₂₀ oxo alcohols and those half esters of secondary alcohols of these chain lengths prefers. Also preferred in the context of the present invention are alk (en) ylsulfates of the aforementioned chain length which contain a synthetic, petrochemical-based straight-chain alkyl radical which has an analogous decomposition behavior to the adequate compounds based on oleochemical raw materials. Of washing technology interest, the C ₁₂ -C ₁₆ alkyl sulfates and C ₁₂ -C ₁₅ alkyl sulfates and C ₁₄ -C ₁₅ alkyl sulfates are preferred. 2,3-alkyl sulfates are also suitable anionic surfactant acids.

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

As well it is also possible Alk (en) yl succinic acid preferably having 8 to 18 carbon atoms in the alk (en) yl chain use.

The The aforementioned anionic surfactants can in the method according to the invention are used as pure substances or as mixtures. In one particularly preferred processes according to the invention are used as anionic surfactant alkylbenzenesulfonic acids, wherein the proportion by weight of alkylbenzenesulfonic acids in the total weight of the used anionic surfactant preferably at least 20% by weight, particularly preferably 40% by weight and in particular at least 75 wt .-% is. In a further preferred embodiment are used as anionic surfactants exclusive alkylbenzenesulfonic acids.

As "low-water" anionic surfactants be in the context of the present application anionic surfactants with a Water content below 4% by weight, preferably below 3% by weight, more preferably below 2.5 wt .-%, in particular below 2 wt .-% and extremely preferred below 1% by weight, in each case based on the total weight of the anionic surfactants, having.

The The foregoing anionic surfactants in their acid form may be used alone or in admixture be used together. But it is also possible and preferred that the Anionic surfactant in acid form the bleaching process further, preferably acidic, ingredients of Washing and cleaning agents in amounts of 0.1 to 40 wt .-%, preferably from 1 to 15% by weight and especially from 2 to 10% by weight, respectively based on the weight of the mixture to be reacted, mixed.

When Other acidic ingredients of the reaction mixture are suitable in the Within the scope of the present invention, in addition to the "surfactant acids", also the fatty acids, phosphonic acids, polymer acids or partially neutralized polymer acids as well as "builder acids" and "complex builder acids" alone as well in any mixtures. As ingredients of detergents and cleaners, that of the anionic surfactant acid can be mixed especially acidic detergents and cleansing ingredients, So for example phosphonic acids, which in neutralized form (phosphonates) as incrustation inhibitors Part of many detergents and cleaners are. Also the use of (partially neutralized) polymeric acids such as polyacrylic acids according to the invention possible. It but it is also possible additional acid and bleach-stable ingredients with the anionic surfactant acid.

Of the oxygen-releasing substances which can be used as bleaching agents, the hydrogen peroxide (H ₂ O ₂ ) is particularly preferred for carrying out the process according to the invention.

Hydrogen peroxide, HOOH, is a colorless, water-miscible and soluble organic solvent. The viscosity of 1.249 mPa · s at 20 ° C is not significantly higher than that of the water (1.002 mPa · s); However, in aqueous solution hydrogen bonds are formed which exceed those in the pure components of starch. This effect is reflected in the heat of mixing and has, inter alia, the increased viscosity result. Very pure hydrogen peroxide is stable at 20 ° C, but the tendency to decompose increases with increasing temperature, especially in the presence of traces of catalytically active organic substances or Cu, Fe or other heavy metal salts. The decomposition can be carried out explosively, if necessary, while a 90% aqueous solution at 20 ° C can not be detonated. With water, hydrogen peroxide is miscible in any ratio; commercially available is up to 70% H ₂ O ₂ as a water-clear, colorless and odorless liquid that reacts very slightly acidic (weaker than carbonic acid) and especially in the heat, in the light, in the presence of dust, heavy metals and alkalis (eg ammonia or the liberated from glass alkalis) gradually in water u. Oxygen breaks down.

In order to delay the decomposition of H ₂ O ₂ during storage, small amounts of stabilizers are added to aqueous hydrogen peroxide solution, e.g. B. sodium phosphates u. stannates. Chelating agents form complex compounds with heavy metal salts so that they can no longer decompose the H ₂ O ₂ .

The first hydrogen peroxide production by Thénard (1818) by the action of sulfuric acid on barium peroxide yielded only dilute aqueous solutions. The 1908 developed in Weissenstein, modified in 1924 by Löwenstein electrolytic production of peroxodisulfuric acid or ammonium peroxodisulfate, which runs on the Caro's acid as an intermediate, or extending over potassium peroxodisulfate Pietzsch-Adolph process provide 35- 45% solutions of H ₂ O ₂ , Today, more than 95% of H ₂ O _{2 is produced} by various variants of the anthraquinone process. Here, the organic "reaction carrier" in a complex solvent. Mixture of aromatics (as quinone solver), and polar compounds, eg. B. Methylcyclohexanolacetat (as hydroquinone solver), recycled; the formed by oxidation with air at 30-80 ° C / 500 kPa H ₂ O ₂ is extracted with water. The resulting about 15-35% H ₂ O ₂ solution is generally concentrated to 70%. The direct preparation of 20% H ₂ O ₂ solution from the elements is achieved with the aid of a catalyst of Pt and Pd salts on a support material of colloidal SiO ₂ (aq) under pressure at 10-17 ° C. Worldwide, around 1.8-1.9 million t of hydrogen peroxide were produced annually in the early 1990s, of which about 50% was produced in Europe.

Commercially available aqueous hydrogen peroxide solutions having a hydrogen peroxide content of between 30 and 70% by weight are particularly suitable for carrying out the process according to the invention. Particularly preferred is 70% H ₂ O ₂ .

hydrogen peroxide forms numerous peroxohydrates, some of which, such as. For example, sodium percarbonate Sodium perborate, peroxypyrophosphates and percarbamide ("solid Hydrogen peroxide "). These peroxohydrates are also suitable for carrying out the inventive method, like the technically far more important substitution compounds, in particular the peroxides and peracids as well as other dioxy and peroxy compounds.

Sodium percarbonate is a nonspecific name used for sodium carbonate-hydrogen peroxide complexes. The commercial product has the average composition 2 Na ₂ CO ₃ .3H ₂ O ₂ and is therefore no peroxocarbonate. Sodium percarbonate forms a white, water-soluble powder that readily decomposes into sodium carbonate and bleaching and oxidizing "active" oxygen.

In the context of the present application, the term "sodium perborate" describes various water-containing sodium peroxyborates such as (sodium peroxoborate trihydrate), NaBO ₂ .H ₂ O ₂ .3H ₂ O or sodium perborate tetrahydrate (NaBO ₃ .4H ₂ O ₂ ) as well summarized as the anhydrous oxoborate. The alkaline aqueous solution of these compounds slowly releases oxygen only after prolonged standing; however, heating will accelerate oxygen evolution.

Percarbamide is a urea-hydrogen peroxide addition compound of the formula H ₂ N-CO-NH ₂ .H ₂ O ₂ , CH ₆ N ₂ O ₃ . Percarbamide forms white crystals which decompose in the presence of moisture above 40 ° C. It is readily soluble in water, alcohol and, with partial decomposition in H ₂ O ₂ and urea, also in ethylene glycol. The melting point of percarbamide is 80-90 ° C (decomposition). By adding sodium or ammonium dihydrogen phosphate or zinc sulfate, the thermal stability of the percarbamide can be improved. Percarbamide is also marketed with starch in the trade.

Organic peracids or their salts are also suitable in the context of the present invention in a special way as a bleaching agent. The organic peracids include, in particular, the citrate perhydrates and H ₂ O ₂ -producing peracidic salts or peracids, such as perbenzoates, peroxophthalates, diperazelaic acid, phthaloimino peracid or diperdodecanedioic acid. Preferred organic bleaching agents are furthermore the diacyl peroxides, such as. B. dibenzoyl peroxide. Other suitable organic bleaching agents are the peroxyacids, examples of which include the alkyl peroxyacids and the aryl peroxyacids. Preferred representatives are (a) the peroxybenzoic acid and its ring-substituted derivatives, such as alkylperoxybenzoic acids, but also peroxy-α-naphthoic acid and magnesium monoperphthalate, (b) the aliphatic or substituted aliphatic peroxyacids, such as peroxylauric acid, peroxystearic acid, ε-phthalimido peroxycaproic acid [Phthaloiminoperoxyhexanoic acid (PAP) ], o-carboxybenzamidoperoxycaproic acid, N-nonenylamidoperadipic acid and N-nonenylamidopersuccinate, and (c) aliphatic and araliphatic peroxydicarboxylic acids such as 1,12-diperoxycarboxylic acid, 1,9-diperoxyazelaic acid, diperoxysebacic acid, diperoxybrassic acid, the diperoxyphthalic acids, 2-decyldiperoxybutan-1 , 4-diacid, N, N-terephthaloyl-di (6-aminopercapronate) can be used.

in the Within the scope of the present application, particularly preferred processes according to the invention are characterized in that as Bleaching agent Hydrogen peroxide and / or inorganic perhydrate and / or organic peracid and / or the salts of organic peracid, preferably in amounts from 0.0001 to 5 wt .-%, in particular from 0.001 to 4 wt .-% and in particular from 0.005 to 0.5 wt .-%, each based on the total weight the anionic surfactant acid (s) is / are used, wherein in a further preferred embodiment the reaction mixture after bleaching a Klett number below 100, preferably below 60 and in particular below 40 has.

When Bleaching agents in the bleaching process of the present invention may also be used Chlorine or bromine releasing substances are used. Under the appropriate chlorine or bromine releasing materials come next to the mentioned Sodium hypochlorite, for example, heterocyclic N-bromo and N-chloroamides, such as trichloroisocyanuric acid, tribromoisocyanuric acid, dibromoisocyanuric acid and / or dichloroisocyanuric (DICA) and / or their salts with cations such as potassium and sodium into consideration. Hydantoin compounds, such as 1,3-dichloro-5,5-dimethylhydanthoin are also suitable.

Suitable stabilizers in the process according to the invention are water and phosphonic acid. The proportion by weight of the phosphonic acid in the total weight of the reaction mixture is, as described above, above 6% by weight, preferably above 7% by weight, more preferably in the range from 7 to 12% by weight and in particular in the range between 8 and 11% by weight .-%. The stabilizer may be added before, simultaneously with or after the addition of the bleach. Particularly preferred in the context of the present invention Accordingly, bleaching processes in which the addition of the stabilizers before, during or after, preferably at least partially after bleaching to a Klettzahl below 100, preferably a Klett number below 60 and in particular a Klett number is below 40.

• (i) 100 Gewichtsanteile Aniontensidsäure(n),
• (ii) x Gewichtsanteile Bleichmittel (Aktivsubstanz) sowie
• (iii) y Gewichtsanteile eines Stabilisators umgesetzt werden, wobei

x Werte zwischen 0,0001 und 5 aufweist und die Summe aus x und y mindestens 7 beträgt.In summary, the method according to the invention in a particularly preferred embodiment is thus characterized in that

• (i) 100 parts by weight of anionic surfactant acid (s),
• (ii) x parts by weight of bleach (active substance) as well as
• (iii) y parts by weight of a stabilizer are reacted, wherein

x has values between 0.0001 and 5 and the sum of x and y is at least 7.

to execution the bleaching process according to the invention It has proved to be particularly advantageous if the reaction mixture while bleaching a temperature below 75 ° C, preferably below 65 ° C, especially preferably between 20 and 60 ° C and in particular between 35 and 55 ° C.

One Another object of the present invention are according to one of Bleached anionic surfactant acids or bleached anionic surfactant acid-containing Mixtures containing a content of the stabilizer phosphorous acid above 6 wt .-%, preferably above 7 wt .-%, more preferably in the range from 7 to 12% by weight and in particular in the range between 8 and 11% by weight, in each case based on the total weight of the bleached anionic acid or of bleached anionic surfactant acid-containing Mixture, exhibit. Bleached are particularly preferred here anionic surfactant or bleached anionic surfactant acid-containing Mixtures which have a number of hooks below 100, preferably below 60 and in particular below 40 have. Such anionic surfactant acids and Anionic surfactant-containing Mixtures are not distinguished due to the low Klett numbers only by an advantageous look, but are also, as before described, especially stable in color and storage.

The when performing, the method according to the invention obtained bleached anionic surfactant acids having a phosphonic acid content above 6 wt .-% are particularly suitable because of their high color stability for the production of detergents or cleaners for private use Consumption. Another object of the present invention is therefore the use of bleached by one of the methods described above anionic surfactant with a phosphonic acid content above 6 wt .-% in detergents or cleaning agents or for the production of detergents or cleaning agents, for example after neutralization the anionic surfactant acids and subsequently Packaging. The preparation of the optionally neutralized or partially neutralized stabilizer-containing anionic surfactant acids according to the invention thereby for example by agglomeration, compaction or extrusion respectively. In the resulting detergents or cleaning agents acts they are preferably solid agents, such as powders, extrudates or Tablets, in particular multilayer tablets with two, three or more phases. The stabilizer-containing, optionally neutralized or partially neutralized anionic surfactant acids, however, can also be used with advantage in liquid Incorporate washing or cleaning agents.

at the use of inventive stabilizer-hastier Anionic surfactants in detergents or cleaners or for manufacture of detergents or cleaning agents, these are surface-active Substances usually with a number of other active substances combined. The group of these active substances includes, for example, bleaching agents, bleach activators, Polymers, builders, Surfactants, enzymes, disintegrants, electrolytes, pH modifiers, fragrances, Perfume carrier, fluorescer, Dyes, hydrotopes, foam inhibitors, silicone oils, anti redeposition agents, optical brighteners, grayness inhibitors, shrinkage inhibitors, Anti-crease agents, color transfer inhibitors, antimicrobial agents, germicides, fungicides, antioxidants, corrosion inhibitors, Antistatic agents, ironing aids, phobizers and impregnating agents, Swelling and anti-slip agents and UV absorbers included. These Active substances are described in more detail below.

As important ingredients, detergents and cleaners may contain bleaches and bleach activators. Among the compounds serving as bleaches in water H ₂ O ₂ , sodium perborate tetrahydrate and sodium perborate monohydrate are of particular importance. Other useful bleaching agents are, for example, sodium percarbonate, peroxypyrophosphates, citrate perhydrates and H ₂ O ₂ -producing peracidic salts or peracids, such as perbenzoates, peroxophthalates, diperazelaic acid, phthaloiminoperacid or diperdodecanedioic acid. Dishwashing detergents may also contain bleaches from the group of organic bleaches. Typical organic bleaching agents are the diacyl peroxides, such as. B. dibenzoyl peroxide. Other typical organic bleaches are the peroxyacids, examples of which include the alkyl peroxyacids and the aryl peroxyacids. Preferred representatives are (a) the peroxybenzoic acid and its ring-substituted derivatives, such as alkylperoxybenzoic acids, but also peroxy-α-naphthoic acid and magnesium monoperphthalate, (b) the aliphatic or substituted aliphatic peroxyacids, such as peroxylaur rinsäure, Peroxystearic acid, ε-Phthalimidoperoxycaproic acid [Phthaloiminoperoxyhexanoic acid (PAP)], o-carboxybenzamidoperoxycaproic acid, N-nonenylamidoperadipic acid and Nnonenylamidopersuccinate, and (c) aliphatic and araliphatic peroxydicarboxylic acids, such as 1,12-diperoxycarboxylic acid, 1,9-Diperoxyazelainsäure, Diperocysebacinsäure, diperoxybrassylic acid, the diperoxyphthalic acids, 2-decyldiperoxybutane-1,4-diacid, N, N-terephthaloyl-di (6-aminopercapronate) can be used.

Around when cleaning at temperatures of 60 ° C and below an improved Bleaching effect can achieve Detergents and cleaning agents contain bleach activators. As bleach activators, compounds, which under perhydrolysis aliphatic peroxycarboxylic acids with preferably 1 to 10 C atoms, in particular 2 to 4 C atoms, and / or optionally substituted perbenzoic acid, are used. Suitable substances are the O and / or N-acyl groups of said carbon atom number and / or optionally substituted Wear benzoyl groups. Preference is given to polyacylated alkylenediamines, in particular tetraacetylethylenediamine (TAED), acylated triazine derivatives, in particular 1,5-diacetyl-2,4-dioxohexahydro-1,3,5-triazine (DADHT), acylated glycolurils, especially tetraacetylglycoluril (TAGU), N-acylimides, especially N-nonanoylsuccinimide (NOSI), acylated Phenolsulfonates, especially n-nonanoyl or isononanoyloxybenzenesulfonate (n- or iso-NOBS), carboxylic acid anhydrides, in particular phthalic anhydride, acylated polyhydric alcohols, especially triacetin, ethylene glycol diacetate and 2,5-diacetoxy-2,5-dihydrofuran.

In addition to The conventional bleach activators or in their place may also so-called bleach catalysts in the detergents or cleaners be incorporated. These substances are bleach-enhancing transition metal salts or transition metal complexes such as Mn, Fe, Co, Ru or Mo saline complexes or carbonyl complexes. Also Mn, Fe, Co, Ru, Mo, Ti, V and Cu complexes with N-containing tripod ligands and Co, Fe, Cu and Ru ammine complexes usable as bleach catalysts.

Next the ingredients mentioned are bleach and bleach activator Builders, especially zeolites, silicates, carbonates, organic cobuilders and where no ecological Prejudice their use - even the phosphates, as well Surfactants important ingredients of detergents.

Suitable crystalline layered sodium silicates have the general formula NaMSi _x O _{2x + 1} .H ₂ O, where M is sodium or hydrogen, x is a number from 1.9 to 4 and y is a number from 0 to 20 and preferred values for x 2, 3 or 4 are. Preferred crystalline layered silicates of the formula given are those in which M is sodium and x assumes the values 2 or 3. In particular, both β- and δ-sodium disilicates Na ₂ Si ₂ O ₅ .yH ₂ O are preferred.

It is also possible to use amorphous sodium silicates with a Na ₂ O: SiO ₂ modulus of from 1: 2 to 1: 3.3, preferably from 1: 2 to 1: 2.8 and in particular from 1: 2 to 1: 2.6, which Delayed and have secondary washing properties. The dissolution delay compared with conventional amorphous sodium silicates may have been caused in various ways, for example by surface treatment, compounding, compaction / densification 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 do not yield sharp X-ray reflections typical of crystalline substances in X-ray diffraction experiments, but at most one or more maxima of the scattered X-rays having a width of several degrees of diffraction angle. However, it may well even lead to particularly good builder properties if the silicate particles provide blurred or even sharp diffraction maxima in electron diffraction experiments. This is to be interpreted as meaning that the products have microcrystalline regions of size 10 to a few hundred nm, values of up to max. 50 nm and in particular up to max. 20 nm are preferred. Such so-called X-ray amorphous silicates likewise have a dissolution delay compared with the conventional water glasses. Particularly preferred are compacted / compacted amorphous silicates, compounded amorphous silicates and overdried X-ray amorphous silicates.

The usable finely crystalline, synthetic and bound water-containing zeolite is preferably zeolite A and / or P. As zeolite P zeolite MAP ^® (commercial product from Crosfield) is particularly preferred. Also suitable, however, are zeolite X and mixtures of A, X and / or P. Commercially available and preferably usable in the context of the present invention is, for example, a cocrystal of zeolite X and zeolite A (about 80% by weight of zeolite X) ), produced by the company CONDEA Augusts S. p. A. sold under the brand name VEGOBOND AX ^® and by the formula nNa ₂ O · (1 - n) K ₂ O · Al ₂ O ₃ · (2 - 2.5) SiO ₂ · (3.5-5.5) H ₂ O can be described. Suitable zeolites have an average particle size of less than 10 μm (volume distribution, measuring method: Coulter Coun ter) and preferably contain 18 to 22 wt .-%, in particular 20 to 22 wt .-% of bound water.

Of course it is also a use of the well-known phosphates as builders possible, unless such use is avoided for environmental reasons should be. Particularly suitable are the sodium salts of orthophosphates, the pyrophosphates and in particular the tripolyphosphates.

Alkali metal phosphates is the summary term for the alkali metal (especially sodium and potassium) salts of various phosphoric acids, in which one can distinguish metaphosphoric acids (HPO ₃ ) _n and orthophosphoric H ₃ PO _{4 in} addition to higher molecular weight representatives. The phosphates combine several advantages: they act as alkali carriers, prevent lime deposits on machine parts or lime incrustations in fabrics and also contribute to the cleaning performance.

Sodium dihydrogen phosphate, NaH ₂ PO ₄ , exists as a dihydrate (density 1.91 gcm ^-3 , melting point 60 °) and as a monohydrate (density 2.04 gcm ^-3 ). Both salts are white powders which are very soluble in water and which lose their water of crystallization when heated and at 200 ° C into the weak acid diphosphate (disodium hydrogen diphosphate, Na ₂ H ₂ P ₂ O ₇ ), at higher temperature in sodium trimetaphosphate (Na ₃ P ₃ O ₉ ) and Maddrell's salt (see below). NaH ₂ PO _{4 is} acidic; It arises when phosphoric acid is adjusted to a pH of 4.5 with sodium hydroxide solution and the mash is sprayed. Potassium dihydrogen phosphate (potassium phosphate primary or monobasic potassium phosphate, KDP), KH ₂ PO ₄ , is a white salt of 2.33 gcm ^-3 density, has a melting point of 253 ° [decomposition to form potassium polyphosphate (KPO ₃ ) _x ] and is light soluble in water.

Disodium hydrogen phosphate (secondary sodium phosphate), Na ₂ HPO ₄ , is a colorless, very slightly water-soluble crystalline salt. It exists anhydrous and with 2 moles (density 2.066 gcm ^-3 , loss of water at 95 °), 7 moles (density 1.68 gcm ^-3 , melting point 48 ° with loss of 5 H ₂ O) and 12 moles water ( Density 1.52 gcm ^-3 , melting point 35 ° with loss of 5 H ₂ O) becomes anhydrous at 100 ° C and, upon increased heating, passes into the diphosphate Na ₄ P ₂ O ₇ . Disodium hydrogen phosphate is prepared by neutralization of phosphoric acid with soda solution using phenolphthalein as an indicator. Dipotassium hydrogen phosphate (secondary or dibasic potassium phosphate), K ₂ HPO ₄ , is an amorphous, white salt that is readily soluble in water.

Trisodium phosphate, tertiary sodium phosphate, Na ₃ PO ₄ , are colorless crystals which have a density of 1.62 gcm ^-3 as dodecahydrate and a melting point of 73-76 ° C (decomposition), as decahydrate (corresponding to 19-20% P ₂ O ₅ ) have a melting point of 100 ° C and in anhydrous form (corresponding to 39-40% P ₂ O ₅ ) have a density of 2.536 gcm ^-3 . Trisodium phosphate is readily soluble in water under alkaline reaction and is prepared by evaporating a solution of exactly 1 mole of disodium phosphate and 1 mole of NaOH. Tripotassium phosphate (tertiary or tribasic potassium phosphate), K ₃ PO ₄ , is a white, deliquescent, granular powder of density 2.56 gcm ^-3 , has a melting point of 1340 ° and is readily soluble in water with an alkaline reaction. It arises z. Example, when heating Thomasschlacke with coal and potassium sulfate. Despite the higher price, the more soluble, therefore highly effective, potassium phosphates are often preferred over the corresponding sodium compounds in the detergent industry.

Tetrasodium diphosphate (sodium pyrophosphate), Na ₄ P ₂ O ₇ , exists in anhydrous form (density 2.534 gcm ^-3 , melting point 988 °, also indicated 880 °) and as decahydrate (density 1.815-1.836 gcm ^-3 , melting point 94 ° with loss of water) , Both substances are colorless crystals which are soluble in water with an alkaline reaction. Na ₄ P ₂ O ₇ is formed on heating of disodium phosphate to> 200 ° or by reacting phosphoric acid with soda in a stoichiometric ratio and dewatering the solution by spraying. The decahydrate complexes heavy metal salts and hardness agents and therefore reduces the hardness of the water. Potassium diphosphate (potassium pyrophosphate), K ₄ P ₂ O ₇ , exists in the form of the trihydrate and is a colorless, hygroscopic powder with a density of 2.33 gcm ^-3 , which is soluble in water, the pH being 1% Solution at 25 ° 10.4.

Condensation of NaH ₂ PO ₄ or KH ₂ PO ₄ results in higher mol. Sodium and potassium phosphates, in which one can distinguish cyclic representatives, the sodium or Kaliummetaphosphate and chain types, the sodium or potassium polyphosphates. In particular, for the latter are a variety of names in use: hot or cold phosphates, Graham's salt, Kurrolsches and Maddrell's salt. All higher sodium and potassium phosphates are collectively referred to as condensed phosphates.

The technically important pentasodium triphosphate, Na ₅ P ₃ O ₁₀ (sodium tripolyphosphate), is an anhydrous or with 6 H ₂ O crystallizing, non-hygroscopic, white, water-soluble salt of the general formula NaO- [P (O) (ONa) -O] _n -Na with n = 3. In 100 g of water dissolve at room temperature about 17 g, at 60 ° about 20 g, at 100 ° around 32 g of the crystal anhydrous salt; after two hours of heating the solution to 100 ° caused by hydrolysis about 8% orthophosphate and 15% diphosphate. In the preparation of pentasodium triphosphate, phosphoric acid is reacted with sodium carbonate solution or sodium hydroxide solution in a stoichiometric ratio and the solution is dehydrated by spraying. Similar to Graham's salt and sodium diphosphate, pentasodium triphosphate dissolves many insoluble metal compounds (including lime soaps, etc.). Pentakaliumtriphosphat, K ₅ P ₃ O ₁₀ (potassium tripolyphosphate), for example, in the form of a 50 wt .-% solution (> 23% P ₂ O ₅ , 25% K ₂ O) in the trade. The potassium polyphosphates are widely used in the washing and cleaning industry. There are also sodium potassium tripolyphosphates which can also be used in the context of the present invention. These arise, for example, when hydrolyzed sodium trimetaphosphate with KOH: (NaPO ₃ ) ₃ + 2 KOH → Na ₃ K ₂ P ₃ O ₁₀ + H ₂ O

These are exact according to the invention such as sodium tripolyphosphate, potassium tripolyphosphate or mixtures can be used from these two; also mixtures of sodium tripolyphosphate and sodium potassium tripolyphosphate or mixtures of potassium tripolyphosphate and sodium potassium tripolyphosphate or mixtures of sodium tripolyphosphate and potassium tripolyphosphate and sodium potassium tripolyphosphate used according to the invention.

useful organic builders are for example, in the form of their alkali and in particular sodium salts usable polycarboxylic acids, like citric acid, adipic acid, Succinic acid, glutaric, Tartaric acid, Sugar acids, amino carboxylic acids, nitrilotriacetic (NTA), if such an operation is not for environmental reasons is objectionable, as well as mixtures of these. Preferred salts are the salts of polycarboxylic acids like citric acid, adipic acid, Succinic acid, glutaric, Tartaric acid, Sugar acids and Mixtures of these.

When other ingredients can Alkali carrier present be. As alkali carrier alkali metal hydroxides, alkali metal carbonates, alkali metal bicarbonates, Alkali metal sesquicarbonates, alkali silicates, alkali metal silicates, and mixtures of the aforementioned substances, wherein for the purposes of this invention preferably the alkali metal carbonates, in particular sodium carbonate, sodium bicarbonate or sodium sesquicarbonate.

Water-soluble builders are another preferred ingredient of detergents or cleaners. Common water-soluble builders are the low molecular weight polycarboxylic acids and their salts homopolymeric and copolymeric polycarboxylic acids and their salts, the carbonates, phosphates and silicates. For the production of automatic dishwashing detergents are preferably trisodium citrate and / or pentasodium tripolyphosphate and / or sodium carbonate and / or sodium bicarbonate and / or gluconates and / or silicate builders from the class of disilicates and / or Metasilicates used. Particularly preferred is a builder system containing a mixture of tripolyphosphate and sodium carbonate. Also particularly preferred is a builder system which is a mixture from tripolyphosphate and sodium carbonate and sodium disilicate.

washing and detergents can except the anionic surfactants described above further detergent-active substances contain.

A large group of washing-active substances form the nonionic surfactants. The nonionic surfactants used are preferably alkoxylated, advantageously ethoxylated, in particular primary, alcohols having preferably 8 to 18 carbon atoms and on average 1 to 12 moles of ethylene oxide (EO) per mole of alcohol, in which the alcohol radical can be linear or preferably methyl-branched in the 2-position or linear and methyl-branched radicals in the mixture can contain, as they are usually present in Oxoalkoholresten. In particular, however, alcohol ethoxylates with linear radicals of alcohols of native origin having 12 to 18 carbon atoms, for. From coconut, palm, tallow or oleyl alcohol, and on average from 2 to 8 EO per mole of alcohol. The preferred ethoxylated alcohols include, for example, C _12-14 alcohols with 3 EO or 4 EO, C _9-11 alcohols 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 of these, 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 means which, for a particular product, may be an integer or a fractional number. 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.

A another class of preferred nonionic surfactants, the either as the sole nonionic surfactant or in combination with other nonionic surfactants are alkoxylated, preferably ethoxylated or ethoxylated and propoxylated fatty acid alkyl esters, preferably having 1 to 4 carbon atoms in the alkyl chain, in particular Fatty acid methyl ester.

Another class of nonionic ten siden, which can be used advantageously, are the alkylpolyglycosides (APG). Usable Alkypolyglycoside meet the general formula RO (G) _z , in which R is a linear or branched, especially in the 2-position methyl branched, saturated or unsaturated, aliphatic radical having 8 to 22, preferably 12 to 18 carbon atoms and G is the Is a symbol which represents a glycose unit having 5 or 6 C atoms, preferably glucose. The degree of glycosidation z is between 1.0 and 4.0, preferably between 1.0 and 2.0 and in particular between 1.1 and 1.4. Preference is given to using linear alkyl polyglucosides, that is to say alkyl polyglycosides in which the polyglycosyl radical is a glucose radical and the alkyl radical is an n-alkyl radical.

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 alkanolamide can be suitable. The amount of these nonionic surfactants is preferably not more than that of the ethoxylated fatty alcohols, in particular not more than half from that.

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.Further suitable surfactants are polyhydroxy fatty acid amides of the formula (I)

wherein RCO is an aliphatic acyl group having 6 to 22 carbon atoms, R ^{1 is} hydrogen, an alkyl or hydroxyalkyl group having 1 to 4 carbon atoms and [Z] is a linear or branched polyhydroxyalkyl group having 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 the R is a linear or branched alkyl or alkenyl radical having 7 to 12 carbon atoms, R ^{1 is} a linear, branched or cyclic alkyl radical or an aryl radical having 2 to 8 carbon atoms and R ^{2 is} a linear, branched or cyclic alkyl radical or an aryl radical or an oxyalkyl radical having from 1 to 8 carbon atoms, with 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 propoxylated Derivatives of this residue.

[Z] is preferably by reductive amination of a reduced sugar obtained, for example, glucose, fructose, maltose, lactose, galactose, Mannose or xylose. The N-alkoxy or N-aryloxy-substituted compounds can then by reaction with fatty acid methyl esters in the presence of an alkoxide as a catalyst in the desired Polyhydroxyfatty acid amides are transferred.

Further preferred nonionic surfactants are the low-foaming nonionic surfactants. Particularly preferred are the alkoxylated alcohols, especially the ethoxylated and / or propoxylated alcohols. The person skilled in the art generally understands, under alkoxylated alcohols, the reaction products of alkylene oxide, preferably ethylene oxide, with alcohols, preferably in the context of the present invention, the longer-chain alcohols (C ₁₀ to C ₁₈ , preferably between C ₁₂ and C ₁₆ , such as, for example, C ₁₁ -, C ₁₂ -, C ₁₃ -, C ₁₄ -, C ₁₅ -, C ₁₆ -, C ₁₇ - and C ₁₈ -alcohols). As a rule, n moles of ethylene oxide and one mole of alcohol, depending on the reaction conditions, form a complex mixture of addition products of different degrees of ethoxylation. A further embodiment consists in the use of mixtures of the alkylene oxides, preferably the mixture of ethylene oxide and propylene oxide. Also, if desired, by a final etherification with short-chain alkyl groups, such as preferably the butyl group, the substance class of "closed" alcohol ethoxylates reach, which can also be used in the context of the invention. Very particularly preferred for the purposes of the present invention are highly ethoxylated fatty alcohols or mixtures thereof with end-capped fatty alcohol ethoxylates.

polymers are another important ingredient of detergents and cleaners, among polymers in the present application in particular Substances with builder or co-builder properties are to be understood. When organic cobuilders can in the washing and cleaning agents, in particular polycarboxylates / polycarboxylic acids, polymers Polycarboxylates, aspartic acid, Polyacetals, dextrins, other organic cobuilders (see below) and phosphonates are used. These classes of substances are hereafter described.

Useful organic builders For example, the sodium salts of the polycarboxylic acids mentioned below as part of the effervescent system. For example, these are the sodium salts of citric acid, adipic acid, succinic acid, glutaric acid, malic acid, tartaric acid, maleic acid, fumaric acid, sugar acids, aminocarboxylic acids, nitrilotriacetic acid (NTA), if such use is not objectionable for ecological reasons, as well as mixtures of these. Preferred salts are the salts of polycarboxylic acids such as citric acid, adipic acid, succinic acid, glutaric acid, tartaric acid, sugar acids and mixtures thereof.

When Builders are further suitable polymeric polycarboxylates, these are for example, the alkali metal salts of polyacrylic acid or polymethacrylic acid, for example, those having a molecular weight of 500 to 70,000 g / mol.

For the purposes of this document, the molecular weights stated for polymeric polycarboxylates are weight-average molar masses M _{w of} the particular acid form, which were determined in principle by means of gel permeation chromatography (GPC), a UV detector being used. The measurement was carried out against an external polyacrylic acid standard, which provides realistic molecular weight values due to its structural relationship with the polymers investigated. These data differ significantly from the molecular weight data, in which polystyrene sulfonic acids are used as standard. The molar masses measured against polystyrenesulfonic acids are generally significantly higher than the molecular weights specified in this document.

suitable Polymers are in particular polyacrylates, which preferably have a molecular weight of 2,000 to 20,000 g / mol. Because of their superior solubility can from this group again the short-chain polyacrylates, the molecular weights from 2,000 to 10,000 g / mol, and more preferably from 3,000 to 5,000 g / mol, be preferred.

Suitable are furthermore copolymeric polycarboxylates, especially those of acrylic acid with methacrylic acid and the acrylic acid or methacrylic acid with maleic acid. Particularly suitable are copolymers of acrylic acid with Proved maleic acid, the 50 to 90 wt .-% acrylic acid and 50 to 10% by weight of maleic acid contain. Your molecular weight, based on free acids, is in general from 2000 to 70000 g / mol, preferably from 20,000 to 50,000 g / mol and in particular 30,000 to 40,000 g / mol.

to Improvement of water solubility can the polymers also include allylsulfonic acids, such as allyloxybenzenesulfonic acid and methallylsulfonic acid, as Contain monomer.

Especially Biodegradable polymers of more than two are also preferred various monomer units, for example, those as monomers Salts of acrylic acid and maleic acid and vinyl alcohol or vinyl alcohol derivatives or as monomers Salts of acrylic acid and 2-alkylallyl sulfonic acid and sugar derivatives.

Further preferred copolymers are those which are preferably used as monomers Acrolein and acrylic acid / acrylic acid salts or acrolein and vinyl acetate.

As well are as further preferred builders polymeric aminodicarboxylic acids, their salts or their precursors to call. Particularly preferred are polyaspartic acids or their Salts and derivatives which, in addition to cobuilder properties, also have a have bleach-stabilizing effect.

Further Suitable builders are polyacetals, which by reaction Dialdehydes with Polyolcarbonsäuren, which 5 to 7 C-atoms and at least 3 hydroxyl groups can be obtained. preferred Polyacetals are made from dialdehydes such as glyoxal, glutaraldehyde, terephthalaldehyde and mixtures thereof and from polyol carboxylic acids such as gluconic acid and / or glucoheptonic receive.

Further suitable organic builders are dextrins, for example Oligomers or polymers of carbohydrates by partial Hydrolysis of starches can be obtained. The Hydrolysis can be carried out according to usual, for example acidic or enzyme-catalyzed processes. Preferably they are hydrolysis products with average molecular weights in the range of 400 to 500,000 g / mol. This is a polysaccharide with a dextrose equivalent (DE) in the range of 0.5 to 40, in particular from 2 to 30 are preferred, wherein DE a common one Measure of the reducing Effect of a polysaccharide compared to dextrose, which DE of 100 is. Useful are both maltodextrins with a DE between 3 and 20 and dry glucose syrup with a DE between 20 and 37 as well as so-called yellow dextrins and white dextrins with higher Molar masses in the range of 2000 to 30,000 g / mol.

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. Also suitable net is an oxidized oligosaccharide. A product oxidized to C _{6 of} the saccharide ring may be particularly advantageous.

Also Oxydisuccinates and other derivatives of disuccinates, preferably Ethylenediamine disuccinate are other suitable cobuilders. there becomes ethylenediamine-N, N'-disuccinate (EDDS) preferably used in the form of its sodium or magnesium salts. Also preferred in this context are glycerol disuccinates and glycerol trisuccinates. Suitable amounts are zeolithhaltigen and / or silicate-containing formulations at 3 to 15 wt .-%.

Further useful organic cobuilders are, for example, acetylated Hydroxycarboxylic acids or their salts, which may also be present in lactone form can and which at least 4 carbon atoms and at least one hydroxy group and a maximum of two acid groups contain.

A another substance class with cobuilder properties are the phosphonates These are in particular hydroxyalkane or aminoalkanephosphonates. Among the hydroxyalkane phosphonates is 1-hydroxyethane-1,1-diphosphonate (HEDP) of particular importance as a co-builder. It is preferably used as the sodium salt, wherein the disodium salt neutral and the tetrasodium salt is alkaline (pH 9). As aminoalkanephosphonates preferably ethylenediamine tetramethylenephosphonate (EDTMP), Diethylentriaminpentamethylenphosphonat (DTPMP) and their higher homologues in question. They are preferably in the form of neutral reacting Sodium salts, e.g. B. as hexasodium salt of EDTMP or hepta- and octa-sodium salt the DTPMP. As a builder it is from the class of Phosphonates preferably used HEDP. The aminoalkane phosphonates also have a pronounced Schwermetallbindeabmögen. Accordingly, can it is preferred, especially when the agents also contain bleach be to use Aminoalkanphosphonate, in particular DTPMP, or Use mixtures of the above phosphonates.

Furthermore can all compounds capable of forming complexes with alkaline earth ions, be used as co-builders.

Detergents or cleaning agents may contain enzymes to increase the washing or cleaning performance, it being possible in principle to use all enzymes established for this purpose in the prior art. These include in particular proteases, amylases, lipases, hemicellulases, cellulases or oxidoreductases, and preferably mixtures thereof. These enzymes are basically of natural origin; Starting from the natural molecules, improved variants are available for use in detergents and cleaners, which are preferably used accordingly. Agents of the invention preferably contain enzymes in total amounts of from 1 × 10 ^-6 to 5 weight percent based on active protein. The protein concentration can be determined by known methods, for example the BCA method or the biuret method.

Among the proteases, those of the subtilisin type are preferable. Examples thereof are the subtilisins BPN 'and Carlsberg, the protease PB92, the subtilisins 147 and 309, the alkaline protease from Bacillus lentus, subtilisin DY and the enzymes thermitase, proteinase K and the subtilases, but not the subtilisins in the narrower sense Proteases TW3 and TW7. Subtilisin Carlsberg in a developed form under the trade names Alcalase ^® from Novozymes A / S, Bagsvaerd, Denmark. The subtilisins 147 and 309 are sold under the trade names Esperase ^®, or Savinase ^® from Novozymes. From the protease from Bacillus lentus DSM 5483 derived under the name BLAP ^® variants are derived.

Other usable proteases are, for example, under the trade names Durazym ^®, relase ^®, Everlase® ^®, Nafizym, Natalase ^®, Kannase® ^® and Ovozymes ^® from Novozymes, under the trade names Purafect ^®, Purafect ^® OxP and Properase.RTM ^® by the company Genencor, that under the trade name Protosol® ^® from Advanced Biochemicals Ltd., Thane, India, under the trade name Wuxi ^® from Wuxi Snyder Bioproducts Ltd., China, under the trade names Proleather® ^® and protease P ^® by the company Amano Pharmaceuticals Ltd., Nagoya, Japan, and the enzyme available under the name Proteinase K-16 from Kao Corp., Tokyo, Japan.

Examples of amylases which can be used according to the invention are the α-amylases from Bacillus licheniformis, B. amyloliquefaciens or B. stearothermophilus and also their further developments improved for use in detergents and cleaners. The enzyme from B. licheniformis is available from Novozymes under the name Termamyl ^® and from Genencor under the name Purastar® ^® ST. Development products of this α-amylase are available from Novozymes under the trade names Duramyl ^® and Termamyl ^® ultra, from Genencor under the name Purastar® ^® OxAm and from Daiwa Seiko Inc., Tokyo, Japan, as Keistase ^®. The α-amylase from B. amyloliquefaciens is marketed by Novozymes under the name BAN ^®, and derived Variants of the α-amylase from B. stearothermophilus under the names BSG ^® and Novamyl ^®, likewise from Novozymes.

Furthermore are for this purpose the α-amylase from Bacillus sp. A 7-7 (DSM 12368) and cyclodextrin glucanotransferase (CGTase) from B. agaradherens (DSM 9948).

In addition, the enhancements available under the trade names Fungamyl.RTM ^® by Novozymes of α-amylase from Aspergillus niger and A. oryzae, which are. Another commercial product is, for example, the amylase ^LT® .

Detergents or cleaners may contain lipases or cutinases, particularly because of their triglyceride-cleaving activities, but also to generate in situ peracids from suitable precursors. These include, for example, the lipases originally obtainable from Humicola lanuginosa (Thermomyces lanuginosus) or further developed, in particular those with the amino acid exchange D96L. They are sold, for example, by Novozymes under the trade names Lipolase ^®, Lipolase Ultra ^®, LipoPrime® ^®, Lipozyme® ^® and Lipex ^®. Furthermore, for example, the cutinases can be used, which were originally isolated from Fusarium solani pisi and Humicola insolens. Likewise useable lipases are available from Amano under the designations Lipase CE ^®, Lipase P ^®, Lipase B ^®, or lipase CES ^®, Lipase AKG ^®, Bacillis sp. ^Lipase® , Lipase ^AP® , Lipase M- ^AP® and Lipase ^{AMI® are} available. From the company Genencor, for example, the lipases, or cutinases can be used, the initial enzymes were originally isolated from Pseudomonas mendocina and Fusarium solanii. Other important commercial products are the originally marketed by Gist-Brocades preparations M1 Lipase ^® and Lipomax® ^® and the enzymes marketed by Meito Sangyo KK, Japan under the names Lipase MY-30 ^®, Lipase OF ^® and lipase PL ^® to mention also the product Lumafast® ^® from Genencor.

Detergents or cleaning agents may contain other enzymes, which are summarized by the term hemicellulases. These include, for example, mannanases, xanthan lyases, pectin lyases (= pectinases), pectin esterases, pectate lyases, xyloglucanases (= xylanases), pullulanases and β-glucanases. Suitable mannanases are available, for example under the name Gamanase ^® and Pektinex AR ^® from Novozymes, under the name Rohapec ^® B1 from AB Enzymes and under the name Pyrolase® ^® from Diversa Corp., San Diego, CA, United States. The obtained from B. subtilis β-glucanase is available under the name Cereflo ^® from Novozymes.

To increase the bleaching effect, detergents or cleaners may contain oxidoreductases, for example oxidases, oxygenases, catalases, peroxidases, such as halo, chloro, bromo, lignin, glucose or manganese peroxidases, dioxygenases or laccases (phenol oxidases, polyphenol oxidases) , Suitable commercial products Denilite® ^® 1 and 2 from Novozymes should be mentioned. Advantageously, it is additionally preferred to add organic, particularly preferably aromatic, compounds which interact with the enzymes in order to enhance the activity of the relevant oxidoreductases (enhancers) or to ensure the flow of electrons (mediators) at greatly varying redox potentials between the oxidizing enzymes and the soils.

The Enzymes used in detergents or cleaners either come from originally from microorganisms, such as the genera Bacillus, Streptomyces, Humicola, or Pseudomonas, and / or are known per se biotechnological processes produced by suitable microorganisms, for example by transgenic expression hosts of the genera Bacillus or filamentous Fungi.

The Purification of the enzymes concerned is conveniently over itself established methods, for example about precipitation, sedimentation, concentration, Filtration of the liquid Phases, microfiltration, ultrafiltration, exposure to chemicals, Deodorization or suitable combinations of these steps.

washing or detergents the enzymes in any form established in the art be added. These include for example, by granulation, extrusion or lyophilization obtained solid preparations or, especially in liquid or gelatinous Means, solutions the enzymes, advantageously as concentrated as possible, low in water and / or added with stabilizers.

Alternatively, the enzymes may be encapsulated for both the solid and liquid dosage forms, for example by spray-drying or extruding the enzyme solution together with a preferably natural polymer or in the form of capsules, for example those in which the enzymes are entrapped as in a solidified gel or in those of the core-shell type, in which an enzyme-containing core is coated with a water, air and / or chemical impermeable protective layer. In deposited layers, further active ingredients, for example stabilizers, emulsifiers, pigments, bleaches or dyes, may additionally be applied. Such capsules are prepared by methods known per se, for example by shaking or rolling granules lation or applied in fluid-bed processes. Advantageously, such granules, for example by applying polymeric film-forming agent, low in dust and storage stable due to the coating.

Farther Is it possible, to assemble two or more enzymes together, so that a single Granules several enzyme activities having.

One in washing or cleaning agents contained protein and / or enzyme especially during storage against damage such as inactivation, denaturation or decay, for example through physical influences, Oxidation or proteolytic cleavage are protected. In microbial Obtaining the proteins and / or enzymes is inhibiting the Proteolysis particularly preferred, especially if the means Contain proteases. Compositions according to the invention can be stabilizers for this purpose contain; the provision of such means is a preferred embodiment of the present invention.

A Group of stabilizers are reversible protease inhibitors. Become frequent Benzamidine hydrochloride, borax, boric acids, boronic acids or their Salts or esters used, including especially derivatives with aromatic Groups, such as ortho-substituted, meta-substituted and para-substituted phenylboronic acids, respectively their salts or esters. As peptidic protease inhibitors are under to mention other ovomucoid and leupeptin; an additional Option is the formation of fusion proteins from proteases and peptide inhibitors.

Other enzyme stabilizers are amino alcohols such as mono-, di-, triethanol- and -propanolamine and mixtures thereof, aliphatic carboxylic acids up to C ₁₂ , such as succinic acid, other dicarboxylic acids or salts of said acids. End-capped fatty acid amide alkoxylates are also suitable. Certain organic acids used as builders are additionally capable of stabilizing a contained enzyme.

low aliphatic alcohols, but especially polyols, such as Glycerine, ethylene glycol, propylene glycol or sorbitol are other frequently used Enzyme stabilizers. Likewise, calcium salts are used, such as Calcium acetate or calcium formate, and magnesium salts.

Polyamide oligomers or polymeric compounds such as lignin, water-soluble vinyl copolymers or cellulose ethers, acrylic polymers and / or polyamides stabilize the enzyme preparation, inter alia, against physical influences or pH fluctuations. Polyamine N-oxide containing polymers act as enzyme stabilizers. Other polymeric stabilizers are the linear C ₈ -C ₁₈ polyoxyalkylenes. Alkylpolyglycosides can stabilize the enzymatic components of the agent according to the invention and even increase their performance. Crosslinked N-containing compounds also act as enzyme stabilizers.

reducing agent and antioxidants increase that stability of the enzymes oxidative decay. A sulfur-containing reducing agent is, for example Sodium sulfite.

Prefers Kombinatonen be used by stabilizers, for example made of polyols, boric acid and / or borax, the combination of boric acid or borate, reducing Salts and succinic acid or other dicarboxylic acids or the combination of boric acid or borate with polyols or polyamino compounds and with reducing salts. The effect of peptide-aldehyde stabilizers is obtained by combination with boric acid and / or boric acid derivatives and polyols increased and by the additional use of divalent Cations, such as calcium ions further amplified.

preferred automatic dishwashing detergents are characterized in that additionally one or more enzymes and / or enzyme preparations, preferably solid and / or liquid Protease preparations and / or amylase preparations, in amounts of 1 to 5 wt .-%, preferably from 1.5 to 4.5 and especially from 2 to 4 wt .-%, each based on the entire remedy, included.

fragrances are added to the detergents or cleaners to the aesthetic To enhance the impression of the products and to give the consumer a sensory "typical" and distinctive "product to disposal to deliver.

As perfume oils or perfumes, individual fragrance compounds, eg. As the synthetic products of the ester type, ethers, aldehydes, ketones, alcohols and hydrocarbons are used. Fragrance compounds of the ester type are e.g. Benzyl acetate, phenoxyethyl isobutyrate, p-tert-butylcyclohexyl acetate, linalyl acetate, dimethylbenzyl carbinyl acetate, phenylethyl acetate, linalyl benzoate, benzyl formate, ethylmethylphenyl glycinate, allyl cyclohexyl propionate, styrallyl propionate and benzyl salicylate. The ethers include, for example, benzyl ethyl ether to the aldehydes z. B. the linear alkanals with 8-18 C-atoms, citral, citronellal, citronellyloxyacetaldehyde, cyclamen aldehyde, hydroxycitronellal, lilial and bourgeonal, to the ketones z. The ionones, α-isomethylionone and methyl cedryl ketone, the alcohols anethole, citronellol, eugenol, geraniol, linalool, phenylethyl alcohol and terpineol, The hydrocarbons mainly include the terpenes such as limonene and pinene. Preferably, however, mixtures of different fragrances are used, which together produce an attractive fragrance. Such perfume oils may also contain natural fragrance mixtures as are available from vegetable sources, e.g. Pine, citrus, jasmine, patchouly, rose or ylang-ylang oil. Also suitable are muscatel, sage, chamomile, clove, lemon balm, mint, cinnamon, lime, juniper, vetiver, olibanum, galbanum and labdanum, and orange blossom, neroliol, orange peel and sandalwood.

The general description of the applicable perfumes (see above) provides generally the different substance classes of fragrances. To be perceptible, one must Perfume volatile being, besides the nature of the functional groups and the structure the molecular weight of the chemical compound also plays an important role plays. So most perfumes have molecular weights up to about 200 Dalton, while Molar masses of 300 daltons and above rather an exception. Due to the different volatility changed by fragrances the smell of a compound of several fragrances perfumes or perfume during of evaporation, whereby the odor impressions in "top note", "heart or Middle note "(middle note or body) and "base note" (end note or dry out). Because the smell perception to a large extent also on the smell intensity is based, the top note of a perfume or fragrance is not alone from volatile Connections while the base note for the most part from less volatile, d. H. adherent fragrances. When composing perfumes can be easier volatile For example, fragrances can be bound to specific fixatives. which prevents it from evaporating too quickly. At the following Classification of the fragrances in "lighter volatile or "adherent" fragrances is over the smell impression and about it, whether the corresponding perfume perceived as a head or middle note nothing is said.

By a suitable choice of said fragrances or perfume oils can be influenced in this way for laundry detergents both the smell of the product, and, after completion of the cleaning and care process, additionally the laundry scent. For the latter odor impression, the use of adhesive odoriferous substances is advantageous, while also more volatile odoriferous substances can be used for product scenting. Adhesive-resistant fragrances which can be used in the context of the present invention are, for example, the essential oils such as angelica root oil, aniseed oil, arnica blossom oil, basil oil, bay oil, bergamot oil, Champacablütenöl, Edeltannöl, Edeltannenzapfenapfen, Elemiöl, eucalyptus oil, fennel oil, spruce alder oil, galbanum oil, geranium oil, gingergrass oil, Guaiac wood oil, gurdy balm oil, helichrysum oil, ho oil, ginger oil, iris oil, cajeput oil, calamus oil, chamomile oil, camphor oil, kanga oil, cardamom oil, cassia oil, pine oil, copaia balsam oil, coriander oil, spearmint oil, caraway oil, cumin oil, lavender oil, lemongrass oil, lime oil, tangerine oil, lemon balm oil, Musk Grain Oil, Myrrh Oil, Clove Oil, Neroli Oil, Niaouli Oil, Olibanum Oil, Orange Oil, Origanum Oil, Palmarosa Oil, Patchouli Oil, Peru Balsam Oil, Petitgrain Oil, Pepper Oil, Peppermint Oil, Pimento Oil, Pine Oil, Rose Oil, Rosemary Oil, Sandalwood Oil, Celery Oil, Spik Oil, Star Aniseed Oil, Turpentine Oil, Thuja Oil, Thyme oil, Ver oil, vetiver oil, juniper berry oil, wormwood oil, wintergreen oil, ylang-ylang oil, hyssop oil, cinnamon oil, cinnamon oil, lemon oil, lemon oil and cypress oil. But also the higher-boiling or solid fragrances of natural or synthetic origin can be used in the context of the present invention as adherent fragrances or fragrance mixtures, ie fragrances. These compounds include the following compounds and mixtures thereof: ambrettolide, α-amylcinnamaldehyde, anethole, anisaldehyde, anisalcohol, anisole, methyl anthranilate, acetophenone, benzylacetone, benzaldehyde, ethyl benzoate, benzophenone, benzyl alcohol, benzyl acetate, benzyl benzoate, benzyl formate, benzyl valerate, borneol , Bornyl acetate, α-bromostyrene, n-decyl aldehyde, n-dodecyl aldehyde, eugenol, eugenol methyl ether, eucalyptol, farnesol, fenchone, fenchyl acetate, geranyl acetate, geranyl formate, heliotropin, heptincarboxylic acid methyl ester, heptaldehyde, hydroquinone dimethyl ether, hydroxycinnamaldehyde, hydroxycinnamyl alcohol, indole, iron, isoeugenol , Isoeugenol methyl ether, isosafrole, jasmon, camphor, karvakrol, karvon, p-cresol methyl ether, coumarin, p-methoxyacetophenone, methyl n-amyl ketone, methyl anthranilate, p-methylacetophenone, methylchavikole, p-methylquinoline, methyl-β-naphthyl ketone, methyl-n nonylacetaldehyde, methyl n-nonyl ketone, Muskon, β-N aphtholethyl ether, β-naphthol methyl ether, nerol, nitrobenzene, n-nonylaldehyde, nonyl alcohol, n-octylaldehyde, p-oxyacetophenone, pentadecanolide, β-phenylethyl alcohol, phenylacetaldehyde dimethyacetal, phenylacetic acid, pulegone, safrole, isoamyl salicylate, methyl salicylate, hexyl salicylate, cyclohexyl salicylate, Santalol, skatole, terpineol, thymen, thymol, γ-undelactone, vaniline, veratrum aldehyde, cinnamaldehyde, cimat alcohol, cinnamic acid, cinnamic acid ethyl ester, cinnamic acid benzyl ester. The more volatile fragrances include in particular the lower-boiling fragrances of natural or synthetic origin, which can be used alone or in mixtures. Examples of more volatile fragrances are alkyl isothiocyanates (alkyl mustard oils), butanedione, limonene, linalool, linayl acetate and propionate, menthol, menthone, methyl-n-heptenone, phellandrene, phenylacetaldehyde, terpinylace did, citral, lemon zest.

Around to facilitate the disintegration of highly compacted detergents or cleaners to shorten the disintegration times, Is it possible, Disintegration aids, so-called tablet disintegrants, in to incorporate these. Among tablet disintegrants and decay accelerators according to Römpp (9th edition, Bd. 6, p. 4440) and Voigt "textbook of pharmaceutical technology "(6th edition, 1987, pp. 182-184) adjuvants understood that for the rapid disintegration of tablets into water or gastric juice and for release provide the pharmaceuticals in resorbable form.

These Substances which are also referred to as "explosives" due to their effect, enlarge at Water entering their volume, on the one hand increasing the intrinsic volume (swelling), on the other hand also over the release of gases can be generated a pressure that the Tablet disintegrates into smaller particles. Well-known disintegration aids are, for example, carbonate / citric acid systems, and others used organic acids can be. Swelling disintegration aids are for example synthetic Polymers such as polyvinylpyrrolidone (PVP) or natural polymers or modified Natural substances such as cellulose and starch and their derivatives, alginates or casein derivatives. All mentioned Disintegration aids are used according to the invention.

When Disintegration aids can in detergents or cleaning agents Destintegrationshilfsmittel on Cellulosic be used, preferably a disintegration aid based on cellulose, preferably in granular, cogranulated or compacted form, in amounts of 0.5 to 10 wt .-%, preferably from 3 to 7% by weight and especially from 4 to 6% by weight, respectively based on the weight of the tablet is used.

Pure cellulose has the formal gross composition (C ₆ H ₁₀ O ₅ ) _n and is formally a β-1,4-polyacetal of cellobiose, which in turn is composed of two molecules of glucose. Suitable celluloses consist of about 500 to 5000 glucose units and therefore have average molecular weights of 50,000 to 500,000. Cellulose-based disintegrating agents which can be used in the context of the present invention are also cellulose derivatives obtainable by polymer-analogous reactions of cellulose. Such chemically modified celluloses include, for example, products of esterifications or etherifications in which hydroxy hydrogen atoms have been substituted. Celluloses in which the hydroxy groups have been replaced by functional groups which are not bonded via an oxygen atom can also be used as cellulose derivatives. The group of cellulose derivatives includes, for example, alkali metal celluloses, carboxymethylcellulose (CMC), cellulose esters and ethers, and aminocelluloses. The cellulose derivatives mentioned are preferably not used alone as disintegrating agents based on cellulose, but used in admixture with cellulose. The content of these mixtures of cellulose derivatives is preferably below 50% by weight, particularly preferably below 20% by weight, based on the cellulose-based disintegrating agent. It is particularly preferred to use cellulose-based disintegrating agent which is free of cellulose derivatives. As a further disintegrating agent based on cellulose or as a component of this component, microcrystalline cellulose can be used. This microcrystalline cellulose is obtained by partial hydrolysis of celluloses under conditions which attack and completely dissolve only the amorphous regions (about 30% of the total cellulose mass) of the celluloses, leaving the crystalline regions (about 70%) intact. Subsequent deaggregation of the microfine celluloses produced by the hydrolysis yields the microcrystalline celluloses which have primary particle sizes of about 5 μm and can be compacted, for example, into granules having an average particle size of 200 μm.

In addition to the previously mentioned ingredients washing or cleaning agents a gas-releasing system of organic acids and carbonates / bicarbonates contain.

As organic acids which release carbon dioxide from the carbonates / bicarbonates in aqueous solution, for example, the solid mono-, oligo- and polycarboxylic acids can be used. Again preferred from this group are citric acid, tartaric acid, succinic acid, malonic acid, adipic acid, maleic acid, fumaric acid, oxalic acid and also polyacrylic acid. Organic sulfonic acids such as sulfamic acid are also usable. A commercially available as an acidifier in the context of the present invention is also preferably usable Sokalan ^® DCS (trademark of BASF), a mixture of succinic acid (max. 31 wt .-%), glutaric acid (max. 50 wt .-%) (and adipic acid at most 33% by weight).

The mentioned acids have to not stoichiometric to the carbonates contained in the detergents or cleaners or bicarbonates are used.

The gas-developing effervescent system consists of the washing and cleaning agent tablets in addition to the organic acids mentioned from carbonates and / or bicarbonates. For representatives of this class are the cost Alka limetall salts clearly preferred. In the case of the alkali metal carbonates or bicarbonates, in turn, the sodium and potassium salts are clearly preferred over the other salts for reasons of cost. Of course, the relevant pure alkali metal carbonates or bicarbonates do not have to be used; Rather, mixtures of different carbonates and bicarbonates may be preferred.

In addition to so far in detail described components can Detergents and cleaning tablets contain other ingredients, which the application technology and / or aesthetic properties Use as a laundry detergent to further improve. For these ingredients For example, it is one or more substances the group of electrolytes, pH adjusters, fluorescers, dyes, Hydrotopes, foam inhibitors, silicone oils, anti redeposition agents, optical brighteners, grayness inhibitors, anti-shrinkage agents, Anti-crease agents, color transfer inhibitors, antimicrobial agents, germicides, fungicides, antioxidants, Antistatic agents, ironing aids, Phobic and impregnating agents, source and Slip Resists and UV absorbers.

As electrolytes from the group of inorganic salts, a wide number of different salts can be used. Preferred cations are the alkali and alkaline earth metals, preferred anions are the halides and sulfates. From a production point of view, the use of NaCl or MgCl ₂ in the agents according to the invention is preferred.

Around the pH of the detergent or cleaning agent in the desired The use of pH-adjusting agents may be indicated be. Can be used here all known acids or Alkalis, provided that their use is not from application technology or ecological establish or for reasons consumer protection. Usually exceeds the amount of these adjusting agents 1 wt .-% of the total formulation not.

Around the aesthetic They can improve the impression of detergents or cleaning agents dyed with suitable dyes. Preferred dyes, the selection of which the expert has no difficulty, own a high storage stability and insensitivity to the rest Ingredients of the agents and against light and no pronounced substantivity to textile fibers, so as not to stain them.

When Foam inhibitors used in detergents or cleaners can come For example, soaps, paraffins or silicone oils, optionally on carrier materials can be applied. Suitable anti redeposition agents, also called soil repellents are, for example, nonionic cellulose ethers such as methylcellulose and methylhydroxypropylcellulose with a proportion at methoxy groups of 15 to 30 wt .-% and hydroxypropyl groups from 1 to 15 wt .-%, each based on the nonionic cellulose ether and the known from the prior art polymers of phthalic acid and / or terephthalic acid or of their derivatives, in particular polymers of ethylene terephthalates and / or polyethylene glycol terephthalates or anionic and / or nonionically modified derivatives of these. Especially preferred of these are the sulfonated derivatives of phthalic acid and Terephthalic acid polymers.

optical Brighteners (so-called "whiteners") can Detergents or cleaners are added to graying and to eliminate yellowing of the treated textiles. These substances attract to the fiber and cause a whitening and fake bleaching effect, by turning invisible ultraviolet radiation into visible longer wavelength Convert light, with the ultraviolet absorbed from sunlight Light as slightly bluish Fluorescence is emitted and with the yellow of the bated or yellowed laundry pure white results. Suitable compounds are derived, for example, from the substance classes of 4,4'-diamino-2,2'-stilbenedisulfonic acids (flavonic acids), 4,4'-distyryl-biphenylene, Methylumbelliferones, coumarins, dihydroquinolinones, 1,3-diarylpyrazolines, naphthalic acid, Benzoxazole, benzisoxazole and benzimidazole systems and the by Heterocycles substituted pyrene derivatives.

graying have the task of suspending the detached from the fiber dirt in the fleet to keep the dirt from being rebuilt. These are water-soluble Colloids mostly organic nature suitable, for example, the water-soluble Salts of polymeric carboxylic acids, Glue, gelatin, salts of ether sulphonic acids or of cellulose or Salts of acidic sulfuric acid esters cellulose or starch. Also water-soluble, Acidic group-containing polyamides are suitable for this purpose. Farther can be soluble Starch preparations and others as the above starch products use, for. Degraded starch, Aldehyde starches, etc. Polyvinylpyrrolidone is also useful. As grayness inhibitors It is also possible to use cellulose ethers such as carboxymethylcellulose (Na salt), methyl cellulose, hydroxyalkyl cellulose and mixed ethers such as Methylhydroxyethylcellulose, methylhydroxypropylcellulose, methylcarboxymethylcellulose and their mixtures.

As textile fabrics, in particular from Reyon, rayon, cotton and their blends, which can crinkle, because the individual fibers against sagging, kinking. Pressing and squeezing are sensitive transversely to the fiber direction, the tablets according to the invention may contain synthetic crease inhibitors. These include, for example, synthetic products based on fatty acids, fatty acid esters. Fatty acid amides, alkylol esters, alkylolamides or fatty alcohols, which are usually reacted with ethylene oxide, or products based on lecithin or modified phosphoric acid ester.

to fight of microorganisms can the detergents or cleaning agents contain antimicrobial agents. Here one differentiates depending on the antimicrobial spectrum and Mechanism of action between bacteriostats and bactericides, fungistatics and fungicides, etc. Important substances from these groups are, for example Benzalkonium chlorides, alkylaryl sulfonates, halophenols and phenol mercuriacetate, wherein in the erfindungemäßen means also completely can be dispensed with these compounds.

Around unwanted, changes caused by oxygen and other oxidative processes on the washing or cleaning agents and / or the treated textiles to prevent the agents contain antioxidants. To this class of connection belong for example, substituted phenols, hydroquinones, catechols and aromatic amines and organic sulfides, polysulfides, dithiocarbamates, Phosphites and phosphonates.

One increased Comfort can come from the extra Use of antistatic agents resulting in detergents or cleansers additionally enclosed become. Antistatic agents increase the surface conductivity and allow thus an improved drainage formed charges. External antistatics are usually substances with at least one hydrophilic molecule ligands and give on the surfaces a more or less hygroscopic film. These mostly surface-active Antistatic agents can be converted into nitrogen-containing (amines, amides, quaternary ammonium compounds), phosphorus-containing (phosphoric acid ester) and sulfur-containing (alkyl sulfonates, alkyl sulfates) antistatic agents. Lauryl (or stearyl) dimethylbenzylammonium chlorides are suitable also as antistatics for Textiles or as an additive to detergents, with an additional Avivageeffekt is achieved.

to Care of the textiles and to improve the textile properties like a softer "handle" (avivage) and reduced electrostatic charge (increased wearing comfort) can the washing or Detergent fabric softener contain. The active ingredients in softener formulations are "esterquats", quaternary ammonium compounds with two hydrophobic radicals, such as the Disteraryldimethylammoniumchlorid, which, however, because of its insufficient biodegradability increasingly through quaternary Ammonium compounds is replaced in their hydrophobic residues Ester groups as breaking points for biodegradation included.

to Improvement of water absorbency, rewettability treated textiles and to facilitate the ironing of the treated Textiles can in the washing or cleaning agents, for example, silicone derivatives be used. These additionally improve the rinsing behavior of the agents according to the invention their foam-inhibiting properties. Preferred silicone derivatives are, for example, polydialkyl or alkylaryl siloxanes in which the alkyl groups one to five Have C atoms and are completely or partially fluorinated. preferred Silicones are polydimethylsiloxanes which may optionally be derivatized can and are then amino-functional or quaternized or Si-OH-, Si-H- and / or Si-Cl bonds

Finally, the Detergents or cleaners also contain UV absorbers on put on the treated textiles and the light resistance improve the fibers. Connections that those desired Properties are, for example, those by radiationless Deactivation of effective compounds and derivatives of benzophenone with substituents in the 2- and / or 4-position. Furthermore, substituted benzotriazoles, in the 3-position phenyl-substituted Acrylates (cinnamic acid derivatives), optionally with cyano groups in the 2-position, salicylates, organic Ni complexes as well as natural products such as umbelliferone and the body's own urocanic suitable.

Claims (11)

Process for bleaching water-poor anionic surfactant acids by reaction with one or more bleach (s), characterized in that in addition to the bleaching agent, an amount of the stabilizers water and phosphonic acid is added to the reaction mixture such that the resulting reaction mixture has a phosphonic acid content above 6 relative to its total weight % By weight. Process according to Claim 1, characterized in that, in addition to the bleaching agent, an amount of the stabilizers is additionally added to the reaction mixture such that the resulting reaction mixture has a stabilizer content above 7% by weight, preferably in the range from 7 to 12% by weight. and in particular in the range between 8 and 11 wt .-%, each based on the total weight of the resulting mixture having. Method according to one of claims 1 or 2, characterized that the Anionic surfactant acids include alkylbenzenesulfonic acids. Method according to one of claims 1 to 3, characterized that as Bleach hydrogen peroxide and / or inorganic perhydrate and / or organic peracid and / or the salts of organic peracid, preferably in amounts from 0.0001 to 5 wt .-%, in particular from 0.001 to 4 wt .-% and in particular from 0.005 to 0.5 wt .-%, each based on the total weight the anionic surfactant acid (s) is / are used. Method according to one of claims 1 to 4, characterized that this Reaction mixture after bleaching a Klett number below 100, preferably below 60 and in particular below 40. Method according to one of claims 1 to 5, characterized that (I) 100 parts by weight of anionic surfactant acid (s), (Ii) x parts by weight bleach (active substance) as well as (Iii) y weight of a stabilizer reacted be, where x has values between 0.4 and 5 and the sum of x and y at least 7 amounts to. Method according to one of claims 1 to 6, characterized that the Adding the stabilizer (s) before, during or after, preferably at least partially after bleaching to a Velcro number below 100, preferably a velcro number below 60 and in particular a velcro number below 40 takes place. Method according to one of claims 1 to 7, characterized that this Reaction mixture during bleaching a temperature below 75 ° C, preferably below 65 ° C, especially preferably between 20 and 60 ° C and in particular between 35 and 55 ° C. Anionic acid or bleached by a process according to claims 1 to 8 bleached anionic surfactant acid-containing Mixture, characterized in that it contains a content of the stabilizer phosphonic above 6 wt .-%, preferably above 7 wt .-%, more preferably in the range of 7 to 12 wt .-% and in particular in the range between 8 and 11 wt .-%, each based on the total weight of the bleached anionic surfactant or the bleached anionic surfactant acid-containing mixture. Bleached anionic surfactant acid or bleached anionic surfactant acid-containing Mixture according to claim 9, characterized in that the bleached anionic surfactant or the bleached anionic surfactant acid-containing Mixture a Klett number below 100, preferably below 60 and in particular below 40. Use of according to a method according to claims 1 to 8 bleached anionic surfactant acids with a phosphonic acid content above 6 wt .-% for the production of detergents or cleaning agents for the private use.