DE10242221A1 - Long-lasting bleaching of anionic surfactants, used in detergents, comprises addition of a stabilizer, especially a hydroxy group-containing compound e.g. an alcohol, and a bleaching agent e.g. a peroxide - Google Patents

Abstract

Bleaching of low water content anionic surfactants comprises inclusion of the bleach with a stabilizer reaction mixture where the total amount of stabilizer in the mixture is above 6 wt.%.

Description

The present invention relates to a method for bleaching anionic surfactant acids. In particular The invention relates to a process for bleaching anionic surfactant acids in which the achieved Bleaching result is preserved by adding a stabilizer.

The term "anionic surfactants" summarizes 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-olefin sulfonates (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 part of the molecule, anionic surfactants reduce the interfacial tension in multiphase material systems and are therefore of great economic importance, particularly in the field of detergents or cleaning agents.

While the anionic surfactants in the form of the pure substances are usually colorless or almost colorless compounds, large-scale production, depending on the respective production process, can also result in changes in color and discoloration during storage of the process products, which may result, for example, from side reactions of excess SO _{3 based} on sulfonation. Such discolorations are particularly unacceptable for the use of anionic surfactants in washing or cleaning agents. Although the cleaning activity of the surfactants is not diminished by the discolorations mentioned, the incorporation of discolored surfactants into detergents and cleaning agents results in an extremely disadvantageous product appearance, which is incompatible with the use of these agents for washing and cleaning textiles, for example.

To avoid such problems and to remove discoloration from anionic surfactants these can be subjected to a bleaching process before further processing. to Such bleaching is carried out by a person skilled in the art in addition to the chlorine-releasing Bleaching agents such as sodium hypochlorite, in particular chlorine-free, active oxygen-releasing agents Bleaching agents such as hydrogen peroxide are used. Although sodium hypochlorite is a simple one effective and effective bleaching agent can be undesirable Side reactions sensitizing substances are formed, which the use of Exclude reaction products, for example in textile detergents.

When bleaching anionic surfactants with oxygen or chlorine-releasing bleaching agents additionally the problem of the temporary stability of the bleaching results obtained; this means, once bleached, mixtures of substances darken after some time, especially with higher ones Temperatures, after; the bleaching process must be repeated. The repeated repetition of the However, the bleaching process is costly. In addition, the low color consistency and Storage stability of bleached anionic surfactants contributes to the number of degrees of process freedom their processing, for example in detergents or cleaning agents.

Trying to solve the above problems and an improved bleaching process for It has now surprisingly been found to provide anionic surfactants that the bleaching effect of Can preserve bleaching agents by adding certain amounts of stabilizers; the bleaching effect remains for a long time even at elevated temperatures, the acid no longer darkens.

A first subject of the present application is therefore a method for bleaching low-water anionic surfactant acids by reaction with one or more bleaching agent (s), thereby characterized in that, in addition to the bleaching agent, the reaction mixture continues to have one Amount of at least one stabilizer is added to the resulting reaction mixture has a stabilizer content above 6% by weight, based on its total weight. In preferred embodiments of the process according to the invention are the reaction mixture in addition to the bleach, such an amount of at least one stabilizer is also added, that the resulting reaction mixture has a stabilizer content above 7 wt .-%, preferably in Range of 7 to 12 wt .-% and in particular in the range between 8 and 11 wt .-%, respectively based on the total weight of the resulting mixture.

All known to the person skilled in the art are suitable for carrying out the method according to the invention Anionic surfactant.

Anion surfactants in acid form are preferably one or more substances from the group of Carboxylic acids, the sulfuric acid half-ester and the sulfonic acids, preferably from the group of Fatty acids, the fatty alkyl sulfuric acids and the alkylarylsulfonic acids used. To adequate The compounds mentioned should have surface-active properties have longer-chain hydrocarbon radicals, i.e. at least 6 carbon atoms in the alkyl or alkenyl radical exhibit. The C chain distributions of the anionic surfactants are usually in the range from 6 to 40, preferably 8 to 30 and in particular 12 to 22 carbon atoms.

Carboxylic acids, which are used as soaps in detergents and cleaning agents in the form of their alkali metal salts, are technically largely obtained from native fats and oils by hydrolysis. While the alkaline saponification that was carried out in the past century led directly to the alkali salts (soaps), today only water is used on an industrial scale that splits the fats into glycerol and the free fatty acids. Large-scale processes are, for example, cleavage in an autoclave or continuous high-pressure cleavage. Carboxylic acids which can be used as an anionic surfactant in acid form in the context of the present invention are, 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. In the context of the present compound, preference is given to Use of fatty acids such as dodecanoic acid (lauric acid), tetradecanoic acid (myristic acid), hexadecanoic acid (palmitic acid), octadecanoic acid (stearic acid), eicosanoic acid (arachic acid), docosanoic acid (behenic acid), tetracosanoic acid (lignoceric acid), triacidic acid (melotinic acid), triacidic acid (melotonic acid), and melonic acid unsaturated species 9c-hexadecenoic acid (palmitoleic acid), 6c-octadecenoic acid (petroselinic acid), 6t-octadecenoic acid (petroselaidic acid), 9c-octadecenoic acid (oleic acid), 9t-octadecenoic acid ((elaidinic acid), 9c, 12c-12-octadecenoic acid, linoleic acid -Octadecadienoic acid (linolaidic acid) and 9c, 12c, 15c- Octadecatreinsäu re (linolenic acid) For reasons of cost, it is preferred not to use the pure species, but rather technical mixtures of the individual acids that are accessible from fat cleavage. Such mixtures are for example, coconut oil fatty acid (about 6 wt .-% C _8, 6 wt .-% C ₁₀ 48 wt .-% C ₁₂ 18 wt .-% _C14, 10 wt .-% C _16, 2 wt .-% _C18, 8 wt .-% _{C18 ',} 1 wt .-% C _18''), palm kernel oil fatty acid (about 4 wt .-% C _8, 5 wt .-% C _10, 50 wt _12% C, 15 wt .-% C _14, 7 wt .-% C _16, 2 wt .-% C ₁₈ 15 wt .-% _{C18 ',} 1 wt .-% C _18''), tallow ( approx. 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 (approx. 2 wt% C ₁₄ , 28 wt% C ₁₆ , 2 wt% C ₁₇ , 63% by weight C ₁₈ , 1% by weight C _{18 '} ), technical oleic acid (approx. 1% by weight C ₁₂ , 3% by weight C ₁₄ , 5% by weight C ₁₆ , 6% by weight C _{16 '} , 1% by weight C ₁₇ , 2% by weight C ₁₈ , 70% by weight C _18' , 110% 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 (approx. 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 semiesters 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, in particular sodium salts, the fatty alcohol sulfates, are commercially available from fatty alcohols which are reacted with sulfuric acid, chlorosulfonic acid, amidosulfonic acid or sulfur trioxide to give the alkyl sulfuric acids concerned and are subsequently neutralized. The fatty alcohols are obtained from the fatty acids or fatty acid mixtures concerned by high-pressure hydrogenation of the fatty acid methyl esters. In terms of quantity, the most important industrial process for the production of fatty alkyl sulfuric acids is the sulfonation of the alcohols with SO ₃ / air mixtures in special cascade, falling film or tube bundle reactors.

Another class of anionic surfactant acids that can be used according to the invention are Alkyl ether sulfuric acids, their salts, the alkyl ether sulfates, differ in comparison to the alkyl sulfates due to higher water solubility and lower sensitivity to water hardness (solubility of Ca salts). Alkyl ether sulfuric acids are made like the alkyl sulfuric acids Fatty alcohols synthesized with ethylene oxide to the fatty alcohol ethoxylates in question be implemented. Instead of ethylene oxide, propylene oxide can also be used. The subsequent sulfonation with gaseous sulfur trioxide in short-term sulfation reactors Yields over 98% of the alkyl ether sulfuric acids in question.

Alkanesulfonic acids and olefin sulfonic acids are also within the scope of the present invention Anionic surfactants can be used in acid form. Alkanesulfonic acids can terminal the sulfonic acid group bound (primary alkanesulfonic acids) or along the C chain (secondary Alkanesulfonic acids), only the secondary alkanesulfonic acids being of commercial importance have. These are by sulfochlorination or sulfoxidation of linear hydrocarbons manufactured. Reed's sulfochlorination uses n-paraffins with sulfur dioxide and chlorine converted to the corresponding sulfochlorides under irradiation with UV light, which upon hydrolysis with alkali directly the alkanesulfonates, when reacting with water the alkanesulfonic acids. There in the sulfochlorination di- and polysulfochlorides as well as chlorinated hydrocarbons as by-products the radical reaction can occur, the reaction is usually only up to Implementation levels of 30% carried out and then canceled.

Another process for the production of alkanesulfonic acids is sulfoxidation, in which n-paraffins can be reacted with sulfur dioxide and oxygen under irradiation with UV light. At this Radical reactions result in successive alkylsulfonyl radicals that add oxygen to the Alkylpersulfonylradiaklen continue to react. The reaction with unreacted paraffin gives one Alkyl radical and the alkyl persulfonic acid, which in an alkyl peroxysulfonyl radical and a Hydroxyl radical disintegrates. The reaction of the two radicals with unreacted paraffin provides the Alkyl sulfonic acids or water, which with alkyl persulfonic acid and sulfur dioxide Sulfuric acid reacts. To the yield of the two end products alkyl sulfonic acid and This reaction will keep sulfuric acid as high as possible and suppress side reactions Usually only carried out up to degrees of conversion of 1% and then terminated.

Olefin sulfonates are produced industrially by the reaction of α-olefins with sulfur trioxide. Intermediate hermaphrodites form here, which cyclize to form so-called sultons. Under These sultones react to suitable conditions (alkaline or acid hydrolysis) Hydroxylalkanesulfonic acids or alkenesulfonic acids, both of which are also anionic surfactant acids can be used.

Alkylbenzenesulfonic acids as powerful anionic surfactants have been around since the 1930s of our century. At that time, by monochlorination of kogasin fractions and subsequent Friedel-Crafts alkylation prepared alkylbenzenes that were sulfonated with oleum.

In the early 1950s, propylene was added to the production of alkylbenzenesulfonic acids branched α-dodecylene and tetramerized the product via a Friedel-Crafts reaction Use of aluminum trichloride or hydrogen fluoride converted to tetrapropylene benzene, the was subsequently sulfonated. This economical way of producing Tetrapropylene benzene sulfonic acids (TPS) led to the breakthrough of this class of surfactants, which follows displaced the soaps as the main surfactant in washing and cleaning agents.

Due to the lack of biodegradability of TPS, there was a need for new ones To represent alkylbenzenesulfonic acids, which are characterized by improved ecological behavior distinguished. These requirements are met by linear alkylbenzenesulfonic acids, which are used today the almost exclusively produced alkylbenzenesulfonic acids and with the abbreviation ABSS be occupied.

Linear alkylbenzenesulfonic acids are made from linear alkylbenzenes, which in turn are made from linear olefins are accessible. For this purpose, petroleum fractions are used on an industrial scale Molecular sieves separated into the n-paraffins of the desired purity and into the n-olefins dehydrated, resulting in both α- and i-olefins. The resulting olefins are then in In the presence of acidic catalysts with benzene to the alkylbenzenes, the choice of Friedel-Crafts catalyst has an influence on the isomer distribution of the resulting linear Alkylbenzenes has: When using aluminum trichloride, the content of the 2-phenyl isomers is in the mixture with the 3, 4, 5 and other isomers at approx. 30% by weight If hydrogen fluoride is used as a catalyst, the 2-phenyl isomer content can be increased to approximately 20% by weight. reduce. Finally, the sulfonation of linear alkylbenzenes is now possible on an industrial scale Oleum, sulfuric acid or gaseous sulfur trioxide, the latter being by far the largest Has meaning. Special film or tube bundle reactors are used for the sulfonation Product to provide a 97 wt .-% alkylbenzenesulfonic acid (ABSS) within the scope of the present Invention is preferably used as anionic surfactant acid.

Particularly preferred alkylbenzenesulfonic acids in the context of 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. Mixtures of linear alkylbenzenesulfonic acids with the abovementioned C ₈ -, C ₉ -, C ₁₀ -, C ₁₁ -, C ₁₂ - or C ₁₃ -alkyl radicals are particularly preferred.

The alk (en) yl sulfates are the sulfuric acid half esters of the C ₁₂ -C ₁₈ fatty alcohols, for example from coconut oil alcohol, tallow fatty alcohol, lauryl, myristyl, cetyl or stearyl alcohol or the C ₁₀ -C ₂₀ oxo alcohols and those half esters of secondary alcohols of this chain length prefers. Also preferred in the context of the present invention are alk (en) yl sulfates of the chain length mentioned which contain a synthetic, straight-chain alkyl radical prepared on a petrochemical basis and which have a degradation behavior similar to that of the adequate compounds based on oleochemical raw materials. The C ₁₂ -C ₁₆ alkyl sulfates and C ₁₂ -C ₁₅ alkyl sulfates as well as C ₁₄ -C ₁₅ alkyl sulfates are preferred from the point of view of washing technology. 2,3-Alkyl sulfates are also suitable anionic surfactant acids.

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

It is also possible to add alk (en) ylsuccinic acid with preferably 8 to 18 carbon atoms to use the alk (en) yl chain.

The aforementioned anionic surfactants can be used as pure substances in the process according to the invention or used as mixtures. In a particularly preferred according to the invention Methods are used as anionic surfactant acids, alkylbenzenesulfonic acids, the Weight fraction of alkylbenzenesulfonic acids in the total weight of the anionic surfactant acids used preferably at least 20% by weight, particularly preferably 40% by weight and in particular is at least 75% by weight. In a further preferred embodiment, as Anionic surfactants used exclusively alkylbenzenesulfonic acids.

In the context of the present application, anionic surfactants are used as "low-water" anionic surfactants a water content below 4% by weight, preferably below 3% by weight, particularly preferred below 2.5% by weight, in particular below 2% by weight and extremely preferably below 1% by weight, each based on the total weight of the anionic surfactants.

The above-mentioned anionic surfactants in their acid form can be used alone or in a mixture can be used together. However, it is also possible and preferred that the anionic surfactant in Acid form before the bleaching process further, preferably acidic ingredients of washing and Detergents in amounts of 0.1 to 410 wt .-%, preferably from 1 to 15 wt .-% and in particular from 2 to 10% by weight, in each case based on the weight of the mixture to be reacted, be added.

Other suitable acidic ingredients of the reaction mixture are suitable in the context of the present In addition to the "surfactant acids", the invention also includes the fatty acids, phosphonic acids, Polymer acids or partially neutralized polymer acids as well as "builder acids" and "Complex builder acids" alone as well as in any mixtures. As ingredients of washing and Detergents that can be mixed with the anionic surfactant are primarily acidic Detergent and cleaning agent ingredients, for example phosphonic acids, which in neutralized form (phosphonates) as incrustation inhibitors part of many washing and Are detergents. Also the use of (partially neutralized) polymer acids such as Polyacrylic acids is possible according to the invention. But it is also possible to add more acidic and bleach-stable ingredients to mix with the anionic surfactant acid.

Of the oxygen-releasing substances which can be used as bleaching agents, 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 liquid that is soluble in many organic solvents. The viscosity of 1.249 mPa.s at 20 ° C is not significantly higher than that of water (1.002 mPa.s); in aqueous solution, however, hydrogen bonds are formed which outperform those in the pure components. This effect is reflected in the heat of the mixture and, among other things, results in the increased viscosity. 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 take place explosively, if necessary, while a 90% aqueous solution cannot be detonated at 20 ° C. Hydrogen peroxide can be mixed with water in any ratio; up to 70% H ₂ O _{2 is} commercially available as a water-clear, colorless and odorless liquid that reacts very weakly acidic (weaker than carbonic acid) and especially in heat, in light, in the presence of traffic jams, heavy metals and alkalis (e.g. ammonia or the alkalis released from glass) gradually in water u. Oxygen decays.

In order to delay the decomposition of the H ₂ O ₂ during storage, small amounts of stabilizers are added to aqueous hydrogen peroxide solutions, 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 only resulted in dilute aqueous solutions. The electrolytic production from peroxodisulfuric acid or ammonium peroxodisulfate, developed in Weißenstein in 1908 and modified by Löwenstein in 1924, which proceeds via Caro's acid as an intermediate, or the Pietzsch-Adolph process, which runs over potassium peroxodisulfate, provides 35 to 45% solutions of H ₂ O ₂ , Today, over 95% of H ₂ O _{2 is produced} using various variants of the anthraquinone process. Here, the organic "reaction carriers" in a complex solvent mixture of aromatics (as a quinone solvent), and polar compounds, eg. B. methylcyclohexanol acetate (as a hydroquinone solvent), circulated; the H ₂ O ₂ formed by oxidation with air at 30-80 ° C / 500 kPa is extracted with water. The approx. 15-35% raw H ₂ O ₂ solution obtained is generally concentrated to 70%. The direct production of 20% H ₂ O ₂ solution from the elements is possible with the aid of a catalyst made of Pt and Pd salts on a support material made of colloidal SiO ₂ (aq) under pressure at 10-17 ° C. Around 1.8-1.9 million tonnes of hydrogen peroxide were produced annually in the early 1990s, around 50% of which in Europe.

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

Hydrogen peroxide forms numerous peroxohydrates, some of which, e.g. B. sodium percarbonate Sodium perborate, peroxypyrophosphate and percarbamide ("solid hydrogen peroxide"). This Peroxohydrates are also suitable for carrying out the process according to the invention, such as Substitution compounds which are technically far more important, in particular the peroxides and peracids as well as other dioxy and peroxy compounds.

Sodium percarbonate is an unspecific term used for sodium carbonate-hydrogen peroxide complexes. The merchandise has the average composition 2 Na ₂ CO ₃ .3 H ₂ O ₂ and is therefore not peroxocarbonate. Sodium percarbonate forms a white, water-soluble powder that easily breaks down into sodium carbonate and bleaching and oxidizing "active" oxygen.

Within the scope of the present application, various sodium peroxoborates, such as (sodium peroxoborate trihydrate), NaBO ₂ .H ₂ O ₂ .3 H ₂ O, or sodium perborate tetrahydrate (NaBO ₃ .4 H ₂ O) are used under the name "sodium perborate". just as summarized as that of the anhydrous oxoborate. The alkaline aqueous solution of these compounds only releases oxygen slowly after standing for a long time; however, the development of oxygen is accelerated by heating.

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 that decompose in the presence of moisture above 40 ° C. It is easily 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). The heat stability of the percarbamide can be improved by adding sodium or ammonium dihydrogen phosphate or zinc sulfate. Percarbamide is also marketed in tablets containing starch.

Organic peracids or their salts are also particularly suitable as bleaching agents in the context of the present invention. The organic peracids include, in particular, the citrate perhydrates and H ₂ O ₂ -producing peracid salts or peracids, such as perbenzoates, peroxophthalates, diperazelaic acid, phthaloiminoperacid or diperdodecanedioic acid. Preferred organic bleaches are also the diacyl peroxides, such as. B. dibenzoyl peroxide. Other suitable organic bleaching agents are peroxy acids, examples of which include alkyl peroxy acids and aryl peroxy acids. 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-phthalimidanoic acidaprooxyacidoxy (poxy) hexoxyacidoxy (poxy) oxoacidoxy (P) , o-carboxybenzamidoperoxycaproic acid, N-nonenylamidoperadipinic acid and N-nonenylamidopersuccinate, and (c) aliphatic and araliphatic peroxydicarboxylic acids, such as 1,12-diperoxycarboxylic acid, 1,9-diperoxyazelaic acid, diperocysebacic acid, diperoxybassoxydiacid-diperoxydiacid-diperoxydiacid-diperoxy-diacid-diperoxydiacid-diperoxy-diacid-diperoxy-diacid-diperoxy-diacid-diperoxydiacid-diperoxy-diacid-diperoxy-diacid-diperoxy-diacid-diperoxy-diacid-diperoxy-diacid-diperoxy-diacid-diperoxy-diacid-diperoxy-diacid-diperoxy-diacid-diacid, diacid, N, N-terephthaloyl-di (6-aminopercapronic acid) can be used.

Processes according to the invention which are particularly preferred in the context of the present application are characterized in that the bleaching agent is 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% by weight, in particular from 0.001 to 4% by weight and in particular from 0.005 to 0.5% by weight, based on the total weight of the anionic surfactant acid (s), in a further preferred embodiment, the reaction mixture after the bleaching Velcro number below 100, preferably below 60 and in particular below 40.

Chlorine or bromine releasing agents can also be used as bleaching agents in the bleaching process according to the invention Substances are used. Among the appropriate chlorine or bromine releasing materials In addition to the sodium hypochlorite mentioned, for example heterocyclic N-bromine and N- Chloramides such as trichloroisocyanuric acid, tribromo isocyanuric acid, dibromo isocyanuric acid and / or Dichloroisocyanuric acid (DICA) and / or its salts with cations such as potassium and sodium into consideration. Hydantoin compounds such as 1,3-dichloro-5,5-dimethylhydanthoin are also suitable.

Particularly suitable stabilizers in the process according to the invention substances containing hydroxyl groups, in a preferred embodiment of the method Water and / or alcohol (s) and / or phosphonic acid (s), in particular water and / or methanol and / or ethanol and / or 1-propanol and / or 2-propanol and / or 1-butanol and / or 2-butanol and / or sec-butanol and / or tert-butanol and / or cyclohexanol and / or 1,2-ethanediol and / or 1,2-propanediol and / or 1,3-propanediol can be used as stabilizers. The weight percentage of Stabilizers on the total weight of the reaction mixture are, as described at the beginning, above 6% by weight, preferably above 7% by weight, particularly preferably in the range from 7 to 12% by weight and in particular in the range between 8 and 11% by weight. The stabilizer can be added before at the same time as or after adding the bleach. Particularly preferred in the context of Bleaching processes in which the addition of the stabilizer / the Stabilizers before, during or after, preferably at least partially after bleaching Velcro number below 100, preferably a Velcro number below 60 and in particular a Velcro number below 40.

• a) 100 Gewichtsanteile Aniontensidsäure(n),
• b) x Gewichtsanteile Bleichmittel (Aktivsubstanz) sowie
• c) 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 characterized in that

• a) 100 parts by weight of anionic surfactant acid (s),
• b) x parts by weight of bleach (active substance) and
• c) y parts by weight of a stabilizer are implemented, wherein

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

It has proven particularly advantageous to carry out the bleaching process according to the invention if the reaction mixture is below 75 ° C during bleaching, preferably below 65 ° C, particularly preferably between 20 and 60 ° C and in particular between 35 and 55 ° C.

The present invention furthermore relates to bleached anionic surfactant acids or bleached mixtures containing anionic surfactant acid, which preferably contain a stabilizer (s) from the group of the hydroxyl-containing substance (s), particularly preferably from the group of Alcohol (s) and / or phosphonic acid (s), in particular from the group methanol and / or ethanol and / or 1-propanol and / or 2-propanol and / or 1-butanol and / or 2-butanol and / or sec Butanol and / or tert-butanol and / or cyclohexanol and / or 1,2-ethanediol and / or 1,2-propanediol and / or 1,3 propanediol above 6% by weight, preferably above 7% by weight, particularly preferably in Range of 7 to 12 wt .-% and in particular in the range between 8 and 11 wt .-%, respectively based on the total weight of the bleached anionic surfactant acid or the bleached Mixture containing anionic surfactant acid. Bleached ones are particularly preferred Anionic surfactant acids or bleached anionic surfactant acid-containing mixtures, which have a Klett number have below 100, preferably below 60 and in particular below 40. such Anionic surfactant acids and mixtures containing anionic surfactant acid are notable for the low Velcro numbers not only have an advantageous appearance, but are also, as described above, particularly stable in color and storage.

Another object of the present invention is the use of stabilizers from the Group of alcohol (s) and / or phosphonic acid (s), in particular from the group methanol and / or ethanol and / or 1-propanol and / or 2-propanol and / or 1-butanol and / or 2-butanol and / or sec-butanol and / or tert-butanol and / or cyclohexanol and / or 1,2-ethanediol and / or 1,2-propanediol and / or 1,3-propanediol and / or as stabilizers in the bleaching of Anionic surfactant.

The bleached anionic surfactant acids obtained when the process according to the invention is carried out with a stabilizer content above 6% by weight are suitable due to their high color stability in particular for the production of detergents or cleaning agents for private consumption. On Another object of the present invention is therefore the use of bleached Anionic surfactant acids with a stabilizer content above 6% by weight in detergents or cleaning agents or for the production of detergents or cleaning agents, for example after neutralization of the Anionic surfactant acids and subsequent packaging. The assembly of the if necessary neutralized or partially neutralized stabilizer-containing anionic surfactant acids according to the invention can be done, for example, by agglomeration, compacting or extrusion. Both resulting washing or cleaning agents 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 However, anionic surfactant acids can also be advantageously used in liquid detergents or cleaning agents incorporated.

When using anionic surfactants containing stabilizers according to the invention in washing or Detergents or for the production of detergents or cleaning agents are these Surface-active substances are usually combined with a number of other active substances. to Group of these active substances include, for example, bleaching agents, bleach activators, polymers, Builders, surfactants, enzymes, disintegrants, electrolytes, pH adjusting agents, fragrances, perfume carriers, Fluorescent agents, dyes, hydrotopes, foam inhibitors, silicone oils, anti-redeposition agents, optical brighteners, graying inhibitors, run-in preventers, anti-crease agents, Color transfer inhibitors, antimicrobial agents, germicides, fungicides, antioxidants, Corrosion inhibitors, antistatic agents, ironing aids, phobing and impregnating agents, swelling and Anti-slip agents and UV absorbers included. These active substances are described in more detail below described.

Detergents and cleaning agents can contain bleach and bleach activators as important components. Among the compounds which serve as bleaching agents and supply H ₂ O ₂ in water, sodium perborate tetrahydrate and sodium perborate monohydrate are of particular importance. Further bleaching agents which can be used are, for example, sodium percarbonate, peroxypyrophosphates, citrate perhydrates and H ₂ O ₂ -producing peracidic salts or peracids, such as perbenzoates, peroxophthalates, diperazelaic acid, phthaloiminoperic acid or diperdodecanedioic acid. Detergents for automatic dishwashing can 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 bleaching agents are peroxy acids, examples of which include alkyl peroxy acids and aryl peroxy acids. 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-phthalimidanoic acidaprooxyacidoxy (poxy) hexoxyacidoxy (poxy) oxoacidoxy (P) , o- Carboxybenzamidoperoxycapronsäure, N-nonenylamidoperadipic acid and N- nonenylamidopersuccinates, and (c) aliphatic and araliphatic peroxydicarboxylic acids, such as 1,12-diperoxycarboxylic acid, 1,9-diperoxyazelaic acid, diperoxysebacic acid, diperoxybrassylic acid, diperoxyphthalic acids, the 2-decyldiperoxybutane-1,4- diacid, N, N-terephthaloyl-di (6-aminopercapronic acid) can be used.

To improve the bleaching effect when cleaning at temperatures of 60 ° C and below detergents and cleaning agents can contain bleach activators. As bleach activators can compounds containing aliphatic peroxocarboxylic acids under perhydrolysis conditions preferably 1 to 10 carbon atoms, in particular 2 to 4 carbon atoms, and / or optionally result in substituted perbenzoic acid can be used. Suitable substances are those that and / or N-acyl groups of the number of carbon atoms mentioned and / or optionally substituted Wear benzoyl groups. Multi-acylated alkylenediamines are preferred, in particular Tetraacetylethylenediamine (TAED), acylated triazine derivatives, especially 1,5-diacetyl-2,4- dioxohexahydro-1,3,5-triazine (DADHT), acylated glycolurils, especially tetraacetylglycoluril (TAGU), N-acylimides, especially N-nonanoylsuccinimide (NOSI), acylated phenol sulfonates, in particular n-nonanoyl- or isononanoyloxybenzenesulfonate (n- or iso-NOBS), Carboxylic anhydrides, especially 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, so-called Bleaching catalysts are incorporated into the washing or cleaning agents. With these fabrics are bleach-enhancing transition metal salts or transition metal complexes such as for example Mn, Fe, Co, Ru or Mo salt complexes or carbonyl complexes. Also Mn, Fe, Co, Ru, Mo, Ti, V and Cu complexes with N-containing tripod ligands as well as Co, Fe, Cu and Ru Amine complexes can be used as bleaching catalysts.

In addition to the ingredients mentioned, bleaching agents and bleach activators are builders, in particular So zeolites, silicates, carbonates, organic cobuilders and - where no ecological prejudices against their use exist - also the phosphates and surfactants important ingredients of washing 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. Preferred crystalline layered silicates of the formula given are those in which M represents sodium and x assumes the values 2 or 3. In particular, both β- and δ-sodium disilicates Na ₂ Si ₂ O ₅ .yH ₂ O are preferred.

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

The finely crystalline, synthetic and bound water-containing zeolite which can be used is preferably zeolite A and / or P. As zeolite P, zeolite MAP (commercial product from Crosfield) is particularly preferred. However, zeolite X and mixtures of A, X and / or P are also suitable. Commercially available and can preferably be used in the context of the present invention, for example a co-crystallizate of zeolite X and zeolite A (about 80% by weight of zeolite X) ), which is sold by CONDEA Augusta SpA 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; measurement method: Coulter Counter) and preferably contain 18 to 22% by weight, in particular 20 to 22% by weight, of bound water.

It goes without saying that the generally known phosphates are also used as builder substances possible if such use should not be avoided for ecological reasons. The sodium salts of orthophosphates, pyrophosphates and especially the tripolyphosphates.

Alkali metal phosphates is the general term for the alkali metal (especially sodium and potassium) salts of the various phosphoric acids, in which one can distinguish between metaphosphoric acids (HPO ₃ ) _n and orthophosphoric acid H ₃ PO _{4 in} addition to higher molecular weight representatives. The phosphates combine several advantages: They act as alkali carriers, prevent limescale deposits on machine parts and lime incrustations in fabrics and also contribute to 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, water-soluble powders, which lose water of crystallization when heated and into the weakly acidic diphosphate (disodium hydrogen diphosphate, Na ₂ H ₂ P ₂ O ₇ ) at 200 ° C, 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 (primary or monobasic potassium phosphate, potassium biphosphate, KDP), KH ₂ PO ₄ , is a white salt with a density of 2.33 gcm ^{-3 and} has a melting point of 253 ° [decomposition to form potassium polyphosphate (KPO ₃ ) _x ] and is easily soluble in water.

Disodium hydrogen phosphate (secondary sodium phosphate), Na ₂ HPO ₄ , is a colorless, very easily water-soluble crystalline salt. It exists anhydrous and with 2 mol. (Density 2.066 gcm ^-3 , water loss at 95 °), 7 mol. (Density 1.68 gcm ^-3 , melting point 48 ° with loss of 5 H ₂ O) and 12 mol. Water ( Density 1.52 gcm ^-3 , melting point 35 ° with the loss of 5 H ₂ O), becomes anhydrous at 100 ° and passes with greater heating into the diphosphate Na ₄ P ₂ O ₇ over disodium hydrogenphosphate is used by neutralizing phosphoric acid with soda solution made from phenolphthalein as an indicator. Dipotassium hydrogen phosphate (secondary or dibasic potassium phosphate), K ₂ HPO ₄ , is an amorphous, white salt that is easily soluble in water.

Trisodium phosphate, tertiary sodium phosphate, Na ₃ PO ₄ , are colorless crystals which, as dodecahydrate, have a density of 1.62 gcm ^-3 and a melting point of 73-76 ° C (decomposition), as decahydrate (corresponding to 19-20% P ₂ O ₅ ) 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 with an alkaline reaction and is produced by evaporating a solution of exactly 1 mol of disodium phosphate and 1 mol of NaOH. Tripotassium phosphate (tertiary or triphase potassium phosphate), K ₃ PO ₄ , is a white, deliquescent, granular powder with a density of 2.56 gcm ^-3 , has a melting point of 1340 ° and is easily soluble in water with an alkaline reaction. It arises e.g. B. when heating Thomas slag with coal and potassium sulfate. Despite the higher price, the more soluble, therefore highly effective, potassium phosphates are often preferred over corresponding sodium compounds in the cleaning agent industry.

Tetrasodium diphosphate (sodium pyrophosphate), Na ₄ P ₂ O ₇ , exists in anhydrous form (density 2.534 gcm ^-3 , melting point 988 °, also given 880 °) and as decahydrate (density 1.815-1.836 gcm ^-3 , melting point 94 ° with loss of water) , Both substances are colorless crystals that are soluble in water with an alkaline reaction. Na ₄ P ₂ O ₇ is formed by heating 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 formers 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 value being 1% Solution at 25 ° is 10.4.

Condensation of the NaH ₂ PO ₄ or the KH ₂ PO ₄ produces higher moles. Sodium and potassium phosphates, in which one can differentiate cyclic representatives, the sodium or potassium metaphosphates and chain-like types, the sodium or potassium polyphosphates. A large number of names are used in particular for the latter: melt or glow phosphates, Graham's salt, Kurrolaches 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 non-hygroscopic, water-soluble salt of the general formula NaO- [P (O) (ONa) -O] _n that crystallizes with 6 H ₂ O. -Na with n = 3. In 100 g of water about 17 g of the salt of water free of water of crystallization dissolve at room temperature, about 209 at 60 ° and around 32 g at 100 °; after heating the solution at 100 ° for two hours, hydrolysis produces about 8% orthophosphate and 15% diphosphate. In the production of pentasodium triphosphate, phosphoric acid is reacted with sodium carbonate solution or sodium hydroxide solution in a stoichiometric ratio and the solution is dewatered by spraying. Similar to Graham's salt and sodium diphosphate, pentasodium triphosphate dissolves many insoluble metal compounds (including lime soaps, etc.). Pentapotassium triphosphate, K ₅ P ₃ O ₁₀ (potassium tripolyphosphate), is commercially available, for example, in the form of a 50% strength by weight solution (> 23% P ₂ O ₅ , 25% K ₂ O). The potassium polyphosphates are widely used in the detergent and cleaning agent industry. There are also sodium potassium tripolyphosphates which can also be used in the context of the present invention. These occur, for example, when hydrolyzing sodium trimetaphosphate with KOH:

(NaPO ₃ ) ₃ + 2 KOH → Na ₃ K ₂ P ₃ O ₁₀ + H ₂ O

According to the invention, these are exactly like sodium tripolyphosphate, potassium tripolyphosphate or Mixtures of these two can be used; 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 can be used according to the invention.

Usable organic builders are, for example, those in the form of their alkali and in particular sodium salts of polycarboxylic acids, such as citric acid, adipic acid, Succinic acid, glutaric acid, tartaric acid, sugar acids, aminocarboxylic acids, nitrilotriacetic acid (NTA), provided that such use is not objectionable for ecological reasons, and Mixtures of these. Preferred salts are the salts of polycarboxylic acids such as citric acid, Adipic acid, succinic acid, glutaric acid, tartaric acid, sugar acids and mixtures of these.

Alkali carriers can be present as further constituents. Are considered to be alkali carriers Alkali metal hydroxides, alkali metal carbonates, alkali metal hydrogen carbonates, Alkali metal sesquicarbonates, alkali silicates, alkali metal silicates, and mixtures of the aforementioned substances, wherein in For the purposes of this invention, the alkali carbonates, in particular sodium carbonate, are preferred. Sodium bicarbonate or sodium sesquicarbonate can be used.

Water-soluble builders are another preferred component of detergents or cleaning agents. Common water-soluble builders are the low molecular weight polycarboxylic acids and their salts, the homopolymeric and copolymeric polycarboxylic acids and their salts, the carbonates, phosphates and Silicates. Trisodium citrate is preferred for the production of automatic dishwashing detergents 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. A builder system containing a mixture of tripolyphosphate is particularly preferred and sodium carbonate. A builder system that is a mixture of is also particularly preferred Contains tripolyphosphate and sodium carbonate and sodium disilicate.

In addition to the anionic surfactants described above, detergents and cleaning agents can be used contain detergent substances.

Nonionic surfactants form a large group of detergent substances. The nonionic surfactants used are preferably alkoxylated, advantageously ethoxylated, in particular primary alcohols having preferably 8 to 18 carbon atoms and an average of 1 to 12 moles of ethylene oxide (EO) per mole of alcohol, in which the alcohol residue can be linear or preferably methyl-branched in the 2-position or may contain linear and methyl-branched radicals in the mixture, as are usually present in oxo alcohol radicals. In particular, however, alcohol ethoxylates with linear residues from alcohols of native origin with 12 to 18 carbon atoms, for. B. from coconut, palm, tallow or oleyl alcohol, and an average of 2 to 8 EO per mole of alcohol preferred. The preferred ethoxylated alcohols include, for example, C _12-14 alcohols with 3 EO or 4 EO, C _9-11 alcohol with 7 EO, C _13-15 alcohols with 3 EO, 5 EO, 7 EO or 8 EO, C _12-18 alcohols with 3 EO, 5 EO or 7 EO and mixtures thereof, such as mixtures of C _12-14 alcohol with 3 EO and C _12-18 alcohol with 5 EO. The degrees of ethoxylation given represent statistical averages, which can be an integer or a fraction for a specific product. Preferred alcohol ethoxylates have a narrow homolog distribution (narrow range ethoxylates, NRE). In addition to these nonionic surfactants, fatty alcohols with more than 12 EO can also be used. Examples include tallow fatty alcohol with 14 EO, 25 EO, 30 EO or 40 EO.

Another class of preferred nonionic surfactants, 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 with 1 to 4 carbon atoms in the alkyl chain, in particular fatty acid methyl ester.

Another class of nonionic surfactants that can be used advantageously are the alkyl polyglycosides (APG). Alkypolyglycosides that can be used satisfy the general formula RO (G) _z , in which R denotes a linear or branched, in particular methyl-branched, saturated or unsaturated, aliphatic radical having 8 to 22, preferably 12 to 18, carbon atoms and G is the Is symbol which stands for a glycose unit with 5 or 6 carbon atoms, preferably for 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. Linear alkyl polyglucosides, ie alkyl polyglycosides, in which the polyglycosyl radical is a glucose radical and the alkyl radical is an n-alkyl radical are preferably used.

Also nonionic surfactants of the amine oxide type, for example N-cocoalkyl-N, N- dimethylamine oxide and N-tallow alkyl-N, N-dihydroxyethylamine oxide, and the fatty acid alkanolamides can be suitable. The amount of these nonionic surfactants is preferably not more than that of ethoxylated fatty alcohols, especially not more than half of them.

Other suitable surfactants are polyhydroxy fatty acid amides of the formula (I),


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

The group of polyhydroxy fatty acid amides also includes compounds of the formula (II)


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

[Z] is preferably obtained by reductive amination of a reduced sugar, for example Glucose, fructose, maltose, lactose, galactose, mannose or xylose. The N-alkoxy or N Aryloxy-substituted compounds can then be reacted with fatty acid methyl esters in In the presence of an alkoxide as a catalyst converted into the desired polyhydroxy fatty acid amides become.

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

Polymers are another important component of laundry detergents and cleaning products, taking under Polymers in the present application, in particular substances with builder or cobuilder Properties are to be understood. As organic cobuilders in the invention Detergents and cleaning agents, especially polycarboxylates / polycarboxylic acids, polymers Polycarboxylates, aspartic acid, polyacetals, dextrins, other organic cobuilders (see below) and phosphonates are used. These classes of substances are described below.

Usable organic builders are, for example, the sodium salts below as part of the shower system called polycarboxylic acids. 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 one 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 of these.

Polymeric polycarboxylates are also suitable as builders, for example those Alkali metal salts of polyacrylic acid or polymethacrylic acid, for example those with a relative molecular mass from 500 to 70,000 g / mol.

In the context of this document, the molecular weights given for polymeric polycarboxylates are weight-average molecular weights M _w , 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 to the polymers investigated. This information differs significantly from the molecular weight information for which polystyrene sulfonic acids are used as standard. The molecular weights measured against polystyrene sulfonic acids are generally significantly higher than the molecular weights given in this document.

Suitable polymers are in particular polyacrylates, which preferably have a molecular weight of 2000 to Have 20,000 g / mol. Because of their superior solubility, this group can turn the short-chain polyacrylates, the molecular weights from 2000 to 10,000 g / mol, and particularly preferred from 3000 to 5000 g / mol, may be preferred.

Also suitable are copolymeric polycarboxylates, especially those of acrylic acid Methacrylic acid and acrylic acid or methacrylic acid with maleic acid. As particularly suitable have proven copolymers of acrylic acid with maleic acid, the 50 to 90 wt .-% acrylic acid and contain 50 to 10% by weight of maleic acid. Their relative molecular mass, based on free acids, is generally 2000 to 70,000 g / mol, preferably 20,000 to 50,000 g / mol and in particular 30,000 to 40,000 g / mol.

To improve water solubility, the polymers can also allylsulfonic acids, such as for example, contain allyloxybenzenesulfonic acid and nlethallylsulfonic acid as a monomer.

Also particularly preferred are biodegradable polymers made from more than two different ones Monomer units, for example those which are salts of acrylic acid and Maleic acid and vinyl alcohol or vinyl alcohol derivatives or the salts of the monomers Acrylic acid and 2-alkylallylsulfonic acid as well as sugar derivatives.

Further preferred copolymers are those which preferably contain acrolein and Acrylic acid-acrylic acid salt Q or acrolein and vinyl acetate.

Likewise, other preferred builder substances are polymeric aminodicarboxylic acids and their salts or to name their precursors. Polyaspartic acids or their salts and derivatives, which in addition to cobuilder properties also have a bleach-stabilizing effect exhibit.

Other suitable builder substances are polyacetals, which are reacted with dialdehydes Polyol carboxylic acids which have 5 to 7 carbon atoms and at least 3 hydroxyl groups can be. Preferred polyacetals are derived from dialdehydes such as glyoxal, glutaraldehyde, Terephthalaldehyde and mixtures thereof and from polyol carboxylic acids such as gluconic acid and / or Obtain glucoheptonic acid.

Other suitable organic builder substances are dextrins, for example oligomers or Polymers of carbohydrates that can be obtained by partial hydrolysis of starches. The Hydrolysis can be carried out by customary, for example acid or enzyme-catalyzed, processes become. They are preferably hydrolysis products with average molecular weights in the range from 400 to 500,000 g / mol. Here is a polysaccharide with a dextrose equivalent (DE) in the range of 0.5 to 40, in particular from 2 to 30, are preferred, DE being a customary measure of the reducing effect of a polysaccharide compared to dextrose, which has a DE of 100, is. Both maltodextrins with a DE between 3 and 20 and dry glucose syrups can be used with a DE between 20 and 37 as well as so-called yellow dextrins and white dextrins with higher ones Molar masses in the range from 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. An oxidized oligosaccharide is also suitable. A product oxidized at C _{6 of} the saccharide ring can be particularly advantageous.

Also oxydisuccinates and other derivatives of disuccinates, preferably ethylenediamine disuccinate, are other suitable cobuilders. Ethylene diamine N, N'-disuccinate (EDDS) is preferred in Form of its sodium or magnesium salts used. Are further preferred in this Also related to glycerol disuccinates and glycerol trisuccinates. Suitable amounts are used in zeolite-containing and / or silicate-containing formulations at 3 to 15% by weight.

Other useful organic cobuilders are, for example, acetylated hydroxycarboxylic acids or their salts, which may also be in lactone form and which have at least 4 Contain carbon atoms and at least one hydroxyl group and a maximum of two acid groups.

Another class of substances with cobuilder properties are the phosphonates it is especially hydroxyalkane or aminoalkanephosphonates. Among the Hydroxyalkane phosphonates, 1-hydroxyethane-1,1-diphosphonate (HEDP) is of particular importance as Co-builders. It is preferably used as the sodium salt, the disodium salt being neutral and the Tetrasodium salt reacts alkaline (pH 9). Preferred aminoalkane phosphonates are Ethylenediaminetetramethylenephosphonate (EDTMP), diethylenetriaminepentamethylenephosphonate (DTPMP) and their higher homologues in question. They are preferably in the form of neutral reacting sodium salts, e.g. B. as the hexasodium salt of EDTMP or as hepta and octa Sodium salt of DTPMP, used. As a builder, the class of phosphonates preferably HEDP used. The aminoalkanephosphonates also have a pronounced Heavy metal binding capacity. Accordingly, it can, especially if the agent also bleach contain, be preferred to use aminoalkane phosphonates, in particular DTPMP, or To use mixtures of the phosphonates mentioned.

In addition, all compounds that are capable of complexing with alkaline earth ions train as cobuilders.

Detergents or cleaning agents can contain enzymes to increase the washing or cleaning performance, although in principle all enzymes established in the prior art can be used for these purposes. These include in particular proteases, amylases, lipases, hemicellulases, cellulases or oxidoreductases, and preferably their mixtures. In principle, these enzymes are of natural origin; Based on the natural molecules, improved variants are available for use in detergents and cleaning agents, which are accordingly preferred. Agents ^according to the invention preferably contain enzymes in total amounts of 1 × 10 ^-6 to 5 percent by weight based on active protein. The protein concentration can be determined using known methods, for example the BCA method or the biuret method.

Among the proteases, those of the subtilisin type are preferred. Examples of this are the subtilisins BPN 'and Carlsberg, the protease PB92, the subtilisins 147 and 309, the alkaline protease Bacillus lentus, Subtilisin DY and those of the subtilases, but no longer of the subtilisins in the narrower range Sensible enzymes Thermitase, Proteinase K and the proteases TW3 and TW7. subtilisin Carlsberg is in a further developed form under the trade name Alcalase® from the company Novozymes A / S, Bagsvaerd, Denmark. Subtilisins 147 and 309 are among the Trade names Esperase® or Savinase® sold by Novozymes. Of of the protease from Bacillus lentus DSM 5483 are derived from those listed under the name BLAP® Variants from.

Further usable proteases are, for example, those under the trade names Durazym®, Relase®, Everlase®, Nafizym, Natalase®, Kannase® and Ovozymes® from Novozymes, which are among the Trade names, Purafect®, Purafect®OxP and Properase® from Genencor, which under the Trade name Protosol® from Advanced Biochemicals Ltd., Thane, India, under the Trade names Wuxi® from Wuxi Snyder Bioproducts Ltd., China, which are among the Trade names Proleather® and Protease P® from Amano Pharmaceuticals Ltd., Nagoya, Japan, and this under the name Proteinase K-16 from Kao Corp., Tokyo, Japan, available enzymes.

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

Furthermore, the α-amylase from Bacillus sp. A 7-7 (DSM 12368) and the Highlight cyclodextrin glucanotransferase (CGTase) from B. agaradherens (DSM 9948).

In addition, those available under the trade names Fungamyl® from Novozymes Further developments of the α-amylase from Aspergillus niger and A. oryzae are suitable. Another one The commercial product is, for example, the Amylase-LT®.

Washing or cleaning agents can lipaseri or cutinases, especially because of their Triglyceride-cleaving activities contain, but also to peracids in situ from suitable precursors produce. These include, for example, those originally from Humicola lanuginosa (Thermomyces lanuginosus) available or further developed lipases, especially those with the Amino acid exchange D96L. They are, for example, from Novozymes under the Trade names Lipolase®, Lipolase®Ultra, LipoPrime®, Lipozyme® and Lipex® sold. Furthermore For example, the cutinases can be used, originally from Fusarlum sotani pisi and Humicoia insolens have been isolated. Lipases which can also be used by Amano are among the Designations Lipase CE®, Lipase P®, Lipase B®, or Lipase CES®, Lipase AKG®, Bacillis sp. Lipasee, Lipase AP®, Lipase M-AP® and Lipase AML® available. By Genencor For example, the lipases or cutinases, their starting enzymes, can be used originally isolated from Pseudomonas mendocina and Fusarlum solanil. As another important commercial products are those originally distributed by the Gist-Brocades company Preparations M1 Lipase® and Lipomax® and those from Meito Sangyo KK, Japan, among the Mention mentioned names Lipase MY-30®, Lipase OF® and Lipase PL®, furthermore the Lumafast® product from Genencor.

Detergents or cleaning agents can contain other enzymes that come under the term Hemicellulases can be summarized. These include, for example, mannanases, Xanthan lyases, pectin lyases (= pectinases), pectin esterases, pectate lyases, xyloglucanases (= Xylanases), pullulanases and β-glucanases. Suitable mannanases are, for example, among the Names Gamanase® and Pektinex AR® from Novozymes, under the name Rohapec® B1L from AB Enzymes and under the name Pyrolase® from Diversa Corp., San Diego, CA, USA available. The β-glucanase obtained from B. subtilis is under the name Cereflo® available from Novozymes.

To increase the bleaching effect, washing or cleaning agents can use 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 are Denilite® 1 and 2 from the company To name Novozymes. Advantageously, organic, in particular, are also preferred preferably aromatic, interacting with the enzymes added to the To increase the activity of the oxidoreductases in question (enhancers) or in the case of strong ones different redox potentials between the oxidizing enzymes and the soiling to ensure the flow of electrons (mediators).

The enzymes used in detergents or cleaning agents either originate from Microorganisms, such as the genera Bacillus, Streptomyces, Humicola, or Pseudomonas, and / or according to known biotechnological methods by suitable Microorganisms produced, for example by transgenic expression hosts of the genera Bacillus or filamentous fungi.

The purification of the enzymes in question is carried out favorably by methods which are established per se, for example via precipitation, sedimentation, concentration, filtration of the liquid phases, Microfiltration, ultrafiltration, exposure to chemicals, deodorization or suitable Combinations of these steps.

Detergents or cleaning agents can use any of the enzymes established in the prior art Form can be added. These include, for example, those by granulation, extrusion or Lyophilization obtained solid preparations or, especially in liquid or gel form Agents, solutions of the enzymes, advantageously as concentrated as possible, low in water and / or with Stabilizers added.

Alternatively, the enzymes can be used for both the solid and the liquid dosage form are encapsulated, for example by spray drying or extrusion of the enzyme solution together with a, preferably natural polymer or in the form of capsules, for example, in to which the enzymes are enclosed as in a solidified gel or in those from the core-shell Type in which an enzyme-containing core is impermeable to water, air and / or chemicals Protective layer is coated. Additional active ingredients, for example, stabilizers, emulsifiers, pigments, bleaches or dyes are applied. Such capsules are made according to methods known per se, for example by shaking or Roll granulation or applied in fluid-bed processes. Such granules are advantageously for example by applying polymeric film formers, low in dust and due to the coating storage stable.

Furthermore, it is possible to assemble two or more enzymes so that one individual granules have multiple enzyme activities.

A protein and / or enzyme contained in washing or cleaning agents can be particularly useful during storage against damage such as inactivation, denaturation or decay, for example protected by physical influences, oxidation or proteolytic cleavage. at microbial extraction of the proteins and / or enzymes is an inhibition of proteolysis in particular preferred, especially if the agents also contain proteases. Agents according to the invention can contain stabilizers for this purpose; the provision of such means is preferred Embodiment of the present invention.

A group of stabilizers are reversible protease inhibitors. Often benzamidine Hydrochloride, borax, boric acids, boronic acids or their salts or esters used, including before all derivatives with aromatic groups, such as ortho-substituted, meta-substituted and para substituted phenylboronic acids, or their salts or esters. As a peptide Protease inhibitors include ovomucoid and leupeptin; an additional Option is the formation of fusion proteins from proteases and peptide inhibitors.

Further enzyme stabilizers are amino alcohols such as mono-, di-, triethanol- and -propanolamine and their mixtures, aliphatic carboxylic acids up to C ₁₂ , such as succinic acid, other dicarboxylic acids or salts of the acids mentioned. End-capped fatty acid amide alkoxylates are also suitable. Certain organic acids used as builders can additionally stabilize an enzyme contained.

Lower aliphatic alcohols, but above all polyols, such as glycerol, ethylene glycol, Propylene glycol or sorbitol are other frequently used enzyme stabilizers. Likewise Calcium salts 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, among other things, against physical influences or pH fluctuations. Polymers containing polyamine N-oxide act as enzyme stabilizers. Other polymeric stabilizers are the linear C ₈ -C ₁₈ polyoxyalkylenes. Alkyl polyglycosides can stabilize the enzymatic components of the agent according to the invention and even increase their performance. Cross-linked N-containing compounds also act as enzyme stabilizers.

Reducing agents and antioxidants increase the stability of the enzymes against oxidative decay. A sulfur-containing reducing agent is, for example, sodium sulfite.

Combinations of stabilizers are preferably used, 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 Polyols or polyamino compounds and with reducing salts. The effect of peptide Aldehyde stabilizers are combined with boric acid and / or boric acid derivatives and Polyols increased and by the additional use of divalent cations, such as Example calcium ions further enhanced.

Preferred machine dishwashing detergents are characterized in that they additionally contain a several enzymes and / or enzyme preparations, preferably solid and / or liquid protease Preparations and / or amylase preparations, in amounts of 1 to 5% by weight, preferably of 1.5 to 4.5 and in particular from 2 to 4 wt .-%, each based on the total agent.

Fragrances are added to the detergents or cleaning agents in order to create an aesthetic impression To improve products and give the consumer a sensory "typical and distinctive" To provide product.

As perfume oils or fragrances, individual fragrance compounds, e.g. B. the synthetic Products of the ester, ether, aldehyde, ketone, alcohol and hydrocarbon type are used become. Fragrance compounds of the ester type are e.g. B. benzyl acetate, phenoxyethyl isobutyrate, p- tert-butylcyclohexyl acetate, linalyl acetate, dimethylbenzylcarbinylacetate, phenylethyl acetate, Linalyl benzoate, benzyl formate, ethyl methylphenyl glycinate, allyl cyclohexyl propionate, styrallyl propionate and benzyl salicylate. The ethers include, for example, benzyl ethyl ether, the aldehydes z. B. the linear alkanals with 8-18 C atoms, citral, citronellal, citronellyloxyacetaldehyde, cyclamenaldehyde, Hydroxycitronellal, Lilial and Bourgeonal, to the ketones z. B. the Jonone, α-isomethyl ionone and Methyl cedryl ketone, to the alcohols anethole, citronellol, eugenol, geraniol, linalool, Phenyiethyl alcohol and terpineol, the hydrocarbons mainly include the terpenes like lime and pinene. However, mixtures of different fragrances are preferably used, which together create an appealing fragrance. Such perfume oils can also be natural Fragrance mixtures contain, as they are accessible from plant sources, for. B. Pine, Citrus, Jasmine, patchouly, rose or ylang-ylang oil. Also suitable are muscatel, sage oil, Chamomile oil, clove oil, lemon balm oil, mint oil, cinnamon leaf oil, linden blossom oil, juniper berry oil, vetiver oil, Olibanum oil, galbanum oil and labdanum oil as well as orange blossom oil, neroliol, orange peel oil and Sandalwood oil.

The general description of the perfumes that can be used (see above) is generally the different substance classes of fragrances. In order to be perceptible, a Fragrance be volatile, being in addition to the nature of the functional groups and the structure of the chemical compound also the molecular weight plays an important role. Most have that Fragrances Molar masses up to about 200 Daltons, while Molar masses of 300 Daltons and above tend to be to be an exception. Changed due to the different volatility of fragrances the smell of a perfume or fragrance composed of several fragrances during evaporation, whereby the olfactory impressions in "top note", "heart or Middle note "(middle note or body) and" base note "(end note or dry out). Since the Odor perception is largely based on the intensity of the odor Top note of a perfume or fragrance not only from volatile compounds, while the Base note for the most part from less volatile, i.e. H. non-stick fragrances. In the Composition of perfumes can make volatile fragrances, for example, to certain fixatives bound, which prevents them from evaporating too quickly. The following Classification of the odoriferous substances into "more volatile" or "adherent" odoriferous substances is therefore about Odor impression and whether the corresponding fragrance as a top or heart note is perceived, nothing is said.

A suitable selection of the fragrances or perfume oils mentioned can be used in this way for Textile detergent both the product smell, as well as, after finishing the cleaning and Care process, in addition, the scent of laundry can be influenced. For the latter smell is the use of more adhesive fragrances is advantageous, while also for product scenting volatile fragrances can be used. Adhesive odoriferous substances that are within the scope of the present Invention are usable, for example, the essential oils such as angelica root oil, anise oil, Arnica flower oil, basil oil, bay oil, bergamot oil, champaca flower oil, noble fir oil, Noble pine cone oil, elemi oil, eucalyptus oil, fennel oil, spruce pine oil, galbanum oil, geranium oil, Ginger grass oil, guaiac wood oil, gurjun balsam oil, helichrysum oil, ho oil, ginger oil, iris oil, kajeput oil, Calamus oil, chamomile oil, camphor oil, Kanaga oil, cardamom oil, cassia oil, pine needle oil, Copaiva balsam oil, coriander oil, spearmint oil, caraway oil, cumin oil, lavender oil, lemon grass oil, Lime oil, mandarin oil, lemon balm oil, musk seed 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, allspice oil, pine oil, rose oil, rosemary oil, sandalwood oil, celery oil, spik oil, stemanis oil, Turpentine oil, thuja oil, thyme oil, verbena oil, vetiver oil, juniper berry oil, wormwood oil, wintergreen oil, Ylang-ylang oil, hyssop oil, cinnamon oil, cinnamon leaf oil, lemon oil, lemon oil and cypress oil. But also the higher-boiling or solid fragrances of natural or synthetic origin can in Within the scope of the present invention as adhesive fragrances or fragrance mixtures, ie Fragrances. These connections include the following Compounds and mixtures of these: ambrettolide, α-amylcinnamaldehyde, anethole, anisaldehyde, Anise alcohol, anisole, anthranilic acid methyl ester, acetophenone, benzylacetone, benzaldehyde, Ethyl benzoate, benzophenone, benzyl alcohol, benzyl acetate, benzyl benzoate, benzyl formate, Benzylvalerianate, borneol, bornyl acetate, α-bromostyrene, n-decylaldehyde, n-dodecylaldehyde, eugenol, Eugenol methyl ether, eucalyptol, farnesol, fenchone, fenchyl acetate, geranyl acetate, geranyl formate, Heliotropin, methyl heptinate, heptaldehyde, hydroquinone dimethyl ether, Hydroxycinnamaldehyde, Hydroxyzimtalkohol, Indol, Iron, Isoeugenol, Isoeugenolmethylether, Isosafrol, Jasmon, Camphor, Kanrakrol, Karvon, p-cresol methyl ether, Cumann, p-methoxyacetophenone, methyl n-amyl ketone, methylanthranilic acid methyl ester, p-methylacetophenone, methylchavicol, p- Methylquinoline, methyl-β-naphthyl ketone, methyl-n-nonylacetaldehyde, methyl-n-nonyl ketone, muscon, β- Naphthol ethyl ether, β-naphthol methyl ether, nerol, nitrobenzene, n-nonylaldehyde, nony alcohol, n- Octylaldehyde, p-oxy-acetophenone, pentadecanolide, β-phenylethyl alcohol, phenylacetaldehyde Dimethyacetal, phenylacetic acid, pulegon, safrole, salicylic acid isoamyl ester, salicylic acid methyl ester, Hexyl saficylic acid, cyclohexyl salicylic acid, Santalol, Skatol, Terpineol, Thymen, Thymol, γ- Undelactone, vanilin, veratrum aldehyde, cinnamaldehyde, cimate alcohol, cinnamic acid, cinnamic acid ethyl ester, Zimtsäurebenzylester. The more volatile fragrances include, in particular, the lower ones boiling fragrances of natural or synthetic origin, alone or in mixtures can be used. Examples of more volatile fragrances are alkyl isothiocyanates (Alkyl mustard oils), butanedione, limonene, linalool, linaylacetate and propionate, menthol, menthone, Methyln-heptenone, pheflandren, phenylacetaldehyde, terpinylacetate, citral, citronellal.

In order to facilitate the disintegration of highly compressed detergents or cleaning agents, to reduce the disintegration times shorten, it is possible to use disintegration aids, so-called tablet disintegrants, in these incorporate. According to Römpp (9. Edition, Vol. 6, p. 4440) and Voigt "Textbook of pharmaceutical technology" (6th edition, 1987, P. 182-184) understood auxiliaries for the rapid disintegration of tablets in water or Gastric juice and release of the pharmaceuticals in an absorbable form.

These substances, which are also referred to as "explosives" due to their effect, enlarge Water ingress their volume, whereby on the one hand the own volume increases (swelling), on the other hand A pressure can also be generated via the release of gases, which breaks the tablet down into smaller ones Particles disintegrate. Well-known disintegration aids are, for example Carbonate / citric acid systems, whereby other organic acids can also be used. 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 its derivatives, alginates or casein derivatives. All disintegration aids mentioned can be used according to the invention.

Disintegration aids can be found in washing or cleaning agents as disintegration aids Cellulose base are used, preferably a disintegration aid Cellulose base, preferably in granular, cogranulated or compacted form, in amounts of 0.5 to 10% by weight, preferably 3 to 7% by weight and in particular 4 to 6% by weight, in each case based on the tablet weight.

Pure cellulose has the formal gross composition (C ₆ H ₁₀ O ₅ ) _n and, formally speaking, is a β-1,4-polyacetal of cellobiose, which in turn is made up of two molecules of glucose. Suitable celluloses consist of approximately 500 to 5000 glucose units and consequently have average molecular weights of 50,000 to 500,000. Cellulose-based disintegrants which can be used in the context of the present invention are also cellulose derivatives which can be obtained from cellulose by polymer-analogous reactions. Such chemically modified celluloses include, for example, products from esterifications or etherifications in which hydroxy hydrogen atoms have been substituted. However, celluloses in which the hydroxyl groups have been replaced by functional groups which are not bound via an oxygen atom can also be used as cellulose derivatives. The group of cellulose derivatives includes, for example, alkali celluloses, carboxymethyl cellulose (CMC), cellulose esters and ethers and aminocelluloses. The cellulose derivatives mentioned are preferably not used alone as a cellulose-based disintegrant, but are used in a mixture with cellulose. The content of cellulose derivatives in these mixtures is preferably below 50% by weight, particularly preferably below 20% by weight, based on the cellulose-based disintegrant. Pure cellulose which is free of cellulose derivatives is particularly preferably used as the cellulose-based disintegrant. Microcrystalline cellulose can be used as a further cellulose-based disintegrant or as a component of this component. This microcrystalline cellulose is obtained by partial hydrolysis of celluloses under conditions which only attack and completely dissolve the amorphous areas (approx. 30% of the total cellulose mass) of the celluloses, but leave the crystalline areas (approx. 70%) undamaged. Subsequent disaggregation of the microfine celluloses produced by the hydrolysis gives the microcrystalline celluloses, which have primary particle sizes of approximately 5 μm and can be compacted, for example, into granules with an average particle size of 200 μm.

In addition to the ingredients mentioned above, detergents or cleaning agents are gas-releasing Contain system of organic acids and carbonates / hydrogen carbonates.

As organic acids from the carbonates / hydrogen carbonates in aqueous solution Releasing carbon dioxide are, for example, the solid mono-, oligo- and polycarboxylic acids used. From this group, preference is again given to citric acid, tartaric acid, succinic acid, Malonic acid, adipic acid, maleic acid, fumaric acid, oxalic acid and polyacrylic acid. organic Sulfonic acids such as amidosulfonic acid can also be used. Commercially available and as Acidifying agent is also preferably used in the context of the present invention Sokalan® DCS (trademark of BASF), a mixture of succinic acid (max. 31% by weight), Glutaric acid (max. 50% by weight) and adipic acid (max. 33% by weight).

The acids mentioned do not have to be stoichiometric in the detergents or cleaning agents contained carbonates or bicarbonates are used.

The gas-developing effervescent system consists of the detergent and cleaning tablets next to the mentioned organic acids from carbonates and / or hydrogen carbonates. With the representatives In this class of substances, the alkali metal salts are clearly preferred for reasons of cost. Both Alkali metal carbonates or bicarbonates, in turn, are the sodium and potassium salts Cost reasons clearly preferred over the other salts. Of course you don't have to the pure alkali metal carbonates or bicarbonates concerned are used; much more Mixtures of different carbonates and hydrogen carbonates may be preferred.

In addition to the components previously described in detail, washing and Detergent tablets contain other ingredients that affect the application technology and / or further improve aesthetic properties when used as a textile detergent. at These ingredients are, for example, one or more substances from the group of electrolytes, pH adjusting agents, fluorescent agents, dyes, hydrotopes, foam inhibitors, Silicone oils, anti-redeposition agents, optical brighteners, graying inhibitors, anti-shrink agents, Anti-crease agents, color transfer inhibitors, antimicrobial agents, germicides, fungicides, Antioxidants, antistatic agents, ironing aids, phobing and impregnating agents, swelling and Anti-slip agent and UV absorber.

A wide number of different salts can be used as electrolytes from the group of inorganic salts. 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.

In order to bring the pH value of the washing or cleaning agents into the desired range, the Use of pH adjusting agents. All known acids or Alkalis, provided that their use is not for technical or ecological reasons or banned for reasons of consumer protection. Usually the amount exceeds this Adjusting agent not 1% by weight of the total formulation.

To improve the aesthetic impression of detergents or cleaning agents, you can use suitable dyes are colored. Preferred dyes, their selection to the expert no difficulty, have a high storage stability and insensitivity to the other ingredients of the agents and against light and no pronounced substantivity compared to textile fibers so as not to stain them.

As foam inhibitors that can be used in washing or cleaning agents, For example, soaps, paraffins or silicone oils come into consideration, which may arise Carrier materials can be applied. Suitable anti-redeposition agent, also called soil Repellents are referred to, for example, nonionic cellulose ethers such as methyl cellulose and methylhydroxypropyl cellulose with a proportion of methoxy groups of 15 to 30% by weight and Hydroxypropyl groups of 1 to 15 wt .-%, each based on the nonionic cellulose ether and the polymers of phthalic acid and / or terephthalic acid known from the prior art or of their derivatives, in particular polymers of ethylene terephthalates and / or Polyethylene glycol terephthalates or anionically and / or nonionically modified derivatives of this. Particularly preferred of these are the sulfonated derivatives of phthalic acid and Terephthalic acid polymers.

Optical brighteners (so-called "whiteners") can be added to the washing or cleaning agents to remove graying and yellowing of the treated textiles. These substances draw on the fiber and cause a lightening and feigned bleaching effect by Convert invisible ultraviolet radiation into visible longer-wave light, which is from the Sunlight absorbed ultraviolet light as a faint bluish fluorescence and is emitted with the yellow tone of the grayed or yellowed laundry results in pure white. Suitable connections originate, for example, from the substance classes of 4,4'-diamino-2,2'-stilbenedisulfonic acids (Flavonic acids), 4,4-distyryl-biphenylene, methylumbelliferone, coumarins, dihydroquinolinones, 1,3- Diarylpyrazolines, naphthalic imides, benzoxazole, benzisoxazole and benzimidazole systems as well of pyrene derivatives substituted by heterocycles.

Graying inhibitors have the task of removing the dirt detached from the fiber in the liquor to keep suspended and thus prevent the dirt from re-opening. For this are Suitable water-soluble colloids mostly organic in nature, for example the water-soluble salts polymeric carboxylic acids, glue, gelatin, salts of ether sulfonic acids of starch or cellulose or salts of acidic sulfuric acid esters of cellulose or starch. Also water soluble, polyamides containing acidic groups are suitable for this purpose. Furthermore, soluble ones Use starch preparations and starch products other than the above, e.g. B. dismantled Starch, aldehyde starches, etc. Polyvinylpyrrolidone can also be used. As graying inhibitors Cellulose ethers such as carboxymethyl cellulose (sodium salt), methyl cellulose, Hydroxyalkyl cellulose and mixed ethers such as methyl hydroxyethyl cellulose, methyl hydroxypropyl cellulose, Methylcarboxymethylcellulose and mixtures thereof.

Since textile fabrics, in particular rayon, rayon, cotton and their mixtures, can be wrinkled because the individual fibers prevent bending, kinking. Presses and The tablets according to the invention can be squeezed across the grain contain synthetic anti-crease agents. These include, for example, synthetic products on the Basis of fatty acids, fatty acid esters, fatty acid amides, alkylol esters, alkylolamides or Fatty alcohols, which are mostly reacted with ethylene oxide, or products based on lecithin or modified phosphoric acid ester.

To combat microorganisms, the washing or cleaning agents can be antimicrobial Contain active ingredients. A distinction is made depending on the antimicrobial spectrum and Mechanism of action between bacteriostatics and bactericides, fungistatics and fungicides etc. Important substances from these groups are, for example, benzalkonium chlorides, alkylarlyl sulfonates, Halogenphenols and Phenolmercuriacetat, whereby also completely with the means according to the invention these connections can be dispensed with.

To unwanted, caused by oxygen and other oxidative processes Changes to the washing or cleaning agents and / or the treated textiles too prevent the agents may contain antioxidants. Belong to this connection class for example substituted phenols, hydroquinones, pyrocatechols and aromatic amines as well organic sulfides, polysulfides, dithiocarbamates, phosphites and phosphonates.

Increased comfort can result from the additional use of antstatics, which Detergents or cleaning agents can also be added. Antistatic agents increase the Surface conductivity and thus enable an improved flow of charges. External antistatic agents are usually substances with at least one hydrophilic molecular ligand and give a more or less hygroscopic film on the surfaces. Mostly Surface-active antistatic agents can be broken down into nitrogen-containing (amines, amides, quaternary Ammonium compounds), phosphorus-containing (phosphoric acid esters) and sulfur-containing (alkyl sulfonates, Subdivide antistatic agents. Lauryl (or stearyl) dimethylbenzylammonium chlorides are suitable also as antistatic agents for textiles or as an additive to detergents, with an additional Finishing effect is achieved.

To care for the textiles and to improve the textile properties such as a softer "handle" (Finish) and reduced electrostatic charge (increased wearing comfort), the washing or detergent containing fabric softener. The active ingredients in fabric softener formulations are "Esterquats", quaternary ammonium compounds with two hydrophobic residues, such as that Disteraryldimethylammoniumchlorid, which however because of its insufficient biological Degradability is increasingly being replaced by quaternary ammonium compounds in their hydrophobic residues contain ester groups as predetermined breaking points for biodegradation.

To improve the water absorption capacity, the rewettability of the treated Textiles and to facilitate the ironing of the treated textiles can be washed or Cleaning agents such as silicone derivatives are used. These also improve that Rinsing behavior of the agents according to the invention due to their foam-inhibiting properties. Preferred silicone derivatives are, for example, polydialkyl or alkylarylsiloxanes, in which the Alkyl groups have one to five carbon atoms and are partially or completely fluorinated. preferred Silicones are polydimethylsiloxanes, which may or may not be derivatized are amino-functional or quaternized or have Si-OH, Si-H and / or Si-Cl bonds.

Finally, the washing or cleaning agents can also contain UV absorbers that act on the treated textiles and improve the lightfastness of the fibers. Connections that these desired properties are, for example, those due to non-radiation Deactivation of active compounds and derivatives of benzophenone with substituents in 2- and / or 4-position. Substituted benzotriazoles are also substituted in the 3-position by phenyl Acrylates (cinnamic acid derivatives), optionally with cyano groups in the 2-position, salicylates, organic Ni complexes as well as natural substances such as umbelliferone and the body's own urocanoic acid are suitable.

Claims (13)

1. Process for bleaching low-water anionic surfactant acids by reaction with one or more bleaching agent (s), characterized in that, in addition to the bleaching agent, such an amount of at least one stabilizer is added that the resulting reaction mixture has a stabilizer content above 6 based on its total weight % By weight. 2. The method according to claim 1, characterized in that the reaction mixture additionally such an amount of at least one stabilizer is further added to the bleach 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 % By weight, based in each case on the total weight of the resulting mixture. 3. The method according to any one of claims 1 or 2, characterized in that the Anionic surfactant acids include alkylbenzenesulfonic acids. 4. The method according to any one of claims 1 or 3, characterized in that as a bleach Hydrogen peroxide and / or inorganic perhydrate and / or organic peracid and / or the salts of organic peracid, preferably in amounts of 0.0001 to 5% by weight, in particular from 0.001 to 4% by weight and in particular from 0.005 to 0.5% by weight, in each case based on the total weight of the anionic surfactant acid (s) is / are used. 5. The method according to any one of claims 1 to 4, characterized in that as Stabilizer (s) substances containing hydroxyl groups, preferably water and / or Alcohol (s) and / or phosphonic acid (s), in particular water and / or methanol and / or Ethanol and / or 1-propanol and / or 2-propanol and / or 1-butanol and / or 2-butanol and / or sec-butanol and / or tert-butanol and / or cyclohexanol and / or 1,2-ethanediol and / or 1,2-propanediol and / or 1,3-propanediol are used. 6. The method according to any one of claims 1 to 5, characterized in that the After bleaching, the reaction mixture has a Klett number below 100, preferably below 60 and in particular below 40. 7. The method according to any one of claims 1 to 6, characterized in that 1. (iv) 100 parts by weight of anionic surfactant acid (s), 2. x parts by weight of bleach (active substance) and 3. y parts by weight of a stabilizer are implemented, wherein x has values between 0.4 and 5 and the sum of x and y is at least 7. 8. The method according to any one of claims 1 to 7, characterized in that the addition of Stabilizers / the stabilizers 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 440 occurs. 9. The method according to any one of claims 1 to 8, characterized in that the Reaction mixture during the bleaching a temperature below 75 ° C, preferably below 65 ° C, particularly preferably between 20 and 60 ° C and in particular between 35 and 55 ° C. 10. Bleached anionic surfactant acid or bleached mixture containing anionic surfactant acid, thereby characterized in that they contain a stabilizer (s), preferably from the group the hydroxyl-containing substance (s), particularly preferably from the group of Alcohol (s) and / or phosphonic acid (s), in particular from the group methanol and / or Ethanol and / or 1-propanol and / or 2-propanol and / or 1-butanol and / or 2-butanol and / or sec-butanol and / or tert-butanol and / or cyclohexanol and / or 1,2-ethanediol and / or 1,2-propanediol and / or 1,3-propanediol above 6% by weight, preferably above 7 wt .-%, particularly preferably in the range of 7 to 12 wt .-% and in particular in Range between 8 and 11 wt .-%, each based on the total weight of the bleached Anionic surfactant acid or of the bleached anionic surfactant acid-containing mixture. 11. After bleached anionic surfactant acid or bleached anionic surfactant acid-containing mixture Claim 10, characterized in that the bleached anionic surfactant acid or bleached anionic surfactant-containing mixture a Klett number below 100, preferably below 60 and in particular below 40. 12. Use of stabilizers from the group of alcohol (s) and / or Phosphonic acid (s), in particular from the group methanol and / or ethanol and / or 1- Propanol and / or 2-propanol and / or 1-butanol and / or 2-butanol and / or sec-butanol and / or tert-butanol and / or cyclohexanol and / or 1,2-ethanediol and / or 1,2-propanediol and / or 1,3 propanediol and / or as stabilizers in the bleaching of anionic surfactant acids. 13. Use of bleached anionic surfactant acids with a stabilizer content above 6% by weight in detergents or cleaning agents.