DE102004020026A1 - Portioned washing or cleaning agent with surfactant phase - Google Patents

Abstract

A washing or cleaning agent in a water-soluble or water-dispersible container comprising a surfactant phase containing by weight 40 to 85% by weight of a neutralized anionic surfactant acid and a particulate solid, characterized in that surfactant phase a) and solid b) together in a receiving chamber of the water-soluble or water-dispersible container are easy to prepare and are characterized by good solubility and improved storage and transport stability.

Description

object The present application is a portioned detergent or cleaning agent with a special surfactant phase. In particular, the present invention relates Application multiphase, portioned detergents or cleaners in water-soluble or water-dispersible packaging.

The portioned packaging of active ingredients or combinations of active ingredients plays in many areas of applied chemistry, for example in pharmacy, plant protection an important role. By the portioning may become one time- and labor-intensive dosage avoided by the user as well, like the direct contact of the user with the corresponding active ingredients.

So WO 93/08095 A1 (Rhone-Poulenc) discloses a bag of water-soluble or water-dispersible material having two horizontal receiving chambers and, for example, for packaging toxic substances suitable is. The bags can be prepared by the thermoforming process.

Also in the field of detergents or cleaners are the original Tender forms powder, compact or gel increasingly in portioned Dosage units in water-soluble or water-dispersible packaging. Especially the packaging of liquids or gels in such dosage units is of great interest. liquids or gels are compared to conventional compressed tablets quickly available in the wash liquor and are thus potentially useful for improving the washing or Cleaning performance especially in short or energy savings of Washing machines or dishwashers. Pre-dosed liquid Agents, especially in combination with solid agents, are suitable thus for the technical implementation and visualization of new concepts of action.

such Dosing units with solid and liquid ingredients can one or have a plurality of receiving chambers. To avoid unwanted interactions between Solid and liquid To avoid these, they are usually spatially separated. In dosing units with a receiving chamber, in which liquid and solid together, the solids will do so for example, with a protective Coating provided.

alternative Dosing units can be produced with several receiving chambers, in which liquid and solid by using a packaging material from each other be separated. Take the manufacturing process for these dosing units With increasing number of receiving chambers of complexity too.

In WO 02/42401 A1 (Procter & Gamble) a method for the automated cleaning of dishes is claimed, which using a container with several receiving chambers he follows. The corresponding containers have a horizontal arrangement of the individual receiving chambers on and are by sequential bonding of individual slides under Training the receiving chambers made, with individual, by thermoforming molding processed films are used can.

object WO 02/85738 A1 (Reckitt Benckiser) are water-soluble containers with at least two on top of each other arranged receiving troughs. The preparation of these containers takes place by gradual sealing of individual foils or prefabricated Individual compartments for the final container.

One One-step process for producing water-soluble containers with at least two receiving chambers describes WO 02/85736 A1 (Reckitt Benckiser). The reception chambers can by injection molding or Deep drawing are made, and are designed so that the closed chambers by folding along a brim in mirror image Fold the arrangement together and glue together. The Folding the adjacent chambers is a necessary component this method and sets the use of a suitably adapted machine ahead. The kinking or flaps along a bridge, however, leads necessarily to weakening a seal running along this bridge and favors on this way leaks. To achieve a favorable product appearance It may still be necessary after folding and gluing to remove part of the brim.

The preparation of the above-described combination products of liquid and solid ingredients is carried out by complex, multi-stage, cost-intensive processes in which the separation of the ingredients by use of coating materials or additional packaging materials is realized. All zi Accordingly, methods are characterized by a complex sequence of numerous process steps. The processes are correspondingly cost-intensive and require a high proportion of packaging.

The Object of the present invention was the above to avoid described disadvantages. In particular, washing or cleaning agents are provided which have the advantages the above-described combination products of liquid and solid, especially their rapid availability in the wash liquor and have their novel look, without an additional Require packaging expenses. The washing and cleaning agents should also be opposite to the usual Means improved storage and transport stability.

It has now been found that the tasks described above a washing or cleaning agent can be achieved in which a particulate solid Phase and a surfactant phase with high anionic surfactant share in common in a receiving chamber of a water-soluble or water-dispersible container.

• a) eine Tensidphase, die bezogen auf ihr Gewicht 40 bis 85 Gew.-% einer neutralisierten Aniontensidsäure enthält; und
• b) einen teilchenförmigen Feststoff,

dadurch gekennzeichnet, dass Tensidphase a) und Feststoff b) gemeinsam in einer Aufnahmekammer des wasserlöslichen oder wasserdispergierbaren Behälters vorliegen.A first subject of the present application is therefore a washing or cleaning agent in a water-soluble or water-dispersible container, comprising

• a) a surfactant phase containing, by weight, 40 to 85% by weight of a neutralized anionic surfactant acid; and
• b) a particulate solid,

characterized in that surfactant phase a) and solid b) are present together in a receiving chamber of the water-soluble or water-dispersible container.

The agents according to the invention are characterized by a fast solubility in the rinsing liquor As well as an advantageous two-phase optics, those of conventional Combination products with solid and liquid phases corresponds. simultaneously is a mixing of solid and liquid phase in the common receiving chamber not to watch. After all can by replacing conventional Liquid phases through the surfactant phase according to the invention the storage and transport stability this means increased significantly become.

The agents according to the invention contain as the first essential ingredient on a surfactant phase Base of neutralized anionic surfactant acids. This surfactant phase has the appearance of a liquid Phase, but mixes under the usual conditions of manufacture, the storage and transport not in the same receiving chamber located particulate Solid and leaves Modify their appearance in many areas.

One particular advantage of the washing or cleaning agents according to the invention lies in the fact that the Advantages of a gel-like Detergent (good washing performance due to high surfactant content) with the convenient handling of firm offer forms combined can. Here, the surfactant phase is under ordinary storage conditions in a nearly solid consistency without washing conditions the for Gel detergent usual good solubility sacrificing. Other general advantages of this type of detergent lie in the absence of drying of the surfactant-containing phase after the Neutralization of the starting fatty acids (e.g., ABS) and greater recipe flexibility. With special Advantage contains the surfactant phase therefore great Amounts of surfactant (s), preferably anionic surfactant (s). Here are inventive washing or Cleaning agents are preferred, which are characterized in that the surfactant phase a) based on their weight 40 to 95 wt .-%, preferably 50 to 90% by weight, particularly preferably 60 to 85% by weight and in particular 65 to 82% by weight Containing surfactant (s).

In Textile detergents are anionic surfactants the most important class of surfactants, while these in detergents for automatic dishwashing have only a minor meaning. With particular advantage are therefore used in products according to the invention, the for the textile laundry are used, anionic surfactants used. Here it is of particular advantage that the Invention allows the use of non-neutralized raw materials, which are processed directly to the surfactant phase, without previously through time-consuming and costly process steps in granules etc. be transferred have to.

As anionic 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 alkylsulfuric acids and alkylarylsulfonic acids. In order to have sufficient surface-active properties, the compounds mentioned should have longer-chain hydrocarbon radicals, ie at least 6 carbon atoms in the alkyl or alkenyl radical. Usually, the C chain distributions of the anionic surfactants are in the range of 6 to 40, preferably 8 to 30 and especially 12 to 22 carbon atoms.

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

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

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

Also alkanesulfonic and olefinsulfonic acids are in the context of the present invention as anionic surfactants in acid form used. alkanesulfonic can the sulfonic acid group terminal bound (primary alkane sulfonic acids) or along the C chain (secondary alkanesulfonic acids), wherein only the secondary alkanesulfonic have commercial significance. These are by sulfochlorination or Sulfoxidation of linear hydrocarbons. In the sulfochlorination According to Reed n-paraffins with sulfur dioxide and chlorine under Irradiation with UV light converted to the corresponding sulfochlorides, on hydrolysis with alkalis directly the alkanesulfonates, upon reaction with water the alkanesulfonic acids, deliver. As in the sulfochlorination di- and Polysulfochloride as well Chlorinated hydrocarbons as by-products of the radical reaction may occur, the reaction usually becomes only up to implementation levels of 30% performed and then canceled.

One another process to Preparation of alkanesulfonic acids is the sulfoxidation, in which n-paraffins under irradiation with UV light can be reacted with sulfur dioxide and oxygen. at This radical reaction generates successive alkylsulfonyl radicals, which react further with oxygen to the Alkylpersulfonylradiaklen. The reaction with unreacted paraffin yields an alkyl radical and the alkylpersulfonic acid, which is an alkyl peroxysulfonyl radical and a hydroxyl radical decays. The reaction of the two radicals with unreacted paraffin provides the alkylsulfonic acids or water which reacts with alkylpersulfonic acid and sulfur dioxide to form sulfuric acid. To the yield of the two end products alkylsulfonic acid and Sulfuric acid as possible To keep high and suppress side reactions, this reaction usually becomes only up to implementation levels of 1% performed and then canceled.

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

alkylbenzenesulfonates As powerful anionic surfactants have been since the thirties known in our century. At that time were by monochlorination of kogasin fractions and subsequent Friedel-Crafts alkylation Alkylbenzenes prepared, which are sulfonated with oleum and sodium hydroxide were neutralized. The early fifties was for manufacturing of alkylbenzenesulfonates propylene to branched α-dodecylene tetramerized and the product over a Friedel-Crafts reaction using aluminum trichloride or hydrogen fluoride is converted to tetrapropylene benzene, the following sulfonated and neutralized. This economic possibility the preparation of tetrapropylene benzene sulfonates (TPS) led to Breakthrough of this class of surfactants, which are the soaps as the main surfactant in detergents and cleaners.

by virtue of The lack of biodegradability of TPS made it necessary to represent new alkylbenzenesulfonates, characterized by an improved ecological Characterize behavior. These requirements are met by linear alkyl benzene sulfonates Fulfills, which today almost exclusively produced alkylbenzenesulfonates are and with the abbreviation ABS or LAS are occupied.

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

in der die Summe aus x und y üblicherweise zwischen 5 und 13 liegt. Erfindungsgemäß bevorzugt als Aniontensid in Säureform sind C_8-16-, vorzugsweise C_9-13-Alkylbenzolsulfonsäuren. Es ist im Rahmen der vorliegenden Erfindung weiterhin bevorzugt, C_8-16-, vorzugsweise C_9-13-Alkybenzolsulfonsäuren einzusetzen, die sich von Alkylbenzolen ableiten, welche einen Tetralingehalt unter 5 Gew.-%, bezogen auf das Alkylbenzol, aufweisen. Weiterhin bevorzugt ist es, Alkylbenzolsulfonsäuren zu verwenden, deren Alkylbenzole nach dem HF-Verfahren hergestellt wurden, so daß die eingesetzten C_8-16-, vorzugsweise C_9-13-Alkybenzolsulfonsäuren einen Gehalt an 2-Phenyl-Isomer unter 22 Gew.-%, bezogen auf die Alkylbenzolsulfonsäure, aufweisen.By choosing the neutralizing agent, a wide variety of salts, ie alkylbenzenesulfonates, can be obtained from the ABSS. For reasons of economy, it is preferred in this case to prepare and use the alkali metal salts and, among these, preferably the sodium salts of ABSS. These can be described by the general formula I:

in which the sum of x and y is usually between 5 and 13. Preferably according to the invention as anion Surfactant in acid form are C _8-16 , preferably C _9-13 -alkylbenzenesulfonic acids. It is further preferred in the context of the present invention to use C _8-16 , preferably C _9-13- alkylbenzenesulfonic acids which are derived from alkylbenzenes which have a tetralin content of less than 5% by weight, based on the alkylbenzene. It is further preferred to use alkylbenzenesulfonic acids whose alkylbenzenes were prepared by the HF process, so that the C _8-16 -, preferably C _9-13 -alkyl benzene sulfonic acids used have a content of 2-phenyl isomer of less than 22% by weight. , based on the alkylbenzenesulfonic acid.

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

When Acid reactants are suitable in the context of the present invention in addition to the "surfactant acids" also mentioned fatty acids, phosphonic, polymer acids or partially neutralized polymeric acids and "builder acids" and "complex builder acids" (details later in the text) alone and in any mixtures. As ingredients of washing and detergents are especially acid detergent and cleaning agent ingredients on, for example, phosphonic acids, which are neutralized in Form (phosphonates) as incrustation inhibitors part of many Detergents and cleaners are. Also the use of (partially neutralized) polymer acids such as polyacrylic acids, is possible according to the invention. It is but also possible acid-stable Ingredients to mix with the anionic surfactant acid. Offer here For example, so-called small components, which otherwise would have to be added in elaborate further steps, ie For example, optical brighteners, dyes, etc., in individual cases the acid stability is to be checked.

According to the invention, the surfactant phase contains preferably from 40 to 85% by weight of alkylbenzenesulfonate (s), based on their weight. Detergents or cleaning agents are particularly preferred in the context of the present invention, their surfactant phase based on their weight 50 to 82.5 wt .-% and in particular 60 to 80 wt .-% alkylbenzenesulfonate (s).

The neutralized form can be directly in the formation of the surfactant phase be produced by adding appropriate amounts of anionic acid, water and neutralizing agents and optionally further ingredients mixed. It increases the temperature, and the mixture is at this temperature easy to process. Upon cooling, the surfactant phase forms, characterized by handling stability, shelf life and good solubility distinguished.

In preferred embodiments of the present invention the surfactant phase in addition Nonionic surfactants. In general, detergents or cleaners according to the invention are preferred in which the surfactant phase based on their weight 0.5 to 20 wt .-%, preferably 0.5 to 15 wt .-% and in particular 1 to 10% by weight of nonionic surfactant (s).

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

In addition, as further nonionic surfactants and alkyl glycosides of the general formula RO (G) _x can be used in which R is a primary straight-chain or methyl-branched, especially in the 2-position methyl-branched aliphatic radical having 8 to 22, preferably 12 to 18 carbon atoms and G is the symbol which represents a glycose unit having 5 or 6 C atoms, preferably glucose. Of the Degree of oligomerization x, which indicates the distribution of monoglycosides and oligoglycosides, is any number between 1 and 10; preferably x is 1.2 to 1.4.

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

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

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

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

in der R für einen linearen oder verzweigten Alkyl- oder Alkenylrest mit 7 bis 12 Kohlenstoffatomen, R¹ für einen linearen, verzweigten oder cyclischen Alkylrest oder einen Arylrest mit 2 bis 8 Kohlenstoffatomen und R² für einen linearen, verzweigten oder cyclischen Alkylrest oder einen Arylrest oder einen Oxy-Alkylrest mit 1 bis 8 Kohlenstoffatomen steht, wobei C_1-14-Alkyl- oder Phenylreste bevorzugt sind und [Z] für einen linearen Polyhydroxyalkylrest steht, dessen Alkylkette mit mindestens zwei Hydroxylgruppen substituiert ist, oder alkoxylierte, vorzugsweise ethoxylierte oder propoxylierte Derivate dieses Restes.The group of polyhydroxy fatty acid amides also includes compounds of the formula III,

in the R is a linear or branched alkyl or alkenyl radical having 7 to 12 carbon atoms, R ^{1 is} a linear, branched or cyclic alkyl radical or an aryl radical having 2 to 8 carbon atoms and R ^{2 is} a linear, branched or cyclic alkyl radical or an aryl radical or an oxy-alkyl radical having 1 to 8 carbon atoms, wherein C _1-14 -alkyl or phenyl radicals are preferred and [Z] is a linear polyhydroxyalkyl radical whose alkyl chain is substituted with at least two hydroxyl groups, or alkoxylated, preferably ethoxylated or propoxylated Derivatives of this residue.

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

in the The scope of the present invention is washing or cleaning agents preferably containing anionic (s) and nonionic (s) surfactant (s), whereby application advantages from certain proportions, in which the individual classes of surfactants are used, resulting can.

So For example, washing and cleaning agents are particularly preferred, where the ratio of Anionic surfactant (s) to nonionic surfactant (s) between 10: 1 and 1:10, preferably between 7.5: 1 and 1: 5 and in particular between 5: 1 and 1: 2. Prefers are also detergents and cleaners, the surfactant (s), preferably anionic and / or nonionic surfactant (s), in quantities of From 5 to 40% by weight, preferably from 7.5 to 35% by weight, more preferably from 10 to 30% by weight, in particular from 12.5 to 25% by weight, in each case based on the weight of the washing or cleaning agent.

It can have advantages from an application point of view, if certain Surfactant classes in some phases of detergents and cleaners or throughout the washing or cleaning agent, i. in all phases, not included. Another important embodiment of the present invention The invention therefore provides that at least a phase of washing or Detergent is free of nonionic surfactants.

Vice versa But also by the content of individual phases or the whole Means, i. all phases, certain surfactants a positive Effect can be achieved. The incorporation of the alkyl polyglycosides described above has proved to be advantageous, so that washing and cleaning agents in which at least one phase of the washing or cleaning agents are preferred Contains alkylpolyglycosides.

It it is preferred that the Detergents and cleaners contain a nonionic surfactant, which has a melting point above room temperature, is preferred a nonionic surfactant having a melting point above 20 ° C. Prefers nonionic surfactants to be used have melting points above 25 ° C, particularly preferred nonionic surfactants have melting points between 25 and 60 ° C, in particular between 26.6 and 43.3 ° C.

suitable nonionic surfactants, the melting or softening points in said Temperature range, for example, low-foaming nonionic Surfactants which may be solid or highly viscous at room temperature. Become used at room temperature highly viscous nonionic surfactants, it is preferred that these a viscosity above 20 Pas, preferably above 35 Pas and especially above 40 Pas. Also nonionic surfactants which are waxy at room temperature Consistency are preferred.

Prefers as at room temperature fixed to be used nonionic surfactants derived the groups of the alkoxylated nonionic surfactants, in particular the ethoxylated primary Alcohols and mixtures of these surfactants with structurally complicated built-up surfactants such as polyoxypropylene / polyoxyethylene / polyoxypropylene (PO / EO / PO) surfactants. Such (PO / EO / PO) nonionic surfactants stand out about it out by good foam control.

In a preferred embodiment The present invention is the nonionic surfactant having a Melting point above room temperature an ethoxylated nonionic surfactant, that from the reaction of a monohydroxyalkanol or alkylphenol with 6 to 20 carbon atoms, preferably at least 12 mol, more preferably at least 15 moles, in particular at least 20 moles of ethylene oxide per Mol alcohol or alkylphenol emerged.

A particularly preferred room temperature solid nonionic surfactant is obtained from a straight chain fatty alcohol having 16 to 20 carbon atoms (C _16-20 alcohol), preferably a C ₁₈ alcohol and at least 12 moles, preferably at least 15 moles and especially at least 20 moles of ethylene oxide , Of these, the so-called "narrow range ethoxylates" (see above) are particularly preferred.

The nonionic surfactant solid at room temperature preferably additionally has propylene oxide units in the molecule. Preferably, such PO units make up to 25% by weight, especially preferably up to 20 wt .-% and in particular up to 15 wt .-% of total molecular weight of the nonionic surfactant. Especially preferred nonionic surfactants are ethoxylated monohydroxyalkanols or Alkylphenols, in addition Having polyoxyethylene-polyoxypropylene block copolymer units. The alcohol or alkylphenol part of such nonionic surfactant molecules makes preferably more than 30% by weight, particularly preferably more than 50% by weight and more preferably more than 70% by weight of the total molecular weight of such Nonionic surfactants.

Further particularly preferred nonionic surfactants with melting points above room temperature contain from 40 to 70% of a polyoxypropylene / polyoxyethylene / polyoxypropylene block polymer blend, the 75% by weight of a reverse block copolymer of polyoxyethylene and polyoxypropylene with 17 moles of ethylene oxide and 44 moles of propylene oxide and 25% by weight of a block copolymer of polyoxyethylene and polyoxypropylene initiated with trimethylolpropane and containing 24 moles of ethylene oxide and 99 moles of propylene oxide per mole of trimethylolpropane.

Nonionic surfactants that may be used with particular preference are available, for example under the name Poly Tergent ^® SLF-18 from Olin Chemicals.

A further preferred surfactant can be defined by the formula R ¹ O [CH ₂ CH (CH ₃ ) O] _x [CH ₂ CH ₂ O] _y [CH ₂ CH (OH) R ² ] in which R ^{1 is} a linear or branched aliphatic hydrocarbon radical having 4 to 18 carbon atoms or mixtures thereof, R ^{2 is} a linear or branched hydrocarbon radical having 2 to 26 carbon atoms or mixtures thereof and x is values between 0.5 and 1, 5 and y is a value of at least 15.

Other preferred nonionic surfactants are the end-capped poly (oxyalkylated) nonionic surfactants of the formula R ¹ O [CH ₂ CH (R ³ ) O] _x [CH ₂ ] _k CH (OH) [CH ₂ ] _j OR ² in which R ¹ and R ^{2 are} linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals having 1 to 30 carbon atoms, R ^{3 is} H or a methyl, ethyl, n-propyl, iso-propyl, n- Butyl, 2-butyl or 2-methyl-2-butyl radical, x are values between 1 and 30, k and j are values between 1 and 12, preferably between 1 and 5. If the value x ≥ 2, each R ³ in the above formula may be different. R ¹ and R ² are preferably linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals having 6 to 22 carbon atoms, with radicals having 8 to 18 carbon atoms being particularly preferred. For the radical R ³ , H, -CH ₃ or -CH ₂ CH _{3 are} particularly preferred. Particularly preferred values for x are in the range from 1 to 20, in particular from 6 to 15.

As described above, each R ³ in the above formula may be different if x ≥ 2. As a result, the alkylene oxide unit in the square bracket can be varied. For example, when x is 3, the radical R ³ can be selected to form ethylene oxide (R ³ = H) or propylene oxide (R ³ = CH ₃ ) units which may be joined in any order, for example (EO) ( PO) (EO), (EO) (EO) (PO), (EO) (EO) (EO), (PO) (EO) (PO), (PO) (PO) (EO) and (PO) ( PO) (PO). The value 3 for x has been selected here by way of example and may well be greater, with the variation width increasing with increasing x values and including, for example, a large number (EO) groups combined with a small number (PO) groups, or vice versa ,

Particularly preferred end-capped poly (oxyalkylated) alcohols of the above formula have values of k = 1 and j = 1, so that the above formula is to R ¹ O [CH ₂ CH (R ³ ) O] _x CH ₂ CH (OH) CH ₂ OR ² simplified. In the latter formula, R ¹ , R ² and R ^{3 are} as defined above and x is from 1 to 30, preferably from 1 to 20 and in particular from 6 to 18. Particularly preferred are surfactants in which the radicals R ¹ and R ^{2 has} 9 to 14 C atoms, R ^{3 is} H and x assumes values of 6 to 15.

The Surfactant phase according to the invention more preferred Washing or cleaning agent preferably further contains a Alkali carriers, preferably an alkali carrier from the group of builders, in particular from the group of alkali metal hydroxides. Washing or cleaning agents, characterized in that the surfactant phase further 0.5 to 12 Wt .-%, preferably 1.0 to 9 wt .-% and in particular 2.0 to 6 % By weight of an alkali carrier, preferably an alkali hydroxide, are particularly preferred.

Farther washing or cleaning agents are preferred in which the water content the surfactant phase between 8 and 24 wt .-%, preferably between 10 and 20 wt .-% and in particular between 12 and 18 wt .-% is.

By the adjustment of the alkali hydroxide content and / or the water content in the aforementioned preferred limits, the physical Properties of the surfactant phase according to the invention, in particular the processability and storage stability as well as the optical properties influence the surfactant phase in a wide range. An important Aspect for The appearance of agents according to the invention is the transparency the surfactant phases, with transparent or translucent surfactant phases particularly preferred. Under transparency is in the sense of this Invention to understand that the permeability within the visible spectrum of light (410 to 800 nm) greater than 20%, preferably greater than 30%, very preferred greater than 40% and in particular greater than 50% is. Thus, once a wavelength of the visible spectrum the light a permeability greater than 20%, it is to be regarded as transparent within the meaning of the invention. Of course can also opaque Tensidphase be realized. Such surfactant phases are preferred colored or opaque.

preferred Means comprise a surfactant phase a), which in addition to the neutralized Anionic acid continue contains a dye.

To the aesthetic impression of the agents according to the invention, in particular the surfactant phase a) improve, they can be colored with suitable dyes. Dyes which are preferred in the context of the present invention and whose selection does not cause any difficulty for the person skilled in the art have a high storage stability and insensitivity to the other constituents of the particulate agents and to light and no pronounced substantivity towards textile fibers so as not to stain them.

Dyeing agents which can be oxidatively destroyed in the washing process and mixtures thereof with suitable blue dyes, so-called blue toners, are preferred. It has proved to be advantageous to use colorants which are soluble in water or at room temperature in liquid organic substances. Suitable examples are anionic colorants, for example anionic nitrosofarbstoffe. One possible dye is, for example, naphthol green (Color Index (CI) Part 1: Acid Green 1; Part 2: 10020). Which as a commercial product ^® for example as Basacid Green 970 from BASF, Ludwigshafen, and mixtures thereof with suitable blue dyes. Further suitable colorants Pigmosol come ^® Blue 6900 (CI 74160), Pigmosol ^® Green 8730 (CI 74260), Basonyl ^® Red 545 FL (CI 45170), Sandolan® ^® rhodamine EB400 (CI 45100), Basacid® ^® Yellow 094 (CI 47005) Sicovit ^® Patentblau 85 e 131 (CI 42051), Acid Blue 183 (CAS 12217-22-0, CI Acidblue 183), pigment Blue 15 (CI 74160), Supranol Blue ^® GLW (CAS 12219-32-8, CI Acidblue 221 )), Nylosan Yellow ^® N-7GL SGR (CAS 61814-57-1, CI Acidyellow 218) and / or Sandolan ^® Blue (CI Acid Blue 182, CAS 12219-26-0) is used.

When choosing the colorant, it must be taken into account that the colorants do not have too high an affinity for textile surfaces and, in particular, for synthetic fibers. At the same time, it should also be taken into account when choosing suitable colorants that colorants have different stabilities to the oxidation. In general, water-insoluble colorants are more stable to oxidation than water-soluble colorants. Depending on the solubility and thus also on the sensitivity to oxidation, the concentration of the colorant in the detergents or cleaners varies. For highly soluble dyes, for example, the above-mentioned Basacid ^® Green or the above-mentioned Sandolan Blue ^®, are typically selected dye concentrations in the range of a few 10 ^-2 to 10 ^-3 wt .-%. In the due to their brilliance, particularly preferred, but are less readily water-soluble pigment dyes, for example the above-mentioned Pigmosol ^® ATTO-dyes, the appropriate concentration of the colorant is in washing or cleaning agents, however, typically a few 10 ^-3 to 10 ^-4 wt .-% ,

In a further preferred embodiment the surfactant phase a) is a viscoelastic phase with a memory module at 20 ° C between 40,000 and 800,000 Pa. Preferred washing or Detergents are characterized in that the surfactant phase a memory module at 20 ° C between 40,000 and 800,000 Pa.

viscoelastic Substances are in the range between solids and liquids classify. While for one ideal elastic solid at any deformations the voltage is directly proportional to Stretching and independent from the deformation speed is (Hooke's law), applies to an ideal-viscous liquid the Newtonian Law, i. the tension is in a linear shear rate proportional to the deformation speed, but independent of Amount of deformation.

viscoelastic Fabrics have both viscous and elastic behavior, the elastic portion being on a viscoelastic Fabric acting deformation is described by the memory module while the viscous portion is called the loss modulus. The memory module G 'and the loss modulus G '' can be with you the reversibly stored per oscillation period or irreversible correlated dissimated deformation work.

The Determination of the elastic or viscous portions of a reaction Viscoelastic substances on defined velocity gradient succeed in vibration viscometers with a Couette measuring system. These Measuring Systems can be structured differently. Depending on the viscosity and amount of the examined Substance can Cylinder / cylinder measuring systems, Plate / plate measuring systems or cone / plate measuring systems be used.

In a coaxial cylinder measuring system, the outer cylinder is subjected to an oscillating movement, whereby the angular velocity of the outer cylinder changes sinusoidally with time. A substance located in the annular gap between the outer cylinder and the inner cylinder receives from the outer cylinder an oscillating variable speed gradient depending on the frequency and amplitude. Then, a resulting shear stress signal can be measured on the inner cylinder, which varies with the same frequency, but has a different amplitude and is more or less phase-shifted with respect to the input signal to the outer cylinder. The differences between the input signal on the outer cylinder and the output signal on the inner cylinder are influenced inter alia by the elastic component.

The mathematical treatment of the data allows the determination of the memory module G '' and the loss module G''. G 'is a measure of in the measuring substance stored energy and thus for the elastic component while G '' a measure of the im viscous flow in heat converted and therefore lost energy.

Storage- and loss modulus measurements can be made in coaxial cylinder systems For example, with a HAAKE Rotovisco RV 20 with the measuring system CV 100 at 20 ° C (Couette system) computer assisted carry out.

at the measuring system from two opposite Plates can be subject a plate to an oscillating motion, wherein the speed of the plate changes sinusoidally with time. A In the gap between the plates located substance gets from the Excitation plate oscillating depending on the frequency and amplitude velocity gradient impressed. Then you can on the measuring plate a resulting shear stress signal can be measured with the same frequency but has a different amplitude and with respect to the input signal to the excitation plate more or is less out of phase. The differences between the Input signal to the exciter plate and the output signal to the measuring plate are influenced by, among other things, the elastic component.

in the Within the scope of the present invention, measurements of sizes G 'and G "were made with the UDS 2000 rheometer from Paar Physika after the measuring system Plate plate 25 mm, 2 mm gap, performed at 20 ° C.

Preferably the loss modulus of the viscoelastic phase is narrower Limits. Here are washing or cleaning agents in which the storage module of the Tenside phase a) at 20 ° C. 50,000 to 750,000 Pa, preferably 60,000 to 700,000 Pa, especially preferably 70,000 to 650,000 Pa and in particular 80,000 to 600,000 Pa is.

In particularly preferred products according to the invention is the loss modulus smaller than the memory module, i. G '> G' '. Here are such laundry detergents according to the invention. or cleaning agents in which the storage module of the Tenside phase a) at 20 ° C. at least twice as big preferably at least four times as large as the loss modulus.

As already mentioned above, can be measured on viscoelastic substances on the measuring surface (second Plate or inner cylinder) a resulting shear stress signal be measured, which varies with the same frequency, but another Amplitude and with respect to the input signal on the outer cylinder more or less out of phase. In preferred embodiments the present invention provides detergents or cleaners, in which the phase shift of the surfactant phase a) 0 to 30 °, preferably 0 to 20 ° and in particular ≤ 17 °.

Detergents or cleaning agents which are preferred according to the invention comprise a surfactant phase having a density of less than 1.8 g / cm ³ , preferably less than 1.6 g / cm ³ and in particular less than 1.4 g / cm ³ .

Next the surfactant phase a) the agents according to the invention furthermore comprise the particulate solid b). In the context of this application, such detergents or cleaning agents particularly preferred in which the particulate solid is selected from the group of powders and / or extrudates and / or granules and / or Agglomerates.

powder is a general term for a form of fragmentation solid substances and / or mixtures of substances obtained by crushing, this means Grinding or crushing in the mortar (pulverizing), grinding in mills or as a result of sputtering or lyophilized. A particularly fine division is often called atomization or micronization; The corresponding powders are called micro-powder designated.

After the grain size is a rough division of the powder in coarse, fine u. Very fine powder usual; A more detailed classification of powdery bulk solids is made by their bulk density and sieve analysis. In the context of the present application, however, preferred powders have upper particle sizes below 5000 .mu.m, preferably less than 3000 .mu.m, preferably less than 1000 .mu.m, most preferably between 50 and 1000 microns and in particular between 100 and 800 microns.

powder can be extruded, pressed, rolled, briquetted, pelletized and compact and agglomerate related processes. Each of the im Prior art for the agglomeration of particulate mixtures known method is in principle suitable, those in the inventive compositions produce solids. In the context of the present Invention are preferably used as a solid (e) agglomerates in addition to the granules, the compacts and extrudates.

When Granules become accumulations of granules designated. A granule (granule) is an asymmetric aggregate from powder particles. Granulation processes are in the state of the art broadly described. Granules can by wet granulation, by dry granulation or compaction and produced by melt solidification granulation.

The common Granulation technology is the wet granulation, since this technique the least restrictions is subject to and safest to granules with favorable Properties leads. The wet granulation is carried out by moistening the powder mixtures with solvents and / or solvent mixtures and / or solutions of binders and / or solutions of adhesives and is preferably used in mixers, fluidized beds or spray towers, wherein said mixer, for example, equipped with stirring and kneading tools could be. For the Granulation, however, are also combinations of fluidized bed (s) and Mixer (s), or combinations of different mixers used. The granulation is dependent from the starting material as well as the desired product properties under the influence of low to high shear forces.

He follows the granulation in a spray tower so can as starting materials, for example, melting (melt solidification) or, preferably aqueous, slurries (Spray drying) solid substances which are at the top of a Turmes be sprayed in a defined droplet size, in free fall solidify or dry and at the bottom of the tower as Granules accumulate. The melt solidification is generally suitable especially for the shaping of low-melting substances in the range the melting temperature are stable (e.g., urea, ammonium nitrate and various formulations such as enzyme concentrates, drugs, etc.), The corresponding granules are also called prills. The spray drying will be especially for the production of detergents or detergent ingredients used.

Further The agglomeration techniques described in the prior art are the Extruder or perforated roll granulation, which optionally with granulating staggered powder mixtures when pressed through perforated disks (extrusion) or plastically deformed on perforated rolls. The products of Extruder granulation are also referred to as extrudates.

• i) 10 bis 65 Gew.-% Dispersionsmittel und
• ii) 30 bis 90 Gew.-% dispergierte Stoffe

umfasst.As a particulate solid b) further solidified melts can be used. Particular preference is given to solidified melts in the form of a dispersion of solid particles in a dispersion medium, which, based on their total weight,

• i) from 10 to 65% by weight of dispersant and
• ii) 30 to 90% by weight of dispersed substances

includes.

When Dispersion in this application is a multi-phase system one of which is continuous (dispersing agent) and at least one more is finely dispersed (dispersed substances). Particularly preferred washing or cleaning agents according to the invention are characterized in that they the dispersant in amounts above 11 wt .-%, preferably above 13 wt .-%, particularly preferably above 15 wt .-%, completely particularly preferably above 17% by weight and in particular above 19% by weight, in each case based on the total weight of the dispersion, contain. Realizable and also preferred are furthermore agents according to the invention, which is a dispersion with a proportion by weight of dispersant above 20 wt .-%, preferably above 21 wt .-% and in particular above 22 wt .-%, each based on the total weight of the dispersion, exhibit. The maximum content of preferred dispersions of the invention of dispersant, preferably less based on the total weight of the dispersion as 63% by weight, preferably less than 57% by weight, more preferably less than 52% by weight, most preferably less than 47% by weight and in particular less than 37 wt .-%. In the context of the present Invention are especially those detergents or cleaning agents preferred, which, based on their total weight, dispersing agent in amounts of from 12 to 62% by weight, preferably from 17 to 49% by weight and in particular from 23 to 38 wt .-%.

The The dispersants used are preferably water-soluble or water-dispersible. The solubility this dispersant is at 25 ° C preferably more than 200 g / l, preferably more than 300 g / l, especially preferably more than 400 g / l, most preferably between 430 and 620 g / l and in particular between 470 and 580 g / l.

When Dispersants are suitable in the context of the present invention preferably the water-soluble or water-dispersible polymers, in particular the water-soluble or water-dispersible nonionic polymers. With the dispersant This can be both a single polymer and mixtures different water-soluble or water-dispersible polymers. In a further preferred embodiment In the present invention, the dispersing agent is at least 50 wt .-% of the polymer mixture of water-soluble or water-dispersible nonionic polymers from the group of polyvinylpyrrolidones, Vinylpyrrolidone / vinyl ester copolymers, cellulose ethers, polyvinyl alcohols, Polyalkylene glycols, in particular polyethylene glycol and / or polypropylene glycol.

Further preferred dispersants are the nonionic surfactants which both alone, but more preferably in combination with a nonionic polymer can be used.

The average particle diameter according to the invention preferably used particulate solids b) are between 5 and 3000 μm, preferably between 10 and 2500 μm, preferably between 100 and 2000 μm and in particular between 200 and 2000 microns.

The weight ratio from surfactant phase a) to particulate Solid b) is preferred in accordance with the invention Washing or cleaning agents between 2: 1 and 1:10, preferably between 1: 1 and 1: 8 and in particular between 1: 2 and 1: 6.

According to the invention preference is given to those detergents or cleaners which are themselves at the water-soluble or water-dispersible container around a thermoforming container or an injection-molded container or a casting container or a blow mold container is. water-soluble or water-dispersible injection molded or thermoformed or Foil bags are called water-soluble or water-dispersible containers prefers.

As "thermoforming body" are in the frame the present application, such containers designated by Deep drawing of a first sheet-like wrapping material can be obtained. The deep drawing is preferably carried out by moving the shell material over a in a thermoforming forming die cavity and molding the wrapping material in this receiving trough by the action of pressure and / or vacuum is deformed. The wrapping material can do this before or during forming by the action of heat and / or solvent and / or conditioning modified by environmental conditions relative humidities and / or temperatures are pretreated. The pressure can be applied through two parts of a tool, which behave as positive and negative to each other and one deforming film when deformed between these tools. When compressive forces However, the action of compressed air and / or is also suitable Dead weight of the film and / or the weight of one on the top the film spent active substance.

The deep-drawn shell materials after deep drawing, preferably by use of a vacuum within the receiving troughs and in their by the deep drawing process Fixed spatial form fixed. The vacuum is preferably continuous from deep drawing to filling preferably until sealed and in particular until dicing created the receiving chambers. With comparable success is however also the use of a discontinuous vacuum, for example for drawing the receiving chambers and (after a break) before and during of filling the admission chambers, possible. Also can the continuous or discontinuous vacuum in its Strength vary and for example at the beginning of the process (deep drawing the film) higher Accept values as their end (when filling or sealing or separating).

As already mentioned, the shell material can be pre-treated by the action of heat before or during the molding into the receiving troughs of the matrices. The shell material, preferably a water-soluble or water-dispersible polymer film, is heated to temperatures above 60 ° C. for up to 5 seconds, preferably for 0.1 to 4 seconds, particularly preferably for 0.2 to 3 seconds and in particular for 0.4 to 2 seconds. preferably above 80 ° C, more preferably between 100 and 120 ° C and in particular heated to temperatures between 105 and 115 ° C. To dissipate this heat, but in particular for the discharge of the filled through the deep-drawn receiving chambers means brought heat (eg melting), it is preferable to cool the matrices used and the receiving troughs located in these matrices. The cooling is preferably carried out at temperatures below 20 ° C, preferably below 15 ° C, more preferably at temperatures between 2 and 14 ° C and in particular at temperatures between 4 and 12 ° C. Preferably, the cooling takes place continuously from the beginning of the deep-drawing process to the sealing and separation of the receiving chambers. Cooling fluids, preferably water, which are circulated in special cooling lines within the matrix, are particularly suitable for cooling.

These cooling has as well as the previously described continuous or discontinuous Applying a vacuum the advantage of shrinking the deep-drawn containers to prevent after deep drawing, which not only the appearance of the Process product is improved, but at the same time the leakage the filled in the receiving chambers Means over the edge of the receiving chamber, for example in the sealing areas the chamber is avoided. Problems with the sealing of the filled chambers are avoided.

at the thermoforming process can be between methods in which the wrapping material is placed horizontally in a forming station and from there in a horizontal manner for filling and / or sealing and / or Separation is led and methods in which the shell material over a Continuously rotating die forming roller (optionally optional with a counter-current out Patrizenformwalze, which the forming upper punches to the cavities of Lead die roll) guided will differ. The first mentioned variant of the method Flatbed process is both continuous and discontinuous to operate, the process variant using a molding roll usually takes place continuously. All the mentioned thermoforming processes are suitable for the preparation of the inventively preferred means. The receiving troughs located in the matrices can be arranged "in series" or offset be.

The Thermoformings can have one, two, three or more receiving chambers. These recording rooms can be arranged in the deep-drawn part next to each other and / or one above the other. In a preferred embodiment the present application, the inventive machine Dishwashing liquid in a water-soluble or water-dispersible thermoforming body, which in addition to the solid according to the invention automatic dishwashing detergent in a separate receiving chamber, a liquid or gel-like Detergent or detergent mixture contains.

The water-soluble or water-dispersible container can except be made by deep drawing by injection molding. Injection molding is called while forming a molding material such that in a mass cylinder for more as an injection molding process contained mass under heat plastically softens and pressurizes through a nozzle into the cavity of a previously enclosed tool flows. The process is mainly at non-curable Applied molding compounds that solidify in the tool by cooling. The injection molding is a very economical modern process for producing non-cutting shaped objects and is especially suitable for the automated mass production. In practical operation, one heats the thermoplastic molding compounds (powders, grains, cubes, pastes and others) until liquefaction (up to 180 ° C) and then injected under high pressure (up to 140 MPa) into closed, two-part, that is from Gesenk (formerly Matrix) and core (formerly Patrize) existing, preferably water-cooled molds, where they cool and solidify. Can be used piston and screw injection molding machines. As molding compounds (injection molding compounds) are water-soluble Polymers such as the above-mentioned cellulose ethers, pectins, Polyethylene glycols, polyvinyl alcohols, polyvinylpyrrolidones, alginates, Gelatin or starch.

The shell materials can However, also be poured into molds. The hollow shape of the resulting preferred according to the invention water-soluble or water-dispersible portioned agent comprises at least a solidified melt. This melt can be melted Be pure substance or a mixture of several substances. It is of course possible that individual substances of a multi-substance melt before melting to mix or produce separate melts, which are then combined become. Melt mixtures of substance mixtures can e.g. be beneficial when eutectic mixtures are formed, which melt much lower and thus lower the process costs.

The prefabricated dosing units described above are preferably dosing units for simple application. In order to be able to be used also via the dosing boxes of the dishwashers, such dosing units preferably have a volume below 25 ml, preferably between 10 and 25 ml, more preferably between 12 and 23 and in particular between 15 and 21 ml. The weight of these prefabricated metering units is preferably between 10 and 30 g, special ders preferably between 13 and 27 g and in particular between 16 and 24 g.

• a) eine Tensidphase, die bezogen auf ihr Gewicht 40 bis 85 Gew.-% einer neutralisierten Aniontensidsäure enthält; und
• b) einen teilchenförmigen Feststoff,

dadurch gekennzeichnet, dass Tensidphase a) und Feststoff b) gemeinsam in einer Aufnahmekammer des tiefgezogenen wasserlöslichen oder wasserdispergierbaren Behälters vorliegen.Particularly preferred according to the invention are detergents or cleaners in a deep-drawn water-soluble or water-dispersible container

• a) a surfactant phase containing, by weight, 40 to 85% by weight of a neutralized anionic surfactant acid; and
• b) a particulate solid,

characterized in that surfactant phase a) and solid b) are present together in a receiving chamber of the deep-drawn water-soluble or water-dispersible container.

• a) Tiefziehen eines wasserlöslichen oder wasserdispergierbaren Materials unter Ausbildung einer Aufnahmekammer;
• b) Befüllen der Aufnahmekammer mit – einer Tensidphase, die bezogen auf ihr Gewicht 40 bis 85 Gew.-% einer neutralisierten Aniontensidsäure enthält; und – einem teilchenförmigen Feststoff;
• c) Versiegeln der Aufnahmekammer.

The preparation of these particularly preferred agents comprises the steps:

• a) deep drawing a water-soluble or water-dispersible material to form a receiving chamber;
• b) filling the receiving chamber with - a surfactant phase containing by weight 40 to 85 wt .-% of a neutralized anionic surfactant acid; and a particulate solid;
• c) sealing the receiving chamber.

For the production inventive agent it has proved to be advantageous in step a) of the process initially prepared receiving chamber with the surfactant phase a) and then with the particulate solid to fill. In the resulting process products then bordered in step c) produced seal seam to the last filled into the receiving chamber particulate solid phase. As surfactant phase a) and particulate phase b) under the usual Conditions of manufacture, storage and transport not In this way, mixing becomes a contact between the surfactant phase a) and prevents the seal produced in step c). such Means are characterized by an increased storage stability and a significantly reduced tendency to leaks in the sealed seams.

to Preparation of the water-soluble or water-dispersible container A variety of different materials are suitable, taking substances from the group (acetalated) polyvinyl alcohol, polyvinylpyrrolidone, Polyethylene oxide, gelatin are particularly preferred.

In In a preferred variant of the method, the container comprises one or more water-soluble (s) Polymer (s), preferably a material from the group (optionally acetalated) polyvinyl alcohol (PVAL), polyvinylpyrrolidone, polyethylene oxide, Gelatin, cellulose, and their derivatives and mixtures thereof.

die in geringen Anteilen (ca. 2%) auch Struktureinheiten des Typs

enthalten."Polyvinyl alcohols" (abbreviated PVAL, occasionally PVOH) is the name for polymers of the general structure

in small proportions (about 2%) also structural units of the type

contain.

Commercially available polyvinyl alcohols, the as white-yellowish Powders or granules with degrees of polymerization in the range of approx. 100 to 2500 (molecular weights of about 4000 to 100,000 g / mol) offered have hydrolysis degrees of 98-99 and 87-89 mol%, respectively So still a residual content of acetyl groups. To be characterized the polyvinyl alcohols from the manufacturers by specifying the Degree of polymerization of the starting polymer, the degree of hydrolysis, the saponification number or the solution viscosity.

Depending on the degree of hydrolysis, polyvinyl alcohols are soluble in water and a few highly polar organic solvents (formamide, dimethylformamide, dimethyl sulfoxide); They are not attacked by (chlorinated) hydrocarbons, esters, fats and oils. Polyvinyl alcohols are classified as toxicologically safe and are biologically at least partially degradable. The water solubility can be through After treatment with aldehydes (acetalization), by complexing with Ni or Cu salts or by treatment with dichromates, boric acid or Borax reduce. The coatings of polyvinyl alcohol are largely impermeable to gases such as oxygen, nitrogen, helium, hydrogen, carbon dioxide, but allow water vapor to pass through.

in the For the purposes of the present invention, it is preferred that the used shell material at least partially comprises a polyvinyl alcohol whose Degree of hydrolysis 70 to 100 mol%, preferably 80 to 90 mol%, especially preferably 81 to 89 mol% and in particular 82 to 88 mol%. In a preferred embodiment this is the case in the process according to the invention used first wrapping material at least 20% by weight, particularly preferably at least 40% by weight, most preferably at least 60 wt .-% and in particular at least 80% by weight of a polyvinyl alcohol, the Degree of hydrolysis 70 to 100 mol%, preferably 80 to 90 mol%, more preferably 81 to 89 mol% and especially 82 to 88 mol%.

Polyvinyl alcohols of a certain molecular weight range are preferably used as materials for the containers, it being preferred according to the invention that the coating material comprises a polyvinyl alcohol whose molecular weight is in the range of 10,000 to 100,000 gmol ^-1 , preferably 11,000 to 90,000 gmol ^-1 , particularly preferably 12,000 to 80,000 gmol ^-1 and in particular from 13,000 to 70,000 gmol ^-1 .

Of the Degree of polymerization of such preferred polyvinyl alcohols is between about 200 to about 2100, preferably between about 220 to about 1890, more preferably between about 240 to about 1680 and especially between about 260 to about 1500th

The polyvinyl alcohols described above are widely available commercially, for example under the trade name Mowiol ^® (Clariant). In the present invention, particularly suitable polyvinyl alcohols are, for example, Mowiol ^® 3-83, Mowiol ^® 4-88, Mowiol ^® 5-88 and Mowiol ^® 8-88.

Further polyvinyl alcohols which are particularly suitable as shell material are shown in the following table:

Other suitable polyvinyl alcohols are as shell material ^® ELVANOL 51-05, 52-22, 50-42, 85-82, 75-15, T-25, T-66, 90-50 (trademark of Du Pont), ALCOTEX 72.5 ^®, 78, B72, F80 / 40, F88 / 4, F88 / 26, F88 / 40, F88 / 47 (trademark of Harlow Chemical Co.), Gohsenol ^® NK-05, A-300, AH-22, C-500, GH-20, GL-03, GM-14L, KA-20, KA-500, KH-20, KP-06, N-300, NH-26, NM11Q, KZ-06 (Trademark of Nippon Gohsei KK).

The Water of PVAL can be obtained by post-treatment with aldehydes (acetalization) or ketones (ketalization) changed become. Being particularly preferred and pronounced because of it good cold water solubility Polyvinyl alcohols have proven particularly advantageous in this case, those with the aldehyde or keto groups of saccharides or polysaccharides or mixtures thereof are acetalated or ketalized. As extremely beneficial to use are the reaction products of PVAL and starch.

Farther let yourself the water solubility by complexation with Ni or Cu salts or by treatment with dichromates, boric acid, Change borax and so targeted to desired Set values. PVAL films are largely impermeable for gases like oxygen, nitrogen, helium, hydrogen, carbon dioxide but pass water vapor.

Examples of suitable water PVAL films are those available under the name "SOLUBLON® ^®" from Syntana Handelsgesellschaft E. Harke GmbH & Co. PVAL films. Their solubility in water can be adjusted to the exact degree, and films of this product series are available which are soluble in aqueous phase in all temperature ranges relevant for the application.

Polyvinylpyrrolidones, referred to as PVP for short, can be described by the following general formula:

PVP are prepared by radical polymerization of 1-vinylpyrrolidone. commercial PVP have molecular weights in the range of about 2,500 to 750,000 g / mol and be as white, hygroscopic powders or offered as aqueous solutions.

Polyethylene oxides, PEOX for short, are polyalkylene glycols of the general formula H- [O-CH ₂ -CH ₂ ] _n -OH the technically by alkaline-catalyzed polyaddition of ethylene oxide (oxirane) in mostly small amounts of water-containing systems are prepared with ethylene glycol as the starting molecule. They have molar masses in the range of about 200 to 5,000,000 g / mol, corresponding to degrees of polymerization n of about 5 to> 100,000. Polyethylene oxides have an extremely low concentration of reactive hydroxy end groups and show only weak glycol properties.

gelatin is a polypeptide (molecular weight: about 15,000 to> 250,000 g / mol), mainly by Hydrolysis of the collagen contained in the skin and bones of animals is obtained under acidic or alkaline conditions. The amino acid composition The gelatin largely corresponds to that of the collagen from which they are made and varies depending on its provenance. The use of gelatin as the water-soluble coating material is in particular in pharmacy in the form of hard or soft gelatin capsules extremely far common. In the form of slides, gelatin is because of their compared to the above-mentioned polymers of high price only small Use.

Prefers are within the scope of the method according to the invention shell materials, which is a polymer from the group starch and starch derivatives, cellulose and Cellulose derivatives, in particular methylcellulose and mixtures thereof include.

Strength is a homoglycan, wherein the glucose units are linked α-glycosidically. Strength is composed of two components of different molecular weight: from about 20 to 30% straight-chain amylose (MW about 50,000 to 150,000) and 70 to 80% branched-chain amylopectin (M.W., about 300,000 to 2,000,000). In addition, there are still small amounts of lipids, phosphoric acid and Contain cations. While the amylose due to binding in the 1,4-position long, helical, entangled Branches with about 300 to 1,200 glucose molecules forms, branches the chain in amylopectin after an average of 25 glucose building blocks by 1,6-bonding to a branch-like Forms with about 1,500 to 12,000 molecules of glucose. Besides pure strength are for producing water-soluble wrappings the detergent, dishwashing detergent and detergent portions within the scope of the present invention also starch derivatives suitable, which are obtainable by polymer-analogous reactions of starch. Such chemically modified starches include, for example, products of esterification or etherification, in which substituted hydroxy hydrogen atoms were. But also strengths, in which the hydroxy groups against functional groups that do not have a Oxygen atom bound, replaced, can be used as starch derivatives deploy. Into the group of starch derivatives fall, for example, alkali, carboxymethyl (CMS), starch ester and ethers, and amino acids.

Pure cellulose has the formal gross composition (C ₆ H ₁₀ O ₅ ) _n and formally represents a (β-1,4-polyacetal of cellobiose, which in turn consists of two molecules of glucose, with suitable celluloses consisting of about 500 to 5,000 glucose units and therefore have average Molar masses from 50,000 to 500,000. Cellulose-based disintegrating agents which can be used in the context of the present invention are also cellulose derivatives obtainable by polymer-analogous reactions of cellulose. Such chemically modified celluloses include, for example, products of esterifications or etherifications in which hydroxy hydrogen atoms have been substituted. Celluloses in which the hydroxy groups have been replaced by functional groups which are not bonded via an oxygen atom can also be used as cellulose derivatives. The group of cellulose derivatives includes, for example, alkali metal celluloses, carboxymethylcellulose (CMC), cellulose esters and ethers, and aminocelluloses.

The water-soluble or water-dispersible container material is preferably transparent. Under transparency is in the sense of this Invention to understand that the permeability within the visible spectrum of light (410 to 800 nm) greater than 20%, preferably greater than 30%, very preferred greater than 40% and in particular greater than 50% is. Thus, once a wavelength of the visible spectrum of the Light a permeability greater than 20%, it is to be regarded as transparent within the meaning of the invention.

Portioned according to the invention Detergent compositions in transparent containers are packed contain as essential ingredient a stabilizer. Stabilizing agents in the context of the invention are materials which the detergent ingredients in their water-soluble, transparent containers Protect against decomposition or deactivation by exposure to light. As special Antioxidants, UV absorbers and fluorescent dyes are suitable here proved.

Particularly suitable stabilizing agents in the context of the invention are the antioxidants. In order to prevent undesirable changes in the formulations caused by light irradiation and thus radical decomposition, the formulations may contain antioxidants. Examples of antioxidants which may be used here are sterically hindered groups, substituted phenols, bisphenols and thiobisphenols. Further examples are propyl gallate, butylhydroxytoluene (BHT), butylhydroxyanisole (BHA), t-butylhydroquinone (TBHQ), tocopherol and the long chain (C8-C22) esters of gallic acid, such as dodecyl gallate. Other substance classes are aromatic amines, preferably secondary aromatic amines and substituted p-phenylenediamines, phosphorus compounds with trivalent phosphorus such as phosphines, phosphites and phosphonites, citric acids and citric acid derivatives such as isopropyl citrate, compounds containing endiol groups, so-called reductones, such as ascorbic acid and its derivatives, such as ascorbic palmitate, organosulfur compounds such as the esters of 3,3'-thiodipropionic acid with C _1-18 alkanols, especially C _10-18 alkanols, metal ion deactivators capable of auto-oxidation catalyzing metal ions such as copper, to complex such as nitrilotriacetic acid and its derivatives and their mixtures. Antioxidants may be present in the formulations in amounts of up to 35% by weight, preferably up to 25% by weight, particularly preferably from 0.01 to 20 and in particular from 0.03 to 20% by weight.

Another class of preferably usable stabilizers are the UV absorbers. UV absorbers can improve the light stability of the formulation ingredients. These are understood to be organic substances (light protection filters) which are able to absorb ultraviolet rays and to release the absorbed energy in the form of longer-wave radiation, for example heat. Compounds having these desired properties include, for example, the non-radiative deactivating compounds and derivatives of benzophenone having substituents in the 2- and / or 4-position. In addition, substituted benzotriazoles, such as the water-soluble benzenesulfonic acid-3- (2H-benzotriazol-2-yl) -4-hydroxy-5- (methylpro pyl-) monosodium salt (Ciba ^® Fast H), 3-phenyl-substituted acrylates ( Cinnamon acid derivatives), optionally with cyano groups in the 2-position, salicylates, organic Ni complexes and natural substances such as umbelliferone and the body's own urocanic acid. The biphenyl and especially stilbene derivatives, which are available as Tinosorb ^® FD or Tinosorb ^® FR ex Ciba commercial. 3-benzylidene camphor or 3-benzylidene norcamphor and derivatives thereof, for example 3- (4-methylbenzylidene) camphor, may be mentioned as UV-B absorbers; 4-aminobenzoic acid derivatives, preferably 2-ethylhexyl 4- (dimethylamino) benzoate, 2-octyl 4- (dimethylamino) benzoate and 4- (dimethylamino) benzoic acid ester; Esters of cinnamic acid, preferably 4-methoxycinnamic acid 2-ethylhexyl ester, propyl 4-methoxycinnamate, isoamyl 4-methoxycinnamate, 2-ethylhexyl 2-cyano-3,3-phenylcinnamate (octocrylene); Esters of salicylic acid, preferably 2-ethylhexyl salicylate, 4-isopropylbenzyl salicylate, homomenthyl salicylate; Derivatives of benzophenone, preferably 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-methoxy-4'-methylbenzophenone, 2,2'-dihydroxy-4-methoxybenzophenone; Esters of benzalmalonic acid, preferably di-2-ethylhexyl 4-methoxybenzmalonate; Triazine derivatives, such as 2,4,6-trianilino- (p-carbo-2'-ethyl-1'-hexyloxy) -1,3,5-triazine and Octyl Triazone or Dioctyl Butamido Triazone (Uvasorb HEB ^®); Propane-1,3-diones such as 1- (4-tert-butylphenyl) -3- (4'-methoxy-phenyl) pro pan-1,3-dione; Ketotricyclo (5.2.1.0) decane derivatives. Also suitable are 2-phenylbenzimidazole-5-sulfonic acid and its alkali metal, alkaline earth metal, ammonium, alkylammonium, alkanolammonium and glucammonium salts; Sulfonic acid derivatives of benzophenones, preferably 2-hydroxy-4-methoxybenzophenone-5-sulfonic acid and its salts; Sulfonic acid derivatives of 3-Benzylidencamphers, such as 4- (2-oxo-3-bomylidenemethyl) benzenesulfonic acid and 2-methyl-5- (2-oxo-3-bomylidene) sulfonic acid and salts thereof.

As a typical UV-A filter in particular derivatives of benzoylmethane are suitable, such as 1- (4'-tert-butylphenyl) -3- (4'-methoxyphenyl) propane-1,3-dione, 4-tert-butyl 4'-methoxydibenzoylmethane (Parsol 1789), 1-phenyl-3- (4'-isopropylphenyl) -propane-1,3-dione and enamine compounds. Of course, the UV-A and UV-B filters can also be used in mixtures. In addition to the soluble substances mentioned, insoluble photoprotective pigments, namely finely dispersed, preferably nano-metal oxides or salts, are also suitable for this purpose. Examples of suitable metal oxides are in particular zinc oxide and titanium dioxide and, in addition, oxides of iron, zirconium, silicon, manganese, aluminum and cerium and mixtures thereof. As salts silicates (talc), barium sulfate or zinc stearate can be used. The oxides and salts are already used in the form of the pigments for skin-care and skin-protecting emulsions and decorative cosmetics. The particles should have an average diameter of less than 100 nm, preferably between 5 and 50 nm and in particular between 15 and 30 nm. They may have a spherical shape, but it is also possible to use those particles which have an ellipsoidal or otherwise deviating shape from the spherical shape. The pigments can also be surface-treated, ie hydrophilized or hydrophobized. Typical examples are coated titanium dioxides, for example Titandioxid T 805 (Degussa) or Eusolex ^® T2000 (Merck). Suitable hydrophobic coating agents are in particular silicones and in particular trialkoxyoctylsilanes or simethicones. Preferably, micronized zinc oxide is used.

UV absorbers can in the washing or cleaning agents in amounts of up to 5 wt .-%, preferably to 3 wt .-%, particularly preferably from 0.01 to 2.0 and in particular be contained from 0.03 to 1 wt .-%.

A Another preferred class of stabilizers to be used are the fluorescent dyes. These include the 4,4'-diamino-2,2'-stilbenesulfonic acids (flavonic acids), 4,4'-distyrylbiphenyls, methyl umbelliferones, Coumarins, dihydroquinolinones, 1,3-diarylpyrazolines, naphthalimides, Benzoxazole, benzisoxazole and benzimidazole systems and the by Heterocycles substituted pyrene derivatives. Really important are the sulfonic acid salts the diaminostilbene derivatives, as well as polymeric fluorescers.

fluorescent substances can in the formulations in amounts of up to 5% by weight, preferably up to 1% by weight, particularly preferably from 0.01 to 0.5 and in particular from 0.03 to Be contained 0.1 wt .-%.

In a preferred embodiment the aforementioned stabilizers are in any mixtures used. The stabilizers are used in amounts of up to 40% by weight, preferably up to 30% by weight, more preferably from 0.01 to 20 Wt .-%, in particular from 0.02 to 5 wt .-% used.

alternative to the above-described transparent container materials may also milky opaque, opaque container materials used become. Such container materials are, for example, water-soluble or water-dispersible composite materials, for example by combining two or more of the above-mentioned water-soluble ones or water-dispersible container materials can be produced. Particularly preferred are water-soluble or water-dispersible container materials used, in addition to PVAL also at least 10 wt .-%, preferably at least 15 wt .-% and in particular at least 20 wt .-% starch.

The used water-soluble or water-dispersible container materials can Dyes contain. Suitable dyes are inorganic like organic substances. As a dye are particularly suitable the pigments. The pigments are inorganic or organic, colored or achromatic colorant. These pigments are preferably sparingly soluble in water or insoluble. The for the pigments preferred insolubility let yourself by the exclusion of solubilizing Groups, insoluble by the formation Salts ("laking") of carbon and in particular sulfonic acids and by the introduction of the solubility reach degrading groups (e.g., carboxylic acid amide groups).

inorganic Pigments are naturally occurring pigments produced by mechanical Treatment like grinding, sludge, Dried substances such as chalk, ocher, Umbra, green earth, Terra di Siena fired or graphite.

synthetic inorganic pigments, in particular white, black, colored and luster pigments, the one from inorganic raw materials by chemical and / or physical transformation such as digestion, precipitation, annealing, etc. are obtained for example, white pigments like titanium white (titanium dioxide), White lead, Zinc white, Lithopone, antimony white; Black pigments like carbon black (over 90% Market share), iron oxide black, manganese black and cobalt black and antimony black. Suitable pigments are lead chromate, red lead, zinc yellow, Zinc green, Cadmium Red, Cobalt Blue, Berlin Blue, Ultramarine, Manganese Violet, Cadmium yellow, Schweinfurter green, Molybdate orange and molybdate red, chrome orange and red, iron oxide red, Chrome oxide green, strontium yellow and many others. Also suitable are luster pigments with metallic effect pigments and pearlescent pigments, vapor-deposited layers, luminescent pigments with fluorescence and phosphorescent pigments.

When Groups can thus be differentiated in the case of inorganic pigments: Metal oxides, hydroxides and oxide hydrates; Mixed phase pigments; Sulfur-containing silicates; Metal sulfides and the like selenides; complex metal cyanides; Metal sulfates, -chromate and -molybdate; Mixed pigments (inorganic-organic) as well as the metals themselves (bronze pigments). Inorganic pigments from the Group of metal salts of iron, copper, titanium, cobalt, zinc, molybdenum and manganese are particularly preferred in the context of the present application.

organic Pigments are naturally occurring pigments such as Umber, Gummigutt, bone charcoal, Kasseler brown, indigo or chlorophyll.

synthetic organic pigments are, for example, azo pigments, indigoids, Dioxazine, quinacridone, phthalocyanine, isoindolinone, perylene and perinone, metal complex, alkali blue and, more recently, the diketopyrrolopyrrole (DPP) -P., which possess extreme light and weather fastness and as clear, pure orange to reds very much used in paints.

Composition according to the invention contain, in addition to the active substances described above, preferably one or several other ingredients of detergents and cleaners, preferably from the group of builders, Surfactants, polymers, bleaches, bleach activators, enzymes, dyes, Perfumes, electrolytes, pH adjusters, perfume carriers, fluorescers, hydrotopes, Foam inhibitors, silicone oils, Anti redeposition agents, optical brighteners, grayness inhibitors, Inlet preventer, anti-crease agents, color transfer inhibitors, antimicrobial Active substances, germicides, fungicides, antioxidants, corrosion inhibitors, antistatic agents, Ironing aids, Phobic and impregnating agents, Swelling and slip-resistant, plasticizers and / or UV absorbers included. These substances will be described in more detail below.

builders

To the builders counting in the context of the present application, in particular the zeolites, Silicates, carbonates, organic cobuilders and -where no ecological Prejudices against their use exist - also the phosphates.

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

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

in the Within the scope of the present invention it is preferred that these Silicate (s), preferably alkali metal silicates, particularly preferably crystalline or amorphous alkali disilicates, in detergents or cleaners in amounts of from 10 to 60% by weight, preferably from 15 to 50% by weight and in particular from 20 to 40 wt .-%, each based on the weight of the washing or cleaning agent are included.

If the silicates are used as constituents of automatic dishwasher detergents, these compositions preferably contain at least one crystalline layered silicate of the general formula NaMSi _x O _{2x + 1} .yH ₂ O, where M is sodium or hydrogen, x is a number from 1.9 to 22, preferably from 1.9 to 4, and y is a number from 0 to 33. The crystalline layer-form silicates of the formula NaMSi _x O _{2x + 1} .yH ₂ O are sold, for example, by the company Clariant GmbH (Germany) under the trade name Na-SKS, eg Na-SKS-1 (Na ₂ Si ₂₂ O ₄₅ .xH ₂ O, Kenyaite), Na-SKS-2 (Na ₂ Si ₁₄ O ₂₉ .xH ₂ O, magadiite), Na-SKS-3 (Na ₂ Si ₈ O ₁₇ .xH ₂ O) or Na-SKS-4 ( Na ₂ Si ₄ O ₉ .xH ₂ O, Makatite).

Particularly suitable for the purposes of the present invention are crystalline phyllosilicates of the formula (I) in which x is 2. Of these, especially Na-SKS-5 (α-Na ₂ Si ₂ O ₅ ), Na-SKS-7 (β-Na ₂ Si ₂ O ₅ , natrosilite), Na-SKS-9 (NaHSi ₂ O ₅ · H ₂ O), Na-SKS-10 (NaHSi ₂ O ₅ · 3H ₂ O, kanemite), Na-SKS-11 (t-Na ₂ Si ₂ O ₅₎ and Na-SKS-13 (NaHSi ₂ O ₅ ), but especially Na-SKS-6 (δ-Na ₂ Si ₂ O ₅ ).

If the silicates are used as constituents of compositions according to the invention, these compositions in the context of the present application contain a proportion _by weight of the crystalline layered silicate of the formula NaMSi _x O _{2x + 1} · yH ₂ O of 0.1 to 20% by weight, preferably of 0 , 2 to 15 wt .-% and in particular from 0.4 to 10 wt .-%, each based on the total weight of these agents. It is particularly preferred in particular if such automatic dishwashing agents have a total silicate content of less than 7% by weight, preferably less than 6% by weight, preferably less than 5% by weight, more preferably less than 4% by weight, most preferably less than 3% by weight % and in particular below 2.5 wt .-%, wherein it is in this silicate, based on the total weight of the silicate contained, preferably at least 70 wt .-%, preferably at least 80 wt .-% and in particular to At least 90 wt .-% of silicate of the general formula NaMSi _x O _{2x + 1} · yH ₂ O is.

The finely crystalline, synthetic and bound water-containing zeolite used is preferably zeolite A and / or P. As zeolite P, zeolite ^MAP® (commercial product from Crosfield) is particularly preferred. Also suitable, however, are zeolite X and mixtures of A, X and / or P. Commercially available and preferably usable in the context of the present invention is, for example, a cocrystal of zeolite X and zeolite A (about 80% by weight of zeolite X) ), which is sold by the company 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. The zeolite can be used both as a builder in a granular compound, as well as to a kind of "powdering" of the entire mixture to be pressed, wherein usually both ways for incorporating the zeolite are used in the premix. Suitable zeolites have an average particle size of less than 10 μm (volume distribution, measuring method: Coulter Counter) and preferably contain 18 to 22% by weight, in particular 20 to 22% by weight, of bound water.

Of course it is also a use of the well-known phosphates as builders possible, if such use is not avoided for environmental reasons should be. This applies in particular to the use of agents according to the invention as automatic dishwashing detergent, which is particularly preferred in the context of the present application is. Among the large number of commercially available phosphates, the Alkali metal phosphates with particular preference for pentasodium or pentakalium triphosphate (sodium or potassium tripolyphosphate) in the wash and Detergent industry the biggest importance.

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

Suitable phosphates are, for example, the sodium dihydrogen phosphate, NaH ₂ PO ₄ , in the form of the dihydrate (density 1.91 gcm ^-3 , melting point 60 °) or in the form of the monohydrate (density 2.04 gcm ^-3 ), the disodium hydrogen phosphate (secondary sodium phosphate) , Na ₂ HPO ₄ , which is anhydrous or with 2 moles (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 loss of 5 H ₂ O) can be used, in particular however the Trisatriumphosphat (tertiary sodium phosphate) Na ₃ PO ₄ , which as Dodecahydrat, as Decahydrat (according to 19 -20% P ₂ O ₅ ) and in anhydrous form (corresponding to 39-40% P ₂ O ₅ ) can be used.

Another preferred phosphate is the tripotassium phosphate (tertiary or tribasic potassium phosphate), K ₃ PO ₄ . Also preferred are the tetrasodium diphosphate (sodium pyrophosphate), Na ₄ P ₂ O ₇ , which is in anhydrous form (density 2.534 gcm ^-3 , melting point 988 °, also indicated 880 °) and as decahydrate (density 1.815-1.836 gcm ^-3 , melting point 94 ° with loss of water), and the corresponding potassium salt potassium diphosphate (potassium pyrophosphate), K ₄ P ₂ O ₇ .

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

The technically important pentasodium triphosphate, Na ₅ P ₃ O ₁₀ (sodium tripolyphosphate), is an anhydrous or with 6 H ₂ O crystallizing, non-hygroscopic, white, water-soluble salt of the general formula NaO- [P (O) (ONa) -O] _n -Na with n = 3. The corresponding potassium salt pentapotassium triphosphate, K ₅ P ₃ O ₁₀ (potassium tripolyphosphate), is marketed, 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 washing and cleaning industry. There are also sodium potassium tripolyphosphates which can also be used in the context of the present invention. These arise, for example, when hydrolyzed sodium trimetaphosphate with KOH: (NaPO ₃ ) ₃ + 2 KOH → Na ₃ K ₂ P ₃ O ₁₀ + H ₂ O

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

Become in the context of the present application phosphates as washing or cleaning active Substances used in detergents or cleaners, so included preferred means these phosphate (s), preferably alkali metal phosphate (s), particularly preferably pentasodium or pentapotassium triphosphate (sodium or potassium tripolyphosphate), in amounts of 5 to 80 wt .-%, preferably from 15 to 75% by weight, in particular, from 20 to 70% by weight, respectively based on the weight of the washing or cleaning agent.

Prefers it is in particular potassium tripolyphosphate and sodium tripolyphosphate in a weight ratio of more than 1: 1, preferably more than 2: 1, preferably more than 5: 1, more preferably more than 10: 1 and in particular more than 20: 1 use. Particularly preferred is exclusively potassium tripolyphosphate to use without admixtures of other phosphates.

Further builders are the alkali carriers. Suitable alkali carriers are, for example, alkali metal hydroxides, alkali metal carbonates, alkali metal hydrogencarbonates, alkali metal sesquicarbonates, the cited alkali metal silicates, alkali metal silicates and mixtures of the abovementioned substances, preference being given to using alkali metal carbonates, in particular sodium carbonate, sodium bicarbonate or sodium sesquicarbonate for the purposes of this invention. Particularly preferred is a builder system comprising a mixture of tripolyphosphate and sodium carbonate. Also particularly preferred is a builder system comprising a mixture of tripolyphosphate and sodium carbonate and sodium disilicate. Because of their low chemical compatibility with the other ingredients of detergents or cleaners compared with other builders, the alkali metal hydroxides are preferably only in small amounts, preferably in amounts below 10 wt .-%, preferably below 6 wt .-%, more preferably below 4 wt .-% and in particular un Below 2 wt .-%, each based on the total weight of the detergent or cleaning agent used. Particularly preferred are agents which, based on their total weight, contain less than 0.5% by weight and in particular no alkali metal hydroxides.

Especially preference is given to the use of carbonate (s) and / or bicarbonate (s), preferably alkali metal carbonate (s), more preferably sodium carbonate, in amounts of from 2 to 50% by weight, preferably from 5 to 40% by weight and in particular from 7.5 to 30 wt .-%, each based on the Weight of washing or cleaning agent. Particularly preferred Means, based on the weight of the detergent or cleaning agent (ie the total weight of the combination product without packaging) less than 20% by weight, preferably less than 17% by weight, preferably less than 13% by weight and in particular less than 9% by weight of carbonate (s) and / or bicarbonate (s), preferably alkali metal carbonates, especially preferably contain sodium carbonate.

When Organic co-builders are in particular polycarboxylates / polycarboxylic acids, polymers Polycarboxylates, aspartic acid, Polyacetals, dextrins, other organic cobuilders (see below) as well as phosphonates. These classes of substances are hereafter described.

useful organic builders For example, they can be used in the form of their sodium salts polycarboxylic where among polycarboxylic acids such carboxylic acids be understood that carry more than one acid function. For example these are citric acid, adipic acid, Succinic acid, Glutaric acid, malic acid, tartaric acid, maleic acid, fumaric acid, sugar acids, aminocarboxylic acids, nitrilotriacetic acid (NTA), if such an application for ecological reasons not is objectionable, as well as mixtures of these. Preferred salts are the salts of polycarboxylic acids like citric acid, adipic acid, Succinic acid, glutaric, Tartaric acid, sugar acids and mixtures of these.

Also the acids in itself can be used. The acids In addition to their builder effect, they also typically have the property an acidifying component and thus serve to set a lower and milder one pH value of detergents or cleaning agents. In particular, here are citric acid, Succinic acid, glutaric, adipic acid, gluconic and to name any mixtures of these.

When builders are further polymeric polycarboxylates suitable, these are for example the alkali metal salts of polyacrylic acid or polymethacrylic acid, for example those with a molecular weight from 500 to 70000 g / mol.

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

suitable Polymers are in particular polyacrylates, which preferably have a molecular mass of 2000 to 20,000 g / mol. Because of their superior solubility can from this group again the short-chain polyacrylates, the molecular weights from 2000 to 10000 g / mol, and more preferably from 3000 to 5000 g / mol, may be preferred.

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

The (co) polymeric polycarboxylates can be used either as a powder or as an aqueous solution. The content of detergents or cleaning agents on (co) polymeric polycarboxylates is preferably 0.5 to 20 wt .-%, in particular 3 to 10 wt .-%.

To improve the water solubility, the polymers may also allylsulfonic, as example Allyloxybenzenesulfonic acid and methallylsulfonic acid, as a monomer.

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

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

As well are as further preferred builders polymeric aminodicarboxylic acids whose Salts or their precursors to call. Particular preference is given to polyaspartic acids or their salts and.

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

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

at the oxidized derivatives of such dextrins are their reaction products with oxidants, which are able are at least one alcohol function of the saccharide ring to the carboxylic acid function to oxidize.

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

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

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

Furthermore can all compounds that are capable of complexes with alkaline earth ions train as builders be used.

Compositions according to the invention which contain 10 to 80% by weight, preferably 15 to 75% by weight, especially be Preferably 20 to 70 wt .-% and in particular 25 to 65 wt .-% of one or more water-soluble builders, are particularly preferred in the context of the present application.

surfactants

to Group of surfactants are in addition to the nonionic described above Surfactants continue to be the anionic, cationic and amphoteric surfactants counted. In place of or in combination with the anionic described above or nonionic surfactants it is also possible to use cationic and / or amphoteric surfactants.

worin jede Gruppe R¹ unabhängig voneinander ausgewählt ist aus C_1-6-Alkyl-, -Alkenyl- oder -Hydroxyalkylgruppen; jede Gruppe R² unabhängig voneinander ausgewählt ist aus C_8-28-Alkyl- oder -Alkenylgruppen; R³ = R¹ oder (CH₂)_n-T-R²; R⁴ = R¹ oder R² oder (CH₂)_n-T-R²; T = -CH₂-, -O-CO- oder -CO-O- und n eine ganze Zahl von 0 bis 5 ist.As cationic active substances, it is possible, for example, to use cationic compounds of the formulas IX, X or XI:

wherein each R ^{1 group is} independently selected from C _1-6 alkyl, alkenyl or hydroxyalkyl groups; each R ^{2 group is} independently selected from C _8-28 alkyl or alkenyl groups; R ³ = R ¹ or (CH ₂ ) _n -TR ² ; R ⁴ = R ¹ or R ² or (CH ₂ ) _n -TR ² ; T = -CH ₂ -, -O-CO- or -CO-O- and n is an integer from 0 to 5.

In automatic dishwashing detergent, is the content of cationic and / or amphoteric surfactants preferably less than 6% by weight, preferably less than 4% by weight, very particularly preferably less than 2% by weight and in particular less than 1% by weight. Automatic dishwashing detergents, which contain no cationic or amphoteric surfactants particularly preferred.

polymers

to Group of polymers count in particular the washing or cleaning-active polymers, for example the rinse aid polymers and / or as a softener effective polymers. Generally in detergents or cleansers in addition to nonionic polymers also cationic, anionic and can be used amphoteric polymers.

As a softener effective polymers, for example, the sulfonic acid-containing polymers, wel be used with particular preference.

bleach

Another preferred ingredient of the compositions of the invention are the bleaches. Among the compounds serving as bleaches in water H ₂ O ₂ , sodium percarbonate, sodium perborate tetrahydrate and sodium perborate monohydrate are of particular importance. Other useful bleaching agents are, for example, peroxypyrophosphates, citrate perhydrates and H ₂ O ₂ -forming peracidic salts or peracids, such as perbenzoates, peroxophthalates, diperazelaic acid, phthaloiminoperacid or diperdodecanedioic acid. Cleaning agents according to the invention may also contain bleaching agents from the group of organic bleaching agents. Typical organic bleaches are the diacyl peroxides such as dibenzoyl peroxide. Other typical organic bleaches are the peroxyacids, examples of which include the alkyl peroxyacids and the aryl peroxyacids. Preferred representatives are (a) the peroxybenzoic acid and its ring-substituted derivatives, such as alkylperoxybenzoic acids, but also peroxy-α-naphthoic acid and magnesium monoperphthalate, (b) the aliphatic or substituted aliphatic peroxyacids, such as peroxylauric acid, peroxystearic acid, ε-phthalimidoperoxycaproic acid [phthaloiminoperoxyhexanoic acid (PAP)] , o-carboxybenzamidoperoxycaproic acid, N-nonenylamidoperadipic acid and N-nonenylamidopersuccinate, and (c) aliphatic and araliphatic peroxydicarboxylic acids, such as 1,12-diperoxycarboxylic acid, 1,9-diperoxyazelaic acid, diperoxysebacic acid, diperoxybrassic acid, the diperoxyphthalic acids, 2-decyldiperoxybutan-1,4-diene diacid, N, N-terephthaloyl-di (6-aminopercapronate) can be used.

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

Bleach activators

Bleach activators are used, for example, in detergents or cleaners, to improve cleaning at temperatures of 60 ° C and below To achieve bleaching effect. As bleach activators, compounds, which under perhydrolysis aliphatic peroxycarboxylic acids with preferably 1 to 10 C atoms, in particular 2 to 4 C atoms, and / or optionally substituted perbenzoic acid, are used. Suitable substances are the O- and / or N-acyl groups of the mentioned C atom number and / or optionally substituted benzoyl groups wear. Preference is given to polyacylated alkylenediamines, in particular Tetraacetylethylenediamine (TAED), acylated triazine derivatives, in particular 1,5-diacetyl-2,4-dioxohexahydro-1,3,5-triazine (DADHT), acylated glycolurils, especially tetraacetylglycoluril (TAGU), N-acylimides, especially N-nonanoylsuccinimide (NOSI), acylated Phenolsulfonates, especially n-nonanoyl or isononanoyloxybenzenesulfonate (n- or iso-NOBS), carboxylic acid anhydrides, in particular phthalic anhydride, acylated polyhydric alcohols, especially triacetin, ethylene glycol diacetate and 2,5-diacetoxy-2,5-dihydrofuran.

in der R¹ für -H, -CH₃, einen C_2-24-Alkyl- oder -Alkenylrest, einen substituierten C_2-24-Alkyl- oder -Alkenylrest mit mindestens einem Substituenten aus der Gruppe -Cl, -Br, -OH, -NH₂, -CN, einen Alkyl- oder Alkenylarylrest mit einer C_1-24-Alkylgruppe, oder für einen substituierten Alkyl- oder Alkenylarylrest mit einer C_1-24-Alkylgruppe und mindestens einem weiteren Substituenten am aromatischen Ring steht, R² und R³ unabhängig voneinander ausgewählt sind aus -CH₂-CN, -CH₃, -CH₂-CH₃, -CH₂-CH₂-CH₃, -CH(CH₃)-CH₃, -CH₂-OH, -CH₂-CH₂-OH, -CH(OH)-CH₃, -CH₂-CH₂-CH₂-OH, -CH₂-CH(OH)-CH₃, -CH(OH)-CH₂-CH₃, -(CH₂CH₂-O)_nH mit n = 1, 2, 3, 4, 5 oder 6 und X ein Anion ist.Further bleach activators preferably used in the context of the present application are compounds from the group of cationic nitriles, in particular cationic nitriles of the formula

in the R ^{1 is} -H, -CH ₃ , a C _2-24 alkyl or alkenyl radical, a substituted C _2-24 alkyl or alkenyl radical having at least one substituent from the group -Cl, -Br, - OH, -NH ₂ , -CN, an alkyl or alkenylaryl radical having a C _1-24 -alkyl group, or represents a substituted alkyl or alkenylaryl radical having a C _1-24 -alkyl group and at least one further substituent on the aromatic ring, R ² and R ^{3 are} independently selected from -CH ₂ -CN, -CH ₃ , -CH ₂ -CH ₃ , -CH ₂ -CH ₂ -CH ₃ , -CH (CH ₃ ) -CH ₃ , -CH ₂ - OH, -CH ₂ -CH ₂ -OH, -CH (OH) -CH ₃ , -CH ₂ -CH ₂ -CH ₂ -OH, -CH ₂ -CH (OH) -CH ₃ , -CH (OH) - CH ₂ -CH ₃ , - (CH ₂ CH ₂ -O) _n H where n = 1, 2, 3, 4, 5 or 6 and X is an anion.

in der R⁴, R⁵ und R⁶ unabhängig voneinander ausgewählt sind aus -CH₃, -CH₂-CH₃, -CH₂-CH₂-CH₃, -CH(CH₃)-CH₃, wobei R⁴ zusätzlich auch -H sein kann und X ein Anion ist, wobei vorzugsweise R⁵ = R⁶ = -CH₃ und insbesondere R⁴ = R⁵ = R⁶ = -CH₃ gilt und Verbindungen der Formeln (CH₃)₃N⁽⁺⁾CH₂-CN X^–, (CH₃CH₂)₃N⁽⁺⁾CH₂-CN X^–, (CH₃CH₂CH₂)₃N⁽⁺⁾CH₂-CN X^–, (CH₃CH(CH₃))₃N⁽⁺⁾CH₂-CN X^–, oder (HO-CH₂-CH₂)₃N⁽⁺⁾CH₂-CN X^– besonders bevorzugt sind, wobei aus der Gruppe dieser Substanzen wiederum das kationische Nitril der Formel (CH₃)₃N⁽⁺⁾CH₂-CN X^–, in welcher X^– für ein Anion steht, das aus der Gruppe Chlorid, Bromid, Iodid, Hydrogensulfat, Methosulfat, p-Toluolsulfonat (Tosylat) oder Xylolsulfonat ausgewählt ist, besonders bevorzugt wird.Particularly preferred is a cationic nitrile of the formula

in which R ⁴ , R ⁵ and R ^{6 are} independently selected from -CH ₃ , -CH ₂ -CH ₃ , -CH ₂ -CH ₂ -CH ₃ , -CH (CH ₃ ) -CH ₃ , wherein R ⁴ additionally also -H may be and X is an anion, preferably R ⁵ = R ⁶ = -CH ₃ and in particular R ⁴ = R ⁵ = R ⁶ = -CH ₃ and compounds of the formulas (CH ₃ ) ₃ N ⁽⁺⁾ CH ₂ -CN X ^- , (CH ₃ CH ₂ ) ₃ N ⁽⁺⁾ CH ₂ -CN X ^- , (CH ₃ CH ₂ CH ₂ ) ₃ N ⁽⁺⁾ CH ₂ -CN X ^- , (CH ₃ CH ( CH ₃ )) ₃ N ⁽⁺⁾ CH ₂ -CN X ^- , or (HO-CH ₂ -CH ₂ ) ₃ N ⁽⁺⁾ CH ₂ -CN X ^{- are} particularly preferred, wherein from the group of these substances turn the cationic Nitrile of the formula (CH ₃ ) ₃ N ⁽⁺⁾ CH ₂ -CN X ^- in which X ^{- represents} an anion selected from the group consisting of chloride, bromide, iodide, hydrogensulfate, methosulfate, p-toluenesulfonate (tosylate) or xylenesulfonate is particularly preferred.

When Bleach activators can furthermore compounds which are aliphatic under perhydrolysis conditions peroxycarboxylic with preferably 1 to 10 C atoms, in particular 2 to 4 C atoms, and / or optionally substituted perbenzoic acid, are used. Suitable substances are the O- and / or N-acyl groups of the mentioned C atom number and / or optionally substituted benzoyl groups. Preference is given to polyacylated alkylenediamines, in particular tetraacetylethylenediamine (TAED), acylated triazine derivatives, in particular 1,5-diacetyl-2,4-dioxohexahydro-1,3,5-triazine (DADHT), acylated glycolurils, especially tetraacetylglycoluril (TAGU), N-acylimides, especially N-nonanoylsuccinimide (NOSI), acylated Phenolsulfonates, especially n-nonanoyl or isononanoyloxybenzenesulfonate (n- or iso-NOBS), carboxylic acid anhydrides, in particular phthalic anhydride, acylated polyhydric alcohols, in particular triacetin, ethylene glycol diacetate, 2,5-diacetoxy-2,5-dihydrofuran, n-methyl-morpholinium-acetonitrile-methylsulfate (MMA) and acetylated sorbitol and mannitol or their Mixtures (SORMAN), acylated sugar derivatives, in particular pentaacetylglucose (PAG), Pentaacetylfruktose, Tetraacetylxylose and Octaacetyllactose and acetylated, optionally N-alkylated glucamine and gluconolactone, and / or N-acylated lactams, for example N-benzoyl-caprolactam. hydrophilic substituted acyl acetals and acyl lactams are also preferred used. Combinations of conventional bleach activators can also be used become.

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

Provided in addition to the Nitrilquats further bleach activators are used are preferred bleach activators from the group of multiple acylated alkylenediamines, especially tetraacetylethylenediamine (TAED), N-acylimides, in particular N-nonanoylsuccinimide (NOSI), acylated Phenolsulfonates, especially n-nonanoyl or isononanoyloxybenzenesulfonate (n- or iso-NOBS), n-methyl-morpholinium-acetonitrile-methyl sulfate (MMA), preferably in amounts of up to 10% by weight, in particular 0.1% by weight to 8 wt .-%, especially 2 to 8 wt .-% and particularly preferably 2 to 6 wt .-%, each based on the total weight of the bleach activator-containing Medium, used.

Bleach-enhancing transition metal complexes, in particular with the central atoms Mn, Fe, Co, Cu, Mo, V, Ti and / or Ru, preferably selected from the group of manganese and / or cobalt salts and / or complexes, particularly preferably the cobalt (ammin) complexes, the cobalt (acetate) complexes, the cobalt (carbonyl) complexes, the chlorides of cobalt or manganese, manganese sulfate in usual Quantities, preferably in an amount up to 5 wt .-%, in particular from 0.0025 wt.% to 1 wt.%, and more preferably from 0.01 Wt .-% to 0.25 wt .-%, each based on the total weight of bleach activator-containing agent used. But in special cases can also more bleach activator can be used.

enzymes

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

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

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

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

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

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

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

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

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

The For example, enzymes are either originally derived from microorganisms, about the genera Bacillus, Streptomyces, Humicola, or Pseudomonas, and / or are used according to known biotechnological processes produced by suitable microorganisms, such as transgenic Expression hosts of the genera Bacillus or filamentous fungi.

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

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

alternative can the enzymes for both the solid as well for the liquid Dosage form can be 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 those in which the enzymes are as in enclosed in a solidified gel or in those of the core-shell type, in which a enzyme-containing core coated with a water, air and / or chemical impermeable protective layer is. In superimposed layers additional active ingredients, For example, stabilizers, emulsifiers, pigments, bleach or Dyes are applied. Such capsules are after known methods, for example by shaking or Roll granulation or applied in fluid-bed processes. Advantageously Such granules, for example by applying polymeric film-forming agents, low in dust and storage-stable due to the coating.

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

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

A Group of stabilizers are reversible protease inhibitors. Become frequent Benzamidine hydrochloride, Borax, boric acids, boronic acids or their salts or esters, including derivatives in particular with aromatic groups, such as ortho-substituted, meta-substituted and para-substituted phenylboronic, or their salts or esters. As peptidic protease inhibitors include ovomucoid and leupeptin; a additional Option is the formation of fusion proteins from proteases and peptide inhibitors.

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

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

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

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

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

Prefers are one or more enzymes and / or enzyme preparations, preferably solid protease preparations and / or amylase preparations, in Amounts of 0.1 to 5 wt .-%, preferably from 0.2 to 4.5 and in particular from 0.4 to 4 wt .-%, each based on the total enzyme-containing Medium, used.

disintegration aid

Around it is to facilitate the disintegration of prefabricated dosing units possible, Disintegration aids, so-called tablet disintegrants, in to incorporate these agents to reduce disintegration times.

Under Tablet disintegrants or disintegrants are used according to Römpp (9. Auflage, Bd. 6, p. 4440) and Voigt "textbook of pharmaceutical technology" (6th edition, 1987, Pp. 182-184) are excipients which are responsible for the rapid disintegration of tablets in water or gastric juice and for ensure the release of the pharmaceuticals in a resorbable form.

These Substances that are also referred to as "explosives" due to their effect increase when water enters their volume, on the one hand increasing the intrinsic volume (swelling), on the other hand also about the Release of gases can create a pressure on the tablet can disintegrate into smaller particles. Well-known Disintegration aids are, for example, carbonate / citric acid systems, although other organic acids can 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 their derivatives, alginates or casein derivatives.

Prefers are disintegration aids in amounts of 0.5 to 10 wt .-%, preferably 3 to 7% by weight and in particular 4 to 6% by weight, respectively based on the total weight of the desintegrationshilfsmittelhaltigen By means of, used.

Preferred disintegrating agents used in the present invention are cellulose-based disintegrating agents, so that preferred washing and cleaning compositions comprise such a cellulose-based disintegrating agent in amounts of from 0.5 to 10% by weight, preferably from 3 to 7% by weight and in particular 4 contain up to 6 wt .-%. Pure cellulose has the formal gross composition (C ₆ H ₁₀ O ₅ ) _n and is formally a β-1,4-polyacetal of cellobiose, which in turn is composed of two molecules of glucose. Suitable celluloses consist of about 500 to 5000 glucose units and therefore have average molecular weights of 50,000 to 500,000. Cellulose-based disintegrating agents which can be used in the context of the present invention are also cellulose derivatives obtainable by polymer-analogous reactions of cellulose. Such chemically modified celluloses include in this case, for example, products of esterifications or etherifications in which hydroxy hydrogen atoms have been substituted. Celluloses in which the hydroxy groups have been replaced by functional groups which are not bonded via an oxygen atom can also be used as cellulose derivatives. The group of cellulose derivatives includes, for example, alkali metal celluloses, carboxymethylcellulose (CMC), cellulose esters and ethers, and aminocelluloses. The cellulose derivatives mentioned are preferably not used alone as disintegrating agents based on cellulose, but used in admixture with cellulose. The content of these mixtures of cellulose derivatives is preferably below 50% by weight, particularly preferably below 20% by weight, based on the cellulose-based disintegrating agent. It is particularly preferred to use cellulose-based disintegrating agent which is free of cellulose derivatives.

The cellulose used as a disintegration aid is preferably not used in finely divided form, but converted into a coarser form, for example granulated or compacted, before it is added to the premixes to be tabletted. The particle sizes of such disintegrating agents are usually above 200 .mu.m, preferably at least 90 wt .-% between 300 and 1600 .mu.m and in particular at least 90 wt .-% between 400 and 1200 microns. The above and described in more detail in the documents cited coarser disintegration aids, are preferred as disintegration aids and are commercially available, for example under the name of Arbocel ^® TF-30-HG from Rettenmaier available in the present invention.

When another disintegrating agent based on cellulose or as an ingredient This component can be used microcrystalline cellulose. This microcrystalline cellulose is made by partial hydrolysis of Celluloses obtained under such conditions, only the amorphous ones Areas (about 30% of the total cellulose mass) of the celluloses attack and completely dissolve, the crystalline areas (about 70%) but leave undamaged. A subsequent disaggregation of the resulting from the hydrolysis microfine celluloses provide the microcrystalline celluloses, the primary particle sizes of approx. 5 μm and compactable, for example, to granules having an average particle size of 200 microns are.

in the Within the scope of the present invention, preferred disintegration aids, preferably a cellulose-based disintegration aid, preferably in granular, cogranulated or compacted form in the disintegrating agent-containing agents in amounts of 0.5 to 10% by weight, preferably from 3 to 7% by weight and especially from 4 to 6% by weight, respectively based on the total weight of the disintegrant-containing By means of, included.

According to the invention preferred can about that in addition, gas-evolving effervescent systems as tablet disintegration aids be used. The gas-developing effervescent system can from a consist of a single substance which releases a gas on contact with water. Among these compounds is in particular the magnesium peroxide to call, which releases oxygen on contact with water. Usually However, the gas-releasing effervescent system in turn from at least two components that are together under gas formation react. While here a variety of systems is thinkable and executable, for example Nitrogen, oxygen or hydrogen will release the in the washing and cleaning compositions used effervescent system both economic and also on the basis of ecological Select points of view to let. Preferred effervescent systems consist of alkali metal carbonate and / or bicarbonate and an acidifier, the is suitable to release carbon dioxide from the alkali metal salts in aqueous solution.

at The alkali metal carbonates or bicarbonates are the sodium and potassium salts for cost reasons across from the other salts clearly preferred. Of course, not the relevant pure alkali metal carbonates or bicarbonates be used; rather, you can Mixtures of different carbonates and bicarbonates preferred be.

Prefers be used as effervescent 2 to 20 wt .-%, preferably 3 to 15 wt .-% and in particular 5 to 10 wt .-% of an alkali metal carbonate or bicarbonates and 1 to 15, preferably 2 to 12 and in particular 3 to 10 wt .-% of an Acidifizierungsmittels, in each case based Total weight of the agent used.

Acidifying agents which release carbon dioxide from the alkali metal salts in aqueous solution include, for example, boric acid and alkali metal hydrogen sulfates, alkali metal dihydrogen phosphates and other inorganic salts. However, preference is given to using organic acidifying agents, the citric acid being a particularly preferred acidifying agent. However, it is also possible in particular to use the other solid mono-, oligo- and polycarboxylic acids. Again preferred from this group are wine acid, succinic acid, malonic acid, adipic acid, maleic acid, fumaric acid, oxalic acid and polyacrylic acid. Organic sulfonic acids such as sulfamic acid are also usable. A commercially available as an acidifier in the context of the present invention also preferably be used is Sokalan ^® DCS (trademark of BASF), a mixture of succinic acid (max. 31 wt .-%), glutaric acid (max. 50 wt .-%) and adipic acid ( at most 33% by weight).

Prefers are in the context of the present invention Acidifizierungsmittel in the shower system from the group of organic di-, tri- and oligocarboxylic acids or Mixtures.

fragrances

When Perfume oils or Fragrances can individual perfume compounds, e.g. the synthetic products of the type of esters, ethers, aldehydes, ketones, alcohols and hydrocarbons be used. Fragrance compounds of the ester type are e.g. Benzyl acetate, phenoxyethyl isobutyrate, p-tert-butylcyclohexyl acetate, linalyl acetate, Dimethylbenzylcarbinylacetate, phenylethylacetate, linalylbenzoate, Benzyl formate, ethyl methyl phenyl glycinate, allyl cyclohexyl propionate, Styrallyl propionate and Benzylsalicylate. For example, the ethers include Benzyl ethyl ether, to the aldehydes e.g. the linear alkanals with 8-18 C-atoms, citral, citronellal, citronellyloxyacetaldehyde, cyclamenaldehyde, Hydroxycitronellal, lilial and bourgeonal, to the ketones e.g. the Jonone, α-isomethylionone and methyl cedryl ketone, to the alcohols anethole, citronellol, eugenol, Geraniol, linalool, phenylethyl alcohol and terpineol, to the hydrocarbons belong mainly the terpenes like limonene and pinene. However, mixtures are preferred different fragrances used, which together create an appealing Create a fragrance. Such perfume oils can also natural fragrance mixtures as available from plant sources, e.g. Pine, Citrus, Jasmine, patchouly, rose or ylang-ylang oil. Also suitable Muscat, sage oil, Chamomile oil, Clove oil, lemon balm oil, mint oil, cinnamon leaf oil, lime blossom oil, juniper berry oil, vetiver oil, olibanum oil, galbanum oil and labdanum oil, and Orange blossom oil, neroliol, Orange peel oil and sandalwood oil.

The Fragrances can can be processed directly, but it can also be beneficial to the Fragrances on carrier The slow release of fragrance for long-lasting Provide scent. As such carrier materials For example, cyclodextrins have proven useful, with the cyclodextrin-perfume complexes additionally still can be coated with other excipients.

dyes

preferred Dyes whose selection does not present any difficulty to the skilled person have a high storage stability and insensitivity to the rest Ingredients of the agents and against light and no pronounced substantivity to the with the dye-containing agents to be treated textiles do not stain them.

In addition to so far in detail described components can the washing and detergents contain other ingredients that are the most application-related and / or aesthetic Properties of these funds continue to improve. In the context of the present Invention preferred means contain one or more substances from the group of electrolytes, pH regulators, fluorescers, dyes, Hydrotopes, foam inhibitors, silicone oils, anti redeposition agents, optical brighteners, grayness inhibitors, anti-shrinkage agents, Anti-crease agents, color transfer inhibitors, antimicrobial agents, germicides, fungicides, antioxidants, Antistatic agents, ironing aids, Phobic and impregnating agents, source and Slip Resists and UV absorbers.

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

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

In order to improve the aesthetic impression of the agents according to the invention, they can with geeigne dyed dyestuffs. Preferred dyes, the selection of which presents no difficulty to the skilled person, have a high storage stability and insensitivity to the other ingredients of the agents and to light and no pronounced substantivity to textile fibers so as not to stain them.

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

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

graying have the task of removing the dirt from the fiber in the fleet to keep it suspended, thus allowing the dirt to be recovered prevent. These are water-soluble Colloids mostly organic nature suitable, for example, the water-soluble Salts of polymeric carboxylic acids, glue, Gelatin, salts of ether sulfonic acids the strength or the cellulose or salts of acidic sulfuric acid esters cellulose or starch. Also water-soluble, Acidic group-containing polyamides are suitable for this purpose. Farther can be soluble Starch preparations and other than the aforesaid starch products use, e.g. degraded starch, aldehyde etc. Also, polyvinylpyrrolidone is useful. As grayness inhibitors Cellulose ethers such as carboxymethylcellulose (Na salt) can also be used, Methylcellulose, hydroxyalkylcellulose and mixed ethers such as methylhydroxyethylcellulose, Methylhydroxypropylcellulose, methylcarboxy-methylcellulose and their mixtures.

There textile fabrics, in particular of rayon, rayon, cotton and mixtures thereof, for Can tend to wrinkles, because the individual fibers against sagging, kinking. Pressing and squeezing are sensitive to transverse to the fiber direction, the compositions of the invention contain synthetic crease inhibitor. These include, for example synthetic products based on fatty acids, fatty acid esters. fatty acid amides, Alkylolestern, -alkylolamiden or fatty alcohols, usually with Ethylene oxide reacted or products based on lecithin or modified phosphoric acid ester.

to fight of microorganisms can the agents according to the invention contain antimicrobial agents. Here one differentiates depending on antimicrobial spectrum and mechanism of action between Bacteriostats and bactericides, fungistats and fungicides, etc. Important substances from these groups are, for example, benzalkonium chlorides, Alkylarlylsulfonates, halophenols and Phenolmercuriacetat, wherein in the inventive compositions also completely can be dispensed with these compounds.

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

An increased wearing comfort can result from the additional use of antistatic agents which are additionally added to the compositions according to the invention. Antistatic agents increase the surface conductivity and thus allow an improved drainage of formed charges. Outer antistatics are usually substances with at least one hydrophilic molecule ligand and give one more on the surfaces less hygroscopic film. These mostly surface-active antistatic agents can be subdivided into nitrogen-containing (amines, amides, quaternary ammonium compounds), phosphorus-containing (phosphoric acid esters) and sulfur-containing (alkyl sulfonates, alkyl sulfates) antistatic agents. Lauryl (or stearyl) dimethylbenzylammonium chlorides are also suitable as antistatic agents for textiles or as an additive to detergents, wherein additionally a softening effect is achieved.

to Care of the textiles and to improve the textile properties like a softer 'handle' (avivage) and reduced electrostatic charge (elevated Wearing comfort) the agents according to the invention softener contain. The active ingredients in softener formulations are "esterquats", quaternary ammonium compounds with two hydrophobic groups, such as the disteraryldimethylammonium chloride, which however, because of its insufficient biodegradability increasingly replaced by quaternary ammonium compounds is in their hydrophobic residues ester groups as Sollbruchstellen for the biological Contain degradation.

to Improvement of water absorbency, rewettability treated textiles and to facilitate ironing treated textiles can in the agents according to the invention, for example Silicone derivatives are used. These additionally improve that rinse behavior the agents according to the invention by their foam-inhibiting properties. Preferred silicone derivatives are, for example, polydialkyl or alkylaryl siloxanes in which the alkyl groups one to five Have C atoms and are completely or partially fluorinated. preferred Silicones are polydimethylsiloxanes which are optionally derivatized could be and are then amino-functional or quaternized or Si-OH-, Si-H- and / or Si-Cl bonds Finally, the agents of the invention also contain UV absorbers which are absorbed by the treated textiles and the light resistance improve the fibers. Connections that those desired Properties are, for example, those by radiationless Deactivation of effective compounds and derivatives of benzophenone with substituents in 2- and / or 4-position. Furthermore, substituted benzotriazoles, in 3-position phenyl-substituted acrylates (cinnamic acid derivatives), optionally with cyano groups in the 2-position, salicylates, organic Ni complexes and natural substances such as umbelliferone and the body's own urocanic acid.

One Finally, the object of the present application is also a purification process for cleaning textiles in a textile washing machine, thereby characterized in that a or several washing and detergent with or without dosing in the washing compartment of the Washing machine and / or inserted into the Einspülkammer and a wash program in the course of which the agent dissolves.

Claims (15)

A washing or cleaning agent in a water-soluble or water-dispersible container, comprising a) a surfactant phase containing from 40 to 85% by weight, based on its weight, of a neutralized anionic surfactant acid; and b) a particulate solid, characterized in that surfactant phase a) and solid b) are present together in a receiving chamber of the water-soluble or water-dispersible container. Washing or cleaning agent according to claim 1, characterized characterized in that Surfactant phase based on their weight 40 to 95 wt .-%, preferably 50 to 90 wt .-%, particularly preferably 60 to 85 wt .-% and in particular 65 to 82 wt .-% surfactant (s). Washing or cleaning agent according to one of claims 1 or 2, characterized in that the surfactant phase based on their weight 40 to 85 wt .-%, preferably 50 to 82.5 % By weight and in particular 60 to 80% by weight of alkyl benzene sulphonate (s) contains. Washing or cleaning agent according to one of claims 1 to 3, characterized in that the Surfactant phase based on their weight 0.5 to 20 wt .-%, preferably 0.5 to 15% by weight and in particular 1 to 10% by weight of nonionic (s) Containing surfactant (s). Washing or cleaning agent according to one of claims 1 to 4, characterized in that the surfactant phase further 0.5 to 12 wt .-%, preferably 1.0 to 9 wt .-% and in particular 2.0 to 6% by weight of an alkali carrier, preferably an alkali hydroxide. Washing or cleaning agent according to one of claims 1 to 5, characterized in that the water content of the surfactant phase between 8 and 24% by weight, preferably between 10 and 20% by weight and in particular between 12 and 18% by weight. Washing or cleaning agent according to one of claims 1 to 6, characterized in that the surfactant phase a) a storage module at 20 ° C between 40,000 and 800,000 Pa. Washing or cleaning agent according to claim 7, characterized characterized in that Storage modulus of the surfactant phase a) 50,000 to 750,000 Pa, preferably 60,000 to 700,000 Pa, more preferably 70,000 to 650,000 Pa and especially 80,000 to 600,000 Pa. Washing or cleaning agent according to one of claims 7 or 8, characterized in that the memory module the surfactant phase a) at least twice as large, preferably at least four times as big as the loss module. Washing or cleaning agent according to one of claims 7 to 9, characterized in that the phase shift the surfactant phase 0 to 30 °, preferably 0 to 20 ° and in particular ≤ 17 °. Washing or cleaning agent according to one of claims 1 to 9, characterized in that the surfactant phase has a density below 1.8 g / cm ³ , preferably below 1.6 g / cm ³ and in particular below 1.4 g / cm ³ . Washing or cleaning agent according to one of claims 1 to 11, characterized in that the particulate solid is selected from the group of powders, extrudates, granules or agglomerates. Washing or cleaning agent according to one of claims 1 to 12, characterized in that the particulate solid has a middle Particle diameter between 5 and 3000 microns, preferably between 10 and 2500 μm, preferably between 100 and 2000 microns and in particular between 200 and 2000 microns. Washing or cleaning agent according to one of claims 1 to 13, characterized in that the weight ratio of Surfactant phase a) to particulate Solid b) between 2: 1 and 1:10, preferably between 1: 1 and 1: 8 and in particular between 1: 2 and 1: 6. Washing or cleaning agent according to one of claims 1 to 14, characterized in that the water-soluble or water-dispersible container a thermoforming container or an injection-molded container or a blow-molded container is.