DE102005005499A1 - Process for the preparation of detergents or cleaners - Google Patents

Abstract

A process in which a mixture of a granule, a separate solid neutralizing agent and at least one acid are granulated in a mixer, wherein the weight fraction of the separate solid neutralizing agent in the total weight of the mixture is more than 10 wt .-% and the weight ratio of separate solid neutralizing agent greater than 2: 1 acid, provide particulate detergents or components therefor having good physical properties.

Description

The The invention relates to a process for the preparation of washing or Detergents which address the problems of known dry neutralization processes solves.

One Known process for the production of granules which are used for washing or detergents are spray-dried. In this case, in an initial step, an aqueous slurry, the so-called slurry formed. The slurry contains thermally stable detergent ingredients that essentially under the conditions of spray-drying neither volatilize still decompose. These ingredients include, for example, surfactants and builder. The slurry will over Pumping in a spray tower promoted and over in the upper part of the spray tower located nozzles sprayed. By means of ascending air with high temperature becomes the slurry dried and the adhering water evaporates, leaving the detergent ingredients obtained at the outlet of the tower as granules. In connection become the resulting granules more, mostly temperaturlabile Components such as bleach or fragrances, mixed.

Spray-drying process have a number of disadvantages. Biggest disadvantage of the spray drying of Slurries is the big one Cost factor due to the necessary for drying the slurry Energy expenditure. Consequently, there is a need for lower cost However, manufacturing processes that allow the benefits of spray drying to use. A solution beats British Patent Application GB-A-1 151 767 which discloses a continuous Process for the preparation of low-bulk detergent compositions disclosed in which in an aqueous Slurry to an organic surfactant an inorganic alkali or Alkaline earth salt or a neutral builder salt. With this Method is to minimize the water content of the composition sought before the drying step and thus a reduction of the required heat of drying.

Another Disadvantage of spray drying process is the grain spectrum width of the granules produced. So included corresponding grain spectra granules with particle sizes up to above 1000 μm and at the same time dust particles with particle sizes below 100 μm. The coarser ones Particles can by agglomeration of the primary particles arise. Wide grain spectra are not for many reasons desirable, For example, storage and transport can cause segregation of the product Granule portions, the products obtained do not correspond to the aesthetic Consumer ideas and have insufficient flow properties.

One High surfactant content, as he often in washing or cleaning agents is desired, leads the spray drying the corresponding slurries to problems, since the flashpoint of the Preparations is reduced. This will lower process temperatures, the throughput in the spray drying drastically diminish, enforced. As a solution proposal discloses the British Patent Application GB-A-1 355 187 discloses a method of preparation for washing powder, which contain a high proportion of synthetic surfactants and an organic Builder and other detergent ingredients such as silicates and Contain carbonates. With a high content of organic surfactants and builders is intended by this method, the inflammation or explosion risk due to over-drying or overheating arises, be reduced. No solution offers this application However, in the task to produce granules with high anionic surfactant content.

The To circumvent some of the problems or disadvantages of spray drying processes Offenlegungsschriften DE-A-199 36 614 and DE-A-199 disclose 36 613. These documents disclose methods for producing particulate wash or detergents or components thereof, which comprise a mixture comprising a granulate, a separate solid neutralizing agent and at least an acid be granulated in a mixer. As granules will in these Procedure a spray-dried Powder containing anionic surfactant and builders used. to increase of the anionic surfactant content, an anionic surfactant acid is sprayed on. consequently is only a part of the final process product by spray drying produced, which compared to the energy requirements of the process pure spray drying process decreases. In a dry neutralization step, the anionic surfactant content becomes the granules increased, so that a low slurry anionic surfactant content, due to the low flashpoint of high anionic surfactant preparations seems, can be balanced and granules with desired Aniontensidgehalt be obtained.

However, such dry neutralization processes have the disadvantage that a surfactant film is formed on the surface of the granules due to the process control. Based on the adhesive properties During the process, the surfactants form agglomerates whose particles have a strong cohesion due to surfactant and, as a result, have a reduced rate of dissolution, poor flowability, increased sedimentation and / or increased clump test values. A further disadvantage of these methods is that the surfactant-based adhesive compound leads from a large number of such agglomerates to a so-called "cluster formation", which is directly associated with the risk of gelation It should be emphasized that such a gelling can already be caused by a number of and / or a few adhesives which are adhesively bonded to the surface, in particular zeolite-free and zeolite-reduced detergents or cleaners can have poor flowability and low storage stability have a strong tendency to gel, since in these products the adhesive properties of the surfactants are much more pronounced than in high-zeolite compositions The basic problem of dry neutralization processes in which, for example, soda and surfactant acids are reacted n, is the low flowability of the solids used. This leads to a poor mixing of the components and thus to the formation of a non-homogeneous product which contains lumps and is sticky. By insufficient mixing, the final process product contains grains or granules containing unreacted acid, so-called "acidic nests." These can react with substances contained in the washing or cleaning agent and are not stable to the acids used, for example fragrances, and decompose them.

Farther usually occurs while dry neutralization associated with granulation, a not inconsiderable increase the bulk density on that just when making detergents or cleansers with low to medium bulk density not desirable is.

task It was the object of the present invention to provide a cost effective method of manufacture solid detergent or detergent or to develop components thereof. This involved further developing known dry neutralization processes and thus overcome the above-described problems of these methods.

It has now been found that the aforementioned problems and disadvantages bypass if used in a dry neutralization process Granules, a separate solid neutralizing agent and at least one Acid mixed wherein the weight fraction of the separate solid neutralizing agent the total weight of the mixture is more than 10 wt .-% and that weight ratio from separate neutralizer to acid is greater than 2: 1.

One The first object of the invention is a process for the preparation a particulate one Washing or cleaning agent or a component thereof, in which a mixture comprising a granulate, a separate solid Neutralizer and at least one acid granulated in a mixer wherein the weight fraction of the separate solid neutralizing agent the total weight of the mixture is more than 10 wt .-% and that weight ratio from separate neutralizer to acid is greater than 2: 1.

Surprisingly It was found that the above problems and disadvantages can be avoided if the specified weight ratios are adhered to and independently from the present molar mass ratios of the constituents used.

Especially those methods are preferred in which as a separate solid neutralizing agent Alkali metal salts, preferably alkali metal carbonate (s) and in particular Sodium carbonate is used.

Of the Proportion of the separate solid neutralizing agent in the total weight of the mixture of granules, separate solid neutralizing agent and acid is more than 10 wt .-%, preferably the proportion is more than 13 wt .-%, more preferably more than 16% by weight and in particular more than 19% by weight. The weight ratio from separate solid neutralizer to acid is greater than 2: 1, preferably greater than 2.2: 1 and in particular is larger as 2.6: 1. The weight ratio between granules and separate solid neutralizing agent is preferred more than 1: 1, more preferably more than 2: 1 and in particular more than 3: 1.

The separate solid neutralizing agent can consist of a single component, for example sodium carbonate, a mixture of several neutralizing agents (neutralizing constituents), for example, comprise a mixture of different alkali metal carbonates, hydroxides and / or bicarbonates or also contain one or more neutralizing agents and additionally admixed salts. In the context of this application, the weight fraction of the separate solid neutralizing agent is determined from the sum of the weight proportions of the neutralizing component (s) (neutralizing agent) and the salts added to the neutralizing agent.

Out The group of salts are predominantly alkali metal salts, especially Alkali metal sulfates and alkali metal phosphates, in particular alkali metal triphosphate, or mixtures of these salts. It is again preferred when the respective sodium salts are used. alkali metal tripolyphosphate is preferably used when in the product to be produced a phosphate-based builder system should be included. Should that Means a soluble Builder system based on carbonate silicate, it is preferred if here alkali metal carbonate, optionally in mixtures with Alkali metal sulfate is used. In principle, are suitable for Admixing all salts which are suitable to bind water However, it is preferred if the ratio of neutralizing acting Ingredients for the added salts at least 5: 1, preferably even at least 10: 1, in particular more than 15: 1. Becomes However, it may also be preferred to add the phosphate Add total amount of phosphate in this step. Then that's it relationship the neutralizing ingredients to the added salts usually in circumstances 2: 1 to 1: 1.

in the Within the scope of the present invention it is particularly preferred if the separate solid neutralizer fluidity of at least 40%, preferably at least 50%, more preferably at least 60% and in particular of at least 70% compared to standard sand having. To determine the flowability is the flow time of 1000 ml of the solid to be determined, here the separate solid Neutralizer, measured from a standard funnel and compared with the discharge speed of standard sand. The Outflow time of the dry standard sand from the Rieselapparatur is set at 100%. The flow time of the solid particles to be determined from the apparatus is set in proportion and as a percent Flow time, compared to the standard sand indicated. The standard sand points a bulk density of 1460 g / l and the following grain spectrum:> 1.6 mm = 0.2%; > 0.8 mm and ≤ 1.6 mm = 11.6%; > 0.4 mm and ≤ 0.8 mm = 56.2%; > 0.2 mm and ≤ 0.4 mm = 26.6%; > 0.1 mm and ≤ 0.2 mm = 4.8%; <0.1 mm = 0.6% (The grain spectrum of the standard sand is from fractionated Bausand weighed up. The standard sand is before calibration the Rieseltrichters by sample division from a larger storage bottle to divide to a volume of 1000 ml.)

During the filling of the standardized funnel is the lower outlet opening of the funnel of the test apparatus close. Simultaneously with the release of the outlet opening of the funnel of the test apparatus start with the determination of the period of time in which the solid sample Completely leaves the test funnel. After five times Determining the flow time, the mean value is calculated. The averaged Termination time of the standard sand in seconds multiplied by 100 and divided by the average flow time of the solid sample in seconds, here the sample of the separate solid neutralizing agent, gives the fluidity in percent.

According to the invention a granulate, a separate solid neutralizing agent and at least one Acid in granulated a mixer. As acid (s) preferably come anionic acid, Phosphonic acids, carboxylic acids, sulfonic acids and acrylic acids or mixtures of these, but preferably anionic surfactant acids to Commitment.

To the anionic surfactants in the form of the acid precursors in the process can be used in particular count Sulfonates and sulfates, but also soaps.

As surfactants of the sulfonate type are preferably C ₉ -C ₁₃ alkylbenzenesulfonates, olefinsulfonates, ie mixtures of alkene and Hydroxyalkansulfonaten and disulfonates, such as those from C ₁₂ -C ₁₈ monoolefins having terminal or internal double bond by sulfonation with gaseous Sulfur trioxide and subsequent alkaline or acidic hydrolysis of the sulfonation obtained.

Also suitable are alkanesulfonates which are obtained from C ₁₂ -C ₁₈ -alkanes, for example by sulfochlorination or sulfoxidation with subsequent hydrolysis or neutralization.

Also suitable are the esters of α-sulfo fatty acids (ester sulfonates), for example the α-sulfonated methyl esters of hydrogenated coconut, palm kernel or tallow fatty acids obtained by α-sulfonation of the methyl esters of fatty acids of plant and / or animal origin with 8 to 20 C Atoms in the fatty acid molecule and follow Neutralization to water-soluble mono-salts are prepared, into consideration. These are preferably the α-sulfonated esters of hydrogenated coconut, palm, palm kernel or tallow fatty acids, although sulfonated products of unsaturated fatty acids, for example oleic acid, in small amounts, preferably in amounts not above about 2 to 3 wt. %, can be present. In particular, α-sulfofatty acid alkyl esters are preferred which have an alkyl chain with not more than 4 C atoms in the ester group, for example, methyl ester, ethyl ester, propyl ester and butyl ester. With particular advantage, the methyl esters of α-sulfo fatty acids (MES), but also their saponified disalts are used.

Further suitable anionic surfactants are sulfated fatty acid glycerol esters, which mono-, Diesters and triesters and mixtures thereof, as in the Preparation by esterification by a monoglycerol with 1 to 3 Mole of fatty acid or in the transesterification of triglycerides with 0.3 to 2 moles of glycerol to be obtained. Preferred sulfated fatty acid glycerol esters are included the sulphonated products of saturated fatty acids with 6 to 22 carbon atoms, for example the caproic acid, caprylic acid, capric acid, myristic acid, lauric acid, palmitic acid, stearic acid or Behenic acid.

Examples of alk (en) ylsulfates are the alkali metal salts and, in particular, the sodium salts of the sulfuric monoesters of C ₁₂ -C ₁₈ fatty alcohols, for example coconut fatty alcohol, tallow fatty alcohol, lauryl, myristyl, cetyl or stearyl alcohol or the C ₁₀ -C ₂₀ oxo alcohols and those half-esters of secondary alcohols of this chain length are preferred. Also preferred are alk (en) ylsulfates of said chain length, which contain a synthetic, produced on a petrochemical basis straight-chain alkyl radical, which have an analogous degradation behavior as the adequate compounds based on oleochemical raw materials. Of washing-technical interest, C ₁₂ -C ₁₆ -alkyl sulfates and C ₁₂ -C ₁₅ -alkyl sulfates and C ₁₄ -C ₁₅ -alkyl sulfates are particularly preferred. 2,3-alkyl sulfates are also suitable anionic surfactants.

Also, the sulfuric acid monoesters of the straight-chain or branched C ₇ -C ₂₁ -alcohols ethoxylated with from 1 to 6 mol of ethylene oxide, such as 2-methyl-branched C ₉ -C ₁₁ -alcohols having on average 3.5 mol of ethylene oxide (EO) or C ₁₂ -C ₁₈ Fatty alcohols containing 1 to 4 EO are suitable. They are used in detergents due to their high foaming behavior only in relatively small amounts, for example in amounts of 1 to 5 wt .-%.

Preferred anionic surfactants are also the salts of alkylsulfosuccinic acid, which are also referred to as sulfosuccinates or as sulfosuccinic acid esters and the monoesters and / or diesters of sulfosuccinic acid with alcohols, preferably fatty alcohols and in particular ethoxylated fatty alcohols. Preferred sulfosuccinates contain C ₈ to C ₁₈ fatty alcohol residues or mixtures of these. Particularly preferred sulfosuccinates contain a fatty alcohol residue derived from ethoxylated fatty alcohols, which in themselves constitute nonionic surfactants (see description below). Sulfosuccinates, whose fatty alcohol residues are derived from ethoxylated fatty alcohols with narrow homolog distribution, are again particularly preferred. Likewise, it is also possible to use alk (en) ylsuccinic acid having preferably 8 to 18 carbon atoms in the alk (en) yl chain or salts thereof.

When other anionic surfactants are fatty acid derivatives of amino acids, for example of N-methyltaurine (Tauride) and / or N-methylglycine (sarcosides). Especially the sarcosides or sarcosinates are preferred here and here especially sarcosinates of higher and optionally monounsaturated or polyunsaturated fatty acids such as Oleyl.

When other anionic surfactants are in particular soaps, preferably in amounts of 0.2 to 5 wt .-%, used. In particular are suitable saturated Fatty acid soaps, such as the salts of lauric, myristic, palmitic, stearic, hydrogenated erucic and behenic acid and in particular of natural fatty acids, e.g. Coconut, palm kernel or tallow fatty acids, derived soap mixtures. Together with these soaps or as a substitute for soaps can also the known Alkenylbernsteinsäuresalze be used.

The surfactants mentioned in the process according to the invention in the form of their Acid precursors with a granule and a separate solid neutralizing agent granulated. Neutralization to sodium, potassium or ammonium salts or too soluble Salts of organic bases, such as mono-, di- or triethanolamine, take place during the inventive method. In the finished wash or Detergents, the anionic surfactants are preferably in the form their sodium or potassium salts, especially in the form of the sodium salts in front.

The acid used may consist of a single component, for example alkylbenzenesulfonic acid, a mixture of several acids, for example a mixture of anionic surfactant and phosphonic acid or in addition to the acid (s) contain further liquid and / or dissolved components. In the context of this application, the weight fraction of the acid (s) is determined from the sum of the proportions by weight of the entire mixture of one or more acids and the components present in admixture therewith, including water.

When more liquid Components come / come for example water, nonionic surfactants or Polymers into consideration. Corresponding embodiments are particular in the cases interesting in which the solids (granules, separate solid Neutralizing agent) should only be granulated with small amounts of acid. Preferably The relationship between acid, in particular anionic surfactant acid, and of this acid deviating components more than 1: 1, preferably more than 1.5: 1 and in particular more than 2: 1. Some detergents or cleaning ingredients, which is preferably introduced into the mixer in admixture with the acid (s) Become, become later described.

The Temperature of the acid (s) is when fed to the mixer, preferably between 15 and 80 ° C, preferably between 20 and 70 ° C, more preferably between 25 and 60 ° C and especially between 30 and 50 ° C. Especially when the supply of acid (s) via nozzles, which a preferred embodiment represents the process, it is advantageous to acid (s) with these temperatures to use, since they then have a favorable viscosity for spraying.

When Granules are preferably used a spray-dried powder. By using such a powder, the advantages can be the spray drying use, but the disadvantages of the spray-drying process by suitable post-treatment, such as changing the grain spectrum by subsequent agglomeration with a binder can.

Of the Proportion of granules to the mixture of granules, separate solid Neutralizing agent and acid (s) is preferably 30 to 90 wt .-%, particularly preferably 45 to 85 wt .-% and in particular 60 to 80 wt .-% makes up.

In a further preferred embodiment is less than 40% by weight, preferably less than 30% by weight, especially preferably less than 20% by weight, most preferably less as 10 wt .-% and in particular no spray-dried powder, based on the mixture of granules, separate solid neutralizing agent and acid (s), used.

in the Within the scope of the present invention it is particularly preferred if the granules have a flowability of at least 40%, preferably at least 50%, more preferably at least 60% and in particular of at least 70% in comparison to standard sand (for measurement method see above). Appropriate Granules are preferred because they are still in mixture with separate solid neutralizing agent and acid good flow properties have and thus facilitate the mixing of the components.

In a preferred embodiment the method according to the invention has at least one of the fersten components (granules, separate solid neutralizing agent) has a flowability of more than 60%, especially preferred over 70%, most preferably over 80% and especially about 90% compared to standard sand on. It is especially preferred if both components (granules, separate solid neutralizing agent) a fluidity from above 60%, more preferably over 70%, most preferably over 80% and especially about 90% compared to standard sand.

is the granules are spray-dried Powder, so it preferably has a content of free water between 0.5 and 10 wt .-%, preferably between 1 and 9 wt .-%, preferably between 1.5 and 8% by weight, more preferably between 2 and 7 Wt .-%, most preferably between 2.5 and 6 wt .-% and in particular between 3 and 5% by weight, based on the spray-dried powder. When free water is referred to in the context of this application that water, not bound as crystal water in the spray-dried powder is.

Acid precursors, such as anionic surfactant acids, phosphonic acids and optionally acidic or partially neutralized polymers, which are treated with a neutralizing agent, are preferably used in the slurry of a spray-dried powder. In a preferred embodiment, the granules, which is preferably a spray-dried powder, also contains anionic surfactants from the above-mentioned classes of compounds. Preferred neutralizing agents are alkali metal hydroxides, in particular sodium hydroxide, or alkali metal carbonate, in particular sodium carbonate. In addition to these neutralized ingredients, the slurry usually contains aluminosilicate, alkali metal carbonate and optionally alkali metal silicate and / or sodium sulfate. Preferably contains the slurry is less than 5 wt .-%, more preferably less than 3 wt .-%, most preferably less than 1 wt .-% and in particular no aluminosilicate. The water content of the slurries used for spray drying is usually in the range of 20-50%. In this case, the slurry preparation and spray drying can be carried out according to the methods known to the person skilled in the art. It may be preferable to use the neutralization heat released in the neutralization of the acid precursors directly for heating the slurries.

One preferred subject of the present invention is a method for producing a particulate Washing or cleaning agent or a component thereof, in which a mixture comprising a spray dried Powder, which preferably contains anionic surfactants, a separate solid neutralizing agent, which is preferably sodium carbonate, and at least one acid which preferably anionic surfactant acid (s), in particular alkylbenzenesulfonic acid (s) is / are to be granulated in a mixer, wherein the weight fraction of the separate solid neutralizing agent in the total weight of the Mixture more than 10 wt .-% is and the weight ratio of Separate solid neutralizer to acid is greater than 2: 1.

The Granules are preferably at a temperature less than 80 ° C, preferably less than 70 ° C, more preferably less than 60 ° C and in particular less than 55 ° C used. If the granules are spray-dried Powder, it is favorable from time and capacity considerations that Powder at temperatures above 25 ° C, preferably above 30 ° C, especially preferably above 35 ° C and in particular above 40 ° C further processing, that is with the separate solid neutralizing agent and at least one Reacting acid. However, it is preferred that the granules have a temperature, at the same time the ingredients with a low melting point in solid form. Molten substances would be the Increase stickiness of the granules and thus the flowability decrease.

The Advantages of the method according to the invention, especially with regard to the flowability and the grain spectrum the final process products, can be determined by the targeted selection increase the educts used. As a result, some become special preferred example formulations listed by embodiments the method according to the invention to process finished products with improved properties to let. The details in the following table are in% by weight, in each case based on the total weight of the granules used, the separate solid neutralizing agent or the / used Acid (s). The listed Ingredients are within the granules used, the separate solid neutralizing agent and the acid (s) used more, even closer identified ingredients, which are listed later, added to 100 wt .-%.

In preferred embodiments the method according to the invention be in the mixer 35 to 90 wt .-%, preferably 50 to 85 wt .-% and in particular 65 to 80 wt .-% of the granules, 5 to 60 wt .-%, preferably 10 to 45 wt .-% and in particular 15 to 30 wt .-% of the separate solid neutralizing agent and 1 to 30 wt .-%, preferably 3 to 20 wt .-% and in particular 5 to 10 wt .-% of the acid (s) granulated.

through the method according to the invention granules are provided which have a narrow grain spectrum low to medium bulk density as well as an aesthetic Have appearance, well soluble and storable are. Furthermore, the granules obtained have a better flowability on, as known from the prior art process end products of dry neutralization processes. Preferably, the flowability is the obtained particles between 50 and 100%, preferably between 55 and 97.5%, preferably between 60 and 95%, more preferably between 65 and 92.5 and in particular between 70 and 90%, in comparison for flowability from standard test sand (Measurement method see above). The narrow grain spectrum of the granules causes a uniform dissolution of Particles and corresponds to the aesthetic Notions of consumers. Because the individual granules are not stick and thus also after a longer time Storage does not agglomerate, no coarse fractions are contained in the granules, which disturb the visual impression, or to a slowed and inconsistent dissolution of the Lead by means would. Due to the procedure is only a negligible Proportion of fines in the granules before, so that the agent in decant or dosing does not dust and thus no health hazard of Worker in the factory or the consumer causes. Surprisingly Also zeolite-free and zeolite-reduced process end products have the above properties, so that the inventive method is particularly suitable for providing zeolite-reduced granules. For this purpose, the mixture of inserted granules, separate solid Neutralizing agent and acid (s) preferably less than 15% by weight, preferably less than 10% by weight, preferably less than 5% by weight, more preferably less than 2 wt .-%, most preferably less than 1 wt .-% and in particular no aluminosilicate.

In the method according to the invention Prepared agents, anionic surfactants are preferably in amounts from 1 to 35% by weight and in particular from 5 to 30% by weight enthaften. Alkyl benzene sulphonate, Alkyl sulfates or mixtures thereof. Furthermore, it is preferred if the remedies also contain soap in addition to other anionic surfactants. The bulk density the process end products is preferably 300 to 1200 g / l, preferably 350 to 1000 g / l, especially preferably 400 to 800 g / l and in particular 400 to 600 g / l.

In a preferred embodiment becomes a separate solid neutralizing agent with granules, which also be a mixture of two, three or more granules can, mixed in a mixer and at least one acid sprayed on. Preferably becomes simultaneous with the spraying carried out a granulation. In a preferred embodiment the method according to the invention will / become a) a slurry, the detergent components suitable for spray drying contains sprayed in a drying tower and to a content of free, that is not bound in the crystal Water of not more than 20% by weight (dried, b) the spray-dried Basic granules mixed with a separate solid neutralizing agent, c) sprayed on the mixture at least one acid, and d) optionally further granules added to the resulting compound.

The Final process product may be treated in an aftertreatment step with acid (s), which also in the mixture with other liquid and / or dissolved substances such as nonionic surfactants and / or polymers used can / can, sprayed become.

To carry out the dry neutralization granulation process, a wide variety of mixing and granulating devices are suitable. Suitable devices are, for example, systems of the type Eirich mixer, a Lödige mixer, such as a ploughshare mixer Lödige, or a mixer from Schugi. Suitable are, for example Eirich mixer ^® Series R or RV (trademark of Maschinenfabrik Gustav Eirich, Hardheim), the Schugi Flexomix ^®, the Fukae ^® FS-G mixers (trade marks of Fukae Powtech, Kogyo Co., Japan), Henschel mixer, Lödige ^® FM, KM and CB mixers (trade marks of Lodige Maschinenbau GmbH, Paderborn, Germany), Drais ^® -series T or KT (trademarks of Drais-Werke GmbH, Mannheim) which Diosna ^® -series (trademark Dierks & Sohne, Germany) or the Fuji ^® -series VG-C (trademark Fuji Sangyo Co., Japan).

Especially however, suitable are mixers that are over a horizontal axis feature, which can be equipped with different tools. Examples such preferred mixers are the Lödige CB and KM mixers.

preferred The present invention is a process for the preparation a particulate one Washing or cleaning agent or a component thereof, in which a mixture comprising a granule, a separate solid neutralizing agent and at least one acid be granulated in a mixer, wherein the weight fraction of separate solid neutralizing agent on the total weight of the mixture more than 10 wt .-% is and the weight ratio from separate neutralizer to acid is greater than 2: 1 and a mixer is used with a horizontal axis.

to execution the method according to the invention have been found to be particularly suitable mixers, a horizontal Have axis, which in a variety of positions devices contains, in the tools can be inserted / installed. By choice and position of the tools it is possible in mixers of this type, the Interior in a feed zone, a mixing zone and a discharge zone to divide.

In a preferred embodiment the method according to the invention contains the feed zone at least 4, preferably 6 and in particular 8 curved intake blades, the with their concave surface in Direction of mixing zone and discharge zone are aligned. The angle between the solder on the mixer axis and the tangent to the intake blades at the point of blade attachment is preferably in the feed zone between 60 ° and 5 °, preferably between 50 ° and 10 ° and especially between 40 ° and 15 °. Preferably Take these angles of the individual intake blades from the first Feed bucket in the feed zone to the last intake bucket off before the mixing zone.

In the mixing zone can Tools and - for promotion of the material in the mixer - additional conveying blades be included. Preferred embodiments However, they are characterized by the fact that in the mixing zone no conveying blades are contained and the material flow in this zone exclusively by nachschiebendes Material is effected. Preferably, in the mixing zone 6 to Contain 20, preferably 10 to 18 mixing tools.

In the discharge zone can after all in addition to the material flow conveyor blades and mixing tools be included. In the context of the present invention it is preferred that in a first section of the discharge zone, which adjoins the Mixing zone connects, the quantity ratio between mixing tools and conveying blades not more than 4: 1, preferably not more than 3.5: 1, more preferably not more than 3: 1, most preferably at most 2.5: 1 and in particular maximum 2: 1. The conveyor blades are with its concave surface aligned in the direction of the material discharge. The angle between the Lot on the mixer axis and the tangent to the conveyor blades at the point of blade attachment is preferably between 60 ° and 10 °, preferably between 50 ° and 20 ° and especially between 40 ° and 30 °. Prefers show in this area all conveyor blades the same inclination. The second section of the discharge zone, the the material discharge is directly upstream, preferably has only Mixing tools on, so that also at this point the material flow exclusively caused by nachschiebendes material.

The Residence time of the mixture in the mixer is preferably between 1 Second and 10 minutes, preferably between 4 seconds and 3 minutes, more preferably between 7 and 60 seconds and in particular between 10 and 30 seconds.

One preferred subject of the present invention is a method for producing a particulate Washing or cleaning agent or a component thereof, in which a mixture comprising a granule, a separate solid neutralizing agent and at least one acid be granulated in a mixer, wherein the weight fraction of separate solid neutralizing agent on the total weight of the mixture more than 10 wt .-% is and the weight ratio from separate neutralizer to acid is greater than 2: 1 and a mixer is used with a horizontal axis by the choice of Tools is divided into different zones, the mixer contains at least two non-adjacent zones, in which only mixing tools, however, no conveying tools are included.

Surprisingly was found that when performing of the inventive method below consideration the preferred process parameters produced process end products can be in terms of their bulk density compared to the granules used a difference of less than 100 g / l, preferably less than 85 g / l, preferably less than 70 g / l, more preferably less than 55 g / l, and especially less than 30 g / l.

The Circulating speed of the tools is preferably in suitable mixers from 100 to 500 rpm, preferably from 110 to 450 rpm, preferably from 120 to 400 rpm, more preferably from 130 to 350 rpm, completely particularly preferably from 140 to 300 rpm and in particular from 150 up to 250 rpm. The drive power of the mixer is preferably at 100 to 500 kW, preferably at 150 to 450 kW, particularly preferred at 200 to 400 kW and in particular at 250 to 350 kW.

In a preferred embodiment the method according to the invention becomes a horizontal axis mixer, preferably a Lödige CB Mixer, used in which the tools at rotational speeds from 100 to 500 rpm, preferably from 110 to 450 rpm, preferably from 120 to 400 rpm, more preferably from 130 to 350 rpm, completely particularly preferably from 140 to 300 rpm and in particular from 150 rotate to 250 rpm.

In some embodiments the acid (s) will pass through one liquid inlet introduced into the mixer, but not under pressure in the mixer sprayed. However, because of a fine spraying of the liquid components a more even distribution the acid guaranteed can be, the use of nozzles is preferred.

To the Spray the liquid Components are all known to those skilled in the art for this purpose Devices. The spraying takes place preferably by means of one-component or high-pressure spray nozzles, two-component spray nozzles or Three materials. To the spray with Einstoffsprühdüsen is the application of a high melt pressure (for example 5-15 MPa) required while the spraying in dual-substance spray nozzles with Help a compressed air flow (for example, at 0.15-0.3 MPa) takes place. The spray with Zweistofsprühdüsen is especially with regard to possible clogging of the nozzle cheaper, but more expensive due to the high compressed air consumption. As modern Further development, there are the three-component spray nozzles, which in addition to the compressed air flow for atomization another air distribution system, to prevent clogging and dripping at the nozzle. As part of the method according to the invention the use of two-component spray nozzles, preferably two-component spray nozzles with a fluid hole between 2 and 6 mm, especially between 3 and 5 mm especially prefers.

Of the Drop diameter of the sprayed liquid Component is preferably between 1 and 100 μm, more preferably between 2 and 80 microns, most preferably between 4 and 70 μm and in particular between 8 and 60 μm. The size of the spray angle is preferably between 10 and 50 °, more preferably between 12.5 and 45 °. For the homogeneous and fine distribution of the acid (s) on the solids are preferred nozzles used that a big one spray angle with values between 20 and 50 °, especially preferably 25 and 45 °, and in particular between 30 and 40 °. When using of nozzles with big spray angle can the overlap the spray cone but only be avoided by the nozzles in far apart Positions are operated. Is a nozzle arrangement provided at the nozzles are arranged close to each other, is a small spray angle from 10 to 20 °, especially 12.5 to 17.5 ° preferred. In preferred methods, there is no overlap of individual spray cones, so that it does not dampen the solid material to individual Make and thus the formation of sticky (over-moistened) granules comes.

In the arrangement of the nozzles in the mixer is a uniform distribution of the nozzles in the entry, in the mixing zone and in the first section of the discharge into consideration and a distribution in which the plurality, preferably the entirety of the nozzles in the entry and / or the Mixing zone are arranged. Preferably, however, all nozzles are operated in the entry zone of the mixer to ensure a sufficiently long and intensive mixing of the mixture of separate solid neutralizing agent, granules and acid (s). The positioning of the nozzles is particularly preferred directly in the solids input, so that the neutralizing agent and the granules are wetted with acid during transport into the mixer. The solids feed, in preferred embodiments of the process, is positioned so that the solids fall into the mixer from a higher-level reservoir or a feed above the mixer. Within the solids feed, the nozzles are preferably angled to the falling or flow direction of the solids. The angle between the solder on the mixer axis and the average spraying direction of the nozzles is preferably between 2 and 90 °, particularly preferably between 3.5 and 60 °, more preferably between 5 and 30 ° and in particular between 6.5 and 20 °. Preferably, the nozzles are arranged in blocks formed by rows of staggered nozzles. In the method, preferably 8 to 10, particularly preferably 10 to 16 and in particular more than 16 nozzles are used for spraying the liquid component (s).

at execution the method according to the invention considering the preferred process parameter has surprisingly been found that process end products can be produced, which are characterized by a temporal constant odor effect, that means by a non-decreasing fragrance intensity and distinguish consistent scent image.

One preferred subject of the present invention is a method for producing a particulate Washing or cleaning agent or a component thereof, in which a mixture comprising 60-80 Wt .-% of an anionic surfactant-containing spray-dried powder with a Free water content between 3 and 5 wt .-%, based on the spray-dried Powder, 10 to 30 wt .-% sodium carbonate and 5 to 10 wt .-% alkylbenzenesulfonic acid in one Mixer, preferably in a mixer with horizontal axis, granulated be, with the alkylbenzenesulfonic already in the product entry on the mixture of spray-dried Powder and sodium carbonate is sprayed on and the mixer at least has two non-adjacent zones where only mixing tools, but no conveying tools are included and wherein the quantities of the spray-dried Powder, sodium carbonate and alkylbenzene sulfonic acid on refer to the mixture of these three components.

at Leaving the mixer, the acid (s) are / are in the process end product to at least 70%, preferably at least 80%, more preferably 90% and especially 100% neutralized in front.

It It is particularly preferred that the final process product when leaving of the mixer is present at 100 neutralized. In completely neutralized Powders are no post-reaction and there are no in the powder acidic nests present.

The Final process products can be coated in post-treatment steps, spray, pollinate, granulate and / or with other components to a washing or Mix detergent. Also the direct filling of the Final process products in large volume Container or small portions containing water-soluble or water-insoluble Wrapped in foil are, comes into consideration. Particularly preferred is in the production so-called pouches the combination of process end products or solid agent obtained by post-treatment steps from the process end products were obtained with liquid or gelatinous Means in two-, three- or four-chamber pouches. Also preferred is the Compression of the process end products or agents by post-treatment were obtained from these to washing or cleaning tablets. Surprisingly corresponding tablets have an increased dissolution rate and improved Washing power, especially when removing grease and oil Stains on.

The produced according to the inventive method described above Means contain in addition to the anionic surfactants already described more washing or cleaning-active substances, preferably washing or cleaning-active substances from the group of builders, other surfactants, polymers, bleaches, bleach activators, enzymes, Corrosion inhibitors, disintegration aids, fragrances and Perfume carriers. These preferred ingredients are described in more detail below. As the inventive method both for the production of detergents and cleaners can be used in the following part are both detergent-specific Ingredients, as well as such ingredients, which, for example in dishwashing detergents, but not used in detergents listed. The The following ingredients are within preferred embodiments the method according to the invention in mixture with the acid (s), mixed with the separate solid neutralizing agent and / or the granules to be used or as additional components in the Mixer introduced or used in post-treatment steps.

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

If zeolite-containing granules are to be produced by preferred embodiments of the process, the finely crystalline, synthetic and bound water-containing zeolite A and / or P is preferably suitable for this purpose. As zeolite P zeolite MAP ^® (commercial product from Crosfield) is particularly preferred. However, zeolite X and mixtures of A, X and / or P are also suitable. Commercially available and in the context of the present invention is preferably used, for example, a co-crystallizate of zeolite X and zeolite A (about 80 wt .-% zeolite X), which is sold by the company CONDEA Augusta SpA under the trade name VEGOBOND AX ^® and by the formula n Na 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 and for a kind of "powdering" of a granular mixture, preferably a mixture to be compressed, whereby usually both ways of incorporating the zeolite into the premix are used an average particle size of less than 10 microns (volume distribution, measuring method: Coulter Counter) and preferably contain 18 to 22 wt .-%, in particular 20 to 22 wt .-% of bound water.

Particular preference is given to using crystalline layer-form silicates of the general formula NaMSi _x O ₂ × _{+ 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, in particular 2, 3 or 4, and y is a number from 0 to 33, preferably from 0 to 20. 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. Examples of these silicates are 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 NaMSi _x O _{2x + 1} .yH ₂ O, 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 · 3 H 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 ).

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 in X-ray diffraction experiments do not give sharp X-ray reflections typical of crystalline substances but at best one or more maxima of the scattered X-radiation which are several angstroms in width of the 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 the size of ten to a few hundred nm, with 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 amorphous silicates, compounded amorphous silicates and overdried X-ray amorphous silicates.

in the Within the scope of the present invention, it is preferred that this (s) Silicate (s), preferably alkali metal silicates, particularly preferably crystalline or amorphous alkali disilicates, in the final process products in Amounts of 5 to 60 wt .-%, preferably from 6 to 50 wt .-% and in particular from 7 to 40 wt .-%, each based on the weight of the washing or cleaning agent or component thereof are.

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. Among the variety of commercially available Phosphates have the alkali metal phosphates under special preference of Pentasodium or pentakalium triphosphate (sodium or potassium tripolyphosphate) in the washing and cleaning industry the greatest 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.

Become in the context of the present application phosphates as washing or cleaning active Sub used punching agents in detergents or cleaners, so preferred agents contain this (s) phosphate (s), preferably alkali metal phosphate (s), more preferably pentasodium or Pentakaliumtriphosphat (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, in each case 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. As alkali carrier For example, alkali metal hydroxides, alkali metal carbonates, Alkali metal bicarbonates, alkali metal sesquicarbonates, the mentioned alkali metal silicates, alkali metal silicates, and mixtures of aforementioned substances, wherein for the purposes of this invention preferably the Alkali carbonates, especially sodium carbonate, sodium bicarbonate or sodium sesquicarbonate. Especially preferred For example, a builder system containing a mixture of tripolyphosphate and sodium carbonate. Also particularly preferred is a Builder system containing a mixture of tripolyphosphate and sodium carbonate and sodium disilicate. Because of their compared with other builders low chemical compatibility with the rest Ingredients of detergents or cleaning agents, the alkali metal hydroxides preferably only in small amounts, preferably in amounts below 10 wt .-%, preferably below 6 wt .-%, more preferably below 4 wt .-% and in particular 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 less than 0.5 wt .-% and in particular no alkali metal hydroxides contain.

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 either as a powder with the separate solid neutralizing agent and the granules or as an aqueous solution in Mixture with the acid (s) be used. An incorporation of the polycarboxylates according to the dry neutralization step is conceivable. The content of washing or detergents on (co) polymeric polycarboxylates is preferably 0.5 to 20 wt .-%, in particular 3 to 10 wt .-%.

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

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

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

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

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 syrups with a DE between 20 and 37 as well as so-called yellow dextrins and white dextrins with higher Molar masses in the range 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.

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

Next The anionic surfactants already described above can be prepared by means of the method according to the invention prepared agents contain other surfactants. To the group of surfactants be the nonionic, the anionic, the canonical and the amphoteric surfactants counted.

The acid (s) preferably contain one or more mixed nonionic surfactants in processes according to the invention. As nonionic surfactants, it is possible to use all nonionic surfactants known to the person skilled in the art. Low-foaming nonionic surfactants are used as preferred surfactants. Detergents or cleaning agents with particular preference contain nonionic surfactants from the group of alkoxylated alcohols. 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 moles of 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 stated degrees of ethoxylation represent statistical averages, which may correspond to a particular product of 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 methyl-branched in the 2-position 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. 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.

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 R 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

wherein R is an aliphatic acyl radical having 6 to 22 carbon atoms, R ^{1 is} hydrogen, an alkyl or hydroxyalkyl radical having 1 to 4 carbon atoms and [Z] is a linear or branched polyhydroxyalkyl radical 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 zyklischen Alkylrest oder einen Arylrest mit 2 bis 8 Kohlenstoffatomen und R2 für einen linearen, verzweigten oder zyklischen Alkylrest oder einen Arylrest oder einen Oxy-Alkylrest mit 1 bis 8 Kohlenstoffatomen steht, wobei C_1-4-Alkyl- oder Phenylreste bevorzugt sind und [Z] für einen linearen Polyhydroxyalkylrest steht, dessen Alkylkette mit mindestens zwei Hydroxylgruppen substituiert ist, oder alkoxylierte, vorzugsweise ethoxylierte oder propxylierte Derivate dieses Restes.The group of polyhydroxy fatty acid amides also includes compounds of the formula

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 _1-4 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 radical.

[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 Connections can by reaction with fatty acid methyl esters in the presence of an alkoxide as a catalyst in the desired Polyhydroxyfatty acid amides are transferred.

With Particular preference is furthermore given to using surfactants which have a or more tallow fatty alcohols with 20 to 30 EO in combination with a silicone defoamer contain.

nonionic surfactants from the group of alkoxylated alcohols, particularly preferably from the group of mixed alkoxylated alcohols and in particular from the group of EO-AO-EO-Niotenside, are also with special Preference used.

Prefers surfactants to be used which are solid at room temperature from 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 are also characterized by good foam control out.

Of particular preference are ethoxylated nonionic surfactants selected from C _6-20 monohydroxyalkanols or C _6-20 alkylphenols or C _6-20 fatty alcohols and more than 12 moles, preferably more than 15 moles and especially more than 20 moles of ethylene oxide per mole of alcohol were used.

The specified C chain lengths and degrees of ethoxylation or degrees of alkoxylation of the abovementioned Nonionic surfactants represent statistical averages that are suitable for a specific Product can be a whole or a fractional number. by virtue of the manufacturing process consist of commercial products of the formulas mentioned mostly not from an individual representative, but from mixtures, which is responsible for both the C chain lengths as well as for the degrees of ethoxylation or degrees of alkoxylation averages and resulting in fractional numbers.

Of course, the aforementioned nonionic surfactants not only as individual substances, but also as surfactant mixtures of two, three, four or more surfactants be used. As surfactant mixtures are not mixtures nonionic surfactants referred to in their entirety one of the above general formulas, but rather such mixtures, the two, three, four or more nonionic Containing surfactants by different of the aforementioned general Formulas can be described.

At Place of said surfactants or in conjunction with them may also cationic and / or amphoteric surfactants are used.

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, for example, cationic compounds of the following formulas can be used:

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.

to Care of the textiles and to improve the textile properties like a softer "grip" (avivage) and reduced electrostatic charge (elevated Wearing comfort) soft tissue-like compounds are used. The active ingredients in these formulations are preferably "esterquats", quaternary ammonium compounds with two hydrophobic residues, such as distearyldimethylammonium chloride, which, however, because of its insufficient biodegradability increasingly through quaternary Ammonium compounds is replaced in their hydrophobic residues Ester groups as breaking points for biodegradation included.

Such "ester quats" with improved biodegradability are available, for example, that mixtures of methyldiethanolamine and / or triethanolamine with fatty acids esterified and the reaction products then in a conventional manner quaternized with alkylating agents. Suitable as a finish is dimethylolethyleneurea.

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. In general, detergents and cleaners are non-ionic Polymers also cationic, anionic and amphoteric polymers can be used. These are preferably mixed with the acid (s) to be used, can However, already in the granules, which is preferably a spray-dried Powder is to be included. Another possibility is the Polymers, as well as all other conventional detergent ingredients, to the granules, the separate solid neutralizing agent and the acid (s) to fill in the mixer and to granulate. Also, the introduction of conventional detergent ingredients in a subsequent to the dry neutralization post-treatment step is concerned.

"Cationic Polymers "in the sense The present invention relates to polymers which are a positive charge in the polymer molecule wear. This can be present, for example, in the polymer chain (Alkyl) ammonium moieties or other positively charged groups will be realized. Particularly preferred cationic polymers are derived from the groups of the quaternized cellulose derivatives, the polysiloxanes with quaternary Groups, the cationic guar derivatives, the polymeric dimethyldiallylammonium salts and their copolymers with esters and amides of acrylic acid and methacrylic acid, the copolymers of vinylpyrrolidone with quaternized derivatives the dialkylamino acrylate and methacrylate, the vinylpyrrolidone-methoimidazolinium chloride copolymers, the quaternized polyvinyl alcohols or the INCI names Polyquaternium 2, Polyquaternium 17, Polyquaternium 18 and Polyquaternium 27 indicated polymers.

"Amphoteric Polymers "in the sense of the present invention have besides a positively charged group in the polymer chain also negatively charged groups or On monomer units. These groups may be, for example to carboxylic acids, sulfonic acids or phosphonic acids act.

Preferred detergents or cleaners are characterized in that they contain a polymer a) which has monomer units of the formula R ¹ R ² C =CR ³ R ⁴ in which each R ¹ , R ² , R ³ and R ⁴ independently of one another is selected from hydrogen, derivatized hydroxy group, C _1-30 linear or branched alkyl groups, aryl, aryl-substituted C _1-30 linear or branched alkyl groups, polyalkoyxylated alkyl groups, heteroatomic organic groups having at least one positive charge without charged nitrogen, at least one quaternized N- Atom or at least one amino group having a positive charge in the partial range of the pH range of 2 to 11, or salts thereof, with the proviso that at least one R ¹ , R ² , R ³ , R ^{4 group is} a heteroatomic organic group having at least one positive charge without charged nitrogen, at least one quaternized N atom or at least one amino group with a positive charge.

washing or detergents contain the aforementioned cationic and / or amphoteric polymers, preferably in amounts between 0.01 and 10 % By weight, based in each case on the total weight of the washing or cleaning agent. In the context of the present application, however, such washing or detergents in which the weight fraction of the cationic and / or amphoteric polymers between 0.01 and 8 wt .-%, preferably between 0.01 and 6 wt .-%, preferably between 0.01 and 4 wt .-%.

The bleaching agents are a particularly preferred washing or cleaning substance. 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.

Farther can Also bleach from the group of organic bleach used become. Typical organic bleaches are the diacyl peroxides, such as. Dibenzoyl. Other typical organic bleaches are the peroxyacids, Examples being the alkyl peroxyacids and the aryl peroxyacids become. Preferred representatives are (a) the peroxybenzoic acid and their ring-substituted derivatives, such as alkylperoxybenzoic acids, but also peroxy-α-naphthoic acid and Magnesium monoperphthalate, (b) the aliphatic or substituted aliphatic peroxyacids, like peroxylauric acid, Peroxystearic acid, ε-phthalimidoperoxycaproic acid [phthaliminoperoxyhexanoic acid (PAP)], o-Carboxybenzamidoperoxycapronsäure, N-nonenylamidoperadipic and N-nonylamido-succinates, and (c) aliphatic and araliphatic peroxydicarboxylic acids, such as 1,12-diperoxycarboxylic acid, 1,9-diperoxyazelaic acid, diperocysebacic acid, diperoxybrassic acid, the diperoxyphthalic acids, 2-decyldiperoxybutane-1,4-dioic acid, N, N-Terephthaloyl-di (6-aminopercapronate) can be used.

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

According to the invention Washing or cleaning agents which are 1 to 35 wt .-%, preferably 2.5 to 30 wt .-%, particularly preferably 3.5 to 20 wt .-% and in particular 5 to 15 wt .-% bleach, preferably sodium percarbonate.

Of the Active oxygen content of detergents or cleaners is, respectively based on the total weight of the agent, preferably between 0.4 and 10 wt .-%, particularly preferably between 0.5 and 8 wt .-% and in particular between 0.6 and 5 wt .-%. Especially preferred Means have an active oxygen content above 0.3 wt .-%, preferably above 0.7 wt .-%, more preferably above 0.8 wt .-% and in particular above 1.0% by weight.

Bleach activators are used in laundry detergents or cleaners, for example, to achieve an improved bleaching effect when cleaned at temperatures of 60 ° C and below. As bleach activators, it is possible to use compounds which, under perhydrolysis conditions, give aliphatic peroxycarboxylic acids having preferably 1 to 10 C atoms, in particular 2 to 4 C atoms, and / or optionally substituted perbenzoic acid. Suitable substances are those which carry O- and / or N-acyl groups of the stated 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, in particular tetraacetylglycoluril (TAGU), N-acylimides, in particular N-nonanoylsuccinimide (NOSI), acylated phenolsulfonates, in particular n -Nonanoyl or Isononanloxybenzolsulfonat (n- or iso-NOBS), carboxylic anhydrides, in particular phthalic anhydride, acylated polyhydric alcohols, in particular triacetin, ethylene glycol diacetate, 2,5-diacetoxy-2,5-dihydrofuran, n-methyl-morpholinium acetonitrile-methyl sulfate (MMA) and acetylated sorbitol and mannitol or mixtures thereof (SORMAN), acylated sugar derivatives, in particular pentaacetylglucose (PAG), pentaacetylfruktose, tetraacetylxylose and octaacetyllactose as well as acetylated, optionally N-alkylated glucamine and gluconolactone, and / or N-acylated lactams, for example N -Benzoylcaprolactam. Hydrophilic substituted acyl acetals and acyl lactams are also preferably used. Combinations of conventional bleach activators can also be used.

in der R¹ für -N, -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} -N, -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 (CN₃)₃N⁽⁺⁾CH₂-CN X^-, (CH₃CH₂)₃N⁽⁺⁾CH₂-CN X^-, (CH₃CH₂CH₂)₃N⁽⁺⁾CH₂-CN X^-, (CH₃CH(CH₃))₃N⁽⁺⁾CH₂-CN X^-, oder (HO-CH₂-CH₃)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, wherein preferably R ⁵ = R ⁶ = -CH ₃ and in particular R ⁴ = R ⁵ = R ⁶ = -CH ₃ and compounds of the formulas (CN 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 ₃ ) 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.

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.

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.

Bleach-enhancing transition metal complexes, in particular having 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 (ammine) Complexes, the cobalt (acetate) complexes, the cobalt (carbonyl) complexes, the chlorides of cobalt or manganese, manganese sulfate are used in conventional amounts, preferably in an amount up to 5 wt .-%, in particular from 0.0025 wt .-% to 1 wt .-% and particularly preferably from 0.01 wt .-% to 0.25 wt .-%, each based on the total weight of bleach activator-containing agents. But in special cases, more bleach activator can be used.

To increase the washing or cleaning performance of detergents or cleaners enzymes can be 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. Detergents or cleaning agents contain enzymes preferably in total amounts of 1 × 10 ^-6 to 5 wt .-% 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 include 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 proteases, but not the subtilases, but rather the subtilisins in the strict sense 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 sold by the company Meito Sangyo KK, Japan under the names Lipase MY-30 ^®, Lipase To mention OF ^® and Lipase PL ^® marketed enzymes, and 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), pectin esterases, pectate lyases, xyloglucanases (= xylanases), pullulanases and β-glucanases. Suitable mannanases are available, for example under the name Gamanase ^® and Pektinex AR ^® from Novozymes, under the name Rohapec ^® B1 from AB Enzymes and under the name Pyrolase® ^® from Diversa Corp., San Diego, CA, United States. The obtained from B. subtilis β-glucanase is available under the name Cereflo ^® from Novozymes.

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, making one individual granules has several enzyme activities.

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. Detergents or cleaners can contain stabilizers for this purpose; the provision of such funds represents a preferred embodiment of the present invention.

One group of stabilizers are reversible protease inhibitors. Frequently, benzamidine hydrochloride, borax, boric acids, boronic acids or their salts or esters are used, including in particular derivatives with aromatic groups, such as ortho-substituted, meta-substituted and para-substituted phenylboronic acids, or their salts or esters. As peptidic protease inhibitors are, inter alia, ovomucoid and leupeptin to mention; An additional option is the formation of fusion proteins from Pro teases and peptide inhibitors.

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

low aliphatic alcohols, but especially polyols, such as Glycerine, ethylene glycol, propylene glycol or sorbitol are other 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. Alkyl polyglycosides can stabilize the enzymatic components 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 through the 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 wt .-% and in particular from 0.4 to 4 wt .-%, each based on the total enzyme-containing agents used.

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

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 obtained 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.

preferred Disintegration aid, preferably a disintegration aid based on cellulose, preferably in granular, cogranulated or compacted form, are in disintegrating agents in amounts of from 0.5 to 10% by weight, preferably from 3 to 7% by weight and in particular from 4 to 6 wt .-%, each based on the total weight of the disintegrant-containing agent.

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 both in the detergents and cleaners used effervescent system on the basis of economic as well as 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 you do not have to the respective 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 hydrogen carbonate and 1 to 15, preferably 2 to 12 wt .-% and in particular from 3 to 10% by weight of an acidifying agent, respectively based on the 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. Preferably, however, organic Acidifizierungsmittel be used, wherein the citric acid is a particularly preferred acidifying agent. However, it is also possible in particular to use the other solid mono-, oligo- and polycarboxylic acids. Tartaric acid, succinic acid, malonic acid, adipic acid, maleic acid, fumaric acid, oxalic acid and polyacrylic acid are again preferred from this group. 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 Acidifizierungsmittel in effervescent system from the group of organic Di-, tri- and oligocarboxylic acids or mixtures.

When Perfume oils or Fragrances can in the context of the present invention, individual fragrance compounds, e.g. the synthetic products of the ester, ether, aldehyde, Ketones, alcohols and hydrocarbons are used. fragrance compounds the type of esters are e.g. Benzyl acetate, phenoxyethyl isobutyrate, p-tert-butylcyclohexyl acetate, linalyl acetate, dimethylbenzyl-carbinyl acetate, Phenylethyl acetate, linalyl benzoate, benzyl formate, ethyl methyl phenyl glycinate, Allyl cyclohexyl propionate, styrallyl propionate and benzyl salicylate. Count to the Ethern for example, 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 ionone, 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 Contain fragrance mixtures, as they are accessible from plant sources, e.g. Pine, citrus, jasmine, patchouly, rose or ylang-ylang oil. Also Muscat, sage, chamomile, clove, lemon balm, mint, cinnamon, lime, juniper, vetiver, olibanum, galbanum and labdanum oils are also suitable Orange blossom oil, neroliol, Orange peel oil and Sandalwood oil.

The general description of the applicable perfumes (see above) provides in general the different substance classes of fragrances In order to be perceptible, a fragrance must be volatile, besides the nature of the functional groups and the structure the molecular weight of the chemical compound also plays an important role plays. So most perfumes have molecular weights up to about 200 Dalton, while Molar masses of 300 daltons and above rather an exception. Due to the different volatility changed by fragrances the smell of a compound of several fragrances perfumes or perfume during vaporizing, whereby the odor impressions in "top note", "middle note" body) and "base note" (end note or dry divided out). Because the smell perception to a large extent also on the smell intensity based, is the top note of a perfume or

fragrance not alone from volatile Connections while the base note for the most part from less volatile, i.e. adherent fragrances. In the composition of perfumes can more easily volatile fragrances For example, be bound to certain fixatives, whereby her too fast evaporation is prevented. In the following classification the fragrances in "lighter volatile or "adherent" fragrances So over the smell impression and about it, whether the corresponding perfume perceived as a head or middle note nothing is said.

Adhesion-resistant fragrances which can be used in the context of the present invention are, for example, the essential oils such as angelica root oil, aniseed oil, arnica blossom oil, basil oil, bay oil, bergamot oil, Champacablütenöl, Edel fir oil, Edeltannenzapfen oil, Elemiöl, eucalyptus oil, fennel oil, spruce needle oil, galbanum oil, geranium oil, ginger grass oil, Guaiac wood oil, gurdy balm oil, helichrysum oil, ho oil, ginger oil, iris oil, cajeput oil, calamus oil, camomile oil, camphor oil, kanga oil, cardamom oil, cassia oil, pine oil, copaiba balsam, coriander oil, spearmint oil, caraway oil, cumin oil, lavender oil, lemongrass oil, lime oil, tangerine oil, lemon balm oil, Musk Grain Oil, Myrrh Oil, Clove Oil, Neroli Oil, Niaouli Oil, Olibanum Oil, Orange Oil, Origanum Oil, Palmarosa Oil, Patchouli Oil, Peru Balsam Oil, Petitgrain Oil, Pepper Oil, Peppermint Oil, Pimento Oil, Pine Oil, Rose Oil, Rosemary Oil, Sandalwood Oil, Celery Oil, Spik Oil, Star Aniseed Oil, Turpentine Oil, Thuja Oil, Thyme oil, Verbe oil, vetiver oil, juniper berry oil, wormwood oil, wintergreen oil, ylang-ylang oil, hyssop oil, cinnamon oil, cinnamon oil, lemon oil, lemon oil and cypress oil. But also the higher-boiling or solid fragrances of natural or synthetic origin can be used in the context of the present invention as adherent fragrances or fragrance mixtures, ie fragrances. These compounds include the compounds listed below and mixtures thereof: ambrettolide, α-amylcinnamaldehyde, anethole, anisaldehyde, anisalcohol, anisole, anthranil methyl ester, acetophenone, benzylacetone, benzaldehyde, ethyl benzoate, benzophenone, benzyl alcohol, benzyl acetate, benzyl benzoate, benzyl formate, benzyl valerate, borneol, bornyl acetate, α-bromostyrene, n-decyl aldehyde, n-dodecyl aldehyde, eugenol, eugenol methyl ether, eucalyptol, farnesol, fenchone, fenchyl acetate, Geranyl acetate, geranyl formate, heliotropin, heptincarboxylic acid methyl ester, heptaldehyde, hydroquinone dimethyl ether, hydroxycinnamaldehyde, hydroxycinnamyl alcohol, indole, iron, isoeugenol, isoeugenol methyl ether, isosafrole, jasmon, camphor, karvakrol, karvon, p-cresol methyl ether, coumarin, p-methoxyacetophenone, methyl n- amyl ketone, methyl methylenedhranilate, p-methylacetophenone, methylchavikole, p-methylquinoline, methyl-β-naphthyl ketone, methyl-n-nonylacetaldehyde, methyl n-nonyl ketone, muscone, β-naphthol ethyl ether, β-naphthol methyl ether, nerol, nitrobenzene, n-nonylaldehyde, Nonyl alcohol, n-octylaldehyde, p-oxy-acetophenone, pentadecanolide, β-phenylethyl alcohol, phenylacetaldehyde Dimethyl acetal, phenylacetic acid, pulegone, safrole, isoamyl salicylate, methyl salicylate, hexyl salicylate, cyclohexyl salicylate, santalol, skatole, terpineol, thymine, thymol, γ-undelactone, vaniline, veratrumaldehyde, cinnamaldehyde, cinnamyl alcohol, cinnamic acid, ethyl cinnamate, cinnamic acid cinnamate. The more volatile fragrances include in particular the lower-boiling fragrances of natural or synthetic origin, which can be used alone or in mixtures. Examples of more readily volatile fragrances are alkyl isothiocyanates (alkyl mustard oils), butanedione, limonene, linalool, linayl acetate and propionate, menthol, menthone, methyl-n-heptenone, phellandrene, phenylacetaldehyde, terpinyl acetate, citral, citronellal.

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.

When choosing the colorant, it must be taken into account that in the case of textile detergents, the colorants do not have too high an affinity for textile surfaces and, in particular, for synthetic fibers, whereas in the case of detergents an excessive affinity for glass, ceramic or plasticware must be avoided. 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 at some 10 ³ to 10 wt .-% ^-4.

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 (GAS 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 (GAS 61814-57-1, CI Acidyellow 218) and / or Sandolan ^® Blue (CI Acid Blue 182, CAS 12219-26-0) is used.

In addition to so far in detail described components can the detergents and cleaners contain other ingredients, which the application and / or aesthetic properties of this Improve funds further. Preferred agents include one or several substances from the group of electrolytes, pH adjusters, fluorescers, 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, Swelling and anti-slip agents as well as 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 the halides and sulfates. From a manufacturing point of view, the use of NaCl or MgCl ₂ in the washing or cleaning agents is preferred.

Around the pH of detergents or cleaners 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.

Suitable foam inhibitors are, inter alia, soaps, oils, fats, paraffins or silicone oils, which may optionally be applied to support materials. Suitable carrier materials are, for example, inorganic salts such as carbonates or sulfates, cellulose derivatives or silicates and mixtures of the abovementioned materials. In the context of the present application preferred agents include paraffins, preferably unbranched paraffins (n-paraffins) and / or silicones, preferably linear-polymeric silicones, which are constructed according to the scheme (R ₂ SiO) x and are also referred to as silicone oils. These silicone oils usually are clear, colorless, neutral, odorless, hydrophobic liquids having a molecular weight between 1,000 and 150,000, and viscosities between 10 and 1,000,000 mPa.s.

suitable Anti redeposition agent, also referred to as soil repellents are, for example, nonionic cellulose ethers such as methyl cellulose and methylhydroxypropylcellulose with a proportion of methoxy groups from 15 to 30% by weight and of hydroxypropyl groups from 1 to 15% by weight, in each case 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 nonionic modified derivatives of these. Especially preferred of these are the sulfonated derivatives of phthalic and terephthalic acid polymers.

optical Brighteners (so-called "whiteners") can Detergents or cleaners are added to graying and to eliminate yellowing of the treated textiles. These Substances attract to the fiber and cause a whitening and feigned Bleaching action by turning invisible ultraviolet radiation into visible length wavy 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 bending, bending, pressing and squeezing are sensitive to the grain direction, synthetic crease inhibitors be used. 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.

Phobic and impregnation processes are used to furnish textiles with substances that prevent the deposition of dirt or facilitate its leaching ability. Preferred repellents and impregnating agents are perfluorinated fatty acids, also in the form of their aluminum u. Zirconium salts, organic silicates, silicones, polyacrylic acid esters with perfluorinated alcohol component or with perfluorinated acyl or sulfonyl radical coupled, polymerizable compounds. Antistatic agents may also be included. The dirt Pointing equipment with repellents and impregnants is often classified as an easy-care finish. The penetration of the impregnating agent in the form of solutions or emulsions of the active substances in question can be facilitated by adding wetting agents which reduce the surface tension. A further field of application of repellents and impregnating agents is the water-repellent finish of textiles, tents, tarpaulins, leather, etc., in which, in contrast to waterproofing, the fabric pores are not closed, so the fabric remains breathable (hydrophobing). The water repellents used for hydrophobizing coat textiles, leather, paper, wood, etc. with a very thin layer of hydrophobic groups, such as longer alkyl chains or siloxane groups. Suitable water repellents are, for example, paraffins, waxes, metal soaps, etc. with additions of aluminum or zirconium salts, quaternary ammonium compounds with long-chain alkyl radicals, urea derivatives, fatty acid-modified melamine resins, chromium complex salts, silicones, tin-organic compounds and glutaric dialdehyde and perfluorinated compounds. The hydrophobized materials do not feel greasy; nevertheless, similar to greasy substances, water droplets emit from them without moistening. For example, silicone-impregnated textiles have a soft feel and are water and dirt repellent; Stains from ink, wine, fruit juices and the like are easier to remove.

to fight of microorganisms can antimicrobial agents are used. This is different depending on the 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 also completely on these compounds can be dispensed with.

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.

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

to Improvement of water absorbency, rewettability treated textiles and to facilitate ironing treated textiles can Silicone derivatives are used. These additionally improve that rinse behavior of detergents or cleaners by their foam-inhibiting Properties. Preferred silicone derivatives are their foam-inhibiting Properties. Preferred silicone derivatives are, for example, polydialkyl or alkylaryl siloxanes, in which the alkyl groups have one to five carbon atoms and completely or partially fluorinated. Preferred silicones are polydimethylsiloxanes, which may optionally be derivatized and then amino-functional or are quaternized or have Si-OH, Si-H and / or Si-Cl bonds. Further preferred silicones are the polyalkylene oxide-modified Polysiloxanes, ie polysiloxanes, which are, for example, polyethylene glycols and the polyalkylene oxide-modified dimetylpolysiloxanes.

Finally, according to the invention, UV absorbers which are applied to the treated textiles and the light resistance improve the fibers. Compounds that have these desired properties are, for example, by radiationless deactivation effective compounds and derivatives of benzophenone with substituents in 2- and / or 4-position. Furthermore, substituted benzotriazoles, in the 3-position phenyl-substituted Acrylates (cinnamic acid derivatives), optionally with cyano groups in the 2-position, salicylates, organic Ni complexes as well Natural substances such as umbelliferone and the body's own urocanic acid are suitable.

Protein hydrolyzates are due to their fiber-care effect further in the context of the present invention preferred active substances from the field of detergents and cleaners. Protein hydrolysates are product mixtures obtained by acid, alkaline or enzymatically catalyzed degradation of proteins (proteins). According to the invention, protein hydrolysates can be used both in plants and in animals of origin. Animal protein hydrolysates are, for example, elastin, collagen, keratin, silk and milk protein protein hydrolysates, which may also be present in the form of salts. Preferred according to the invention is the use of protein hydrolysates of plant origin, for example soybean, almond, rice, pea, potato and wheat protein hydrolysates. Although the use of the protein hydrolysates is preferred as such, amino acid mixtures or individual amino acids obtained otherwise, such as, for example, arginine, lysine, histidine or pyrroglutamic acid, may also be used in their place. Also possible is the use of derivatives of protein hydrolysates, for example in the form of their fatty acid condensation products.

Claims (17)

A process for the preparation of a particulate detergent or a component thereof in which a mixture comprising granules, a separate solid neutralizing agent and at least one acid are granulated in a mixer, characterized in that the proportion by weight of the separate solid neutralizing agent in the total weight of the Mixture is more than 10 wt .-% and the weight ratio of separate neutralizing agent to acid is greater than 2: 1. Method according to claim 1, characterized in that the proportion of the separate solid neutralizing agent in the total weight of the mixture of granules, separate solid neutralizing agent and acid more than 13 wt .-%, more preferably more than 16 wt .-% and in particular more than 19 wt .-% is. Method according to one of claims 1 or 2, characterized that the weight ratio of Separate solid neutralizing agent to acid is greater than 2.2: 1 and in particular is larger as 2.6: 1. Method according to one of claims 1 to 3, characterized that the weight ratio between Granules and separate solid neutralizing agent more than 1: 1, preferably more than 2: 1 and in particular more than 3: 1. Method according to one of claims 1 to 4, characterized that the proportion by weight of the granules used in the mixture of granules, separate solid neutralizing agent and acid (s) 30 to 90 wt .-%, preferably 45 to 85 wt .-% and in particular 60 to 80 Wt .-% is. Method according to one of claims 1 to 5, characterized that in the mixer 35 to 90 wt .-%, preferably 50 to 85 wt .-% and in particular 65 to 80 wt .-% of the granules, 5 to 60 wt .-%, preferably 10 to 45 wt .-% and in particular 15 to 30 wt .-% of the separate solid neutralizing agent and 1 to 30 wt .-%, preferably 3 to 20 wt .-% and in particular 5 to 10 wt .-% of the acid (s) are granulated. Method according to one of claims 1 to 6, characterized that as a separate solid neutralizing agent alkali metal salts, preferably alkali metal carbonates and in particular sodium carbonate is used. Method according to one of claims 1 to 7, characterized that the separate solid neutralizing agent has a fluidity of at least 40%, preferably at least 50%, more preferably at least 60% and in particular of at least 70% compared to standard sand having. Method according to one of claims 1 to 8, characterized that the acid (s) are selected from the group of anionic surfactant acids, phosphonic, Carboxylic acids, sulfonic acids and acrylic acids, preferably the group of anionic surfactant acids. Method according to one of claims 1 to 9, characterized that as granules a spray-dried Powder with a water content between 0.5 and 10 wt .-%, preferably between 1 and 9% by weight, preferably between 1.5 and 8% by weight, especially preferably between 2 and 7 wt .-%, most preferably between 2.5 and 6 wt .-% and in particular between 3 and 5 wt .-%, based on the spray dried Powder is used. Method according to one of claims 1 to 10, characterized that the granules have a flowability of at least 40%, preferably at least 50%, more preferably at least 60% and in particular of at least 70% in comparison to standard sand. Method according to one of claims 1 to 11, characterized that the mixer with a drive power of 100 to 500 kW, preferably from 150 to 450 kW, more preferably from 200 to 400 kW and in particular from 250 to 350 kW is operated. Method according to one of claims 1 to 12, characterized that the speed of rotation of the tools in the mixer of 100 to 500 rpm, preferably from 110 to 450 rpm, preferably from 120 to 400 rpm, more preferably from 130 to 350 rpm, especially preferably from 140 to 300 rpm and in particular from 150 to 250 rpm is. Method according to one of claims 1 to 13, characterized that the residence time of the mixture in the mixer between 1 second and 10 minutes, preferably between 4 seconds and 3 minutes, especially preferably between 7 and 60 seconds and especially between 10 and 30 seconds. Method according to one of claims 1 to 14, characterized that the mixture of used granules, separate solid neutralizing agent and acid (s) less than 15% by weight, preferably less than 10% by weight, preferably less than 5 wt .-%, more preferably less than 2 wt .-%, completely more preferably less than 1% by weight and in particular no aluminosilicate contains. Method according to one of claims 1 to 15, characterized that the obtained particles have flowabilities between 50 and 100 %, preferably between 55 and 97.5%, preferably between 60 and 95 %, more preferably between 65 and 92.5% and especially between 70% and 90%, compared to the flowability of standard test sand. Method according to one of claims 1 to 16, characterized that the difference in bulk weights of the final process product and the granules used less than 100 g / l, preferably less than 85 g / l, preferably less than 70 g / l, more preferably less than 55 g / l, and especially less than 30 g / l.