EP1366142B1 - Washing and/or cleaning agents - Google Patents

Abstract

The invention relates to a method for washing textiles using surfactants, enzymes and optionally other usual components. The invention is characterized in that the surfactants and optionally the enzymes which are selected from amylase, lipase and cellulase are released in the washing liquor after a time t1 = (to to 1 min.) in an amount of from 80 to 100 % by weight, based on the amount used, the enzymes selected from proteases are released after a time t2 = (to + 5 to 10 min.) in an amount of from 60 to 100 % by weight, based on the amount used, and the alkalization agents are released after a time t3 = (to + 5 to 10 min.) in an amount of from 80 to 100 % by weight, based on the amount used, with to being the onset of water feed. The inventive method makes it possible to avoid interactions of the individual components and modifications of soilings by prematurely released components by specific and defined release kinetics of individual components, thereby improving washing results.

Description

The present invention relates to a process for washing textile fabrics using surfactants, enzymes and optionally other conventional components and a detergent and / or cleaning agent containing surfactants, enzymes and optionally other conventional components.

The controlled release of individual detergent components at certain times of the washing process is advantageous from an economic and ecological point of view and accordingly the subject of intensive research work. It plays an important role in the order in which the stains come into contact with the individual ingredients, but also the interaction of individual ingredients is of importance, here in particular the interaction of bleaching and enzymatic cleaning is to be considered.

Many papers address the problem of timing separation of bleaching and enzymatic purification, as the bleaching agents reduce enzyme performance. In principle, two ways are conceivable. Delayed release of the bleach, so that the enzymatic purification is complete before the bleaches are released in the wash liquor, or delayed release of the enzymes when the bleaching process is already nearly completed. A further advantage resulting from the coating of the enzymes or bleaches is the increased storage stability, as uncoated enzymes and bleaches are rapidly destroyed on prolonged storage, especially in the presence of moisture, and the detergent compositions thus lose their detergency.

For the coating of the detergent ingredients, numerous means are available. Here, depending on the agent, the most diverse factors such as the temperature, the pH, the dissolution kinetics or the hydrolysis of the shell material can be used for release. A melt-coating, which makes the sheath permeable only from a certain temperature is difficult to realize because of today's preferred low washing temperatures, since at low Softening problems such as lumps occur. Covers that hydrolyze by mere moisture also have disadvantages in terms of storage stability of the agents. It must therefore be searched for a wrapping material that is soluble on the one hand under certain conditions in the wash liquor quickly and without affecting the washing process, but on the other hand is so stable that storage is easily possible.

Washing and bleaching compositions containing a hydrogen peroxide source and a peroxyacid bleach precursor (bleach activator) and in the wash liquor provide an initial pH in alkaline (pH 10-11), as well as the delayed release of acid into the wash liquor, to a lowered pH to get into the fleet, are described in the prior art and, for example in the European Patent Applications EP-A-0 290 081 (Unilever ) and EP-A-0 396 287 (Clorox ) or EP 0 651 053 (P & G).

Delayed release of individual ingredients in bleach-containing detergent compositions is mentioned in a number of patents. The international patent applications WO95 / 28454 (Procter & Gamble) as well as the series of WO95 / 28464 to WO95 / 28469 (all Procter & Gamble) and the WO95 / 28473 (Procter & Gamble) disclose bleach-containing detergent compositions containing a hydrogen peroxide precursor and a peroxyacid precursor, wherein the delivery of the peroxyacid is controlled so that 50% of the peroxyacid concentration (so-called T50 test) is reached between 180 and 480 seconds. The controlled release of the constituents is achieved by coating individual constituents, defined particle sizes, compaction and mechanical or manual addition. In the individual applications vary the respective coated ingredients: So is in the WO95 / 28464 delays the delivery of peracid to the delivery of a complexing agent in which WO95 / 28465 the delivery of the peracid is delayed from the delivery of a builder and in the WO95 / 28467 An enzyme is released before the delivery of the peracid. The WO95 / 28466 describes the delayed release of an enzyme compared to the release of a surfactant and the W095128468 respectively. WO95 / 28469 describe detergent compositions, in which the delivery of an enzyme to the delivery of a complexing agent for heavy metal ions or against a water-soluble builder is delayed.

In the DE 197 04 634 A1 discloses a washing process for washing textile fabrics, wherein the pH of the wash liquor after dissolution of the composition is below 8 and gradually increases to more than 8.5 as the wash proceeds by dissolution of a coated alkalizer, resulting in the release of a specially coated ingredient and a delayed effect of this ingredient allows. Examples of alkalizing agents include bleaching agents, such as sodium percarbonate, which may be coated with a coating material which dissolves slowly in water, regardless of the pH, while a bleach activator, preferably tetraacetylethylenediamine (TAED), is used as the specially coated ingredient.

WO-A2-02 / 06431 discloses a washing method and a detergent comprising a plurality of phases contained in compartments in a dimensionally stable hollow body comprising a detergent portion. The water-solubility of the walls / compartmentation devices surrounding the phases may be adjusted so that 5 to 10 minutes after each compartment is opened until the contents of the next compartment are released.

DE 198 56 213 discloses a laundry detergent and cleaning product molded article of compressed particulate material comprising a core and a shell enclosing this core, wherein the core consists of at least two phases. The solubility of individual shaped body areas or the entire point tablet can be influenced by components and / or compounds for solubility acceleration or solubility delaying.

When developing new detergents and / or cleaners for textiles, it should also be borne in mind that modern textiles are often washed only at low temperatures, usually up to 40 ° C, because of the sensitivity of the textiles themselves or the colors. At low temperatures, in particular, the bleachable stains and the enzymatically removable stains, such as blood; special requirements for detergents and / or cleaning agents.

Another problem is that the interaction of individual ingredients with each other can lead to a reduction of their activity, for example, bleaching agents and alkalizing agents can reduce the activity of enzymes such as protease.

It is also known that the removal of enzymatic soils, such as blood, is made more difficult when these soils have come into contact with bleaches before the enzymes can develop their activity.

It is an object of the present invention to develop a washing and / or cleaning agent which makes it possible, during the washing process, through the targeted and defined release kinetics of individual ingredients, in particular bleach, so that interactions of the individual ingredients and changes in the soils due to premature release Ingredients can be avoided and thereby improve the washing performance can be achieved. The improvement of the washing performance should be achieved especially at low washing temperatures.

The present invention is a process for washing textile fabrics using surfactant (s), enzyme (s), alkalizing agent (s) and optionally other conventional components, which is characterized in that
the surfactants and optionally enzymes selected from amylase, lipase and cellulase, in the wash liquor after a time t ₁ = (t _o to 1 min.) In an amount of 80 to 100 wt .-%, based on the amount of surfactant and possibly enzyme,
the enzymes selected from proteases after a time t ₂ = (t _o + 5 to 10 min.) In an amount of 60 to 100 wt .-%, based on the amount of enzyme used, and
Alkalizing agent after a time t ₃ = (t _o + 5 to 10 min.) Are released in an amount of 80 to 100 wt .-%, based on the amount of alkalizing agent used, where t _{o is} the beginning of the water feed.

Surprisingly, it has been found that the performance of detergents and / or cleaners can be improved, especially at low temperatures and both enzymatic and bleachable stains, by the fact that the agents contain enzymes and alkalizing agents and optionally bleach, each at a defined time the water supply and released over a defined period in the wash liquor, so that these ingredients can unfold their full activity without mutual interactions.

It has proved to be particularly suitable if in a phase I of the washing process first surfactants or a partial amount thereof and the enzymes are released. Preferably, surfactants and enzymes selected from amylase, lipase and / or cellulase are initially released (phase I). In a phase II, the release of the enzymes is selected from the proteases and alkalizing agent, wherein the proteases preferably after a time t ₂ = (t ₀ + 5 to 10 minutes) in an amount of 60 to 100 wt .-%, based on the amount of proteases used, and alkalizing preferably after a time t ₃ = (t ₀ + 5 to 10 minutes), during this period, in particular an amount of 80 to 100 wt .-%, based on the amount of alkalizing agent released become.

By adding the alkalizing agent, the pH of the washing liquor is shifted from the neutral to the alkaline range. It has proven to be particularly advantageous to release the bleaching components only when the wash liquor has a pH in this range, since the bleaching components unfold their full activity at a pH between 9 and 10. The bleaching components are preferably liberated in a phase III at a time t ₄ = (t ₀ + 10 to 20 minutes). During this period, preferably from 80 to 100 wt .-%, based on the amount of bleaching components used, released. Since bleaching agent can impair the activity of protease, the release of bleach should preferably take place only when 90% by weight of the protease (s) have already been released, more preferably the release of protease is complete and it is already bound to the substrate.

In a further possible embodiment of the present invention, in a phase IV so-called aftertreatment agents, such as components for laundry aftertreatment, such as fabric softening components, soil repellents, optical brighteners, conditioners, ironing aids or fragrances, or in the case of dishwashing detergents, rinse aid surfactants, fragrances, optionally silver protectants ect. , released. The release of these components preferably takes place only in a rinse cycle after the main wash cycle, preferably in the last rinse cycle.

The washing and / or cleaning agent according to the invention is preferably used in mechanical processes. The machine textile washing in a common European household washing machine usually takes 40 to 60 minutes at 60 ° C and 30 to 60 minutes at 30 ° C or 40 ° C. Dishwashing in a standard household dishwasher at 55 ° C or 65 ° C usually takes 20 to 60 minutes. The individual ingredients of the washing and cleaning agents according to the invention are released with a time delay, wherein the periods during which the release of the components takes place can also overlap. As already mentioned, it is preferred if the release of protease and bleach intersects only slightly, and more preferably these components are not released simultaneously.

Another object of the present invention is accordingly a washing and / or cleaning agent containing surfactant (s), enzyme (s), alkalizing agent and optionally further conventional ingredients, which is characterized in that the surfactants and optionally enzymes selected from amylase, Lipase and cellulase, in the wash liquor after a time t ₁ = (t _o to 1 min.) In an amount of 80 to 100 wt.%, Based on the amount of surfactant and optionally enzyme, the enzymes selected from proteases after a Time t ₂ = (t _o + 5 to 10 min.) In an amount of 60 to 100 wt.%, Based on the amount of enzyme used, and
Alkalizing agent after a time t ₃ = (t _o + 5 to 10 min.) Are released in an amount of 80 to 100 wt.%, Based on the amount of alkalizing agent used, where t _{o is} the beginning of the water supply and the means in Form of a multiphase molding is present.

The individual ingredients are described below.

From an application point of view, it is particularly preferred if the agent according to the invention is realized in a single product, so that the users only have to give a single product into the corresponding machine. According to the invention, the agents in the form of so-called moldings, in the state of Technique also referred to as tablets, made-up. According to the invention, the shaped bodies have several phases. For the purposes of the present invention, "phases" are understood to mean partial regions of the shaped bodies. These subregions can be either successive or juxtaposed areas. In one possible embodiment, the phases are arranged as ringlets. It is also possible that a phase forms a shaped body which has a trough and the second phase is inserted or glued in as solid in this trough.

The release of the individual ingredients at times t ₁ and t ₂ and optionally t ₃ and t ₄ is preferably adjusted by the different solubility of the different phases containing the individual ingredients.

1. a) Verpressen von festen Komponenten, wobei die Löslichkeit durch den Pressdruck eingestellt wird und ggf. durch Zusatz von Bindemitteln.
2. b) Beschichten einer oder mehrerer Phasen mit einer die Löslichkeit retardierenden Substanz, wobei die Löslichkeit durch die Art der Beschichtung und die Schichtdicke eingestellt werden kann,
3. c) Zusatz von Bindemittel(n), wobei, wenn alle Phasen Bindemittel enthalten, die Löslichkeit durch den unterschiedlichen Gehalt an Bindemittel eingestellt werden kann
4. d) Zusatz von Desintegrationsmittel(n) (Sprengmitteln), wobei, wenn alle Phasen Desintegrationsmittel enthalten, die Löslichkeit durch den unterschiedlichen Gehalt eingestellt werden kann.

The setting of the solubility can be done for example by

1. a) pressing solid components, wherein the solubility is adjusted by the pressing pressure and possibly by the addition of binders.
2. b) coating one or more phases with a solubility-retarding substance, wherein the solubility can be adjusted by the type of coating and the layer thickness,
3. c) Addition of binder (s), wherein, if all phases contain binders, the solubility can be adjusted by the different content of binder
4. d) Addition of disintegrating agent (s) (disintegrants), wherein, if all phases contain disintegrants, the solubility can be adjusted by the different content.

Different methods for adjusting the solubility can also be used. For a two-phase system, the following possible combinations are mentioned by way of example: Phase 1 Phase 2 Pressing with pressing pressure a and if necessary addition of binders Pressing with pressing pressure b, where a ≠ b Pressing with pressing pressure a and if necessary addition of binders coating Pressing with pressing pressure a and if necessary addition of binders Addition of disintegrating agent Pressing with pressing pressure a and if necessary addition of binders Addition of binder coating Pressing with pressing pressure b, where a ≠ b coating coating coating Addition of disintegrating agent coating Addition of binders Addition of disintegrating agent Pressing with pressing pressure b, where a ≠ b Addition of disintegrating agent coating Addition of disintegrating agent Addition of disintegrating agent Addition of disintegrating agent Addition of binder Addition of binder Pressing with pressing pressure b, where a ≠ b Addition of binder coating Addition of binder Addition of disintegrating agent Addition of binder, concentration c1 Addition of binder Conc. C2 ≠ c1

The individual ingredients as well as the manufacturing processes are described below.

For coating the individual phases, these are provided with shell materials which dissolve in the wash liquor at a defined kinetics. After its dissolution, as far as possible, a stepped, ideally sudden, release of the coated phase occurs. Preferred shell materials are fatty alcohols or fatty acids, which may optionally be mixed in a mixture with other coating materials. An example of this is a mixture of Called fatty alcohols and aluminum stearate. Other shell materials known from the prior art are summarized in the following like keywords: magnesium sulfate and sodium hexaphosphate, dihydrogen phosphate or pyrophosphates, phosphonic acids, sodium metaborate and silicate, water glass and sodium polyphosphate, sodium sulfate, and silicate, or sodium bicarbonate, borax and magnesium sulfate, boric acid, but also to Part organic components such as fatty derivatives, paraffins and waxes (melting point of the compounds between 25 and 90 ° C), polyethylene glycols and fatty acid esters thereof having a molecular weight of 300 to 1700, combinations with magnesium oxide, vinyl chloride-ethylene copolymer emulsions or vinyl chloride-ethylene-methacrylate copolymer emulsions, polycarboxylates or other water-soluble polymers such as PVAI, cellulose ethers (MC, HEC, HPC, HPMC, CMC .....), polysaccharides (starch, guar, xanthan ....), proteins (gelatin, keratin hydrolysates)
The coating materials can be applied from the melt or from solutions or dispersions, the solvent or emulsifier being removed by evaporation. It is also possible to apply it as a fine powder, for example by means of electrostatic techniques, although this method leads to irregular and poorly adhering coatings. The shell materials can be applied to particles in stirring, mixing and granulating. However, preference is given to applying the shell materials in a fluidized bed, wherein at the same time size classification of the particles can take place. If, under certain circumstances, the shell materials lead to sticky products, it may be advisable to additionally apply finely divided substances to the coated phases ("dusting off"). Suitable fining agents are all finely divided substances, it also being possible to use other detergent constituents, such as builder substances. Zeolites, silicates, polymeric polycarboxylates, carbonates, citrates, starch, cellulose derivatives, etc. are preferably used as additional powdering agents.

As shell materials, in particular for tablet phases, which are to become effective only in the rinse cycles, so-called LCST substances can also be used. LCST substances are substances that have better solubility at low temperatures than at higher temperatures.

They are also referred to as substances with lower critical demixing temperature. Depending on the conditions of use, the lower critical demixing temperature should be between room temperature and the temperature of the heat treatment, for example between 20 ° C, preferably 25 ° C and 100 ° C, in particular between 25 ° C and 50 ° C. The LCST substances are preferably selected from alkylated and / or hydroxyalkylated polysaccharides, cellulose ethers, polyisopropylacrylamide, copolymers of polyisopropylacrylamide and blends of these substances.

Examples of alkylated and / or hydroxyalkylated polysaccharides are hydroxypropylmethylcellulose (HPMC), ethyl (hydroxyethyl) cellulose (EHEC), hydroxypropylcellulose (HPC), methylcellulose (MC), ethylcellulose (EC), propylcellulose (PC), carboxymethylcellulose (CMC), carboxymethylmethylcellulose ( CMMC), hydroxybutyl cellulose (HBC), hydroxybutylmethyl cellulose (HBMC), hydroxyethyl cellulose (HEC), hydroxyethyl carboxymethyl cellulose (HECMC), hydroxyethyl ethyl cellulose (HEEC), hydroxypropyl cellulose (HPC), hydroxypropyl carboxymethyl cellulose (HPCMC), hydroxyethylmethyl cellulose (HEMC), methyl hydroxyethyl cellulose (MHEC), methyl hydroxyethyl propyl cellulose ( MHEPC) and mixtures thereof, with carboxymethylcellulose, methylcellulose, methylhydroxyethylcellulose and methylhydroxypropellulose, as well as the alkali salts of CMC and the slightly ethoxylated MC or mixtures of the foregoing, being preferred.

Further examples of LCST substances are polyvinyl caprolactam, cellulose ethers and mixtures of cellulose ethers with carboxymethyl cellulose (CMC). Other polymers which exhibit a lower critical demixing temperature in water and which are also suitable are polymers of mono- or di-N-alkylated acrylamides, copolymers of mono- or di-N-substituted acrylamides with acrylates and / or acrylic acids or mixtures of interconnected networks of the above (co) polymers. Also suitable are polyethylene oxide or copolymers thereof, such as ethylene oxide / propylene oxide copolymers and graft copolymers of alkylated acrylamides with polyethylene oxide, polymethacrylic acid, polyvinyl alcohol, and copolymers thereof, Polyvinyl methyl ether, certain proteins such as poly (VATGW), a repeating unit in the natural protein elastin, and certain alginates. Mixtures of these polymers with salts, low molecular weight organic compounds or surfactants can also be used as LCST substance. By doing so, the LCST (lower critical demixing temperature) can be modified accordingly.

The shell materials are used in amounts such that an optimal interaction of the individual components and thus a precisely controlled release is made possible. Depending on the period of time within which the release is to be largely suppressed and depending on the size of the coated particles, the amount of shell material is measured. Preferred embodiments use less than 20% by weight of shell material, based on the amount of coated particles, in particular less than 10% by weight of shell materials are preferred.

In order to facilitate the disintegration of highly compacted moldings, it is possible to incorporate disintegration aids, so-called tablet disintegrating agents, in order to shorten the disintegration times. These substances are suitable, for example, for accelerating the release of individual shaped body regions in relation to other regions. Among tablet disintegrants and disintegrants are according to Römpp (9th edition, Bd. 6, p 4440) and Voigt "textbook of pharmaceutical technology" (6th edition, 1987, pp. 182-184 ) Excipients, which ensure the rapid disintegration of tablets in water or gastric juice and for the release of the pharmaceuticals in resorbable form.

These substances, which are also referred to as "explosives" due to their effect, increase their volume upon ingress of water, on the one hand increasing the intrinsic volume (swelling), and on the other hand creating a pressure via the release of gases which can break the tablet into smaller particles disintegrates. 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.

Preferred detergent tablets contain from 0.5 to 20% by weight, preferably from 3 to 15% by weight and in particular from 4 to 10% by weight of one or more disintegration aids, in each case based on the weight of the tablet. Contains only a portion of the molded body disintegration aid, so the above information refers only to the weight of this share.

Disintegrating agents based on cellulose are used as preferred disintegrating agents in the context of the present invention, so that preferred washing and cleaning agent tablets use such cellulose-based disintegrating agents in amounts of from 0.5 to 10% by weight, preferably from 3 to 7% by weight and in particular 4 to 6% by weight. 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, more preferably below 20% by weight, based on the cellulose-based disintegrant. 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. Detergents and cleaning product tablets containing disintegrators in granular or optionally cogranulated form are incorporated into the German patent applications DE 197 09 991 (Stefan Herzog ) and DE 197 10 254 (Henkel ) as well as the international patent application WO98 / 40463 (Henkel ). Further details of the production of granulated, compacted or cogranulated cellulose explosives can be found in these publications. 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 in the present invention as disintegration aids and are commercially available, for example under the name of Arbocel ^® TF-30-HG from Rettenmaier.

As a further disintegrating agent based on cellulose or as a component of this component, microcrystalline cellulose can be used. This microcrystalline cellulose is obtained by partial hydrolysis of celluloses under conditions which attack and completely dissolve only the amorphous regions (about 30% of the total cellulose mass) of the celluloses, leaving the crystalline regions (about 70%) intact. Subsequent deaggregation of the microfine celluloses produced by the hydrolysis yields the microcrystalline celluloses which have primary particle sizes of about 5 μm and can be compacted, for example, into granules having an average particle size of 200 μm.

In the context of the present invention, preferred detergent tablets also contain a disintegration aid, preferably a cellulose-based disintegration assistant, preferably in granular, cogranulated or compacted form, 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 molding weight.

As further ingredients, with the aid of which the release of the active substances can be controlled, binders may be mentioned, both surface-active and non-surfactant binders can be used.

Examples of surfactant binders are solid nonionic surfactants as described below for the surfactants.

The term "non-surfactant binder" in the context of the present application characterizes binders which do not belong to the class of surfactants. "Water-soluble" binders in the sense of the present application are binders which are completely filled with water at room temperature, i. without miscibility, are miscible. Finally, the term "liquid binder" refers to the state of aggregation of the binder at 25 ° C and 1013.25 mbar.

Preferred amounts in which the one or more non-surfactant, water-soluble or liquid binders are used are within a narrower range, so that preferred washing and cleaning agent tablets have a content of non-surfactant, water-soluble, liquid binders of 0.5 to 7.5% by weight. %, preferably from 0.75 to 5 wt .-% and in particular from 1 to 3 wt.%, in each case based on the molding weight, have.

In general, only the requirement profile is set for the binders contained in the detergent tablets in accordance with the invention so that they completely mix with water or in Disperse water. In particular, substances from the group of polyethylene glycols and polypropylene glycols, glycerol, glycerol carbonate, ethylene glycol, propylene glycol and propylene carbonate have proven to be suitable binders from the multitude of usable binders. In addition, waxes and paraffins are mentioned as examples of water-insoluble but dispersible binders. Also polymers binders such as polycarboxylates can be used.

Polyethylene glycols which can be used according to the invention (abbreviated PEG) are polymers of ethylene glycol which correspond to general formula I

H- (O-CH ₂ -CH ₂ ) _n -OH (I)

n, where n can assume values between 1 (ethylene glycol, see below) and about 16. Decisive in the assessment of whether a polyethylene glycol is used according to the invention, is the state of aggregation of the PEG at room temperature, ie the solidification point of the PEG must be below 25 ° C. For polyethylene glycols there are various nomenclatures that can lead to confusion. Technically common is the indication of the average relative molecular weight following the indication "PEG", so that "PEG 200" characterizes a polyethylene glycol having a relative molecular weight of about 190 to about 210. According to this nomenclature, the commercially available polyethylene glycols PEG 200, PEG 300, PEG 400 and PEG 600 can be used in the context of the present invention.

For cosmetic ingredients, another nomenclature is used in which the abbreviation PEG is hyphenated and directly followed by the hyphen followed by a number corresponding to the number n in formula I above. According to this nomenclature ( INCI nomenclature, CTFA International Cosmetic Ingredient Dictionary and Handbook, 5th Edition, The Cosmetic, Toiletry and Fragrance Association, Washington, 1997 ) According to the invention, for example, PEG-4, PEG-6, PEG-8, PEG-9, PEG-10, PEG-12, PEG-14 and PEG-16 can be used according to the invention.

Commercially available polyethylene glycols are, for example, under the trade name Carbowax ^® PEG 200 (Union Carbide), Emkapol ^® 200 (ICI Americas), Lipoxol ^® 200 MED (Huls America), polyglycol ^® E-200 (Dow Chemical), Alkapol ^® PEG 300 (Rhone -Poulenc), Lutrol ^® E300 (BASF) and the corresponding trade names with higher numbers.

genügen, wobei n Werte zwischen 1 (Propylenglycol, siehe unten) und ca. 12 annehmen kann. Technisch bedeutsam sind hier insbesondere Di-, Tri- und Tetrapropylenglycol, d.h. die Vertreter mit n=2, 3 und 4 in Formel II.Polypropylene glycols which can be used according to the invention (abbreviated PPG) are polymers of propylene glycol which correspond to the general formula II

n, where n can assume values between 1 (propylene glycol, see below) and about 12. Of particular technical importance here are di-, tri- and tetrapropylene glycols, ie the representatives with n = 2, 3 and 4 in formula II.

Glycerin is a colorless, clear, heavy-bodied, odorless sweet-tasting hygroscopic liquid of density 1.261 that solidifies at 18.2 ° C. Glycerol was originally a by-product of fat saponification but is now technically synthesized in large quantities. Most technical processes are based on propene, which is processed into glycerol via the intermediates allyl chloride, epichlorohydrin. Another technical process is the hydroxylation of allyl alcohol with hydrogen peroxide at the WO ₃ contact via the glycide step.

Glycerol carbonate is accessible by transesterification of ethylene carbonate or dimethyl carbonate with glycerol, as by-products of ethylene glycol or methanol incurred. Another synthetic route is based on glycidol (2,3-epoxy-1-propanol), which is converted under pressure in the presence of catalysts with CO ₂ to glycerol carbonate. Glycerine carbonate is a clear, easily agitated liquid with a density of 1.398 gcm ^-3 , which boils at 125-130 ° C (0.15 mbar).

Ethylene Glycol (1,2-Ethanediol, "Glycol") is a colorless, viscous, sweet-tasting, highly hygroscopic liquid that is miscible with water, alcohols and acetone and has a density of 1.113. The solidification point of ethylene glycol is -11.5 ° C, the liquid boils at 198 ° C. Technically, ethylene glycol is recovered from ethylene oxide by heating with water under pressure. Promising manufacturing processes can also be built on the acetoxylation of ethylene and subsequent hydrolysis or on synthesis gas reactions.

There are two isomers of propylene glycol, 1,3-propanediol and 1,2-propanediol. 1,3-Propanediol (trimethylene glycol) is a neutral, colorless and odorless, sweet-tasting liquid of density 1,0597, which solidifies at -32 ° C and boils at 214 ° C. The preparation of 1,3-propanediol succeeds from acrolein and water with subsequent catalytic hydrogenation.

Technically much more significant is 1,2-propanediol (propylene glycol), which is an oily, colorless, almost odorless liquid, density 1.0381, which solidifies at -60 ° C and boils at 188 ° C. 1,2-Propanediol is prepared from propylene oxide by water addition.

Propylene carbonate is a water-bright, easily agitated liquid, with a density of 1.2057 gcm ^-3 , the melting point is -49 ° C, the boiling point at 242 ° C. Also propylene carbonate is industrially accessible by reaction of propylene oxide and CO ₂ at 200 ° C and 80 bar.

As surfactants nonionic, anionic surfactants, zwitterionic and cationic surfactants can be used.

As anionic surfactants, for example, those of the sulfonate type and sulfates are used. The surfactants of the sulfonate type are preferably C _9-13 -alkylbenzenesulfonates, olefinsulfonates, ie mixtures of alkene and hydroxyalkanesulfonates and disulfonates, such as those obtained from C _12-18 monoolefins having terminal or internal double bonds by sulfonating with gaseous sulfur trioxide and subsequent alkaline or acidic hydrolysis of the sulfonation obtained. Also suitable are alkanesulfonates which are obtained from C _12-18 alkanes, for example by sulfochlorination or sulfoxidation with subsequent hydrolysis or neutralization. Likewise suitable are the esters of sulfo fatty acids (ester sulfonates), for example the α-sulfonated methyl esters of hydrogenated coconut, palm kernel or tallow fatty acids.

Further suitable anionic surfactants are sulfated fatty acid glycerol esters. Fatty acid glycerol esters are to be understood as meaning the mono-, di- and triesters and mixtures thereof, as obtained in the preparation by esterification of a monoglycerol with 1 to 3 moles of fatty acid or in the transesterification of triglycerides with 0.3 to 2 moles of glycerol. Preferred sulfated fatty acid glycerol esters are the sulfonation products of saturated fatty acids having 6 to 22 carbon atoms, for example caproic acid, caprylic acid, capric acid, myristic acid, lauric acid, palmitic acid, stearic acid or behenic acid.

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 these chain lengths 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 technology interest, the C ₁₂ -C ₁₆ alkyl sulfates and C ₁₂ -C ₁₅ alkyl sulfates and C ₁₄ -C ₁₅ alkyl sulfates are preferred. Also 2,3-alkyl sulfates, which, for example, according to the U.S. Patents 3,234,258 or 5,075,041 are manufactured and can be obtained as commercial products from Shell Oil Company under the name DAN ^®, are suitable anionic surfactants.

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

Further suitable 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 _8-18 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 a 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.

As further anionic surfactants are particularly soaps into consideration. Suitable are saturated fatty acid soaps, such as the salts of lauric acid, myristic acid, palmitic acid, stearic acid, hydrogenated erucic acid and behenic acid, and in particular of natural fatty acids, e.g. Coconut, palm kernel or tallow fatty acids, derived soap mixtures.

The anionic surfactants, including the soaps, may be in the form of their sodium, potassium or ammonium salts and as soluble salts of organic bases, such as mono-, di- or triethanolamine. The anionic surfactants are preferably present in the form of their sodium or potassium salts, in particular in the form of the sodium salts.

Preferably, at least a portion, preferably at least 50%, of the anionic surfactants are on one. Applied carrier material. Examples of carrier materials are alkali metal carbonates, alkali metal sulphates, alkali citrates, alkali metal phosphates, Silicas, zeolites, citric acid and mixtures thereof. In order not to influence the pH at the beginning of the washing process, it has proved to be advantageous to use as support material pH-neutral support materials, such as silica gel, starch, cellulose and cellulose derivatives, neutral-reacting phosphates, alkali metal sulfates, polyacrylate derivatives, etc.

In addition to the anionic surfactants, the agents according to the invention may also contain other surfactants, eg. As nonionic and amphoteric surfactants.

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

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

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

Nonionic surfactants of the amine oxide type, for example N-cocoalkyl-N, N-dimethylamine oxide and N-tallowalkyl-N, N-dihydroxyethylamine oxide, and the fatty acid alkanolamides may also be suitable. The amount of these nonionic surfactants is preferably not more than that of the ethoxylated fatty alcohols, especially not more than half thereof.

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

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

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

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

[Z] is preferably obtained by reductive amination of a reduced sugar, for example glucose, fructose, maltose, lactose, galactose, mannose or xylose. The N-alkoxy- or N-aryloxy-substituted compounds can then, for example, according to the teaching of the international application WO-A-95/07331 be converted by conversion with fatty acid methyl esters in the presence of an alkoxide as catalyst into the desired Polyhydroxyfettsäureamide.

Examples of cationic surfactants are, in particular, quaternary ammonium compounds, cationic polymers and emulsifiers. The cationic surfactants are usually used as fabric softeners. Their release is therefore preferably only in the rinse, ie in phase V of the method according to the invention.

wobei in (III) R^a und R^b für einen acyclischen Alkylrest mit 12 bis 24 Kohlenstoffatomen, R^c für einen gesättigten C₁-C₄ Alkyl- oder Hydroxyalkylrest steht, R^d entweder gleich R^a, R^b oder R^c ist oder für einen aromatischen Rest steht. X steht entweder für ein Halogenid-, Metho-sulfat-, Methophosphat- oder Phosphation sowie Mischungen aus diesen. Beispiele für kationische Verbindungen der Formel (III) sind Didecyldimethylammoniumchlorid, Ditalgdimethylammoniumchlorid oder Dihexadecylammoniumchlorid.Suitable examples are quaternary ammonium compounds of the formulas (III) and (IV),

wherein in (III) R ^a and R ^{b is} an acyclic alkyl radical having 12 to 24 carbon atoms, R ^{c is} a saturated C ₁ -C ₄ alkyl or hydroxyalkyl radical, R ^{d is} either R ^a , R ^b or R ^c is or represents an aromatic radical. X is either a halide, methosulfate, methophosphate or phosphate ion and mixtures of these. Examples of cationic compounds of the formula (III) are didecyldimethylammonium chloride, ditallowdimethylammonium chloride or dihexadecylammonium chloride.

Compounds of formula (IV) are so-called ester quats. Esterquats are characterized by excellent biodegradability. Here R ^{e is} an aliphatic acyl radical having 12 to 22 carbon atoms with 0, 1, 2 or 3 double bonds; R ^f is H, OH or O (CO) R ^h , R ^g is independently of R ^{f is} H, OH or O (CO) R ⁱ , wherein R ^h and R ⁱ are each independently an aliphatic acyl radical having 12 to 22 carbon atoms with 0, 1, 2 or 3 double bonds. m, n and p can each independently be 1, 2 or 3. X ^- may be either a halide, methosulfate, methophosphate or phosphate ion, as well as mixtures of these. Preference is given to compounds which contain the group O (CO) R ^h for R ^f and for R ^c and R ^h contain alkyl radicals having 16 to 18 carbon atoms. Particularly preferred are compounds in which R ^{g is} also OH. Examples of compounds of the formula (IV) are methyl N- (2-hydroxyethyl) -N, N-di (tallowacyl oxyethyl) ammonium methosulfate, bis (palmitoyl) ethyl hydroxyethyl, methyl ammonium methosulfate or methyl N , N-bis (acyloxyethyl) -N- (2-hydroxyethyl) ammonium methosulfate. Quaternized compounds of the formula (IV) are used, the unsaturated Alkyl chains, the acyl groups are preferred whose corresponding fatty acids have an iodine value between 5 and 80, preferably between 10 and 60 and in particular between 15 and 45 and which has a cis / trans isomer ratio (in wt .-%) of greater than 30: 70, preferably greater than 50: 50 and in particular greater than 70: 30 have. Commercial examples are sold by Stepan under the tradename Stepantex ^® methylhydroxyalkyldialkoyloxyalkylammonium or those known under Dehyquart ^® Cognis products known under or Rewoquat ^® manufactured by Goldschmidt-Witco. Further preferred compounds are the diesterquats corresponding to formula (V) which are obtainable under the name Rewoquat ^® 3099 W 222 LM or CR and provide in addition to the softness also for stability and color protection.

R ^k and R ¹ are each independently an aliphatic acyl radical having 12 to 22 carbon atoms with 0, 1, 2 or 3 double bonds.

wobei R^m für H oder einen gesättigten Alkylrest mit 1 bis 4 Kohlenstoffatomen, Rⁿ und R⁰ unabhängig voneinander jeweils für einen aliphatischen, gesättigten oder ungesättigten Alkylrest mit 12 bis 18 Kohlenstoffatomen, Rⁿ alternativ auch für O(CO)R^p stehen kann, wobei R^p einen aliphatischen, gesättigten oder ungesättigten Alkylrest mit 12 bis 18 Kohlenstoffatomen bedeutet, und Z eine NH-Gruppe oder Sauerstoff bedeutet und X^- ein Anion ist. q kann ganzzahlige Werte zwischen 1 und 4 annehmen.In addition to the quaternary compounds described above, it is also possible to use other known compounds, for example quaternary imidazolinium compounds of the formula (VI),

wherein R ^{m is} H or a saturated alkyl radical having 1 to 4 carbon atoms, R ⁿ and R ⁰ are each independently an aliphatic, saturated or unsaturated alkyl radical having 12 to 18 carbon atoms, R ⁿ alternatively also O (CO) R ^p where R ^{p is} an aliphatic, saturated or unsaturated alkyl radical having 12 to 18 carbon atoms, and Z is an NH group or oxygen and X ^{- is} an anion. q can take integer values between 1 and 4.

wobei R^q, R^r und R^s unabhängig voneinander für eine C_1-4-Alkyl-, Alkenyl- oder Hydroxyalkylgruppe steht, R^t und R^u jeweils unabhängig ausgewählt eine C_8-28-Alkylgruppe darstellt und r eine Zahl zwischen 0 und 5 ist.Further suitable quaternary compounds are described by formula (VII)

wherein R ^q , R ^r and R ^s independently represent a C _1-4 alkyl, alkenyl or hydroxyalkyl group, each of R ^t and R ^u independently represents a C _8-28 alkyl group and r represents a number between 0 and 5 is.

In addition to the compounds of the formulas III to VII, it is also possible to use short-chain, water-soluble, quaternary ammonium compounds, such as trihydroxyethylmethylammonium methosulfate or the alkyltrimethylammonium chlorides, dialkyldimethylammonium chlorides and trialkylmethylammonium chlorides, eg. Cetyl trimethyl ammonium chloride, stearyl trimethyl ammonium chloride, distearyl dimethyl ammonium chloride, lauryl dimethyl ammonium chloride, lauryl dimethyl benzyl ammonium chloride and tricetylmethyl ammonium chloride.

Also protonated alkylamine compounds which have plasticizing effect, as well as the non-quaternized, protonated precursors of cationic emulsifiers are suitable.

Further cationic compounds which can be used according to the invention are the quaternized protein hydrolysates.

Suitable cationic polymers include the polyquaternium polymers as described in the CTFA Cosmetic Ingredient Dictionary (The Cosmetic, Toiletry and Fragrance, Inc., 1997), in particular the Polyquaternium-6, Polyquaternium-7, Polyquaternium, also known as Merquats. 10 polymers (Ucare Polymer IR 400, Amerchol), polyquaternium 4 copolymers, such as graft copolymers with a cellulose backbone and quaternary ammonium groups bonded via allyldimethylammonium chloride, cationic cellulose derivatives such as cationic guar such as guar hydroxypropyl triammonium chloride, and similar quaternized guar derivatives (eg Cosmedia Guar, manufacturer: Cognis GmbH), cationic quaternary sugar derivatives (cationic Alkyl polyglucosides), e.g. , The commercial product Glucquat ^® 100, according to CTFA nomenclature a "lauryl methyl Gluceth-10 Hydroxypropyl Dimonium Chloride", copolymers of PVP and dimethylaminomethacrylate, copolymers of vinylimidazole and vinylpyrrolidone, aminosilicone polymers and copolymers,

Polyquaternized polymers (for example, Luviquat Care by BASF.), And cationic biopolymers based on chitin and derivatives thereof, for example, under the trade designation chitosan ^® (manufacturer: Cognis) polymer obtainable.

Also suitable in the present invention are cationic silicone oils such as the commercially available products Q2-7224 (manufactured by Dow Corning, a stabilized trimethylsilylamodimethicone), Dow Corning 929 emulsion (containing a hydroxylamino-modified silicone, also referred to as amodimethicones), SM -2059 (manufacturer: General Electric), SLM-55067 (manufacturer: Wacker) Abil ^® -Quat 3270 and 3272 (manufacturer: Goldschmidt-Rewo; diquaternary polydimethylsiloxanes, quaternium-80), and Silicone quat Rewoquat ^® SQ 1 (Tegopren ^® 6922, Manufacturer: Goldschmidt-Rewo).

die Alkylamidoamine in ihrer nicht quaternierten oder, wie dargestellt, ihrer quaternierten Form, sein können. R^v kann ein aliphatischer Acylrest mit 12 bis 22 Kohlenstoffatomen mit 0, 1, 2 oder 3 Doppelbindungen sein. s kann Werte zwischen 0 und 5 annehmen. R^w und R^x stehen unabhängig voneinander jeweils für H, C_1-4-Alkyl oder Hydroxyalkyl. Bevorzugte Verbindungen sind Fettsäureamidoamine wie das unter der Bezeichnung Tego Amid^®S 18 erhältliche Stearylamidopropyldimethylamin oder das unter der Bezeichnung Stepantex^® X 9124 erhältliche 3-Talgamidopropyl-trimethylammonium-methosulfat, die sich neben einer guten konditionierenden Wirkung auch durch farbübertragungsinhibierende Wirkung sowie speziell durch ihre gute biologische Abbaubarkeit auszeichnen.It is likewise possible to use compounds of the formula (VIII)

the alkylamidoamines may be in their quaternized or, as shown, their quaternized form. R ^v can be an aliphatic acyl radical having 12 to 22 Be carbon atoms with 0, 1, 2 or 3 double bonds. s can take values between 0 and 5. R ^w and R ^x are each independently H, C _1-4 alkyl or hydroxyalkyl. Preferred compounds are fatty acid amidoamines such as Stearylamidopropyldimethylamin available under the name Tego Amid ^® S 18 or 3-Talgamidopropyl-trimethylammonium methosulfate available under the name Stepantex ^® X 9124, which in addition to a good conditioning effect by color transfer inhibiting effect and especially by their good distinguish biodegradability.

Surfactants are preferably present in the detergents or detergents according to the invention in a total amount of from 5% by weight to 50% by weight, in particular from 8% by weight to 30% by weight, based on the finished composition.

Suitable enzymes which can be used in the compositions are those from the class of the oxidases, proteases, lipases, cutinases, amylases, pullulanases, cellulases, hemicellulases, xylanases and peroxidases and mixtures thereof, for example proteases such as BLAP®, Optimase®, Opticlean®, Maxacal ®, Maxapem®, Alcalase®, Esperase® and / or Savinase®, amylases such as Termamyl®, Amylase-LT®, Maxamyl®, Duramyl® and / or Purafect® OxAm, lipases such as Lipolase®, Lipomax®, Lumafast® and / or Lipozym®, cellulases such as Celluzyme® and or Carezyme®. Particularly suitable are from fungi or bacteria, such as Bacillus subtilis, Bacillus licheniformis, Streptomyces griseus, Humicola lanuginosa, Humicola insolens, Pseudomonas pseudoalcaligenes or Pseudomonas cepacia derived enzymatic agents. The optionally used enzymes can, for example in the European Patent EP 0 564 476 or in the international patent applications WO 94/23005 be adsorbed to carriers and / or embedded in encapsulating substances to protect against premature inactivation. They are preferably present in the detergents according to the invention in amounts of up to 10% by weight, in particular from 0.2% by weight to 2% by weight. contain, with particular preference against oxidative degradation stabilized enzymes are used.

Suitable alkalizing agents are all substances known in the field of detergents and / or cleaners which react alkaline in water. Soluble alkalizing agents, such as alkali carbonates and their hydrates and peroxyhydrates, phosphates, e.g. Sodium tripolyphosphate, soluble silicates, e.g. Water glasses, alkali metal hydroxides, carboxylates or so-called. Persalze, such as Na-perborate, are used. Suitable examples are the insoluble alkali metal silicates, also known as builders, as described in more detail below. Mixtures of several alkalizing agents are also suitable. In order to adjust a release of the alkalizing agent to the period defined according to the invention, it has proved to be advantageous to retard the solubility by a suitable coating and / or by a coarse particle size.

The compositions according to the invention generally contain one or more builders, in particular zeolites, silicates, carbonates, organic cobuilders and - where there are no ecological prejudices against their use - also the phosphates. The latter are particularly preferred builders to be used in automatic dishwashing detergent tablets. The builders mentioned below are, as described above, also suitable as alkalizing agents.

The builders are, if they are insoluble, usually in finely divided form, ie in a particle size of 0.1 to 10 microns before. Many builders show latent alkaline properties, ie overall they are pH-neutral because of their insolubility, but have alkaline groups on their surface. Since the particles are filtered out of the textiles and therefore come into intensive contact with the stains, they locally produce an alkaline environment which has a negative effect on the leachability of, in particular, bleachable stains, although macroscopically a neutral pH value may be present. A further increase in the washing effect can be achieved if the insoluble, finely divided builders to larger agglomerates be granulated using neutral Granulierhilfsmitteln or they are present as coarser particles. These agglomerates decompose slowly during the washing process and release the primary particles. Due to the coarser particles, a fine dispersion is prevented in the first minutes of the wash cycle. Cellulosic derivatives, polyvinyl alcohols, polycarboxylates, polyvinylpyrrolidone and copolymers thereof are particularly suitable as granulating aids.

Suitable crystalline layered sodium silicates have the general formula NaMSi _x O _2x-1 · H ₂ O, where M is sodium or hydrogen, x is a number from 1.9 to 4 and y is a number from 0 to 20 and preferred values for x 2, 3 or 4 are. Preferred crystalline layered silicates of the formula given are those in which M is sodium and x assumes the values 2 or 3. In particular, both β- and δ-sodium disilicates Na ₂ Si ₂ O ₅ .yH ₂ O are preferred.

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

Particularly preferred are compacted / compacted amorphous silicates, compounded amorphous silicates and overdried X-ray amorphous silicates.

The finely crystalline, synthetic and bound water-containing zeolite used is preferably zeolite A and / or P. As zeolite P, zeolite ^MAP® (commercial product from Crosfield) is particularly preferred. Also suitable, however, are zeolite X and mixtures of A, X and / or P. Commercially available and preferably usable in the context of the present invention is, for example, a cocrystal of zeolite X and zeolite A (about 80% by weight of zeolite X) ), which is sold by the company CONDEA Augusta SpA under the brand name VEGOBOND AX ^® and by the formula

nNa ₂ O • (1-n) K ₂ O • Al ₂ O ₃ • (2 - 2.5) SiO ₂ • (3.5-5.5) H ₂ O

can be described. Suitable zeolites have an average particle size of less than 10 μm (volume distribution, measuring method: Coulter Counter) and preferably contain 18 to 22% by weight, in particular 20 to 22% by weight, of bound water.

Of course, a use of the well-known phosphates as builders is possible, unless such use should not be avoided for environmental reasons. Among the large number of commercially available phosphates, the alkali metal phosphates, with a particular preference for pentasodium or pentapotassium triphosphate (sodium or potassium tripolyphosphate), have the greatest importance in the washing and cleaning agent industry.

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

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

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

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

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

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

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

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

These can be used just like sodium tripolyphosphate, potassium tripolyphosphate or mixtures of these two; Mixtures of sodium tripolyphosphate and sodium potassium tripolyphosphate or mixtures of potassium tripolyphosphate and sodium potassium tripolyphosphate or mixtures of sodium tripolyphosphate and potassium tripolyphosphate and sodium potassium tripolyphosphate can also be used according to the invention.

As organic cobuilders it is possible in particular to use polycarboxylates / polycarboxylic acids, polymeric polycarboxylates, aspartic acid, polyacetals, dextrins, further organic cobuilders (see below) and phosphonates in the laundry detergent and / or detergent tablets according to the invention. These classes of substances are described below.

Useful organic builder substances are, for example, the polycarboxylic acids which can be used in the form of their sodium salts, polycarboxylic acids meaning those carboxylic acids which 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 use is not objectionable for ecological reasons, and mixtures thereof. Preferred salts are the salts of polycarboxylic acids such as citric acid, adipic acid, succinic acid, glutaric acid, tartaric acid, sugar acids and mixtures thereof.

The acids themselves can also be used. In addition to their builder action, the acids typically also have the property of an acidifying component and thus also serve to set a lower and milder pH of detergents or cleaners. In particular, citric acid, succinic acid, glutaric acid, adipic acid, gluconic acid and any desired mixtures of these can be mentioned here.

Further suitable builders are polymeric polycarboxylates, for example the alkali metal salts of polyacrylic acid or polymethacrylic acid, for example those having a relative molecular mass of from 500 to 70,000 g / mol.

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

Suitable polymers are, in particular, polyacrylates which preferably have a molecular weight of 2,000 to 20,000 g / mol. Because of their superior solubility, this group can again be the short chain polyacrylates, the Molar masses of 2000 to 10,000 g / mol, and more preferably from 3000 to 5000 g / mol, be preferred.

Also suitable are copolymeric polycarboxylates, in particular those of acrylic acid with methacrylic acid and of acrylic acid or methacrylic acid with maleic acid. Copolymers of acrylic acid with maleic acid which contain 50 to 90% by weight of acrylic acid and 50 to 10% by weight of maleic acid have proven to be particularly suitable. Their relative molecular weight, based on free acids, is generally from 2000 to 70000 g / mol, preferably from 20,000 to 50,000 g / mol and in particular from 30,000 to 40,000 g / mol.

The (co) polymeric polycarboxylates can be used either as a powder or as an aqueous solution. The content of (co) polymeric polycarboxylates in the compositions is preferably 0.5 to 20% by weight, in particular 3 to 10% by weight.

To improve the water solubility, the polymers may also contain allylsulfonic acids such as allyloxybenzenesulfonic acid and methallylsulfonic acid as a monomer.

Also particularly preferred are biodegradable polymers of more than two different monomer units, for example those which contain 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-alkylallylsulfonic acid and sugar derivatives ,

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

Also to be mentioned as further preferred builders polymeric aminodicarboxylic acids, their salts or their precursors. Particular preference is given to polyaspartic acids or their salts and derivatives.

Further suitable builder substances are polyacetals which can be obtained by reacting dialdehydes with polyolcarboxylic acids which have 5 to 7 C atoms and at least 3 hydroxyl groups. Preferred polyacetals are obtained from dialdehydes such as glyoxal, glutaraldehyde, terephthalaldehyde and mixtures thereof and from polyol carboxylic acids such as gluconic acid and / or glucoheptonic acid.

Further suitable organic builder substances are dextrins, for example oligomers or polymers of carbohydrates, which can be obtained by partial hydrolysis of starches. The hydrolysis can be carried out by customary, for example acid or enzyme catalyzed processes. Preferably, it is hydrolysis products having average molecular weights in the range of 400 to 500,000 g / mol. In this case, a polysaccharide with a dextrose equivalent (DE) in the range from 0.5 to 40, in particular from 2 to 30 is preferred, DE being a common measure of the reducing action of a polysaccharide compared to dextrose, which has a DE of 100 , is. Usable are both maltodextrins with a DE between 3 and 20 and dry glucose syrups with a DE between 20 and 37 and so-called yellow dextrins and white dextrins with higher molecular weights in the range from 2000 to 30,000 g / mol.

The oxidized derivatives of such dextrins are their reaction products with oxidizing agents which are capable of oxidizing at least one alcohol function of the saccharide ring to the carboxylic acid function. Also suitable is an oxidized oligosaccharide, e.g. B. oxidized at C _{6 of} the saccharide ring product.

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

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

Another class of substances with cobuilder properties are the phosphonates. These are, in particular, hydroxyalkane or aminoalkanephosphonates. Among the hydroxyalkane phosphonates, 1-hydroxyethane-1,1-diphosphonate (HEDP) is of particular importance as a co-builder. It is preferably used as the sodium salt, the disodium salt neutral and the tetrasodium salt alkaline (pH 9). Preferred aminoalkanephosphonates are ethylenediamine tetramethylenephosphonate (EDTMP), diethylenetriaminepentamethylenephosphonate (DTPMP) and their higher homologs. They are preferably in the form of neutral sodium salts, eg. B. as the hexasodium salt of EDTMP or as hepta- and octa-sodium salt of DTPMP used. The builder used here is preferably HEDP from the class of phosphonates. The aminoalkanephosphonates also have a pronounced heavy metal binding capacity. Accordingly, in particular if the agents also contain bleach, it may be preferable to use aminoalkanephosphonates, in particular DTPMP, or to use mixtures of the phosphonates mentioned.

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

The amount of builder is usually between 10 and 70 wt .-%, preferably between 15 and 60 wt .-% and in particular between 20 and 50 wt .-%.

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

The content of the bleaching agents may be from 1 to 40% by weight and in particular from 10 to 20% by weight, with perborate mono- or tetrahydrate or percarbonate being advantageously used.

The bleaching agents which may be present may also serve as alkalizing agents, since many react alkaline in the aqueous medium. It has proven to be advantageous to use the bleaching agents in coated form. During the washing process, the coating dissolves and releases the alkaline-reacting bleach retarded, whereby the stepwise increase of the pH according to the invention takes place. For coating the bleach the same shell materials can be used as for the coating of the alkalizing agent. The application of the shell materials can also be done in the same way.

In order to achieve an improved bleaching effect when washing or cleaning at temperatures of 60 ° C and below, bleach activators can be incorporated. 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 isononanoyloxybenzenesulfonate (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 and acetylated sorbitol and mannitol or their in the European patent application EP 0 525 239 (Ausimont SPA) described mixtures (SORMAN), acylated sugar derivatives, especially Pentaacetylglukose (PAG), pentaacetyl, tetraacetylxylose and Octaacetyllactose and acetylated, optionally N-alkylated glucamine and gluconolactone, and / or N-acylated lactams, such as N-benzoylcaprolactam, which the international patent applications WO 94/27970 . WO 94/28102 . WO 94/28103 . WO 95/00626 (all Procter & Gamble ) WO 95/14759 (Warwick ) and WO 95/17498 (Procter & Gamble ) are known. Those from the international patent application WO 95/14075 (Degussa ) acyl lactams are also preferably used. Also from the German patent application DE 44 43 177 (Henkel ) known combinations of conventional bleach activators can be used become. Such bleach activators are present in amounts of from 0.5% to 15% by weight, based on total agent.

In addition to or in place of the conventional bleach activators, so-called bleach catalysts may also be included. These substances are bleach-enhancing transition metal salts or transition metal complexes such as Mn, Fe, Co, Ru or Mo saline complexes or - carbonyl complexes. Mn, Fe, Co, Ru, Mo, Ti, V and Cu complexes with N-containing tripod ligands and also Co, Fe, Cu and Ru ammine complexes are suitable as bleach catalysts, wherein those compounds are preferably used, which in the DE 197 09 284 A1 are described.

In a preferred embodiment, the agent according to the invention contains a buffer system. Due to the buffer system, the pH in the wash liquor when adding the detergent composition and retarding the alkali carriers is comparatively low, i. it is between 6 and 8, preferably between 6.3 and 7.7, more preferably between 6.5 and 7.5. In particular, the washing effect of the surfactants against bleachable soils such as tea, coffee, red wine or fruit and vegetable juices comes into play at this pH.

The buffer system is preferably used in amounts of 0.1 to 40, preferably from 1 to 25 wt .-%, based on the finished composition. As buffer system, it is possible to use all water-soluble substances which are suitable for buffering the pH of an aqueous solution below the value 8.

In conjunction with the other components of the compositions according to the invention, a starting pH can be achieved in this way, which is increased in the course of the washing process in the form of a step in the period defined according to the invention (release of the alkalizing agent and exhaustion of the buffer system).

Preferred buffer systems are partially neutralized inorganic and organic acids, for example the solid mono-, oligo- and polycarboxylic acids such as citric, tartaric and succinic acids, polycarboxylic acids such as polyacrylic acid or acrylic acid-maleic acid copolymers, but also acids such as malonic acid, adipic acid, maleic acid, fumaric acid, Oxalic acid, boric acid or sulfamic acid and mixtures of said acids. Also, substances such as hydrogen sulfates or carbonates can be used as a buffer system, again paying attention only to compliance with the pH conditions. In order to obtain as fast as possible a wash liquor having a pH within defined limits when dissolving the compositions according to the invention, the buffer systems should be selected so that they dissolve quickly and bring the pH rapidly to the desired values. A coating that would cause a dissolution delay is undesirable for the buffer systems in the present invention. The buffer capacity of the buffer system must be so high that different amounts of residual alkalinity in the washing machine or the laundry from previous washes can be neutralized or that from coatings of the coatings of the alkali carriers emerging alkalinity is neutralized, in the event that a pH jump to be realized.

From the point of view of application technology, the requirement for the buffer system is that they are not volatile. From this point of view, solid buffer systems that combine low sublimation tendency and high melting point with good water solubility are clearly preferred. Liquid or pasty buffer systems can be used only in minor amounts below 5 wt .-% of the total composition and in their use confectioning measures must be taken to ensure formulability and storage stability even at elevated humidity. Of course, when selecting the buffer system (s), care must also be taken to ensure that the resulting wash liquor does not damage the textiles or the human skin.

In one possible embodiment of the present invention, the washing and / or cleaning agent is used as a so-called heavy-duty detergent, i. for washing any textiles and at any temperatures. Heavy-duty detergents usually contain, in addition to the surfactants, enzymes and builders, organic and / or especially inorganic bleaches.

In addition to the surfactants, enzymes, bleaches and builders can be used in the detergents of the invention, a variety of other compounds, for example, sequestering agents, electrolytes, optical brighteners, Vergonungsinhibitorsen, Farbübertragunsinhibitoren, dye fixatives, foam regulators, additional bleach activators, dyes and fragrances.

When used in automatic washing processes, it may be advantageous to add conventional foam inhibitors to the compositions. As foam inhibitors are, for example, soaps of natural or synthetic origin, which have a high proportion of C ₁₈ -C ₂₄ fatty acids. Suitable non-surfactant foam inhibitors are, for example, organopolysiloxanes and mixtures thereof with microfine, optionally silanized silica and paraffins, waxes, microcrystalline waxes and mixtures thereof with silanated silica or bistearylethylenediamide. It is also advantageous to use mixtures of different foam inhibitors, for example those of silicones, paraffins or waxes. The foam inhibitors, in particular silicone or paraffin-containing foam inhibitors, are preferably bound to a granular, water-soluble or dispersible carrier substance. In particular, mixtures of paraffins and bistearylethylenediamides are preferred. If the vehicle of the foam inhibitor reacts alkaline in aqueous solution, it is an alkali carrier in the context of the invention, it can be treated as described above and used as an alkalizing agent. Conversely, an alkaline carrier foam inhibitor according to the invention should be delayed in solubility in order to maintain the required pH conditions at the beginning of the wash cycle. It may also be within the meaning of the invention be advantageous to use foam inhibitors with neutral-acting carrier, such as starch or cellulose derivatives.

The salts of polyphosphonic acids used are preferably the neutral-reacting sodium salts of, for example, 1-hydroxyethane-1,1-diphosphonate, diethylenetriamine penta-methylenephosphonate or ethylenediamine tetramethylenephosphonate in amounts of from 0.1 to 1.5% by weight.

The compositions according to the invention can contain, as optical brighteners, derivatives of diaminostilbenedisulfonic acid or its alkali metal salts. Suitable are e.g. Salts of 4,4'-bis (2-anilino-4-morpholino-1,3,5-triazinyl-6-amino) stilbene-2,2'-disulfonic acid or similarly constructed compounds which, instead of the morpholino group, a diethanolamino group , a methylamino group, an anilino group or a 2-methoxyethylamino group. Furthermore, brighteners of the substituted diphenylstyrene type may be present, e.g. the alkali salts of 4,4'-bis (2-sulfostyryl) -diphenyl, 4,4'-bis (4-chloro-3-sulfostyryl) -diphenyl, or 4- (4-chlorostyryl) -4 '- (2- sulfostyryl). Mixtures of the aforementioned brightener can be used.

If the composition according to the invention is used as a so-called universal detergent, it preferably contains from 5 to 25% by weight of anionic surfactants, from 1 to 25% by weight of nonionic surfactants, from 5 to 70% by weight of builder materials, from 1 to 40% by weight of bleaching agent , 1 to 10 wt .-% bleach activators, 0.1 to 5 wt .-% enzymes and from 1 wt .-% to 30 wt .-% pH regulators (buffering agent), besides other active ingredients, such as optical brighteners.

In a further preferred embodiment, the agent according to the invention is used as a so-called mild detergent or color detergent for washing delicate textiles, in particular at temperatures up to 40.degree. A mild detergent preferably contains from 5 to 25% by weight of anionic surfactants, 1 to 25% by weight of nonionic surfactants, 5 to 70% by weight of builder materials, 0.1 to 5% by weight of enzymes and 1 part by weight of % to 30% by weight pH regulators (buffering agent).

The color detergents are characterized by the fact that they especially protect the colors of delicate textiles and discoloration is prevented. Color detergents preferably contain from 5 to 25% by weight of anionic surfactants, 1 to 25% by weight of nonionic surfactants, 5 to 70% by weight of builder materials, 0.1 to 5% by weight of enzymes and 1% by weight to 30 wt .-% pH regulators (buffering agent), besides other active ingredients such as discoloration inhibitors.

The washing and / or cleaning agents can be used in liquid to gelatinous and also in solid form, with solid states of aggregation being preferred. In solid form, the agents may be in the form of powders, granules, extrudates or shaped articles, so-called tablets.

The powders can be prepared in a manner known per se by spray-drying methods and by simply mixing the pulverulent components.

If the compositions are to have higher bulk densities, they are preferably present in compacted form. The compact data include z. As the granules, extrudates and moldings.

The granules can be obtained by granulating the components in a variety of apparatus commonly used in the detergent industry. Thus, it is possible, for example, to use the usual in pharmacy Verrunder. In such turntable apparatus, the residence time of the granules is usually less than 20 seconds. Conventional mixers and mixed granulators are also suitable for granulation. Both high-intensity mixers ("high-shear mixers") and normal mixers with lower speeds of rotation can be used as mixers. Suitable mixers are, for example, Eirich® mixers of the R or RV series (trademarks of the Maschinenfabrik Gustav Eirich, Hardheim), the Schugi® Flexomix, the Fukae® FS-G mixers (trademarks of the Fukae Powtech, Kogyo Co., Japan), the Lödige® FM, KM and CB mixers (trademark of Lödige Maschinenbau GmbH, Paderborn) or the Drais® series T or KT (trademark of Drais-Werke GmbH, Mannheim). The residence times of the granules in the mixers are in the range of less than 60 seconds, wherein the residence time also depends on the rotational speed of the mixer. In this case, the residence times are shortened accordingly, the faster the mixer runs. Preferably, the residence times of the granules in the mixer / rounder are less than one minute, preferably less than 15 seconds. In slow-running mixers, eg a Lödige KM, residence times of up to 20 minutes are set, wherein residence times of less than 10 minutes are preferred because of the process economy.

In the process of press agglomeration, the surfactant-containing granules are compacted under pressure and under the action of shear forces and thereby homogenized and then discharged by shaping from the apparatus. The most technically important press agglomeration processes are extrusion, roll compaction, pelleting and tableting. In the context of the present invention, preferred pressure agglomeration processes used for the production of the surfactant-containing granules are extrusion, roll compaction and pelleting.

Upon completion of the granulation, a dry product is obtained which need not be subjected to any further drying step.

The granules obtained, to further improve their processability and meterability, can be powdered with an oil absorption component. By this final Abpuderungsschritt with a finely divided component, the liquids are set on the granule surface, so that the granules can not agglutinate during storage. The oil absorption component should have an oil absorption capacity of at least 20 g / 100 g, more preferably at least 50 g / 100 g, preferably at least 80 g / 100 g, more preferably at least 120 g / 100 g and especially at least 140 g / 100 g.

The oil absorption capacity is a physical property of a substance that can be determined by standardized methods. For example, there are the British standard methods BS1795 and BS3483: Part B7: 1982 , both of which refer to the ISO 787/5 standard. In the test methods, a well-balanced sample of the substance in question is placed on a plate and treated dropwise with refined linseed oil (density: 0.93 gcm ^-3 ) from a burette. After each addition, the powder is mixed thoroughly with the oil using a spatula, with the addition of oil continuing until a paste of smooth consistency is achieved. This paste should flow or run without crumbling. The oil absorption capacity is now the amount of oil dropped, based on 100 g absorbent and is given in ml / 100g or g / 100g, with conversions on the density of linseed oil are easily possible.

The oil absorption component preferably has the smallest possible average particle size, since the active surface increases with decreasing particle size. Preferred washing and / or cleaning agents contain a component having an oil absorption capacity of at least 20 g / 100 g, which has an average particle size of less than 50 μm, preferably less than 20 μm and in particular less than 10 μm.

As the oil absorption component, a variety of substances are suitable. There are a large number of both inorganic and organic substances which have a sufficiently large oil absorption capacity. By way of example, finely divided substances which are obtained by precipitation may be mentioned here. The substances used are, for example, silicates, aluminosilicates, calcium silicates, magnesium silicates and calcium carbonate. However, kieselguhr (diatomaceous earth) and finely divided cellulose fibers or derivatives thereof can also be used in the context of the present invention. Preferred detergents are characterized in that the component contained in them having an oil absorption capacity of at least 20 g / 100 g is selected from silicates and / or aluminosilicates, in particular from the group of silicic acids and / or zeolites. Come here For example, finely divided zeolites in question, but also pyrogenic silicas (Aerosil ^® ) or silicic acids, which were obtained by precipitation.

For the preparation of extrudates, a process is preferred in which first a premix of detergent ingredients is prepared. This solid preferably homogeneous premix is extruded using a plasticizer and / or lubricant via hole shapes with opening widths of the predetermined Exdrudatdimension at high pressures between 25 and 200 bar stranded. The strand is cut directly after emerging from the hole shape by means of a cutting device to the predetermined granule dimension. The application of the high working pressure causes the plasticization of the premix in granulation and ensures the cutting ability of the freshly extruded strands. The premix consists, at least in part, of solid, preferably finely divided, customary ingredients of detergents and / or cleaners, to which liquid constituents are optionally admixed. The solid ingredients may be obtained by spray drying Turpululver, but also agglomerates, each selected constituents of the mixture as pure substances which are mixed together in the finely divided state, and mixtures thereof. Following this, the liquid ingredients are added and then optionally a plasticizer and / or lubricant mixed. As plasticizers and / or lubricants, aqueous solutions of polymeric polycarboxylates and highly concentrated anionic surfactant pastes and nonionic surfactants are preferably used.

The production of moldings is carried out by methods known from the prior art. Usually, the individual components, which may be pre-granulated in whole or in part, are dry-mixed and subsequently shaped, in particular by compression into tablets, it being possible to resort to conventional methods. For the production of moldings, the premix is compressed in a so-called matrix between two punches to a solid compressed. This process, referred to below as tableting, is divided into four sections: Dosing, compaction (elastic deformation), plastic deformation and ejection.

First, the premix is introduced into the die, wherein the filling amount and thus the weight and the shape of the resulting shaped body are determined by the position of the lower punch and the shape of the pressing tool. The constant dosage even at high molding throughputs is preferably achieved via a volumetric metering of the premix. As the tableting progresses, the upper punch contacts the pre-mix and continues to descend toward the lower punch. In this compression, the particles of the premix are pressed closer to each other, with the void volume within the filling between the punches decreasing continuously. From a certain position of the upper punch (and thus from a certain pressure on the premix) begins the plastic deformation, in which the particles flow together and it comes to the formation of the molding. Depending on the physical properties of the premix, some of the premix particles are also crushed, and even higher pressures cause sintering of the premix. With increasing pressing speed, so high throughputs, the phase of the elastic deformation is shortened more and more, so that the resulting moldings may have more or less large cavities. In the last step of tableting, the finished molded body is pushed out of the die by the lower punch and carried away by subsequent transport means. At this time, only the weight of the molded article is finally determined, since the compacts due to physical processes (re-expansion, crystallographic effects, cooling, etc.) can change their shape and size.

The tabletting is carried out in commercial tablet presses, which can be equipped in principle with single or double punches. In the latter case, not only the upper punch is used for pressure build-up, also the lower punch moves during the pressing operation on the upper punch, while the upper punch presses down. For small production quantities, eccentric tablet presses are preferably used in which the one or more Stamp are attached to an eccentric disc, which in turn is mounted on an axis at a certain rotational speed. The movement of these punches is comparable to the operation of a conventional reciprocating engine. The compression can be done with a respective upper and lower punch, but it can also be attached more stamp on an eccentric disc, the number of Matrizenbohrungen is extended accordingly. Depending on the type, the throughputs of eccentric presses vary from a few hundred to a maximum of 3000 tablets per hour.

For larger throughputs, rotary tablet presses are selected in which a larger number of dies are arranged in a circle on a so-called die table. The number of matrices varies between 6 and 55 depending on the model, although larger matrices are commercially available. Each die on the die table is assigned an upper and lower punch, in turn, the pressing pressure can be actively built only by the upper or lower punch, but also by both stamp. The die table and the punches move about a common vertical axis, the punches are brought by means of rail-like cam tracks during the circulation in the positions for filling, compression, plastic deformation and ejection. At the points where a particularly serious raising or lowering of the punches is required (filling, compaction, ejection), these curved paths are supported by additional low-pressure pieces, Niederzugschienen and lifting tracks. The filling of the die via a rigidly arranged supply device, the so-called filling shoe, which is connected to a reservoir for the premix. The pressing pressure on the premix is individually adjustable via the pressing paths for upper and lower punches, the pressure being built up by the rolling of the punch shaft heads on adjustable pressure rollers.

Concentric presses can be provided to increase the throughput with two filling shoes, which only a semicircle must be run through to produce a tablet. For the production of two- and multi-layer moldings several filling shoes are arranged one behind the other, without the slightly pressed first layer is ejected before further filling. By suitable process control coat and point tablets can be produced in this way, which have a zwiebelschalenartigen structure, wherein in the case of the point tablets, the top of the core or the core layers is not covered and thus remains visible. Even rotary tablet presses can be equipped with single or multiple tools, so that, for example, an outer circle with 50 holes and an inner circle with 35 holes are used simultaneously for pressing. The throughputs of modern rotary tablet presses amount to over one million moldings per hour.

• Verwendung von Kunststoffeinlagen mit geringen Dickentoleranzen
• Geringe Umdrehungszahl des Rotors
• Große Füllschuhe
• Abstimmung des Füllschuhflügeldrehzahl auf die Drehzahl des Rotors
• Füllschuh mit konstanter Pulverhöhe
• Entkopplung von Füllschuh und Pulvervorlage

When tableting with rotary presses, it has proven to be advantageous to carry out the tableting with the lowest possible weight fluctuations of the tablet. In this way, the hardness fluctuations of the tablet can be reduced. Small variations in weight can be achieved in the following ways:

• Use of plastic inserts with small thickness tolerances
• Low number of revolutions of the rotor
• Big filling shoes
• Tuning of the filling paddle speed to the speed of the rotor
• Filling shoe with constant powder height
• Decoupling of filling shoe and powder template

To reduce Stempelanbackungen offer all known from the art non-stick coatings. Plastic coatings, plastic inserts or plastic stamps are particularly advantageous. Rotary punches have also proved to be advantageous, wherein, if possible, upper and lower punches should be rotatable. With rotating punches can be dispensed with a plastic insert usually. Here, the stamp surfaces should be electropolished.

It also showed that long press times are advantageous. These can be adjusted with pressure rails, several pressure rollers or low rotor speeds become. Since the hardness variations of the tablet are caused by the fluctuations of the pressing forces, systems should be used which limit the pressing force. Here can elastic stamp; pneumatic compensators or resilient elements are used in the force path. Also, the pressure roller can be made resilient.

Usually, the pressing takes place at pressing pressures of 0.01 to 50 kNcm ^-2 , preferably from 0.1 to 40 kNcm ^-2 and in particular from 1 to 25 kNcm ^-2 .

Suitable tableting machines are available, for example, from Apparatebau Holzwarth GbR, Asperg, Wilhelm Fette GmbH, Schwarzenbek, Hofer GmbH, Weil, Horn & Noack Pharmatechnik GmbH, Worms, IMA Verpackungssysteme GmbH Viersen, KILIAN, Cologne, KOMAGE, Keil am See, KORSCH Presses AG, Berlin, as well as Romaco GmbH, Worms. Other providers include Dr. med. Herbert Pete, Vienna (AU), Mapag Maschinenbau AG, Berne (CH), BWI Manesty, Liverpool (GB), I. Holand Ltd., Nottingham (GB), Courtoy NV, Halle (BE / LU) and Mediopharm Kamnik (SI ). Particularly suitable is, for example, the hydraulic double pressure press HPF 630 LAEIS, D. Tablettierwerkzeuge are for example from the company Adams tabletting tools, Dresden, Wilhelm Fett GmbH, Schwarzenbek, Klaus Hammer, Solingen, Herber% Sons GmbH, Hamburg, Hofer GmbH, Weil, Horn & Noack, Pharmatechnik GmbH, Worms, Ritter Pharamatechnik GmbH, Hamburg, Romaco, GmbH, Worms and Notter Werkzeugbau, Tamm available. Other providers are e.g. Senss AG, Reinach (CH) and Medicopharm, Kamnik (SI).

The moldings can be made in a predetermined spatial form and predetermined size, they always consist of several phases, ie layers, inclusions or cores and rings. As a form of space practically all useful manageable configurations come into consideration, for example, the training as a blackboard, the bar or bar shape, cubes, cuboids and corresponding space elements with flat side surfaces and in particular cylindrical configurations with circular or oval cross-section.

This last embodiment covers the presentation form of the tablet up to compact cylinder pieces with a ratio of height to diameter above 1.

The portioned compacts can be designed in each case as separate individual elements, which corresponds to the predetermined dosage amount of the washing and / or cleaning agent. However, it is also possible to form compacts which connect a plurality of such mass units in a compact, wherein in particular by predetermined predetermined breaking points, the easy separability portioned smaller units is provided. For the use of laundry detergents in machines of the type commonly used in Europe with horizontally arranged mechanics, the formation of the portioned tablets as tablets, in cylindrical or cuboidal form may be appropriate, with a diameter / height ratio in the range of about 0.5: 2 to 2: 0.5 is preferred. Commercially available hydraulic presses, eccentric presses or rotary presses are suitable devices, in particular for producing such compacts.

The spatial form of another embodiment of the moldings is adapted in their dimensions of the dispenser of commercial household washing machines, so that the moldings can be metered without dosing directly into the dispenser, where it dissolves during the dispensing process. Of course, however, a use of detergent tablets via a dosing is easily possible.

Another preferred multiphase molding that can be made has a plate-like or tabular structure with alternating thick long and thin short segments so that individual segments of this "multi-phase bar" are broken at the predetermined breaking points that constitute the short thin segments and can be entered into the machine. This principle of the "bar-shaped" shaped body wash can also be realized in other geometric shapes, for example vertical triangles, which are joined together only on one side thereof. Here it offers itself for optical reasons, the triangular basis, the connects individual segments together to form as a phase, while the triangular tip forms the second phase. A different staining of both phases is particularly attractive in this embodiment.

After pressing, the washing and / or cleaning agent tablets have a high stability.

The detergent tablets may be packaged after production, wherein the use of certain packaging systems has proven particularly useful, since these packaging systems on the one hand increase the storage stability of the ingredients, but on the other hand surprisingly also significantly improve the long-term adhesion of the trough filling. In a preferred embodiment of the present invention, the laundry detergent and / or detergent tablets are combined with a packaging system containing the detergent tablets, the packaging system having a moisture vapor transmission rate of from 0.1 g / m ² / day to less than 20 g / m ² / day when the packaging system is stored at 23 ° C and a relative equilibrium moisture content of 85%.

berechnen, wobei A die Fläche des zu testenden Materials in cm², x die Gewichtszunahme des Calciumchlorids in g und y die Expositionszeit in h bedeutet.The packaging system of the combination of detergent tablets and packaging system preferably has a moisture vapor transmission rate of from 0.1 g / m ² / day to less than 20 g / m ² / day when the packaging system is at 23 ° C and a relative equilibrium moisture content of 85% is stored. The temperature and humidity conditions mentioned are the test conditions specified in DIN standard 53122, with minimum deviations permissible according to DIN 53122 (23 ± 1 ° C, 85 ± 2% relative humidity). The moisture vapor transmission rate of a given packaging system or material can be determined by other standard methods and is also, for example, in the ASTM standard E-96-53T (test for measuring water vapor transmission of material in sheet form) and TAPPI standard T464 m-45 ("Water Vapor Permeability of Sheet Materials at High Temperature Humidity"). The measuring principle of common methods is based on the water absorption of anhydrous Calcium chloride, which is stored in a container in the appropriate atmosphere, the container is sealed at the top with the material to be tested. From the surface of the container, which is closed with the material to be tested (permeation surface), the increase in weight of the calcium chloride and the exposure time, the moisture vapor transmission rate decreases $$\mathit{FDDR}=\frac{24\cdot 10000}{A}\cdot \frac{x}{y}\left[G/m^2/24H\right]$$

where A is the area of the material to be tested in cm ² , x is the weight gain of calcium chloride in g and y is the exposure time in h.

The relative equilibrium moisture, often referred to as "relative humidity", in the measurement of moisture vapor transmission rate in the present invention is 85% at 23 ° C. The absorption capacity of air for water vapor increases with the temperature up to a respective maximum content, the so-called saturation content, and is expressed in g / m ³ . For example, 1 m ^{3 of} air is saturated by 17 ° with 14.4 g of water vapor, at a temperature of 11 ° saturation is already present with 10 g of water vapor. The relative humidity is the percentage expressed ratio of the actually existing water vapor content to the saturation content corresponding to the prevailing temperature. For example, if air at 17 ° contains 12 g / m ^{3 of} water vapor, then the relative humidity is (12 / 14.4) x 100 = 83%. If this air is cooled off, the saturation (100% RH) is reached at the so-called dew point (in the example: 14 °), ie, upon further cooling, a precipitate forms in the form of mist (dew). Hygrometers and psychrometers are used to quantify moisture.

The relative equilibrium humidity of 85% at 23 ° C can be, for example, in laboratory chambers with moisture control depending on the device type to +/- 2% RH set exactly. Even saturated solutions of certain salts form constant and well-defined relative humidities in closed systems at a given temperature, which are based on the phase equilibrium between the partial pressure of the water, the saturated solution and the body of the soil.

Combinations of detergent tablets and / or detergent tablets and packaging systems can, of course, in turn be packaged in secondary packaging, for example cardboard or trays, whereby no further requirements have to be placed on the secondary packaging. The secondary packaging is therefore possible, but not necessary.

Packaging systems preferred in the present invention have a moisture vapor transmission rate of from 0.5 g / m ² / day to less than 15 g / m ² / day.

Depending on the embodiment of the invention, the packaging system encloses one or more detergent tablets and / or detergent tablets. It is preferred to either design a shaped body in such a way that it comprises an application unit of the washing and / or cleaning agent, and to individually package this shaped body, or to pack the number of shaped bodies in a packaging unit, which in total comprises an application unit. With a nominal dosage of 80 g detergent and / or cleaning agent, it is thus possible to produce a 80 g heavy detergent and / or detergent tablets and package individually, but it is also possible, two 40 g each heavy detergent and / or detergent tablets to pack in a package to arrive at a combination. Of course, this principle can be expanded so that combinations can also contain three, four, five or even more detergent and / or cleaning agent tablets in one packaging unit. Of course, two or more moldings in a package may have different compositions. In this way, it is possible to spatially separate certain components, for example to avoid stability problems.

The above-described packaging system may be made of a variety of materials and take any external forms. For economic reasons and for reasons of easier processability, however, packaging systems are preferred in which the packaging material has a low weight, is easy to process and inexpensive. In preferred combinations, the packaging system consists of a sack or pouch of single-layer or laminated paper and / or plastic film.

The washing and / or detergent tablets may be unsorted, i. as a loose filling, be filled in a bag of the materials mentioned. However, for aesthetic reasons and for sorting the combinations in secondary packaging, it is preferred to fill the laundry detergent and / or detergent tablets individually or in a plurality of different sizes into bags or bags. For individual application units of the laundry detergent and / or detergent tablets, which are located in a bag or sack, the term "flow pack" has become common in the art. Such "flow packs" can then - again preferably sorted - optionally be packaged in outer packaging, which emphasizes the compact form of the molded article.

The preferably used as packaging system bags or bags of single-layer or laminated paper or plastic film can be designed in a variety of ways, such as inflated bag without center seam or bags with center seam, which closed by heat (heat fusion), adhesives or adhesive tapes become. Single-layer bag or bag materials are the known papers, which may optionally be impregnated, as well as plastic films, which may optionally be coextruded. Plastic films that can be used in the context of the present invention as a packaging system are, for example, in Hans Domininghaus "The plastics and their properties", 3rd edition, VDI Verlag, Dusseldorf, 1988, page 193 , stated. The figure 111 shown there also provides clues to the water vapor permeability of the materials mentioned.

In the context of the present invention particularly preferred combinations contain as packaging system a bag or bag of single-layer or laminated plastic film having a thickness of 10 to 200 .mu.m, preferably from 20 to 100 .mu.m and in particular from 25 to 50 microns.

Although it is possible to use wax-coated papers in the form of cardboard as a packaging system for the laundry detergent and / or detergent tablets in addition to the foils or papers mentioned above, it is preferred for the present invention if the packaging system does not comprise cardboard boxes of wax-coated paper. The term "packaging system" in the context of the present invention always characterizes the primary packaging of the moldings, i. the packaging, which is in direct contact with the molding surface on its inside. No requirements are placed on optional secondary packaging, so that all common materials and systems can be used here.

As already mentioned above, the laundry detergent and / or detergent tablets of the combination described contain, depending on their intended use, further ingredients of detergents and / or cleaning agents in varying amounts. Regardless of the intended use of the molded bodies, it is preferred that the detergent tablets and / or detergent tablets have / have a relative equilibrium moisture content of less than 30% at 35 ° C.

The relative equilibrium moisture content of the washing and / or cleaning agent shaped bodies can be determined by conventional methods, the following procedure being selected in the context of the present investigations: A water-impermeable 1-liter vessel with a lid which has a closable opening for the introduction of samples , Was filled with a total of 300 g of detergent tablets and held for 24 h at a constant 23 ° C to ensure a uniform temperature of the vessel and substance. Of the Water vapor pressure in the space above the moldings can then be determined with a hygrometer (Hygrotest 6100, Testoterm Ltd., England). The water vapor pressure is now measured every 10 minutes until two consecutive values show no deviation (equilibrium humidity). The above-mentioned hygrometer allows a direct display of the recorded values in% relative humidity.

Also preferred are embodiments in which the packaging system is reclosable. Even combinations in which the packaging system has a micro perforation can be realized with preference.

Examples

Detergents having the composition shown in Table 1 were prepared. <b> Table 1 </ b> component Quantity [g / wash load] Phase I Phase II Phase III Phase IV C ₁₂ -C ₁₈ -alkylbenzenesulfonate 9.75 x C ₁₂ -C ₁₈ alkyl sulfate 1.95 x C _12/18 fatty alcohol x 7 EO 2.93 x Zeolite A 14.63 x soda 7.31 x water glass 2.91 x Sokalan ^® CP 5 ¹ 2.44 x Na Percarbonate 11.25 x TAED 4.5 x protease 0.75 x amylase 0.23 x lipase 0.75 x cellulase 0.23 x Auxiliaries (foam inhibitors, perfume oil) 3.75 x water 6.5 x sodium sulphate ad 100 x Esterquat ² 7 x 1 Sokalan CP 5 ^® (polymeric polycarboxylate, manufactured by BASF AG, Ludwigshafen)
2 Esterquat Stepantex VL 90 (Stepan)

Claims (14)

1. Process for washing textile fabrics using surfactant(s), enzyme(s), alkalizing agent(s) and optionally further customary components,
   characterized in that
   the surfactants and any enzymes selected from amylase, lipase and cellulase are released in the wash liquor after a time t₁ = (t₀ to 1 min) in an amount of 80 to 100% by weight, based on the amount of surfactant and any enzyme used,
   the enzymes selected from proteases after a time t₂ = (t₀ + 5 to 10 min) in an amount of 60 to 100% by weight, based on the amount of enzyme used, and
   alkalizing agents after a time t₃ = (t₀ + 5 to 10 min) in an amount of 80 to 100% by weight, based on the amount of alkalizing agent used,
   where t₀ is the commencement of water supply.
2. Process according to Claim 1, characterized in that bleach components which, after a time t₄ = (t₀ + 10 to 20 min), are released in an amount of 80 to 100% by weight, based on the amount of bleach components used, are used.
3. Process according to Claim 1 or 2, characterized in that components for laundry aftertreatment which are released in a rinse cycle after the main wash cycle, preferably in the last rinse cycle, are used.
4. Process according to one of Claims 1 to 3, characterized in that the ingredients are formulated in a single composition.
5. Washing and/or cleaning composition comprising surfactant(s), enzyme(s), alkalizing agents and optionally further customary ingredients, characterized in that
   the surfactants and any enzymes selected from amylase, lipase and cellulase are released in the wash liquor after a time t₁ = (t₀ up to 1 min) in an amount of 80 to 100% by weight, based on the amount of surfactant and any enzyme used,
   the enzymes selected from proteases after a time t₂ = (t₀ + 5 to 10 min) in an amount of 60 to 100% by weight, based on the amount of enzyme used, and
   alkalizing agents after a time t₃ = (t₀ + 5 to 10 min) in an amount of 80 to 100% by weight, based on the amount of alkalizing agent used,
   where t₀ is the commencement of water supply, and the composition is present in the form of a multiphasic shaped body.
6. Composition according to Claim 5, characterized in that it comprises bleach components which are released after a time t₄ = (t₀ + 10 to 20 min) in an amount of 80 to 100% by weight, based on the amount used.
7. Composition according to Claim 5 or 6, characterized in that the alkalizing agent is selected from alkali metal carbonates and their hydrates and perhydrates, phosphates, soluble silicates, alkali metal hydroxides, carboxylates or persalts, builder substances and any mixtures thereof.
8. Composition according to one of Claims 5 to 7, characterized in that it comprises a buffer system which adjusts the pH of the wash liquor on addition of the washing composition to a value between 6 and 8.
9. Composition according to one of Claims 5 to 8, characterized in that the ingredients which are released at different times are divided between different phases.
10. Composition according to one of Claims 5 to 8, characterized in that the different phases have different disintegration times.
11. Composition according to one of Claims 5 to 10, characterized in that at least one of the phases is compressed, the disintegration time being adjusted via the compression pressure.
12. Composition according to one of Claims 5 to 10, characterized in that at least one of the phases is coated with a substance which retards the solubility.
13. Composition according to one of Claims 5 to 10, characterized in that at least one of the phases comprises binders for adjusting the disintegration time.
14. Composition according to one of Claims 5 to 10, characterized in that at least one of the phases comprises disintegrants for adjusting the disintegration time.