DE10110886A1 - Detergents and / or cleaning agents - Google Patents

Abstract

A method for washing textile fabrics using surfactants, enzymes and possibly other customary components is claimed, which is characterized in that the surfactants and optionally enzymes selected from amylase, lipase and cellulase in the wash liquor after a period of time t¶1¶ = (t¶o¶ to 1 min.) in an amount of 80 to 100 wt .-%, based on the amount used, the enzymes selected from proteases after a time t¶2¶ = (t¶o ¶ + 5 to 10 minutes) in an amount of 60 to 100 wt .-%, based on the amount used, and alkalizing agent after a time t¶3¶ = (t¶o¶ + 5 to 10 minutes) in one Amount of 80 to 100 wt .-%, based on the amount used, are released, where t¶o¶ is the start of the water supply. The method enables the targeted and defined release kinetics of individual ingredients to avoid interactions between the individual ingredients and changes in soiling due to prematurely released ingredients, thereby improving washing performance.

Description

The present invention relates to a method for washing textile fabrics under Use of surfactants, enzymes and possibly other, conventional components and a Detergents and / or cleaning agents, the surfactants, enzymes and possibly other, conventional ones Contains components.

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

Many publications deal with the solution to the problem, bleaching and separate enzymatic cleaning from each other, because the bleaching agents Reduce enzyme performance. There are basically two ways of doing this: Delayed Release of the bleach so that the enzymatic cleaning is completed before the Bleach are released in the wash liquor, or delayed release of the Enzymes when the bleaching process is almost complete. Another benefit that the result of the coating of the enzymes or bleaching agents is the increased storage stability, since uncoated enzymes and bleaching agents after prolonged storage, especially at Presence of moisture, quickly destroyed and the Detergent compositions lose their washing power.

Numerous agents are available for coating the detergent ingredients. in this connection Depending on the agent, a wide variety of factors such as temperature, pH Value, the kinetics of dissolution or the hydrolysis of the shell material, used for release become. A melt coating that only allows the casing to pass from a certain temperature is difficult to do because of today's preferred low washing temperatures Realize problems like clumping at low softening temperatures occur. Envelope materials that hydrolyze through sheer moisture also have  Disadvantages with regard to the storage stability of the funds. So it has to be a wrapping material searched for, on the one hand, quickly and under certain conditions in the wash liquor is soluble without affecting the washing process, but on the other hand is so stable that storage is easily possible.

Detergent and bleaching compositions comprising a source of hydrogen peroxide and a Contain peroxyacid bleach precursors (bleach activator) and one in the wash liquor Provide initial pH in alkaline (pH 10-11), as well as the delayed release of Acid in the wash liquor in order to achieve a reduced pH in the liquor 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) published.

The delayed release of individual components in detergent containing bleach compositions is mentioned in a number of patents. The international Patent applications WO 95/28454 (Procter & Gamble) and the series from WO 95/28464 bis WO 95/284469 (all Procter & Gamble) and WO 95/28473 (Procter & Gamble) disclose detergent compositions containing bleach containing a hydrogen peroxide precursor and contain a peroxyacid precursor, thus controlling the delivery of the peroxyacid 50% of the peroxyacid concentration (so-called T50 test) is between 180 and 480 seconds have been reached. The controlled delivery of the components is done by coating individual components, defined particle sizes, compacting and mechanical or manual addition achieved. The respective coated ones vary in the individual registrations Ingredients: So in WO 95/28464 is the release of the peracid versus the release a complexing agent is delayed; WO 95/28465 describes the release of peracid compared to the delivery of a builder, and in WO 95/28467 before delivery an enzyme is released from the peracid. WO 95/28466 describes the delayed delivery of an enzyme compared to the release of a surfactant, and WO 95/28468 or WO 95/28469 describe detergent compositions in which the delivery of a Enzyme against the release of a complexing agent for heavy metal ions or is delayed compared to a water-soluble builder.

DE 197 04 634 A1 describes a washing method for washing textile fabrics discloses, wherein the pH of the wash liquor after dissolution of the agent is below 8 and as the washing process progresses gradually by dissolving a coated one Alkalizing agent rises above 8.5, which is a release of a specific coated ingredient and a delayed effect of this ingredient  allows. Examples of alkalizing agents are bleaching agents such as Sodium percarbonate, which can be coated with a coating material, which dissolves slowly in water regardless of the pH value, while as a specially coated Ingredient a bleach activator, preferably tetraacetylethylene diamine (TAED), use place.

When developing new detergents and / or cleaning agents for textiles, too take into account that modern textiles often only at low temperatures, usually up to 40 ° C, because of the sensitivity of the textiles themselves or the colors. At low temperatures, the bleachable stains and the enzymatically removable stains, such as blood, have special requirements Detergents and / or cleaning agents.

Another problem is that the interaction of individual ingredients among themselves can lead to a reduction in their activity, for example Bleaching and alkalizing agents reduce the activity of enzymes such as protease.

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

The present invention was based on the object of a washing and / or cleaning agent to develop that through the targeted and defined release kinetics of individual Ingredients, especially the bleach, allows during the washing process, so that Interactions of the individual ingredients and changes in soiling avoided by prematurely released ingredients and thereby an improvement in Washing performance can be achieved. The improvement in washing performance should can be achieved especially at low washing temperatures.

The present invention relates to a method for washing textile fabrics using surfactant (s), enzyme (s), alkalizing agent (s) and, if appropriate, other, conventional components, which is characterized in that the surfactants and optionally enzymes are selected the enzymes selected from amylase, lipase and cellulase in the wash liquor after a time t ₁ = (t ₀ to 1 min.) in an amount of 80 to 100% by weight, based on the amount of surfactant and possibly enzyme used from proteases after a time t ₂ = (t ₀ + 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 t ₃ = (t ₀ + 5 to 10 minutes) in an amount of 80 to 100% by weight, based on the amount of alkalizing agent used, with t _{0 being} the start of the water feed.

Surprisingly, it was found that the performance of washing and / or Detergents especially at low temperatures and both opposite enzymatic and bleachable stains can be improved if the Agents contain enzymes and alkalizing agents and, if necessary, bleaching agents, each in one defined time from the water supply and over a defined period in the Wash liquor can be released, so these ingredients without mutual Interactions can develop their full activity.

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

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

In a further possible embodiment of the present invention, in a Phase IV so-called post-treatment agents, such as components for post-treatment,  such as fabric softener components, soil repellents, optical brighteners, Care substances, ironing aids or fragrances, or in the case of dishwashing detergents, Rinse aid surfactants, fragrances, possibly silver protection agents etc. released. The These components are preferably released only in a rinse after Main wash, preferably in the last rinse.

The washing and / or cleaning agent according to the invention is preferably in machine processes used. The machine textile washing in a usual, European household washing machine usually takes 40 to 60 minutes at 60 ° C and 30 to 60 minutes at 30 ° C or 40 ° C. A dishes cleaning in a usual Domestic dishwashers at 55 ° C or 65 ° C usually take 20 to 60 minutes. The individual ingredients of the washing and cleaning agents according to the invention are released with a delay, the periods during which the release of the Components takes place, can also overlap. As mentioned earlier, it is preferred when the release of protease and bleach is only marginal overlaps and particularly preferably does not release these components at the same time become.

The present invention accordingly furthermore relates to a washing and / or cleaning agent containing surfactant (s), enzyme (s), alkalizing agent and, if appropriate, other customary ingredients, which is characterized in that:
the surfactants and any enzymes selected from amylase, lipase and cellulase in the wash liquor after a time t ₁ = (t ₀ to 1 min.) in an amount of 80 to 100% by weight, based on the amount of surfactant used and possibly enzyme,
the enzymes, selected from proteases after a time t ₂ = (t ₀ + 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 t ₃ = (t ₀ + 5 to 10 minutes) in an amount of 80 to 100% by weight, based on the amount of alkalizing agent used,
are released, where t _{0 is} the beginning of the water supply.

The individual ingredients are described in more detail below.

From an application point of view, it is particularly preferred if the inventive Means is realized in a single product, so users only a single product put into the corresponding machine. In a particularly preferred Embodiments are the agents according to the invention in the form of so-called shaped bodies, also known as tablets in the prior art. In one particularly  In a preferred embodiment of the present invention, the shaped bodies have a plurality Phases on. For the purposes of the present invention, phases are sub-areas of Shaped body understood. These subareas can either be on top of each other or adjacent areas. In one possible embodiment, the Phases arranged as a ring / core. It is also possible for a phase to be a shaped body forms which has a trough and the second phase as a solid in this trough is inserted or glued.

The release of the individual ingredients at times t ₁ and t ₂ and, if appropriate, t ₃ and t ₄ is preferably adjusted by the different solubility of the different phases which the individual ingredients contain.

The solubility can be set, for example, by:

• a) pressing of solid components, the solubility by the pressing pressure is set and, if necessary, by adding binders;
• b) coating one or more phases with a solubility-retarding Substance, the solubility due to the type of coating and the layer thickness can be adjusted;
• c) addition of binder (s), where, if all phases contain binders, the solubility can be adjusted by the different content of binder;
• d) addition of disintegrant (s) (disintegrants), being if all phases Disintegrants contain the solubility due to the different content can be adjusted.

Different methods for adjusting the solubility can also be used. The following possible combinations are mentioned as examples for a two-phase system:

The individual ingredients as well as the manufacturing process are as follows described.

To coat the individual phases, these are provided with coating materials, which are dissolve in the wash liquor with a defined rate. After their dissolution it comes if possible to a step-like, ideally sudden release of the enveloped Phase. Preferred enveloping materials are fatty alcohols or fatty acids, which, if appropriate can be mixed with other coating materials. Here is an example Mixture of fatty alcohols and aluminum stearate called. Others from the state of the Envelope materials known in the art are summarized below in brief: Magnesium sulfate and sodium hexaphosphate, dihydrogen phosphate or pyrophosphate, 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 partly organic components such as fat derivatives, paraffins and waxes (Melting temperature of the compounds between 25 and 90 ° C), polyethylene glycols and Fatty acid esters thereof with a molecular weight of 300 to 1,700, 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 ether (MC, HEC, HPC, HPMC, CMC...), polysaccharides (starch, guar, Xanthan. , .), Proteins (gelatin, keratin hydrolyzates).

The coating materials can be applied from the melt or from solutions or Dispersions take place, the solvent or emulsifier being removed by evaporation becomes. Application as a fine powder, for example by electrostatic techniques, is possible, although this method is too irregular and poorly adherent Coatings leads. The casing materials can be mixed, mixed and Granulators are applied to particles. However, application of the Coating materials in a fluidized bed, with a simultaneous size classification of the particles can be done. The wrapping materials should become sticky under certain circumstances Products, it may make sense to add finely divided phases to the coated phases To apply substances ("powdering"). All fine particles come as powdering agents Substances in question, whereby other detergent components, such as builder substances, can be used. Preferred additional powdering agents are zeolites, Silicates, polymeric polycarboxylates, carbonates, citrates, starch, cellulose derivatives, etc. used.

As wrapping materials, especially for tablet phases, which are only effective in the rinse cycles So-called LCST substances can also be used. At LCST Substances are substances that perform better at low temperatures Have solubility than at higher temperatures. They are also used as substances lower critical separation temperature. Depending on the application conditions the lower, critical segregation temperature should be between room temperature and Temperature of the heat treatment, for example between 20 ° C, preferably 25 ° C and 100 ° C, especially 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 hydroxypropyl methyl cellulose (HPMC), ethyl (hydroxyethyl) cellulose (EHEC), hydroxypropyl cellulose (HPC), methyl cellulose (MC), ethyl cellulose (EC), propyl cellulose (PC), Carboxymethyl cellulose (CMC), carboxymethyl methyl cellulose (CMMC), Hydroxybutylcellulose (HBC), Hydroxybutylmethylcellulose (HBMC), Hydroxyethylcellulose (HEC), Hydroxyethylcarboxymethylcellulose (HECMC), Hydroxyethylethylcellulose (HEEC), Hydroxypropyl cellulose (HPC), hydroxypropyl carboxymethyl cellulose (HPCMC), hydroxy ethyl methyl cellulose (HEMC), methyl hydroxyethyl cellulose (MHEC), methyl hydroxyethyl propyl cellulose  (MHEPC) and mixtures thereof, carboxymethyl cellulose, methyl cellulose, Methylhydroxyethylcellulose and methylhydroxyproplcellulose as well as the alkali salts of the CMC and the slightly ethoxylated MC or mixtures of the foregoing are preferred.

Other examples of LCST substances are polyvinyl caprolactam, cellulose ether and Mixtures of cellulose ethers with carboxymethyl cellulose (CMC). Other polymers that show a lower, critical segregation 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 intertwined networks of the above (co) polymers. Are suitable also polyethylene oxide or copolymers thereof, such as ethylene oxide / propylene oxide copo polymers and graft copolymers of alkylated acrylamides with polyethylene oxide, polymeth acrylic acid, polyvinyl alcohol and copolymers thereof, polyvinyl methyl ether, certain pro teine, such as poly (VATGVV), 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 the LCST substance become. Such can the LCST (lower critical separation temperature) be modified accordingly.

The envelope materials are used in such quantities that an optimal one Interaction of the individual components and thus a precisely controlled release is made possible. Depending on the period within which the release is largely should be suppressed and depending on the size of the coated particles, you will see the amount measured on wrapping material. Preferred embodiments use less than 20% by weight % Shell material, based on the amount of coated particles; are in particular less than 10 wt% wrapping materials preferred.

In order to facilitate the disintegration of highly compressed moldings, it is possible to Disintegration aids, so-called tablet disintegrants, to be incorporated into them in order to Shorten disintegration times. These substances are suitable, for example, for the release accelerate individual shaped body areas compared to other areas. Under Tablet disintegrants or accelerators of disintegration are according to Römpp (9th edition, Vol. 6, p. 4440) and Voigt "Textbook of pharmaceutical technology" (6th edition, 1987, p. 182-184) Excipients understood for the rapid disintegration of tablets in water or Gastric juice and release of the pharmaceuticals in an absorbable form.  

These substances, which are also known as "explosives" due to their effectiveness, increase their volume when water enters, and on the one hand increases their own volume (Swelling), on the other hand, a pressure can be generated via the release of gases that breaks the tablet into smaller particles. Well-known Disintegration aids are, for example, carbonate / citric acid systems, and also other organic acids can be used. Swelling disintegration aids are, for example, synthetic polymers such as polyvinylpyrrolidone (PVP) or natural ones Polymers or modified natural products, such as cellulose and starch and their derivatives, alginates or casein derivatives.

Preferred detergent tablets contain 0.5 to 20% by weight, preferably 3 to 15% by weight and in particular 4 to 10% by weight of one or more Disintegration aid, each based on the weight of the molded body. Contains only a portion of the shaped body disintegration aid, the information given relates only to the weight of that portion.

Disintegrants based on cellulose are used as preferred disintegrants in the context of the present invention, so that preferred detergent tablets have such a disintegrant based on cellulose in amounts of 0.5 to 10% by weight, preferably 3 to 7% by weight and in particular 4 contain up to 6 wt .-%. Pure cellulose has the formal gross composition (C ₆ H ₁₀ O ₅ ) _n and, formally speaking, is a β-1,4-polyacetal of cellobiose, which in turn is made up of two molecules of glucose. Suitable celluloses consist of approximately 500 to 5000 glucose units and consequently have average molecular weights of 50,000 to 500,000. Cellulose-based disintegrants which can be used in the context of the present invention are also cellulose derivatives which can be obtained from cellulose by polymer-analogous reactions. Such chemically modified celluloses include, for example, products from esterifications or etherifications in which hydroxyl hydrogen atoms have been substituted. However, celluloses in which the hydroxyl groups have been replaced by functional groups which are not bound via an oxygen atom can also be used as cellulose derivatives. The group of cellulose derivatives includes, for example, alkali celluloses, carboxymethyl cellulose (CMC), cellulose esters and ethers and aminocelluloses. The cellulose derivatives mentioned are preferably not used alone as a cellulose-based disintegrant, but are used in a mixture with cellulose. The content of cellulose derivatives in these mixtures is preferably below 50% by weight, particularly preferably below 20% by weight, based on the cellulose-based disintegrant. Pure cellulose which is free of cellulose derivatives is particularly preferably used as the cellulose-based disintegrant.

The cellulose used as disintegration aid is preferably not in finely divided form Form used, but before mixing to the premixes to be pressed in transferred a coarser form, for example granulated or compacted. Washing and Detergent tablets, the disintegrant in granular or optionally contain cogranulated form, are in German patent applications DE 197 09 991 (Stefan Herzog) and DE 197 10 254 (Henkel) and the international patent application WO 98/40463 (Henkel). These writings are also details on Manufacture of granulated, compacted or cogranulated cellulose disintegrants remove. The particle sizes of such disintegrants are usually above 200 μm, preferably at least 90% by weight between 300 and 1600 µm and in particular at least 90% by weight between 400 and 1200 µm. The above and in the cited writings described in more detail, coarser disintegration aids based on cellulose are preferred as disintegration aids in the context of the present invention used and commercially, for example under the name Arbocel® TF-30-HG by available from Rettenmaier.

As another disintegrant based on cellulose or as a component of this component microcrystalline cellulose can be used. This microcrystalline cellulose is made by partial hydrolysis of celluloses obtained under such conditions that only the amorphous Attack areas (approx. 30% of the total cellulose mass) of the celluloses and completely dissolve, but leave the crystalline areas (approx. 70%) undamaged. A subsequent one The disaggregation of the microfine celluloses resulting from the hydrolysis provides the microcrystalline celluloses with primary particle sizes of approx. 5 µm and for example compactible to granules with an average particle size of 200 microns are.

Preferred detergent tablets in the context of the present invention additionally contain a disintegration aid, preferably a disintegration aid based on cellulose, preferably in granular, cogranulated or compacted form, in Amounts from 0.5 to 10% by weight, preferably from 3 to 7% by weight and in particular from 4 up to 6 wt .-%, each based on the weight of the molded body.  

As further ingredients, with the help of which the release of the active substances is controlled can be mentioned binders, both surfactant and non-surfactant Binders can be used.

Examples of surfactant binders are liquid, nonionic surfactants, such as those below Surfactants are described.

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

Preferred amounts in which the non-surfactant, water-soluble or liquid Binders used are within a narrow range, so preferred Detergent tablets contain a content of non-surfactant, water-soluble, liquid binders from 0.5 to 7.5 wt .-%, preferably from 0.75 to 5 wt .-% and in particular from 1 to 3% by weight, based in each case on the molding weight. Generally, according to the invention in the detergent tablets contained binders only the requirement that they deal with water mix completely or disperse in water. From the multitude of usable Binders have in particular substances from the group of polyethylene glycols and Polypropylene glycols, glycerin, glycerol carbonate, ethylene glycol, propylene glycol and Propylene carbonate proved to be a suitable binder. In addition, waxes and paraffins are considered To name examples of a water-insoluble but dispersible binder. Polymers too Binders such as B. polycarboxylates can be used.

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

H- (O-CH ₂ -CH ₂ ) _n -OH (I)

are sufficient, where n can have values between 1 (ethylene glycol, see below) and approx. 16. The decisive factor in evaluating whether a polyethylene glycol can be used according to the invention is the physical state of the PEG at room temperature, d. H. the freezing point of the  PEG must be below 25 ° C. Various exist for polyethylene glycols Nomenclatures that can lead to confusion. The specification is technically common of the average relative molecular weight following the specification "PEG", so that "PEG 200" characterized a polyethylene glycol with a relative molecular weight of about 190 to about 210. According to this nomenclature are technical in the context of the present invention common polyethylene glycols PEG 200, PEG 300, PEG 400 and PEG 600 can be used.

A different nomenclature is used for cosmetic ingredients, in which the abbreviation PEG is provided with a hyphen and immediately after the hyphen is followed by a number which corresponds to the number n in the formula I mentioned above. According to this nomenclature (known as 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.

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

Polypropylene glycols (abbreviation PPG) which can be used according to the invention are polymers of propylene glycol which have the general formula II:

are sufficient, with n assuming values between 1 (propylene glycol, see below) and approx. 12 can. Technically important here are in particular di-, tri- and tetrapropylene glycol, i.e. H. the representatives with n = 2, 3 and 4 in formula II.  

Glycerin is a colorless, clear, difficult to move, odorless, sweet tasting, hygroscopic liquid with a density of 1.261 that solidifies at 18.2 ° C. Glycerin was originally only 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 intermediate stages allyl chloride, epichlorohydrin. Another technical process is the hydroxylation of allyl alcohol with hydrogen peroxide at the WO ₃ contact via the glycide stage.

Glycerol carbonate can be obtained by transesterification of ethylene carbonate or dimethyl carbonate with glycerin, ethylene glycol or methanol being obtained as by-products. Another synthetic route starts from glycidol (2,3-epoxy-1-propanol), which is converted under pressure in the presence of catalysts with CO ₂ to form glycerol carbonate. Glycerine carbonate is a clear, easily movable liquid with a density of 1.398 gcm ^-3 that boils at 125-130 ° C (0.15 mbar).

Ethylene glycol (1,2-ethanediol, "glycol") is a colorless, viscous, sweet-tasting, strong hygroscopic liquid which is miscible with water, alcohols and acetone and a Density of 1.113. The freezing point of ethylene glycol is -11.5 ° C; the Liquid boils at 198 ° C. Technically, ethylene glycol is made from ethylene oxide by heating with Extracted water under pressure. Promising manufacturing processes can also be found the acetoxylation of ethylene and subsequent hydrolysis or on synthesis gas Build 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 with a density of 1.0597, which solidifies at -32 ° C and boils at 214 ° C. The production of 1,3-propanediol succeeds from acrolein and water with subsequent catalytic Hydrogenation.

Technically far more important is 1,2-propanediol (propylene glycol), which is an oily, colorless, almost odorless liquid with a density of 1.0381, which solidifies at -60 ° C and at 188 ° C boils. 1,2-propanediol is made from propylene oxide by adding water.

Propylene carbonate is a water-bright, easily moving liquid with a density of 1.2057 gcm ^-3 ; the melting point is -49 ° C, the boiling point is 242 ° C. Large quantities of propylene carbonate can also be obtained by reacting propylene oxide and CO ₂ at 200 ° C and 80 bar.

Nonionic, anionic, zwitterionic and also cationic can be used as surfactants Surfactants are used.

Anionic surfactants used are, for example, those of the sulfonate and sulfate type. The surfactants of the sulfonate type are preferably C _9-13 -alkylbenzenesulfonates, olefin sulfonates, ie mixtures of alkene and hydroxyalkanesulfonates and disulfates such as are obtained, for example, from C _12-18 monoolefins with a terminal or internal double bond by sulfonation Gaseous sulfur trioxide and subsequent, alkaline or acidic hydrolysis of the sulfonation products. Also suitable are alkanesulfonates obtained from C _12-18 alkanes, for example by sulfochlorination or sulf oxidation with subsequent hydrolysis or neutralization. Likewise, the esters of sulfo fatty acids (ester sulfonates), e.g. B. the α-sulfonated methyl ester of hydrogenated coconut, palm kernel or tallow fatty acids.

Other suitable anionic surfactants are sulfonated fatty acid glycerol esters. Under fatty acid glyce The mono-, di- and triesters as well as their mixtures are to be understood as Rinestern, as in the production by esterification of a monoglycerin with 1 to 3 moles of fatty acid or obtained in the transesterification of triglycerides with 0.3 to 2 mol of glycerol. preferred sulfated fatty acid glycerol esters are the sulfonation products of saturated fatty acids 6 to 22 carbon atoms, for example caproic acid, caprylic acid, capric acid, My ristic acid, lauric acid, palmitic acid, stearic acid or behenic acid.

As alk (en) yl sulfates, the alkali and especially the sodium salts of sulfuric acid are half-esters of C ₁₂ -C ₁₈ fatty alcohols, for example made from coconut fatty alcohol, tallow fatty alcohol, lauryl, myristyl, cetyl or stearyl alcohol or the C ₁₀ -C ₂₀ - Oxo alcohols and those half esters of secondary alcohols of this chain length are preferred. Also preferred are alk (en) yl sulfates of the chain length mentioned which contain a synthetic, petrochemical-based, straight-chain alkyl radical which have a degradation behavior analogous to that of the appropriate compounds based on oleochemical raw materials. From the washing, the C ₁₂ -C ₁₆ alkyl sulfates and C ₁₂ -C ₁₅ alkyl sulfates and C ₁₄ are - C ₁₅ alkyl sulfates. 2,3-Alkyl sulfates, which are produced, for example, according to US Pat. Nos. 3,234,258 or 5,075,041 and can be obtained as commercial products from the Shell Oil Company under the name DAN®, are also suitable anionic surfactants.

The sulfuric acid monoesters of the straight-chain or branched C _7-21 alcohols ethoxylated with 1 to 6 mol ethylene oxide, such as 2-methyl branched C _9-11 alcohols with an average of 3.5 mol ethylene oxide (EO) or C _{12 18} fatty alcohols with 1 to 4 EO are suitable. Because of their high foaming behavior, they are used in cleaning agents only in relatively small amounts, for example in amounts of 1 to 5% by weight.

Other suitable anionic surfactants are also the salts of alkylsulfosuccinic acid, which are also referred to as sulfosuccinates or as sulfosuccinic acid esters and which are monoesters and / or diesters of sulfosuccinic acid with alcohols, preferably fatty alcohols and especially ethoxylated fatty alcohols. Preferred sulfosuccinates contain C _8-18 fatty alcohol residues or mixtures thereof. Particularly preferred sulfosuccinates contain a fatty alcohol residue which is derived from ethoxylated fatty alcohols, which in themselves are nonionic surfactants (description see below). Again, sulfosuccinates whose fatty alcohol residues are derived from ethoxylated fatty alcohols with a narrow homolog distribution are particularly preferred. It is also possible to use alk (en) ylsuccinic acid with preferably 8 to 18 carbon atoms in the alk (en) yl chain or salts thereof.

Soaps are particularly suitable as further anionic surfactants. Suitable are ge saturated fatty acid soaps, such as the salts of lauric acid, myristic acid, palmitic acid, stearin acid, hydrogenated erucic acid and behenic acid and in particular from natural fatty acids, z. B. coconut, palm kernel or tallow fatty acids, derived soap mixtures.

The anionic surfactants including the soaps can be in the form of their sodium, potassium or ammonium salts and as soluble salts of organic bases, such as mono-, di- or tri ethanolamine. The anionic surfactants are preferably in the form of their sodium or potassium salts, especially in the form of the sodium salts.

Preferably at least a portion, preferably at least 50%, of the anionic Surfactants applied to a carrier material. Examples of carrier materials are Alkali carbonates, alkali sulfates, alkali citrates, alkali phosphates, silicas, Zeolites, citric acid and their mixtures. To adjust the pH at the beginning of the Not influencing the washing process, it has proven to be advantageous to use pH use neutral carrier materials such as silica gel, starch, cellulose and Cellulose derivatives, neutral reacting phosphates, alkali sulfates, polyacrylate derivatives, etc.

In addition to the anionic surfactants, the agents according to the invention can also use other agents Surfactants, e.g. B. 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 an average of 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 may contain linear and methyl-branched radicals in the mixture, as are usually present in oxo alcohol radicals. In particular, however, alcohol ethoxylates with linear residues from alcohols of native origin with 12 to 18 carbon atoms, for. B. from coconut, palm, tallow or oleyl alcohol, and an average of 2 to 8 EO per mole of alcohol preferred. The preferred ethoxylated alcohols include, for example, C _12-14 alcohols with 3 EO or 4 EO, C _9-11 alcohol with 7 EO, C _13-15 alcohols with 3 EO, 5 EO, 7 EO or 8 EO, C _12-18 alcohols with 3 EO, 5 EO or 7 EO and mixtures thereof, such as mixtures of C _12-14 alcohol with 3 EO and C _12-18 alcohol with 5 EO. The degrees of ethoxylation given represent statistical averages, which can be an integer or a fraction for a specific product. Preferred alcohol holoxylates 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 non-ionic surfactants, which either as sole, nonionic surfactant or in combination with other, nonionic surfactants are used are alkoxylated, preferably ethoxylated or ethoxylated and propoxylated fatty acid alkyl esters, preferably having 1 to 4 carbon atoms in the Alkyl chain, especially fatty acid methyl esters, such as those found in Japanese Patent application JP 58/217598 are described or preferably according to the in the international patent application WO-A-90/13533 who described processes the.

Another class of nonionic surfactants that can be used advantageously are the alkyl polyglycosides (APG). Alkypolyglycosides which can be used satisfy the general formula RO (G) _z , in which R denotes a linear or branched, in particular methyl-branched, saturated or unsaturated, aliphatic radical having 8 to 22, preferably 12 to 18, carbon atoms and G is Is symbol which stands for a glycose unit with 5 or 6 carbon atoms, preferably for glucose. The degree of glycosidation z is between 1.0 and 4.0, preferably between 1.0 and 2.0 and in particular between 1.1 and 1.4. Linear alkyl polyglucosides, ie alkyl polyglycosides, in which the polyglycosyl radical is a glucose radical and the alkyl radical is an n-alkyl radical are preferably used.

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

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

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

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

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

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

Examples of cationic surfactants are, in particular, quaternary ammonium compounds, cationi cal polymers and emulsifiers. The cationic surfactants are usually called Textile plasticizers used. Their release is therefore preferably only in Rinse cycle, d. H. in phase V of the process according to the invention.

Suitable examples are quaternary ammonium compounds of the formulas (III) and (IV):

where in (III) R ^a and R ^{b are} 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 equal to R ^a , R ^b or R ^c or represents an aromatic radical. X ^- stands for either a halide, methosulfate, methophosphate or phosphate ion and mixtures of these. Examples of cationic compounds of the formula (III) are didecyldimethylammonium chloride, ditallow dimethylammonium chloride or dihexadecylammonium chloride.

Compounds of formula (IV) are so-called ester quats. Esterquats are characterized by excellent biodegradability. Here R ^e stands for an aliphatic acyl radical having 12 to 22 carbon atoms with 0, 1, 2 or 3 double bonds; R ^f stands for H, OH or O (CO) R ^h , R ^g independently of R ^{f stands} for H, OH or O (CO) R ⁱ , where R ^h and R ⁱ independently of one another each represent an aliphatic acyl radical with 12 to 22 carbon atoms with 0, 1, 2 or 3 double bonds. m, n and p can each independently have the value 1, 2 or 3. X ^- can be either a halide, methosulfate, methophosphate or phosphate ion, as well as mixtures of these. Preferred compounds are those which contain the group O (CO) R ^h for R ^f and alkyl radicals having 16 to 18 carbon atoms for R ^c and R ^h . Compounds in which R ^{g is} also OH are particularly preferred. Examples of compounds of the formula (IV) are methyl-N- (2-hydroxyethyl) -N, N-di (tallow acyl-oxyethyl) ammonium methosulfate, bis- (palmitoyl) -ethyl-hydroxyethyl-methyl-amonium methosulfate or methyl-N, N-bis (acyloxyethyl) -N- (2-hydroxyethyl) ammonium methosulfate. If quaternized compounds of the formula (IV) are used which have unsaturated alkyl chains, preference is given to the acyl groups whose corresponding fatty acids have an iodine number between 5 and 80, preferably between 10 and 60 and in particular between 15 and 45 and which have a cis / trans isomer ratio (in% by weight) of greater than 30:70, preferably greater than 50:50 and in particular greater than 70:30. Commercial examples are the methylhydroxyalkyldialkoyloxyalkylammonium methosulfates sold by Stepan under the trademark Stepantex® or the products from Cognis known under De hyquart® or the products from Goldschmidt-Witco known under Rewoquat®. Other preferred compounds are the diesterquats of the formula (V), which are available under the names Rewoquat® W 222 LM or CR 3099 and, in addition to their softness, also ensure stability and color protection:

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

In addition to the quaternary compounds described above, other known compounds can also be used, such as quaternary imidazolinium compounds of the formula (VI):

where R ^{m is} H or a saturated alkyl radical with 1 to 4 carbon atoms, R ⁿ and R ^o independently of one another each represent an aliphatic, saturated or unsaturated alkyl radical with 12 to 18 carbon atoms, R ⁿ alternatively also for O (CO) R ^p may, 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.

Further suitable quaternary compounds are described by formula (VII):

where R ^q , R ^r and R ^s independently of one another represent a C ^1-4 alkyl, alkenyl or hydroxyalkyl group, R ^t and R ^u each independently represent a C _8-28 alkyl group and r is a number between 0 and 5 is.

In addition to the compounds of the formulas III to VII, short-chain, water-soluble, quaternary ammonium compounds are used, such as trihydroxyethylmethylammonium methosulfate or the alkyltrimethylammonium chlorides, dialkyldimethylammonium chlorides and Trialkylmethylammoniumchloride, e.g. B. Cetyltrimethylammonium chloride, stearyltrimethylam monium chloride, distearyldimethylammonium chloride, lauryldimethylammonium chloride, lauryl dimethylbenzylammonium chloride and tricetylmethylammonium chloride.

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

The quaternized compounds represent further cationic compounds which can be used according to the invention Protein hydrolyzates.

Suitable, cationic polymers include the polyquaternium polymers as described in CTFA Cosmetic Ingredient Dictionary (The Cosmetic, Toiletry and Fragrance, Inc., 1997), in particular the polyquaternium-6, polyquaternium-7, also known as merquats Polyquaternium-10 polymers (Ucare Polymer IR 400; Amerchol), Polyquaternium-4-Copoly mers, such as graft copolymers with a cellulose skeleton and quaternary ammonium groups, the are bound via allyldimethylammonium chloride, cationic cellulose derivatives, such as cationic guar, such as guar hydroxypropyl triammonium chloride and the like, quaternized Guar derivatives (e.g. Cosmedia Guar, manufacturer: Cognis GmbH), cationic, quaternary sugar derivatives (cationic alkyl polyglucosides), e.g. B. the commercial product Glucquat® 100, according to CTFA nomenclature a "Lauryl Methyl Gluceth-10 Hydroxypropyl Dimonium Chloride", Co polymers of PVP and dimethylaminomethacrylate, copolymers of vinylimidazole and vinyl pyrrolidone, aminosilicone polymers and copolymers.

Polyquaternized polymers (e.g. Luviquat Care from BASF) and also cationic chitin-based biopolymers and their derivatives, for example the one below polymer available under the trade name Chitosan® (manufacturer: Cognis).  

Also suitable according to the invention are cationic silicone oils, such as those in the Commercially available products Q2-7224 (manufacturer: Dow Corning; a stabilized trimethyl silylamodimethicone), Dow Corning 929 emulsion (containing a hydroxylamino modified Silicon, which is also called Amodimethicone), SM-2059 (Manufacturer: General Elec tric), SLM-55067 (manufacturer: Wacker) Abil®-Quat 3270 and 3272 (manufacturer: Goldschmidt- Rewo; diquartary polydimethylsiloxanes, Quaternium-80), and silicone quat Rewoquat® SQ 1 (Tegopren® 6922, manufacturer: Goldschmidt-Rewo).

Compounds of the formula (VIII) can also be used:

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

Surfactants are preferred in the cleaning or washing agents according to the invention in total in an amount from 5% by weight to 50% by weight, in particular from 8% by weight to 30 wt .-%, based on the finished agent, included.

Enzymes that can be used in the compositions come from the class of oxidases, Pro teases, 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 like Celluzyme® and or Carezyme®. Are particularly suitable from fungi or bacteria, such as  Bacillus subtilis, Bacillus licheniformis, Streptomyces griseus, Humicola lanuginosa, Humicola insolens, Pseudomonas pseudoalcaligenes or Pseudomonas cepacia, enzy active ingredients. The optionally used enzymes can, as for example in European patent EP 0 564 476 or in the international patent application WO 94/23005 described, adsorbed on carrier substances and / or in coating substances be bedded to protect them against premature inactivation. You are in the fiction contemporary detergents preferably in amounts up to 10 wt .-%, in particular of 0.2 wt .-% to 2 wt .-%, contain, with particular preference against oxidative degradation stabilized enzymes are used.

Alkalizing agents are all in the field of washing and / or cleaning agents known substances into consideration which have an alkaline reaction in water. It can be soluble Alkalizing agents, such as alkali carbonates and their hydrates and peroxyhydrates, phosphates such as As sodium tripolyphosphate, soluble silicates such as. B. water glasses, alkali hydroxides, Carboxylates or so-called persalts, such as Na perborate, can be used. Suitable examples are the insoluble alkali silicates also known as builders, as detailed below to be discribed. Mixtures of several alkalizing agents are also suitable. Around a release of the alkalizing agent over the period defined according to the invention it has proven to be advantageous to adjust the solubility by a suitable Retard coating and / or by a coarseness.

The agents according to the invention generally contain one or more builders, especially zeolites, silicates, carbonates, organic cobuilders and - where none There are ecological prejudices against their use - including phosphates. The latter are especially preferred in detergent tablets for automatic dishwashing Builders to be used. The builders mentioned below are as above described, also suitable as an alkalizing agent.

If they are insoluble, the builders are usually in finely divided form, i. H. in a particle size of 0.1 to 10 microns before. Many builders show latent alkaline Properties, d. H. overall, they are pH-neutral because of their insolubility, but they have alkaline groups on their surface. Because the particles from the textiles are filtered out and therefore come into intensive contact with the soiling, they create an alkaline environment locally, since they negatively affect washability especially bleachable stains, although macroscopically neutral pH can be present. A further increase in the washing effect can be achieved if the insoluble, finely divided builders become larger agglomerates using  neutral granulation aids are granulated or are present as coarser particles. These agglomerates slowly disintegrate during the washing process and set them Primary particles free. Due to the coarser particles, the Wash finishes a fine dispersion. As granulation aids are in particular Cellulose derivatives, polyvinyl alcohols, polycarboxylates, polyvinyl pyrrolidone and their Copolymers suitable.

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

Amorphous sodium silicates with a modulus Na ₂ O: SiO ₂ of 1: 2 to 1: 3.3, preferably from 1: 2 to 1: 2.8 and in particular from 1: 2 to 1: 2.6, can also be used are delayed in dissolving and have secondary washing properties. The delay in dissolution compared to conventional, amorphous sodium silicates can have been brought about in various ways, for example by surface treatment, compounding, compacting / compaction, 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 in X-ray diffraction experiments do not provide sharp X-ray reflections, as are typical for crystalline substances, but at most one or more maxima of the scattered X-rays, which have a width of several degree units of the diffraction angle. However, it can very well lead to particularly good builder properties if the silicate particles deliver washed-out or even sharp diffraction maxima in electron diffraction experiments. This is to be interpreted as meaning that the products have microcrystalline areas of size 10 to a few hundred nm, values up to max. 50 nm and in particular up to max. 20 nm are preferred. Compacted / compacted, amorphous silicates are particularly preferred; compounded, amorphous silicates and over-dried, 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. However, zeolite X and mixtures of A, X and / or P are also suitable. Commercially available and can preferably be used in the context of the present invention, for example a co-crystallizate of zeolite X and zeolite A (about 80% by weight of zeolite X) ), developed by CONDEA Augusta S. p. A. is sold under the brand name VEGOBOND AX® and by the formula:

nNa ₂ O. (1 - n) K ₂ O.Al ₂ O _3. (2-2.5) SiO _2. (3.5-5.5) H ₂ O

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

It goes without saying that the generally known phosphates are also used as Builder substances possible, provided that such use is not for ecological reasons should be avoided. Have among the variety of commercially available phosphates the alkali metal phosphates with particular preference for pentasodium or Pentapotassium triphosphate (sodium or potassium tripolyphosphate) in the washing and Detergent industry the most important.

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

Sodium dihydrogen phosphate, NaH ₂ PO ₄ , exists as a dihydrate (density 1.91 gcm ^-3 , melting point 60 °) and as a monohydrate (density 2.04 gcm ^-3 ). Both salts are white powders that are very easily soluble in water, which lose water of crystallization when heated and into the weakly acidic diphosphate (disodium hydrogen diphosphate, Na ₂ H ₂ P ₂ Q ₇ ) at 200 ° C, in sodium trimetaphosphate (Na ₃ P ₃ O ₉ ) and Maddrell's salt (see below). NaH ₂ PO _{4 is} acidic; it occurs when phosphoric acid is adjusted to a pH of 4.5 with sodium hydroxide solution and the mash is sprayed. Potassium dihydrogen phosphate (primary or monobasic potassium phosphate, potassium biphosphate, KDP), KH ₂ PO ₄ , is a white salt with a density of 2.33 gcm ^-3 , 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 easily water-soluble, crystalline salt. It exists anhydrous and with 2 moles (density 2.066 gcm ^-3 water loss at 95 °), 7 moles (density 1.68 gcm ^-3 melting point 48 ° with loss of 5 H ₂ O) and 12 moles of water (density 1.52 gcm ^-3 melting point 35 ° with loss of 5 H ₂ O), becomes anhydrous at 100 ° and changes to diphosphate Na ₄ P ₂ O ₇ when heated more strongly. Disodium hydrogen phosphate is prepared by neutralizing 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 easily soluble in water.

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

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

Condensation of the NaH ₂ PO ₄ or the KH ₂ PO ₄ produces higher molecular weight sodium and potassium phosphates, in which one can distinguish cyclic representatives, the sodium or potassium metaphosphates and chain-like types, the sodium or potassium polyphosphates. A large number of terms are used in particular for the latter: melt or glow phosphates, Graham's salt, Kurrol's and Maddrell's salt. All higher sodium and potassium phosphates are collectively referred to as condensed phosphates.

The technically important pentasodium triphosphate, Na ₅ P ₃ O ₁₀ (sodium tripolyphosphate), is an anhydrous or non-hygroscopic, water-soluble salt of the general formula NaO- [P (O) (ONa) -O] _n that crystallizes with 6 H ₂ O. -Na with n = 3. In 100 g of water about 17 g of the crystal water-free salt dissolve at room temperature, about 20 g at 60 ° and about 32 g at 100 °; After heating the solution at 100 ° for two hours, hydrolysis produces about 8% orthophosphate and 15% diphosphate. In the production of pentasodium triphosphate, phosphoric acid is reacted with sodium carbonate solution or sodium hydroxide solution in a stoichiometric ratio and the solution is dewatered by spraying. Similar to Graham's salt and sodium diphosphate, pentasodium triphosphate dissolves many insoluble metal compounds (including lime soaps, etc.). Pentapotassium triphosphate, K ₅ P ₃ O ₁₀ (potassium tripolyphosphate), is commercially available, for example, in the form of a 50% strength by weight solution (<23% P ₂ O ₅ , 25% K ₂ O). The potassium polyphosphates are widely used in the detergent and cleaning agent industry. There are also sodium potassium tripolyphosphates which can also be used in the context of the present invention. These occur, for example, when hydrolyzing sodium trimetaphosphate with KOH:

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

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

As organic cobuilders in the washing and / or Detergent tablets, in particular polycarboxylates / polycarboxylic acids, polymers Polycarboxylates, aspartic acid, polyacetals, dextrins, other organic cobuilders (see below) and phosphonates are used. These classes of substances are as follows described.

Usable organic builders are, for example, those in the form of their sodium salts usable polycarboxylic acids, such polycarboxylic acids being among polycarboxylic acids can be understood that carry more than one acid function. For example, these are  Citric acid, adipic acid, succinic acid, glutaric acid, malic acid, tartaric acid, Maleic acid, fumaric acid, sugar acids, aminocarboxylic acids, nitrilotriacetic acid (NTA), if such use is not objectionable for ecological reasons, and Mixtures of these. Preferred salts are the salts of polycarboxylic acids, such as Citric acid, adipic acid, succinic acid, glutaric acid, tartaric acid, sugar acids and Mixtures of these.

The acids themselves can also be used. The acids have besides theirs Builder effect typically also the property of an acidifying component and serve thus also for setting a lower and milder pH value of washing or Detergents. In particular, citric acid, succinic acid, glutaric acid, Adipic acid, gluconic acid and any mixtures of these.

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

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

Suitable polymers are in particular polyacrylates, which preferably have a molecular weight of Have 2000 to 20,000 g / mol. Because of their superior solubility, this can Group in turn the short-chain polyacrylates, the molar masses from 2000 to 10000 g / mol, and particularly preferably from 3000 to 5000 g / mol, may be preferred.

Also suitable are copolymeric polycarboxylates, especially those of acrylic acid Methacrylic acid and acrylic acid or methacrylic acid with maleic acid. As special copolymers of acrylic acid with maleic acid which have 50 to 90% by weight have proven suitable Contain acrylic acid and 50 to 10 wt .-% maleic acid. Your relative  Molecular weight, based on free acids, is generally 2,000 to 70,000 g / mol, preferably 20,000 to 50,000 g / mol and in particular 30,000 to 40,000 g / mol.

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

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

Biodegradable polymers of more than two are also particularly preferred various monomer units, for example those which are salts of the monomers Acrylic acid and maleic acid and vinyl alcohol or vinyl alcohol derivatives or as Monomeric salts of acrylic acid and 2-alkylallylsulfonic acid as well as sugar derivatives contain.

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

Likewise, as further preferred builder substances, polymeric aminodicarboxylic acids, to name their salts or their precursors. Are particularly preferred Polyaspartic acids or their salts and derivatives.

Other suitable builder substances are polyacetals, which are obtained by converting Dialdehydes with polyol carboxylic acids, which have 5 to 7 carbon atoms and at least 3 Have hydroxyl groups can be obtained. Preferred polyacetals are made from Dialdehydes, such as glyoxal, glutaraldehyde, terephthalaldehyde and mixtures thereof and from Polyol carboxylic acids, such as gluconic acid and / or glucoheptonic acid, are obtained.

Other suitable organic builder substances are dextrins, for example oligomers or polymers of carbohydrates obtained by partial hydrolysis of starches can be. The hydrolysis can be carried out according to conventional methods, for example acid or enzyme lysed procedures are carried out. It is preferably hydrolysis pro Products with average molecular weights in the range of 400 to 500,000 g / mol. There is one Polysaccharide with a dextrose equivalent (DE) in the range of 0.5 to 40, in particular from 2 to 30 preferred, DE being a common measure of the reducing effect of a polysaccharide compared to dextrose, which has a DE of 100. Useful  are both maltodextrins with a DE between 3 and 20 and dry glucose syrups with a DE between 20 and 37 as well as so-called yellow dextrins and white dextrins higher molar masses in the range from 2000 to 30000 g / mol.

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

Oxydisuccinates and other derivatives of disuccinates are also preferred Ethylene diamine disuccinate are other suitable cobuilders. Here, ethylenediamine-N, N'- disuccinate (EDDS) preferably used in the form of its sodium or magnesium salts. Glycerol disuccinates and are also preferred in this context Glycerol trisuccinates. Suitable amounts are in zeolite and / or formulations containing silicate at 3 to 15% by weight.

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

Another class of substances with cobuilder properties are the phosphonates it is especially hydroxyalkane or aminoalkanephosphonates. Among the Hydroxyalkanephosphonates is 1-hydroxyethane-1,1-diphosphonate (HEDP) from of particular importance as a cobuilder. It is preferably used as the sodium salt the disodium salt being neutral and the tetrasodium salt being alkaline (pH 9). As Aminoalkane phosphonates preferably come from ethylenediaminetetramethylenephosphonate (EDTMP), diethylenetriaminepentamethylenephosphonate (DTPMP) and their higher Homologues in question. They are preferably in the form of neutral reactions Sodium salts, e.g. B. as the hexasodium salt of EDTMP or as the hepta and octa sodium salt the DTPMP. Preferred as a builder from the class of phosphonates HEDP used. The aminoalkanephosphonates also have a pronounced Heavy metal binding capacity. Accordingly, it can, especially if the means too Contain bleach, be preferred, aminoalkanephosphonates, in particular DTPMP, to use, or to use mixtures of the phosphonates mentioned.  

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

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

Among the compounds which serve as bleaching agents and supply H ₂ O ₂ in water, sodium perborate tetrahydrate and sodium perborate monohydrate are of particular importance. Other usable bleaching agents are, for example, sodium percarbonate, peroxypyrophosphates, citrate perhydrates and H ₂ O ₂ -supplying, acidic salts or peracids such as perbenzoates, peroxophthalates, diperazelaic acid, phthaloiminoperacid or diperdodecanedioic acid. Bleaching agents from the group of organic bleaching agents can also be used. Typical organic bleaches are the diacyl peroxides, such as. B. dibenzoyl peroxide. Further, typical, organic bleaching agents are the peroxyacids, examples of which include the alkylperoxyacids and the arylperoxyacids. 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-phthalimidoperanoic acid prooperoxyacro (p) , o-carboxybenzamidoperoxycaproic acid, N-nonenylamidoperadipinic acid and N-nonenylamidopersuccinate, and c) aliphatic and araliphatic peroxydicarboxylic acids, such as 1,12-diperoxycarboxylic acid, 1,9-diperoxyazelaic acid, diperoxysebacic acid, diperoxydiperoxybiperylthanoic acid, diperoxybrassyldiacid-diperoxybrassylacid, -diacid, N, N-terephthaloyl-di (6-aminopercapronic acid) can be used.

The bleaching agent content of the agents can be 1 to 40% by weight and in particular 10 to 20% by weight. amount, advantageously perborate mono- or tetrahydrate or percarbonate is used.

The bleaching agents which may be present can also serve as alkalizing agents, since many in the alkaline aqueous medium. It has proven beneficial to use the bleach in coated form. The coating loosens during the washing process and releases the alkaline-reacting bleaching agent with a delay, causing the gradual increase in pH according to the invention takes place. To coat the Bleaching agents can use the same coating materials as for the coating the alkalizing agent. The application of the wrapping materials can also be carried out in the same way respectively.  

To improve when washing or cleaning at temperatures of 60 ° C and below To achieve bleaching effect, bleach activators can be incorporated. As Bleach activators can be compounds that are aliphatic under perhydrolysis conditions Peroxocarboxylic acids with preferably 1 to 10 C atoms, in particular 2 to 4 C atoms, and / or optionally substituted perbenzoic acid can be used.

Substances containing O and / or N-acyl groups of the number of carbon atoms mentioned are suitable and / or optionally substituted benzoyl groups. Multiple are preferred acylated alkylenediamines, especially 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 phenol sulfonates, especially n-nonanoyl or Isononanoyloxybenzenesulfonat (n- or iso-NOBS), carboxylic anhydrides, in particular Phthalic anhydride, acylated, polyhydric alcohols, especially triacetin, Ethylene glycol diacetate, 2,5-diacetoxy-2,5-dihydrofuran and acetylated sorbitol and mannitol or their in European patent application EP 0 525 239 (Ausimont SPA) described mixtures (SORMAN), acylated sugar derivatives, in particular Pentaacetylglucose (PAG), Pentaacetylfructose, Tetraacetylxylose and Octaacetyllactose as well as acetylated, optionally N-alkylated glucamine and gluconolactone, and / or N- acylated lactams, for example N-benzoylcaprolactam, which are from 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 described in international patent application WO 95/14075 (Degussa) Acyl lactams are also preferred. Even those from Germany Patent application DE 44 43 177 (Henkel) known combinations of conventional Bleach activators can be used. Such bleach activators are in quantities of 0.5 wt .-% to 15 wt .-%, based on the total, included.

In addition to the conventional bleach activators or in their place, too so-called bleach catalysts can be included. These substances are bleach-enhancing transition metal salts or transition metal complexes such as for example Mn, Fe, Co, Ru or Mo salt complexes or carbonyl complexes. Also Mn, Fe, Co, Ru, Mo, Ti, V and Cu complexes with N-containing tripod ligands as well as Co, Fe, Cu and Ru amine complexes are suitable as bleaching catalysts Compounds are preferably used, which are described in DE 197 09 284 A1.  

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 is increased when the Detergent composition and delay of the alkali carriers comparatively low, d. H. it is between 6 and 8, preferably between 6.3 and 7.7, particularly preferably between 6.5 and 7.5. At this pH, the washing effect of the Surfactants against bleachable soiling, such as tea, coffee, red wine or fruit and Vegetable juices to carry.

The buffer system is preferably used in amounts of 0.1 to 40, preferably 1 to 25% by weight, based on the finished agent used. As a buffer system, everyone can water-soluble substances are used, which are suitable for the pH of an aqueous Buffer the solution below the value 8.

In interaction with the other components of the agent according to the invention, this way a starting pH value can be achieved as the wash progresses is increased 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 acid, 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 amidosulfonic acid and mixtures of the acids mentioned. Also Substances such as hydrogen sulfates or carbonates can be used as a buffer system, Again, only the pH conditions have to be observed. Around when dissolving the agents according to the invention as quickly as possible a wash liquor with a pH To maintain the value within the limits defined above, the buffer systems must be selected so that they dissolve quickly and quickly bring the pH to the desired values. A Coating that would cause a delay in release is essential for the buffer systems in the Unwanted within the scope of the present invention. The buffer capacity of the buffer system must be chosen so high that different amounts of residual alkalinity in the Washer or laundry from previous washes can be neutralized can or that alkalinity emerging from lacquers of the coatings of the alkali carriers is neutralized in the event that a pH jump is to be realized.

From a technical point of view, the buffer system must be required to: are not volatile. From this point of view, fixed buffer systems are low  Sublimation tendency and a high melting point with good water solubility agree, clearly preferred. Liquid or pasty buffer systems can only be used in minor amounts below 5 wt .-% of the total composition used and when they are used, packaging measures must be taken in order to Ensure formulability and storage stability even with increased air humidity. When selecting the buffer system (s), it is of course also important to ensure that the resulting wash liquor does not harm the textiles or human skin.

In a possible embodiment of the present invention, the washing and / or Detergent used as a so-called full detergent, d. H. for washing any textiles and at any temperature. Detergent included Usually, in addition to the surfactants, enzymes and builder materials, organic and / or especially inorganic bleaches.

In addition to the surfactants, enzymes, bleaches and builders, the detergents according to the invention used a variety of other compounds become; examples include sequestering agents, electrolytes, optical brighteners, Phosphonates, graying inhibitors, color transfer inhibitors, color fixers, Foam regulators, additional bleach activators, colors and fragrances included.

When used in machine washing processes, it can be advantageous to add conventional foam inhibitors to the agents. Suitable 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-like foam inhibitors are, for example, organopolysiloxanes and their mixtures with microfine, optionally silanized silica, and paraffins, waxes, microcrystalline waxes and their mixtures with silanized silica or bistearylethylenediamide. Mixtures of different foam inhibitors are also used with advantages, for. B. from silicone, 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. Mixtures of paraffins and bistearylethylenediamids are particularly preferred. If the carrier substance of the foam inhibitor reacts alkaline in aqueous solution, it is an alkali carrier in the sense of the invention; it can be treated as described above and used as an alkalizing agent. Conversely, a foam inhibitor with an alkaline carrier in the sense of the invention should be delayed in solubility in order to maintain the required pH conditions at the start of the washing cycle. For the purposes of the invention, it can also be advantageous to use foam inhibitors with neutral-acting carriers, e.g. B. starch or cellulose derivatives.

The salts of polyphosphonic acids are preferably the neutral ones Sodium salts of, for example, 1-hydroxyethane-1,1-diphosphonate, diethylene triamine pentamethylene phosphonate or ethylenediaminetetramethylene phosphonate in quantities from 0.1 to 1.5% by weight.

The agents according to the invention can be derivatives of diaminostilbene di as optical brighteners contain sulfonic acid or its alkali metal salts. Are suitable for. B. 4,4'-bis (2- anilino-4-morpholino-1,3,5-triazinyl-6-amino) stilbene-2,2'-disulfonic acid or the like built-up compounds that instead of the morpholino group a diethanolamino group, carry a methylamino group, an anilino group or a 2-methoxyethylamino group. In addition, brighteners of the substituted diphenylstyryl type may be present, e.g. B. 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) diphenyl. Mixtures of the aforementioned brighteners can be used.

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

In a further preferred embodiment, the agent according to the invention is used as So-called mild detergent or color detergent for washing delicate Textiles, especially at temperatures up to 40 ° C, used. Contains a mild detergent preferably from 5 to 25% by weight of anionic surfactants, 1 to 25% by weight of nonionic Surfactants, 5 to 70% by weight builder materials, 0.1 to 5% by weight enzymes and from 1% by weight up to 30% by weight of pH regulators (buffering agents).

The color detergents are characterized by the fact that they are especially the colors of protect delicate textiles and prevent staining. Colorwaschmittel preferably contain from 5 to 25% by weight of anionic surfactants, 1 to 25% by weight nonionic surfactants, 5 to 70% by weight builder materials, 0.1 to 5% by weight enzymes and  from 1% by weight to 30% by weight pH regulators (buffering agents), in addition other active ingredients, like discoloration inhibitors.

The washing and / or cleaning agents according to the invention can be in liquid up to gel-like and also in solid form are used, whereby solid aggregate states are preferred. In solid form, the agents can be powder, granules, extrudates or as tablets, so-called tablets.

The powders can be spray dried and in a manner known per se simple mixing of the powdery components can be made.

If the agents are to have higher bulk densities, they are preferably in compact form. The compacts include e.g. B. the granules, extrudates and Moldings.

The granules can be obtained by granulating the components in a variety of ways Detergents and cleaning agents industry usually used equipment become. For example, it is possible to close the rounders common in pharmacy use. The residence time of the granules is in such turntable apparatuses usually less than 20 seconds. Also conventional mixers and mixing granulators are suitable for granulation. Both high-intensity mixers can be used as mixers ("high-shear mixer") as well as normal mixers with lower circulation speeds be used. Suitable mixers are, for example, Eirich® mixers of the R or series RV (trademark of Maschinenfabrik Gustav Eirich, Hardheim), the Schugi®-Flexomix, the Fukae®-FS-G mixer (trademark of Fukae Powtech, Kogyo Co., Japan), the Lödige® FM, KM and CB mixers (trademark of Lödige Maschinenbau GmbH, Paderborn) or the Drais® series T or K-T (trademark of Drais-Werke GmbH, Mannheim). The Residence times of the granules in the mixers are less than 60 seconds, the residence time also depends on the speed of rotation of the mixer. in this connection the dwell times are reduced accordingly the faster the mixer runs. Prefers the residence times of the granules in the mixer / rounder are less than one minute, preferably less than 15 seconds. In slow running mixers, e.g. B. a Lödige® KM, dwell times of up to 20 minutes are set, dwell times below 10 minutes are preferred because of the economics of the process.

In the press agglomeration process, the surfactant-containing granules are under pressure and compressed under the influence of shear forces and homogenized and then  discharged form-giving from the apparatus. The most technically significant Press agglomeration processes are extrusion, roller compaction, pelleting and tableting. In the context of the present invention preferably for the production of Press agglomeration processes used in the presence of surfactant-containing granules are extrusion Roll compacting and pelleting.

After the granulation is complete, a dry product is obtained, which is no other Drying step must be subjected.

The granules obtained can further increase their processability and meterability improve, be powdered with an oil absorption component. Through this final powdering step with a finely divided component Liquids set on the surface of the granules, so that the granules are stored cannot clump together. The oil absorption component should have an oil absorption capacity of at least 20 g / 100 g, more suitable at least 50 g / 100 g, preferably at least 80 g / 100 g, particularly preferably at least 120 g / 100 g and in particular at least 140 g / 100 g exhibit.

The oil absorption capacity is a physics 27053 00070 552 001000280000000200012000285912694200040 0002010110886 00004 26934al property of a substance, which can be determined according to standardized methods. For example, the British standard methods BS1795 and BS3483: Part B7: 1982 exist, both of which refer to the ISO 787/5 standard. In the test methods, a balanced sample of the substance in question is placed on a plate and refined flaxseed oil (density: 0.93 gcm ^-3 ) from a burette is added dropwise. After each addition, the powder is mixed intensively with the oil using a spatula, the addition of oil being continued until a paste of smooth consistency is obtained. This paste should flow or run without crumbling. The oil absorption capacity is now the amount of the added oil, based on 100 g of absorbent, and is given in ml / 100 g or g / 100 g, conversions about the density of the linseed oil being possible without any problems.

The oil absorption component preferably has the smallest possible medium Particle size, since the active surface increases with decreasing particle size. preferred Detergents and / or cleaning agents contain a component with a Oil absorption capacity of at least 20 g / 100 g, which has an average particle size of below 50 microns, preferably less than 20 microns and in particular less than 10 microns.  

A large number of substances are suitable as an oil absorption component. There is a big one Number of both inorganic and organic substances that are sufficiently large Have oil absorption capacity. Examples are finely divided substances that are produced by precipitation be won. For example, silicates, aluminosilicates, Calcium silicates, magnesium silicates and calcium carbonate use. But also diatomaceous earth (Diatomaceous earth) and finely divided cellulose fibers or derivatives thereof are included in the present invention can be used. Preferred detergents are characterized by that the component they contain has an oil absorption capacity of at least 20 g / 100 g is selected from silicates and / or aluminosilicates, in particular from Group of silicas and / or zeolites. Here, for example, finely divided zeolites come in question, but also pyrogenic silicas (Aerosil®) or silicas, which are caused by precipitation were obtained.

For the production of extrudates, a method is preferred in which a premix is initially used is made from detergent ingredients. This solid, preferably homogeneous Premixing is carried out using a plasticizer and / or lubricant via hole forms Opening widths of the predetermined extrudate dimension at high pressures between 25 and 200 bar extruded. The strand is immediately after exiting the hole shape cut to the predetermined granule dimension by means of a cutting device. The application of the high working pressure causes the premix to be plasticized granulate formation and ensures the cutting ability of the freshly extruded strands. The premix consists at least in part of solid, preferably finely divided, usual ingredients of detergents and / or cleaning agents, which may be liquid Components are mixed. The solid ingredients can be spray dried Extracted tower powders, but also agglomerates, the selected one Mixture components as pure substances that mix with each other in the finely divided state will be, as well as mixtures of these. Subsequently, the liquid Ingredients added and then optionally a plasticizer and / or lubricant mixed. Aqueous solutions of polymers are used as plasticizers and / or lubricants Polycarboxylates as well as highly concentrated anionic surfactant pastes and non-ionic surfactants preferably used.

Shaped bodies are produced in accordance with the state of the art Method. Usually the individual components, all or part can be pre-granulated, mixed dry and then shaped, in particular by pressing into tablets, using conventional methods can be used. The premix is produced in a  so-called die between two stamps compressed into a solid compressed. This The process, which is briefly referred to below as tableting, is divided into four Sections: dosage, compression (elastic deformation), plastic deformation and Ejection.

First, the premix is introduced into the die, the filling quantity and thus the weight and shape of the resulting molded body through the position of the lower one Stamp and the shape of the press tool can be determined. The constant one Dosage even at high molding throughputs is preferably over a volumetric dosage of the premix reached. In the further course of tableting the upper stamp touches the premix and continues to lower in the direction of the Lower stamp. With this compression, the particles of the premix become closer pressed together, the void volume within the filling between the Stamping decreases continuously. From a certain position of the upper stamp (and thus from a certain pressure on the premix), the plastic deformation begins at the particles flow together and the molded body is formed. Depending on the physical properties of the premix also become part of the premix particles crushed, and sintering of the premix occurs at even higher pressures. at increasing press speed, i.e. high throughput, becomes the phase of elastic deformation is continuously shortened, so that the resulting molded body more or may have smaller cavities. In the last step of tableting the Finished molded articles are pressed out of the die by the lower punch and through subsequent transport devices transported away. At this point, it's just that The weight of the molded body is finally determined because the compacts are physical Processes (stretching, crystallographic effects, cooling etc.) their shape and size can still change.

Tableting takes place in commercially available tablet presses, which are basically single or Double stamps can be equipped. In the latter case, it is not only the upper stamp used to build up pressure; the lower stamp also moves during the Pressing process towards the upper punch while the upper punch presses down. For Small production quantities are preferably used with eccentric tablet presses which the one or more stamps are attached to an eccentric, which in turn on one Axis is mounted with a certain rotational speed. The movement of this Press stamps are comparable to the way a conventional reciprocating piston engine works. The Pressing can be done with an upper and lower stamp; but it can also several stamps can be attached to an eccentric disc, the number of  Die holes are expanded accordingly. The throughputs of eccentric presses vary depending on the type from a few hundred to a maximum of 3000 tablets per hour.

For larger throughputs, rotary tablet presses are selected, on which one so-called die table a larger number of dies is arranged in a circle. The The number of matrices varies between 6 and 55, depending on the model, with larger matrices in the Are available commercially. Each die on the die table is an upper and lower stamp assigned, whereby again the pressing pressure is active only through the upper or lower stamp, but can also be built using both stamps. The matrix table and the stamp move around a common, vertical axis, using the stamp rail-like cam tracks during the circulation in the positions for filling, Compression, plastic deformation and discharge are brought. In the places where a particularly serious increase or decrease in the stamp is required (Filling, compacting, ejecting), these cam tracks are replaced by additional ones Low-pressure pieces, pull-down rails and lifting tracks supported. Filling the Die is made via a rigidly arranged feed device, the so-called filling shoe, which is connected to a storage container for the premix. The pressure on the Premix can be individually adjusted via the press paths for upper and lower punches, whereby the pressure build-up by rolling the stamp shaft heads past adjustable pressure rollers happens.

Rotary presses can also be used with two filling shoes to increase the throughput be provided, with only a semicircle to produce a tablet must become. Several are used to produce two-layer and multi-layer moldings Filling shoes arranged one behind the other without the slightly pressed first layer in front of the further filling is ejected. By appropriate process control this way also coated and dot tablets can be produced, which have an onion skin-like structure, in the case of the point tablets, the top of the core or the core layers are not is covered and thus remains visible. Rotary tablet presses are also or multiple tools can be equipped, so that, for example, an outer circle with 50 and an inner circle with 35 holes can be used simultaneously for pressing. The Throughputs of modern rotary tablet presses are over one million tablets per Hour.

When tableting with rotary presses, it has proven to be advantageous to carry out the tabletting with the smallest possible fluctuations in the weight of the tablet. The fluctuations in hardness of the tablet can also be reduced in this way. Small fluctuations 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
• - Matching the filler paddle speed to the speed of the rotor
• - Filling shoe with constant powder height
• - Decoupling of filling shoe and powder feed

All known from the art can be used to reduce stamp caking Non-stick coatings. Plastic coatings are particularly advantageous, Plastic inlays or plastic stamps. Rotating stamps have also proven to be advantageous proven, where possible the upper and lower stamps should be rotatable. In the case of rotating stamps, a plastic insert can generally be dispensed with. Here the stamp surfaces should be electropolished.

It was also shown that long press times are advantageous. You can use Pressure rails, several pressure rollers or low rotor speeds can be set. There the fluctuations in hardness of the tablet are caused by the fluctuations in the pressing forces systems should be used that limit the pressing force. Here you can elastic stamps, pneumatic compensators or spring elements in the force path be used. The pressure roller can also be designed to be resilient.

The compression is usually carried out at pressures of from 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 the Apparatebau company Holzwarth GbR, Asperg; Wilhelm Fette GmbH, Schwarzenbek; Hofer GmbH, Weil; Horn & Noack Pharmatechnik GmbH, Worms; IMA Verpackungssysteme GmbH, Viersen; KILIAN, Cologne; KOMAGE, Kell am See; KORSCH Pressen AG, Berlin, and Romaco GmbH, Worms. Other providers include Dr. Herbert Pete, Vienna (AU); Mapag Maschinenbau AG, Bern (CH); BWI Manesty, Liverpool (GB); I. Holand Ltd., Nottingham (GB); Courtoy N.V., Halle (BE / LU) and Mediopharm Kamnik (SI). For example, the Hydraulic double pressure press HPF 630 from LAEIS, D. Tablettierwerkzeuge are for example from Adams Tablettierwerkzeuge, Dresden; Wilhelm Fett GmbH, Schwarzenbek; Klaus Hammer, Solingen; Herber & Söhne GmbH, Hamburg; Hofer GmbH,  Because; Horn & Noack, Pharmatechnik GmbH, Worms; Ritter Pharamatechnik GmbH, Hamburg; Romaco, GmbH, Worms, and Notter Werkzeugbau, Tamm available. Other providers are z. B. Senss AG, Reinach (CH) and Medicopharm, Kamnik (SI).

The moldings can be made in a predetermined spatial shape and a predetermined size are, they always consist of several phases, i.e. H. Layers, inclusions or cores and wrestling. Practically all sensibly manageable come as a room shape Configurations into consideration, for example, the training as a board, the staff or Bar shape, cubes, cuboids and corresponding room elements with flat side surfaces and in particular cylindrical configurations with a circular or oval cross cut. This last embodiment covers the form of presentation from the tablet to compact cylinder pieces with a ratio of height to diameter above 1.

The portioned compacts can each be separate individual elements be formed, the predetermined dosage of detergents and / or cleaning agents equivalent. It is also possible, however, to form compacts that have a plurality of them Connect mass units in a compact, in particular by predetermined target breaks, easy separation of portioned, smaller units is provided. For the use of textile detergents in machines of the type common in Europe with horizontal arranged mechanics can the formation of the portioned pellets as tablets, in Cylindrical or cuboid shape, be appropriate, with a diameter / height ratio in Range of about 0.5: 2 to 2: 0.5 is preferred. Commercial hydraulic presses, Exzen Terpressen or rotary presses are suitable devices especially for the manufacture provision of such compacts.

The spatial shape of another embodiment of the shaped body is in its dimensions Detergent dispenser of commercial household washing machines adapted so that the Shaped bodies can be metered directly into the induction bowl without a metering aid, where they are dissolves during the induction process. It goes without saying that the Detergent tablets easily possible using a dosing aid.

Another, preferred, multi-phase molded body that can be produced has one plate or panel-like structure with alternating thick, long and thin, short segments elements, so that individual segments of this "multiphase bolt" to the predetermined breaking point len, which represent the short, thin segments, broken off and inserted into the machine can be used. This principle of the "bar-shaped" molded article detergent can also in other geometric shapes, for example vertically standing triangles, which only  are connected to each other along one side, can be realized. Here For optical reasons, it is advisable to use the triangular base that the individual segments use connects each other as one phase, while the triangle tip the second Phase forms. Different coloring of both phases is in this embodiment particularly appealing.

After pressing, the detergent tablets have a high Stability on.

The detergent tablets can be packaged after production, the use of certain packaging systems having 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 detergent tablets are combined with a packaging system containing the detergent tablets, the packaging system having a moisture vapor transmission rate of 0.1 g / m ² / day to less than 20 g / m ² / day if the packaging system is stored at 23 ° C and a relative equilibrium humidity of 85%.

The packaging system of the combination of detergent tablets and / or packaging system and packaging system preferably has a moisture vapor permeability rate of 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 humidity of 85% is stored. The specified temperature and humidity conditions are the test conditions that are mentioned in DIN standard 53122, whereby according to DIN 53122 minimal deviations are permissible (23 ± 1 ° C, 85 ± 2% relative humidity). The moisture vapor permeability rate of a given packaging system or material can be determined by further standard methods and is, for example, also in the ASTM standard E-96-53T ("Test for measuring Water Vapor transmission of Materials in Sheet form") and in the TAPPI standard T464 m- 45 ("Water Vapor Permeability of Sheet Materials at high temperature an Humidity"). The measuring principle of current methods is based on the water absorption of anhydrous calcium chloride, which is stored in a container in the appropriate atmosphere, the container being closed at the top with the material to be tested. The moisture vapor permeability rate can be determined from the surface of the container which is sealed with the material to be tested (permeation surface), the weight gain of the calcium chloride and the exposure time:

calculate, 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 humidity, often referred to as "relative humidity", is 85% at 23 ° C. when measuring the moisture vapor transmission rate in the context of the present invention. 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 given in g / m ³ . For example, 1 m ^{3 of} air at 17 ° is saturated with 14.4 g of water vapor; at a temperature of 11 ° there is saturation with just 10 g of water vapor. The relative humidity is the ratio of the actual water vapor content to the saturation content corresponding to the prevailing temperature. For example, if air contains 17 ° 12 g / m ³ water vapor, then the relative humidity = (12 / 14.4) .100 = 83%. If you cool this air, then the saturation (100% r.L.) is reached at the so-called dew point (in the example: 14 °), ie, if it cools further, a precipitate is formed in the form of fog (dew). Hygrometers and psychrometers are used for the quantitative determination of moisture.

The relative equilibrium humidity of 85% at 23 ° C can be found, for example, in Laboratory chambers with humidity control to +/- 2% r. Depending on the device type. Adjust L. exactly. Even over saturated solutions of certain salts form in closed systems at a given temperature, constant and well-defined, relative air humidities on the phase equilibrium between partial pressure of water, saturated solution and Soil bodies are based.

Combinations of detergent tablets and packaging systems can of course in turn in secondary packaging, for example cardboard boxes or trays, are packaged, with no additional to the secondary packaging Requirements must be made. The secondary packaging is therefore possible, however unnecessary.  

Packaging systems preferred in the context of the present invention have a moisture vapor permeability rate of 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 several detergent and / or detergent tablets. It is preferred either to design a shaped body such that it is an application unit of the washing and / or Detergent includes, and to pack this molded article individually, or the number Pack molded articles in a packaging unit, the sum of one Application unit includes. With a nominal dosage of 80 g washing and / or Detergent, it is therefore possible to use a 80 g heavy detergent and / or Manufacture detergent tablets and pack them individually; but it is also possible two 40 g heavy detergent tablets in one package pack to get a combination. This principle can be of course expand so that combinations also three, four, five or more Detergent and / or detergent tablets can contain in a packaging unit. Of course, two or more molded articles can be different in one package Have compositions. This way it is possible to have certain components to separate them spatially from each other, for example to avoid stability problems.

The packaging system described above can be of the most varied Materials exist and take any external form. For economic reasons and for reasons of easier processability, however, are packaging systems preferred, where the packaging material is light in weight, easily process and is inexpensive. This is in preferred combinations Packaging system consisting of a sack or bag made of single-layer or laminated paper and / or plastic film.

The detergent tablets can be unsorted, i. H. as loose Fill, be filled into a bag from the materials mentioned. But it's over aesthetic reasons and for sorting the combinations in secondary packaging preferred, the detergent and / or detergent tablets individually or in groups sorted into sacks or bags. For individual application units of the washing and / or detergent tablets which are in a sack or pouch the term "flow pack" is naturalized in technology. Such "flow packs" can then - again preferably sorted - optionally packaged in outer packaging, what the compact offer form of the molded body underlines.  

The sacks or bags to be used preferably as packaging systems Single-layer or laminated paper or plastic film can be used in a wide variety of ways Be fashioned, for example as a blown bag without a central seam or as a bag with central seam, which by heat (hot melting), adhesives or Adhesive tapes are closed. Single-layer bag or sack materials are the known papers, which may or may not be impregnated, and plastic films, which can optionally be co-extruded. Plastic films that are part of the present invention can be used as a packaging system for example in Hans Domininghaus "The plastics and their properties", 3rd edition, VDI-Verlag, Düsseldorf, 1988, page 193. Figure 111 shown there gives at the same time indications of the water vapor permeability of the materials mentioned.

Combinations particularly preferred in the context of the present invention contain as Packaging system a sack or pouch made of single-layer or laminated plastic film with a thickness of 10 to 200 microns, preferably from 20 to 100 microns and in particular of 25 to 50 µm.

Although it is possible, wax-coated in addition to the films or papers mentioned Papers in the form of cardboard boxes as a packaging system for washing and / or To use detergent tablets, it is within the scope of the present invention preferred if the packaging system does not have boxes made of wax-coated paper includes. The term "packaging system" in the context of the present Invention always the primary packaging of the moldings, d. H. the packaging on your The inside is in direct contact with the molded body surface. An optional Secondary packaging has no requirements, so all the usual ones Materials and systems can be used.

As already mentioned above, the detergent and / or detergent tablets contain the combination described, depending on its purpose, other ingredients from Detergents and / or cleaning agents in varying amounts. Independent of It is preferred that the shaped body be used for the washing or washing and / or Detergent tablets have a relative equilibrium moisture content of less than 30% 35 ° C.

The relative equilibrium moisture content of the detergent tablets can be determined using common methods, whereby within the scope of the present The following procedure was chosen for investigations:  Liter jar with a lid, which has a closable opening for the introduction of Has samples, was with a total of 300 g detergent tablets filled and kept at a constant 23 ° C for 24 h in order to maintain an even temperature of the vessel and to ensure substance. The water vapor pressure in the room above the moldings can then be determined with a hygrometer (Hygrotest 6100, Testoterm Ltd., England) become. The water vapor pressure is now measured every 10 minutes to two successive values show no deviation (equilibrium moisture). The above Hygrometer allows a direct display of the recorded values in% relative Humidity.

Also preferred are embodiments in which the packaging system is resealable. Combinations where the packaging system has a micro perforation, can be realized with preference.

Claims (16)

1. A method for washing textile fabrics using surfactant (s), enzyme (s), alkalizing agent (s) and, if appropriate, other, conventional components, characterized in that
the surfactants and any enzymes selected from amylase, lipase and cellulase in the wash liquor after a time t ₁ = (t ₀ to 1 min.) in an amount of 80 to 100% by weight, based on the amount of surfactant used and possibly enzyme,
the enzymes, selected from proteases, after a time t ₂ = (t ₀ + 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 t ₃ = (t _o + 5 to 10 min.) Are used in an amount of from 80 to 100 wt .-% on the amount of alkalizing agent released, where t _{0 is} the start of the water supply is. 2. The method according to claim 1, characterized in that bleaching components are used which are released after a time t ₄ = (t ₀ + 10 to 20 minutes) in an amount of 80 to 100, based on the amount of bleaching component used. 3. The method according to claim 1 or 2, characterized in that components used for post-washing, which are carried out in one rinse after Main wash cycle, preferably in the last rinse cycle. 4. The method according to any one of claims 1 to 3, characterized in that the Ingredients are packaged in a single agent. 5. washing and / or cleaning agent, containing surfactant (s), enzyme (s), alkalizing agent and, if appropriate, further, conventional ingredients, characterized in that
the surfactants and any enzymes selected from amylase, lipase and cellulase in the wash liquor after a time t ₁ = (t ₀ to 1 min.) in an amount of 80 to 100% by weight, based on the amount of surfactant used and possibly enzyme,
the enzymes, selected from proteases, after a time t ₂ = (t ₀ + 5 to 10 min.) in an amount of 60 to 100% by weight, based on the amount of enzyme used, and
Alkalizing agents are released after a time t ₃ = (t ₀ + 5 to 10 minutes) in an amount of 80 to 100% by weight, based on the amount of alkalizing agent used, where t _{0 is} the start of the water feed. 6. Composition according to claim 5, characterized in that it contains bleaching components which are released after a time t ₄ = (t ₀ + 10 to 20 minutes) in an amount of 80 to 100, based on the amount used. 7. Composition according to claim 5 or 6, characterized in that the Alkalizing agent is selected from alkali carbonates and their hydrates and Perhydrates, phosphates, soluble silicates, alkali hydroxides, carboxylates or Persalts, builder substances and any mixtures thereof. 8. Composition according to one of claims 5 to 7, characterized in that it is a Buffer system contains the pH of the wash liquor when adding the Set detergent composition between 6 and 8. 9. Composition according to one of claims 5 to 8, characterized in that it is in solid Form, in particular as a powder, granulate, extrudate or in the form of a shaped body is present. 10. Composition according to claim 9, characterized in that it is in the form of a multiphase molded body is present. 11. A composition according to claim 10, characterized in that the ingredients which are released at different times, are spread over different phases. 12. Composition according to claim 9 or 10, characterized in that the different Phases have different disintegration times. 13. Composition according to one of claims 10 to 12, characterized in that at least one of the phases is pressed, the disintegration time via the pressing pressure is set. 14. Composition according to one of claims 10 to 12, characterized in that at least one of the phases with a substance that retards solubility is coated. 15. Composition according to one of claims 10 to 12, characterized in that contains at least one of the phases binder to adjust the disintegration time.   16. Composition according to one of claims 10 to 12, characterized in that at least one of the phases of disintegration agent for setting the disintegration time contains.