DE10062857A1 - Detergent, detergent or cleaning agent portions with transparent wrapping - Google Patents

Abstract

The invention relates to a detergent, detergent or cleaning agent portion, comprising a completely or partially water-soluble envelope in capsule shape, spherical shape or in the form of a bag, the wrapping material being transparent and the portions containing a stabilizing agent. DOLLAR A A washing process, rinsing process or cleaning process using the above detergent, detergent or cleaning agent portion is also described.

Description

The present invention relates to detergents, dishwashing detergents or stabilizers Detergent servings that are completely or partially water-soluble and transparent Have wrapping.

Traditionally, detergents and cleaning agents have traditionally been available in larger quantities to consumers Containers containing large quantities such as plastic bottles given. The dosing was then carried out as required (degree of contamination of the washing, rinsing or items to be cleaned, amount of items to be washed, washed or cleaned) or, based on experience, in each In individual cases with suitable devices for measuring amounts of liquid.

Pre-dosed detergent, detergent or cleaning agent portions, the water-free Alcohol ether sulfates (isopropanol ammonium ether sulfates) as components of highly concentrated Detergent and cleaning agent systems are included in the article "U. Schoenkaes et al .; Water-free Alcohol Ether Sulfates - New high-active surfactants for super concentrated detergent Formulations ". Such systems are described as having excellent washing activity and are suitable for the stable incorporation of bleaches and others against water sensitive detergent, detergent and detergent components.

The detergent, cleaning agent or detergent portions are, however, in opaque or whole opaque, water-soluble coatings, such as soft gelatin, offered or must be in opaque, d. H. little or no translucent outer packaging become. To underline the aesthetic characteristics of the agents, however, it is advantageous if the detergent, cleaning agent or detergent portions in transparent, water-soluble envelopes can be offered.

The problem with this is the inconsistency of the coated washing, cleaning or Detergent ingredients against light. Because of the transparency and the given Light transmission (range 250 to 800 nm), in particular the transmission of UV light (250 up to 460 nm), the water-soluble coating materials often show signs of decomposition (e.g. radical decomposition of polymeric thickeners, dyes, etc.) or too Deactivation symptoms of active agent components (e.g. enzymes, bleach, etc.).  

WO 00/36062 and WO 00/36067 describe transparent or transparent, liquid, enzyme detergents containing clear bottles or containers made of water-insoluble polymers or Glass. The enzymes are made by antioxidants or by encapsulation protected.

WO 00/36068 and WO 00/36074 disclose transparent or transparent liquid detergents, which are presented in clear bottles or containers made of water-insoluble polymers or glass become. The detergent dyes or the detergent enzymes are by Fluorescent dyes or UV absorbers protected.

However, none of the documents described above deals with the problem of Lightfastness of washing, cleaning or detergent components in washing, cleaning or portions of detergent in a transparent, completely or partially water-soluble Wrapping present.

The object of the invention was washing, cleaning and detergent portions in one transparent, completely or partially water-soluble covering are available. The ingredients in the portions are intended to counteract the radiation-related decomposition and signs of deactivation are stabilized.

Surprisingly, it has now been found that the ingredients used in washing, cleaning and Portions of detergent in a transparent, completely or partially water-soluble coating are present, by means of stabilizers against signs of decomposition and deactivation can be stabilized.

The invention therefore relates to a detergent, dishwashing or cleaning agent portion, comprising a completely or partially water-soluble encapsulation in capsule form, the at least one Completely surrounds the formulation of a wash-active, rinse-active or cleaning-active material, and the serving contains at least one stabilizing agent, the water-soluble coating has a transmittance above 20% at wavelengths from 410 to 800 nm.

The subject of the invention in an alternative embodiment is a detergent, detergent or detergent portion comprising a completely or partially water-soluble coating in Spherical shape, the at least one formulation of a wash-active, rinse-active or completely surrounds cleaning-active material, and the portion at least one stabilizing agent contains, wherein the water-soluble coating has a permeability above 20% Has wavelengths from 410 to 800 nm.

The subject of the invention in a further alternative embodiment is a detergent, Serving of detergent or cleaning agent, comprising a completely or partially water-soluble  Envelope in the form of a pouch containing at least one formulation of a detergent, completely flushing active or cleaning-active material, and the portion at least one Contains stabilizing agents, the water-soluble coating having a permeability above of 20% at wavelengths from 410 to 800 nm.

The invention also relates to a washing process, a rinsing process and a cleaning process using the detergent, detergent or Cleaner portions.

The term "detergent, dish soap or detergent portion" is used in the context of present invention for a washing, rinsing or taking place in an aqueous phase Cleaning process sufficient amount of a detergent, detergent or cleaning agent Roger that. This can be, for example, a machine washing, rinsing or cleaning process be like him with commercial washing machines or dishwashers or cleaning machines is carried out. According to the invention, however, this term also includes a (for example in the hand wash basin or in a bowl) hand wash cycle or a dishwashing cycle carried out by hand or one in a cleaning liquor Container as in a bucket or other process of cleaning Understanding washing, rinsing or cleaning. According to the invention, the Detergent, dishwashing or cleaning agent portions for machine washing, dishwashing or Cleaning processes used.

Under the term "detergent portion" or "detergent portion" or "detergent Partial portion "in the context of the present invention is a partial amount of a detergent, Detergent or cleaning agent portion understood that in a different detergent, Detergent or detergent portions in separate phases in spatial connection with other portions of detergent, dishwashing liquid or detergent of the same detergent, Serving of detergent or detergent and prepared by suitable measures is that it is separate from other detergent, detergent or detergent portions the same detergent, detergent or cleaning agent portion in the fleet and can optionally be dissolved or suspended in it. A detergent, Portion of detergent or detergent the same ingredients as another Detergent, dishwashing or cleaning agent portion of the same detergent, dishwashing or detergent serving included; however, preferably contain two detergents, or detergent portions of the same detergent, dish soap or detergent Serving different ingredients, especially different washing-active, rinse-active or active cleaning preparations.

According to the detergent, detergent or cleaning agent portions contained abge measured amounts of at least one wash-active, rinse-active or cleaning-active preparation,  Usually measured quantities of several wash-active, rinse-active or cleaning-active Preparations. It is possible that the portions only wash-active, rinse-active or contain cleaning-active preparations of a certain composition. According to the However, it is preferred according to the invention that several, usually at least two, washing-active, active or cleaning active preparations of different compositions in the Detergent, detergent or cleaning agent portions are included. The composition With regard to the concentration of the individual components of the washing-active, rinsing-active or cleaning-active preparation (quantitative) and / or with regard to the type of individual components of the wash-active, rinse-active or cleaning-active preparation be (qualitatively) different. It is particularly preferred that the components with regard to Art and concentration are adapted to the tasks that the detergent, detergent or Portion of detergent must be fulfilled in the washing, rinsing or cleaning process.

The detergent, dishwashing or cleaning agent portion according to the invention comprises one completely or partially water-soluble coating. The shape of the envelope is according to the invention not limited to certain shapes. Basically all Archimedean and Plato come African body, i.e. three-dimensional shaped bodies, as forms of the envelope. Examples capsules, cubes, spheres, egg-shaped moldings, cuboids, cones, Rods or bags. Hollow bodies with one or more compartments, such as those in the pending patent application No. DE 100 33 827.5 entitled "Compartment- Hollow bodies "are described, are used as a covering for the wash-active, wash-active or suitable cleaning-active materials. In preferred embodiments of the invention the envelopes are in the form of capsules, as used, for example, in pharmacy Administration of drugs can be used, from bullets or from sachets. The latter are preferably welded or glued to at least one side, with particular use as an adhesive preferred embodiments of the invention, an adhesive is used which is water-soluble.

In principle, all come as materials for the completely or partially water-soluble coating Materials in question under the given conditions of a wash, rinse or cleaning process (temperature, pH value, concentration of detergent active Components) can completely or partially dissolve in the aqueous phase. The polymer materials can particularly preferably the groups (optionally partially acetalized) polyvinyl alcohol, polyvinylpyrrolidone, polyethylene oxide, gelatin, cellulose and their derivatives, starch and their derivatives, in particular modified starches, and mixtures (polymer blends, composites, Coextrudates etc.) of the materials mentioned. Gelatin and Polyvinyl alcohols and the two materials mentioned, each in combination with starch or modified strength. Inorganic salts and mixtures thereof also come as materials for the at least partially water-soluble coating.  

Polyvinyl alcohols (PVAL for short) are polymers of the general structure

[-CH ₂ -CH (OH) -] _n

those in small quantities also structural units of the type

[-CH ₂ -CH (OH) -CH (OH) -CH ₂ -]

contain. Since the corresponding monomer (vinyl alcohol) is not stable in free form, Polyvinyl alcohols via polymer-analogous reactions by hydrolysis, technically in particular by alkali-catalyzed transesterification of polyvinyl acetates with alcohols, preferably with Methanol. These technical processes also make PVAL accessible, some of them contain predetermined residual proportion of acetate groups.

Commercial PVALs (e.g. Mowiol® grades from Hoechst) come as white-yellowish powders or granules with degrees of polymerization in the range from about 500 to 2500 (corresponding Molar masses of about 20,000 to 100,000 g / mol) in the trade and have different Degrees of hydrolysis of, for example, 98 to 99 or 87 to 89 mol%. So they are partially saponified Polyvinyl acetates with a residual acetyl group content of, for example, approximately 1 to 2 or 11 up to 13 mol%.

The water solubility of PVAL can be increased by post-treatment with aldehydes (acetalization) or Ketones (ketalization) can be changed. As particularly preferred and because of their Extremely good cold water solubility has been particularly advantageous here Highlighted polyvinyl alcohols with the aldehyde or keto groups of saccharides or Polysaccharides or mixtures thereof can be acetalized or ketalized. As extreme The reaction products made of PVAL and starch can be used advantageously.

Furthermore, water solubility can be achieved by complexing with Ni or Cu salts or by Change treatment with dichromates, boric acid, borax and thus target the desired values to adjust. PVAL films are largely impenetrable for gases such as oxygen, nitrogen, Helium, hydrogen, carbon dioxide, however, allow water vapor to pass through.

Examples of suitable water-soluble PVAL films are those called "SOLUBLON®" by PVAL films available from Syntana Handelsgesellschaft E. Harke GmbH & Co. their Solubility in water can be adjusted to the degree, and they are films of this product range available in all relevant temperature ranges in the aqueous phase are soluble.  

Polyvinylpyrrolidones, abbreviated as PVP, can be described by the following general formula:

PVP are made by radical polymerization of 1-vinyl pyrrolidone. commercial PVP have molar masses in the range from approx. 2,500 to 750,000 g / mol and are hygroscopic powder or offered as aqueous solutions.

Polyethylene oxides, PEOX for short, are polyalkylene glycols of the general formula

H- [O-CH ₂ -CH ₂ ] _n -OH

the technically by basic catalyzed polyaddition of ethylene oxide (oxirane) in mostly low Systems containing water can be produced with ethylene glycol as the starting molecule. she have molecular weights in the range of approx. 200 to 5,000,000 g / mol, corresponding to Polymerisa degrees of approx. 5 to <100,000. Polyethylene oxides have an extremely low concentration tration on reactive hydroxyl end groups and show only weak glycol properties.

Gelatin is a polypeptide (molar mass: approx. 15,000 to <250,000 g / mol), which is mainly due to Hydrolysis of the collagen contained in the skin and bones of animals under acid or alkaline conditions is obtained. The amino acid composition of the gelatin ent speaks largely that of the collagen from which it was obtained and varies depending on of its provenance. The use of gelatin as a water-soluble shell material is very widely, especially in pharmacy in the form of hard or soft gelatin capsules spreads. Gelatin is found in the form of foils because of its compared to the above Low cost polymers of low use.

In the context of the present invention, detergents, dishwashing detergents and cleaning agents are also preferred Serving agent portions, the packaging of which is at least partially made of water-soluble film at least one polymer from the group starch and starch derivatives, cellulose and cellulose derivatives, especially methyl cellulose and mixtures thereof.

Starch is a homoglycan, with the glucose units linked α-glycosidically. Strength is made up of two components of different molecular weights: approx. 20 to 30% straight chain amylose (MW approx. 50,000 to 150,000) and 70 to 80% branched chain amylopectin  (MG.approx. 300,000 to 2,000,000). There are also small amounts of lipids, Contain phosphoric acid and cations. During the amylose due to the binding in the 1,4-position forms long, helical, intertwined chains with about 300 to 1,200 glucose molecules, In the case of amylopectin, the chain branches after an average of 25 glucose units through 1.6- Binding to a knot-like structure with about 1,500 to 12,000 molecules of glucose. Next pure starch are used to produce water-soluble coatings for detergents, detergents and Detergent portions also suitable for starch derivatives in the context of the present invention, which can be obtained from starch by polymer-analogous reactions. Such chemically modified Starches include, for example, products from esterifications or etherifications, in which have substituted hydroxy hydrogen atoms. But also strengths in which the hydroxy Groups replaced by functional groups that are not bound via an oxygen atom were used as starch derivatives. Fall into the group of starch derivatives for example alkali starches, carboxymethyl starch (CMS), starch esters and starches and Aminostarches.

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 5,000 glucose units and consequently have average molecular weights of 50,000 to 500,000. Cellulose-based disintegrants which can be used in the context of the present invention are also cellulose derivatives which can be obtained from cellulose by polymer-analogous reactions. Such chemically modified celluloses include, for example, products from esterifications or etherifications in which hydroxy hydrogen atoms have been substituted. However, celluloses in which the hydroxyl groups have been replaced by functional groups which are not bound via an oxygen atom can also be used as cellulose derivatives. The group of cellulose derivatives includes, for example, alkali celluloses, carboxymethyl cellulose (CMC), cellulose esters and ethers and aminocelluloses.

Preferred casings made of at least partially water-soluble film contain at least one Polymer with a molecular weight between 5,000 and 500,000 g / mol, preferably between 7,500 and 250,000 g / mol and in particular between 10,000 and 100,000 g / mol. The water soluble The film that forms the covering preferably has a thickness of 1 to 300 μm, preferably of 2 to 200 µm, particularly preferably from 5 to 150 µm and in particular from 10 to 100 µm.

These water-soluble films can be produced by various manufacturing processes. In principle, blowing, calendering and casting processes should be mentioned here. With a preferred one The process is based on a melt with air through a blow dome blown a hose. In the calendering process, which is also preferred among the used manufacturing processes, the raw plasticized by suitable additives materials for forming the films are atomized. In particular, it may be necessary to contact the  Spray to connect drying. In the casting process, which is also the one before production process is heard, an aqueous polymer preparation is heated to a Drying roller given, after evaporation of the water is optionally cooled and the film printed as a film. If necessary, this film becomes additional before or during the peeling powdered.

As materials for the coating of detergent, dishwashing detergent or cleaning agents according to the invention Organic and / or inorganic salts are also suitable. Examples for this are salts that can be formed into a coating, for example by means of crystals sation, pressing, compacting or other suitable processes, and which are subject to the conditions the washing, rinsing or cleaning process in sufficient time in water or water Solve fleet. Ideally, in particularly preferred embodiments of the invention such salts used in a washing, rinsing or cleaning process also others Can take over functions.

An embodiment is preferred according to the invention, according to which the covering as a whole is water soluble, d. H. when used as intended for washing, rinsing or Cleaning, for example during machine washing, rinsing or cleaning, completely dissolves, when the conditions for loosening are reached. Particularly preferred as a whole Water-soluble coatings are e.g. B. capsules made of gelatin, advantageously made of soft gelatin, or Pouch made of (optionally partially acetalized) PVAL or balls made of gelatin or (optionally partially acetalized) PVAL or one or more organic and / or inorganic salts, preferably balls of soft gelatin. Significant advantage this embodiment is that the wrapper is within a practically relevant short time - As a non-limiting example, a few seconds to 5 minutes can be defined under exactly Conditions in the wash liquor, rinse liquor or cleaning liquor at least partially dissolves and thus the wrapped content according to the requirements, d. H. the wash-active, rinse-active or cleaning-active material or several materials into the fleet.

In another embodiment, which is also preferred due to advantageous properties Invention encompasses the water-soluble coating less or not water-soluble or at all areas that are water-soluble only at higher temperatures and water-soluble areas or at lower ones Temperature water soluble areas. In other words, the wrapper does not consist of one uniform material, which has the same water solubility in all areas, but from Materials of different water solubility. Areas of good water solubility are one to be distinguished from areas with less good water solubility, with poor or even lack of water solubility or in areas where water solubility is only at higher levels Temperature or only at a different pH value or only when the electrolyte has changed concentration reached the desired value, on the other hand. This can lead to Intended use under adjustable conditions certain areas of the  Loosen the wrap while other areas remain intact. So one forms with pores or Holed casing into which water and / or liquor penetrate, wash-active, rinse-active or detach active ingredients and can discharge them from the casing. In the same Wrapping systems in the form of multi-chamber bags or in the form of in mutually arranged hollow bodies (eg balls: "onion system") can be provided. So systems with controlled release of washing-active, rinsing-active or cleaning produce active ingredients.

The invention is not subject to any restrictions for the formation of such systems. So can Envelopes are provided in which a single polymer material has small areas incorporated compounds (for example salts) which are more water soluble than the polymer material. On the other hand, several polymer materials can also be used different water solubility are mixed (polymer blend), so that the faster soluble polymer material under defined conditions by water or the liquor faster is disintegrated than the more slowly soluble.

It corresponds to a particularly preferred embodiment of the invention that the less well water-soluble areas or areas that are not water-soluble at all, or only in higher areas Temperature water-soluble areas of the wrapping areas are made of a material chemically essentially that of the readily water-soluble areas or at lower Temperature corresponds to water-soluble areas, but has a higher layer thickness and / or has a changed degree of polymerization of the same polymer and / or has a higher degree of crosslinking of the same polymer structure and / or a higher aceta Degree of lisation (in PVAL, for example with saccharides, polysaccharides, such as starch) and / or has a content of water-insoluble salt components and / or a content of a water-insoluble polymer. Even taking into account the fact that detergent, dishwashing detergent or cleaning agents can thus not come off completely Serving agent portions are provided according to the invention, the advantageous properties in the release of the wash-active, rinse-active or cleaning-active components in the have respective fleets.

According to the invention, the water-soluble covering material is transparent. Under transparency is in mind this invention to understand that the permeability within the visible spectrum of the Light (410 to 800 nm) greater than 20%, preferably greater than 30%, most preferably greater than 40% and in particular greater than 50%. As soon as a wavelength of the visible Spectrum of light has a transmittance greater than 20%, it is in the sense of the invention to be regarded as transparent.

The transparent, water-soluble portions contain at least one essential component a stabilizer. Stabilizing agents in the sense of the invention are materials that Detergent, detergent or detergent ingredients in their water-soluble, transparent  Protect envelopes from decomposition or deactivation by exposure to light. As special Antioxidants, UV absorbers and fluorescent dyes have proven suitable here.

Particularly suitable stabilizers in the sense of the invention are the antioxidants. In order to prevent undesired changes in the formulations caused by light radiation and thus radical decomposition, the formulations can contain antioxidants. Phenols, bisphenols and thiobisphenols substituted by sterically hindered groups can be used as antioxidants. Further examples are propyl gallate, butylated hydroxytoluene (BHT), butylated hydroxyanisole (BHA), t-butylhydroquinone (TBHQ), tocopherol and the long-chain (C8-C22) esters of gallic acid, such as dodecyl gallate. Other substance classes are aromatic amines, preferably secondary aromatic amines and substituted p-phenylenediamines, phosphorus compounds with trivalent phosphorus such as phosphines, phosphites and phosphonites, citric acids and citric acid derivatives, such as isopropyl citrate, compounds containing endiol groups, so-called reductones, such as ascorbic acid and its Derivatives, such as ascorbic acid palmitate, organosulfur compounds, such as the esters of 3,3'-thiodipropionic acid with C _1-18 alkanols, in particular C _10-18 alkanols, metal ion deactivators which are able to catalyze the auto-oxidation metal ions, such as, for , As copper, to complex, such as Nitrilotri acetic acid and its derivatives and their mixtures. A large number of examples of such antioxidants is summarized in DE 196 16 570 (BASF AG) - the antioxidants mentioned there can be used in the context of the present invention.

Antioxidants can be present in the formulations in amounts of up to 35% by weight, preferably up to 25% by weight. particularly preferably from 0.01 to 20 and in particular from 0.03 to 20% by weight be included.

Another class of stabilizers that can preferably be used are the UV absorbers.

UV absorbers can improve the lightfastness of the formulation components. Among them are understand organic substances (light protection filters) that are able to transmit ultraviolet rays to absorb and the absorbed energy in the form of longer-wave radiation, for. B. heat like to deliver. Compounds that have these desired properties are exemplary as the compounds and derivatives of the effective by radiationless deactivation Benzophenones with substituents in the 2- and / or 4-position. There are also substituted ones Benzotriazoles, such as the water-soluble benzenesulfonic acid 3- (2H-benzotriazol-2-yl) - 4-hydroxy-5- (methylpropyl) monosodium salt (Cibafast® H), phenyl substituted in the 3-position Acrylates (cinnamic acid derivatives), optionally with cyano groups in the 2-position, salicylates, organic Ni complexes as well as natural substances such as umbelliferone and the body's own urocanoic acid suitable. Biphenyl and especially stilbene derivatives, such as those, are of particular importance be described in EP 0728749 A and commercially as Tinosorb® FD or Tinosorb® FR ex Ciba are available. 3-Benzylidene camphor or 3- Benzylidene norcampher and its derivatives, e.g. B. 3- (4-methylbenzylidene) camphor, as in EP 0693471 B1  described; 4-aminobenzoic acid derivatives, preferably 4- (dimethylamino) benzoic 2-ethylhexyl acid, 4- (dimethylamino) 2-octyl benzoate and 4- (dimethylamino) ben zoesäureamylester; Esters of cinnamic acid, preferably 2-ethylhexyl 4-methoxycinnamate, 4- Propyl methoxy cinnamate, isoamyl 4-methoxy cinnamate, 2- 2-cyano-3,3-phenyl cinnamate ethylhexyl ester (octocrylene); Esters of salicylic acid, preferably 2-ethylhexyl salicylic acid, Salicylic acid 4-isopropyl benzyl ester, salicylic acid homomethyl ester; Derivatives of benzophenone, preferably 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-methoxy-4'-methylbenzophenone, 2,2'-dihydroxy-4-methoxybenzophenone; Esters of benzalmalonic acid, preferably 4-methoxy benzmalonsduredi-2-ethylhexyl ester; Triazine derivatives, such as. B. 2,4,6-Trianilino- (p-carbo-2'-ethyl-1 hexyloxy) -1,3,5-triazine and octyl triazone, as described in EP 0818450 A1 or dioctyl Butamido Triazone (Uvasorb® HEB); Propane-1,3-diones such as e.g. B. 1- (4-tert-Butylphenyl) -3- (4'meth oxyphenyl) propane-1,3-dione; Ketotricyclo (5.2.1.0) decane derivatives, as in EP 0694521 B1 described. Also suitable are 2-phenylbenzimidazole-5-sulfonic acid and its alkali, earth alkali, ammonium, alkylammonium, alkanolammonium and glucammonium salts; sulfonic acid Derivatives of benzophenones, preferably 2-hydroxy-4-methoxybenzophenone-5-sulfonic acid and their salts; Sulfonic acid derivatives of 3-benzylidene camphor, such as. B. 4- (2-Oxo-3-bomylidene thyl) benzenesulfonic acid and 2-methyl-5- (2-oxo-3-bornylidene) sulfonic acid and their salts.

Derivatives of benzoylmethane are particularly suitable as typical UV-A filters, such as for example 1- (4'-tert-butylphenyl) -3- (4'-methoxyphenyl) propane-1,3-dione, 4-tert-butyl-4'-meth oxydibenzoylmethane (Parsol 1789), 1-phenyl-3- (4'-isopropylphenyl) propane-1,3-dione and Enamine compounds as described in DE 197 12 033 A1 (BASF). The UV-A and UV-B filters can of course also be used in mixtures. In addition to the soluble For this purpose, substances also come with insoluble light protection pigments, namely finely dispersed, preferably nanoised metal oxides or salts. Examples of suitable metal oxides are in particular zinc oxide and titanium dioxide and also oxides of iron, zirconium, silicon, Manganese, aluminum and cerium and their mixtures. Silicates (talc), Barium sulfate or zinc stearate can be used. The oxides and salts are in the form of Pigments for skin-care and skin-protecting emulsions and decorative cosmetics used. The particles should have an average diameter of less than 100 nm, preferably have between 5 and 50 nm and in particular between 15 and 30 nm. she can have a spherical shape, but such particles can also be used come that are ellipsoidal or otherwise deviating from the spherical shape To have shape. The pigments can also be surface treated, i.e. H. hydrophilized or hydro to be phobic. Typical examples are coated titanium dioxide, such as. B. Titanium dioxide T 805 (Degussa) or Eusolex® T2000 (Merck). The main hydrophobic coating agents are Silicones and especially trialkoxyoctylsilanes or simethicones in question. Preferably micronized zinc oxide is used. Further suitable UV light protection filters can be found in the overview from P. Finkel in SÖFW-Journal 122, 543 (1996).  

UV absorbers can be present in the formulations in amounts of up to 5% by weight, preferably up to 3% by weight, particularly preferably from 0.01 to 2.0 and in particular from 0.03 to 1% by weight be included.

Another class of stabilizers to be used with preference is fluorine eszenzfarbstoffe. These include the 4,4'-diamino-2,2'-stilbene disulfonic acids (flavonic acids), 4,4'-distyrylbiphenyls, methyl umbelliferones, coumarins, dihydroquinone, 1,3-diarylpyrazolines, Naphthalimide, benzoxazole, benzisoxazole and benzimidazole systems as well as by Heterocyclic substituted pyrene derivatives. The sulfones are of particular importance acid salts of the diaminostilbene derivatives, as described in US 2,784,220 or US 2,612,510 are described as well as polymeric fluorescent materials as disclosed in US Pat. No. 5,082,578 become.

Fluorescent substances can be present in the formulations in amounts of up to 5% by weight, preferably up to 1% by weight. particularly preferably from 0.01 to 0.5 and in particular from 0.03 to 0.1% by weight be included.

In a preferred embodiment, the aforementioned stabilizing agents are used in any Mixtures used. The stabilizing agents are preferably used in amounts of up to 40% by weight up to 30% by weight, particularly preferably from 0.01 to 20% by weight, in particular from 0.02 to 5 wt .-% used.

Under the term "wash-active preparation" or "rinse-active preparation" or "cleaning-active Preparation "(or washing-active etc. material" or "washing-active etc. component") are in the Preparations, materials or components of all within the scope of the present invention conceivable, relevant in connection with a washing, rinsing or cleaning process punch understood. These are primarily the actual detergents, detergents or Detergents with their individual explained in the further course of the description components. This includes active substances such as surfactants (anionic, non-ionic, cationic and amphoteric surfactants), builder substances (inorganic and organic builder substances), bleach medium (such as peroxo bleach and chlorine bleach), bleach activators, bleach stabilizers, bleaching catalysts, enzymes, special polymers (e.g. those with Cobuilder properties), graying inhibitors, dyes and fragrances (perfumes) without the term is restricted to these substance groups.

Components of such "wash-active preparations (materials, components)", rinse-active additives preparations (materials, components) "or" cleaning-active preparations (materials, Components) "can also include washing aids, rinsing aids and cleaning aids his. Examples of these are optical brighteners, so-called soil repellents, i.e. polymers that are one Counteract re-soiling of fibers or hard surfaces, as well as silver retardants. Also laundry treatment agents, such as fabric softener or dishwashing detergent additives  According to the invention, like rinse aids are used as wash-active or rinse-active preparations considered.

The completely or partially water-soluble coating of the detergent according to the invention portions of detergent or cleaning agent completely surrounds a formulation according to the invention, preferably a liquid-based, at least one wash-active, rinse-active or pure active material.

In the context of the present invention, the term "liquid-based" means that the Formulation of a wash-active, rinse-active or cleaning-active material or several wash-active, rinse-active or cleaning-active materials at least during the manufacture of one The formulation based on liquid components is as detailed below are explained, even if this formulation contains solid components (suspen dated or dispersed) contains.

Formulations completely surrounded by the coatings, advantageously liquid-based the detergent, detergent or cleaning agent portions according to the invention can ent be neither low-water formulations nor essentially water-free formulations. Low-water formulations include water as an essential component in an amount of, for example, ≦ 15% by weight, based on the weight of all components of the formulation. On the other hand, non-aqueous or essentially water-free formulations comprise water only in small amounts, preferably in amounts less than 10% by weight, more preferably in amounts of 1 to 5% by weight, in each case based on the weight of old components of the formulation, where non-aqueous or essentially water-free formulations are particularly preferred.

In the low-water and in the water-free systems, the formulations contain surfactant (s), wherein anionic, nonionic, cationic and / or amphoteric surfactants are used. From an application point of view, preference is given to mixtures of anionic and nonionic Surfactants, the proportion of nonionic surfactants should advantageously be greater than the proportion of anionic surfactants. The total surfactant content of detergent, dish soap or detergent Serving agent portions are preferably above 25 wt .-%, based on the total Liquid detergent.

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 moles of EO per mole of alcohol preferred. The preferred ethoxylated alcohols include, for example, C _12-14 alcohols with 3 EO, 4 EO or 7 EO, C _9-11 alcohols with 7 EO, C _13-15 alcohols with 3 EO, 5 EO, 7 EO or 8 EO, C _12-18 alcohols with 3 EO, 5 EO or 7 EO and mixtures thereof, such as mixtures of C _12-14 alcohol with 3 EO and C _12-18 alcohol with 7 EO. The degrees of ethoxylation given represent statistical averages, which can be an integer or a fraction for a specific product. Preferred alcohol ethoxylates have a narrow homolog distribution (narrow range ethoxylates, NRE). In addition to these nonionic surfactants, fatty alcohols with more than 12 EO can also be used. Examples include tallow fatty alcohol with 14 EO, 25 EO, 30 EO or 40 EO. Nonionic surfactants which contain EO and PO groups together in the molecule can also be used according to the invention. Here, block copolymers with EO-PO block units or PO-EO block units can be used, but also EO-PO-EO copolymers or PO-EO-PO copolymers. Of course, mixed alkoxylated nonionic surfactants can also be used, in which the EO and PO units are not distributed in blocks, but are statistically distributed. Such products can be obtained by the simultaneous action of ethylene and propylene oxide on fatty alcohols.

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

Another class of preferred nonionic surfactants, either as the sole nonionic surfactant or used in combination with other nonionic surfactants are, are alkoxylated, preferably ethoxylated or ethoxylated and propoxylated fatty acid alkyl esters, preferably with 1 to 4 carbon atoms in the alkyl chain, especially fat Acid methyl esters, as described, for example, in Japanese Patent Application JP 58/217598 or which are preferably written according to that in international patent application WO 90113533 described methods are produced.

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

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

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

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

in which R represents a linear or branched alkyl or alkenyl radical having 7 to 12 carbon atoms, R ^{1 represents} a linear, branched or cyclic alkylene radical or an arylene 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 ² ] representing a linear polyhydroxyalkyl radical whose alkyl chain is substituted by at least two hydroxyl groups, or alkoxylated, preferably ethoxylated or propylated derivatives of this residue.

[Z ² ] is preferably obtained by reductive amination of a 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 95/07331, be converted into the desired polyhydroxy fatty acid amides by reaction with fatty acid methyl esters in the presence of an alkoxide as catalyst.

The content of preferred formulations of nonionic surfactants is up to 95% by weight, preferably 10 to 60 wt .-% and in particular 15 to 50 wt .-%, each based on the total funds.

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 disulfonates such as are obtained, for example, from C _12-18 monoolefins having an end or internal double bond by sulfonating with gaseous Sulfur trioxide and subsequent alkaline or acidic hydrolysis of the sulfonation products is considered. Also suitable are alkanesulfonates obtained from C _12-16 alkanes, for example by sulfochlorination or sulfoxidation with subsequent hydrolysis or neutralization. Likewise, the esters of α-sulfofatty acids (ester sulfonates), e.g. B. the α-sulfonated methyl ester of hydrogenated coconut, palm kernel or tallow fatty acids suitable.

Other suitable anionic surfactants are sulfonated fatty acid glycerol esters. Among fatty acid glycerol esters the mono-, di- and triesters and their mixtures are to be understood as they are in the production by esterification of a monoglycerin with 1 to 3 moles of fatty acid or in the transesterification of Triglycerides with 0.3 to 2 moles of glycerin can be obtained. Preferred sulfonated fatty acid glycerol esters are the sulfonation products of saturated fatty acids with 6 to 22 carbon atoms, for example caproic acid, caprylic acid, capric acid, myristic acid, lauric acid, Palmitic acid, stearic acid or behenic acid.

Alk (en) yl sulfates are the alkali and in particular the sodium salts of the sulfuric acid half esters of C ₁₂ -C ₁₈ fatty alcohols, for example from coconut oil alcohol, tallow fatty alcohol, lauryl, myristyl, cetyl or stearyl alcohol or the C ₁₀ -C ₂₀ oxo alcohols and those half-esters of secondary alcohols of this chain length are preferred. Also preferred are alk (en) yl sulfates of the chain length mentioned which contain a synthetic, straight-chain alkyl radical prepared on a petrochemical basis and which have a degradation behavior analogous to that of the adequate compounds based on oleochemical raw materials. The C ₁₂ -C ₁₆ alkyl sulfates and C ₁₂ -C ₁₅ alkyl sulfates and C ₁₄ -C ₁₅ alkyl sulfates are preferred from the point of view of washing technology. 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 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 of ethylene oxide, such as 2-methyl-branched C _9-11 alcohols with an average of 3.5 mol of ethylene oxide (EO) or C _12-18 - Fatty alcohols with 1 to 4 EO are suitable. Because of their high foaming behavior, they are used in cleaning agents only in relatively small amounts, for example in amounts of 1 to 5% by weight.

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 in particular ethoxyated 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 (for description see above). 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. Saturated ones are suitable and unsaturated fatty acid soaps, such as the salts of lauric acid, myristic acid, palmitic acid, Stearic acid, hydrogenated erucic acid and behenic acid and in particular from natural Fatty acids, e.g. B. coconut, palm kernel, olive oil 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 Triethanolamine, monoisopropanolamine or triisopropanolamine. Preferably lie the anionic surfactants in the form of their ammonium salts, especially their ammonium salts at least one long-chain alkyl radical or alkanolamine radical on ammonium nitrogen.

The content of preferred detergent, detergent or cleaning agent portions of anionic Surfactants is up to 95% by weight, preferably 10 to 60% by weight and in particular 15 to 50% by weight, each based on the entire portion.

In addition to the one or more surfactant (s), the washing according to the invention can portions of detergent, detergent or detergent - irrespective of whether they contain water or have little water or essentially water-free - contain other ingredients that the application technology and / or further improve the aesthetic properties of the agent. As part of the present Invention contain preferred detergent, detergent or cleaning agent portions in addition to the surfactant (s) one or more substances from the group of builders, Bleaching agents, bleach activators, enzymes, electrolytes, non-aqueous solvents, pH adjusting agents, Fragrances, perfume carriers, dyes, hydrotropes, foam inhibitors, silicone oils, anti-depositions medium, optical brighteners, graying inhibitors, run-in preventers, anti-crease agents, colors transmission inhibitors, antimicrobial agents, germicides, fungicides, corrosion inhibitors, Antistatic agents, ironing aids, phobing and impregnating agents, swelling and anti-slip agents and rheological additives.

As builders in the detergents, dishwashing detergents or cleaning agents according to the invention Portions can be included, in particular silicates, aluminum silicates (in particular Zeolites), carbonates, salts of organic di- and polycarboxylic acids and mixtures of these substances to call.

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 × 2, 3 or 4. Such crystalline layered silicates are described, for example, in European patent application EP-A 0 164 514. Preferred crystalline phyllosilicates of the formula given are those in which M is sodium and x is 2 or 3. In particular, both β- and δ-sodium disilicate Na ₂ Si ₂ O ₅ .yH ₂ O are preferred, wherein β-sodium disilicate can be obtained, for example, by the method described in international patent application WO-A 91/08171.

Amorphous sodium silicates with a Na ₂ O: SiO ₂ modulus of 1: 2 to 1: 3.3, preferably 1: 2 to 1: 2.8 and in particular 1: 2 to 1: 2.6, can also be used are delayed in dissolving and have secondary washing properties. The delay in dissolution compared to conventional amorphous sodium silicates can be caused in various ways, for example by surface treatment, compounding, compacting / compression or by overdrying. In the context of this invention, the term “amorphous” is also understood to mean “X-ray amorphous”. This means that the silicates in X-ray diffraction experiments do not provide sharp X-ray reflections, as are typical for crystalline substances, but at most one or more maxima of the scattered X-rays, which have a width of several degree units of the diffraction angle. However, it can very well lead to particularly good builder properties if the silicate particles provide washed-out or even sharp diffraction maxima in electron diffraction experiments. This is to be interpreted as meaning that the products have microcrystalline areas of size 10 to a few hundred nm, values up to max. 50 nm and in particular up to max. 20 nm are preferred. Such so-called X-ray amorphous silicates, which also have a delay in dissolution compared to conventional water glasses, are described for example in German patent application DE-A-44 00 024 be. Compacted / compacted amorphous silicates, compounded amorphous silicates and over-dried X-ray amorphous silicates are particularly preferred.

The finely crystalline, synthetic and bound water-containing zeolite 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, in the context of the present invention, a co-crystallizate of zeolite X and zeolite A (about 80% by weight of zeolite) is preferably used X), which was developed by CONDEA Augusta S. p. A. is sold under the brand name VEGOBOND AX® and through the formula

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

can be described. The zeolite can be used as a spray-dried powder or as an undried stabilized suspension that is still moist from its manufacture. In the event that the zeolite is used as a suspension, it may contain minor additions of nonionic surfactants as stabilizers, for example 1 to 3% by weight, based on zeolite, of ethoxylated C ₁₂ -C ₁₈ fatty alcohols with 2 to 5 ethylene oxide groups , C ₁₂ -C ₁₄ fatty alcohols with 4 to 5 ethylene oxide groups or ethoxylated isotridecanols. Suitable zeolites have an average particle size of less than 10 μm (volume distribution; measurement method: Coulter Counter) and preferably contain 18 to 22% by weight, in particular 20 to 22% by weight, of bound water.

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

Among the compounds which serve as bleaching agents and supply H ₂ O ₂ in water, sodium percarbonate, sodium perborate tetrahydrate and sodium perborate monohydrate are of particular importance. Further bleaching agents that can be used are, for example, peroxopyrophosphates, citrate perhydrates and H ₂ O ₂ -producing peracid salts or peracids, such as persulfates or persulfuric acid. The urea peroxohydrate percarbamide can also be used, which can be described by the formula H ₂ N-CO-NH ₂ .H ₂ O ₂ . In particular, when using the agents for cleaning hard surfaces, for example in automatic dishwashing, they can, if desired, also contain bleaching agents from the group of organic bleaching agents, although their use is in principle also possible for agents for textile washing. Typical organic bleaching agents are the diacyl peroxides, such as dibenzoyl peroxide. Other typical organic bleaching agents are peroxy acids, examples of which include alkyl peroxy acids and aryl peroxy acids. Preferred representatives are peroxybenzoic acid and its ring-substituted derivatives, such as alkylperoxybenzoic acids, but also peroxy-α-naphthoic acid and magnesium monoperphthalate, the aliphatic or substituted aliphatic peroxyacids, such as peroxylauric acid, peroxystearic acid, ε-phthalimidoperoxy caproic acid, phanoimidoproacid (phthalimidoproacid), Carboxybenzamidoperoxycaproic acid, N-nonenylamidoperadipic acid and N-nonenylamidopersuccinate, and aliphatic and araliphatic peroxydicarboxylic acids, such as 1,12-diperoxycarboxylic acid, 1,9-diperoxyazelaic acid, diperoxysebacic acid, diperoxybrassyl acid, the diperoxybutanoic acid, 1,4-diperoxybutanoic acid, Terephthaloyl-di (6-aminopercaproic acid) can be used.

To improve the bleaching effect when washing at temperatures of 60 ° C and below bleach activators can be incorporated into the detergent portions. As Bleach activators can be compounds that are aliphatic peroxo under perhydrolysis conditions carboxylic acids with preferably 1 to 10 carbon atoms, in particular 2 to 4 carbon atoms, and / or result in optionally substituted perbenzoic acid can be used. Sub are suitable punch, the O- and / or N-acyl groups of the number of carbon atoms mentioned and / or optionally carry substituted benzoyf groups. Multi-acylated alkylenediamines are preferred, in particular  Tetraacetylethylene diamine (TAED), acylated triazine derivatives, especially 1,5-diacetyl 2,4-dioxohexahydro-1,3,5-triazine (DADHT), acylated glycolurils, especially tetraacetylglycoluril (TAGU), N-acylimides, especially N-nonanoylsuccinimide (NOSI), acylated phenol sulfonates, in particular n-nonanoyl- or isononanoyloxybenzenesulfonate (n- or iso-NOBS), Carboxylic anhydrides, especially phthalic anhydride, acylated polyhydric alcohols, especially triacetin, triethylacetyl citrate (TEAC), ethylene glycol diacetate, 2,5-diacetoxy-2,5- dihydrofuran and those from German patent applications DE 196 16 693 and DE 196 16 767 known enol esters and acetylated sorbitol and mannitol or their in the European patent application EP 0 525 239 described mixtures (SORMAN), acylated Sugar derivatives, especially pentaacetylglucose (PAG), pentaacetylfructose, tetraacetylxylose and octaacetyl lactose and acetylated, optionally N-alkylated, glucamine and gluco nolactone, and / or N-acylated lactams, for example N-benzoylcaprolactam, which are derived from the international patent applications WO 94/27970, WO 94/28102, WO 94/28103, WO 95/00626, WO 95/14759 and WO 95/17498 are known. The from the German patent application DE 196 16 769 known hydrophilically substituted acylacetals and those in German Patent application DE 196 16 770 and international patent application WO 95/14075 Acyllactams described are also preferably used. Even those from Germany Patent application DE 44 43 177 known combinations of conventional bleach activators can be used.

In addition to the conventional bleach activators or in their place, so-called Bleaching catalysts in the wash-active preparations for the portions according to the invention be incorporated. These fabrics are bleach-enhancing Transition metal salts or transition metal complexes such as Mn, Fe, Co, Ru or Mo-salt complexes or carbonyl complexes. Also Mn, Fe, Co, Ru, Mo, Ti, V and Cu Are complexes with nitrogen-containing tripod ligands as well as Co, Fe, Cu and Ru amine complexes usable as bleaching catalysts.

Enzymes for use in detergent, detergent or cleaning agent portions come in particular those from the classes of hydrolases such as proteases, esterases, lipases or lipolytic enzymes, amylases, cellulases or other glycosyl hydrolases and Mixtures of the enzymes mentioned in question. The hydrolases wear, for example, in the laundry for the removal of stains such as stains containing protein, fat or starch and Graying at. Cellulases and other glycosyl hydrolases can also by the Removal of pilling and microfibrils to maintain color and increase the softness of the Textiles contribute. To bleach or to inhibit the transfer of color can also Oxireductases are used. Bacterial strains or fungi are particularly suitable such as Bacillus subtilis, Bacillus licheniformis, Streptomyceus griseus and Humicola insolens obtained enzymatic active ingredients. Proteases of the subtilisin type and in particular proteases obtained from Bacillus lentus are used. Are there Enzyme mixtures, for example from protease and amylase or protease and lipase or lipolytic enzymes or protease and cellulase or from cellulase and lipase or  lipolytically active enzymes or from protease, amylase and lipase or lipolytically active Enzymes or protease, lipase or lipolytically acting enzymes and cellulase, in particular however, protease and / or lipase-containing mixtures or mixtures with lipolytically active Enzymes of particular interest for the detergent, dishwashing or Cleaner portions. Examples of such lipolytically active enzymes are the known ones Cutinases. Peroxidases or oxidases have also proven to be suitable in some cases. Suitable amylases include in particular α-amylases, iso-amylases, pullulanases and Pectinases. Cellobiohydrolases, endoglucanases and β- Glucosidases, which are also called cellobiases, or mixtures of these are used. There different types of cellulase differ in their CMCase and avicelase activities, the desired activities can be set by targeted mixtures of the cellulases.

The enzymes can be adsorbed on carriers or embedded in enveloping substances around them protect against premature decomposition. The proportion of enzymes, enzyme mixtures or Enzyme granules can, for example, about 0.01 to 5 wt .-%, preferably 0.012 to about 2 wt .-% be.

A wide number of different salts can be used as electrolytes from the group of inorganic salts. Preferred cations are the alkali and alkaline earth metals, preferred anions are the halides and sulfates. From a manufacturing perspective, the use of NaCl or MgCl ₂ in the agents according to the invention is preferred. The proportion of electrolytes in the agents according to the invention is usually 0.5 to 5% by weight.

Non-aqueous solvents which are used in the detergent, dishwashing or Detergent portions can be used, for example, come from the group mono- or polyhydric alcohols, alkanolamines or glycol ethers, provided that they are specified in the Concentration range are miscible with water. The solvents are preferred selected from ethanol, n- or i-propanol, butanols, glycol, propane or butanediol, glycerin, Diglycol, propyl or butyl diglycol, hexylene glycol, ethylene glycol methyl ether, polyethylene glycol, Dipropylene glycol, ethylene glycol ethyl ether, ethylene glycol propyl ether, ethylene glycol mono-n-butyl ether, diethylene glycol methyl ether, diethylene glycol ethyl ether, propylene glycol methyl, ethyl or propyl ether, dipropylene glycol monomethyl or ethyl ether, di-isopropylene glycol monomethyl or -ethyl ether, methoxy, ethoxy or butoxy triglycol, 1-butoxyethoxy-2-propanol, butoxypropoxy propanol (BPP), 3-methyl-3-methoxybutanol, propylene glycol t-butyl ether, N-butoxypropoxy propanol and mixtures of these solvents. Non-aqueous solvents can be found in the Detergent, dishwashing or cleaning agent portions according to the invention in quantities between 0.5 and 90% by weight, but preferably below 80% by weight and in particular below 70% by weight be used.  

In order to bring the pH of the agents according to the invention into the desired range, the Use of pH adjusting agents. All known acids or Lyes, provided that their use is not for technical or ecological reasons or for reasons of consumer protection. Usually the amount exceeds this adjusting agent does not contain 2% by weight of the total formulation.

As foam inhibitors in the detergents, dishwashing detergents or cleaning agents according to the invention medium portions can be used, for example, soaps, paraffins or Silicone oils into consideration, which can optionally be applied to carrier materials.

Suitable anti-deposition agents, which are also referred to as "soil repellents", are examples as non-ionic cellulose ethers such as methyl cellulose and methyl hydroxypropyl cellulose a proportion of methoxy groups from 15 to 30 wt .-% and of hydroxypropyl groups from 1 to 15% by weight, based in each case on the nonionic cellulose ether, and those from the prior art Polymers of phthalic acid and / or terephthalic acid or of their known technology Derivatives, especially polymers made from ethylene terephthalates and / or polyethylene glycol terephthalates or anionically and / or nonionically modified derivatives of these. The sulfonated derivatives of are particularly preferred among the compounds mentioned Phthalic and terephthalic polymers.

Graying inhibitors have the task of removing the dirt detached from the fibers in the liquor to keep suspended and thus prevent the dirt from re-opening. For this are Suitable water-soluble colloids mostly organic, for example glue, gelatin, salts of ether sulfonic acids of starch or cellulose or salts of acidic sulfuric acid esters cellulose or starch. Water-soluble polyamides containing acidic groups are also suitable for suitable for this purpose. Soluble starch preparations and others other than that can also be used Use the above starch products, e.g. B. degraded starch, aldehyde starches, etc. Also Polyvinyl pyrrolidone is useful. However, cellulose ethers such as carboxymethyl are preferred cellulose (sodium salt), methyl cellulose, hydroxyalkyl cellulose and mixed ethers such as methyl hydroxy ethyl cellulose, methyl hydroxypropyl cellulose, methyl carboxymethyl cellulose and mixtures thereof in amounts of 0.1 to 5% by weight, based on the composition. According to the invention are also Graying inhibitors based on optionally modified polyacrylates and their copoly merisate suitable.

Because textile fabrics, especially made of rayon®, rayon, cotton and their blends can tend to crease, because the individual fibers prevent bending, kinking, pressing and squeezing across the grain are sensitive, the invention Detergents contain synthetic anti-crease. These include, for example, synthetic Products based on fatty acids, fatty acid esters, fatty acid amides, alkylolestems,  -alkylolamides or fatty alcohols, which are mostly reacted with ethylene oxide, or products on the Base of lecithin or modified phosphoric acid ester.

To control microorganisms, the detergent, dishwashing detergent according to the invention or portions of detergent containing antimicrobial agents. A distinction is made here according to the antimicrobial spectrum and mechanism of action between bacteriostatics and Bactericides, fungistatics and fungicides etc. Important substances from these groups are among for example benzalkonium chlorides, alkylarlyl sulfonates, halophenols and phenol mercuric acetate, these connections being dispensed with entirely in the portions according to the invention can be.

Increased comfort can result from the additional use of antistatic agents can also be added to the detergent portions according to the invention. antistatic agents increase the surface conductivity and thus enable an improved drainage formed charges. External antistatic agents are usually substances with at least one hydrophilic molecular ligands and give a more or less on the surfaces hygroscopic film. These mostly surface-active antistatic agents can be dissolved in nitrogen containing (amines, amides, quaternary ammonium compounds), phosphorus-containing (phosphoric acid esters) and divide sulfur-containing (alkyl sulfonates, alkyl sulfates) antistatic agents. External antistatic agents are for example in patent applications FR 1,156,513, GB 873 214 and GB 839 407 described. The lauryl (or stearyl) dimethylbenzylammonium chlorides disclosed here are suitable themselves as antistatic agents for textiles or as an additive to detergents, with an additional Finishing effect is achieved.

To improve the water absorption capacity and the rewettability of the treated textiles and to facilitate the ironing of the treated textiles can in the Detergent portions according to the invention, for example silicone derivatives. These additionally improve the rinsing behavior of the portions according to the invention through their foam-inhibiting properties. Preferred silicone derivatives are, for example, polydialkyl or alkylarylsiloxanes in which the alkyl groups have one to five carbon atoms and all or are partially fluorinated. Preferred silicones are polydimethylsiloxanes, which are optionally deriva can be tized and then amino functional or quaternized or Si-OH-, Si-H- and / or Have Si-Cl bonds. The viscosities of the preferred silicones are around 25 ° C between 100 and 100,000 mPas, the silicones in amounts between 0.2 and 5% by weight, based on the total agent can be used.

To prevent the decomposition of certain detergent ingredients catalyzed by heavy metals avoid substances that complex heavy metals can be used advantageously. Suitable heavy metal complexing agents are, for example, the alkali salts of ethylenediamine tetraacetic acid (EDTA) or nitrilotriacetic acid (NTA) or their derivatives or  Derivatives and alkali metal salts of anionic polyelectrolytes such as polymaleates and Polysulfonates.

A preferred class of complexing agents are the phosphonates, which are preferred in washing detergent, detergent or cleaning agent portions in quantities of 0.01 to 2.5% by weight, preferably 0.02 to 1 wt .-% and in particular from 0.03 to 0.5 wt .-% are included. To These preferred compounds include, in particular, organophosphonates such as, for example 1-hydroxyethane-1,1-diphosphonic acid (HEDP), aminotri (methylenephosphonic acid) (ATMP), Diethy lentriamine-penta (methylenephosphonic acid) (DTPMP or DETPMP) and 2-phosphonobutane 1,2,4-tricarboxylic acid (PBS-AM), mostly in the form of their ammonium or alkali metal salts be used.

In further preferred embodiments of the detergent or dishwashing detergent according to the invention Detergent portions comprise the low-water and advantageously liquid formulation a rheological additive. This can consist of one or more components. consist. The rheological additives often serve as thickeners. These also swellings medium-sized, organic high-molecular substances that absorb liquids, thereby swell and eventually go into viscous real or colloidal solutions come from the groups of natural polymers, modified natural polymers and fully synthetic polymers.

Natural polymers that are used as rheological additives for example agar-agar, carrageenan, tragacanth, gum arabic, alginates, pectins, polyoses, Guar flour, carob flour, starch, dextrins, gelatin and casein.

Modified natural products mainly come from the group of modified starches and Celluloses, examples include carboxymethyl cellulose and cellulose ethers, hydroxyethyl and propyl cellulose as well as core meal ether called.

A large group of rheological additives, widely used in a wide variety of applications Find application areas are the fully synthetic polymers such as polyacrylic and Polymethacrylic compounds, vinyl polymers, polycarboxylic acids, polyethers, polyimines, polyamides and polyurethanes.

Rheological additives from the substance classes mentioned are commercially available and are, for example, under the trade names Acusol®-820 (methacrylic acid (stearyl alcohol-20-EO-) ester-acrylic acid copolymer, 30% in water, Rohm & Haas), Dapral®-GT-282-S (Alkyl polyglycol ether, Akzo), Deuterol®-Polymer-11 (dicarboxylic acid copolymer, Schönes GmbH), Deuteron®-XG (anionic heteropolysaccharide based on β-D-glucose, D-manose, D-glucuronic acid, Schönes GmbH), Deuteron®-XN (non-ionic polysaccharide, Schönes GmbH),  Dicrylan®-Thickener-O (ethylene oxide adduct, 50% in water / isopropanol, Pfersse Chemie), EMA®-81 and EMA®-91 (ethylene-maleic anhydride copolymer, Monsanto), thickener-QR-1001 (Polyurethane emulsion, 19 to 21% in water / diglycol ether, Rohm & Haas), Mirox®-AM (anionic acrylic acid-acrylic acid ester copolymer dispersion, 25% in water, Stockhausen), SER-AD-FX-1100 (hydrophobic urethane polymer, Servo Delden), Sheliflo® -S (high molecular weight Polysaccharide, stabilized with formaldehyde, Shell) and Shellflo® -XA (xanthan biopolymer, with Formaldehyde stabilized, Shell) available.

In cases where the formulation is washing-active, rinsing-active or cleaning-active Materials is a water-poor or water-free formulation, this includes water-poor or anhydrous formulation to adjust its rheological parameters, preferably a or material comprising multiple anionic surfactant (s) and / or one or more nonionic surfactant (s). In a In a particularly preferred embodiment, the anionic surfactant (s) are selected from the group the sulfonates and sulfates and their mixtures and / or the nonionic surfactant (s) is / are selected from the group of alkoxylated alcohols, alkoxylated fatty acid alkyl esters, alkyl glycosides and their Mixtures. The connection groups mentioned were explained in detail above.

In low-water or essentially water-free formulations that are wash-active, rinse-active or active cleaning materials in the detergent, detergent or cleaning agent portions according to the invention can be included in a preferred embodiment Anionic surfactants, if appropriate in the presence of further anionic and / or nonionic surfactants, the isopropanolammonium ether sulfates according to the article "U. Schoenkaes et al .; Water-free Alcohol Ether Sulfates - New high-active surfactants for superconcentrated Detergent Formulations "are used, of which monoisopropanolammonium ether sulfate (MIPA ether sulfate) and triisopropanol ammonium ether sulfate (TIPA ether sulfate) due to their outstanding anionic surfactant properties are particularly preferred.

Rheological additives with a thickening effect, which can also be used as an associative thickener, are advantageously used in low-water or essentially water-free systems. These can be, for example (but not necessarily), acrylate-based polymers which, for. T. can have relatively high molecular weights in the range of <1,000,000 g / mol. They are used in the washing-active, rinsing-active or cleaning-active formulations in amounts of 0.01 to 10% by weight, for example in amounts of 0.5 to 4% by weight. Suitable products are, for example, the products marketed by Rohm & Haas under the name Acusol ^R , which are predominantly polyacrylates with different alkylation or crosslinking or hydrophobically modified nonionic polyols, or the products marketed by BF Goodrich under the name Carbopol ^R Polyacrylates or copolymers of acrylic acid and alkylated (preferably C ₅ - to C ₁₀ -alkylated) acrylic acids, or the products marketed by the company BF Goodrich under the name Pemulen ^R , which are high-molecular acrylic copolymers of the type acrylic / C ₁₀ bis C ₃₀ alkyl acrylate cross polymer. In addition to the aforementioned associative thickeners, polyacrylate or polyurethane thickeners can also be used in water-free or essentially water-free systems, which offer the possibility of adjusting the viscosity in the presence of small amounts of water via a different mode of action (ie not associatively).

Preferred low-water formulations contain rheological additives in amounts from 0.01 to 10% by weight, preferably 0.1 to 5% by weight and in particular 0.2 to 3% by weight.

According to the invention, detergents, detergents or cleaning agents are further preferred. Portions in which the liquid-based formulations have non-Newtonian flow behavior show, preferably show thixotropic or pseudoplastic flow behavior. Especially preferred embodiments of the portions are provided by the liquid-based formulations low viscosity, for example a viscosity in the range of 10 to 50 mPa.s and the liquid-based formulations have a higher storage, etc. Viscosity, for example in the range from 10 to 100,000 mPa.s, preferably from 100 to 20,000 mPa.s, more preferably a viscosity in the range from 200 to 10,000 mPa.s. It can the viscosity of clear systems is lower than that of systems in which solid Components (which are visually noticeable in a cloudiness) are present; latter thickens regularly during storage (setting ") and can even become pasty.

Detergent, detergent or cleaning agent portions according to the present invention, the for example in capsule form, in spherical form or in the form of bags, can be in the Coatings of the detergent, detergent or cleaning agent portion contained liquid based formulation of at least one wash-active, rinse-active or cleaning-active Materials can be clear solutions of one or more wash-active, wash-active or have active cleaning component (s) or microemulsions. However, it is in accordance with the invention it is also possible for liquid-based formulations to suspend one or more solids or contain dispersed, especially when low or substantially anhydrous Formulations are used. This is an advantage over the prior art because Components that are sensitive to water are more active in washing, rinsing or cleaning Materials can be kept stable and evenly distributed in the liquid phase and There are no problems with decreased activity.

The invention also relates to a washing method, in particular a method for machine washing in a commercially available washing machine, comprising the steps that
enters a detergent portion according to the detailed description above into the washing machine, in particular into the dispenser or into the washing drum;
makes contact between the detergent portion and the washing liquor by adding water;
sets the desired washing conditions; and
when the desired conditions occur, the wash-active material (s) of the detergent portion is released into the wash liquor and brings it into contact with the items to be washed.

The invention also relates to a washing method, in particular a method for machine washing in a commercially available dishwasher, comprising the steps that
enters a detergent portion according to the detailed description above into the dishwasher, in particular into the dispensing compartment or into the washing compartment;
makes contact between the detergent portion and the washing liquor by adding water;
sets the desired rinsing conditions; and
When these conditions occur, the rinsing active material (s) of the detergent portion is released into the rinsing solution and brought into contact with the items to be rinsed.

The invention also relates to a cleaning process comprising the steps that one
adding a detergent serving to the cleaning liquor as detailed above;
sets the desired cleaning conditions; and
When these conditions occur, the cleaning-active material (s) of the detergent portion are released into the cleaning liquor and brought into contact with the goods to be cleaned.

In addition to the aforementioned areas, the portions according to the present invention can also are used in other areas. For example, they are also used as a cleaner for Toilet cisterns for the continuous delivery of a cleaning and Disinfectant to the toilet rinse water or as a cleaner for pipes etc. conceivable. For special purposes, such cleaners can also use gas (e) releasing systems (e.g. an acid such as citric acid with a carbonate such as sodium carbonate) contain.

The transparency of the films was determined using a commercially available UV / Vis spectrophotometer, for example using a Milton Roy Spectronic 601. The permeability (T) was defined according to the Lambert-Beer law as:

For the purposes of the invention, such water-soluble envelopes are transparent, in which Wavelength range from 410 to 800 nm, with at least one wavelength, a transmittance (T) is measured above 20%.

Claims (18)

1. Detergent, dishwashing or cleaning agent portion, comprising a completely or partially water-soluble capsule-shaped envelope which completely surrounds at least one formulation of a detergent-active, detergent-active or cleaning-active material, characterized in that the portion contains at least one stabilizing agent, the water-soluble Coating has a transmittance above 20% at wavelengths from 410 to 800 nm. 2. Detergent, detergent or cleaning agent portion, comprising a whole or in part water-soluble envelope in spherical form, which is at least one formulation of a wash completely surrounds active, rinse-active or cleaning-active material records that the portion contains at least one stabilizing agent, the water soluble cladding a transmittance above 20% at wavelengths from 410 to 800 nm having. 3. Detergent, dishwashing or cleaning agent portion, comprising a whole or in part water-soluble envelope in the form of a bag, the at least one formulation of a completely surrounds washing-active, rinsing-active or cleaning-active material characterized in that the portion contains at least one stabilizing agent, the water-soluble coating has a transmittance above 20% at wavelengths of 410 up to 800 nm. 4. detergent, detergent or cleaning agent portion according to one of claims 1 to 3, characterized in that the permeability of the water-soluble coating is greater 30%, preferably greater than 40% and in particular greater than 50%. 5. detergent, detergent or cleaning agent portion according to one of claims 1 to 4, comprising a completely or partially water-soluble envelope made of a material from the Group (optionally fully or partially acetalized and / or ketalized) Polyvinyl alcohol, polyvinyl pyrrolidone, polyethylene oxide, gelatin, cellulose and their derivatives, Starch and its derivatives, blends and composites, inorganic salts and mixtures of mentioned materials. 6. detergent, detergent or cleaning agent portion according to one of claims 1 to 5, comprising a completely water-soluble covering from the group of capsules made of gelatin, preferably soft gelatin or (optionally fully or partially acetalized and / or ketalized) polyvinyl alcohol, in particular PVAL, which acetalizes with starch was made of (optionally fully or partially acetalized and / or  ketalized) polyvinyl alcohol, in particular PVAL, which has been acetalized with starch, Ball of (optionally partially or completely acetalized and / or ketalized) Polyvinyl alcohol, in particular PVAL, which has been acetalized with starch, or gelatin, preferably soft gelatin, or an inorganic salt or a mixture inorganic salts. 7. detergent, detergent or cleaning agent portion according to claim 5 or claim 6, in which the water-soluble coating is less water-soluble or not water-soluble at all or only at higher temperature water-soluble areas and water-soluble areas or at lower Temperature includes water soluble areas. 8. detergent, dish soap or detergent portion according to claim 7, wherein the less well water-soluble areas or areas that are not water-soluble at all or only in higher areas Temperature water-soluble areas of the wrapping areas are made of a material chemically essentially that of the readily water-soluble areas or at lower Temperature corresponds to water-soluble areas, but has a higher layer thickness and / or has a changed degree of polymerization and / or a higher one Has degree of crosslinking and / or has a higher degree of acetalization and / or has a content of water-insoluble salt components and / or a content of a water-insoluble polymer. 9. detergent, detergent or cleaning agent portion according to one of claims 1 to 8, in which the completely or partially water-soluble coating contains one or more washing-active, contains flush-active or cleaning-active components, in particular those Components found in detergents, dishwashing detergents or cleaning agents only in small quantities Quantities are present. 10. detergent, detergent or cleaning agent portion according to one of claims 1 to 9, where the formulation is liquid-based. 11. detergent, dish soap or detergent portion according to claim 10, wherein the low-water formulation contains a rheological additive. 12. detergent, detergent or cleaning agent portion according to one of claims 10 or 11, wherein the liquid-based formulation of at least one wash-active, rinse-active or cleaning-active material a non-aqueous or substantially water-free formulation is preferably a formulation comprising less than 10% by weight of water preferred is a formulation comprising 1 to 5% by weight of water, most preferred is an anhydrous formulation.   13. detergent, detergent or cleaning agent portion according to one of claims 1 to 12, wherein the formulation is an anionic surfactant and / or nonionic surfactant containing formulation. 14. detergent, detergent or cleaning agent portion according to any one of claims 1 to 13, where the anionic surfactant (s) is / are selected from the group of the sulfonates and sulfates and their mixtures and / or in which the nonionic surfactant (s) is / are selected from the group alkoxylated alcohols, alkoxylated fatty acid alkyl esters, alkyl glycosides and mixtures thereof. 15. detergent, detergent or cleaning agent portion according to any one of claims 1 to 14, wherein the stabilizing agent is selected from the group of UV absorbers, antioxidants and fluorescent dyes. 16. detergent, detergent or cleaning agent portion according to any one of claims 1 to 15, wherein the stabilization is present in an amount of up to 40% by weight, preferably up to 30% by weight, particularly preferably from 0.01 to 20% by weight and in particular from 0.02% by weight to 5% by weight. 17. rinsing method, in particular method for machine rinsing in a commercially available dishwasher, comprising the steps that

• - A portion of detergent according to any one of claims 1 to 16 in the dishwasher, in particular in the dispenser or in the washroom, enters;
• - makes contact between the detergent portion and the washing liquor by adding water;
• - sets the desired rinsing conditions; and
• - If these conditions occur, the active detergent material (s) of the detergent portion is released into the washing solution and brought into contact with the items to be washed.

18. Cleaning process comprising the steps that one

• - A detergent portion according to one of claims 1 to 16 enters the cleaning liquor;
• - sets the desired cleaning conditions; and
• - When these conditions occur, the cleaning-active material (s) of the detergent portion is released into the cleaning liquor and brings them into contact with the items to be cleaned.