WO2002048309A1

WO2002048309A1 - Washing, rinsing or cleaning agent portions with transparent shell

Info

Publication number: WO2002048309A1
Application number: PCT/EP2001/014386
Authority: WO
Inventors: Hans-Jürgen Riebe; Thomas Escher
Original assignee: Henkel Kommanditgesellschaft Auf Aktien
Priority date: 2000-12-16
Filing date: 2001-12-07
Publication date: 2002-06-20
Also published as: DE10062857A1; AU2002229632A1

Abstract

The invention relates to a washing, rinsing or cleaning agent portion, comprising a completely or partially water soluble shell in the form of a capsule or bag, whereby the shell material is transparent and the portions contain a stabiliser. The invention further relates to a washing, rinsing or cleaning method using the above washing, rinsing or cleaning agent portions.

Description

"Detergent, detergent or cleaning agent portions with transparent wrapping"

The present invention relates to detergent, detergent or cleaning agent portions containing stabilizing agents which have a completely or partially water-soluble and transparent covering.

Traditionally, detergents and cleaning agents were usually given to the consumer in containers containing large volumes, such as plastic bottles. The dosing was then carried out as required (degree of contamination of the items to be washed, washed or cleaned, amount of items to be washed, washed or cleaned) or, based on experience, in each individual case using suitable devices for measuring amounts of liquid. Pre-metered portions of detergent, detergent or cleaning agent containing water-free alcohol ether sulfates (isopropanolammonium ether sulfates) as components of highly concentrated washing and cleaning agent systems are described in the article “U. Schoenkaes et al .; Water-free Alcohol Ether Sulfates - New high-active surfactants for superconcentrated detergent formulations ". Such systems are described as having excellent washing activity and are suitable for the stable incorporation of bleaches and other water-sensitive detergents, detergent and cleaning agent components.

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

However, the problem is the inconsistency of the coated detergent, cleaning or rinsing agent components in relation to light. Due to the transparency and the predetermined light permeability (range 250 to 800 nm), in particular the permeability of UV light (250 to 460 nm), the water-soluble coating materials, there are often signs of decomposition (e.g. radical decomposition of polymeric thickeners, dyes, etc.). ) or to signs of deactivation of active agent components (e.g. enzymes, bleach, etc.).

WO 00/36062 and WO 00/36067 describe transparent or transparent, liquid, enzyme-containing detergents, which are presented in clear bottles or containers made of water-insoluble polymers or glass. The enzymes are protected by antioxidants or by encapsulation. 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. The detergent dyes or the detergent enzymes are protected by fluorescent dyes or UV absorbers.

However, none of the documents described above deals with the problem of the lightfastness of washing, cleaning or rinsing agent components in washing, cleaning or rinsing agent portions which are present in a transparent, completely or partially water-soluble coating.

The object of the invention was to provide washing, cleaning and rinsing agent portions which are in a transparent, completely or partially water-soluble coating. The components present in the portions are to be stabilized against the radiation-related decomposition and deactivation phenomena.

Surprisingly, it has now been found that the constituents which are present in washing, cleaning and rinsing agent portions which are in a transparent, completely or partially water-soluble coating can be stabilized by means of stabilizing agents against signs of decomposition and deactivation.

The invention therefore relates to a 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, and the portion contains at least one stabilizing agent, the water-soluble coating has a transmittance above 20% at wavelengths of 410 to 800 nm.

In an alternative embodiment, the invention relates to a detergent, dishwashing or cleaning agent portion, comprising a completely or partially water-soluble envelope in spherical form, which completely surrounds at least one formulation of a detergent-active, detergent-active or cleaning-active material, and the portion contains at least one stabilizing agent, wherein the water-soluble coating has a transmittance above 20% at wavelengths from 410 to 800 nm.

In a further alternative embodiment, the invention relates to a detergent, dishwashing or cleaning agent portion, comprising a completely or partially water-soluble envelope in the form of a bag, which completely surrounds at least one formulation of a detergent-active, detergent-active or cleaning-active material, and at least the portion contains a stabilizing agent, the water-soluble coating having a transmittance above 20% at wavelengths of 410 to 800 nm. The invention also relates to a washing process, a rinsing process and a cleaning process using the detergent, detergent or cleaning agent portions described below.

In the context of the present invention, the term “detergent, detergent or cleaning agent portion” is understood to mean a sufficient amount of a detergent, detergent or cleaning agent for a washing, rinsing or cleaning process taking place in an aqueous phase. This can be, for example, a machine Washing, rinsing or cleaning process, such as is carried out with commercially available washing machines or dishwashers or cleaning machines, but according to the invention this term also includes a handwashing cycle (for example carried out in a hand wash basin or in a bowl) or a dishwashing cycle carried out by hand or by means of a cleaning liquor in a vessel, such as a cleaning cycle carried out in a bucket or another process of washing, rinsing or cleaning. According to the invention, the detergent, washing-up liquid or cleaning agent portions are preferred in the case of machines Washing, rinsing or cleaning processes are used.

In the context of the present invention, the term “portion of detergent” or “portion of detergent” or “portion of detergent” is understood to mean a portion of a portion of detergent, dishwashing detergent or detergent which is contained in another detergent or dishwashing detergent. or detergent portion portions separate phase in spatial connection with other detergent, dishwashing or cleaning agent portion portions of the same detergent, dishwashing or cleaning agent portion and is prepared by suitable measures so that it is separated from other detergent, dishwashing or cleaning agent portions the same detergent, detergent or cleaning agent portion can be added to the liquor and optionally dissolved or suspended in it, whereby a detergent, washing-up liquid or cleaning agent portion can contain the same ingredients as another detergent, washing-up liquid or cleaning agent -Teilpo rtion of the same detergent, dish soap or detergent portion; However, two portions of detergent, dishwashing detergent or cleaning agent preferably contain the same portion of detergent, dishwashing detergent or cleaning agent, different ingredients, in particular different detergent-active, dishwashing-active or detergent-active preparations.

According to the invention, the detergent, dishwashing or cleaning agent portions contain measured amounts of at least one washing-active, washing-active or cleaning-active preparation, usually measured amounts of several washing-active, washing-active or cleaning-active preparations. It is possible that the portions contain only wash-active, rinse-active or cleaning-active preparations of a certain composition. According to the invention, however, it is preferred that several, usually at least two, wash-active, wash-active or cleaning-active preparations of different compositions are contained in the detergent, detergent or cleaning agent portions. The composition can differ in terms of the concentration of the individual components of the wash-active, rinse-active or cleaning-active preparation (quantitative) and / or in terms of the type of individual components of the wash-active, rinse-active or cleaning-active preparation (qualitative). It is particularly preferred that the components are adapted in terms of type and concentration to the tasks which the detergent, dishwashing or cleaning agent portions have to perform in the washing, washing or cleaning process.

The detergent, dishwashing or cleaning agent portion according to the invention comprises a completely or partially water-soluble casing. The shape of the envelope is not limited to certain shapes according to the invention. Basically, all Archimedean and Platonic bodies, i.e. three-dimensional shaped bodies, can be used as forms of wrapping. Examples of the shape of the covering are capsules, cubes, spheres, egg-shaped moldings, cuboids, cones, rods or bags. Hollow bodies with one or more compartments, as described in co-pending patent application No. DE 100 33 827.5 with the title “compartment hollow body”, are also suitable as a covering for the washing-active, rinsing-active or cleaning-active materials. In preferred embodiments of the invention the envelopes are in the form of capsules, such as those used in pharmacy for the administration of pharmaceuticals, of spheres or sachets, the latter preferably being welded or glued on at least one side, an adhesive being the adhesive in particularly preferred embodiments of the invention is used, which is water-soluble.

In principle, all materials which can dissolve completely or partially in the aqueous phase under the given conditions of a washing process, rinsing process or cleaning process (temperature, pH value, concentration of detergent components) are suitable as materials for the completely or partially water-soluble coating. The polymer materials can particularly preferably be the groups (optionally partially acetalized) of polyvinyl alcohol, polyvinyl pyrrolidone, polyethylene oxide, gelatin, cellulose and their derivatives, starch and their derivatives, in particular modified starches, and mixtures (polymer blends, composites, coextrudates, etc.) of the belong to the materials mentioned. Gelatin and polyvinyl alcohols and the two materials mentioned are particularly preferred in each case in combination with starch or modified starch. Inorganic salts and mixtures thereof can also be used 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 are obtained via polymer-analogous reactions by hydrolysis, technically in particular by alkaline-catalyzed transesterification of polyvinyl acetates with alcohols, preferably with methanol. These technical processes also make PVAL accessible which contain a predetermined residual proportion of acetate groups.

Commercial PVAL (eg Mowiol ^® types from Hoechst) are commercially available as white-yellowish powders or granules with degrees of polymerization in the range from approximately 500 to 2500 (corresponding to molar masses from approximately 20,000 to 100,000 g / mol) and have different degrees of hydrolysis for example 98 to 99 or 87 to 89 mol%. They are therefore partially saponified polyvinyl acetates with a residual acetyl group content of, for example, about 1 to 2 or 11 to 13 mol%.

The water solubility of PVAL can be changed by post-treatment with aldehydes (acetalization) or ketones (ketalization). Polyvinyl alcohols which have been acetalized or ketalized with the aldehyde or keto groups of saccharides or polysaccharides or mixtures thereof have proven to be particularly preferred and particularly advantageous because of their extremely good solubility in cold water. The reaction products made of PVAL and starch are extremely advantageous to use.

Furthermore, the solubility in water can be changed by complexing with Ni or Cu salts or by treatment with dichromates, boric acid, borax and thus specifically adjusted to the desired values. PVAL films are largely impenetrable for gases such as oxygen, nitrogen, helium, hydrogen, carbon dioxide, but allow water vapor to pass through.

Examples of suitable water-soluble PVAL films are the PVAL films available from Syntana Handelsgesellschaft E. Harke GmbH & Co. under the name "SOLUBLON ^® ". Their solubility in water can be adjusted to the degree, and films of this product series are available, which are soluble in the aqueous phase in all temperature ranges relevant to the application. Polyvinylpyrrolidones, abbreviated as PVP, can be described by the following general formula:

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

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

H- [0-CH ₂ -CH ₂ ] _n -OH

which are technically produced by base-catalyzed polyaddition of ethylene oxide (oxirane) in systems containing mostly small amounts of water with ethylene glycol as the starting molecule. They have molar masses in the range from approx. 200 to 5,000,000 g / mol, corresponding to degrees of polymerization n from approx. 5 to> 100,000. Polyethylene oxides have an extremely low concentration of reactive hydroxyl end groups and show only weak glycol properties.

Gelatin is a polypeptide (molecular weight: approx. 15,000 to> 250,000 g / mol), which is primarily obtained by hydrolysis of the collagen contained in the skin and bones of animals under acidic or alkaline conditions. The amino acid composition of the gelatin largely corresponds to that of the collagen from which it was obtained and varies depending on its provenance. The use of gelatin as a water-soluble coating material is extremely widespread, especially in the pharmaceutical industry in the form of hard or soft gelatin capsules. In the form of films, gelatin is used only to a minor extent because of its high price in comparison to the abovementioned polymers.

In the context of the present invention, detergent, detergent and cleaning agent portions are also preferred, the packaging of which consists of at least partially water-soluble film made from at least one polymer from the group starch and starch derivatives, cellulose and cellulose derivatives, in particular methyl cellulose and mixtures thereof.

Starch is a homoglycan, with the glucose units linked α-glycosidically. Starch is made up of two components of different molecular weights: approx. 20 to 30% wheel-chain amylose (MW. approx. 50,000 to 150,000) and 70 to 80% branched-chain amylopectin (MW. approx. 300,000 to 2,000,000). It also contains small amounts of lipids, phosphoric acid and cations. While the amylose forms long, helical, intertwined chains with about 300 to 1,200 glucose molecules due to the binding in the 1,4-position, the chain in the amylopectin branches after an average of 25 glucose units through 1,6-binding to form a knot-like structure with about 1,500 to 12,000 molecules of glucose. In addition to pure starch, starch derivatives which are obtainable by polymer-analogous reactions from starch are also suitable for producing water-soluble coatings for the detergent, dishwashing detergent and cleaning agent portions in the context of the present invention. Such chemically modified starches include, for example, products from esterifications or etherifications in which hydroxy hydrogen atoms have been substituted. Starches in which the hydroxyl groups have been replaced by functional groups which are not bound via an oxygen atom can also be used as starch derivatives. The group of starch derivatives includes, for example, alkali starches, carboxymethyl starch (CMS), starch esters and starches and amino starches.

Pure cellulose has the formal gross composition (C ₆ H ₁₀ θ5) _n and, viewed formally, is a ß-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 coverings 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 film which forms the covering preferably has a thickness of 1 to 300 μm, preferably 2 to 200 μm, particularly preferably 5 to 150 μm and in particular 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. In a preferred method, the films are blown from a melt with air through a blow mandrel to form a tube. In the calendering process, which is also one of the preferred manufacturing processes, the raw materials plasticized by suitable additives become Forming the foils atomized. Here it may be necessary to connect drying to the atomization. In the casting process, which is also one of the preferred production processes, an aqueous polymer preparation is placed on a heatable drying roller; after the water has evaporated, cooling is optional and the film is removed as a film. If necessary, this film is additionally powdered before or during the removal.

Organic and / or inorganic salts are also suitable as materials for the coating of the detergent, detergent or cleaning agent portion according to the invention. Examples of these are salts which can be formed into a coating, for example by crystallization, pressing, compacting or other suitable processes, and which dissolve in sufficient time in water or aqueous liquor under the conditions of the washing, rinsing or cleaning process. Ideally, in particularly preferred embodiments of the invention, salts are used which can also perform other functions in a washing, rinsing or cleaning process.

According to the invention, an embodiment is preferred in which the covering is water-soluble as a whole, ie. H. dissolves completely when used as intended for washing, rinsing or cleaning, for example machine washing, rinsing or cleaning, if the conditions provided for the detachment have been reached. Particularly preferred as completely water-soluble coatings are, for. B. capsules made of gelatin, advantageously made of soft gelatin, or bags made of (optionally partially acetalized) PVAL or balls of gelatin or (optionally partially acetalized) PVAL or of one or more organic and / or inorganic salts, preferably balls made of soft gelatin. A significant advantage of this embodiment is that the sheath dissolves at least partially within a practically relevant short time - as a non-limiting example, a few seconds to 5 minutes - under precisely defined conditions in the washing liquor, rinsing liquor or cleaning liquor and thus the enveloped in accordance with the requirements Content, d. H. brings the wash-active, rinse-active or cleaning-active material or several materials into the fleet.

In another embodiment of the invention, which is also preferred on account of advantageous properties, the water-soluble covering comprises areas which are less or not water-soluble or only water-soluble at a higher temperature and areas which are water-soluble or water-soluble at a low temperature. In other words, the covering does not consist of a uniform material which has the same water solubility in all areas, but of materials of different water solubility. Areas of good water solubility are to be distinguished on the one hand from areas with less good water solubility, with poor or no water solubility or from areas in which water solubility is only at a higher temperature or at a different pH value or only when the electrolyte concentration has changed achieved, on the other hand. This can lead to Intended use under adjustable conditions, loosen certain areas of the wrapping while other areas remain intact. This creates an envelope with pores or holes into which water and / or liquor penetrate, detach active, rinse-active or cleaning-active ingredients and can discharge them from the envelope. In the same way, encapsulation systems in the form of multi-chamber bags or in the form of hollow bodies arranged one inside the other (eg spheres: “onion system”) can also be provided. In this way, systems with controlled release of the wash-active, rinse-active or cleaning-active ingredients can be produced.

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

It corresponds to a particularly preferred embodiment of the invention that the less water-soluble areas or non-water-soluble areas or only at higher temperatures water-soluble areas of the casing are areas made of a material which chemically essentially corresponds to that of the readily water-soluble areas or at lower temperatures water-soluble areas corresponds, but has a higher layer thickness and / or a changed degree of polymerization of the same polymer and / or a higher degree of crosslinking of the same polymer structure and / or a higher degree of acetalization (in PVAL, for example with saccharides, polysaccharides, such as starch) and / or a content has water-insoluble salt components and / or contains a water-insoluble polymer. Even taking into account the fact that the casing does not completely detach, detergent, detergent or cleaning agent portions according to the invention can thus be provided which have advantageous properties when releasing the detergent-active, detergent-active or detergent-active components into the respective liquor.

According to the invention, the water-soluble covering material is transparent. For the purposes of this invention, transparency is understood to mean that the transmittance within the visible spectrum of light (410 to 800 nm) is 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 the light has a transmittance greater than 20%, it is to be regarded as transparent in the sense of the invention.

The transparent, water-soluble portions contain at least one stabilizing agent as an essential component. Stabilizing agents in the sense of the invention are materials that Protect detergent, detergent or detergent ingredients in their water-soluble, transparent coatings against decomposition or deactivation by exposure to light. Antioxidants, UV absorbers and fluorescent dyes have proven to be particularly suitable here.

Particularly suitable stabilizers in the sense of the invention are the antioxidants. In order to prevent undesirable 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 As- corbinsäurepalmitat, organosulfur compounds, such as the esters of 3,3 ^{'thiodipropionic} acid with Ci.-is-alkanols, in particular C ₁₀ .ι ₈ alkanols, metal ion deactivators that are capable of catalyzing the auto-oxidation Me - complex ions such as copper, such as nitrilotriacetic 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.

Another class of stabilizers that can preferably be used are the UV absorbers. UV absorbers can improve the lightfastness of the formulation components. These include organic substances (light protection filters) that are able to absorb ultraviolet rays and release the absorbed energy in the form of longer-wave radiation, eg heat. Compounds which have these desired properties are, for example, the compounds and derivatives of benzophenone which are active by radiationless deactivation and have substituents in the 2- and / or 4-position. Also suitable are substituted Benzotri- azole, such as the water-soluble benzenesulfonic acid-3- (2H-benzotriazol-2-yl) -4-hydroxy-5- (methylpropyl) monosodium salt (Ciba ^® Fast H), 3-phenyl-substituted acrylates ( Cinnamic acid derivatives), optionally with cyano groups in the 2-position, salicylates, organic Ni complexes and natural substances such as umbelliferone and the body's own urocanoic acid. The biphenyl and, above all, stilbene derivatives described, for example in EP 0728749 A and are available as Tinosorb FD ^® ^® or Tinosorb FR ex Ciba commercially. 3-Benzylidene camphor or 3- Benzylidene norcamphor and its derivatives, for example 3- (4-methylbenzylidene) camphor, as described in EP 0693471 B1; 4-aminobenzoic acid derivatives, preferably 2-ethylhexyl 4- (dimethylamino) benzoate, 2-octyl 4- (dimethylamino) benzoate and amyl 4- (dimethylamino) benzoate; Esters of cinnamic acid, preferably 2-ethylhexyl 4-methoxycinnamate, propyl 4-methoxycinnamate, isoamyl 4-methoxycinnamate, 2-ethylhexyl 2-cyano-3,3-phenylcinnamate (octocrylene); Esters of salicylic acid, preferably salicylic acid 2-ethylhexyl ester, salicylic acid 4-isopropylbenzyl 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 di-2-ethylhexyl 4-methoxybenzmalonate; Triazine derivatives, such as, for example, 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 Bu- tamido triazone (Uvasorb® HEB); Propane-1,3-diones such as 1- (4-tert-butylphenyl) -3- (4'methoxyphenyl) propane-1,3-dione; Ketotricyclo (5.2.1.0) decane derivatives, as described in EP 0694521 B1. Also suitable are 2-phenylbenzimidazole-5-sulfonic acid and its alkali, alkaline earth, ammonium, alkylammonium, alkanolammonium and glucammonium salts; Sulfonic acid derivatives of benzophenones, preferably 2-hydroxy-4-methoxybenzophenone-5-sulfonic acid and its salts; Sulfonic acid derivatives of 3-benzylidene camphor, such as 4- (2 ~ oxo-3-bornylidene methyl) benzene sulfonic acid and 2-methyl-5- (2-oxo-3-bornylidene) sulfonic acid and their salts. Derivatives of benzoylmethane, such as 1- (4'-tert-butylphenyl) -3- (4'-methoxyphenyl) propane-1,3-dione, 4-tert-butyl, are particularly suitable as typical UV-A filters -4'-meth-oxydibenzoylmethane (Parsol 1789), 1-phenyl-3- (4'-isopropylphenyl) propane-1,3-dione and enamine compounds, as described in DE 19712033 A1 (BASF). The UV-A and UV-B filters can of course also be used in mixtures. In addition to the soluble substances mentioned, insoluble light-protection pigments, namely finely dispersed, preferably nanoized metal oxides or salts, are also suitable for this purpose. Examples of suitable metal oxides are, in particular, zinc oxide and titanium dioxide and, in addition, oxides of iron, zirconium, silicon, manganese, aluminum and cerium and mixtures thereof. Silicates (talc), barium sulfate or zinc stearate can be used as salts. The oxides and salts are already used in the form of the pigments for skin-care and skin-protecting emulsions and decorative cosmetics. The particles should have an average diameter of less than 100 nm, preferably between 5 and 50 nm and in particular between 15 and 30 nm. They can have a spherical shape, but it is also possible to use particles which have an ellipsoidal shape or a shape which differs from the spherical shape in some other way. The pigments can also be surface-treated, ie hydrophilized or hydrophobicized. Typical examples are coated titanium dioxides, such as titanium dioxide T 805 (Degussa) or Eusolex® T2000 (Merck). Silicones, and in particular trialkoxyoctylsilanes or simethicones, are particularly suitable as hydrophobic coating agents. Micronized zinc oxide is preferably used. Further suitable UV light protection filters can be found in the overview by 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.

Another preferred class of stabilizers is the fluorescent dyes. They include the ^{^{4,4'-diamino-2,2'-stilbenedisulfonic}} acids (flavonic), 4,4 ^{'-Distyrylbiphenylen,} methyl umbelliferone, coumarins, dihydroquinolinones, 1, 3-diaryl pyrazolines, naphthalimides, benzoxazole, benzisoxazole, and Benzimidazole systems and the pyrene derivatives substituted by heterocycles. Of particular importance here are the sulfonic acid salts of the diaminostilbene derivatives, as are described in US Pat. No. 2,784,220 or US Pat. No. 2,612,510, and polymeric fluorescent agents, as are disclosed in US Pat. No. 5,082,578.

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.

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

The term “wash-active preparation” or “rinse-active preparation” or “cleaning-active preparation” (or “wash-active etc. material” or “wash-active etc. component”) in the context of the present invention relates to preparations, materials or components of all conceivable relevant substances with a washing, rinsing or cleaning process. These are primarily the actual detergents, rinsing agents or cleaning agents with their individual components, which are explained in more detail below. These include active substances such as surfactants (anionic, non-ionic, cationic and amphoteric surfactants), builder substances (inorganic and organic builder substances), bleaching agents (such as peroxo bleaching agents and chlorine bleaching agents), bleach activators, bleach stabilizers, bleaching catalysts, enzymes, special polymers (e.g. those with cobuilder properties), graying inhibitors, dyes and the like d fragrances (perfumes), without the term being restricted to these substance groups.

Components of such "wash-active preparations (materials, components)", rinse-active preparations (materials, components) "or" cleaning-active preparations (materials, components) "can also be washing aids, rinsing aids and cleaning aids. Examples of these are optical brighteners , so-called soil repellents, i.e. polymers that counteract re-soiling of fibers or hard surfaces, as well as silver Retardants. Laundry treatment agents, such as fabric softener or dishwashing detergent additives, such as rinse aid, are also considered according to the invention as wash-active or rinse-active preparations.

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

In the context of the present invention, the term “liquid-based” is understood to mean that the formulation of a wash-active, rinse-active or cleaning-active material or a plurality of wash-active, rinse-active or cleaning-active materials is, at least during production, a formulation based on liquid components, as is the case are explained in detail below, even if this formulation contains solid components (suspended or dispersed) in large quantities.

Formulations of the detergent, dishwashing detergent or cleaning agent portions according to the invention completely surrounded by the envelopes, advantageously liquid-based formulations, can be either low-water formulations or essentially anhydrous formulations. Low-water formulations comprise water as an essential component in an amount of, for example, 15 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 all components of the formulation, 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), anionic, nonionic, cationic and / or amphoteric surfactants being used. From an application point of view, preference is given to mixtures of anionic and nonionic surfactants, the proportion of nonionic surfactants advantageously being greater than the proportion of anionic surfactants. The total surfactant content of the detergent, detergent or cleaning agent portions is preferably above 25% by weight, 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 example 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 ₂ -C ₄ alcohols with 3 EO, 4 EO or 7 EO, Cg-n alcohols with 7 EO, C ₁₃ -C ₅ alcohols with 3 EO, 5 EO, 7 EO or 8 EO, Ci ₂ -i ₈ ~ alcohols with 3 EO, 5 EO or 7 EO and mixtures of these, such as mixtures of C ₁₂ . ₁₄ - alcohol with 3 EO and C ₁₂ -i ₈ 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 of this are 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 methyl-branched aliphatic radical having 8 to 22, preferably 12 to 18, C 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 preferably used nonionic surfactants, which are used either as the sole nonionic surfactant or in combination with other nonionic surfactants, are alkoxylated, preferably ethoxylated or ethoxylated and propoxylated fatty acid alkyl esters, preferably with 1 to 4 carbon atoms in the alkyl chain, in particular fatty acid methyl ester, as described for example in Japanese patent application JP 58/217598 or which are preferably produced by the process described in international patent application WO 90/13533.

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

Other suitable surfactants are polyhydroxy fatty acid amides of the formula I, R1

I

R-CO-N- [Z ¹ ] I in the RCO for an aliphatic acyl radical having 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

R ¹ -0-R ²

R-CO-N- [Z ² ] 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 -C 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% by weight and in particular 15 to 50% by weight, in each case based on the total composition.

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 as they are for example from C ₁₂ -ι ₈ monoolefins with terminal or internal double bond by sulfonating with gaseous sulfur trioxide and subsequent alkaline or acidic hydrolysis of the sulfonation products. Alkanesulfonates which are derived from C ₁₂ are also suitable. ₁₈ - Alkanes can be obtained, for example, by sulfochlorination or sulfoxidation with subsequent hydrolysis or neutralization. The esters of α-sulfofatty acids (ester sulfonates), for example the α-sulfonated methyl esters of hydrogenated coconut, palm kernel or tallow fatty acids, are also suitable.

Other suitable anionic surfactants are sulfonated fatty acid glycerol esters. Fatty acid lycerol esters are to be understood as meaning the mono-, di- and triesters and their mixtures as obtained in the production by esterification of a monoglycerol with 1 to 3 moles of fatty acid or in the transesterification of triglycerides with 0.3 to 2 moles of glycerol. Preferred sulfonated fatty acid lycerol 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.

The 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 fatty alcohol, tallow fatty alcohol, lauryl, myristyl, cetyl or stearyl alcohol or 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 ₆ alkyl sulfates and C ₁₂ -C ₅ alkyl sulfates and C ₁₄ -C ₁₅ alkyl sulfates are preferred from a washing-technical point of view. Also 2,3-alkyl sulfates, which are produced for example in accordance with US Patent No. 3,234,258 or 5,075,041 and can be obtained as commercial products from Shell Oil Company under the name DAN ^®, are suitable anionic surfactants.

The sulfuric acid monoesters of straight-chain or branched C ₇ ethoxylated with 1 to 6 mol of ethylene oxide. ₂₁ alcohols, such as 2-methyl-branched C ₉ . _ι Alcohols with an average of 3.5 moles of ethylene oxide (EO) or C ₁₂ -i ₈ 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 ethoxylated fatty alcohols. Preferred sulfosuccinates contain C ₈ . ₁₈ fatty alcohol residues or mixtures thereof. Particularly preferred sulfosuccinates contain a fat Ikoholrest, which is derived from ethoxylated fatty alcohols, which in themselves are non-ionic surfactants (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 and unsaturated fatty acid soaps are suitable, 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. 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 also as soluble salts of organic bases, such as, for example, mono-, di- or triethanolamine, monoisopropanolamine or triisopropanolamine. The anionic surfactants are preferably in the form of their ammonium salts, in particular their ammonium salts with 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, in each case based on the total portion.

In addition to the one or more surfactant (s), the detergent, dishwashing or cleaning agent portions according to the invention - irrespective of whether they contain water or low in water or essentially water-free - can contain further ingredients which further improve the technical and / or aesthetic properties of the agent improve. In the context of the present invention, preferred detergent, detergent or cleaning agent portions contain, 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, perfumes, perfume carriers, dyes, hydrotropes, foam inhibitors, silicone oils, anti-redeposition agents, transfer inhibitors optical brighteners, graying inhibitors, shrink preventatives, anticrease agents, dyes, antimicrobial active ingredients, germicides, fungicides, corrosion inhibitors, antistats, ironing aids, waterproofing and impregnating agents, swelling and Anti-slip agents and theological additives.

As builders, which may be contained in the detergent, detergent or cleaning agent portions according to the invention, in particular silicates, aluminum silicates (in particular zeolites), carbonates, salts of organic di- and polycarboxylic acids and mixtures of these substances are mentioned. Suitable crystalline, layered sodium silicates have the general formula NaMSi _x 0 _{x +} ι ^' H ₂ 0, where M is sodium or hydrogen, x is a number from 1.9 to 4 and y is a number from 0 to 20 and preferred values for x 2 , 3 or 4 are. 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 ß- and δ-sodium disilicate

Na ₂ Si ₂ 0 ₅ -yH ₂ 0 is preferred, β-sodium disilicate being able to be obtained, for example, by the process described in international patent application WO-A 91/08171.

Amorphous sodium silicates with a module Na ₂ 0: Si0 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 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 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. 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. Compacted / compacted amorphous silicates, compounded amorphous silicates and over-dried X-ray amorphous silicates are particularly preferred.

The finely crystalline, synthetic zeolite containing bound water used is preferably zeolite A and / or P. The zeolite P, zeolite MAP ^® (commercially available from Crosfield) is especially 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) ), which is sold by CONDEA Augusta SpA under the brand name VEGOBOND AX ^® and by the formula

nNa ₂ 0 '(1-n) K ₂ 0' Al ₂ 0 ₃ ^■ (2 - 2.5) Si0 ₂ '(3.5 - 5.5) H ₂ 0 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.

Of course, it is also possible to use the generally known phosphates as builders, provided that such use should not be avoided for ecological reasons. The sodium salts of orthophosphates, pyrophosphates and in particular tripolyphosphates are particularly suitable.

Among the compounds which serve as bleaching agents and supply H ₂ 0 ₂ in water, sodium percarbonate, sodium perborate tetrahydrate and sodium perborate monohydrate are of particular importance. Further usable bleaching agents are, for example, peroxopyrophosphates, citrate perhydrates and H ₂ 0 ₂ -supplying 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 Η ₂ 0 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-phthalimidoperoxycaproic acid, phthalimidaproacid (hexthalimide), 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, diperoxybrassyldiperoxyacid, 4-diperoxyacid N-terephthaloyl-di (6-aminopercaproic acid) can be used.

In order to achieve an improved bleaching effect when washing at temperatures of 60 ° C. and below, bleach activators can be incorporated into the detergent portions. Bleach activators which can be used are compounds which, under perhydrolysis conditions, aliphatic peroxo- carboxylic acids with preferably 1 to 10 carbon atoms, in particular 2 to 4 carbon atoms, and / or optionally substituted perbenzoic acid are used. Suitable substances are those which carry O- and / or N-acyl groups of the number of carbon atoms mentioned and / or optionally substituted benzoyl groups. Multi-acylated alkylenediamines, in particular tetraacetylethylene diamine (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, especially N-nonanoylsuccinimide (NOSI), acylated phenolsulfonates, especially n-nonanoyl- or isononanoyloxybenzenesulfonate (n- or iso-NOBS), carboxylic acid anhydrides, especially phthalic anhydride, acylated polyhydric alcohols, especially triethyl acetic acid, triethyl acetic acid, acetic acid triethyl acetic acid , 2,5-diacetoxy-2,5-dihydrofuran and the enol esters known from German patent applications DE 196 16 693 and DE 196 16 767 as well as acetylated sorbitol and mannitol or their mixtures described in European patent application EP 0 525 239 (SORMAN), acylated sugar derivatives, especially pentaacetylglucose (PAG), pentaacetylfructose, tetraacetylxylose and octaacetyllactose as well as acetyli first, optionally N-alkylated glucamine and gluconolactone, and / or N-acylated lactams, for example N-benzoylcaprolactam, which are known from 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 hydrophilically substituted acylacetals known from German patent application DE 196 16 769 and the acyl lactams described in German patent application DE 196 16 770 and international patent application WO 95/14075 are also preferably used. The combinations of conventional bleach activators known from German patent application DE 4443 177 can also be used.

In addition to the conventional bleach activators or in their place, so-called bleach catalysts can also be incorporated into the wash-active preparations for the portions according to the invention. 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. Mn, Fe, Co, Ru, Mo, Ti, V and Cu complexes with nitrogen-containing tripod ligands as well as Co, Fe, Cu and Ru amine complexes can also be used as bleaching catalysts.

Enzymes for use in detergent, detergent or cleaning agent portions are, in particular, those from the classes of hydrolases such as proteases, esterases, lipases or lipolytically active enzymes, amylases, cellulases or other glycosyl hydrolases and mixtures of the enzymes mentioned. The hydrolases help remove stains such as protein, fat or starchy stains and graying in laundry, for example. Cellulases and other glycosyl hydrolases can also help to retain color and increase the softness of the textile by removing pilling and microfibrils. Oxireductases can also be used to bleach or inhibit the transfer of color. Enzymes obtained from bacterial strains or fungi such as Bacillus subtilis, Bacillus licheniformis, Streptomyceus griseus and Humicola insolens are particularly suitable. Substances. Proteases of the subtilisin type and in particular proteases which are obtained from Bacillus lentus are preferably used. Enzyme mixtures, for example, from protease and amylase or protease and lipase or lipolytically active 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 active enzymes and cellulase, but especially protease and / or lipase-containing mixtures or mixtures with lipolytically active enzymes of particular interest for the detergent, detergent or cleaning agent portions according to the invention. Known cutinases are examples of such lipolytically active enzymes. 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 thereof, are preferably used as cellulases. Since different cellulase types 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 coating substances to protect them against premature decomposition. The proportion of the enzymes, enzyme mixtures or enzyme granules can be, for example, about 0.01 to 5% by weight, preferably 0.012 to about 2% by weight.

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 point of view, 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 that can be used in the detergent, detergent or cleaning agent portions according to the invention come, for example, from the group of mono- or polyhydric alcohols, alkanolamines or glycol ethers, provided that they are miscible with water in the concentration range indicated. The solvents are preferably selected from ethanol, n- or i-propanol, butanols, glycol, propane or butanediol, glycerol, 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, diisopropylene glycol monomethyl or ethyl ether, methoxy, ethoxy or butoxytriglycol, 1-butoxyethoxy-2- propanol, butoxy-propoxy-propanol (BPP), 3-methyl-3-methoxybutanol, propylene glycol t-butyl ether, N-butoxypropoxypropanol and mixtures of these solvents. Non-aqueous solvents can be portions of detergent, detergent or cleaning agent are used in amounts between 0.5 and 90% by weight, but preferably below 80% by weight and in particular below 70% by weight.

In order to bring the pH of the agents according to the invention into the desired range, the use of pH adjusting agents can be indicated. All known acids or alkalis can be used here, provided that their use is not prohibited for application-related or ecological reasons or for reasons of consumer protection. The amount of these adjusting agents usually does not exceed 2% by weight of the total formulation.

Foam inhibitors that can be used in the detergent, detergent or cleaning agent portions according to the invention are, for example, soaps, paraffins or silicone oils, which can optionally be applied to carrier materials.

Suitable anti-redeposition agents, which are also referred to as “soil repellents”, are, for example, nonionic cellulose ethers such as methyl cellulose and methyl hydroxypropyl cellulose with a proportion of methoxy groups of 15 to 30% by weight and of hydroxypropyl groups of 1 to 15% by weight, based in each case on the nonionic cellulose ethers, and the polymers of phthalic acid and / or terephthalic acid known from the prior art or of their derivatives, in particular polymers of ethylene terephthalates and / or polyethylene glycol terephthalates or anionically and / or nonionically modified derivatives thereof, particularly preferred among the compounds mentioned the sulfonated derivatives of phthalic acid and terephthalic acid polymers.

Graying inhibitors have the task of keeping the dirt detached from the fiber suspended in the liquor and thus preventing the dirt from being re-absorbed. For this purpose, water-soluble colloids of mostly organic nature are suitable, for example glue, gelatin, salts of ether sulfonic acids of starch or cellulose or salts of acidic sulfuric acid esters of cellulose or starch. Water-soluble polyamides containing acidic groups are also suitable for this purpose. Soluble starch preparations and starch products other than those mentioned above can also be used, e.g. degraded starch, aldehyde starches, etc. Polyvinyl pyrrolidone can also be used. However, cellulose ethers such as carboxymethyl cellulose (sodium salt), methyl cellulose, hydroxyalkyl cellulose and mixed ethers such as methyl hydroxyethyl cellulose, methyl hydroxypropyl cellulose, methyl carboxymethyl cellulose and mixtures thereof are preferably used in amounts of 0.1 to 5% by weight, based on the composition. According to the invention, graying inhibitors based on optionally modified polyacrylates and their copolymers are also suitable.

Since textile fabrics, in particular made of rayon, rayon, cotton and their blends, can tend to wrinkle because the individual fibers are sensitive to bending, kinking, pressing and squeezing transversely to the direction of the fibers, contain synthetic anti-crease agents. These include, for example, synthetic products based on fatty acids, fatty acid esters, fatty acid amides, alkylol esters, alkylolamides or fatty alcohols, which are mostly reacted with ethylene oxide, or products based on lecithin or modified phosphoric acid esters.

To combat microorganisms, the detergent, dishwashing or cleaning agent portions according to the invention can contain antimicrobial active ingredients. Depending on the antimicrobial spectrum and mechanism of action, a distinction is made between bacteriostatics and bactericides, fungistatics and fungicides etc. Important substances from these groups are, for example, benzalkonium chlorides, alkylarlylsulfonates, halogenophenols and phenol mercuric acetate, although these compounds can be dispensed with entirely in the portions according to the invention.

Increased wearing comfort can result from the additional use of antistatic agents which are additionally added to the detergent portions according to the invention. Antistatic agents increase the surface conductivity and thus enable the flow of charges that have formed to improve. External antistatic agents are generally substances with at least one hydrophilic molecular ligand and give a more or less hygroscopic film on the surfaces. These usually surface-active antistatic agents can be subdivided into nitrogen-containing (amines, quaternary ammonium compounds ^■ amides), phosphorus (organophosphate) and sulfur-containing (alkylsulfonates, alkyl sulfates) antistats. External antistatic agents are described, for example, in patent applications FR 1, 156.513, GB 873 214 and GB 839 407. The lauryl (or stearyl) dimethylbenzylammonium chlorides disclosed here are suitable as antistatic agents for textiles or as an additive to detergents, an additional finishing effect being achieved.

To improve the water absorption capacity or the rewettability of the treated textiles and to facilitate the ironing of the treated textiles, for example silicone derivatives can be used in the detergent portions according to the invention. These additionally improve the rinsing behavior of the portions according to the invention due to 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 are wholly or partly fluorinated. Preferred silicones are polydimethylsiloxanes, which can optionally be derivatized and then are amino-functional or quaternized or have Si-OH, Si-H and / or Si-Cl bonds. The viscosities of the preferred silicones at 25 ° C. are in the range between 100 and 100,000 mPas, and the silicones can be used in amounts between 0.2 and 5% by weight, based on the total agent.

In order to avoid the decomposition of certain detergent ingredients catalyzed by heavy metals, substances which complex heavy metals can advantageously be used. Suitable heavy metal complexing agents are, for example, the alkali salts of ethylenediamine tetraacetic acid (EDTA) or nitrilotriacetic acid (NTA) or its 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 in preferred detergent, dishwashing or cleaning agent portions in amounts of 0.01 to 2.5% by weight, preferably 0.02 to 1% by weight and in particular 0 , 03 to 0.5 wt .-% are included. These preferred compounds include, in particular, organophosphonates such as, for example, 1-hydroxyethane-1,1-diphosphonic acid (HEDP), aminotri (methylene phosphine acid) (ATMP), diethylene triamine penta (methylene phosphine acid) (DTPMP or DETPMP) and 2-phosphonobutane-1, 2,4-tricarboxylic acid (PBS-AM), which are mostly used in the form of their ammonium or alkali metal salts.

In further preferred embodiments of the detergent, detergent or cleaning agent portions according to the invention, the low-water and advantageously liquid formulation comprises a rheological additive. This can consist of one or more components. The rheological additives often serve as thickeners. These organic high-molecular substances, also called swelling agents, which absorb liquids, swell up and finally change into viscous real or colloidal solutions, come from the groups of natural polymers, the modified natural polymers and the fully synthetic polymers.

Polymers originating from nature and used as rheological additives are, for example, agar agar, carrageenan, tragacanth, arabic gum, alginates, pectins, polyoses, guar flour, carob bean flour, starch, dextrins, gelatin and casein.

Modified natural products come primarily from the group of modified starches and celluloses, examples include carboxymethyl cellulose and cellulose ethers, hydroxyethyl and propyl cellulose and core meal ether.

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

Rheological additives from the mentioned classes of compounds are widely available commercially and are sold for example under the trade name 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 ß-D-glucose, D-manose, D-glucuronic acid, Schönes GmbH), Deuteron -XN (non-ionic polysaccharide, Schönes GmbH), Dicrylan ^® thickener-0 (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), Shellflo ^® -S (high molecular polysaccharide, stabilized with formaldehyde, Shell) and Shellflo ^® -XA (xanthan biopolymer, with formaldehyde stabilized, shell) available.

In cases where the formulation of the wash-active, rinse-active or cleaning-active materials is a water-poor or water-free formulation, this water-poor or water-free formulation preferably comprises one or more anionic surfactant (s) and / or one or more nonionic surfactant () to adjust its rheological parameters. e) comprehensive material. In a particularly preferred embodiment, the anionic surfactant (s) is / are selected from the group of the sulfonates and sulfates and their mixtures and / or the / 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 of wash-active, rinse-active or cleaning-active materials which are contained in the detergent, dishwashing or cleaning agent portions according to the invention, in a preferred embodiment, as anionic surfactants, optionally in the presence of further anionic and / or not -ionic 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 triisopropanolammonium ether sulfate (TIPA ether sulfate) are particularly preferred because of their excellent anionic surfactant properties.

Rheological additives with a thickening effect, which can also be used as associative thickeners, are advantageously used in low-water or essentially water-free systems. These can be, for example (but not necessarily), acrylic-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 sold by Rohm & Haas under the name Aculos ^R , which are predominantly polyacrylates with different alkylation or crosslinking or hydrophobically modified nonionic polyols, or the products sold by BF Goodrich under the name Carbopol ^R , which are polyacrylates or copolymers of acrylic acid and alkylated (preferably C ₅ - to C ₁₀ -alkylated) acrylic acids, or the products sold by BF Goodrich under the name Pemulen ^R , the are high molecular acrylic copolymers of the type acrylic Iat C ₁₀ to 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 via a different mode of action (ie not associatively) in the presence of small amounts of water.

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

Also preferred according to the invention are detergent, detergent or cleaning agent portions in which the liquid-based formulations show non-Newtonian flow behavior, preferably thixotropic or pseudoplastic flow behavior. In particularly preferred embodiments of the portions, the liquid-based formulations have a low viscosity during production, for example a viscosity in the range from 10 to 50 mPa.s, and the liquid-based formulations have a higher viscosity during storage, for example in the range of 10 to 100,000 mPa-s, preferably 100 to 20,000 mPa ^• s, more preferably a viscosity in the range of 200 to 10,000 mPa s. In the case of clearly present systems, the viscosity can be lower than in systems in which solid components (which are visually noticeable in a turbidity) are present; the latter thickens regularly during storage ("setting") and can even become pasty.

Detergent, dishwashing or cleaning agent portions according to the present invention, which are present, for example, in capsule form, spherical shape or in the form of bags, can contain a liquid-based formulation contained in the wrappings of the detergent, dishwashing agent or cleaning agent portion of at least one detergent-active formulation , rinse-active or cleaning-active material can have clear solutions of one or more wash-active, rinse-active or cleaning-active component (s) or microemulsions. However, it is also possible according to the invention that liquid-based formulations contain one or more solids suspended or dispersed, in particular when low-water or essentially water-free formulations are used. This is an advantage over the prior art, since water-sensitive components of wash-active, rinse-active or cleaning-active materials can be kept stable and uniformly distributed in the liquid phase and problems with a reduction in activity do not occur.

The invention also relates to a washing method, in particular a method for machine washing in a commercially available washing machine, comprising the steps of introducing a detergent portion into the washing machine, in particular into the dispenser or the washing drum, according to the detailed description above; 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 of inserting a detergent portion into the dishwasher, in particular into the washing-up chamber or into the washing-up compartment, according to the detailed description above; 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 rinsing agent portion releases into the rinsing liquor and brings them into contact with the items to be rinsed.

The invention also relates to a cleaning process comprising the steps of adding a detergent portion 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 is released into the cleaning liquor and brings it into contact with the goods to be cleaned. In addition to the aforementioned areas, the portions according to the present invention can also be used in other areas. For example, they are also conceivable as a cleaner for toilet cisterns for the continuous delivery of a cleaning agent and disinfectant to the toilet flushing water, if necessary, or as a cleaner for pipes, etc. For special purposes, such cleaners can also contain gas-releasing systems (e.g. an acid such as citric acid with a carbonate such as sodium carbonate).

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, those water-soluble coatings are transparent in which a transmittance (T) above 20% is measured in the wavelength range from 410 to 800 nm, at least one wavelength.

Claims

claims

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, dishwashing or cleaning agent portion, comprising a completely or partially water-soluble envelope in spherical form, which completely surrounds at least one formulation of a detergent-active, detergent-active or detergent-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.

3. Detergent, dishwashing or cleaning agent portion, comprising a completely or partially water-soluble envelope in the form of a bag, 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, wherein the water-soluble coating has a transmittance above 20% at wavelengths from 410 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 than 30%, preferably greater than 40% and in particular greater than 50%.

5. detergent, detergent or cleaning agent portion according to any one of claims 1 to 4, comprising a completely or partially water-soluble coating made of a material from the group (optionally fully or partially acetalized and / or ketalized) polyvinyl alcohol, polyvinylpyrrolidone, polyethylene oxide , Gelatin, cellulose and their derivatives, starch and their derivatives, blends and composites, inorganic salts and mixtures of the materials mentioned.

6. detergent, detergent or cleaning agent portion according to one of claims 1 to 5, comprising a completely water-soluble coating from the group of capsules made of gelatin, preferably soft gelatin or (optionally completely or partially acetalized and / or ketalized) polyvinyl alcohol, in particular PVAL, which has been acetalized with starch, bags made of (optionally fully or partially acetalized and / or ketalized Sized) polyvinyl alcohol, especially PVAL, which was acetalized with starch, ball of (optionally partially or completely acetalized and / or ketalized) polyvinyl alcohol, in particular PVAL, which was acetalized with starch, or gelatin, preferably soft gelatin, or an inorganic salt or a mixture inorganic salts.

7. Detergent, dishwashing or cleaning agent portion according to claim 5 or claim 6, wherein the water-soluble coating comprises less or not water-soluble or water-soluble areas only at higher temperatures and water-soluble or water-soluble areas at low temperature.

8. detergent, detergent or cleaning agent portion according to claim 7, wherein the less water-soluble areas or non-water-soluble areas or only at higher temperature water-soluble areas of the casing are areas made of a material which chemically essentially that of the well water-soluble areas or corresponds to water-soluble regions at a lower temperature, but has a higher layer thickness and / or has a changed degree of polymerization and / or has a higher 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 one has water-insoluble polymers.

9. detergent, dishwashing or cleaning agent portion according to one of claims 1 to 8, wherein the wholly or partially water-soluble coating contains one or more washing-active, dishwashing-active or cleaning-active components, in particular those components which are only present in detergents, washing-up liquids or cleaning agents are present in small quantities.

10. Detergent, dishwashing or cleaning agent portion according to one of claims 1 to 9, wherein the formulation is liquid-based.

11. A detergent, dishwashing or cleaning agent portion according to claim 10, wherein the low-water formulation contains a rheological additive.

12. Detergent, dishwashing or cleaning agent portion according to one of claims 10 or 11, wherein the liquid-based formulation of at least one washing-active, rinsing-active or cleaning-active material is a non-aqueous or essentially water-free formulation, preferably a less than 10 Formulation comprising% by weight of water, more preferably is a formulation comprising 1 to 5% by weight of water, most preferably is an anhydrous formulation.

13. Detergent, dishwashing 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, dishwashing or cleaning agent portion according to one of claims 1 to 13, wherein the anionic surfactant (s) is / are selected from the group of sulfonates and sulfates and their mixtures and / or wherein the nonionic surfactant ( e) is / are selected from the group of alkoxylated alcohols, alkoxylated fatty acid alkyl esters, alkyl glycosides and mixtures thereof.

15. Detergent, dishwashing or cleaning agent portion according to one of claims 1 to 14, wherein the stabilizing agent is selected from the group of UV absorbers, antioxidants and fluorescent dyes.

16. detergent, dish soap or detergent portion according to any one of claims 1 to 15, wherein the stabilization is present in an amount up to 40 wt .-%, preferably up to 30 wt .-%, particularly preferably from 0.01 to 20 wt .-% and in particular from 0.02 wt .-% to 5 wt .-%.

17. rinsing method, in particular method for machine rinsing in a commercially available dishwasher, comprising the steps that

• enters a detergent portion according to any one of claims 1 to 16 in the dishwasher, in particular in the dispenser or in the wash cabinet;

• makes contact between the detergent portion and the washing liquor by adding water;

• sets the desired rinsing conditions; and

• When these conditions occur, the rinse-active material (s) in the detergent portion is released into the rinsing solution and brought into contact with the items to be rinsed.

18. Cleaning process comprising the steps that one

• enters a detergent portion according to one of claims 1 to 16 into 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.