EP1095131B1 - Portioned washing agent and detergent composition - Google Patents

Abstract

A portioned detergent composition in a bag of water-soluble film in which at least 70% by weight of the particles of the detergent composition have particle sizes above 800 mu m. The choice of this particular particle size range eliminates otherwise typical production-related problems arising out of the permeability of the bag seams and resulting difficulties.

Description

The present invention relates to portioned detergent and cleaning agent compositions, the consumer the dosage of detergents and cleaning agents facilitate. In particular, the invention relates to portioned detergent and cleaning agent compositions, which is packaged in a bag made of water-soluble film are and are briefly referred to as "portion bags".

Detergents and cleaning agents and processes for their production are well known and in Accordingly, the prior art is broadly described. Usually they become the consumer in the form of spray-dried or granulated powder products or as liquid goods made available. Following the consumer's desire for simple dosing, In addition to these two classic variants, products have been pre-portioned established in the market and are also described extensively in the prior art, whereby in particular pressed molded articles, that is tablets, blocks, briquettes and the like as well Portions of solid or liquid detergents and cleaning agents packed in bags become.

In the case of single-dose amounts of detergents and cleaning agents, packed in sachets have come onto the market, bags made of water-soluble film have prevailed, which make it unnecessary for the consumer to tear open the packaging. On this is a convenient dosage of a single serving by inserting the sachet directly into the washing machine or dishwasher or into its dispenser or through Throw in a predetermined amount of water, for example in a bucket or in Hand wash or sink possible. Packaged in bags made of water-soluble film Detergents and cleaning agents are therefore described in large numbers in the prior art.

For example, German Auslegeschrift 11 30 547 (Procter & Gamble) discloses packages made of water-soluble films of polyvinyl alcohol which are filled with non-liquid synthetic detergents. This document does not comment on the particle sizes of the packaged detergents.

A single dose of a detergent or bleach in a bag that has one or more seams made of water-sensitive material is described in European patent application EP 143 476 (Akzo NV). In this publication, a mixture of anionic and / or nonionic water-binding polymer and cationic polymer adhesive material is proposed as the water-sensitive suture material. This document indicates that the bags according to the invention can be good containers for pellets and extrudates, but cannot be said about the particle sizes of the detergents or bleaches included.

European patent application EP 158 464 (Clorox) describes low-temperature detergents which can be packaged in a bag made of water-soluble film. Information on particle sizes of the packaged detergents can be found in this document only with regard to the builder used (sodium tripolyphosphate), the particle sizes being between 75 and 400 μm.

Extremely large particles which are enclosed by a water-insoluble film are described in EP 385 529 (Procter & Gamble). This document discloses a jumbo-particulate fabric softening composition whose 5 to 30 mm large dryer-activated softener particles are enclosed with a non-water-soluble, porous film.

It has been shown that the detergent and cleaning agent compositions packaged in sachets of the prior art result in manufacturing problems. When packaging the detergent and cleaning agent compositions in the water-soluble Foil, fine particles adhere to the foil and reach the seal the film to the closed bag in the seams forming the bag. Through these particles the seams in question are not complete in the seal against the atmosphere tight, leading to stability problems of the detergent and cleaning agent composition can lead. In the case of hygroscopic ingredients, this continues to exist Problem that the detergent and cleaning composition moisture from the Absorbs ambient air and clumps with the bag despite wrapping. In serious In some cases, the detergent and cleaning agent composition becomes so moist that it softens the bag film and affects its stability so far that the consumer can no longer take a single dose, but a soaked product-film conglomerate found in the outer packaging.

With temperature-sensitive ingredients, it can also happen that particles that are included in the seam to be formed using a heat seal process be thermally stressed and cause further leaks, discoloration or can even lead to accidents due to thermal decomposition of the particles in an emergency.

Avoiding these problems and providing a portioned wash and Detergent composition in which the seams of the water-soluble film Bags were sealed from the atmosphere was the object of the present invention. It could be shown that the problem mentioned leaky seams and the resulting problems can be excluded if the portioned Detergent and cleaning agent compositions with regard to certain criteria meet their particle size.

The invention therefore relates to a portioned detergent and cleaning agent composition in a bag made of water-soluble film, in which at least 70% by weight the particles of the detergent and cleaning agent composition particle sizes in the range of Have 800 µm to 3000 µm.

The above-mentioned problems of sealing occur in the particle size range mentioned particles sticking to the film in the seams, no longer. At least they are 70% by weight of the particles and the 800 μm are to be understood as lower limits, for example this means that, for technical reasons, powdering the washing and Detergent composition is desired, which depends on the process Share fine grain in the detergent and cleaning agent. Can also at Production and further processing even after the screening of unwanted fines the proportion of coarser particles reduced by abrasion to form fine fractions become. In the context of the present invention, however, it is preferred to use one if possible high and well over 70% by weight of coarse particles in the washing and Detergent composition to have. With preferred portioned Detergent and cleaning agent compositions have at least 80% by weight, preferably at least 85% by weight, particularly preferably at least 90% by weight and in particular at least 95% by weight of the particles of the detergent and cleaning composition Particle sizes above 800 microns, preferably above 900 microns, particularly preferred above 1000 µm and in particular above 1200 µm.

Another advantage of the present invention is that existing or emerging Fine particles within the tightly sealed bag and thus within a portion of the Detergents and cleaning agents remain. With usual packaging it happens during of transport to segregation, since the fine particles through the particle pile of the coarse particles fall through.

The portioned detergent and cleaning agent compositions according to the invention are packed in bags made of water-soluble film. Such bag materials or foils are known from the prior art and originate, for example, from the group (acetalized) Polyvinyl alcohol, polyvinyl pyrrolidone, polyethylene oxide, gelatin and mixtures thereof.

Polyvinyl alcohols, abbreviated as PVAL, are polymers of the general structure [-CH ₂ -CH (OH) -] _n which in small proportions also structural units of the type [-CH ₂ -CH (OH) -CH (OH) -CH ₂ ] contain. Since the corresponding monomer, the vinyl alcohol, is not stable in free form, polyvinyl alcohols are prepared in solution via polymer-analogous reactions by hydrolysis, but technically in particular by alkaline-catalyzed transesterification of polyvinyl acetates with alcohols (preferably methanol). These technical processes also make PVAL accessible which contain a predeterminable residual proportion of acetate groups.

Commercial PVAL (e.g. Mowiol® grades from Hoechst) come as white-yellow Powder or granules with degrees of polymerization in the range of approx. 500-2500 (corresponding to molar masses of approx. 20,000-100,000 g / mol) in the trade and have different Degrees of hydrolysis of 98-99 and 87-89 mol%. So they are partially saponified polyvinyl acetates with a residual acetyl group content of approx. 1-2 or 11-13 mol%.

The water solubility of PVAL can be improved by post-treatment with aldehydes (acetalization), by complexing with Ni or Cu salts or by treatment with dichromates, Reduce boric acid, borax and adjust them to the desired values. films made of PVAL are largely impenetrable for gases such as oxygen, nitrogen, helium, Hydrogen, carbon dioxide, however, allow water vapor to pass through.

beschreiben.Polyvinylpyrrolidones, abbreviated as PVP, can be identified by the general formula

describe.

PVPs are made by radical polymerization of 1-vinyl pyrrolidone. commercial PVP have molar masses in the range of approx. 2500-750,000 g / mol offered as white, hygroscopic powder or as aqueous solutions.

Polyethylene oxides, PEOX for short, are polyalkylene glycols of the general formula H- [O-CH ₂ -CH ₂ ] _n -OH which are produced industrially 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 of approx. 200-5,000,000 g / mol, corresponding to degrees of polymerization n of approx. 5 to> 100,000. Polyethylene oxides have an extremely low concentration of reactive hydroxy end groups and show only weak glycol properties.

Gelatin is a polypeptide (molecular weight: approx.15,000-> 250,000 g / mol), which is primarily by hydrolysis of the collagen contained in the skin and bones of animals under acid 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 Envelope material is particularly in the pharmaceutical industry in the form of hard or soft gelatin capsules extremely widespread. Gelatin is found in the form of foils because of their comparison only little use for the above-mentioned high-cost polymers.

Portioned detergent and cleaning agent compositions are also preferred in the context of the present invention, whose bags made of water-soluble film from at least a 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. 20-30% straight-chain amylose (MW.approx. 50,000-150,000) and 70-80% branched-chain Amylopectin (MG. Approx. 300,000-2,000,000), in addition there are still small amounts of lipids, Contain phosphoric acid and cations. During the amylose due to the binding in the 1,4-position long, helical, intertwined chains with about 300-1200 glucose molecules forms, the chain branches in amylopectin after an average of 25 Glucose building blocks through 1,6-binding to a knot-like structure with about 1500-12000 Molecules of glucose. In addition to pure starch, they are more water-soluble for production Bags within the scope of the present invention also contain starch derivatives polymer-analogous reactions from starch are available. 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 versus functional groups that do not have an oxygen atom bound, replaced, can be used as starch derivatives. In the group of Starch derivatives include, for example, alkali starches, carboxymethyl starch (CMS), Starch esters and ethers as well as amino starches.

Pure cellulose has the formal gross composition (C ₆ H ₁₀ O ₅ ) _n and, viewed formally, is a β-1,4-polyacetal of cellobiose, which in turn is made up of two molecules of glucose. Suitable celluloses consist of approximately 500 to 5000 glucose units and consequently have average molecular weights of 50,000 to 500,000.

Can be used as disintegrants based on cellulose in the context of the present Invention also cellulose derivatives made by polymer-analogous reactions from cellulose are available. Such chemically modified celluloses include, for example Products from esterifications or etherifications, in which hydroxy hydrogen atoms were substituted. But also celluloses, in which the hydroxyl groups against functional Groups that are not linked via an oxygen atom have been replaced are used as cellulose derivatives. For example, the group of cellulose derivatives Alkaline celluloses, carboxymethyl cellulose (CMC), cellulose esters and ethers as well as aminocelluloses.

Preferred bags made of water-soluble film consist of a polymer with a molecular weight between 5000 and 500,000 daltons, preferably between 7500 and 250,000 Daltons and especially between 10,000 and 100,000 Daltons. The water-soluble film, which forms the bag preferably has a thickness of 1 to 150 microns, preferably of 2 to 100 µm, particularly preferably from 5 to 75 µm and in particular from 10 to 50 µm, on.

The washing and packaging packed in the bags made of water-soluble film in the form of a single dose Detergent composition is preferred in the required particle size by Granulation produced. The term "granulation" denotes in the context of the present Registration of any shaping process that can be predetermined into particles Greatness leads. In addition to the conventional granulation and agglomeration processes, which are used in the various mixing granulators and mixing agglomerators can be carried out, For example, press agglomeration processes can also be used.

Granulation can be found in a wide variety of industries in the laundry and home care industries usually used apparatus are carried out. For example, it is possible to use the rounders commonly used in pharmacy. In such turntable devices the residence time of the granules is usually less than 5 minutes. Also conventional mixers and mixing granulators are suitable for granulation. As a mixer can both high-intensity mixers ("high-shear mixer") and normal Mixers with lower circulation speeds and especially combinations used by both. Suitable mixers are, for example, Eirich® mixers Series R or RV (trademark of Maschinenfabrik Gustav Eirich, Hardheim), the Schugi® Flexomix, the Fukae® FS-G mixer (trademark of Fukae Powtech, Kogyo Co., Japan), the Lödige® FM, KM and CB mixers (trademarks of Lödige Maschinenbau GmbH, Paderbom) or the Drais® series T or K-T (trademark of Drais-Werke GmbH, Mannheim). The residence times of the granules in the mixer combination are in the range of less than 60 seconds in the high-speed mixer and less than 7 minutes in the slow-running mixer, the residence time also depending on the circulation speed depends on the mixer. The dwell times are reduced accordingly, the faster the mixer runs.

In the process of press agglomeration, the detergent and cleaning agent composition in the plastic solidification area of the casing under pressure and under The action of shear forces is compressed and homogenized, and then gives shape discharged from the apparatus. The most technically significant press agglomeration processes are extrusion, roller compaction, pelleting and tableting. In the context of the present invention preferably for the production of washing and Press agglomeration processes used in detergent compositions are Extrusion, roller compaction and pelletizing.

In a preferred embodiment of the invention, the detergent and cleaning agent composition preferably continuously a planetary roller extruder or a 2-shaft extruder or 2-screw extruder with co-rotating or counter-rotating Screw guide fed, its housing and its extruder pelletizing head can be heated to the predetermined extrusion temperature. Under the The premixing is sheared by the extruder under pressure, which is preferred is at least 10 bar, with extremely high throughputs depending on the used machine but can also be below, compressed, plasticized, in shape fine strands extruded through the perforated die plate in the extruder head and finally that Extrudate by means of a rotating knock-off knife, preferably to approximately spherical down to cylindrical granules. The hole diameter of the hole nozzle plate and the strand cut length are matched to the selected granule dimension. In this embodiment, the production of granules essentially succeeds uniformly predeterminable particle size, with the absolute particle sizes in detail can be adapted to the intended purpose. Important embodiments see the production of uniform granules in the millimeter range, for example in the range of 0.8 to 5 mm and in particular in the range of approximately 1.0 to 3 mm in front. The length / diameter ratio of the chipped primary granules In an important embodiment, it is in the range from about 0.7: 1 to about 3: 1. Furthermore, it is preferred that the still plastic primary granules give a further shape To supply processing step; the raw extrudate is present Rounded edges so that ultimately spherical to approximately spherical extrudate grains can be obtained. Alternatively, extrusions / pressings can also be carried out in low pressure in the Kahl press, in the extruder, or in the plastic agglomerator (company Pallmann).

In a further preferred embodiment of the present invention, the manufacturing process for the detergent and cleaning agent composition by means of roller compaction carried out. Here the detergent and cleaning agent composition in the plastic solidification area of the coating between two smooth or dosed rollers of defined shape are metered in and between the two rollers under pressure to form a leaf-shaped compact, the so-called Schülpe, rolled out. The rollers exert a high line pressure on the premix and can be additionally heated or cooled as required. When using from smooth rollers one obtains smooth, unstructured sash bands, while through the Use of structured rollers with correspondingly structured slugs or individual pellets can be generated in which, for example, certain forms of the later granules or moldings can be specified. The cuff band is below broken down into smaller pieces by a knock-off and crushing process and can processed in this way to Granulatkömem, known by others Surface treatment process further remunerated, especially in approximately spherical Can be brought into shape.

In a further preferred embodiment of the present invention, the washing and cleaning agent composition to be packaged is produced by means of pelleting. Here, the detergent and cleaning agent composition is applied to a perforated surface in the plastic solidification area of the casing and pressed through the holes by means of a pressure-generating body. In conventional embodiments of pellet presses, the detergent and cleaning agent composition is compressed under pressure, plasticized, pressed by means of a rotating roller in the form of fine strands through a perforated surface and finally comminuted into granules with a knock-off device. The most varied configurations of the pressure roller and perforated die are conceivable here. For example, flat perforated plates are used as well as concave or convex ring matrices through which the material is pressed using one or more pressure rollers. The press rolls can also be conical in the plate devices, in the ring-shaped devices dies and press roll (s) can have the same or opposite direction of rotation. An apparatus suitable for carrying out the method according to the invention is described, for example, in German laid-open specification DE 38 16 842 (Schlüter GmbH). The ring die press disclosed in this document consists of a rotating ring die interspersed with press channels and at least one press roller which is operatively connected to its inner surface and which presses the material supplied to the die space through the press channels into a material discharge. Here, the ring die and the press roller can be driven in the same direction, which means that a reduced shear stress and thus a lower temperature increase in the premix can be achieved. Of course, it is also possible to work with heatable or coolable rollers in the pelletizing in order to set a desired temperature of the premix.

Another press agglomeration process used to manufacture the detergent and cleaning composition Tableting can be used. With this The process of shaping the detergent and cleaning agent composition in a die pressed, with the design of the upper or lower punch of the tablet press coated solid particles can be produced in a wide variety of forms.

Preferred portioned detergent and cleaning agent compositions are by a granulation or press agglomeration process, in particular by extrusion.

The portioned detergent and cleaning agent compositions according to the invention contain one or more substances from the group of surfactants, surfactant compounds, builders, Bleaching agents, bleach activators, enzymes, foam inhibitors, colors and fragrances as well as binding and disintegration aids. These classes of substances are as follows described.

To develop the washing performance, the portioned washing and washing according to the invention Detergent compositions surfactants from the group containing anionic, nonionic, zwitterionic or cationic surfactants, taking anionic surfactants for economic reasons and because of their range of services are clearly preferred.

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 with an end or internal double bond by sulfonation with gaseous sulfur trioxide and subsequent receives alkaline or acidic hydrolysis of the sulfonation products. Also suitable are alkanesulfonates obtained from C _12-18 alkanes, 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. Among fatty acid glycerin esters the mono-, di- and triesters and their mixtures are to be understood as they are the production by esterification of a monoglycerin with 1 to 3 moles of fatty acid or obtained in the transesterification of triglycerides with 0.3 to 2 mol of glycerol. preferred sulfated fatty acid glycerol esters are the sulfonation products of saturated fatty acids 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.

As alk (en) yl sulfates are the alkali and especially 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 the C ₁₀ -C ₂₀ oxo alcohols and those half-esters of secondary alcohols of this chain length are preferred. Also preferred are alk (en) yl sulfates of the chain length mentioned, which contain a synthetic, petrochemical-based straight-chain alkyl radical which have a degradation behavior analogous to that of the adequate compounds based on oleochemical raw materials. The C ₁₂ -C ₁₆ alkyl sulfates and C ₁₂ -C ₁₅ alkyl sulfates as well as 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 the Shell Oil Company under the name DAN®, are also suitable anionic surfactants.

The sulfuric acid monoesters of the straight-chain or branched C _7-21 alcohols ethoxylated with 1 to 6 mol 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 especially ethoxylated fatty alcohols. Preferred sulfosuccinates contain C _8-18 fatty alcohol residues or mixtures thereof. Particularly preferred sulfosuccinates. contain a fatty alcohol residue, which is derived from ethoxylated fatty alcohols, which in themselves are non-ionic surfactants (description see below). Again, sulfosuccinates, the fatty alcohol residues of which 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. Are suitable saturated fatty acid soaps, such as the salts of lauric acid, myristic acid, palmitic acid, Stearic acid, hydrogenated erucic acid and behenic acid and in particular from natural Fatty acids, e.g. Coconut, palm kernel or tallow fatty acids, derived soap mixtures.

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

Portioned detergent and cleaning agent compositions are within the scope of the present invention preferably, the 5 to 50 wt .-%, preferably 7.5 to 40 wt .-% us in particular 15 to 25 wt .-% anionic surfactant (s), based in each case on the washing and Detergent composition included.

When choosing the anionic surfactants that are portioned in the invention Detergent and cleaning agent compositions are used, the freedom of formulation no framework conditions to be observed in the way. Preferred portioned However, detergent and cleaning agent compositions have a content Soap, which is 0.2% by weight, based on the total weight of the detergent and cleaning agent composition, exceeds. Anionic surfactants to be used with preference the alkyl benzene sulfonates and fatty alcohol sulfates, with preferred detergent and cleaning agent compositions 2 to 20 wt .-%, preferably 2.5 to 15 wt .-% and in particular 5 to 10 wt .-% fatty alcohol sulfate (s), each based on the weight of the Detergent and cleaning composition

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 can contain linear and methyl-branched radicals in the mixture, as are usually present in oxo alcohol radicals. However, alcohol ethoxylates with linear residues of alcohols of native origin with 12 to 18 carbon atoms, for example from coconut, palm, tallow fat or oleyl alcohol, and an average of 2 to 8 EO per mole of alcohol are particularly preferred. The preferred ethoxylated alcohols include, for example, C _12-14 alcohols with 3 EO or 4 EO, C _9-11 alcohol with 7 EO, C _13-15 alcohols with 3 EO, 5 EO, 7 EO or 8 EO, C _12-18 alcohols with 3 EO, 5 EO or 7 EO and mixtures thereof, such as mixtures of C _12-14 alcohol with 3 EO and C _12-18 alcohol with 5 EO. The degrees of ethoxylation given represent statistical averages, which can be an integer or a fraction for a specific product. Preferred alcohol ethoxylates have a narrow homolog distribution (narrow range ethoxylates, NRE). In addition to these nonionic surfactants, fatty alcohols with more than 12 EO can also be used. Examples include tallow fatty alcohol with 14 EO, 25 EO, 30 EO or 40 EO.

Another class of 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 esters, such as them for example, are described in Japanese patent application JP 58/217598 or which are preferably produced by the process described in international patent application WO-A-90/13533 .

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

Linear alkyl polyglucosides, ie alkyl polyglycosides, are preferably used in which the polyglycosyl radical is a glucose radical and the alkyl radical is an n-alkyl radical.

The detergent and cleaning agent compositions according to the invention can be preferred Contain alkylpolyglycosides, contents of detergent and cleaning compositions of APG over 0.2% by weight, based on the total molded body, is preferred are. Particularly preferred detergent and cleaning agent compositions contain APG in amounts of 0.2 to 10 wt .-%, preferably 0.2 to 5 wt .-% and in particular from 0.5 to 3% by weight.

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

in der RCO für einen aliphatischen Acylrest mit 6 bis 22 Kohlenstoffatomen, R¹ für Wasserstoff, einen Alkyl- oder Hydroxyalkylrest mit 1 bis 4 Kohlenstoffatomen und [Z] für einen linearen oder verzweigten Polyhydroxyalkylrest mit 3 bis 10 Kohlenstoffatomen und 3 bis 10 Hydroxylgruppen steht. Bei den Polyhydroxyfettsäureamiden handelt es sich um bekannte Stoffe, die üblicherweise durch reduktive Aminierung eines reduzierenden Zukkers mit Ammoniak, einem Alkylamin oder einem Alkanolamin und nachfolgende Acylierung mit einer Fettsäure, einem Fettsäurealkylester oder einem Fettsäurechlorid erhalten werden können.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] 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.

in der R für einen linearen oder verzweigten Alkyl- oder Alkenylrest mit 7 bis 12 Kohlenstoffatomen, R¹ für einen linearen, verzweigten oder cyclischen Alkylrest oder einen Arylrest mit 2 bis 8 Kohlenstoffatomen und R² für einen linearen, verzweigten oder cyclischen Alkylrest oder einen Arylrest oder einen Oxy-Alkylrest mit 1 bis 8 Kohlenstoffatomen steht, wobei C_1-4-Alkyl- oder Phenylreste bevorzugt sind und [Z] für einen linearen Polyhydroxyalkylrest steht, dessen Alkylkette mit mindestens zwei Hydroxylgruppen substituiert ist, oder alkoxylierte, vorzugsweise ethoxylierte oder propxylierte Derivate dieses Restes. [Z] wird vorzugsweise durch reduktive Aminierung eines reduzierten Zuckers erhalten, beispielsweise Glucose, Fructose, Maltose, Lactose, Galactose, Mannose oder Xylose. Die N-Alkoxy- oder N-Aryloxy-substituierten Verbindungen können dann beispielweise nach der Lehre der internationalen Anmeldung WO-A-95/07331 durch Umsetzung mit Fettsäuremethylestem in Gegenwart eines Alkoxids als Katalysator in die gewünschten Polyhydroxyfettsäureamide überführt werden.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 alkyl radical or an aryl radical having 2 to 8 carbon atoms and R ^{2 represents} a linear, branched or cyclic alkyl radical or an aryl radical or an oxyalkyl radical having 1 to 8 carbon atoms, C _1-4 -alkyl or phenyl radicals being preferred and [Z] being a linear polyhydroxyalkyl radical whose alkyl chain is substituted by at least two hydroxyl groups, or alkoxylated, preferably ethoxylated or propylated Derivatives of this remainder. [Z] is preferably obtained by reductive amination of a reduced sugar, for example glucose, fructose, maltose, lactose, galactose, mannose or xylose. The N-alkoxy- or N-aryloxy-substituted compounds can then, for example according to the teaching of international application WO-A-95/ 07331, be converted into the desired polyhydroxy fatty acid amides by reaction with fatty acid methyl esters in the presence of an alkoxide as catalyst.

In addition to the washing-active substances, builders are the most important ingredients of Detergents and cleaning agents. In the detergent and cleaning agent compositions according to the invention can usually all in detergents and cleaning agents builders used, in particular thus zeolites, silicates, carbonates, organic cobuilders and - where there are no ecological prejudices against their use - also the phosphates.

Suitable crystalline, layered sodium silicates have the general formula NaMSi _x O _{2x + 1} .H ₂ O, where M is sodium or hydrogen, x is a number from 1.9 to 4 and y is a number from 0 to 20 and preferred values for x 2, 3 or 4. Such crystalline layered silicates are described, for example, in European patent application EP-A-0 164 514 . Preferred crystalline layered silicates of the formula given are those in which M represents sodium and x assumes the values 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 modulus Na ₂ O: SiO ₂ 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. 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 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 O ^· (1-n) K ₂ O ^· Al ₂ O ₃ ^· (2 - 2.5) SiO ₂ ^· (3.5 - 5.5) H ₂ O can be described. Suitable zeolites have an average particle size of less than 10 μm (volume distribution; measurement method: Coulter Counter) 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, provided that such use is not avoided for ecological reasons should be. The sodium salts of orthophosphates, pyrophosphates, are particularly suitable and especially the tripolyphosphates.

Useful organic builders are, for example, those in the form of their sodium salts usable polycarboxylic acids, such as citric acid, adipic acid, succinic acid, glutaric acid, Tartaric acid, sugar acids, aminocarboxylic acids, nitrilotriacetic acid (NTA), if provided such use is not objectionable for ecological reasons, as well as mixtures from these. Preferred salts are the salts of polycarboxylic acids such as citric acid, Adipic acid, succinic acid, glutaric acid, tartaric acid, sugar acids and mixtures of this.

In addition to the ingredients mentioned surfactant and builder, the inventive Detergents and cleaning agents further ingredients common in detergents and cleaning agents from the group of bleaching agents, bleach activators, enzymes, fragrances, perfume carriers, Fluorescent agents, dyes, foam inhibitors, silicone oils, anti-redeposition agents, optical brighteners, graying inhibitors, color transfer inhibitors and corrosion inhibitors contain.

Among the compounds which serve as bleaching agents and supply H ₂ O ₂ in water, sodium perborate tetrahydrate and sodium perborate monohydrate are of particular importance. Further bleaching agents which can be used are, for example, sodium percarbonate, peroxypyrophosphates, citrate perhydrates and H ₂ O ₂ -producing peracidic salts or peracids, such as perbenzoates, peroxophthalates, diperazelaic acid, phthaloiminoperic acid or diperdodecanedioic acid. If cleaning or bleaching agent compositions for machine dishwashing are produced, bleaching agents from the group of organic bleaching agents can also be used. 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 (a) the peroxybenzoic acid and its ring-substituted derivatives, such as alkylperoxybenzoic acids, but also peroxy-α-naphthoic acid and magnesium monoperphthalate, (b) the aliphatic or substituted aliphatic peroxyacids, such as peroxylauric acid, peroxystearic acid, ε-phthalimidthanoic acid paproacidaproacidoxyhexanoic acid , o-Carboxybenzamidoperoxycapronsäure, N-nonenylamidoperadipic acid and N-nonenylamidopersuccinates, and (c) aliphatic and araliphatic peroxydicarboxylic acids, such as 1,12-diperoxycarboxylic acid, 1,9-diperoxyazelaic acid, Diperocysebacinsäure, diperoxybrassylic acid, diperoxyphthalic acids, the 2-decyldiperoxybutane-1,4- diacid, N, N-terephthaloyl-di (6-aminopercapronic acid) can be used.

Can also be used as bleach in machine dishwashing compositions Chlorine or bromine releasing substances are used. Among the appropriate chlorine or bromine-releasing materials come, for example, heterocyclic N-bromine and N-chloramides, for example trichloroisocyanuric acid, tribromoisocyanuric acid, Dibromo isocyanuric acid and / or dichloroisocyanuric acid (DICA) and / or their salts with Cations such as potassium and sodium are considered. Hydantoin compounds such as 1,3-dichloro-5,5-dimethylhydanthoin are also suitable.

To improve when washing or cleaning at temperatures of 60 ° C and below To achieve bleaching effect, bleach activators can be used in the detergent and cleaning agent composition be incorporated. As bleach activators, compounds which are preferred under perhydrolysis conditions with aliphatic peroxocarboxylic acids 1 to 10 carbon atoms, in particular 2 to 4 carbon atoms, and / or optionally result in substituted perbenzoic acid can be used. Substances containing O and / or are suitable N-acyl groups of the number of carbon atoms mentioned and / or optionally substituted Wear benzoyl groups. Multi-acylated alkylenediamines are preferred, in particular Tetraacetylethylenediamine (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 Phenolsulfonates, especially n-nonanoyl or isononanoyloxybenzenesulfonate (n- or. iso-NOBS), carboxylic anhydrides, especially phthalic anhydride, acylated polyhydric alcohols, especially triacetin, ethylene glycol diacetate and 2,5-diacetoxy-2,5-dihydrofuran.

In addition to the conventional bleach activators or in their place, too so-called bleach catalysts in the detergent and cleaning agent composition be incorporated. These substances 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 complexes with N-containing tripod ligands as well as Co, Fe, Cu and Ru amine complexes can be used as bleaching catalysts.

Enzymes come from the class of proteases, lipases, amylases, cellulases or their mixtures in question. Bacterial strains or are particularly well suited Mushrooms such as Bacillus subtilis, Bacillus licheniformis and Streptomyces griseus enzymatic agents. Proteases of the subtilisin type and in particular are preferred Proteases obtained from Bacillus lentus are used. Here are enzyme mixtures, for example from protease and amylase or protease and lipase or Protease and cellulase or from cellulase and lipase or from protease, amylase and lipase or protease, lipase and cellulase, but especially mixtures containing cellulase of special interest. Peroxidases or oxidases have also been found in some Cases proved to be suitable. The enzymes can be adsorbed on carriers and / or be embedded in coating substances to protect them against premature decomposition. The Proportion of the enzymes, enzyme mixtures or enzyme granules in the inventive Compositions can be, for example, about 0.1 to 5% by weight, preferably 0.1 to be about 2% by weight.

In addition, the detergent and cleaning agent compositions can also contain components contain, which have a positive influence on the oil and fat washability from textiles (so-called soil repellents). This effect is particularly evident when a textile is soiled, which has previously been repeatedly washed with a detergent according to the invention, that contains this oil and fat-dissolving component has been washed. Among the preferred Oil- and fat-dissolving components include, for example, nonionic cellulose ethers such as Methyl cellulose and methyl hydroxypropyl cellulose with a proportion of methoxyl groups from 15 to 30% by weight and from 1 to 15% by weight of hydroxypropoxyl groups, each based on the nonionic cellulose ether, as well as those from the prior art known polymers of phthalic acid and / or terephthalic acid or of their derivatives, in particular polymers of ethylene terephthalates and / or polyethylene glycol terephthalates or anionically and / or nonionically modified derivatives of these. Of these, the sulfonated derivatives of phthalic and are particularly preferred Terephthalic acid polymers.

The detergent and cleaning agent compositions can be used as optical brighteners contain the diaminostilbenedisulfonic acid or its alkali metal salts. Suitable are e.g. Salts of 4,4'-bis (2-anilino-4-morpholino-1,3,5-triazinyl-6-amino) stilbene-2,2'disulfonic acid or similarly structured compounds that replace the morpholino group a diethanolamino group, a methylamino group, an anilino group or carry a 2-methoxyethylamino group. Brighteners of the substituted type can also be used Diphenyl styrenes are present, e.g. the alkali salts of 4,4'-bis (2-sulfostyryl) diphenyl, 4,4'-bis (4-chloro-3-sulfostyryl) diphenyl, or 4- (4-chlorostyryl) -4 '- (2-sulfostyryl) diphenyl. Mixtures of the aforementioned brighteners can also be used become.

Dyes and fragrances are added to the washing and cleaning agents according to the invention, to improve the aesthetic impression of the products and the consumer alongside the softness performance a visually and sensory "typical and unmistakable" To provide product. As perfume oils or fragrances, individual olfactory joints, e.g. synthetic products of the ester, ether, aldehyde type, Ketones, alcohols and hydrocarbons can be used. fragrance compounds of the ester type are e.g. Benzyl acetate, phenoxyethyl isobutyrate, p-tert-butylcyclohexyl acetate, Linalyl acetate, dimethylbenzylcarbinylacetate, phenylethyl acetate, Linalyl benzoate, benzyl formate, ethyl methylphenyl glycinate, allyl cyclohexyl propionate, Styrallyl propionate and benzyl salicylate. The ethers include, for example, benzyl ethyl ether, to aldehydes e.g. the linear alkanals with 8-18 C atoms, citral, citronellal, Citronellyloxyacetaldehyde, Cyclamenaldehyde, Hydroxycitronellal, Lilial and Bourgeonal, to the ketones e.g. the Jonone, ∝-isomethyl ionone and methyl cedryl ketone, to the Alcohols anethole, citronellol, eugenol, geraniol, linalool, phenylethyl alcohol and terpineol, The hydrocarbons mainly include terpenes such as limonene and Pinene. However, mixtures of different odoriferous substances are preferably used create an appealing fragrance together. Such perfume oils can also be natural Fragrance mixtures contain, as are available from vegetable sources, e.g. Pine, citrus, jasmine, patchouly, rose or ylang-ylang oil. Are also suitable Muscatel, sage oil, chamomile oil, clove oil, lemon balm oil, mint oil, cinnamon leaf oil, linden blossom oil, Juniper berry oil, vetiver oil, olibanum oil, galbanum oil and labdanum oil as well Orange blossom oil, neroliol, orange peel oil and sandalwood oil.

The dye content of the compositions according to the invention is usually less than 0.01% by weight, while fragrances can make up up to 2% by weight of the total formulation.
The fragrances can be incorporated directly into the agents according to the invention, but it can also be advantageous to apply the fragrances to carriers which increase the adhesion of the perfume to the laundry and ensure a long-lasting fragrance of the textiles due to a slower fragrance release. Cyclodextrins, for example, have proven useful as such carrier materials, and the cyclodextrin-perfume complexes can additionally be coated with further auxiliaries.

In order to improve the aesthetic impression of the agents according to the invention, they can be dyed with suitable dyes. Preferred dyes, the selection of which Specialist poses no difficulty, have a high storage stability and insensitivity compared to the other ingredients of the agents and against light and none pronounced substantivity towards textile fibers so as not to stain them.

Examples:

Portion bags were made from a 25 µm thick polyvinyl alcohol film from Aquafilm Ltd., which is made up of various Mowiol® types (trademark of HOECHST AG), into each of which 40 g of a detergent composition were filled. The bags were sealed thermally using permanently heated sealing strips. For comparative example V, the detergent composition was produced by means of a granulation process, in example E according to the invention the identically composed detergent and cleaning agent composition was produced by extrusion and had a significantly narrower particle size distribution. The following table shows the sieve analyzes of the two compositions: Siebzahlen e V > 1.6 mm 2.5 27.0 > 0.8 mm 93.2 26.0 > 0.4 mm 4.2 30.0 <0.4 mm 0.1 17.0

In the portioned detergent compositions E according to the invention dense and optically isotropic seams are obtained in which there were no product residues. In Comparative Example V, the seams were partially leaky and optically anisotropic.

Claims (8)

1. Portioned detergent and cleaner composition in a bag made of water-soluble film, characterized in that at least 70% by weight of the particles of the detergent and cleaner composition have particle sizes in the range from 800 to 3000 µm.
2. Portioned detergent and cleaner composition according to Claim 1, characterized in that at least 80% by weight, preferably at least 85% by weight, particularly preferably at least 90% by weight and in particular at least 95% by weight, of the particles of the detergent and cleaner composition have particle sizes above 800 µm, preferably above 900 µm, particularly preferably above 1000 µm and in particular above 1200 µm.
3. Portioned detergent and cleaner composition according to either of Claims 1 and 2, characterized in that the bag made of water-soluble film consists of at least one polymer from the group consisting of optionally acetalated polyvinyl alcohol, polyvinylpyrrolidone, polyethylene oxide, gelatin and mixtures thereof.
4. Portioned detergent and cleaner composition according to either of Claims 1 and 2, characterized in that the bag made of water-soluble film consists of at least one polymer from the group consisting of starch and starch derivatives, cellulose and cellulose derivatives, in particular methylcellulose and mixtures thereof.
5. Portioned detergent and cleaner composition according to one of Claims 1 to 4, characterized in that the bag made of water-soluble film consists of a polymer with a molar mass between 5000 and 500 000 daltons, preferably between 7500 and 250 000 daltons and in particular between 10 000 and 100 000 daltons.
6. Portioned detergent and cleaner composition according to one of Claims 1 to 5, characterized in that the water-soluble film which forms the bag has a thickness of from 1 to 150 µm, preferably from 2 to 100 µm, particularly preferably from 5 to 75 µm and in particular from 10 to 50 µm.
7. Portioned detergent and cleaner composition according to one of Claims 1 to 6, characterized in that the detergent and cleaner composition has been prepared by a granulation or compression agglomeration process, in particular by extrusion.
8. Portioned detergent and cleaner composition according to one of Claims 1 to 7, characterized in that the detergent and cleaner composition comprises one or more substances from the group of surfactants, surfactant compounds, builders, bleaches, bleach activators, enzymes, foam inhibitors, dyes and fragrances, and binding and disintegration auxiliaries.