WO2001029172A1 - Dishwasher detergent portion - Google Patents

Abstract

The invention relates to a portion of low-water-content detergent, in particular a dishwasher detergent, comprising one or several compositions of at least one water-soluble polymer material and at least one rinsing preparation which is entirely or partially surrounded by said water-soluble polymer material.

Description

 "Dishwashing detergent portion"

The present invention relates to a dishwashing detergent portion with a casing made of a water-soluble polymer material and at least one active detergent preparation.

Detergent and cleaning agents in single dose amounts are known from the prior art. For example, the older patent application DE 198 31 703 discloses a portioned detergent or cleaning agent preparation in a bag made of water-soluble film for use in washing machines or dishwashers, in which at least 70% by weight of the particles of the preparation have particle sizes of> 800 μm. Furthermore, the older patent application DE 199 09 271 describes the production of multi-phase detergent tablets for use in machine washing or rinsing, the tablets being dimensioned in terms of the active substance content in such a way that the detergent-active preparations for exactly one wash - or rinse in the machine is sufficient.

Dishwashing detergents for use in washing in the sink or in a sink have been provided in the prior art in liquid form, regularly filled in bottles or containers provided with closable pourers or metering openings. The advantage of such forms of filling was that the consumer was able to dose the dishwashing detergent freely and, if necessary, to add more detergent according to need and feeling. However, the disadvantage of such forms of filling was that precise dosing of the dishwashing detergent required a certain amount of experience and the detergent was often under or overdosed. The former regularly required re-dosing of dishwashing detergent during the washing process, which in turn was associated with the risk of overdosing, while the latter was and is generally undesirable for ecological and economic reasons. Another disadvantage was that residues of the dishwashing detergent often remained in the pouring spouts or metering openings, which either ran down the outside of the bottles or containers and which X, wanted to leave residues on the bottles or containers or on the shelves or to block the spouts or dosing openings.

Another disadvantage of the dishwashing detergents provided in the conventional packaging was that they had to be homogeneous, in particular clear, according to the wishes of the consumers. This requirement dictated by consumption habits meant that components could not be incorporated into agents which were not evenly distributed in the ready-made dishwashing detergent or which deposited during the course of storage or during the time the opened bottle or container was left to stand ,

Another problem with conventional dishwashing detergents was that no components could be incorporated whose stability during storage is impaired by other components of the dishwashing detergent. This was the reason, for example, that enzymes which were active during the rinsing process could not be incorporated into dishwashing detergents, in particular those for washing dishes by hand, since problems with the stability of the enzymes occurred in the aqueous environment of conventional dishwashing detergents.

An object of the invention was therefore to overcome the above-mentioned disadvantages of the prior art. In particular, it was an object of the invention to provide dishwashing detergents in portions ready for use in a wash cycle. It was a further object of the invention to provide dishwashing detergents which can comprise components which usually cannot be distributed homogeneously in hand dishwashing detergents without them precipitating, settling out or otherwise separating out. A further object of the invention was to provide dishwashing detergents for washing dishes by hand, which can comprise components which are not stable in conventional dishwashing detergents in the presence of individual components normally contained in such detergents. 2>

Surprisingly, it has now been found that low-water dishwashing detergents, in particular those for washing dishes by hand, can be economically packaged in portions which contain a dishwashing detergent preparation in an amount dosed sufficiently for a wash cycle, which may contain components in a dishwashing detergent portion may contain, whose homogeneous distribution in a large amount of the same agent in a bottle or in a container for a long period of storage in the prior art was not possible, and which optionally contain components whose stability in the presence of other components of the agent is low or at least was insufficient.

The invention relates to a portion of a low-water cleaning agent comprising one or more enclosures made of at least one water-soluble polymer material and at least one rinse-active preparation partially or completely surrounded by the at least one water-soluble polymer material. The detergent is preferably a detergent for cleaning hard surfaces, more preferably for manual cleaning of hard surfaces, most preferably a dishwashing detergent in the form of portions.

In the context of the present invention, the term “dishwashing detergent portion” is understood to mean an amount of a detergent which is sufficient for a process of cleaning dishes in an aqueous phase. This can be, for example, a machine cleaning process such as is carried out with commercially available dishwashers However, this term also means a dishwashing cycle (for example carried out in a hand wash basin or in a bowl) or another cleaning process. According to the invention, the present cleaning agent portions or dishwashing agent portions are preferably used in manual dishwashing processes. Dishwashing detergent portion "in the context of the present invention is understood to mean a portion of a dishwashing detergent portion which in a phase separated from other dishwashing detergent portions in spatial connection with other portions of dishwashing detergent in the same portion of dishwashing detergent M is present and is prepared by suitable measures such that it can be added to the washing liquor separately from other or simultaneously with other portions of dishwashing detergent in the same dishwashing detergent portion and, if appropriate, dissolved or suspended in it. A portion of dishwashing detergent may contain the same ingredients as another portion of dishwashing detergent in the same portion of dishwashing detergent; however, preferably two portions of dishwashing detergent containing the same portion of dishwashing detergent contain different ingredients, in particular different dishwashing preparations.

According to the invention, the dishwashing agent portions contain measured amounts of at least one wash-active preparation, usually measured amounts of several wash-active preparations. It is possible that the portions contain only rinse-active preparations of a certain composition. According to the invention, however, it is preferred that several, usually at least two, rinse-active preparations of different compositions are contained in the dishwasher detergent portions. The composition can differ in terms of the concentration of the individual components of the rinse-active preparation (quantitative) and / or in terms of the type of the individual components of the rinse-active preparation (qualitative). It is particularly preferred that the components are adapted in terms of their type and concentration to the tasks which the portions of dishwashing detergent have to perform in the cleaning process. In the context of the present invention, the partial portions are preferably the first, second and possibly third or even higher (fourth, fifth, etc.) measured amounts of one or more rinsing-active preparation (s) which are comprised of the same or different water-soluble materials and which are used for cleaning purposes. or dishwashing detergent portion are combined according to the invention.

In the context of the present invention, the term “rinse-active preparation” is understood to mean preparations of all conceivable substances which are relevant in connection with a process of cleaning dishes. These are primarily the actual cleaning agents with their subsequent use. Spelling of individual components explained in more detail. This includes active substances such as surfactants (anionic, non-ionic, cationic and amphoteric surfactants), enzymes, special polymers, dyes and fragrances (perfumes), without the term being restricted to these substance groups.

However, the term “rinse-active preparations” is also understood to mean cleaning aids. Examples of these are solvents, solubilizers, UV stabilizers, so-called soil repellents, that is to say polymers which counteract the re-soiling of hard surfaces, and also silver preservatives. According to the invention, additives such as rinse aid are considered as rinse-active preparations.

According to the invention, the detergent portion or dishwashing detergent portion contains one or more enclosures made of one or more water-soluble polymer material (s) which partially or completely comprise the at least one rinse-active preparation. It is possible that the dishwashing detergent portion contains an enclosure made of one or more water-soluble polymer material (s) or that several enclosures are included. In the context of the present invention, the presence of an enclosure is preferred, which brings advantages in the choice of material and also with regard to the requirement that the water-soluble polymer material must dissolve without residue in the cleaning liquor or rinsing liquor. The enclosure (s) can be made of a single water-soluble polymer material or can be made of several different polymer materials. In principle, the use of several polymer materials is possible. In view of the present task, the use of a single polymer material is particularly preferred according to the invention, which will be discussed in more detail below.

According to a preferred embodiment of the invention, the water-soluble polymer material that partially or completely surrounds the at least one rinse-active preparation is a water-soluble packaging. This is understood to mean a flat or spatially formed part that has at least one flushing accessory. part or all of the horse. The exact form of such packaging is not critical and can be largely adapted to the conditions of use. There are, for example, various shapes (such as hoses, pillows, cylinders, bottles, disks or the like) worked plastic foils or plates, capsules and other conceivable shapes. According to the invention, particular preference is given to films which, for example, can be glued and / or sealed to form packaging, such as hoses, pillows or the like, after they have been filled themselves with partial portions of the dishwasher detergent portions according to the invention or with the dishwasher detergent portions according to the invention.

According to the invention, plastic film packaging made of water-soluble polymer materials is further preferred due to the properties which can be perfectly adapted to the desired physical conditions. Such films are basically known from the prior art.

In principle, all polymer materials which can dissolve completely in the aqueous phase under the given conditions (temperature, pH value, concentration of rinse-active components) are suitable as water-soluble polymer materials. The polymer materials can particularly preferably belong to the groups (acetalized) polyvinyl alcohol, polyvinyl pyrrolidone, polyethylene oxide, gelatin, cellulose and their derivatives and mixtures of the materials mentioned.

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 ("acetalized PVAL").

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 from 98 to 99 or 87 to 89 mol%. They are therefore partially saponified polyvinyl acetates with a residual acetyl group content of about 1 to 2 or 11 to 13 mol%.

The water solubility of PVAL can be reduced by post-treatment with aldehydes (acetalization), by complexing with Ni or Cu salts or by treatment with dichromates, boric acid, borax and thus specifically adjusted to desired values. PVAL foils 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 made by radical polymerization of 1-vinyl pyrrolidone. Commercial PVPs have molar masses in the range from approx. 2500 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 ] _π -OH which are produced industrially by base-catalyzed polyaddition of ethylene oxide (oxirane) in mostly small amounts of water-containing systems 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 hydroxy end groups and only show 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. 3

Also preferred in the context of the present invention are dishwasher detergent portions, the packaging of which consists of 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% straight-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 infoige of the bond in the 1,4 position forms long, helical, intertwined chains with about 300 to 1200 glucose molecules, the chain in the amylopectin branches after an average of 25 glucose units through 1,6 bond to form a knot-like structure with about 1,500 to 12,000 molecules of glucose. In addition to pure starch, for the production of water-soluble enclosures of the detergent or dishwashing agent portions in the context of the present invention, starch derivatives are also obtainable from starch by polymer-analogous reactions. Such chemically modified starches include, for example, products from esterifications or etherifications in which hydroxyl 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 (C6Hι ₀ O ₅ ) _n and, formally speaking, 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 5000 glucose units and consequently have average molecular weights of 50,000 to 500,000. Cellulose-based disintegrants which can be used in the context of the present invention are also cellulose Derivatives that can be obtained from cellulose by polymer-analogous reactions. Such chemically modified celluloses include, for example, products from esterifications or etherifications in which hydroxyl hydrogen atoms have been substituted. However, celluloses in which the hydroxyl groups have been replaced by functional groups which are not bound via an oxygen atom can also be used as cellulose derivatives. The group of cellulose derivatives includes, for example, alkali celluloses, carboxymethyl cellulose (CMC), cellulose esters and ethers and aminocelluloses.

Preferred enclosures 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 in particular between 10,000 and 100,000 daltons. The water-soluble film which forms the enclosure usually has a thickness of 1 to 150 μm, preferably 2 to 100 μm, particularly preferably 5 to 75 μm and in particular 10 to 50 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 are atomized to form the films. 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.

Capsules as enclosures for the rinse-active preparation (s) of the dishwashing detergent portion according to the invention are likewise produced by methods known from the prior art and can preferably be made from (given) II optionally acetalized) PVAL or gelatin, for example soft gelatin or hard gelatin.

According to a preferred embodiment of the invention, the one or more enclosures for the rinse-active preparation (s) comprise a PVAL film which is water-soluble at a certain temperature. Such a film can advantageously be processed by gluing, for example with a water-soluble adhesive, or by heat sealing to form enclosures for rinse-active preparations. The advantage of such a film enclosure is that it has a water solubility that can be set precisely with regard to the desired temperature and that it dissolves quickly and without residue when added to the rinsing or cleaning liquor, the active rinsing agent (s) covered by the film Preparation (s) can be quickly released into the rinsing or cleaning liquor. This is particularly important when washing dishes manually, since - in contrast to machine dishwashing - mechanical movement of the liquor does not take place automatically, but should be carried out by the consumer.

In a still further preferred embodiment of the invention, the at least one water-soluble polymer material of the enclosure (s) contains one or more components (s) of the rinse-active preparation (s). This concept is the subject of the older patent application DE 199 29 098.9, according to which certain additives of rinse-active preparations, in particular individual components which control the effectiveness of the rinse-active preparation or also increase its consumer acceptance, are wholly or predominantly physically incorporated into the water-soluble polymer material of the enclosure , According to the invention, such components, which may be incorporated into the polymer material of the enclosure (s), for example UV protection substances, dyes, fragrances, antibacterial agents, polymers such as, for example, a soil repellent polymer, corrosion inhibitors or bitter substances (the latter can prevent unauthorized persons) , for example, children who take enclosures) in their mouths) without being limited to these examples. As long as the important properties of the enclosure as its mechanical Stability (even over a long period of time) and its complete water solubility are not adversely affected, one or more such additive (s) can be incorporated into the polymer material in any combination and amount. Preferred amounts are 0.1 to 10% by weight of the additive, based on the total weight of the film or capsule material, more preferably 1 to 7% by weight, very particularly preferably 3 to 6% by weight.

In view of the fact that at least one polymer material is used as the enclosure (s) of the rinse-active preparations), the essential properties of which include solubility in the aqueous medium used for rinsing, it is an essential feature of the present invention that the rinse-active (n) Preparation (s) of the dishwashing agent portion according to the invention are low in water. "Low water" is understood to mean that the dishwashing detergent portion contains as little free water as possible (and thus capable of reaction with the material of the enclosure (s)) in all its components. The rinse-active preparation (s) preferably have water contents of less than 15% by weight, based on the total weight of the rinse-active preparations), more preferably water contents of less than 10% by weight.

In a preferred embodiment of the invention, the components of the rinse-active preparation (s) are selected from the group consisting of anionic, non-ionic, cationic and amphoteric surfactants, non-aqueous carriers, enzymes, dyes, fragrances, antibacterial agents, polymers and Rinse aid, the amounts given each refer to the total weight of the active detergent preparation (s).

Substances that also serve as ingredients of cosmetic products are referred to below in accordance with the International Nomenclature Cosmetic Engineering (INCI) nomenclature. Chemical compounds have an INCI name in English, herbal ingredients are only listed according to Linne in Latin. So-called trivial names such as "water", "honey" or "sea salt" are also given in Latin. The INCI names are the "International Cosmetic." Refer Ingredient Dictionary and Handbook, Seventh Edition (1997) ", which is published by The Cosmetic, Toiletry and Fragrance Association (CTFA), 1101 17 ^th Street NW, Suite 300, Washington, DC 20036, USA and more than 9,000 INCI names as well as references to more than 37,000 trade names and technical names including the associated distributors from over 31 countries. The International Cosmetic Ingredient Dictionary and Handbook classifies the ingredients into one or more chemical classes (chemical classes), for example "Polymeric Ethers", and one or more functions (functions), for example "Surfactants - Cleansing Agents", which it in turn explains in more detail. These may also be referred to below.

To develop good cleaning performance during washing, the dishwasher detergent portions according to the invention can contain surface-active substances from the group of anionic, nonionic, cationic or amphoteric or zwitterionic surfactants. Anionic surfactants are particularly preferred for economic reasons and because of their range of services. Surfactants from the individual groups can be used as individual substances. It is preferred to use mixtures of surfactants, advantageously mixtures of surfactants from several of the aforementioned groups.

Anionic surfactants according to the present invention can be aliphatic sulfates such as fatty alcohol sulfates, fatty alcohol ether sulfates, dialkyl ether sulfates, monoglyceride sulfates as well as aliphatic and aromatic sulfonates such as alkane sulfonates, olefin sulfonates, ether sulfonates, n-alkyl ether sulfonates, ester sulfonates and lingbenzene sulfonates, lingbenzene sulfonates. Fatty acid cyanamides, sulfosuccinic acid esters, fatty acid isethionates, acylaminoalkane sulfonates (fatty acid taurides), fatty acid sarcosinates, ether carboxylic acids and alkyl (ether) phosphates can also be used in the context of the present invention.

As alk (en) yl sulfates, the alkali and in particular the sodium salts of the sulfuric acid semiesters of the C ₁ -C ₈ fatty alcohols, for example from coconut fatty alcohol, tallow fatty alcohol, lauryl, myristyl, cetyl or stearyl alcohol or the »*.

Cιo-C ₂₀ oxo alcohols and the half esters of secondary alcohols (secondary alkyl sulfates, SAS) of these chain lengths are preferred. Also preferred are alk (en) yl sulfates of the chain length mentioned which contain a synthetic, straight-chain alkyl radical which is produced on a petrochemical basis and which have a degradation behavior analogous to that of the adequate compounds based on oleochemical raw materials. Spültechnischem of interest are the C ₁₂ -C ₆ - alkyl sulfates and C ₁₂ -C ₁₅ alkyl sulfates and C-ι ₄ -C ₅ alkyl sulfates are preferred. Suitable secondary alkyl sulfates contain 2- and / or 3-alkyl sulfates and optionally higher homologues (4-, 5-, 6-alkyl sulfates etc.), can be prepared, for example, according to US Pat. Nos. 3,234,258 or 5,075,041 and are commercially available from Shell Oil Company at available under the name DAN ^® , e.g. B. the products mentioned in US Pat. Nos. 5,529,724 and H 1, 665 DAN® 214, a Cι ₄ -SAS with 99% 2- and 3-alkyl sulfate, DAN® 216, a Cι ₆ -SAS with 99% 2- and 3-alkyl sulfate, and DAN® 100, a SAS with 62% 2- and 3-alkyl sulfate.

The fatty alcohol ether sulfates are particularly preferred in the context of the present invention. Fatty alcohol ether sulfates are products of sulfation reactions on alkoxylated alcohols. The person skilled in the art generally understands alkoxylated alcohols to mean the reaction products of one or more alkylene oxides, preferably of ethylene oxide, with alcohols, preferably in the sense of the present invention the longer-chain alcohols, for example straight-chain or branched alcohols with chain lengths of C to C ₂ ι such as 2 -Methyl-branched C ₈ to Cn fatty alcohols with an average of 3.5 EO or the C ₁₂ to Cis fatty alcohols with 1 to 4 EO. As a rule, a complex mixture of addition products of different degrees of ethoxylation is formed from n moles of ethylene oxide and one mole of alcohol, depending on the reaction conditions. A further embodiment consists in the use of mixtures of the alkylene oxides, preferably the mixture of ethylene oxide and propylene oxide. Low-ethoxylated fatty alcohols (0.5 to 4 mol EO, preferably 1 to 2 mol EO) are very particularly preferred in the sense of the present invention. 1

Suitable surfactants of the sulfonate type are preferably alkylbenzenesulfonates, olefinsulfonates finsulfonate, ie mixtures of alkene and hydroxyalkane sulfonates, and di-, into consideration, as they, for example, Cι ₂ -i ₈ -Monoolefιnen with terminal or internal double bond by sulfonation with Gaseous sulfur trioxide and subsequent alkaline or acid hydrolysis of the sulfonation products. Alkylbenzenesulfonates in the sense of the teaching according to the invention are alkylbenzenesulfonates with straight-chain or branched, saturated or unsaturated C6-22-alkyl radicals, preferably Cβ-.s-alkyl radicals, in particular Cg-u-alkyl radicals, extremely preferably Cιo-1 ₃ -alkyl radicals. They are used as alkali metal and / or alkaline earth metal salts, in particular sodium, potassium, magnesium and / or calcium salts, and also as ammonium salts or mono-, di- or tri-alkanolammonium salts, preferably mono-, di- or triethanol and / or -isopropanolammonium salts, especially mono-, di- or triethanolammonium salts, but also used as alkylbenzenesulfonic acid together with the corresponding alkali metal or alkaline earth metal hydroxide and / or ammonia or mono-, di- or trialkanolamine. In a particularly preferred embodiment, the dishwasher detergent portions contain mono-, di- and / or trialkanolammonium alkylbenzenesulfonate, in particular monoethanolammonium alkylbenzenesulfonate, in amounts of 10 to 100% by weight, preferably 30 to 100% by weight, in particular of 50 to 100 wt .-%, based on the total amount by weight of alkylbenzenesulfonates. It is particularly preferred that the dishwashing portions according to the invention exclusively contain mono-, di- and / or trialkanolammonium alkylbenzenesulfonate as alkylbenzenesulfonates, further preferably exclusively monoethanolammoniumalkylbenzenesulfonate. Also suitable are alkanesulfonates, the chlorination or C-ι -i _{2 8} alkanes, for example by sulfo sulfoxidation be recovered and subsequent hydrolysis or neutralization. The esters of 2-sulfofatty acids (ester sulfonates), for example the 2-sulfonated methyl esters of hydrogenated coconut, palm kernel or tallow fatty acids, are also suitable. The anionic surfactants are preferably used in amounts between 0.2 and 80% by weight, preferably in amounts of 10 to 70% by weight, particularly preferably 25 to 60% by weight, extremely preferably 40 to 60% by weight ,

Particularly suitable surfactant mixtures are those composed of anionic surfactants in combination with one or more nonionic surfactants or betaine surfactants, the betaine surfactants in this connection being equated with the class of amphoteric surfactants. The joint additional use of nonionic surfactants and betaine surfactants in a mixture can also be advantageous for many applications.

Nonionic surfactants in the context of the present invention can be alkoxylates, such as polyglycol ethers, fatty alcohol polyglycol ethers, alkylphenol polyglycol ethers, end-capped polyglycol ethers, mixed ethers and hydroxy mixed ethers and fatty acid polyglycol esters. Ethylene oxide, propylene oxide, block polymers and fatty acid alkanolamides and fatty acid polyglycol ether can also be used. An important class of nonionic surfactants that can be used according to the invention are the polyol surfactants and here in particular the glycotene surfactants, such as alkyl polyglycosides and fatty acid glucamides. The alkyl polyglucosides are particularly preferred.

Alcohol alkoxylates, ie alkoxylated, advantageously ethoxylated, in particular primary alcohols with 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 residue is linear or preferred, are preferably used as nonionic surfactants in the 2-position - can be methyl-branched 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 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 _{2 to 14} alcohols with 3 EO or 4 EO, C ₉ n alcohol with 7 EO, C ₃ -i5 alcohols with 3 EO, 5 EO, 7 EO or 8 EO, C 1 ₂ -ι ₈ -alcohols with 3 EO, 5 EO or 7 EO and mixtures gene from these, as well as mixtures of C ₁₂ -ι alcohol with 3 EO and C ₁₂ - _.8 - 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 of this are 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 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-A-90/13533.

Another class of nonionic surfactants that can be used advantageously are the alkyl polyglycosides (APG). Alkyl polyglycosides are surfactants which can be obtained by the reaction of sugars and alcohols according to the relevant methods of preparative organic chemistry, which, depending on the type of production, results in a mixture of monoalkylated, oligomeric or polymeric sugars. Preferred alkyl polyglycosides can be alkyl polyglucosides, the alcohol being particularly preferably a long-chain fatty alcohol or a mixture of long-chain fatty alcohols with branched or unbranched alkyl chain lengths between Cβ and Cι ₈ and the degree of oligomerization of the sugars being between 1 and 10. Alkypolyglycosides which can be used advantageously satisfy the general formula RO (G) _z , in which R is a linear or branched, in particular methyl-branched, saturated or unsaturated, aliphatic radical having 8 to 22, preferably 12 to 18, carbon atoms stands and G is the 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. \

The alkyl polyglycosides, in particular alkyl polyglucosides, are particularly preferably used in amounts of between 0.1 to 15.0% by weight, preferably in amounts of 0.2 to 10.0% by weight, more preferably in amounts of 0, 5 to 8.0% by weight and particularly preferably in amounts of 1.0 to 6.0% by weight.

Nonionic surfactants of the amine oxide and fatty acid alkanolamide type 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.

The amine oxides suitable according to the invention include alkylamine oxides, in particular alkyldimethylamine oxides, alkylamidoamine oxides and alkoxyalkylamine oxides. Preferred amine oxides satisfy the formula R ¹ R ² R ³ N ⁺ -O ^~, in which R ¹ is a saturated or unsaturated C _6-22 alkyl radical, preferably Cβ-iβ alkyl radical, particularly a saturated Cι ₀ -16 alkyl radical, for example, a saturated C _12. -alkyl radical, which in the alkylamidoamine oxides via a carbonylamidoalkylene group -CO-NH- (CH ₂ ) _z - and in the alkoxyalkylamine oxides via an oxalkylene group -O- (CH ₂ ) _z - to the Nitrogen atom N is bonded, where z is in each case a number from 1 to 10, preferably 2 to 5, in particular 3, and R ² and R ^{3 are,} independently of one another, an optionally hydroxy-substituted C 1 - r alkyl radical, such as, for example, a hydroxyethyl radical, in particular a methyl radical ,

Examples of suitable amine oxides are the following compounds named according to INCI: Almondamidopropylamine Oxide, Babassuamidopropylamine Oxide, Behenamine Oxide, Cocamidopropyl Amine Oxide, Cocamidopropylamine Oxide, Cocamine Oxide, Coco-Morpholine Oxide, Decylamine Oxide, Decyltetradecylamine Oxide, Diaminoproxyimidine Oxide, Caminopyrimidine Oxide Alkoxypropylamine Oxide, Dihydroxyethyl C9-11 Alkoxypropylamine Oxide, Dihydroxyethyl C12-15 Alkoxypropylamine Oxide, Dihydroxyethyl Cocamine Oxide, Dihydroxyethyl Lauramine Oxide, Dihydroxyethyl Stearamine Oxide, Dihydroxyethyl Taliowamine Oxide, Hydrogenated Palm Kernel Amine Oxide, Hydrogenated Hydroxyethyl- Hydroxypropyl Oxide, Oxyl , Isostearamidopropyiamine Oxide, Isostearamidopropyl Morpholine Oxide, Lauramido- propylamine oxides, lauramine oxides, methyl morpholine oxides, milkamidopropyl amine oxides, minkamidopropylamine oxides, myristamidopropylamine oxides, myristamine oxides, myristyl / cetyl amine oxides, oleamidopropylamine oxides, oleamine oxides, olivamidopropylamine oxides, palmitamidopropylamine oxides, palmitamidopropylamine oxides 3 Lauramine Oxide, Potassium Dihydroxyethyl Cocamine Oxide Phosphate, Potassium Trisphosphonomethylamine Oxide, Sesamidopropylamine Oxide, Soyamidopropylamine Oxide, Stearamidopropylamine Oxide, Stearamine Oxide, Tallowamidopropylamine Oxide, Tallowamine Oxide, Undecyleneamidopropylamine Oxide and Wheat Germamide. Preferred amine oxide (s) are, for example, cocamine oxides (N-coconut alkyl-N, N-dimethylamine oxide), dihydroxyethyl tallowamine oxides (N-tallow alkyl-N, N-dihydroxyethylamine oxide) and / or cocamidopropylamine oxides (Cocoamidopro- pylamine oxide), especially cocamidopropylamine oxides.

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

R ¹

I R-CO-N- [Z] (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.

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

R ¹ -OR ²

I R-CO-N- [Z] (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, where

or phenyl radicals are preferred and [Z] stands for a linear polyhydroxyalkyl radical, the alkyl chain of which is substituted with at least two hydroxyl groups, or alkoxylated, preferably ethoxylated or propylated, derivatives of this radical.

[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.

Nonionic surfactants in total are preferably used in amounts of from 1 to 80% by weight, preferably from 5 to 50% by weight, particularly preferably from 7 to 35% by weight and very preferably from 10 to 25% by weight.

The zwitterionic surfactants or amphoteric surfactants which can be used according to the invention include betaines and alkylamidoalkylamines (INCI alkylamido alkylamines) as well as alkyl-substituted amino acids (INCI alkyl-substituted amino acids), in particular aminopropionates, acylated amino acids and biosurfactants. A preferred ingredient is betaine, especially alkyl amido betaine.

Suitable betaines are the alkylbetaines, the alkylamidobetaines, the imidazoliniumbetaines, the sulfobetaines (INCI Sultaines) and the phosphobetaines and preferably satisfy the formula (III),

R - [CO-X- (CH ₂ ) _n ] χ-N ⁺ (R ² ) (R ³ HCH ₂ ) _m - [CH (OH) -CH ₂ ] _y -Y- (III) ZI in which R is a saturated or unsaturated C ^{_6: 1} - ₂₂ alkyl, preferably Cβ-iβ alkyl group, preferably a saturated C ₁₀ -. ₆ -alkyl radical, for example a saturated C ₁ -C ₄ -alkyl radical,

X is NH, NR ⁴ with the C 1-4 alkyl radical R ⁴ , O or S, n is a number from 1 to 10, preferably 2 to 5, in particular 3, x is 0 or 1, preferably 1,

R ² , R ^{3 are,} independently of one another, an optionally hydroxy-substituted C 4 alkyl radical such as, for example, a hydroxyethyl radical, but in particular a methyl radical, m is a number from 1 to 4, in particular 1, 2 or 3, y is 0 or 1 and

Y is COO, SO ₃ , OPO (OR ⁵ ) 0 or P (O) (OR ⁵ ) O, where R ^{5 is} a hydrogen atom or a

is.

The alkyl and alkyl amido betaines, betaines of formula (I) with a carboxylate group (Y ^~ = COO ^" ), are also called carbobetaines.

Preferred amphoteric surfactants are the alkyl betaines of the formula (lilac), the alkyl amido betaines of the formula (IIIb), the sulfobetaines of the formula (Never) and the amidosulfobetaines of the formula (IIId),

R ¹ -N ⁺ (CH ₃ ) ₂ -CH ₂ COO- (purple)

R ¹ -CO-NH- (CH ₂ ) ₃ -N ⁺ (CH ₃ ) ₂ -CH ₂ COO- (IIIb)

R ¹ -N ⁺ (CH ₃ ) 2-CH ₂ CH (OH) CH ₂ SO ₃ ^~ (IIIc)

R ¹ -CO-NH- (CH ₂ ) ₃ -N ⁺ (CH ₃ ) ₂ -CH ₂ CH (OH) CH ₂ S0 ₃ - (llld)

in which R ^{1 has} the same meaning as in formula (I).

Particularly preferred amphoteric surfactants are the carbobetaines, in particular the carbobetaines of the formulas (purple) and (IIIb), most preferably the alkylamidobetaines of the formula (IIIb). J ^

Examples of suitable betaines and sulfobetaines are the following compounds named according to INCI: Almondamidopropyl betaines, apricotamidopropyl betaines, avocadamidopropyl betaines, Babassuamidopropyl betaines, behenamidopropyl betaines, behenyl betaines, betaines, canolamidopropyl betaines, Capyl / Capramidopropyl betaines, Carnitine Cocamidoethyl Betaine, Cocamidopropyl Betaine, Cocamidopropyl Hydroxysultaine, Coco-Betaine, Coco-Hydroxysultaine, Coco / Oleamidopropyl Betaine, Coco-Sultaine, Decyl Betaine, Dihydroxyethyl Oleyl Glycinate, Dihydroxyethyl Soy Glycinate, Dihydroxyethyl Stearyl Glycinate, Dihydroxyethyl Tallethicine Propane , Erucamidopropyl Hydroxysultaine, Hydrogenated Tallow Betaine, Isostearamidopropyl Betaine, Lauramidopropyl Betaine, Lauryl Betaine, Lauryl Hydroxysultaine, Lauryl Sultaine, Milkamidopropyl Betaine, Minkamidopropyl Betaine, Myristamidopropyl Betaine, Myristyl Betaine, Oleamidopropyl Betaine, Oleamidopropyl Hydro xysultaine, oleyl betaine, olivamidopropyl betaine, palamamidopropyl betaine, palmitamidopropyl betaine, palmitoyl carnitine, palm kernelamidopropyl betaine, polytetrafluoroethylene acetoxypropyl betaine, ricinoleamidopropyl betaine, sesamidopropyl betaine, soyamidopropyl betaine, stearamidamidopropyl betaine, stearamidamidopropyl betaine, stearamidamidopropyl betaine, stearamidamidopropyl betaine, stearamidamidopropyl betaine Tallow Betaine, Tallow Dihydroxyethyl Betaine, Undecylenamidopropyl Betaine and Wheat Germamidopropyl Betaine. A preferred betaine is, for example, cocamidopropyl betaine (cocoamidopropyl betaine).

These amphoteric surfactants are preferably used in amounts between 0.1 and 14.9% by weight, preferably 0.5 to 8% by weight and particularly preferably 1 to 6% by weight.

In a preferred embodiment of the invention, the dishwashing detergent portion contains as surfactant mixture (a) 0.2 to 80% by weight, preferably 10 to 70% by weight, particularly preferably 25 to 60% by weight, extremely preferably 40 to 60 % By weight of one or more anionic surfactants, preferably alkylbenzenesulfonates) and / or fatty alcohol ether sulfate (s), (b) 1 to 80% by weight, preferably 5 to 50% by weight, particularly preferably 7 to 35% by weight % and extremely preferably 10 to 25% by weight, of one or more nonionic surfactants, preferably alcohol alkoxylate (s), alkyl polyglycoside (s) and / or amine oxide (s), in particular alcohol alkoxylate (s) or combinations of alcohol alkoxylate (s) with alkyl polyglycoside ( en) and / or amine oxide (s), and (c) 0.1 to 14.9% by weight, preferably 0.5 to 8% by weight and particularly preferably 1 to 6% by weight, of one or more Betaine surfactants, preferably alkyl amido betaines.

In addition to or instead of the water content according to the invention of preferably less than 15% by weight, based on the total weight of the rinse-active preparation (s), and in particular less than 10% by weight, the rinse-active preparation (s) contain (s) preferably one or more non-aqueous carriers. The non-aqueous carrier (s) is / are preferably water-soluble or water-miscible and at least one, in particular each, non-aqueous carrier (s) is liquid at room temperature (20 ° C.).

The non-aqueous carrier (s) serve (i) as a filling component for filling the remaining components of the rinse-active preparation (s) to the desired portion quantity, (ii) for controlling the flowability or the flow behavior, in particular the viscosity, of the rinse-active Preparation (s), (iii) for controlling the solubility or solubility behavior, in particular the rate of dissolution, of the rinse-active preparation (s) in aqueous media and / or (iv) as a solvent or solubilizer (hydrotrope) for other components of the rinse-active preparation ( s).

Suitable non-aqueous carriers are, for example, solvents and polyalkylene glycols. In the context of the teaching according to the invention, polyalkylene glycols are understood to mean the tetramers and higher representatives, while the di- and trimers belong to the solvents according to the invention.

Preferred solvents contain one or more hydroxyl groups "OH", one or more ester groups "CO-OC" and / or one or more ether groups "COC", preferably one or more hydroxyl groups or one or more hydroxyl groups and one or more ether groups. I

In particular, solvents are used in the context of the non-aqueous carrier component according to the invention as a hydrotrope, viscosity regulator and / or cold stabilizer. They have a solubilizing effect, in particular for surfactants and perfume / fragrance and dye, and thus contribute to their incorporation, prevent the formation of liquid-crystalline phases and play a part in the formation of clear products. The viscosity decreases with increasing amount of solvent. Finally, the clouding and clearing point decrease with increasing amount of solvent.

Particularly preferred solvents are, for example, saturated or unsaturated, preferably saturated, branched or unbranched C 1. ₂₀ - hydrocarbons, preferably C ₂ -i5 hydrocarbons, with at least one hydroxyl group and possibly one or more ether functions COC, ie oxygen atoms interrupting the carbon atom chain, without being interrupted by an ether function not more than 8, preferably not more than 6, in particular not more than 4, carbon atoms are connected to each other.

These include C _{2, which may be} etherified on one side with a d-β-alkanol. ₆ -alkylene glycols and poly-C ₂ -3-alkylene glycol ethers with an average of 1 to 9, preferably 2 to 3, identical or different, preferably identical, alkylene glycol groups per molecule, in particular 1, 2-propylene glycol, as well as the Cι- ₆ - Alcohols, preferably ethanol, n-propanol or / ^' so-propanol (2-propanol), in particular ethanol, and glycerin.

Exemplary solvents are the following compounds named according to INCI: Alcohol (ethanol), buteth-3, butoxyethanol, butoxypropanol, n-butyl alcohol, t-butyl alcohol, butylene glycol, butyl octanol, diethylene glycol, dimethoxy diglycol, dimethyl ether, dipropylene glycol , Ethoxydiglycol, Ethoxyethanol, Ethyl Hexanediol, Glycol (ethylene glycol), Hexanediol, 1, 2,6-Hexanetriol, Hexyl Alcohol, Hexylene Glycol, Isobutoxypropanol, Isopentyldiol, Isopropyl Alcohol (/ so-Propanol), 3-Methoxybutanol, Methoxyethanol, Methoxymethylbutanol Methoxy PEG-10, Methylal, Methyl Alcohol, Methyl Hexyl Ether, Methylpropanediol, Neopentyl Glycol, PEG-6 Methyl Ether, Pentylene Glycol, PPG-2-Buteth-3, Pro 23 panediol, propyl alcohol (n-propanol), propylene glycol, propylene glycol butyl ether, tetrahydrofurfuryl alcohol, trimethylhexanol.

Particularly preferred solvents are aliphatic continue with Cι- ₆ - or aromatic alcohols, for example methanol, ethanol, n-propanol, n-butanol, TETF-butanol or phenol, etherified or with carboxylic acids, such as acetic acid or carbonic acid esterified monomeric or homo - or heteropolymers, in particular monomers and homodimers and trimers, C ₂ -C ₄ alkylene glycols, for example those sold under the trade name DowanoP by Dow Chemical and those sold under the trade names Arcosolv ^® and Arconate ^® by Arco Chemical and products named below with their / Λ / C / name, e.g. butoxydiglycol (DowanoF DB), methoxydiglycol (DowanoP DM), PPG-2 methyl ether (Dowanoi ^® DPM), PPG-2 methyl ether acetate (Dowanor ^' DPMA), PPG-2 Butyl Ether (DowanoP DPnB), PPG-2 Propyl Ether (DowanoP DPnP), Butoxyethanol (DowanoF EB), Phenoxyethanol (Dowano EPh), Methoxyisopropanol (DowanoF PM), PPG-1 Methyl Ether Acetate (DowanoP PMA) , Butoxyisopropanol (DowanoF PnB), Pro pylene glycol propyl ether (DowanoF PnP), phenoxyisopropanol (DowanoF PPh), PPG-3 methyl ether (DowanoP TPM) and PPG-3 butyl ether (Dowanoi ^® TPnB) as well as ethoxyisopropanol (Arcosolv ^® PE), tetτ-butoxyisopropanol (Arcosolv ^® PTB), PPG-2 tett-butyl ether (Arcosolv ^® DPTB) and propylene carbonate (Arconate ^® PC), especially butoxyisopropanol (DowanoP PnB).

Solvents are preferably used in an amount of 0.1 to 80% by weight, preferably 1 to 50% by weight, in particular 5 to 40% by weight, particularly preferably 7 to 30% by weight, extremely preferably 10 to 20 % By weight.

Polyalkylene glycols (polyglycols, polyglycol ethers; INCI Chemical Class: Polymeric Ethers) are known, predominantly linear, but in some cases branched polyethers, which are polymers with terminal hydroxyl groups. The polyalkylene glycols with higher molecular weights are polymolecular, ie they consist of groups of macromolecules with different molecular weights. Preferred polyalkylene glycols are liquid at room temperature (20 ° C.) and preferably have a melting point of not more than 20 ° C., in particular not more than 15 ° C., particularly preferably not more than 10 ° C. and very preferably not more than 5 ° C. or even not at all 0 ° C. The melting point here means the temperature at the transition point from the solid to the liquid state. The melting point of a certain polyalkylene glycol is - if not mentioned below - mostly known from the literature or routinely by one of the usual methods for determining the melting point.

The molecular weights of the polyalkylene glycols are preferably in the range from 200 to 5,000, in particular from 300 to 4,000, particularly preferably from 400 to 3,000 and extremely preferably from 500 to 2,000. With the various polyalkylene glycols described below, certain areas can again be particularly advantageous.

Linear or branched, in particular linear, polyalkylene glycols of the general formula HO- [RO] rf-H, in which R represents (CH ₂ ) ₂ , CH ₂ CH (CH ₃ ) and / or for (CH ₂ ) and n, are preferred according to the invention stand for values or mean values from 4 to about 100 and which can be prepared by ring-opening polymerization of ethylene oxide, propylene oxide and / or tetrahydrofuran. These are in particular the polyethylene glycols with R = (CH) ₂ , the polypropylene glycols with R = CH ₂ CH (CH ₃ ), the polytetrahydrofurans with R = (CH ₂ ) and the copolymers of ethylene oxide, propylene oxide and / or tetrahydrofuran.

According to the invention, preference is given to polyethylene glycols (PEG) with an average relative molecular weight of up to about 4,000. Finally, PEG with molecular weights above 4,000 are all no longer liquid and are therefore less suitable according to the invention. The molecular weights of the polyethylene glycols are very preferably not only not more than 2,000 but even only up to 1,500, in particular only up to 1,000 or even only up to 800, for example 400 or 600. There are various nomenclatures for polyethylene glycols which can lead to confusion. The specification of the average relative molecular weight after the specification "PEG" is technically customary, so that "PEG 200" is a position characterized with a relative molecular weight of about 190 to about 210. According to /Λ/C. nomenclature, the abbreviation PEG is provided with a hyphen and immediately follows the hyphen a number that corresponds to the number n in the general formula above. Commercially available polyethylene glycols are, for example, PEG 200 / PEG-4, PEG 300 / PEG-6, PEG-7, PEG-8, PEG 400, PEG-9, PEG-10, PEG-12, PEG 600, PEG-14, PEG -16, PEG 800 / PEG-18, PEG- 20, PEG 1000, PEG 1200, PEG 1500 / PEG-32, PEG-40, PEG 2000, PEG-55, PEG-60, PEG 3000, PEG 3350 / PEG- 75 and PEG 4000 / PEG-90, the names according to the two nomenclatures for corresponding polyethylene glycols being separated by the "/" symbol. The polyethylene glycols commercially available, for example, under the trade names Carbowax ^® (Union Carbide), Emkapol ^® and Renex ^® PEG (ICI), Li poxol ^® (DEA), polyglycol ^® E (Dow), Pluracol ^® E, Pluriol® ^® E and Lutrol ^® E (BASF) and Polydiol (Cognis) available. Clariant also sells polyethylene glycols. Sources of supply for the polyethylene glycols, which are also used as cosmetic ingredients and are named according to INCI, can be found in the International Cosmetic Ingredient Dictionary and Handbook.

Polypropylene glycols (PPG) are clear, almost colorless liquids over a broad molecular weight range from 250 (PPG-4) to 4,000 (PPG-69), for whose description the // VC / nomenclature described above is used analogously. The polypropylene glycols of the above general formula with values n of 5 or 6 are referred to as PEG-5 or PEG-6. The low molecular weight polypropylene glycols are miscible with water, while the higher molecular weight representatives are less water soluble. For example, the polypropylene glycols PPG-7, PPG-9, PPG-12, PPG-13, PPG-15, PPG-17, PPG-20, PPG-26, PPG-30, PPG-33, PPG are commercially available -34, PPG-51 and PPG-69. Sources of supply can be found in the International Cosmetic Ingredient Dictionary and Handbook.

The copolymers are preferably statistical copolymers and in particular block copolymers of ethylene and propylene oxide, ethylene oxide and tetrahydrofuran, propylene oxide and tetrahydrofuran or ethylene oxide, 2G propylene oxide and tetrahydrofuran, preferably from ethylene and propylene oxide, particularly preferably around block copolymers from ethylene and propylene oxide. The molecular weights of the copolymers are extremely preferably not only at least 500, as mentioned above, but even at least about 1,000.

Statistical copolymers of a ethylene and b propylene oxide units which are preferred according to the invention are, for example, the following copolymers (molecular weight) designated PEG / PPG-a / b in accordance with the International Cosmetic Ingredient Dictionary and Handbook, with a and b representing mean values: PEG / PPG-18 / 4 copolymer (1000), PEG / PPG-17/6 copolymer (1100), PEG / PPG-35/9 copolymer (2100) and PEG / PPG-23/50 copolymer (3900).

Block copolymers of ethylene and propylene oxide preferred according to the invention satisfy the formula HO (CH ₂ CH ₂ O) χ (CH (CH ₃ ) CH ₂ O) _y (CH2CH ₂ O) Η, in which x and x 'for mean values from 2 to 130 and z stand for mean values from 15 to 67, and are designated with the international free name Poloxamer, which is also used in the International Cosmetic Ingredient Dictionary and Handbook. Each poloxamer is identified by a three-digit number. The first two digits multiplied by 100 indicate the average molar mass of the polypropylene glycol portion and the last digit multiplied by 10 the polyethylene glycol portion in% by weight. This is 10 to 80% by weight, preferably not more than 50% by weight, in particular not more than 40% by weight, particularly preferably not more than 30% by weight, for example 10, 20 or 30% by weight. %. The poloxamers are prepared in two stages, with propylene oxide initially being added to propylene glycol in a controlled manner and the polypropylene glycol block obtained being bordered by two polyethylene glycol blocks by subsequent addition of ethylene oxide. Particularly preferred block copolymers are, for example, the following liquid poloxamer types (x, y, x '; molecular weight; partly melting point): Poloxamer 101 (2, 16, 2; 1100; -32), Poloxamer 122 (5, 21, 5; 1630; -26), Poloxamer 123 (7, 21, 7; 1900; -1), Poloxamer 105 (11, 16, 11; 1850; 7), Poloxamer 181 (3, 30, 3; 2000; -29), Poloxamer 124 (11, 21, 11; 2200; 16), poloxamer 182 (8, 30, 8; 2500; -4), poloxamer 183 (10, 30, 10; 2650; 10), poloxamer 212 (8, 35, 8; 2750; -7), Poloxamer 231 (6, 39, 6; 2750; -37), Poloxamer 184 (13, 30, 13; 2900; 16), Poloxamer 185 (19, 30, 19; 3400), Poloxamer 282 (10, 47, 10; 3650; 7), Poloxamer 331 (7, 54, 7; 3800; -23), Poloxamer 234 (22, 39 , 22; 4200; 18), Poloxamer 401 (6, 67, 6; 4400; 5), Poloxamer 284 (21, 47, 21; 4600) and Poloxamer 402 (13, 67, 13; 5000; 20). The poloxamers are commercially available under the trade names Pluronic ^® and Synperonic ^® PE, followed by a letter from the groups L, P and F and a two or three-digit number. The last digit is identical to the last digit of the poloxamer nomenclature and the preceding one or two-digit numbers multiplied by 300 give the approximate molar mass of the polypropylene glycol fraction or multiplied by 3 roughly the one from the first two digits of the poloxamer nomenclature number formed number, ie 3, 4, 6, 7, 8, 9, 10 and 12 in this order correspond to the two-digit numbers 10, 12, 18, 21, 23, 28, 33 and 40 at the beginning of the number according to the poloxamer nomenclature , The letters distinguish liquid (L), pasty (P) and solid (F) poloxamers. For example, the Poloxamer 101 is available as Pluronic ^® L 31 and Synperonic ^® PE L 31.

Another class of suitable block copolymers of ethylene and propylene oxide suffice the formula HO (CH (CH ₃ ) CH ₂ O) _y (CH ₂ CH2θ) _x (CH2CH (CH ₃ ) O) _y .H. Here a polyethylene glycol block is framed by two polypropylene glycol blocks, while in the poloxamers a polypropylene glycol block is framed by two polyethylene glycol blocks. The production is again carried out in two stages, with ethylene oxide initially being added to ethylene glycol in a controlled manner and the polyethylene glycol block obtained being bordered by two polypropylene glycol blocks by subsequent addition of propylene oxide. Commercially available, these block copolymers such as the poloxamers sold under the trade name Pluronic ^® (BASF), which in each case followed by an alphanumeric code of three digits and the shifted between the second and third digits are letters R. The meaning of the digits is identical to the meaning in the context of the poloxamer nomenclature. The inserted letter R (for English reverse) indicates the inverted structure compared to the poloxamers. The following Pluronic ^® types (molecular weight; melting point) are preferred representatives of this class: Pluronic ^® 10R5 (1950; 15), Pluronic ^® 12R3 (1800; -20), Pluronic ^® 17R1 (1900; -27), Pluronic ^® 17R2 (2150; -25), Pluronic ^® 17R4 (2650; 18), Pluronic ^® 25R1 (2700; -5), Pluronic ^® 25R2 (3100; -5), Pluronic ^® 31 R1 (3250; -25) and Pluronic ^® 31 R2 (3300; 9).

Polyalkylene glycols are preferably used in an amount of 0.1 to 80% by weight, preferably 1 to 40% by weight, in particular 3 to 25% by weight, particularly preferably 5 to 15% by weight, extremely preferably 7 to 10 % By weight.

Non-aqueous carriers are / are preferably used in a total amount of 0.1 to 80% by weight, preferably 5 to 50% by weight, in particular 10 to 40% by weight, particularly preferably 15 to 35% by weight. %, most preferably 20 to 30 wt .-%, used.

In a particular embodiment, at least two non-aqueous carriers are used, in particular at least one solvent and at least one polyalkylene glycol, preferably in a weight ratio of solvent (s) to polyalkylene glycol (s) from 10: 1 to 1:10, in particular from 5: 1 to 1: 3, particularly preferably from 3: 1 to 1: 2 and extremely preferably from 2: 1 to 1: 1.

To improve the cleaning effect in the washing process, in particular in the case of residues which are difficult to remove, the dishwasher detergent portions according to the invention can contain enzymes. Suitable enzymes are those from the class of proteases, lipases, amylases, cellulases or mixtures thereof. Enzymatic active ingredients obtained from bacterial strains or fungi such as Bacillus subtilis, Bacillus licheniformis and Streptomyces griseus are particularly suitable. Proteases of the subtilisin type and in particular proteases which are obtained from Bacillus lentus are preferably used. Enzyme mixtures, for example of protease and amylase or protease and lipase or protease and cellulase or of cellulase and lipase or of protease, amylase and lipase or protease, lipase and cellulase, but in particular mixtures containing cellulase, are of particular interest. Peroxidases or oxidases have also proven to be suitable in some cases. 3.1 pointed. The enzymes can be adsorbed on carriers and / or embedded in coating substances in order to protect them against premature decomposition. The enzymes are furthermore preferably optimized for use under the conditions of manual rinsing, for example as regards the temperature of the rinsing process. The proportion of enzymes, enzyme mixtures or enzyme granules in the dishwasher detergent portions according to the invention can be, for example, about 0.1 to 5% by weight, preferably 0.1 to about 2% by weight.

According to the state of the art, enzymes are added to multi-phase detergent preparations, primarily detergent preparations such as machine dishwashing detergents, which are intended for the main wash cycle of a dishwasher. The disadvantage here was that problems repeatedly occurred with the stability of the enzymes in the strongly alkaline aqueous environment. With the portions of dishwashing detergent according to the invention, it is possible to use enzymes also in the manual dishwashing process and thus to use the cleaning action of enzymes also to remove soiling of the dishes during manual dishwashing. The enzyme-containing component of a rinse-active preparation can, in a form separated from the other components or from other components of the rinse-active preparations which are harmful to the enzyme action), be comprised of a casing made of a water-soluble polymer material, as a result of which the enzyme activity is retained even after prolonged storage.

Another group of additives preferred according to the invention are dyes, in particular water-soluble or water-dispersible dyes. Dyes are preferred here, as are usually used to improve the optical product appearance in cleaning agents. The choice of such dyes does not pose any difficulties for the person skilled in the art, in particular since such customary dyes have a high storage stability and are insensitive to the other ingredients of the rinse-active preparations and to light. According to the invention, the dyes are present in the dishwasher detergent portions in amounts of less than 0.01% by weight. 2> Z-

Fragrances are added to the portions of dishwashing detergent according to the invention in order to improve the overall aesthetic impression of the products and, in addition to the technical performance (good washing result), to provide the consumer with a sensorially typical and unmistakable product. Individual fragrance compounds can be used as perfume oils or fragrances, for example the synthetic products of the ester, ether, aldehyde, ketone, alcohol and hydrocarbon type. Fragrance compounds of the ester type are, for example, benzyl acetate, phenoxyethyl isobutyrate, p-t-butylcyclohexyl acetate, linalyl acetate, dimethylbenzylcarbyl acetate, phenylethyl acetate, linalyl benzoate, benzyl formate, ethyl methylphenyl glycinate, allyl cyclohexyl benzylatepylpionate, allyl cyclohexyl propylatepionate. The ethers include, for example, benzyl ethyl ether. The aldehydes include e.g. B. linear alkanals with 8 to 18 carbon atoms, citral, citronellal, citronellyl-oxyacetaldehyde, cyclamenaldehyde, hydroxycitronellal, lileal and bourgeonal.

The ketones include the ionones, α-isomethyl ionone and methyl cedryl ketone. Alcohols include anethole, citronellol, eugenol, geraniol, linalool, phenylethyl alcohol and terpineol. The hydrocarbons mainly include terpenes such as limonene and pinene. Mixtures of different fragrances are preferably used which are coordinated with one another in such a way that together they produce an appealing fragrance. Such perfume oils can also contain natural fragrance mixtures, such as are obtainable from plant sources. Examples are pine, citrus, jasmine, patchouli, rose or ylang-ylang oil. Also suitable are nutmeg oil, 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 as orange blossom oil, neroliol, orange peel oil and sandalwood oil.

The fragrance content is usually in the range of up to 2% by weight of the total dishwashing detergent portion.

The fragrances can be incorporated directly into the rinse-active preparations; but it can also be advantageous to apply the fragrances to carriers, which ensure a long-lasting scent when rinsing due to a slower fragrance release. Cyclodextrins, for example, have proven themselves as such carrier materials. The cyclodextrin-perfume complexes can also be coated with other auxiliaries. Since such complexes are not soluble in the dishwashing detergents, their separate accommodation in a rinse-active preparation or even separately from the rinse-active preparations is possible according to the invention as part of a separate enclosure with a water-soluble polymer material.

The perfumes and fragrances can in principle be contained in each of the partial portions (rinse-active preparations) of the dishwasher detergent portions according to the invention. However, it is particularly preferred that they are contained in a portion of dishwashing detergent, the ingredients of which do not react undesirably with these components with decomposition or degradation.

As further additives according to the invention, the dishwashing detergent portions can also contain polymers, for example polymers that build up on hard surfaces (for example on porcelain and glass), have a positive effect on the oil and grease washability of these surfaces and thus counteract any soiling in a targeted manner (so-called soil repellents ). This effect is particularly evident when a hard object (porcelain, glass) is soiled that has already been washed several times beforehand with a dishwashing detergent according to the invention which contains this oil- and fat-dissolving component. The preferred oil- and fat-dissolving components include, for example, nonionic cellulose ethers such as methylcellulose and methylhydroxypropylcellulose with a proportion of methoxy groups from 15 to 30% by weight and of hydroxypropoxy groups from 1 to 15% by weight, based in each case on the nonionic Cellulose ethers, as well as the polymers of phthalic acid and / or terephthalic acid or their derivatives known from the prior art, in particular polymers of ethylene terephthalates and / or polyethylene glycol terephthalates or anionically and / or nonionically modified derivatives thereof. Of these, the sulfonated derivatives of phthalic acid and terephthalic acid polymers are particularly preferred. In a preferred embodiment, further conceivable components of the detergent-active preparations in the dishwasher detergent portions according to the invention can be antibacterial or bacteriostatic agents. Suitable as such are, for example, singly or in appropriate combination in question: Triclo- san (2,4,4'-trichloro-2'-hydroxydiphenyl ether), chloramine-T (rechloramid toluenesulfonic acid sodium salt), Germall ^® 115 (imidazolidinyl urea), sodium formate , 2-phenoxyethanol, 1-phenoxy-2-propanol, 2-phenoxy-1-propanol, benzoic acid and its salts, lactic acid and its salts, salicylic acid and its salts, sorbic acid and its salts, and natural or nature-identical plant extracts such as, for. B. Extracts from orange peel, pine oil, geraniol and nerol. When using the aforementioned salts of benzoic acid or carboxylic acids, sodium, potassium, magnesium and calcium salts are primarily considered.

In further preferred embodiments, the dishwashing agent portions can contain one or more additional component (s) which are selected from the group consisting of solubilizers, UV stabilizers, defoamers, structuring agents, corrosion inhibitors, preservatives, silver preservatives and skin-protecting additives.

Advantages with regard to the clarity of the products are obtained - especially in the case of mixtures containing high surfactants - if the formulation contains one or more dicarboxylic acids and / or their salts, alone or in a mixture, preferably a composition of sodium salts of adipic, succinic and glutaric acid , adds. Such a composition is available, for example, under the trade name Sokalan ^® DSC Na. The use of 0.1 to 8% by weight, preferably 1 to 6% by weight, particularly preferably 2.5 to 5% by weight, has proven to be particularly advantageous.

The optional presence of solubilizers, in particular for perfume and dyes, for example alkanoamines and / or alkylbenzenesulfonates having 1 to 3 carbon atoms in the alkyl radical, in particular cumene, to-, toluene and xylene sulfonate, in amounts of up to 5% by weight, preferably 0.05 to 3% by weight, in particular 0.1 to 2% by weight.

Another preferred group of additives in the sense of the invention are silver protection agents. These are a large number of mostly cyclic organic compounds which are likewise familiar to the person skilled in the art and which help to prevent tarnishing of silver-containing objects during the cleaning process. Specific examples can be benzotriazoles, triazoles and their complexes with metals such as Mn, Co, Zn, Fe, Mo, W or Cu.

In addition to the previously mentioned ingredients, other ingredients common in hand dishwashing detergents, such as UV stabilizers, defoamers (such as silicone oils, paraffin oils or mineral oils), structuring agents, corrosion inhibitors, preservatives, skin-protecting additives or the like, preferably in amounts of up to 5% by weight.

The rinse-active preparations of the dishwashing agent portions according to the invention can be prepared by stirring the individual components together in any order and leaving the mixture to stand until there are no bubbles. The order of preparation is not critical for the preparation of the dishwashing detergent portion according to the invention.

The correspondingly obtained rinse-active preparations can then be surrounded in a manner known per se from the prior art with enclosures made of one or more water-soluble polymer material (s). A preferred embodiment of the invention consists, for example, in providing a rinse-active preparation with an enclosure, which forms a compartment or a chamber and is made of a water-soluble polymer material. This can be, for example, a foil pillow, a foil pocket or a capsule. In this case, the dishwashing detergent portion with all the components of the wash-active preparation required for the cleaning or rinsing cycle is contained in a closed compartment which adheres in the conventional way, welded or closed in any other manner known from the prior art.

A further, likewise preferred embodiment of the dishwashing detergent portion according to the invention can consist in that at least two rinse-active preparations are encompassed by an enclosure made of a water-soluble polymer material and forming at least two compartments. This embodiment can be advantageous, for example, if individual components are to be contained in the dishwashing detergent portion, which react with other components immediately or only after prolonged storage or only when moisture or the like has entered, leading to a reduction in the Effectiveness of the rinse-active preparation (s) overall or in connection with the effectiveness of individual components. A typical example can be enzymes which are subject to a loss of activity over time in a strongly alkaline environment and in particular in the presence of water. In the same way it can be achieved with this embodiment that components of the rinse-active preparation can be added which cannot be distributed uniformly in a larger volume of the finished product or which, despite the initial uniform distribution, settle out. These can be admixed with an amount of the rinse-active preparation dosed for a rinse cycle or be provided in a separate compartment or a separate chamber which is connected to the compartment with the remaining components of the rinse-active preparation.

The amount of the active wash preparation (s) in a compartment or a chamber of the dishwashing detergent portion is in principle freely selectable. However, the compartment (s) or the compartments of the dishwasher detergent portions according to the invention preferably contain an amount of at least 1 ml of one or more rinse-active preparation (s), more preferably an amount of 1 to 10 ml of one or more rinse-active preparation (s) , very particularly preferably an amount of 1 to 5 ml of one or more rinse-active preparations). In the form of portions of dishwashing detergent according to the invention which are filled in, for example, foil cushions, welded foil pockets, capsules, etc., can then be added to the optionally tempered cleaning or rinsing liquor before a manual rinse cycle. The enclosure made of the water-soluble polymer material (s) then quickly dissolves and we release the rinse-active preparation (s) into the liquor.

The rinse-active preparations, in the form provided with the enclosure (s), have superior storage stability. The rinse-active preparation is dosed reliably into the liquor; under- or overdosing is systematically avoided. In the case of a content of sensitive components in the rinse-active preparation (s), there is no reduction in effectiveness due to a lack of interaction with other components of the rinse-active preparation. For example, the effectiveness of enzymes is retained because they are kept separate from alkaline components of the preparation (s) and are only added in the actual rinse cycle.

The invention is explained in more detail by the following examples, but without being limited to these.

Examples

By stirring together the listed in the following table components and filling of the preparations so obtained in pad of PVAL films (Solublon ^® PT Company Synthana trading company E. rake GmbH & Co .; heat-sealed) in an amount of 2 dishwashing portions were ml accordance made of the invention.

The dishwasher detergent portions had good storage stability in the temperature range between 5 and 40 ° C. The rinsing and emulsifying properties were excellent. The films quickly dissolved in water suitable for a manual rinse at a temperature of 35 to 45 ° C without leaving any residue.

² 9

Table 1

Example 1 2 3 4 5 6 7 8 9

C _10/13 -ABS-monoethanol- amine salt 30 30 34 34 34 34 34 - -

Ci _{2 /} ι ₄ -2EO-FAES-monoisopropanolamine salt 18 18 22.5 18 18 - - 45 45

Cι _{2 /} ι -1, 3EO-FAES-

Sodium salt - - - - 14 14 - -

Cocoamidopropyl betaine 4 - 4 2 2 2 2 2 -

Ci _{2 /} i ₆ -alkyl poly-

Glucoside (z = 1, 4) - - 2.5 2.5 2.5 2.5 2.5 5

Cocoamidopropylamine oxide 3 - - - - - - -

C _{8 /} ιo-5EO fatty alcohol ethoxylate 10 10 7.5 20 12.5 15 12.5 10 10

1, 2-propylene glycol 19 19 - - - - 10 19 19

Ethanol - 13 - - 7.5 - - -

Butoxyisopropanol - - - 5 10 - - - -

Polydiol 400 10 10 7 - 10 10 10 10 10

Polydiol 600 - - 7.5 - - - - -

Perfume 1 1 1 1 1 1 1 1 1

Water 8 9 11 10 10 14 14 10.5 10

Remarks:

Amounts in% by weight of active substance butoxyisopropanol = Dowanor ^® PnB ABS = alkylbenzenesulfonate polydiol 400 = PEG 400 FAES = fatty alcohol ether sulfate polydiol 600 = PEG 600

Claims

MOPatentansprüche

1. portion of a low-water cleaning agent from one or more enclosures) made of at least one water-soluble polymer material and at least one rinse-active preparation partially or completely surrounded by the at least one water-soluble polymer material.

2. detergent portion according to claim 1, wherein the at least one water-soluble polymer material of the enclosure (s) is selected from the group consisting of (optionally acetalized) polyvinyl alcohol, polyvinyl pyrrolidone, polyethylene oxide, gelatin, cellulose and their derivatives and Mixtures of the materials mentioned.

3. Detergent portion according to claim 1 or claim 2, wherein the at least one water-soluble polymer material of the enclosure (s) is in the form of foil bags or capsules.

4. Detergent portion according to one of claims 1 to 3, wherein the at least one water-soluble polymer material of the enclosure (s) contains one or more components (s) of the rinse-active preparation (s) incorporated.

5. detergent portion according to any one of claims 1 to 4, wherein the rinse-active preparation (s) have water contents <15 wt .-%, preferably <10 wt .-%, based on the total weight of the rinse-active preparations).

6. detergent portion according to any one of claims 1 to 5, wherein the components of the rinse-active preparation (s) are selected from the group consisting of anionic, non-ionic, cationic and amphoteric surfactants, non-aqueous carriers, enzymes, dyes , Fragrances, antibacterial agents, polymers and rinse aids. H l

7. detergent portion according to claim 6, wherein further components of the rinse-active preparation (s) are selected from the group consisting of solubilizers, UV stabilizers, defoamers, structuring agents, corrosion inhibitors, preservatives, silver preservatives and skin-protecting additives.

8. detergent portion according to any one of claims 1 to 7, wherein a rinse-active preparation is comprised of a compartment forming a compartment from a water-soluble polymer material.

9. detergent portion according to one of claims 1 to 7, wherein at least two rinse-active preparations are comprised of an at least two compartment-forming enclosure made of a water-soluble polymer material.

10. A detergent portion according to claim 8 or claim 9, wherein the compartment (s) comprises an amount of at least 1 ml of a rinse-active preparation.

11. Detergent portion according to one of claims 1 to 10 for cleaning hard surfaces.

12. Detergent portion according to one of claims 1 to 11 for manual cleaning of hard surfaces.

13. detergent portion according to one of claims 1 to 12 for washing dishes.