DE19950925A1 - Portion of detergent containing little water, used for cleaning hard surface, preferably for washing dishes by hand, comprises detergent formulation in water-soluble polymer envelope - Google Patents

Abstract

Portion of detergent containing little water comprises detergent formulation(s) (partly) enclosed in envelope(s) of water-soluble polymer(s).

Description

The present invention relates to a dishwashing detergent serving with one order frame made of a water-soluble polymer material and at least one flushing preparation.

Detergent and cleaning agents in single dose quantities are state of the art Technology known. For example, the older patent application DE 198 31 703 discloses one portioned detergent or cleaning agent preparation in a bag water-soluble film for use in washing machines or dishwashers nen, wherein at least 70 wt .-% of the particles of the preparation particle size have dimensions of <800 µm. The older patent application also describes DE 199 09 271 the production of multi-phase detergents or cleaning agents Moldings for use in machine washing or rinsing where dimensioned in this way with regard to the active substance contents are that the washing or rinsing active preparations for exactly one washing or rinse in the machine is sufficient.

Dishwashing detergent for use in the sink or in an egg ner rinsing bowl were in the prior art in liquid, regularly in with closable pouring spouts or dispensing bottles or Containers filled form provided. Advantage of such forms of filling was that the consumer dosed the dishwashing detergent freely could also refill as needed and feeling. Disadvantage of such Forms of bottling, however, was that accurate dosing of the dishes  detergents required a certain amount of experience and the detergent was often under or was overdosed. The former required regular replenishment of Ge dishwashing detergent during the washing process, again with the risk of Overdose was linked, while the latter from ecological and eco was generally undesirable for nomological reasons. Another disadvantage consisted in the fact that residues of the Dishwashing detergent remained, either on the outside of the bottle or containers ran down and unwanted residues on the bottles or containers or on the shelves or the off pourer or dosing openings blocked.

Another disadvantage of that provided in the conventional packaging Dishwashing detergent consisted of the fact that it was used according to the wishes of the consumer had to be homogeneous, especially clear. This through consumption Habits dictated that components could not be incorporated into such means that are not evenly in the ready-made dishwashing liquid was distributed or in the course of during storage or while the opened ones are left to stand Put down the bottle or the opened container.

Another problem with conventional dishwashing detergents was that kei ne components could be incorporated, their stability in position tion is impaired by other components of the dishwasher detergent. This was the reason, for example, that it worked during the rinsing process Same enzymes not in dishwashing detergents, especially not in those for the Rinsing dishes by hand, could be incorporated, since in the water problems with the stability of the enzymes in the environment of common dishwashing detergents occurred.

An object of the invention was therefore the disadvantages of the above To overcome the state of the art. In particular, it was the task of the inventor  dung, dishwashing detergent in por ready for use in a rinse cycle to provide. It was another object of the invention to dishes To provide detergents, which may include components that are common not homogeneously distributed in hand dishwashing detergents without they fail, settle or separate in any other way. A another object of the invention was dishwashing detergent for washing Ge provide dishes by hand, which may include components included in usual dishwashing detergents in the presence of individual, usually in such Components contained are not stable.

Surprisingly, it has now been found that low-water dishwashing detergent, in particular special ones for washing dishes by hand, economical in por can be packed in a dishwashing liquid preparation contain a sufficient amount for a rinse cycle may contain components in a dishwashing detergent portion, their homogeneous distribution in a large amount of the same agent in one Bottle or in a container for a long period of storage in the state of the Technology was not possible and may contain components their stability in the presence of other components of the agent is low or was at least insufficient.

The invention relates to a portion of a low-water cleaning agent one or more enclosures from at least one water-soluble Polymer material and at least one of the at least one water-soluble Chen polymer material partially or completely surrounded flush-active accessories riding. The cleaning agent is preferably a cleaning agent for cleaning hard surfaces, further preferred for manual cleaning of hard surfaces surfaces, most preferably a dishwashing detergent in the form of portions.

The term "dishwashing detergent portion" is used in the context of the invention for a process taking place in an aqueous phase  sufficient amount of detergent to clean dishes stood. This can be a mechanical cleaning process, for example, as it is done with standard dishwashers. Erfin However, according to this term, a (for example in Hand wash basin or dishwashing done in a bowl or any other process of cleaning understood. According to the invention The present detergent portions or dishes are preferred portions of detergent for manual cleaning of dishes puts. The term "dishwashing detergent portion" is used in the context of present invention ver a subset of a dish detergent serving standing in a separate portion from other detergent portions Phase in spatial connection with other portions of dishwashing detergent same dishwashing detergent portion and by appropriate measures is prepared so that it is separated from others or simultaneously with others portions of the same detergent portion into the Given rinse liquor and, if necessary, dissolved or suspended in it can. A portion of dishwashing detergent can contain the same ingredients like another dish detergent portion of the same dish detergent Portion included; however, preferably contain two dishwashing detergents Partial portions of the same dishwashing portion of different ingredients fe, in particular different rinse-active preparations.

According to the invention, the dishwasher detergent portions contain measured portions Amounts of at least one active detergent preparation, usually measured ne quantities of several rinse-active preparations. It is possible that the Portions only rinse-active preparations of a certain composition contain. According to the invention, however, it is preferred that several, usual Usually at least two, rinse-active preparations of different preparations composition in the detergent portions are included. The To The composition of the individual com components of the rinse-active preparation (quantitative) and / or with regard to Art  of the individual components of the active wash preparation (qualitative) under be different. It is particularly preferred that the components with regard to Art and concentration are adapted to the tasks that Portions have to be fulfilled in the cleaning process. The partial portions are in connection with the present invention preferably those of the same or various water-soluble materials included first, second and third or even higher (fourth, fifth, etc.) where appropriate Amounts of one or more active rinse preparation (s) that form a rice Detergent or dishwashing detergent portion are combined according to the invention.

The term "rinse-active preparation" is used in the context of the the invention preparations of all conceivable, in connection with a Process of cleaning dishes relevant substances understood. This are primarily the actual cleaning agents with their later ver individual components explained in more detail during the description. 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" also includes Reini aids understood. Examples of these are solvents, solutions Mediators, UV stabilizers, so-called soil repellents, i.e. polymers that are one Counteract re-soiling of hard surfaces, as well as silver protective means. Dishwashing liquid additives such as rinse aid are also invented appropriately considered as flushing preparations.

According to the invention, the detergent portion or dishwashing contains medium portion one or more enclosures from one or more water-soluble polymer material (ien), which the at least one rinse-active addition preparation partially or completely comprises. There is the possibility Lichity that the dishwashing detergent portion of a or  contains several water-soluble polymer material (s) or that several Inclusions are included. In the context of the present invention Presence of an enclosure is preferred, which benefits when choosing materials and also in view of the requirement that the water-soluble Dissolve the polymer material without residue in the cleaning liquor or rinsing liquor got to. The enclosure (s) can be made from a single water-soluble Polymer material or can be made from several different polymer Materials are formed. The use of multiple polymer materials is at least possible. With regard to the task at hand, he is according to the invention, the use of a single polymer material in particular preferred, which is particularly discussed below.

According to a preferred embodiment of the invention, this is the least a partially active or completely surrounding water-soluble preparation che polymer material a water-soluble packaging. Below it becomes a flat understood or spatially formed part, the at least one flushing active Preparation partially or completely surrounds. The exact form of such Packaging is not critical and can be widely used be adjusted accordingly. There are various forms, for example (such as hoses, pillows, cylinders, bottles, discs, etc.) worked Plastic films or sheets, capsules and other conceivable shapes are possible. According to the invention, particular preference is given to films which, for example, for Ver packs such as hoses, pillows or the like are glued and / or sealed can, after with partial portions of the dishwashing according to the invention medium portions or with the dishwasher detergent portions according to the invention were filled.

More preferred according to the invention due to the excellent ge desirable physical conditions adaptable properties plastic Foil packaging made of water-soluble polymer materials. Such films are generally known from the prior art.  

In principle, all polymer materials come as water-soluble polymer materials. Materials in question under the given conditions (temperature, pH value, concentration of rinse-active components) in the aqueous phase can solve constantly. The polymer materials can be particularly preferred the groups (acetalized) polyvinyl alcohol, polyvinyl pyrrolidone, polyethylene oxide, gelatin, cellulose and their derivatives and mixtures of the above Belong to materials.

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 in free form is stable, polyvinyl alcohols through polymer-analogous reactions Hydrolysis, technically in particular by alkaline-catalyzed transesterification of Polyvinyl acetates with alcohols, preferably with methanol, are obtained. By these technical processes are also accessible to PVAL, agreed residual portion of acetate groups contain ("acetalized PVAL").

Commercial PVAL (e.g. Mowiol® types from Hoechst) come as white-yellowish powder or granules with degrees of polymerization in the range of approx. 500 to 2500 (corresponding to molecular weights of approx. 20,000 to 100,000 g / mol) on the market and have different degrees of hydrolysis from 98 to 99 or 87 to 89 mol%. They are therefore partially saponified polyvinyl acetates with a residue holds on acetyl groups of about 1 to 2 or 11 to 13 mol%.

The water solubility of PVAL can be checked by post-treatment with aldehyde den (acetalization), by complexing with Ni or Cu salts or by  Reduce treatment with dichromates, boric acid, borax and so on Set the desired values. PVAL films are largely impenetrable Lich for gases such as oxygen, nitrogen, helium, hydrogen, carbon dioxide, read water vapor, however.

Examples of suitable water-soluble PVAL films are those under designation "SOLUBLON®" from Syntana Handelsgesellschaft E. Harke GmbH & Co. available PVAL films. Their solubility in water can be determined to the degree set, and there are films in this range available, all of them for the Application relevant temperature ranges are soluble in the aqueous phase.

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

PVP are produced by radical polymerization of 1-vinylpyrrolidone poses. Commercial PVPs have molar masses in the range from approx. 2500 to 750,000 g / mol and are available as white, hygroscopic powders or as aqueous Solutions offered.

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

H- (O-CH ₂ -CH ₂ ) -OH

the technically by base-catalyzed polyaddition of ethylene oxide (oxirane) in systems containing mostly small amounts of water with ethylene glycol as Starting molecule can be produced. They have molecular weights in the range of approx. 200 up to 5,000,000 g / mol, corresponding to degrees of polymerization n of  approx. 5 to <100,000. Polyethylene oxides have an extremely low concentration reactive hydroxy end groups and only show weak glycol Characteristics.

Gelatin is a polypeptide (molecular weight: approx. 15,000 to <250,000 g / mol) that before conveniently by hydrolysis of the contained in animal skin and bones Collagen is obtained under acidic or alkaline conditions. The Amino acid composition of the gelatin largely corresponds to that of Collagen from which it was obtained and varies depending on the provenance. The use of gelatin as a water-soluble covering material is especially in pharmacy in the form of hard or soft gelatine cape extremely widespread. Gelatine is found in the form of foils because of its im Only low compared to the high-cost polymers mentioned above Use.

Dishwasher detergents are also preferred in the context of the present invention. Portions, the packaging of which consists of water-soluble film of at least one Polymer from the group starch and starch derivatives, cellulose and cellulose de derivatives, especially methyl cellulose and mixtures thereof.

Starch is a homoglycan, the glucose units ver. Α-glycosidic are knotted. Starch is made up of two components with different molecular weights weight built up: from approx. 20 to 30% straight-chain amylose (MW. approx. 50,000 up to 150,000) and 70 to 80% branched chain amylopectin (MW. approx. 300,000 up to 2,000,000). There are also small amounts of lipids, phosphoric acid and Cations included. During the amylose due to the binding in the 1,4-position long, helical, intertwined chains with about 300 to 1200 gluco forms se molecules, the chain branches through in amylopectin on average 25 glucose building blocks through 1,6 binding to a knot-like one Formations with about 1,500 to 12,000 molecules of glucose. In addition to pure strength are for the production of water-soluble enclosures of the cleaning or Ge  Dishwasher detergent portions in the context of the present invention also starch Derivatives obtainable from starch by polymer-analogous reactions. Sol chemically modified starches include products, for example from esterifications or etherifications in which hydroxy hydrogen atoms were substituted. But also strengths in which the hydroxy groups are against functional groups that are not linked via an oxygen atom are replaced were used as starch derivatives. In the group of strength Derivatives fall, for example, alkali starches, carboxymethyl starch (CMS), starch keester and ether as well as amino starches.

Pure cellulose has the formal gross composition (C ₆ H ₁₀ O ₅ ) _n and, formally speaking, is a β-1,4-polyacetal of cellobiose, which in turn is made up of two molecules of glucose. Suitable celluloses consist of approximately 500 to 5000 glucose units and therefore have average molecular weights of 50,000 to 500,000. Cellulose-based disintegrants which can be used in the context of the present invention are also cellulose derivatives which can be obtained from cellulose by polymer-analogous reactions. Such chemically modified celluloses include, for example, products from esterifications or etherifications in which hydroxyl hydrogen atoms have been substituted. However, celluloses in which the hydroxy 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, car boxymethyl cellulose (CMC), cellulose esters and ethers and aminocelluloses.

Preferred enclosures made of water-soluble film consist of a poly mer with a molecular weight between 5000 and 500,000 daltons, preferably between between 7,500 and 250,000 Daltons and especially between 10,000 and 100,000 daltons. The water-soluble film that forms the border has übli chichlich a thickness of 1 to 150 microns, preferably from 2 to 100 microns, be particularly preferably from 5 to 75 μm and in particular from 10 to 50 μm.  

These water-soluble films can be made using various manufacturing processes getting produced. In principle, blowing, calendering and casting processes are closed here call. In a preferred method, the foils are starting out blown from a melt with air over a blow mandrel to a hose. In the calendering process, which is also one of the preferred ones Manufacturing processes are heard, the plasticized by suitable additives Raw materials for forming the films are atomized. Here it can be especially be necessary to connect a drying to the atomization. In which Casting process, which is also one of the preferred manufacturing processes an aqueous polymer preparation placed on a heatable drying roller, after the water has evaporated, cooling is optional and the film as a film deducted. If necessary, this film is before or during the peeling additionally powdered.

Capsules as enclosures for the rinse-active preparation (s) of the invention according to dishwashing detergent portion are also from the state of the Technically known processes are produced and can preferably from (given if necessary acetalized) PVAL or from gelatin, for example soft gelatin or hard gelatin.

It corresponds to a preferred embodiment of the invention that the one or more enclosures (s) for the rinse-active preparation (s) water-soluble PVAL film at a certain temperature. Such a film can advantageously by gluing, for example with a water-soluble adhesive, or by heat sealing to enclosures for flushing active Preparations are processed. The advantage of such a foil solution is that it is accurate with respect to the desired temperature has adjustable water solubility and changes when entering the rinsing or Cleaning liquor dissolves quickly and residue-free, leaving the film included (s) active (s) preparation (s) quickly in the rinsing or cleaning fleet will be released. This is especially the case with manual rinsing or cleaning  of dishes is important because - in contrast to machine dishwashing - mechanical movement of the fleet does not take place automatically, but from Consumers should be brought about.

In a still further preferred embodiment of the invention, this contains at least one water-soluble polymer material enclosing one or several components of the rinse-active preparation (s) incorporated. This Concept is the subject of the older patent application DE 199 29 098.9, according to the certain additives of purging active preparations, especially individual com components that control the effectiveness of the rinse-active preparation or also increase their consumer acceptance, entirely or predominantly in the water soluble polymer material of the enclosure are physically incorporated. According to the invention, such components can be incorporated into the polymer material the enclosure (s) may be incorporated, for example UV Protective substances, dyes, fragrances, antibacterial agents, polymers such as for example a soil repellent polymer, corrosion inhibitors or bitters substances (the latter can prevent unauthorized persons, for example children, from Put the embrace (s) in your mouth) without referring to these examples to be restricted. As long as the important features of the enclosure like theirs mechanical stability (even over long periods) and their complete water solubility can not be adversely affected, one or more such additive (s) in any combination and amount in the polymer Material incorporated. Preferred amounts are 0.1 to 10% by weight of the additive, based on the total weight of the film or capsule material than, even more preferably 1 to 7% by weight, very particularly preferably 3 up to 6% by weight.

In view of the fact that as the enclosure (s) of the active preparation device (s) at least one polymer material is used, the essential Properties the solubility in the aqueous medium used for rinsing To include, it is an essential feature of the present invention that  the rinse-active preparation (s) of the dishwashing detergent according to the invention Portion are low in water. It is understood by "low water" that the Ge Dishwasher detergent portion in all its components as little free (and thus water capable of reaction with the material of the enclosure (s) contains. The rinse-active preparation (s) preferably have water keep from less than 15 wt .-%, based on the total weight of the flushing preparation (s), more preferably water content of less than 10% by weight.

In a preferred embodiment of the invention, the components of the flushing preparation (s) selected from the group consisting of anioni , non-ionic, cationic and amphoteric surfactants, non-aqueous Carriers, enzymes, dyes, fragrances, antibacterial agents, polymers and rinse aid, the amounts given each based on the Ge Obtain the total weight of the active wash (s).

Substances that also serve as ingredients of cosmetic products are referred to below in accordance with the International Nomenclature Cosmetic Ingredient (INCI) nomenclature. Chemical compounds have an INCI name in English, herbal ingredients are only listed according to Linné in Latin. So-called tri-vial names such as "water", "honey" or "sea salt" are also given in Latin. The INCI designations can be found in the "International Cosmetic Ingredient Dictionary and Handbook, Seventh Edition (1997)" by The Cosmetic, Toiletry and Fragrance Association (CTFA), 1101, 17 ^th Street NW, Suite 300, Washington, DC 20036, USA, and contains 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 assigns the ingredients one or more chemical classes (Chemical Classes), for example "Polymeric Ethers", and one or more functions (Functions), for example "Surfactants - Cleansing Agents", which in turn gives it a closer look explained. This will also be referred to below where appropriate.

To develop a good cleaning performance when washing, the inventors portions of surface-active substances according to the invention from the group of anionic, nonionic, cationic or amphoteric or zwitterionic surfactants. Anionic surfactants are from eco mix reasons and especially because of their range of services moves. Surfactants from the individual groups can be used as individual substances become. It is preferred to use mixtures of surfactants, advantageously mixtures tensides 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, Mo noglyceride sulfates and aliphatic and aromatic sulfonates such as alkane sulfo nates, olefin sulfonates, ether sulfonates, n-alkyl ether sulfonates, ester sulfonates, Lingninsulfonate and alkylbenzenesulfonates. Also within the framework of the Fatty acid cyanamides, sulfosuccinic acid can be used according to the invention reesters, fatty acid isothionates, acylaminoalkanesulfonates (fatty acid taurides), fat acid sarcosinates, ether carboxylic acids and alkyl (ether) phosphates.

The 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 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 prepared on a petrochemical basis and which have a degradation behavior analogous to that of the adequate compounds based on oleochemical raw materials. The C ₁₂ -C ₁₅ alkyl sulfates and C ₁₂ -C ₁₅ alkyl sulfates and C ₁₄ -C ₁₅ alkyl sulfates are preferred prior to washing technology. Suitable secondary alkyl sulfates contain 2- and / or 3-alkyl sulfates and optionally higher homologues (4-, 5-, 6-alkyl sulfates etc.), can be produced for example according to US Pat. Nos. 3,234,258 or 5,075,041 and are commercially available from Shell Oil Company 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 C ₁₄ -SAS with 99% 2- and 3-alkyl sulfate, DAN® 216, a C ₁₆ -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 alk alkylated 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 the straight-chain or branched alcohols with chain lengths of C ₇ to C ₂₁ such as 2- Methyl-branched C ₉ to C ₁₁ fatty alcohols with an average of 3.5 EO or the C ₁₂ to C ₁₈ 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.

Suitable surfactants of the sulfonate type are preferably alkylbenzenesulfonates, olefin sulfonates, ie mixtures of alkene and hydroxyalkanesulfonates and disulfonates, as obtained, for example, from C ₁₂ -C ₁₈ monoolefins with an end or internal double bond by sulfonating 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 C _6-22- alkyl radicals, preferably C _8-18 -alkyl radicals, in particular C _9-14- alkyl radicals, very preferably C _10-13 -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 trialkanolammonium salts, preferably mono-, di- or triethanol and / or -isopropanolammonium salts, especially mono-, di- or triethanolammonium salts, but also used as alkyl benzenesulfonic 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 monoethanolammoniumalkylbenzenesulfonate, in quantities 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 alkyl benzenesulfonates. 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 obtained from C _12-18 alkanes, for example by sulfochlorination or sulfoxidation with subsequent hydrolysis or neutralization. Likewise, the esters of 2-sulfo fatty acids (ester sulfonates), e.g. B. the 2-sulfonated methyl esters of hydrogenated coconut, palm kernel or tallow fatty acids.

The anionic surfactants are preferred in amounts between 0.2 and 80 wt .-% used, preferably in amounts of 10 to 70 wt .-%, esp more preferably 25 to 60% by weight, most preferably 40 to 60% by weight.  

Particularly suitable surfactant mixtures are those from anionic in combination nation with one or more nonionic surfactants or betaine surfactants, the betaine surfactants in this connection with the class of ampho tere tensides are to be equated. Also the joint additional effort of nonionic surfactants and betaine surfactants in a mixture can be used for many Applications can be beneficial.

Nonionic surfactants in the context of the present invention can alkoxy be late, such as polyglycol ether, fatty alcohol polyglycol ether, alkylphenol polygly kolether, end-capped polyglycol ethers, mixed ethers and hydroxy mixed ether and fatty acid polyglycol ester. Ethy can also be used lenoxide, propylene oxide, block polymers and fatty acid alkanolamides and fatty acid repolyglycol ether. An important class of nonionic surfactants can be used according to, are the polyol surfactants and especially those Glycosurfactants such as alkyl polyglycosides and fatty acid glucamides. Especially be the alkyl polyglucosides are 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 radical is linear or - before, are preferably used as nonionic surfactants pulls in the 2-position - may be methyl-branched or may contain linear and methyl-branched radicals in the mixture, as are usually present in oxo alcohol radicals. In particular, however, alcohol ethoxylates with linear residues from alcohols of native origin with 12 to 18 carbon atoms, for. B. from coconut, palm, tallow or oleyl alcohol, and an average of 2 to 8 EO per mole of alcohol preferred. The preferred ethoxylated alcohols include, for example, C _12-14 alcohols with 3 EO or 4 EO, C _9-11 alcohol with 7 EO, C _13-15 alcohols with 3 EO, 5 EO, 7 EO or 8 EO, C _12-18 alcohols with 3 EO, 5 EO or 7 EO and mixtures thereof, and 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 preferred non-ionic surfactants, which either which as the sole non-ionic surfactant or in combination with other non- Ionic surfactants are used are alkoxylated, preferably ethoxy lated 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 for example in the Japanese patent application JP 58/217598 be are written or which are preferably according to the international Pa The method described in WO-A-90/13533 can be produced.

Another class of nonionic surfactants that can be used advantageously are the alkyl polyglycosides (APG). Alkyl polyglycosides are tensides which can be obtained by the reaction of sugars and alcohols according to the relevant methods of preparative organic chemistry, where, depending on the type of production, a mixture of monoalkylated, oligomeric or polymeric sugars occurs. 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 C ₈ and C ₁₈ 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 represents 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 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 Al, are particularly preferably used kylpolyglucoside, in amounts between 0.1 to 15.0 wt .-%, preferably in men gen from 0.2 to 10.0 wt .-%, 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.

Also nonionic surfactants of the amine oxide and fat types Acid alkanolamides may be suitable. The amount of this nonionic Surfactants is preferably not more than that of the ethoxylated fatty alcohols, especially not more than half of them.

The amine oxides suitable according to the invention include alkylamine oxides, in particular alkyldimethylamine oxides, alkylamidoamine oxides and alkoxyalkyl amine 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 C _8-18 alkyl radical, in particular a saturated C _10-16 alkyl radical, for example, a saturated C _12-14 alkyl radical, which is bonded to the nitrogen atom N in the alkylamidoamine oxides via a carbonylamidoal kylene group -CO-NH- (CH ₂ ) _z - and in the alkoxyalkylamine oxides via an oxaalkylene group -O- (CH ₂ ) _z is, 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 independently of one another are an optionally hydroxy-substituted C _1-4 -alkyl radical such as, for. B. is a hydroxyethyl radical, in particular a methyl radical.

Examples of suitable amine oxides are the following named according to INCI compounds: Almondamidopropylamine oxides, Babassuamidopropylamine oxides, Behenamine oxides, Cocamidopropyl Amine Oxide, Cocamidopropylami ne oxides, Cocamine Oxide, Coco-Morpholine Oxide, Decylamine Oxide, De cyltetradecylamine oxides, Diaminopyrimidine Oxide, Dihydroxyethyl C _{8- 10} alk oxypropylamine oxides, dihydroxyethyl C _9-11 alkoxypropylamine oxides, dihydroxyethyl C _12-15 alkoxypropylamine oxides, dihydroxyethyl cocamine oxides, dihydroxyethyl lauramine oxides, dihydroxyethyl stearamine oxides, dihydroxyethyl tallowamine oxides, hydrogenated palm kernel amine oxides oxides, hy d Hydroxyethyl hydroxypropyl C _12-15 alkoxy propylamine oxides, isostearamidopropylamine oxides, isostearamidopropyl morpholine oxides, lauramidopropylamine oxides, lauramine oxides, methyl morpholine oxides, milkamidopropyl amine oxides, minkamidopropylamine oxides, myristamidopropylamine oxides, myristamine oxides, myristamines oxides, myristamines oxides, myristamines oxides l Amine Oxide, Oleamidopropylamine Oxide, Oleamine Oxide, Olivamidopropylamine Oxide, Palmitamidopropylamine Oxide, Palmitamine Oxide, PEG-3 Lauramine Oxide, Potassium Dihydroxyethyl Cocamine Oxide Phosphate, Potassium Trisphosphonomethylamine Oxide, Sesamidopropylamine Oxide, Soyamido Stearylamine Amide Oxamine Oxide, Amine Oxamine Oxide, Amylopropylamine Oxide Oxides, Tallowamine Oxide, Undecylenamidopropylamine Oxide and Wheat Germamidopropylamine Oxide. 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 (cocoamidopropylamine oxide), in particular other cocamidopropylamine oxides.

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

in the 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)

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] representing a linear polyhydroxyalkyl radical whose alkyl chain is substituted by at least two hydroxyl groups, or alkoxylated, preferably ethoxylated or propoxylated derivatives of this residue.

[Z] is preferably obtained by reductive amination of a reduced sugar obtained, for example glucose, fructose, maltose, lactose, galactose, Man nose or xylose. The N-alkoxy or N-aryloxy substituted compounds can then, for example, after teaching the international application WO-A-95/07331 by reaction with fatty acid methyl esters in the presence of a Alkoxide as a catalyst in the desired polyhydroxy fatty acid amides leads.

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

To the zwitterionic surfactants or amphoteric surfactants, the fiction can be used according to include betaines and alkylamidoalkyl  amines (INCI alkylamido alkylamines) as well as the alkyl-substituted amines nonacids (INCI alkyl-substituted amino acids), especially aminopropio nate, the acylated amino acids and the biosurfactants. A preferred content The substance is betaine, especially alkyl amido betaine.

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

R ¹ [CO-X- (CH ₂ ) _n ] _x -N ⁺ (R ² ) (R ³ ) - (CH ₂ ) _m - [CH (OH) -CH ₂ ] _y -Y ^- (III)

in the
R ^{1 is} a saturated or unsaturated C _6-22 alkyl radical, preferably C _8-18 alkyl radical, in particular a saturated C _10-16 alkyl radical, for example a saturated C _12-14 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 independently of one another are an optionally hydroxy-substituted C _1-4 alkyl radical such as, for. B. are a hydroxyethyl radical, but especially 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 ) O or P (O) (OR ⁵ ) O, where R ^{5 is} a hydrogen atom H or a C _1-4 alkyl radical.

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 alkylbetaines of the formula (IIIa), the alkylamido betaines of the formula (IIIb), the sulfobetaines of the formula (IIIc) and the amido sulfobetaines of the formula (IIId),

R ¹ -N ⁺ (CH ₃ ) ₂ -CH ₂ COO ^- (IIIa)
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 SO ₃ ^- (IIId)

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

Particularly preferred amphoteric surfactants are the carbobetaines, especially those Carbobetaines of the formulas (IIIa) and (IIIb), most preferably the alkylamido betaine of formula (IIIb).

Examples of suitable betaines and sulfobetaines are the following according to INCI designated compounds: Almondamidopropyl Betaine, Apricotamidopropyl Betaine, avocadamidopropyl betaine, babassuamidopropyl betaine, behen amidopropyl betaine, behenyl betaine, betaine, canolamidopropyl betaine, Capryl / Capramidopropyl Betaine, Carnitine, Cetyl Betaine, Cocamidoethyl Be taine, cocamidopropyl betaine, cocamidopropyl hydroxysultaine, coco Betaines, coco-hydroxysultaine, coco / oleamidopropyl betaines, coco-sultaine, Decyl betaine, dihydroxyethyl oleyl glycinate, dihydroxyethyl soy glycinate, Dihydroxyethyl Stearyl Glycinate, Dihydroxyethyl Tallow Glycinate, Dimethicone Propyl PG betaines, erucamidopropyl hydroxysultaine, hydrogenated tallow Betaines, isostearamidopropyl betaines, lauramidopropyl betaines, lauryl betai ne, Lauryl Hydroxysultaine, Lauryl Sultaine, Milkamidopropyl Betaine, Minkami dopropyl betaines, myristamidopropyl betaines, myristyl betaines, oleamidopropyl Betaine, oleamidopropyl hydroxysultaine, oleyl betaine, olivamidopropyl Be taine, palmamidopropyl betaine, palmitamidopropyl betaine, palmitoyl carniti ne, Palm Kernelamidopropyl Betaine, Polytetrafluoroethylene Acetoxypropyl Betaines, ricinoleamidopropyl betaines, sesamidopropyl betaines, soyamidopro pyl betaine, stearamidopropyl betaine, stearyl betaine, tallowamidopropyl Betaine, Tallowamidopropyl Hydroxysultaine, Tallow Betaine, Tallow Dihydr oxyethyl betaines, undecylenamidopropyl betaines and wheat germamidopropyl  Betaine. A preferred betaine is, for example, cocamidopropyl betaine (Cocoamidopropyl betaine).

These amphoteric surfactants are preferred 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 dishwasher contains medium portion as a surfactant mixture (a) 0.2 to 80 wt .-%, 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 alkylbenes zolsulfonate (e) and / or fatty alcohol ether sulfate (e), (b) 1 to 80 wt .-%, before 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), ins special alcohol alkoxylate (s) or combinations of alcohol alkoxylate (s) with Alkyl polyglycoside (s) and / or amine oxide (s), and (c) 0.1 to 14.9% by weight, be preferably 0.5 to 8% by weight and particularly preferably 1 to 6% by weight, one or several betaine surfactants, preferably alkyl amido betaines.

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

The non-aqueous carrier (s) serve (i) as a filling component for filling len of the other components of the rinse-active preparation (s) to the ge Desired portion amount, (ii) to control the flowability or the flow  behavior, especially the viscosity, of the rinse-active preparation (s), (iii) to control the solubility or solubility behavior, in particular the Dissolving speed of the rinse-active preparation (s) in aqueous media and / or (iv) as a solvent or solubilizer (hydrotrope) for ex other components of the rinse-active preparation (s).

Suitable non-aqueous carriers are, for example, solvents and polyalky lenglycols. In the context of the teaching according to the invention under Polyalky lenglycols understood 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-O-C" and / or one or more Ether groups "C-O-C", preferably one or more hydroxyl groups or one or more hydroxy groups and one or more ether groups.

In particular, solvents are used in the context of the invention non-aqueous carrier component as a hydrotrope, viscosity regulator and / or cold stabilizer used. They have a solubilizing effect in particular for surfactants as well as perfume / fragrance and dye and thus contribute to them Incorporation, prevent the formation of liquid-crystalline phases and ha ben share in the formation of clear products. The viscosity decreases with too increasing amount of solvent. Finally, the solution decreases with increasing average amount of cold cloud and clear point.

Particularly preferred solvents are, for example, saturated or unsaturated, preferably saturated, branched or unbranched C _1-20 hydrocarbons, preferably C _2-15 hydrocarbons, with at least one hydroxyl group and optionally one or more ether functions COC, ie oxygen atoms interrupting the carbon atom chain, wherein without interruption by an ether function not more than 8, preferably not more than 6, in particular not more than 4, carbon atoms are connected to one another.

These include the C _2-6 alkylene glycols and poly-C _2-3 alkylene glycol ethers with an average of 1 to 9, preferably 2 to 3, the same or different, preferably the same, alkylene glycol groups, optionally etherified on one side with a C _1-6 alkanol per molecule, in particular 1,2-propylene glycol, as well as the C _1-6 alcohols, preferably ethanol, n-propanol or iso-propanol (2-propanol), in particular ethanol, and glycerol.

Exemplary solvents are the following compound named according to INCI : Alcohol (ethanol), buteth-3, butoxyethanol, butoxypropanol, n-butyl Alcohol, t-butyl alcohol, butylene glycol, butyl octanol, diethylene glycol, di methoxydiglycol, dimethyl ether, dipropylene glycol, ethoxydiglycol, Ethoxyethanol, ethyl hexanediol, glycol (ethylene glycol), hexanediol, 1,2,6- Hexanetriol, hexyl alcohol, hexylene glycol, isobutoxypropanol, isopentyl diol, Isopropyl alcohol (iso-propanol), 3-methoxybutanol, methoxyethanol, methoxy methylbutanol, methoxy PEG-10, methylal, methyl alcohol, methyl hexyl ether, Methyl propanediol, neopentyl glycol, PEG-6 methyl ether, pentylene glycol, PPG-2-buteth-3, propanediol, propyl alcohol (n-propanol), propylene glycol, Propylene glycol butyl ether, tetrahydrofurfuryl alcohol, trimethylhexanol.

Particularly preferred solvents are also those with C _1-6 aliphatic or aromatic alcohols, e.g. As methanol, ethanol, n-propanol, n-butanol, tert-butanol or phenol, etherified or with carboxylic acids, for. B. acetic or carbonic acid, esterified monomeric or homo- or heteropolymeric, in particular monomeric and homodi- and trimers, C ₂ -C ₄ alkylene glycols, for example the under the trade name Dowanol® from Dow Chemical and the under the trade names Arcosolv® and Arconate® from Arco Chemical and subsequently referred to by their INCI name, e.g. B. Butoxydiglycol (Dowanol® DB), Methoxydiglycol (Dowanol® DM), PPG-2 Methyl Ether (Dowanol® DPM), PPG-2 Methyl Ether Acetate (Dowanol® DPMA), PPG-2 Butyl Ether (Dowanol® DPnB), PPG-2 Propyl Ether (Dowanol® DPnP), Butoxyethanol (Dowanol® EB), Phenoxyethanol (Dowanol® EPh), Methoxyisopropanol (Dowanol® PM), PPG-1 Methyl Ether Acetate (Dowanol® PMA), Butoxyisopropanol (Dowanol® PnB ), Propylene Glycol Propyl Ether (Do wanol® PnP), Phenoxyisopropanol (Dowanol® PPh), PPG-3 Methyl Ether (Do wanol® TPM) and PPG-3 Butyl Ether (Dowanol® TPnB) as well as Ethoxyisopropa nol (Arcosolv® PE) , tert-butoxyisopropanol (Arcosolv® PTB), PPG-2 tert-butyl ether (Arcosolv® DPTB) and propylene carbonate (Arconate® PG), especially butoxyisopropanol (Dowanol® PnB).

Solvents are preferred in an amount of 0.1 to 80% by weight preferably 1 to 50% by weight, in particular 5 to 40% by weight, especially before added 7 to 30 wt .-%, most preferably 10 to 20 wt .-%, used.

Polyalkylene glycols (polyglycols, polyglycol ethers; INCI Chemical Class: Polyme ric ethers) are well-known, predominantly linear, e.g. T. but also branched bottom lyethers, which are polymers with terminal hydroxyl groups acts. The higher molecular weight polyalkylene glycols are polymolecular, d. H. they consist of groups of macromolecules with different Molar masses.

Preferred polyalkylene glycols are liquid and at room temperature (20 ° C.) preferably have a melting point of not more than 20 ° C, especially not above 15 ° C, particularly preferably not above 10 ° C and extremely preferred not above 5 ° C or even not even above 0 ° C. Under the enamel the temperature at the transition point from the fixed to the rivers becomes the point understood condition. The melting point of a particular polyalky If not mentioned below, lenglykols is mostly known from the literature or routinely according to one of the usual methods for melting point determination to investigate.  

The molecular weights of the polyalkylene glycols are preferably in the range of 200 to 5,000, in particular from 300 to 4,000, particularly preferably from 400 to 3,000 and most preferably from 500 to 2,000. The following described Various polyalkylene glycols can still be used in certain areas be particularly advantageous.

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

Poryethylene glycols (PEG) with an average are preferred according to the invention relative molecular weight up to about 4,000. PEG with molecular weights above Finally, 4,000 are no longer liquid and therefore according to the invention less suitable. The molecular weights of the polyethylene are extremely preferred lenglycols not only not more than 2,000 but even up to 1,500, in particular especially only up to 1,000 or even up to 800, for example 400 or 600. Various nomenclatures exist for polyethylene glycols Can cause confusion. The specification of the average is technically common relative molecular weight following the indication "PEG", so that "PEG 200 "a polyethylene glycol with a relative molecular weight of approx. 190 to approx. 210 characterized. According to the INCI nomenclature, the abbreviation PEG with a Hyphen and immediately follows the hyphen a number, that of the number n in the general formula above corresponds. Commercially available poly ethylene 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 separated by the character "/" ne are placed side by side. The commercially available polyethylene glycols are for example under the trade names Carbowax® (Union Carbide), Emkapol® and Renex® PEG (ICI), Lipoxol® (DEA), Polyglykol® E (Dow), Pluracol® E, Pluri ol® E and Lutrol® E (BASF) and polydiol (Cognis) available. The company too Clariant sells polyethylene glycols. Sources of supply for the also as kosmeti Ingredients are polyethylene glycols designated according to INCI can be found in the International Cosmetic Ingredient Dictionary and Handbook.

Polypropylene glycols (PPG) are available over a wide range of molecular weights 250 (PPG-4) to 4,000 (PPG-69) clear, almost colorless liquids, for their The INCI nomenclature described above is used analogously. So the polypropylene glycols of the above general formula with values n of 5 and 6 respectively referred to as PEG-5 and PEG-6. The low molecular weight poly propylene glycols are miscible with water, while the higher molecular weight Ver treads are less soluble in water. For example, the according to INCI designated polypropylene glycols PPG-7, PPG-9, PPG-12, PPG-13, PPG-15, PPG-17, PPG-20, PPG-26, PPG-30, PPG-33, PPG-34, PPG-51 and PPG-69. Sources of supply are the International Cosmetic Ingredient Dictio nary and handbook.

The copolymers are preferably statistical copolymers re and in particular block copolymers of ethylene and propylene oxide, Ethylene oxide and tetrahydrofuran, propylene oxide and tetrahydrofuran or ethyl lenoxide, propylene oxide and tetrahydrofuran, preferably from ethylene and propy lenoxid, particularly preferably around block copolymers of ethylene and propylene oxide. The molecular weights of the copolymers are extremely preferably not just how previously mentioned at least 500 but even at least about 1,000.  

Statistical copolymers of a ethylene and b preferred according to the invention Propylene oxide units are, for example, the following according to International Cos Metic Ingredient Dictionary and Handbook Co called PEG / PPG-a / b polymeric (molecular weight), where a and b represent mean values: PEG / PPG-18/4 Copolymer (1000), PEG / PPG-17/6 Copolymer (1100), PEG / PPG-35/9 Copoly mer (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) _x (CH (CH ₃ ) CH ₂ O) _y (CH ₂ CH ₂ O) _{x '} H in which x and x' for mean values of 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 polypro glycol block obtained being bordered by subsequent addition of ethylene oxide by two poly ethylene glycol blocks. Particularly preferred block copolymers are, for example, the following liquid poloxamer types (x, y, x '; molecular weight; in some cases 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), Poloxa mer 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 mer nomenclature and gives the preceding one or two-digit numbers multiplied by 300 the approximate molar mass of the polypropylene glycol portion or multiplied by 3 roughly that from the first two digits of the Poloxamomomenclature 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 CH ₂ O) _x (CH ₂ CH (CH ₃ ) O) _y'H . Here a polyethylene glycol block framed by two polypropylene glycol blocks, while in the case of 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 subsequent addition of propylene oxide by two polypropylene glycol blocks. These block copolymers, such as the poloxamers, are commercially available under the trade name Pluronic® (BASF), which is followed by an alphanumeric code consisting of three digits and the letter R between the second and third digits. The meaning of the digits is identical to the meaning in the context of the Poloxamer mer nomenclature. The inserted letter R (for English reverse) indicates the inverted structure compared to the poloxamers. Preferred representatives of this class are the following Pluronic® types (molar mass; melting point): Pluronic® 10R5 (1950; 15), Pluronic® 12R3 (1800; -20), Pluro nic® 17R1 (1900; -27), Pluronic® 17R2 (2150; -25), Pluronic® 17R4 (2650; 18), Pluronic® 25R1 (2700; -5), Pluronic® 25R2 (3100; -5), Pluronic® 31R1 (3250; -25) and Pluronic® 31R2 (3300; 9).

Polyalkylene glycols are preferred in an amount of 0.1 to 80 wt .-%, preferably 1 to 40% by weight, in particular 3 to 25% by weight, particularly be preferably 5 to 15 wt .-%, most preferably 7 to 10 wt .-%, used.

Non-aqueous vehicles are preferred in a total amount 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, extremely preferably 20 to 30 wt .-%, used.

In a particular embodiment, at least two are non-aqueous Carrier used, in particular at least one solvent and at least a polyalkylene glycol, preferably in a weight ratio of solution agent (s) for 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 rinsing process, especially for residues difficult to remove, the Ge according to the invention Dishwasher detergent servings contain enzymes. Such come out as enzymes the class of proteases, lipases, amylases, cellulases or their mixtures questionable. From bacterial strains or fungi, such as Bacillus subtilis, Bacillus licheniformis and Streptomyces griseus ne enzymatic agents. Proteases from subtilisin are preferably Type and in particular proteases obtained from Bacillus lentus, used. Enzyme mixtures, for example of protease and Amylase or protease and lipase or protease and cellulase or from Cel lulase and lipase or from protease, amylase and lipase or protease, Lipa se and cellulase, but especially cellulase-containing mixtures of be  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 prevent them from premature decomposition protect tongue. The enzymes are further preferred for use among Manual rinsing conditions optimized, for example, what the tempe rature of the flushing process. The proportion of enzymes, enzyme mixtures or Enzyme granules in the dishwasher detergent portions according to the invention for example about 0.1 to 5% by weight, preferably 0.1 to about 2% by weight be.

According to the state of the art, enzymes are Preparations added, primarily detergent preparations such as Machine dishwashing detergent used for the main wash cycle of a dishwasher machine are determined. The disadvantage was that there were always problems the stability of the enzymes occurred in the strongly alkaline aqueous environment. With The dishwasher detergent portions according to the invention can contain enzymes also to be used in the manual rinsing process and thus the cleaning we Enzymes are also used to remove dirt from the wash ware to use in manual dishwashing. The enzyme-containing component of a flushing preparation can be in one of the other components or by other components of the flushing active which are harmful to the enzyme action preparation (s) separate form from an enclosure from a water-soluble Chen polymer material are included, which also increases the enzyme activity longer storage is preserved.

Another group of additives preferred according to the invention is color substances, in particular water-soluble or water-dispersible dyes. Be Dyes are preferred here as they improve the optical product appearance in cleaning agents are usually used. The selection Such dyes pose no difficulties for the person skilled in the art, in particular because such conventional dyes have a long shelf life and insensitivity  sensitivity to the other ingredients of the active detergent preparations and have against light. The dyes are according to the invention in the dishes detergent portions in amounts of less than 0.01% by weight.

Fragrances are added to the dishwasher detergent portions according to the invention to improve the overall aesthetic impression of the products and the consumer in addition to the technical performance (good washing result) to provide a sensorially typical and distinctive product. Individual fragrance compounds can be used as perfume oils or fragrances are used, for example synthetic products of the ester type, Ethers, aldehydes, ketones, alcohols and hydrocarbons. Fragrance Compounds of the ester type are, for example, benzyl acetate, phenoxy ethyl isobutyrate, p-t-butylcyclohexyl acetate, linalyl acetate, dimethylbenzyl carbinyl acetate, phenyl ethyl acetate, linalyl benzoate, benzyl formate, ethyl methyl phenylglycinate, allylcyclohexylpropionate, styrallylpropionate and benzyl salicylate. The ethers include, for example, benzyl ethyl ether. Tough to the aldehydes len z. 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 and Phe nylethyl alcohol and terpineol. The main hydrocarbons include Lich terpenes like limes and pinene. Mixtures are preferred whose odoriferous substances are used, which are coordinated so that they ge together create an appealing fragrance. Such perfume oils can also contain natural fragrance mixtures, such as those from vegetable sources len are accessible. Examples are pine, citrus, jasmine, patchouli, rose or ylang-ylang oil. 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 up to 2% by weight entire dish detergent serving.

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

The perfumes and fragrances can basically in each of the portions (active detergent preparations) of the dishwashing detergent according to the invention Servings included. However, it is particularly preferred that they are in a Dishwashing detergent portion are included, the ingredients of which are not uncommon desirably rea with these components with decomposition or degradation yaw.

The dishwasher detergent portions can be used as further additives according to the invention also contain polymers, for example polymers that stick to hard surfaces (at for example on porcelain and glass), the oil and fat washability of these areas positively influence and thus a re-contamination counteract them in a targeted manner (so-called soil repellents). This effect becomes special clearly if a hard object (porcelain, glass) is soiled, that already several times with a dishwasher according to the invention medium containing this oil and fat-dissolving component has been washed. To the preferred oil and fat dissolving components include, for example non-ionic cellulose ethers such as methyl cellulose and methyl hydroxypropylcel  lulose with a proportion of methoxy groups of 15 to 30 wt .-% and Hy droxypropoxy groups of 1 to 15 wt .-%, each based on the nonio African cellulose ether, as well as the poly known from the prior art mers of phthalic acid and / or terephthalic acid or their derivatives, in particular polymers of ethylene terephthalates and / or polyethylene glycol Kolterephthalaten or anionically and / or nonionically modified derivatives of these. Of these, the sulfonated derivatives of are particularly preferred Phthalic acid and terephthalic acid polymers.

Other conceivable components of the flushing preparations in the inventions Dishwasher detergent portions according to the invention can be preferred Embodiment be antibacterial or bacteriostatic agents. As such come individually or in a suitable combination in Fra ge: triclosan (2,4,4'-trichloro-2'-hydroxydiphenyl ether), chloramine-T (toluenesul fonic acid chloramide sodium salt), Germall® 115 (imidazolidinyl urea), natri reformate, 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, as well as natural or nature-identical plants zen extracts such as B. Extracts from orange peel, pine oil, geraniol and nerol. When using the aforementioned salts of benzoic acid or carbon Acids come primarily from sodium, potassium, magnesium and calcium salts ze into consideration.

The dishwasher detergent portions can be in a further preferred embodiment Form one or more additional component (s) containing the chosen one are from the group consisting of solubilizers, UV stabilizers, Defoamers, structuring agents, corrosion inhibitors, preservatives agents, silver protection agents and skin-friendly additives.

There are advantages with regard to the clarity of the products - especially with high surfactant-containing mixtures - if one or more of the formulation  Other dicarboxylic acids and / or their salts, alone or in a mixture, are preferred as a composition of sodium salts of adipine, amber and Glutaric acid. Such a composition is e.g. B. under the Han Sokalan® DSC Na available. Has proven to be particularly favorable the use of 0.1 to 8 wt .-%, preferably 1 to 6 wt .-%, especially before added 2.5 to 5 wt .-%, proven.

The agents according to the invention also have an advantageous effect in this regard the optional presence of solubilizers - especially for perfume and dyes - from, for example, alkanolamines and / or alkylbenzene sulfonates with 1 to 3 carbon atoms in the alkyl radical, in particular cumene, Toluene and xylene sulfonate, in amounts of up to 5% by weight, preferably 0.05 up to 3% by weight, in particular 0.1 to 2% by weight.

Another preferred group of additives for the purposes of the invention are Sil protective means. This is a large number of mostly cyclic or ganic compounds, which are also addressed to the expert here are common and help tarnishing silver containing counterparts to prevent during the cleaning process. Specific examples can Benzotriazoles, triazoles and their complexes with metals such as Mn, Co, Zn, Fe, Mo, W or Cu.

In addition to the ingredients mentioned so far, other ingredients can be found in Handge Dishwashing detergents usual, ingredients such. B. UV stabilizers, defoamers (such as silicone oils, paraffin oils or mineral oils), structuring agents, corrosis onsinhibitors, preservatives, skin-friendly additives or the like, preferably in Amounts of up to 5% by weight may be included.

The rinse-active preparations of the dishwashing detergent according to the invention Portions can be mixed in by mixing the individual components any order and let the mixture stand until there are no bubbles  produce. The order of preparation is for the production of the Portion according to the invention is not critical.

The corresponding rinse-active preparations obtained can then be opened from the prior art in a manner known per se with enclosures surrounded by one or more water-soluble polymer material (s). A preferred embodiment of the invention is, for example, a form an active preparation with a compartment or a chamber to provide the enclosure from a water-soluble polymer material. This can, for example, a foil cushion, a foil bag or a capsule his. In this case, the dish detergent portion with all for the Rei Components of the active wash preparation required for cleaning or rinsing tion contained in a closed compartment that is based on conventional chem way glued, welded or otherwise, from the prior art is closed in a known manner.

Another, also preferred embodiment of the invention Dishwashing detergent portion can consist of at least two active detergents Preparations of an enclosure forming at least two compartments are comprised of a water-soluble polymer material. This execution shape can be advantageous if, for example, Portion of individual components should be included with other compo immediately or only after long storage or only at Admission of moisture or similar reactions that lead to a reduction in the Effectiveness of the rinse-active preparation (s) as a whole or in combination depend on the effectiveness of individual components. A typical case play can be enzymes that are in a strongly alkaline environment and in particular loss of activity over time in the presence of water. In the same way can be achieved with this embodiment that Kompo nenten can be added to the rinse-active preparation, which are not Spread evenly in a larger volume of the finished product  or that - despite the initial even distribution - settle. The You can use a quantity of the active rinse preparation dosed for one rinse cycle tion mixed or in a separate compartment or in a separate Chamber will be provided with the compartment with the rest Components of the flushing preparation is connected.

The amount of the active detergent preparation (s) in a compartment or The chamber of the dishwashing detergent portion is basically freely selectable. Prefers contain the compartment or compartments or the chambers of the invention however, portions of dishwashing detergent are at least 1 ml or more rinse-active preparation (s), more preferably an amount from 1 to 10 ml of one or more active washing preparation (s), especially preferably an amount of 1 to 5 ml of one or more rinse-active additives preparation (s).

In the form of for example in foil pillows, welded foil bags, Capsules etc. filled dishwasher detergent portions according to the invention can then be put into the optionally tempered before a manual rinse cycle Cleaning or rinsing liquor are given. The enclosure from the / the water-soluble polymer material (ien) then quickly dissolves and sets the rinse-active preparation (s) into the fleet.

The flushing preparations show in the verse (s) with the enclosure (s) superior form of storage stability. The dosage of the flushing active Preparation in the fleet is reliable; an under or overdosing will systematically avoided. In the case of a content of sensitive components The effectiveness of the rinse-active preparation (s) remains reduced lack of interaction with other components of the flushing active Preparation from. For example, the effectiveness of enzymes is retained, as they are kept separate from alkaline components of the preparation (s) and only be added in the actual rinse cycle.  

The invention is illustrated by the following examples, without ever but to be limited to them.  

Examples

By mixing the com. Listed in the table below components and filling of the preparations thus obtained into pillows made of PVAL Films (Solublon® PT from Synthana Handelsgesellschaft E. Harke GmbH & Co .; heat-sealed) in an amount of 2 ml Portions made according to the invention.

The dishwasher detergent portions were in the temperature range between 5 and 40 ° C good storage stability. The rinse and emulsify properties were excellent. The foils detached for a manual rinse net water at a temperature of 35 to 45 ° C in a short time without residue on.  

Table 1

Claims (13)

1. Portion of a low-water cleaning agent from one or more Enclosure (s) made from at least one water-soluble polymer material and at least one of the at least one water-soluble polymer Material partially or completely surrounded by active washing preparation. 2. Detergent portion according to claim 1, wherein the at least one what The water-soluble polymer material of the enclosure (s) is selected from the group pe, which consists of (optionally acetalized) polyvinyl alcohol, Po lyvinylpyrrolidone, 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 we at least a water-soluble polymer material of the enclosure (s) is present in the form of foil bags or capsules. 4. detergent portion according to any one of claims 1 to 3, wherein the we at least one water-soluble polymer material enclosing (s) one or more components of the rinse-active preparation (s) are incorporated contains. 5. detergent portion according to any one of claims 1 to 4, wherein the rinse-active preparation (s) water content <15% by weight, preferred <10 wt .-%, based on the total weight of the rinsing active Preparation (s). 6. detergent portion according to any one of claims 1 to 5, wherein the Components of the active washing preparation (s) are selected from the group pe, which consists of anionic, non-ionic, cationic and ampho tere surfactants, non-aqueous carriers, enzymes, dyes, fragrances, antibacterial agents, polymers and rinse aids.   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 agents, corrosion inhibitors, preservatives, silver preservatives and skin-friendly additives. 8. detergent portion according to any one of claims 1 to 7, wherein a rinse-active preparation of a compartment forming a compartment is comprised of a water-soluble polymer material. 9. detergent portion according to any one of claims 1 to 7, wherein little At least two active preparations from at least two compartments element-forming enclosure made of a water-soluble polymer material are included. 10. A detergent serving according to claim 8 or claim 9, wherein the Compartment (s) an amount of at least 1 ml of an active flushing accessory horse riding includes / comprise. 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 hard surfaces. 13. detergent portion according to one of claims 1 to 12 for dishes do the washing up.