DE102004039921A1 - Rinse aid containing washing and cleaning agents with sulfur-containing amino acids - Google Patents

Abstract

Machinery Detergents containing at least one sulfur-containing amino acid and at least one rinse aid substance from the group of hydroxy mixed ethers, the polymers with cationic Contain monomer unit and the copolymers of sulfonic acid-containing monomers, are characterized by a significantly improved silver corrosion protection out.

Description

The The invention relates to a washing or cleaning agent which is at least a rinse aid substance and contains at least one sulfur-containing amino acid, a process for the preparation this detergent or cleaning agent and the use of the washing or detergent as a means for machine dishwashing.

silverware corroded on its surface as a result of the reaction with constituents of the air and forms thin layers the corrosion products. These layers call interference colors or reduce the gloss of the silver surfaces. The formation of the blackish, iridescent layers also takes place when the silverware is not in use instead of and usually becomes referred to as "start-up" of the silver.

Also in the machine cleaning of silverware occur in practice again and again problems in the form of tarnishing and discoloring the silver surfaces on. Silver can here on sulphurous substances in the rinse water solved or dispersed, react, because when cleaning dishes in household dishwashers are food particles and thus u. a. also mustard, peas, egg and others Sulfur-containing compounds introduced into the rinsing liquor. Also the while of machine washing much higher temperatures and the longer ones Favor contact times with the sulfur-containing food residues compared to manual rinsing the start of silver. Through the intensive cleaning process in the dishwasher becomes the silver surface Furthermore Completely degreased and thus more sensitive to chemical influences.

at the application of active chlorine-containing cleaner can start by Sulfur compounds are largely prevented, as these Compounds by oxidation of sulfidic functions in secondary reaction be converted to sulfones or sulfates.

The However, the problem of silver tarnish became current again, as an alternative to the active chlorine compounds active oxygen compounds, such as Sodium perborate or sodium percarbonate were used, which for the removal of bleachable stains, such as tea stains / tea stains, coffee residues, dyes from vegetables, Lipstick remnants and the like are used.

These Active oxygen compounds are combined with bleach activators especially in modern low alkaline machine dishwashing detergents used the new cleaner generation. These modern means exist generally from the following function modules: Builder component (Complexing agent / dispersant), alkali carrier, bleach system (bleach + Bleach activator), enzymes and wetting agents (surfactants).

On the changed Recipe parameters of the new active chlorine-free cleaner generation react with lowered pH values and activated oxygen bleaching the silver surfaces in principle sensitive. While of machine washing these agents put the actually bleaching in the cleaning cycle Agent hydrogen peroxide or active oxygen free. The blanching Effect of the active oxygen-containing cleaner is by bleach activators strengthened so that even at low temperatures a good bleaching effect is achieved. In the presence of these bleach activators forms as reactive intermediate peracetic acid. Among these changed flushing In the presence of silver, not only sulphide, but also form by the oxidizing attack of intermediately formed peroxides or of the active oxygen preferably oxide coatings on the silver surfaces. Under high salt load can additionally Chloride coatings arise. reinforced In addition, the tarnishing of the silver is accompanied by higher residual water hardness during the Cleaning cycle.

The Avoidance of silver corrosion is already the subject of numerous Publications in the field of machine dishwashing. As a corrosion inhibitor for silver are in many cases benzotriazoles used.

From the British patent GB 1 131 738 For example, alkaline dishwashing detergents containing benzotriazoles as a corrosion inhibitor for silver are known. In the US patent US 3,549,539 describes highly alkaline, machine-usable dishwashing detergents, which may contain as an oxidizing agent, inter alia, perborate with an organic bleach activator. As start-up preventive additives are also recommended by benzotriazole and iron (III) chloride. In the European patents EP 135 226 and EP 135 227 Be weak alkaline machine dishwashing machine containing peroxy compounds and activators which may contain benzotriazoles and fatty acids as silver protectants. In the application GB 1 400 444 Granules are described which are incorporated into surfactant powder and contain, inter alia, benzotriazoles as corrosion inhibitors.

at higher water hardness (e.g., 21 ° dH) however, the anti-corrosion effect of benzotriazoles is not more adequate. It comes to discoloration of the dishes and for the formation of unsightly coverings. In addition, benzotriazoles tend to oxidize in the solid phase of detergent tablets and yellowing cause.

By the use of cysteine / cystine at the site of the benzotriazoles can the above-mentioned disadvantages are avoided.

So WO 96/41860 describes the preparation of an enzyme-containing granulate, in which cystine is present as silver protection agent. The enzyme granules can used for the production of solid, in particular particulate detergent become.

In WO 96/37596 discloses a means for cleaning dishes, which contains cystine as silver protection agent. The use of cysteine as a corrosion inhibitor in a mildly alkaline machine cleaning agent of dishes describes WO 94/07891.

There however, the silver protectants known from the prior art not always the consumer demands sufficient There is a need for new, improved, for use in machine dishwashers suitable silver protectants or synergistic combinations from silver protectants.

Of the Present invention was based on the object, a washing or Detergent available to put that the repression of silver represses and thus allows silver-containing laundry or ware which is not blackish or bluish Discoloration / deposits of corrosion products having. additionally the agent should have optimal washing and rinsing properties and the means of the prior art both in washing and cleaning action as well as in the field of silver corrosion protection.

Surprisingly It has now been found that the silver protection effect of the sulphurous amino acids Cysteine, cystine and methionine in combination with certain rinse aids the silver protection effect of the sulfur-containing amino acids and also surpasses the benzotriazoles.

• a) mindestens eine Klarspülsubstanz aus der Gruppe a') der Hydroxymischether, a'') der Polymere mit kationischer Monomereinheit und a''') der Copolymere aus Sulfonsäure-haltigen Monomeren und
• b) mindestens eine schwefelhaltige Aminosäure.

The present invention is a washing or cleaning agent containing

• a) at least one rinse aid from the group a ') of the mixed hydroxy ether, a'') of the polymers with cationic monomer unit and a''') of the copolymers of sulfonic acid-containing monomers and
• b) at least one sulfur-containing amino acid.

Washing according to the invention or cleaning agents, in addition to at least one sulfur-containing amino acid Hydroxymix ethers and / or polymers with cationic monomer unit and / or copolymers of sulfonic acid-containing Containing monomers, show to recipe-like detergents or cleaning agents, which the above rinsing compounds not included, a significantly increased silver protection effect.

The silver corrosion preventive according to the invention The effect is more automatic within a wide range of recipes Dishwashing liquid to observe, e.g. in the presence of builder systems consisting predominantly of Citrate, or those based on citrate and polycarboxylate, phosphate-free Builder systems or even in the presence of phosphate builders. Also the alkali system can be varied widely, e.g. Soda / hydrogen, Disilicate or soda / disilicate.

• a) mindestens eine Klarspülsubstanz aus der Gruppe a') der Hydroxymischether, a'') der Polymere mit kationischer Monomereinheit und a''') der Copolymere aus Sulfonsäure-haltigen Monomeren und
• b) mindestens eine schwefelhaltige Aminosäure und
• c) Buildersysteme auf Citrat- und/oder Polycarboxylat-Basis,

in denen 20 bis 60 Gew.-%, bevorzugt 25 bis 55 Gew.-%, insbesondere 30 bis 50 Gew.-% Citrat und 5 bis 60 Gew.-%, bevorzugt 15 bis 55 Gew.-% und insbesondere 25 bis 50 Gew.-% Polycarboxylat, jeweils bezogen auf das gesamte Mittel, enthalten sind.The present invention is a washing or cleaning agent containing

• a) at least one rinse aid from the group a ') of the mixed hydroxy ether, a ") of the polymers having a cationic monomer unit and a ''') of the copolymers of sulfonic acid-containing monomers and
• b) at least one sulfur-containing amino acid and
• c) citrate and / or polycarboxylate based builder systems,

in which 20 to 60 wt .-%, preferably 25 to 55 wt .-%, in particular 30 to 50 wt .-% citrate and 5 to 60 wt .-%, preferably 15 to 55 wt .-% and in particular 25 to 50 Wt .-% polycarboxylate, in each case based on the total agent, are included.

• a) mindestens eine Klarspülsubstanz aus der Gruppe a') der Hydroxymischether, a'') der Polymere mit kationischer Monomereinheit und a''') der Copolymere aus Sulfonsäure-haltigen Monomeren und
• b) mindestens eine schwefelhaltige Aminosäure und
• c) Buildersysteme auf Phosphat-Basis,

in denen 5 bis 65 Gew.-%, bevorzugt 15 bis 60 Gew.-%, besonders bevorzugt 25 bis 55 Gew.-% und insbesondere 25 bis 50 Gew.-% Phosphat, bezogen auf das gesamte Mittel, enthalten sind.However, the subject of the present invention is also a washing or cleaning agent containing

• a) at least one rinse aid from the group a ') of the mixed hydroxy ether, a'') of the polymers with cationic monomer unit and a''') of the copolymers of sulfonic acid-containing monomers and
• b) at least one sulfur-containing amino acid and
• c) phosphate-based builder systems,

in which 5 to 65 wt .-%, preferably 15 to 60 wt .-%, particularly preferably 25 to 55 wt .-% and in particular 25 to 50 wt .-% of phosphate, based on the total agent, are included.

The Sulfur-containing amino acids are characterized by increased stability compared to benzotriazoles. she are ecological harmless and can, since their action is enhanced by the above-mentioned rinse-aid substances, in significantly lower quantities than the benzotriazoles in detergents or cleaners be used.

Under the term "sulphurous Amino acids "are both here the acids, as well as their salts and esters understood. Preference is given to the acid hydrohalides, the salts of alkali and alkaline earth metals, aluminum, zinc, silicon and the esters of acids used. Particularly preferred are the hydrochloric acid salts, the sodium, Potassium, magnesium, calcium and zinc salts and the alkyl esters the acids.

Rinse aid substances a)

The according to the invention or detergents contain at least one rinse aid the group of hydroxy mixed ethers a '), the polymers with cationic monomer unit a ") and the copolymer from sulfonic acid-containing Monomers a '' '). These compounds act synergistically combined with the sulfur-containing amino acid used. By the combination of rinse aid substance (s) and sulfur-containing amino acid (s) a silver corrosion protection is achieved, which is that of conventional Silver protection significantly exceeds. The weight fraction of the final rinse substance is preferably between 0.01 and 80% by weight, preferably 0.5 to 65% by weight, particularly preferably 0.8 to 50% by weight, very particularly preferably 1.1 to 35 wt .-% and in particular 1.4 to 20 wt .-% based on the entire means.

Hydroxymix ether a ')

In a preferred embodiment the method according to the invention Hydroxymischether be used as a rinse aid. The hydroxy mixed ethers can as the only of the rinse agents listed under a) are combined with the sulfur-containing amino acid (s) which Combination with one or two further rinse aids however, the group a) is also preferred.

Preferably contains the washing or detergent hydroxy mixed ether in a proportion of 0.5 to 15% by weight, preferably preferably 1 to 12.5% by weight, especially preferably 1.5 to 10% by weight, very particularly preferably 2 to 8% by weight and in particular 2.5 to 6 wt .-% based on the total agent. In this area are the largest synergistic Effects between hydroxymix ether and sulfur-containing amino acid with respect to Silver protection observed.

Within the method according to the invention can all hydroxymix ethers known to those skilled in the art are used. However, the use of hydroxy mixed ethers is particularly preferred with alternating ethylene oxide-alkylene oxide units.

Preferred in the present invention are hydroxy mixed ethers (a ') of the formula R ^{1 is} -O- [CH ₂ CH (R ³ ) O] _x - [CH ₂ CH (OH)) - R ² used in the
R ¹ and R ^{2 may be} different or the same, where
R ^{1 is} a linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radical having 1 to 30 carbon atoms or mixtures thereof,
R ^{2 is} a linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radical having 1 to 30 carbon atoms, which optionally contains up to 5 hydroxyl and / or up to 3 ether functions,
R ^{3 is} H or a methyl, ethyl, n-propyl, iso-propyl, n-butyl, 2-butyl or 2-methyl-butyl radical, where each R ³ may be different at x ≥ 2 and
x stands for values greater than 1.

Hydroxymix ethers of the formula R ¹ O [CH ₂ CH (CH ₃ ) O] _x [CH ₂ CH ₂ O] _y CH ₂ CH (OH) R ² , in which R ^{1 is} a linear or branched aliphatic hydrocarbon radical having 4 to 18 carbon atoms or mixtures thereof, R ² denotes a linear or branched hydrocarbon radical having 2 to 26 carbon atoms or mixtures thereof and x for values between 0.5 and 1.5 and y is a value of at least 15, are particularly preferred.

Further preferred hydroxy mixed ethers are the end-capped poly (oxyalkylated) nonionic surfactants of the formula R ¹ O [CH ₂ CH (R ³ ) O] _x [CH ₂ ] _k CH (OH) [CH ₂ ] _j OR ² , in which R ¹ and R ^{2 are} linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals having 1 to 30 carbon atoms, R ^{3 is} H or a methyl, ethyl, n-propyl, iso-propyl, n- Butyl, 2-butyl or 2-methyl-2-butyl radical, x are values between 1 and 30, k and j are values between 1 and 12, preferably between 1 and 5. When the value x = 2, each R ³ in the above formula R ¹ O [CH ₂ CH (R ³ ) O] _x [CH ₂ ] _k CH (OH) [CH ₂ ] _j OR ^{2 may be} different. R ¹ and R ² are preferably linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals having 6 to 22 carbon atoms, with radicals having 8 to 18 carbon atoms being particularly preferred. For the radical R ³ , H, -CH ₃ or -CH ₂ CH _{3 are} particularly preferred. Particularly preferred values for x are in the range from 1 to 20, in particular from 6 to 15.

As described above, each R ³ in the above formula may be different if x = 2. As a result, the alkylene oxide unit in the square bracket can be varied. For example, when x is 3, the radical R ³ can be selected to form ethylene oxide (R ³ = H) or propylene oxide (R ³ = CH ₃ ) units which may be joined in any order, for example (EO) ( PO) (EO), (EO) (EO) (PO), (EO) (EO) (EO), (PO) (EO) (PO), (PO) (PO) (EO) and (PO) ( PO) (PO). The value 3 for x has been selected here by way of example and may well be greater, with the variation width increasing with increasing x values and including, for example, a large number (EO) groups combined with a small number (PO) groups, or vice versa ,

Particularly preferred hydroxy mixed ethers of the above formula have values of k = 1 and j = 1, so that the above formula zu R ¹ O [CH ₂ CH (R ³ ) O] _x CH ₂ CH (OH) CH ₂ OR ² simplified. In the last-mentioned formula, R ¹ , R ² and R ^{3 are} as defined above and x is from 1 to 30, preferably from 1 to 20 and in particular from 6 to 18. Particular preference is given to hydroxy mixed ethers in which the radicals R ¹ and R ^{2 has} 9 to 14 C atoms, R ^{3 is} H and x assumes values of 6 to 15.

Summarizing the latter statements, end-capped hydroxy mixed ethers of the formula R ¹ O [CH ₂ CH (R ³ ) O] _x [CH ₂ ] _k CH (OH) [CH ₂ ] _j OR ² , in which R ¹ and R ^{2 are} linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals having 1 to 30 carbon atoms, R ^{3 is} H or a methyl, ethyl, n-propyl, iso-propyl, n-butyl, 2-butyl or 2-methyl-2-butyl radical, x are values between 1 and 30, k and j are values between 1 and 12, preferably between 1 and 5, preferably wherein hydroxy mixed ethers of the type R ¹ O [CH ₂ CH (R ³ ) O] _x CH ₂ CH (OH) CH ₂ OR ² , in which x is from 1 to 30, preferably from 1 to 20 and in particular from 6 to 18, are particularly preferred.

Low-foaming nonionic surfactants which have alternating ethylene oxide and alkylene oxide units have proven to be particularly preferred hydroxy mixed ethers in the context of the present invention. Among these, in turn, hydroxy mixed ethers having EO-AO-EO-AO blocks are preferred, wherein one to ten EO or AO groups are bonded to each other before one block from the other groups follows. Here are hydroxy mixed ethers of the general formula R ¹ O [CH ₂ CH ₂ O] _w [CH ₂ CH (R ² ) O] _x [CH ₂ CH ₂ O] _y [CH ₂ CH (R ³ ) O] _z H in which R ^{1 is} a straight-chain or branched, saturated or mono- or polyunsaturated C _6-24 alkyl or alkenyl radical, each R ² or R ^{3 group is} independently selected from -CH ₃ , - CH ₂ CH ₃ , -CH ₂ CH ₂ -CH ₃ , CH (CH ₃ ) ₂ and the indices w, x, y, z independently represent integers from 1 to 6.

The preferred hydroxy mixed ethers of the above formula can be prepared by known methods from the corresponding alcohols R ¹ -OH and ethylene or alkylene oxide. The radical R ¹ in the above formula may vary depending on the origin of the alcohol. If native sources are used, the radical R ^{1 has} an even number of carbon atoms and is usually unbranched, the linear radicals being selected from alcohols of natural origin having 12 to 18 C atoms, for example from coconut, palm, tallow or Oleyl alcohol, are preferred. Alcohols which are accessible from synthetic sources are, for example, the Guerbet alcohols or methyl-branched or linear and methyl-branched radicals in the 2-position, as they are usually present in oxo alcohol radicals. Independently of the nature of the alcohol used to prepare the hydroxy mixed ethers used in the compositions, hydroxy mixed ethers are preferred in which R ¹ in the above formula is an alkyl radical having 6 to 24, preferably 8 to 20, particularly preferably 9 to 15 and in particular 9 to 11 Carbon atoms.

As the alkylene oxide unit which is contained in the preferred hydroxy mixed ether in alternation with the ethylene oxide unit, in particular butylene oxide is considered in addition to propylene oxide. But also other alkylene oxides in which R ² or R ^{3 are} independently selected from -CH ₂ CH ₂ -CH ₃ or CH (CH ₃ ) ₂ are suitable. Preference is given to using hydroxy mixed ethers of the above formula in which R ² or R ^{3 are} independently -CH ₃ , w and x independently of one another for values of 3 or 4 and y and z independently of one another for values of 1 or 2.

In summary, particularly preferred are mixed hydroxy ethers having a C _9-15 alkyl group having 1 to 4 ethylene oxide units followed by 1 to 4 propylene oxide units followed by 1 to 4 ethylene oxide units followed by 1 to 4 propylene oxide units. These surfactants have the required low viscosity in aqueous solution and can be used according to the invention with particular preference.

Further preferred hydroxy mixed ethers are the end-capped poly (oxyalkylated) nonionic surfactants of the formula R ¹ O [CH ₂ CH (R ³ ) O] _x R ² , in which R ^{1 represents} linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals having 1 to 30 carbon atoms, R ^{2 represents} linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals having 1 to 30 carbon atoms, which preferably between 1 and have 5 hydroxy groups and are preferably further functionalized with an ether group, R ^{3 is} H or a methyl, ethyl, n-propyl, iso-propyl, n-butyl, 2-butyl or 2-methyl-2- Butyl radical and x stands for values between 1 and 40.

In a particularly preferred embodiment of the present application, R ³ in the abovementioned general formula is H. From the group of the resulting end-capped poly (oxyalkylated) nonionic surfactants of the formula R ¹ O [CH ₂ CH ₂ O] _x R ² in particular those hydroxy mixed ethers are preferred in which R ^{1 is} linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals having 1 to 30 carbon atoms, preferably having 4 to 20 carbon atoms, R ^{2 is} linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals having 1 to 30 carbon atoms, which preferably have between 1 and 5 hydroxyl groups and x stands for values between 1 and 40.

In particular, those end-capped hydroxy mixed ethers are preferred which are in accordance with the formula R ¹ O [CH ₂ CH ₂ O] _x CH ₂ CH (OH) R ² in addition to a radical R ¹ , which is linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals having 1 to 30 carbon atoms, preferably having 4 to 20 carbon atoms, furthermore a linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radical R ² having 1 to 30 carbon atoms adjacent to a monohydroxylated intermediate group -CH ₂ CH (OH) -. x in this formula stands for values between 1 and 90.

Particularly preferred are hydroxy mixed ethers of the general formula R ¹ O [CH ₂ CN ₂ O] _x CH ₂ CH (OH) R ² , which in addition to a radical R ¹ , which is linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals having 1 to 30 carbon atoms, preferably having 4 to 22 carbon atoms, further a linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radical R ² having 1 to 30 carbon atoms, preferably 2 to 22 carbon atoms, which is adjacent to a monohydroxylated intermediate group -CH ₂ CH (OH) - and in which x is between 40 and 80, preferably between 40 and 60.

The corresponding end-capped hydroxy mixed ethers of the above formula can be obtained, for example, by reacting a terminal epoxide of the formula R ² CH (O) CH ₂ with an ethoxylated alcohol of the formula R ¹ O [CH ₂ CH ₂ O] _x-1 CH ₂ CH ₂ OH ,

Particular preference is furthermore given to those end-capped hydroxy mixed ethers of the formula R ¹ O [CH ₂ CH ₂ O] _x [CH ₂ CH (CH ₃ ) O] _y CH ₂ CH (OH) R ² , in which R ¹ and R ² independently of one another are a linear or branched, saturated or mono- or polyunsaturated hydrocarbon radical having 2 to 26 carbon atoms, R ^{3 is} independently selected from -CH ₃ -CH ₂ CH ₃ , -CH ₂ CH ₂ -CH ₃ , CH (CH ₃ ) ₂ , but preferably -CH ₃ , and x and y independently of one another represent values between 1 and 32, wherein hydroxy mixed ethers having values of x of 15 to 32 and y of 0, 5 and 1.5 are very particularly preferred.

Hydroxymix ethers of the general formula R ¹ O [CH ₂ CH ₂ O] _x [CH ₂ CH (R ³ ) O] _y CH ₂ CH (OH) R ² , in which R ¹ and R ² independently of one another are a linear or branched, saturated or mono- or polyunsaturated hydrocarbon radical having 2 to 26 carbon atoms, R ^{3 is} independently selected from -CH ₃ -CH ₂ CH ₃ , -CH ₂ CH ₂ -CH ₃ , CH (CH ₃ ) ₂ , but preferably represents -CH ₃ , and x and y independently of one another are values between 1 and 32 are preferred according to the invention, wherein hydroxy mixed ethers with values of x from 15 to 32 and y of 0.5 and 1.5 are very particularly preferred.

The stated C chain lengths and degrees of ethoxylation or degrees of alkoxylation of the abovementioned hydroxy mixed ethers represent statistical average values which, for a specific product, may be an integer or a fractional number. Due to the manufacturing process, commercial products of the formulas mentioned mostly do not consist of an individual representative, but of mixtures, which results in mean values for the C chain lengths as well as for the degrees of ethoxylation or alkoxylation can result in broken numbers.

Of course, the above hydroxymix ethers not only as individual substances, but also as mixtures of two, three, four or more hydroxy mixed ethers be used. Mixtures are not mixtures of Hydroxymischethern called in their entirety under a the general formulas above, but rather such mixtures containing two, three, four or more hydroxy mixed ethers contained by different of the aforementioned general Formulas can be described.

Especially preferred are hydroxy mixed ethers having a melting point above Have room temperature. Hydroxymix ether with a melting point above 20 ° C, preferably above 25 ° C, especially preferably between 25 and 60 ° C and especially between 26.6 and 43.3 ° C, are particularly preferred.

• a) mindestens eine Klarspülsubstanz aus der Gruppe a') der Hydroxymischether, welche einen Schmelzpunkt oberhalb von 20°C, vorzugsweise oberhalb von 25°C, besonders bevorzugt zwischen 25 und 60°C und insbesondere zwischen 26,6 und 43,3°C aufweisen, a'') der Polymere mit kationischer Monomereinheit und a''') der Copolymere aus Sulfonsäure-haltigen Monomeren und
• b) mindestens eine schwefelhaltige Aminosäure.

The present invention is a washing or cleaning agent containing

• a) at least one rinse aid from the group a ') of the hydroxy mixed ethers having a melting point above 20 ° C, preferably above 25 ° C, more preferably between 25 and 60 ° C and in particular between 26.6 and 43.3 ° C. , a '') of the polymers having a cationic monomer unit and a ''') of the copolymers of sulfonic acid-containing monomers and
• b) at least one sulfur-containing amino acid.

Become Hydroxymischether used, which is highly viscous at room temperature are, it is preferred that this has a viscosity above 20 Pa · s, preferably above 35 Pa · s and in particular above 40 Pa · s (Brookfield, Spindle 31, 30 rpm, 20 ° C). Also hydroxymix ethers, the waxy consistency at room temperature own, are preferred.

Contains the machine according to the invention Dishwashing liquid two, three, four or more hydroxy mixed ethers, so is the ratio of the in the agent contained hydroxy mixed ether preferably within narrow borders. If a mixture of two hydroxy mixed ethers (H 1 and H 2) used, it is weight ratio the hydroxymix ether used (weight ratio H 1 to H 2) preferably between 10: 1 and 1:10, preferably between 8: 1 and 1: 8, more preferably between 6: 1 and 1: 6 and in particular between 4: 1 and 1: 4.

Contains the machine according to the invention Dishwashing liquid a mixture of two, three, four or more hydroxy mixed ethers, see above is preferred if at least one of the hydroxy mixed ethers has a Weight fraction above 1.0% by weight, preferably above 1.75% by weight and in particular above 2.5% by weight, based on the total agent, having.

• a) mindestens eine Klarspülsubstanz aus der Gruppe a') der Hydroxymischether, wobei wenigstens einer der Hydroxymischether einen Gewichtsanteil oberhalb 1,0 Gew.-%, vorzugsweise oberhalb 1,75 Gew.-% und insbesondere oberhalb 2,5 Gew.-%, bezogen auf das gesamte Mittel, aufweist, a'') der Polymere mit kationischer Monomereinheit und a''') der Copolymere aus Sulfonsäure-haltigen Monomeren und
• b) mindestens eine schwefelhaltige Aminosäure.

The present invention is a washing or cleaning agent containing

• a) at least one rinse aid substance from the group a ') of the hydroxy mixed ethers, where at least one of the hydroxy mixed ethers has a weight fraction above 1.0 wt.%, preferably above 1.75 wt.% and in particular above 2.5 wt. based on the total agent comprises, a '') of the polymers with cationic monomer unit and a ''') of the copolymers of sulfonic acid-containing monomers and
• b) at least one sulfur-containing amino acid.

Polymers with cationic Monomer unit a ")

When further rinse aid substances, which in combination with the sulfur-containing amino acid (s) a high Silver protection effect, are preferably polymers with cationic Monomer unit a "). The Polymers can as the only one listed under a) Klarspülsubstanzen are combined with the sulfur-containing amino acid (s) which Combination with one or two further rinse aids however, the group a) is also preferred.

Prefers are polymers with cationic monomer unit in the washing or cleaning agent according to the invention in a proportion of 0.01 to 7.5% by weight, preferably 0.02 to 5% by weight, more preferably 0.03 to 2.5 wt .-%, most preferably 0.04 to 1 wt .-% and in particular 0.05 to 1 wt .-%, based on the entire remedy, used.

Prefers contains the washing or detergent Polymers with cationic functional group a ''), which belongs to the group of the cationic polymers.

"Cationic Polymers "or im The meaning of the present invention are polymers which are a positive charge in the polymer molecule wear. This can be present, for example, in the polymer chain (Alkyl) ammonium moieties or other positively charged groups will be realized. Particularly preferred cationic polymers are derived from the groups of the quaternized cellulose derivatives, the polysiloxanes with quaternary Groups, the cationic guar derivatives, the polymeric dimethyldiallylammonium salts and their copolymers with esters and amides of acrylic acid and methacrylic acid, the copolymers of vinylpyrrolidone with quaternized derivatives the dialkylamino acrylate and methacrylate, the vinylpyrrolidone-methoimidazolinium chloride copolymers, the quaternized polyvinyl alcohols or the INCI names Polyquaternium 2, Polyquaternium 17, Polyquaternium 18 and Polyquaternium 27 Polymers.

Farther the use of amphoteric polymers as polymers is preferred with cationic functional group a '') in the washing or detergents.

"Amphoteric Polymers "in the sense of the present invention have besides a positively charged group in the polymer chain also negatively charged groups or On monomer units. These groups may be, for example to carboxylic acids, sulfonic acids or phosphonic acids act.

Preferred washing or cleaning agents, in particular preferred automatic dishwasher detergents, are characterized in that they contain a polymer which has monomer units of the formula R ¹ R ² C =CR ³ R ⁴ , in which each R ¹ , R ² , R ³ , R ^{4 is} independently selected from hydrogen, derivatized hydroxy, C _1-30 linear or branched alkyl groups, aryl, aryl substituted C _1-30 linear or branched alkyl groups, polyalkoxylated alkyl groups, heteroatomic organic groups having at least one positive charge without charged nitrogen, at least a quaternized N atom or at least one amino group having a positive charge in the partial range of the pH range of 2 to 11, or salts thereof, with the proviso that at least one R ¹ , R ² , R ³ , R ^{4 is} a heteroatomic organic Group having at least one positive charge without charged nitrogen, at least one quaternized N atom or at least one amino group e is with a positive charge.

bei der R¹ und R⁴ unabhängig voneinander für H oder einen linearen oder verzweigten Kohlenwasserstoffrest mit 1 bis 6 Kohlenstoffatomen steht; R² und R³ unabhängig voneinander für eine Alkyl-, Hydroxyalkyl-, oder Aminoalkylgruppe stehen, in denen der Alkylrest linear oder verzweigt ist und zwischen 1 und 6 Kohlenstoffatomen aufweist, wobei es sich vorzugsweise um eine Methylgruppe handelt; x und y unabhängig voneinander für ganze Zahlen zwischen 1 und 3 stehen. X-repräsentiert ein Gegenion, vorzugsweise ein Gegenion aus der Gruppe Chlorid, Bromid, Iodid, Sulfat, Hydrogensulfat, Methosulfat, Laurylsulfat, Dodecylbenzolsulfonat, p-Toluolsulfonat (Tosylat), Cumolsulfonat, Xylolsulfonat, Phosphat, Citrat, Formiat, Acetat oder deren Mischungen.In the context of the present application, particularly preferred cationic or amphoteric polymers contain as monomer unit a compound of the general formula

in which R ¹ and R ⁴ are each independently H or a linear or branched hydrocarbon radical having 1 to 6 carbon atoms; R ² and R ^{3 are} independently an alkyl, hydroxyalkyl, or aminoalkyl group in which the alkyl group is linear or branched and has from 1 to 6 carbon atoms, preferably a methyl group; x and y independently represent integers between 1 and 3. X represents a counterion, preferably a counterion from the group chloride, bromide, iodide, sulfate, hydrogen sulfate, methosulfate, lauryl sulfate, dodecylbenzenesulfonate, p-toluenesulfonate (tosylate), cumenesulfonate, xylenesulfonate, phosphate, citrate, formate, acetate or mixtures thereof.

Preferred radicals R ¹ and R ⁴ in the above formula are selected from -CH ₃ , -CH ₂ -CH ₃ , -CH ₂ -CH ₂ -CH ₃ , -CH (CH ₃ ) -CH ₃ , -CH ₂ -OH , -CH ₂ -CH ₂ -OH, -CH (OH) -CH ₃ , -CH ₂ -CH ₂ -CH ₂ -OH, -CH ₂ -CH (OH) -CH ₃ , -CH (OH) -CH ₂ -CH ₃ , and - (CH ₂ CH ₂ -O) _n H.

werden im Falle von X^-= Chlorid auch als DADMAC (Diallyldimethylammonium-Chlorid) bezeichnet. Gegenstand der vorliegenden Erfindung ist ein Wasch- oder Reinigungsmittel enthaltend

• a) mindestens eine Klarspülsubstanz aus der Gruppe a') der Hydroxymischether, a'') der Polymere mit kationischer Monomereinheit, welche durch die Formel
  
  repräsentiert wird, in der R¹ und R⁴ unabhängig voneinander für H oder einen linearen oder verzweigten Kohlenwasserstoffrest mit 1 bis 6 Kohlenstoffatomen steht; R² und R³ unabhängig voneinander für eine Alkyl-, Hydroxyalkyl-, oder Aminoalkylgruppe stehen, in denen der Alkylrest linear oder verzweigt ist und zwischen 1 und 6 Kohlenstoffatomen aufweist, wobei es sich vorzugsweise um eine Methylgruppe handelt; x und y unabhängig voneinander für ganze Zahlen zwischen 1 und 3 stehen. X^- repräsentiert ein Gegenion, vorzugsweise ein Gegenion aus der Gruppe Chlorid, Bromid, Iodid, Sulfat, Hydrogensulfat, Methosulfat, Laurylsulfat, Dodecylbenzolsulfonat, p-Toluolsulfonat (Tosylat), Cumolsulfonat, Xylolsulfonat, Phosphat, Citrat, Formiat, Acetat oder deren Mischungen, a''') der Copolymere aus Sulfonsäure-haltigen Monomeren und
• b) mindestens eine schwefelhaltige Aminosäure.

Very particular preference is given to polymers which have a cationic monomer unit of the above general formula in which R ¹ and R ^{4 are} H, R ² and R ^{3 are} methyl and x and y are each 1. The corresponding monomer unit of the formula

in the case of X ^- = chloride, they are also referred to as DADMAC (diallyldimethylammonium chloride). The present invention is a washing or cleaning agent containing

• a) at least one rinse aid substance from the group a ') of the hydroxymix ethers, a ") of the polymers having a cationic monomer unit which are represented by the formula
  
  is represented in which R ¹ and R ^{4 are} independently H or a linear or branched hydrocarbon radical having 1 to 6 carbon atoms; R ² and R ^{3 are} independently an alkyl, hydroxyalkyl, or aminoalkyl group in which the alkyl group is linear or branched and has from 1 to 6 carbon atoms, preferably a methyl group; x and y independently represent integers between 1 and 3. X ^- represents a counterion, preferably a counterion from the group consisting of chloride, bromide, iodide, sulfate, hydrogensulfate, methosulfate, laurylsulfate, dodecylbenzenesulfonate, p-toluenesulfonate (tosylate), cumene sulfonate, xylenesulfonate, phosphate, citrate, formate, acetate or mixtures thereof, a ''') of the copolymers of sulfonic acid-containing monomers and
• b) at least one sulfur-containing amino acid.

in der R¹, R², R³, R⁴ und R⁵ unabhängig voneinander für einen linearen oder verzweigten, gesättigten oder ungesättigen Alkyl-, oder Hydroxyalkylrest mit 1 bis 6 Kohlenstoffatomen, vorzugsweise für einen linearen oder verzweigten Alkylrest ausgewählt aus -CH₃, -CH₂-CH₃, -CH₂-CH₂-CH₃, -CH(CH₃)-CH₃, -CH₂-OH, -CH₂-CH₂-OH, -CH(OH)-CH₃, -CH₂-CH₂-CH₂-OH, -CH₂-CH(OH)-CH₃, -CH(OH)-CH₂-CH₃, und -(CH₂CH₂-O)_nH steht und x für eine ganze Zahl zwischen 1 und 6 steht.Further particularly preferred cationic or amphoteric polymers contain a monomer unit of the general formula

in which R ¹ , R ² , R ³ , R ⁴ and R ⁵ independently of one another are a linear or branched, saturated or unsaturated alkyl or hydroxyalkyl radical having 1 to 6 carbon atoms, preferably a linear or branched alkyl radical selected from -CH ₃ , -CH ₂ -CH ₃ , -CH ₂ -CH ₂ -CH ₃ , -CH (CH ₃ ) -CH ₃ , -CH ₂ -OH, -CH ₂ -CH ₂ -OH, -CH (OH) -CH ₃ , -CH ₂ -CH ₂ -CH ₂ -OH, -CH ₂ -CH (OH) -CH ₃ , -CH (OH) -CH ₂ -CH ₃ , and - (CH ₂ CH ₂ -O) _n H and x is an integer between 1 and 6.

werden im Falle von X^-= Chlorid auch als MAPTAC (Methyacrylamidopropyl-trimethylammonium-Chlorid) bezeichnet.For the purposes of the present application, very particular preference is given to polymers which have a cationic monomer unit of the above general formula in which R ^{1 is} H and R ² , R ³ , R ⁴ and R ^{5 are} methyl and x is 3. The corresponding monomer units of the formula

in the case of X ^- = chloride, also referred to as MAPTAC (methylacrylamidopropyltrimethylammonium chloride).

According to the invention preferred Polymers are used which are diallyldimethylammonium salts as monomer units and / or acrylamidopropyltrimethylammonium salts.

The previously mentioned Amphoteric polymers have not only cationic groups, but also anionic groups or monomer units. Such anionic For example, monomer units are from the linear group or branched, saturated or unsaturated Carboxylates, linear or branched, saturated or unsaturated Phosphonates, which are linear or branched, saturated or unsaturated Sulfates or the linear or branched, saturated or unsaturated Sulfonates. Preferred monomer units are the acrylic acid, the (Meth) acrylic acid, the (dimethyl) acrylic acid, the (ethyl) acrylic acid, the cyanoacrylic acid, the vinylessing acid, the allylacetic acid, the crotonic acid, the maleic acid, the fumaric acid, the cinnamic acid and their derivatives, the allylsulfonic acids, such as allyloxybenzenesulfonic acid and methallyl or the allylphosphonic acids.

Preferred employable amphoteric polymers are from the group of the alkylacrylamide / acrylic acid copolymers, the alkylacrylamide / methacrylic acid copolymers, the alkylacrylamide / methylmethacrylic acid copolymers, the alkylacrylamide / acrylic acid / alkylaminoalkyl (meth) acrylic acid copolymers, the alkylacrylamide / methacrylic acid / alkylaminoalkyl (meth) acrylic acid copolymers, the alkylacrylamide / methylmethacrylic acid re / alkylaminoalkyl (meth) acrylic acid copolymers, the alkylacrylamide / alkymethacrylate / alkylaminoethyl methacrylate / alkyl methacrylate copolymers and the copolymers of unsaturated carboxylic acids, cationically derivatized unsaturated carboxylic acids and optionally further ionic or nonionic monomers.

Prefers usable zwitterionic polymers are from the group of Acrylamidoalkyltrialkylammonium chloride / acrylic acid copolymers and their Alkali and ammonium salts of acrylamidoalkyltrialkylammonium chloride / methacrylic acid copolymers and their alkali metal and ammonium salts and the Methacroylethylbetain / methacrylate copolymers.

Prefers are further amphoteric polymers, which in addition to one or more anionic monomers as cationic monomers Methacrylamidoalkyl-trialkylammonium chloride and dimethyl (diallyl) ammonium chloride.

Especially preferred amphoteric polymers are from the group of the Methacrylamidoalkyl-trialkylammonium chloride / dimethyl (diallyl) ammonium chloride / acrylic acid copolymers, the Methacrylamidoalkyltrialkylammoniumchlorid / dimethyl (diallyl) ammonium chloride / methacrylic acid copolymers and the methacrylamidoalkyltrialkylammonium chloride / dimethyl (diallyl) ammonium chloride / alkyl (meth) acrylic acid copolymers as well as their alkali and ammonium salts.

Especially preferred are amphoteric polymers from the group of methacrylamidopropyltrimethylammonium chloride / dimethyl (diallyl) ammonium chloride / acrylic acid copolymers, the methacrylamidopropyltrimethylammonium chloride / dimethyl (diallyl) ammonium chloride / acrylic acid copolymers and the methacrylamidopropyltrimethylammonium chloride / dimethyl (diallyl) ammonium chloride / alkyl (meth) acrylic acid copolymers, as well as their alkali and ammonium salts.

• – die Verkapselung der Polymere mittels wasserlöslicher oder wasserdispergierbarer Beschichtungsmittel, vorzugsweise mittels wasserlöslicher oder wasserdispergierbarer natürlicher oder synthetischer Polymere;
• – die Verkapselung der Polymere mittels wasserunlöslicher, schmelzbarer Beschichtungsmittel, vorzugsweise mittels wasserunlöslicher Beschichtungsmittel aus der Gruppe der Wachse oder Paraffine mit einem Schmelzpunkt oberhalb 30°C;
• – die Cogranulation der Polymere mit inerten Trägermaterialien, vorzugsweise mit Trägermaterialien aus der Gruppe der wasch- oder reinigungsaktiven Substanzen, besonders bevorzugt aus der Gruppe der Builder (Gerüststoffe) oder Cobuilder.

In a particularly preferred embodiment of the present invention, the polymers are present in prefabricated form. For the preparation of the polymers is suitable inter alia

• The encapsulation of the polymers by means of water-soluble or water-dispersible coating compositions, preferably by means of water-soluble or water-dispersible natural or synthetic polymers;
• - The encapsulation of the polymers by means of water-insoluble, fusible coating compositions, preferably by means of water-insoluble coating agents from the group of waxes or paraffins having a melting point above 30 ° C;
• - The cogranulation of the polymers with inert support materials, preferably with support materials from the group of washing or cleaning-active substances, particularly preferably from the group of builders (builders) or cobuilders.

• a) mindestens eine Klarspülsubstanz aus der Gruppe a') der Hydroxymischether, a'') der Polymere mit kationischer Monomereinheit, wobei die Polymere verkapselt oder cogranuliert vorliegen und a''') der Copolymere aus Sulfonsäure-haltigen Monomeren und
• b) mindestens eine schwefelhaltige Aminosäure.

The present invention is a washing or cleaning agent containing

• a) at least one rinse aid from the group a ') of the hydroxymix ether, a ") of the polymers having a cationic monomer unit, wherein the polymers are encapsulated or co-granulated and a''') of the copolymers of sulfonic acid-containing monomers and
• b) at least one sulfur-containing amino acid.

Copolymers with sulfonic acid-containing Monomers a '' ')

copolymers with sulfonic acid-containing Monomers are preferred in the process according to the invention as Klarspülsubstanz used. The copolymers with sulfonic acid-containing monomers may be the only the one listed under a) Klarspülsubstanzen are combined with the sulfur-containing amino acid (s) which Combination with one or two further rinse aids however, the group a) is also preferred.

Preferably are copolymers with sulfonic acid-containing Monomers in the washing or detergent in a proportion of 0.1 to 70 wt .-%, preferably 0.25 to 50 wt .-%, particularly preferably 0.5 to 35 wt .-%, completely particularly preferably 0.75 to 20% by weight and in particular 1 to 15% by weight, based on the total mean used. In this area is the mutual reinforcement the copolymers with sulfonic acid-containing Monomers and the sulfur-containing amino acid (s) largest.

Within the process according to the invention, all copolymers known to the person skilled in the art can be used be used from sulfonic acid-containing monomers. However, copolymers which may be used with particular preference as sulfonic acid-containing polymers are copolymers of unsaturated carboxylic acids, monomers containing sulfonic acid groups and, if appropriate, further ionogenic or nonionogenic monomers.

In the context of the present invention are as unsaturated monomer carboxylic acids of the formula R ¹ (R ² ) C = C (R ³ ) COOH in which R ¹ to R ³ independently of one another are -H, -CH ₃ , a straight-chain or branched saturated alkyl radical having 2 to 12 carbon atoms, a straight-chain or branched, mono- or polyunsaturated alkenyl radical having 2 to 12 carbon atoms, NH ₂ , -OH or -COOH substituted alkyl or alkenyl radicals or -COOH or -COOR ⁴ , wherein R ^{4 is} a saturated or unsaturated, straight-chain or branched hydrocarbon radical having 1 to 12 carbon atoms.

Among the unsaturated carboxylic acids which can be described by the above formula are in particular acrylic acid (R ¹ = R ² = R ³ = H), methacrylic acid (R ¹ = R ² = H, R ³ = CH ₃ ) and / or maleic acid (R ¹ = COOH; R ² = R ³ = H) is preferred.

In the sulfonic acid-containing monomers are those of the formula R ⁵ (R ⁶ ) C = C (R ⁷ ) -X-SO ₃ H in which R ⁵ to R ⁷ independently of one another are -H, -CH ₃ , a straight-chain or branched saturated alkyl radical having 2 to 12 carbon atoms, a straight-chain or branched, mono- or polyunsaturated alkenyl radical having 2 to 12 carbon atoms, NH ₂ , -OH or -COOH substituted alkyl or alkenyl radicals or -COOH or -COOR ⁴ , wherein R ^{4 is} a saturated or unsaturated, straight-chain or branched hydrocarbon radical having 1 to 12 carbon atoms, and X is an optional spacer group which is selected from - (CH ₂ ) _n with n = 0 to 4, -COO- (CH ₂ ) _k - with k = 1 to 6, -C (O) -NH-C (CH ₃ ) ₂ - and -C (O) -NH-CH (CH ₂ CH ₃ ) -.

Preferred among these monomers are those of the formulas H ₂ C = CH-X-SO ₃ H H ₂ C = C (CH ₃ ) -X-SO ₃ H HO ₃ SX- (R ⁶ ) C = C (R ⁷ ) -X-SO ₃ H, in which R ⁶ and R ^{7 are} independently selected from -H, -CH ₃ , -CH ₂ CH ₃ , -CH ₂ CH ₂ CH ₃ , -CH (CH ₃ ) ₂ and X is an optional spacer group which is selected from - (CH ₂ ) _n with n = 0 to 4, -COO- (CH ₂ ) _k - with k = 1 to 6, -C (O) -NH-C (CN ₃ ) ₂ - and -C (O) -NH-CH (CH ₂ CH ₃ ) -.

Especially preferred sulfonic acid group-containing Monomers are 1-acrylamido-1-propanesulfonic acid, 2-acrylamido-2-propanesulfonic acid, 2-acrylamido-2-methyl-1-propanesulfonic acid, 2-methacrylamido-2-methyl-1-propanesulfonic acid, 3-methacrylamido-2-hydroxy propanesulfonic acid, allylsulfonic acid, methallylsulfonic acid, allyloxybenzenesulfonic acid, methallyloxybenzenesulfonic acid, 2-hydroxy-3- (2-propenyloxy) propanesulfonic acid, 2-methyl-2-propene-1-sulfonic acid, styrenesulfonic acid, vinylsulfonic acid, 3-sulfopropyl acrylate, 3-sulfopropyl methacrylate, Sulfomethacrylamide, sulfomethylmethacrylamide and water-soluble salts the acids mentioned.

Particularly suitable other ionic or nonionic monomers are ethylenically unsaturated compounds. The content of the polymers used in these other ionic or nonionic monomers is preferably less than 20% by weight, based on the polymer. Particularly preferred polymers to be used consist only of monomers of the formula R ¹ (R ² ) C =C (R ³ ) COOH and monomers of the formula R ⁵ (R ⁶ ) C =C (R ⁷ ) -X-SO ₃ H.

• i) ungesättigten Carbonsäuren der Formel R¹(R²)C=C(R³)COOH in der R¹ bis R³ unabhängig voneinander für -H, -CH₃, einen geradkettigen oder verzweigten gesättigten Alkylrest mit 2 bis 12 Kohlenstoffatomen, einen geradkettigen oder verzweigten, ein- oder mehrfach ungesättigten Alkenylrest mit 2 bis 12 Kohlenstoffatomen, mit -NH₂, -OH oder -COOH substituierte Alkyl- oder Alkenylreste wie vorstehend definiert oder für -COOH oder -COOR⁴ steht, wobei R⁴ ein gesättigter oder ungesättigter, geradkettigter oder verzweigter Kohlenwasserstoffrest mit 1 bis 12 Kohlenstoffatomen ist,
• ii) Sulfonsäuregruppen-haltigen Monomeren der Formel R⁵(R⁶)C=C(R⁷)-X-SO₃H in der R⁵ bis R⁷ unabhängig voneinander für -H, -CH₃, einen geradkettigen oder verzweigten gesättigten Alkylrest mit 2 bis 12 Kohlenstoffatomen, einen geradkettigen oder verzweigten, ein- oder mehrfach ungesättigten Alkenylrest mit 2 bis 12 Kohlenstoffatomen, mit -NH₂, -OH oder -COOH substituierte Alkyl- oder Alkenylreste wie vorstehend definiert oder für -COOH oder -COOR⁴ steht, wobei R⁴ ein gesättigter oder ungesättigter, geradkettigter oder verzweigter Kohlenwasserstoffrest mit 1 bis 12 Kohlenstoffatomen ist, und X für eine optional vorhandene Spacergruppe steht, die ausgewählt ist aus -(CH₂)_n- mit n = 0 bis 4, -COO-(CH₂)_k- mit k = 1 bis 6, -C(O)-NH-C(CH₃)₂- und -C(O)-NH-CH(CH₂CH₃)
• (iii) gegebenenfalls weiteren ionogenen oder nichtionogenen Monomeren besonders bevorzugt.

In summary, copolymers are made of

• i) unsaturated carboxylic acids of the formula R ¹ (R ² ) C = C (R ³ ) COOH in the R ¹ to R ³ independently of one another are -H, -CH ₃ , a straight-chain or branched saturated alkyl radical having 2 to 12 carbon atoms, a straight-chain or branched, mono- or polyunsaturated alkenyl radical having 2 to 12 carbon atoms, alkyl or alkenyl radicals substituted by -NH ₂ , -OH or -COOH as defined above or -COOH or -COOR ⁴ , where R ^{4 is} a saturated or unsaturated, straight-chain or branched hydrocarbon radical having 1 to 12 carbon atoms,
• ii) sulfonic acid group-containing monomers of the formula R ⁵ (R ⁶ ) C =C (R ⁷ ) -X-SO ₃ H in the R ⁵ to R ⁷ independently of one another are -H, -CH ₃ , a straight-chain or branched saturated alkyl radical with 2 to 12 carbon atoms, a straight-chain or branched, mono- or polyunsaturated alkenyl radical having 2 to 12 carbon atoms, with -NH ₂ , -OH or -COOH substituted alkyl or alkenyl radicals as defined above or is -COOH or -COOR ⁴ in which R ^{4 is} a saturated or unsaturated, straight-chain or branched hydrocarbon radical having 1 to 12 carbon atoms, and X is an optionally present spacer group which is selected from - (CH ₂ ) _n - where n = 0 to 4, -COO- (CH ₂ ) _k - with k = 1 to 6, -C (O) -NH-C (CH ₃ ) ₂ - and -C (O) -NH-CH (CH ₂ CH ₃ )
• (iii) optionally further ionogenic or nonionic monomers are particularly preferred.

• i) einer oder mehreren ungesättigter Carbonsäuren aus der Gruppe Acrylsäure, Methacrylsäure und/oder Maleinsäure
• ii) einem oder mehreren Sulfonsäuregruppen-haltigen Monomeren der Formeln: H₂C=CH-X-SO₃H H₂C=C(CH₃)-X-SO₃H HO₃S-X-(R⁶)C=C(R⁷)-X-SO₃H, in der R⁶ und R⁷ unabhängig voneinander ausgewählt sind aus -H, -CH₃, -CH₂CH₃, -CH₂CH₂CH₃, -CH(CH₃)₂ und X für eine optional vorhandene Spacergruppe steht, die ausgewählt ist aus -(CH₂)_n- mit n = 0 bis 4, -COO-(CH₂)_k- mit k = 1 bis 6, -C(O)-NH-C(CH₃)₂- und -C(O)-NH-CH(CH₂CH₃)-
• iii) gegebenenfalls weiteren ionogenen oder nichtionogenen Monomeren.

Further particularly preferred copolymers consist of

• i) one or more unsaturated carboxylic acids from the group of acrylic acid, methacrylic acid and / or maleic acid
• ii) one or more sulfonic acid group-containing monomers of the formulas: H ₂ C = CH-X-SO ₃ H H ₂ C = C (CH ₃ ) -X-SO ₃ H HO ₃ SX- (R ⁶ ) C = C (R ⁷ ) -X-SO ₃ H, in which R ⁶ and R ^{7 are} independently selected from -H, -CH ₃ , -CH ₂ CH ₃ , -CH ₂ CH ₂ CH ₃ , -CH (CH ₃ ) ₂ and X is an optional spacer group which is selected from - (CH ₂ ) _n - with n = 0 to 4, -COO- (CH ₂ ) _k - with k = 1 to 6, -C (O) -NH-C (CH ₃ ) ₂ - and - C (O) -NH-CH (CH ₂ CH ₃ ) -
• iii) optionally further ionogenic or nonionic monomers.

The Copolymers can the monomers from groups i) and ii) and optionally iii) contained in varying amounts, all representatives from the group i) with all Representatives from group ii) and all representatives from the group Group iii) can be combined. Particularly preferred polymers have certain structural units on, which are described below.

For example, copolymers which are structural units of the formula are preferred - [CH ₂ -CHCOOH] _m - [CH ₂ -CHC (O) -Y-SO ₃ H] _p - in which m and p are each an integer between 1 and 2,000 and Y is a spacer group selected from substituted or unsubstituted aliphatic, aromatic or substituted aromatic hydrocarbon radicals having 1 to 24 carbon atoms, wherein spacer groups in which Y. for -O- (CH ₂ ) _n with n = 0 to 4, for -O- (C ₆ H ₄ ) -, for -NH-C (CH ₃ ) ₂ - or -NH-CH (CH ₂ CH ₃ ) - stands, are preferred.

These polymers are prepared by copolymerization of acrylic acid with a sulfonic acid-containing acrylic acid derivative. When the acrylic acid derivative containing sulfonic acid groups is copolymerized with methacrylic acid, another polymer is obtained whose use is likewise preferred. The corresponding copolymers contain the structural units of the formula - [CH ₂ -C (CH ₃ ) COOH] _m - [CH ₂ -CHC (O) -Y-SO ₃ H] _p -, in which m and p are each an integer between 1 and 2000 and Y is a spacer group selected from substituted or unsubstituted aliphatic, aromatic or substituted aromatic hydrocarbon radicals having 1 to 24 carbon atoms, wherein O- (CH ₂ ) _n where n = 0 to 4, -O- (C ₆ H ₄ ) -, -NH-C (CH ₃ ) ₂ - or -NH-CH (CH ₂ CH ₃ ) - , are preferred.

Acrylic acid and / or methacrylic acid can also be copolymerized completely analogously with methacrylic acid derivatives containing sulfonic acid groups, as a result of which the structural units in the molecule are changed. Thus, copolymers which are structural units of the formula - [CH ₂ -CHCOOH] _m - [CH ₂ -C (CH ₃ ) C (O) -Y-SO ₃ H] _p - in which m and p are each an integer between 1 and 2,000 and Y is a spacer group selected from substituted or unsubstituted aliphatic, aromatic or substituted aromatic hydrocarbon radicals having 1 to 24 carbon atoms, wherein spacer groups in which Y. for -O- (CH ₂ ) _n - with n = 0 to 4, for -O- (C ₆ H ₄ ) -, for -NH-C (CH ₃ ) ₂ - or -NH-CH (CH ₂ CH ₃ ) -, as preferred as copolymers, the structural units of the formula - [CH ₂ -C (CH ₃ ) COOH] _m - [CH ₂ -C (CH ₃ ) C (O) -Y-SO ₃ H] _p - in which m and p are each an integer between 1 and 2,000 and Y is a spacer group selected from substituted or unsubstituted aliphatic, aromatic or substituted aromatic hydrocarbon radicals having 1 to 24 carbon atoms, wherein spacer groups in which Y. for -O- (CH ₂ ) with n = 0 to 4, for -O- (C ₆ H ₄ ) -, for -NH-C (CH ₃ ) ₂ - or -NH-CH (CH ₂ CH ₃ ) - is, are preferred.

Instead of acrylic acid and / or methacrylic acid or in addition thereto, maleic acid can also be used as a particularly preferred monomer from group i). This gives way to inventively preferred copolymers, the structural units of the formula - [HOOCCH-CHCOOH] _m - [CH ₂ -CHC (O) -Y-SO ₃ H] _p - in which m and p are each an integer between 1 and 2000 and Y is a spacer group selected from substituted or unsubstituted aliphatic or aromatic hydrocarbon radicals having 1 to 24 carbon atoms, wherein spacer groups in which Y is -O - (CH ₂ ) _n where n = 0 to 4, -O- (C ₆ H ₄ ) -, -NN-C (CH ₃ ) ₂ - or -NH-CH (CH ₂ CH ₃ ) -, are preferred. Also preferred according to the invention are copolymers which contain structural units of the formula - [HOOCCH-CHCOOH] _m - [CH ₂ -C (CH ₃ ) C (O) OY-SO ₃ H] _p - in which m and p are each an integer between 1 and 2000 and Y is a spacer group selected from substituted or unsubstituted aliphatic, aromatic or substituted aromatic hydrocarbon radicals having 1 to 24 carbon atoms, wherein spacer groups in which Y. for -O- (CH ₂ ) _n - with n = 0 to 4, for -O- (C ₆ H ₄ ) -, for -NH-C (CH ₃ ) ₂ - or -NH-CH (CH ₂ CH ₃ )- stands.

In summary, such copolymers are preferred according to the invention, the structural units of the formulas - [CH ₂ -CHCOOH] _m - [CH ₂ -CHC (O) -Y-SO ₃ H] _p - - [CH ₂ -C (CH ₃ ) COOH] _m [CH ₂ -CHC (O) -Y-SO ₃ H] _p - - [CH ₂ -CHCOOH] _m - [CH ₂ -C (CH ₃ ) C (O) -Y-SO ₃ H] _p - - [CH ₂ -C (CH ₃ ) COOH] _m - [CH ₂ -C (CH ₃ ) C (O) -Y-SO ₃ H] _p - - [HOOCCH-CHCOOH] _m - [CH ₂ -CH _C (O) -Y-SO ₃ H] _p - - [HOOCCH-CHCOOH] _m - [CH ₂ -C (CH ₃ ) C (O) OY-SO ₃ H] _p - in which m and p are each an integer between 1 and 2,000 and Y is a spacer group selected from substituted or unsubstituted aliphatic, aromatic or substituted aromatic hydrocarbon radicals having from 1 to 24 carbon atoms, wherein spacer groups in which Y for -O- (CH ₂ ) _n - with n = 0 to 4, for -O- (C ₆ H ₄ ) -, for -NH-C (CH ₃ ) ₂ - or -NH-CH (CH ₂ CH ₃ ) - are, are preferred.

• a) mindestens eine Klarspülsubstanz aus der Gruppe a') der Hydroxymischether, a'') der Polymere mit kationischer Monomereinheit und a''') der Copolymere aus Sulfonsäure-haltigen Monomeren, die Struktureinheiten der Formeln -[CH₂-CHCOOH]_m-[CH₂-CHC(O)-Y-SO₃H]_p- -[CH₂-C(CH₃)COOH]_m-[CH₂-CHC(O)-Y-SO₃H]_p- -[CH₂-CHCOOH]_m-[CH₂-C(CH₃)C(O)-Y-SO₃H]_P- -[CH₂-C(CH₃)COOH]_m-[CH₂-C(CH₃)C(O)-Y-SO₃H]_p- -[HOOCCH-CHCOOH]_m-[CH₂-CHC(O)-Y-SO₃H]_P- und -[HOOCCH-CHCOOH]_m-[CH₂-C(CH₃)C(O)O-Y-SO₃H]_p- enthalten und
• b) mindestens eine schwefelhaltige Aminosäure.

The present invention is a washing or cleaning agent containing

• a) at least one rinse aid from the group a ') of the mixed hydroxy ether, a ") of the polymers having a cationic monomer unit and a ''') of the copolymers of sulfonic acid-containing monomers, the structural units of the formulas - [CH ₂ -CHCOOH] _m - [CH ₂ -CHC (O) -Y-SO ₃ H] _p - - [CH ₂ -C (CH ₃ ) COOH] _m - [CH ₂ -CHC (O) -Y-SO ₃ H] _p - - [CH ₂ -CHCOOH] _m - [CH ₂ -C (CH ₃ ) C (O) -Y-SO ₃ H] _P - - [CH ₂ -C (CH ₃ ) COOH] _m - [CH ₂ -C (CH ₃ ) C (O) -Y-SO ₃ H] _p - - [HOOCCH-CHCOOH] _m - [CH ₂ -CHC (O) -Y-SO ₃ H] _P - and - [HOOCCH-CHCOOH] _m - [CH ₂ -C (CH ₃ ) C (O) OY-SO ₃ H] _p - included and
• b) at least one sulfur-containing amino acid.

In the polymers can the sulfonic acid groups wholly or partly in neutralized form, i. that the acidic acid atom of the sulfonic acid group in some or all of them Sulfonic acid groups against Metal ions, preferably alkali metal ions and in particular against Sodium ions, can be replaced. The use of partial or fully neutralized sulfonic acid group-containing Copolymer is preferred according to the invention.

The Monomer distribution of the copolymers preferably used according to the invention is for copolymers containing only monomers from groups i) and ii), preferably in each case from 5 to 95% by weight of i) or ii), particularly preferably 50 to 90% by weight of monomer from group i) and 10 to 50% by weight Monomer from group ii), in each case based on the polymer.

at Terpolymers are particularly preferred which contain from 20 to 85% by weight. Monomer from group i), 10 to 60 wt .-% monomer from the group ii) and 5 to 30 wt .-% of monomer from group iii).

The molar mass of the sulfo copolymers preferably used according to the invention can be varied in order to adapt the properties of the polymers to the desired end use. Preferred detergents or cleaners are characterized in that the copolymers have molar masses of 2000 to 200,000 gmol ^-1 , preferably of 4,000 to 25,000 gmol ^-1 and in particular of 5,000 to 15,000 gmol ^-1 (weight-average molar masses M _w determined by gel permeation chromatography (GPC) and UV detector).

• a) mindestens eine Klarspülsubstanz aus der Gruppe a') der Hydroxymischether, a'') der Polymere mit kationischer Monomereinheit und a''') der Copolymere aus Sulfonsäure-haltigen Monomeren, wobei die Copolymere Molmassen von 2000 bis 200.000 gmol^-1, vorzugsweise von 4000 bis 25.000 gmol^-1 und insbesondere von 5000 bis 15.000 gmol^-1 aufweisen und
• b) mindestens eine schwefelhaltige Aminosäure.

The present invention is a washing or cleaning agent containing

• a) at least one rinse aid substance from the group a ') of the hydroxymix ether, a ") of the polymers having a cationic monomer unit and a''') of the copolymers of sulfonic acid-containing monomers, where the copolymers have molar masses of 2000 to 200,000 gmol ^-1 , preferably from 4000 to 25,000 gmol ^-1 and in particular from 5000 to 15,000 gmol ^-1 and
• b) at least one sulfur-containing amino acid.

While the Copolymers with sulfonic acid-containing Counteract monomers, in particular phosphate-containing deposits, Sulfur-containing amino acids prevent the formation of deposits Silver. In combination, the substance classes show a synergistic Effect in the field of silver protection.

In preferred embodiments In the present invention, this effect of reduced deposit formation and thus the prevention of blackish deposits on the Silver by the addition of rinse aid substances of groups a ') (hydroxymix ether) and / or a ") (polymers with cationic Monomer unit) is still increased.

In a preferred embodiment In the present invention, as rinse aids, hydroxy mixed ethers are used and copolymers of sulfonic acid-containing Monomers used. In this case, the weight ratio of Components preferably between 1: 100 and 10: 1, preferably between 1:75 and 7.5: 1, more preferably between 1:50 and 5: 1, whole particularly preferably between 1:25 and 2.5: 1 and in particular between 1:10 and 1: 1.

The use of polymers with cationic monomer and copolymers with sulfonic acid-containing monomers provides a further preferred embodiment of the washing or cleaning invention To optimize the synergistic effects of this rinse aid combination with the sulfur-containing amino acid (s), the proportion by weight of the copolymers with sulfonic acid-containing monomers is preferably between 1: 700 and 1:10, preferably between 1: 500 and 1:30 , more preferably between 1: 300 and 1:50 and especially between 1: 150 and 1:50.

In phosphate-free formulations, the use of which phosphate formation Deposits are rarely observed, sulfur-containing amino acids are preferred with hydroxy mixed ethers and polymers with cationic monomer unit combined.

at the combination of the sulfur-containing amino acid (s) with hydroxy mixed ethers and polymers with cationic monomer unit it is preferred the proportion by weight of the hydroxy mixed ether in relation to the weight fraction the polymer is at least ten times as high.

Prefers is the weight ratio the hydroxymix ether a ') to the polymers with cationic monomer unit a ") between 10: 1 and 200: 1, preferably between 12.5: 1 and 150: 1, more preferably between 15: 1 and 100: 1, more preferably between 17.5: 1 and 50: 1 and in particular between 20: 1 and 40: 1.

Sulfur-containing amino acid (b)

The Washing according to the invention or detergent at least one sulfur-containing amino acid. Preference is given to methionine, Cysteine and / or cystine, cysteine being particularly preferred and cystine, preferably cysteine and especially L-cysteine Corrosion inhibitor for Silver is used.

In a preferred embodiment The invention relates to the sulfur-containing amino acid in a proportion by weight from 0.01 to 10 wt .-%, preferably 0.05 to 8 wt .-%, preferably 0.10 to 6% by weight, more preferably 0.15 to 4 wt .-%, most preferably 0.20 to 2 wt .-% and in particular 0.20 to 1 wt .-%, based on the entire remedy, used.

The Amino acids) b) and the rinse aid substance (s) used a) reinforce effect each other so that washing or cleaning agent significantly higher silver corrosion protection as described in the prior art means. To achieve the biggest synergistic Effects is the weight ratio the rinse aid substances a) to the sulfur-containing amino acid (s) b) preferably between 450: 1 and 1: 100, preferably between 350: 1 and 1:80, especially preferably between 250: 1 and 1:60, very particularly preferably between 200: 1 and 1:40 and especially between 100: 1 and 1:20.

In a further preferred embodiment of the invention the weight ratio the rinse aid substance (s) a) to the sulfur-containing amino acid b) preferably between 400: 1 and 1:10, preferably between 350: 1 and 10: 1 and in particular between 300: 1 and 30: 1.

• a) mindestens eine Klarspülsubstanz aus der Gruppe a') der Hydroxymischether, a'') der Polymere mit kationischer Monomereinheit und a''') der Copolymere aus Sulfonsäure-haltigen Monomeren und
• b) mindestens eine schwefelhaltige Aminosäure,

wobei das Gewichtsverhältnis der Klarspülsubstanzen) a) zu der schwefelhaltigen Aminosäure b) vorzugsweise zwischen 400:1 und 1:10, bevorzugt zwischen 350:1 und 10:1 und insbesondere zwischen 300:1 und 30:1 beträgt.The present invention is a washing or cleaning agent containing

• a) at least one rinse aid from the group a ') of the mixed hydroxy ether, a'') of the polymers with cationic monomer unit and a''') of the copolymers of sulfonic acid-containing monomers and
• b) at least one sulfur-containing amino acid,

wherein the weight ratio of the rinse aid substances a) to the sulfur-containing amino acid b) is preferably between 400: 1 and 1:10, preferably between 350: 1 and 10: 1 and in particular between 300: 1 and 30: 1.

It can Klarspülsubstanzen from one, from two or from all three groups a) in the agent according to the invention be included.

Around one possible size positive reinforcement the effects of sulfur-containing amino acid and rinse aid substances to reach the weight ratios between sulfur-containing amino acid and the respective rinse aids be respected.

there is the weight ratio the hydroxymix ether a ') to the sulfur-containing amino acid b) preferably between 55: 1 and 2: 1, preferably 50: 1 and 4: 1, especially preferably between 45: 1 and 6: 1, very particularly preferably between 40: 1 and 8: 1 and especially between 35: 1 and 10: 1.

The weight ratio the polymers with cationic monomer unit a ") to the sulfur-containing amino acid b) amounts to preferably between 30: 1 and 1: 100, preferably between 20: 1 and 1:80, more preferably between 10: 1 and 1:60, especially preferably between 5: 1 and 1:40 and in particular between 1: 1 and 1:20.

One preferred washing or cleaning agent is characterized that the weight ratio the copolymers of sulfonic acid-containing Monomers a '' ') to the sulfur-containing amino acid b) between 250: 1 and 12: 1, preferably between 200: 1 and 13: 1, more preferably between 150: 1 and 14: 1, most preferably between 100: 1 and 15: 1, and more preferably between 50: 1 and 16: 1.

supply forms

The Incorporation of the synergistically cooperating rinse aid substances and the sulfur-containing amino acids in detergents or cleaning agents no restriction regarding the The form or formulas of these products. The funds can therefore both solid and liquid Be provided form.

Prefers the washing or cleaning agent is in liquid form. as it were preferred in the context of the present invention is the provision a washing or cleaning agent which has a gel-like consistency having.

Liquid detergents, in the context of the present invention, are aqueous and non-aqueous agents based on liquid Ingredients with dynamic viscosities in the range between 0.2 and 1000 mPa · s, but also higher viscosity Means with viscosities above 1000 mPa · s up to cut-resistant and dimensionally stable gels are possible forms of supply (Brookfield, spindle 31, 30 rpm, 20 ° C).

• a) mindestens eine Klarspülsubstanz aus der Gruppe a') der Hydroxymischether, a'') der Polymere mit kationischer Monomereinheit und a''') der Copolymere aus Sulfonsäure-haltigen Monomeren und
• b) mindestens eine schwefelhaltige Aminosäure.

The present invention is a liquid aqueous washing or cleaning agent containing

• a) at least one rinse aid from the group a ') of the mixed hydroxy ether, a'') of the polymers with cationic monomer unit and a''') of the copolymers of sulfonic acid-containing monomers and
• b) at least one sulfur-containing amino acid.

• a) mindestens eine Klarspülsubstanz aus der Gruppe a') der Hydroxymischether, a'') der Polymere mit kationischer Monomereinheit und a''') der Copolymere aus Sulfonsäure-haltigen Monomeren und
• b) mindestens eine schwefelhaltige Aminosäure.

The present invention is also a liquid non-aqueous detergent or cleaning agent containing

• a) at least one rinse aid from the group a ') of the mixed hydroxy ether, a'') of the polymers with cationic monomer unit and a''') of the copolymers of sulfonic acid-containing monomers and
• b) at least one sulfur-containing amino acid.

Aqueous wash or detergents contain by definition more than 7% by weight, preferably more as 17% by weight and in particular more than 27% by weight of water, while non-aqueous detergents or cleaners by definition up to 7 wt .-%, preferably less than 5 wt .-% and preferably less than 3 wt .-% water, each based on the total agent included.

A preferred embodiment the agents according to the invention is liquid or gel and can be used as a cleaning agent for the manual dishwashing are used.

preferred non-aqueous liquid Detergents contain solvents from the group of ethanol, n-propanol, i-propanol, 1-butanol, 2-butanol, Glycol, propanediol, butanediol, glycerol, diglycol, propyldiglycol, butyldiglycol, Hexylene glycol, ethylene glycol methyl ether, ethylene glycol ethyl ether, Ethylene glycol propyl ether, etheylene glycol mono-n-butyl ether, diethylene glycol methyl ether, Diethylene glycol ethyl ether, propylene glycol methyl, ethyl or propyl ethene, Dipropylene glycol methyl, or ethyl ether, methoxy, ethoxy or Butoxytriglycol, 1-butoxyethoxy-2-propanol, 3-methyl-3-methoxybutanol, propylene glycol t-butyl ether or mixtures thereof.

to Adjustment of viscosity liquid Offer forms of cleaning agents according to the invention these typically still contain one or more thickening agents. Preferred thickening agents are agar-agar, carrageenan, tragacanth, Gum arabic, alginates, pectins, polyoses, guar flour, locust bean gum, Strength, Dextrins, gelatin, casein, carboxymethylcellulose, hydroxyethylcellulose, Hydroxypropylcellulose, hydroxypropylmethylcellulose, gum ethers, Polyacrylic u. Polymethacrylic compounds, vinyl polymers, polycarboxylic acids, polyethers, Polyimines, polyamides, polysilicic acids, clay minerals such as montmorillonites, Zeolites and silicas.

One Another typical ingredient of liquid aqueous cleaning agents are Hydrotropes. The addition of such substances causes a poorly soluble substance becomes water-soluble in the presence of the hydrotrope, which itself is not a solvent. Substances that improve solubility cause, are called hydrotropes or hydrotropes. typical Hydrotrope, e.g. in the packaging of liquid detergents or cleaners, are xylene and cumene sulfonate. Other substances, e.g. urea od. N-methylacetamide, increase the solubility by a structure-breaking Effect where the water structure in the environment of the hydrophobic Group of a sparingly soluble Material is degraded.

firm Offer forms of machine according to the invention dishwashing detergent are, for example, fine to coarse-grained powder, as for example by spray drying or granulation, compressed mixtures of substances the Walzenkompaktierung, but also solidified melts or by Extrusion or tabletting obtained moldings.

A The first preferred prefabricated dosage unit is the tablet. to Preparation of tablets are particulate premixes in one so-called matrix between two stamps to a fixed Comprimat compacted. This process, hereinafter briefly referred to as tableting is divided into four sections: metering, compaction, plastic deformation and ejection.

First, will introduced the premix in the die, wherein the filling amount and thus the weight and the shape of the resulting molded body the position of the lower punch and the shape of the pressing tool be determined. The constant dosage even at high molding throughputs is preferably over reached a volumetric dosage of the premix. In the further Touched the course of tableting the upper stamp the pre-mix and lower in the direction of of the lower punch. In this compression, the particles become closer to the premix pressed together wherein the void volume within the filling between the punches decreases continuously. From a certain position of the upper punch (and thus from a certain pressure on the premix) begins the plastic deformation, in which the particles flow together and it for the formation of the molding comes. Depending on the physical properties of the premix Part of the premix particles is also crushed and it comes at even higher pressures a sintering of the premix. With increasing pressing speed, So high throughput, the phase of elastic deformation is always further shortened, so that the resulting shaped body more or less big cavities can have. In the last step of tabletting the finished molding is through pushed the lower punch out of the die and through subsequent Transportation transported away. At this time, only the weight of the molded article is finally determined, since the compacts due to physical processes (re-stretching, crystallographic effects, cooling etc.) can change their shape and size.

The Tableting is done in commercial Tablet presses, in principle with single or double punches equipped could be. In the latter case, not only the upper punch for pressure build-up also the lower punch moves up during the pressing process the upper temple too, during the Upper punch presses down. For small Production quantities are preferably used eccentric tablet presses, where the stamp or attached to an eccentric disc are, in turn, on an axis with a certain rotational speed is mounted. The movement of this press-stamp is with the working method a usual one Four-stroke engine comparable. The compression can be done with one upper and stamped, it can but also several stamps attached to an eccentric disc, wherein the number of die holes is extended accordingly. The throughputs of eccentric presses vary by type from a few hundred to maximum 3000 tablets per hour.

at Eccentric presses will be the lower punch during the pressing process in the Normally not moved. One consequence of this is that the resulting Tablet a hardness gradient has, i. in the areas closer to the upper temple, harder is as in the areas closer to the lower stamp.

For larger throughputs you can choose rotary tablet presses, where on a so-called Ma Trizentisch a larger number of matrices is arranged in a circle. The number of matrices varies between 6 and 55 depending on the model, although larger matrices are commercially available. Each die on the die table is assigned an upper and lower punch, in turn, the pressing pressure can be actively built only by the upper or lower punch, but also by both stamp. The die table and the punches move about a common vertical axis, the punches are brought by means of rail-like cam tracks during the circulation in the positions for filling, compression, plastic deformation and ejection. At the points where a particularly serious raising or lowering of the punches is required (filling, compaction, ejection), these curved paths are supported by additional low-pressure pieces, Niederzugschienen and lifting tracks. The filling of the die via a rigidly arranged supply device, the so-called filling shoe, which is connected to a reservoir for the premix. The pressing pressure on the premix is individually adjustable via the pressing paths for upper and lower punches, the pressure being built up by the rolling of the punch shaft heads on adjustable pressure rollers.

Rotary presses can to increase the throughput with two filling shoes be provided, wherein for the preparation of a tablet only one Semicircle must be traversed. For the production of two- and multi-layered moldings be several filling shoes arranged one behind the other, without the slightly pressed first Layer before further filling pushed out becomes. Through suitable process management In this way coat and point tablets can also be produced, which have a onion - bowl - like structure, in the case of the Punkttabletten the top of the core or the core layers not covered and thus remains visible. Also rotary tablet presses are Equipped with single or multiple tools, so that, for example an outer circle with 50 and an inner circle with 35 holes at the same time for pressing to be used. The throughputs modern rotary tablet presses amount to over one million moldings per Hour.

Of course, let the tablets in the context of the present invention also multiphase, in particular multi-layered, designed. The moldings can thereby be made in a predetermined spatial form and predetermined size. As a spatial form Virtually all sensibly manageable configurations come into consideration, for example, the training as a blackboard, the bar or bar form, Cube, Cuboid and corresponding room elements with flat side surfaces as well in particular cylindrical Embodiments with circular or oval section. This last embodiment covers the presentation form of the tablet to compact cylinder pieces with a relationship of height to diameter above 1.

• a) mindestens eine Klarspülsubstanz aus der Gruppe a') der Hydroxymischether, a'') der Polymere mit kationischer Monomereinheit und a''') der Copolymere aus Sulfonsäure-haltigen Monomeren und
• b) mindestens eine schwefelhaltige Aminosäure.

The present invention is a washing or cleaning agent in the form of a multilayer tablet containing

• a) at least one rinse aid from the group a ') of the mixed hydroxy ether, a'') of the polymers with cationic monomer unit and a''') of the copolymers of sulfonic acid-containing monomers and
• b) at least one sulfur-containing amino acid.

preferred tableted agents are within the scope of the present invention two or more phases, for example, their composition, their share of the total volume of the molding and / or their optical Can distinguish appearance. The invention contained Ingredients a) and b) can both in one phase and on different ones Phases are distributed. It is particularly preferred that the hydroxymix ethers a '), the polymers with cationic monomer unit a ") and the copolymers of sulfonic acid-containing Monomers a '' ') do not contain together in one phase are, but in each case in community with the sulfur-containing Amino acid (s) are present.

The Phases of such multiphase moldings may additionally by a different dissolution behavior in water Phase out. Such moldings are suitable for the time controlled release of certain ingredients (controlled release), for example in certain rinses of the machine washing or washing program.

In a preferred embodiment, one of the phases of the tablet as a main component meltable or softenable substances from the group of waxes, paraffins and / or polyalkylene glycols. Furthermore, it has proved to be advantageous if the tablets or tablet components containing these meltable or softenable substances is at least substantially insoluble in water. The solubility in Water should not exceed about 10 mg / l at a temperature of about 30 ° C and preferably be below 5 mg / l. In such cases, however, the meltable or softenable substances should have the lowest possible water solubility, even in water at elevated temperature, in order to avoid as much as possible a temperature-independent release of the active substances. The release of the active substance takes place in this way upon reaching the melting or softening point.

The Room shape of another embodiment the tablets is in their dimensions of the dispenser of commercial Household washing machines or the dosing chamber commercially available dishwashers adjusted so that the tablets without dosing directly into the bleach dispenser can be metered in, where they are during the flushing process dissolve, or from where they are during of the cleaning process are released. Of course it is but also the use of washing and cleaning agent tablets via dosing aids easily possible.

• a) mindestens eine Klarspülsubstanz aus der Gruppe a') der Hydroxymischether, a'') der Polymere mit kationischer Monomereinheit und a''') der Copolymere aus Sulfonsäure-haltigen Monomeren und
• b) mindestens eine schwefelhaltige Aminosäure

in handelsüblichen Geschirrspülmaschinen.The present invention is the use of a detergent or cleaning agent tablet containing

• a) at least one rinse aid from the group a ') of the mixed hydroxy ether, a'') of the polymers with cationic monomer unit and a''') of the copolymers of sulfonic acid-containing monomers and
• b) at least one sulfur-containing amino acid

in commercially available dishwashers.

In a further preferred embodiment According to the invention, the composition comprises a water - soluble packaging, which in Shape of a deep-drawn part and / or injection-molded part and / or blow-molded part is present.

As a "deep-drawn part" or "thermoforming body" are in the frame the present application, such containers designated by Deep drawing of a first sheet-like wrapping material can be obtained. The deep drawing is preferably carried out by moving the shell material over a in a thermoforming forming die cavity and molding the wrapping material in this receiving trough by the action of pressure and / or vacuum is deformed. The wrapping material can do this before or during the Forming by the action of heat and / or solvent and / or conditioning modified by environmental conditions relative humidities and / or temperatures are pretreated. The pressure can be applied through two parts of a tool, which behave as positive and negative to each other and one deforming film when deformed between these tools. As pressure forces However, the action of compressed air and / or is also suitable Dead weight of the film and / or the weight of one on the top the film spent active substance.

The deep-drawn shell materials after deep drawing, preferably by use of a vacuum within the receiving troughs and in their by the deep drawing process Fixed spatial form fixed. The vacuum is preferably continuous from deep drawing to filling preferably until sealed and in particular until dicing created the receiving chambers. With comparable success, however also the use of a discontinuous vacuum, for example for drawing the receiving chambers and (after a break) before and during of filling the admission chambers, possible. Also, the continuous or discontinuous vacuum in his strength vary and for example at the beginning of the process (deep drawing the film) higher Accept values as their end (when filling or sealing or separating).

As already mentioned, the shell material can be pre-treated by the action of heat before or during the molding into the receiving troughs of the matrices. The shell material, preferably a water-soluble or water-dispersible polymer film, is heated to temperatures above 60 ° C. for up to 5 seconds, preferably for 0.1 to 4 seconds, particularly preferably for 0.2 to 3 seconds and in particular for 0.4 to 2 seconds. preferably above 80 ° C, more preferably between 100 and 120 ° C and in particular heated to temperatures between 105 and 115 ° C. In order to dissipate this heat, but in particular also to dissipate the heat introduced by the means filled into the deep-drawn receiving chambers (eg melting), it is preferable to cool the dies used and the receiving troughs located in these dies. The cooling is preferably carried out at temperatures below 20 ° C, preferably below 15 ° C, more preferably at temperatures between 2 and 14 ° C and in particular at temperatures between 4 and 12 ° C. Preferably, the cooling takes place continuously from the beginning of the deep-drawing process to the sealing and separation of the receiving chambers. Suitable for cooling in particular cooling liquids, preferably water, which are circulated in special cooling lines within the matrix.

These cooling has as well as the previously described continuous or discontinuous Applying a vacuum the advantage of shrinking the deep-drawn containers to prevent after deep drawing, which not only the appearance of the Process product is improved, but at the same time the leakage the filled in the receiving chambers Means over the edge of the receiving chamber, for example in the sealing areas the chamber is avoided. Problems with the sealing of the filled chambers are avoided.

at leaves the thermoforming process between methods in which the wrapping material is moved horizontally into a forming station and from there in a horizontal manner for filling and / or sealing and / or Separation is led and methods in which the shell material over a Continuously rotating die forming roller (optionally optional with a counter-current out Patrizenformwalze, which the forming upper punches to the cavities of Lead die roll) guided will differ. The first mentioned variant of the method Flatbed process is both continuous and discontinuous to operate, the process variant using a molding roll usually takes place continuously. All the mentioned thermoforming processes are suitable for the preparation of the inventively preferred means. The receiving troughs located in the matrices can be arranged "in series" or offset be.

The Thermoformings can have one, two, three or more receiving chambers. These recording rooms can be arranged in the deep-drawn part next to each other and / or one above the other. Preferably, the individual receiving chambers of the thermoforming body with filled with different resources. In particular, it is preferably at least one receiving chamber of a Thermoforming body with a liquid to fill while at least one further receiving chamber of this thermoforming body with a solid is filled.

• a) mindestens eine Klarspülsubstanz aus der Gruppe a') der Hydroxymischether, a'') der Polymere mit kationischer Monomereinheit und a''') der Copolymere aus Sulfonsäure-haltigen Monomeren und
• b) mindestens eine schwefelhaltige Aminosäure.

The present invention is a detergent or cleaning agent comprising a package in the form of a deep-drawn part, which has one, two, three or more receiving chambers containing

• a) at least one rinse aid from the group a ') of the mixed hydroxy ether, a'') of the polymers with cationic monomer unit and a''') of the copolymers of sulfonic acid-containing monomers and
• b) at least one sulfur-containing amino acid.

The water-soluble Packaging can also be made by injection molding. Injection molding is called while forming a molding material such that in a mass cylinder for more as an injection molding process contained mass under heat plastically softened and pressurized through a nozzle into the cavity of a previously enclosed tool flows. The process is mainly at non-curable Applied molding compounds that solidify in the tool by cooling. Injection molding is a very economical modern method of manufacture non-cutting shaped objects and is especially suitable for the automated mass production. In practical operation, one heats the thermoplastic molding compounds (powders, granules, cubes, pastes and others) up to the liquefaction (up to 180 ° C) and then injected under high pressure (up to 140 MPa) into closed, two-part, that is from Gesenk (formerly Matrix) and core (formerly Patrize) existing, preferably water-cooled molds, where they cool and solidify. Piston and screw injection molding machines can be used. Suitable molding compounds (injection molding compounds) are water-soluble polymers such as the above-mentioned cellulose ethers, pectins, polyethylene glycols, Polyvinyl alcohols, polyvinylpyrrolidones, alginates, gelatin or Strength.

A another possibility for producing water-soluble Packaging represents blow molding. Blow molding becomes one Plastic granules melted using an extruder and shaping tools supplied as a preform. The forming tool / blow molding tool surrounds the preform, from which in the viscous state by means of compressed air a hollow body is blown.

According to the invention preferred Blow molding processes include extrusion blow molding, coextrusion blow molding, injection stretch blow molding and dipping bubbles.

The wall thicknesses of the moldings can be produced by blow molding partially different, by the wall thicknesses of the preform, preferably along its vertical axis, according to different thickness, preferably by regulating the amount of thermoplastic material before preferably by means of an adjusting spindle during application of the preform from the extruder die, forms. In this way you can also blow the molding with areas of different outer circumference and constant wall thickness.

On This way, different geometrical configurations can be achieved of the molding blow molding with and without compartments. In a single work cycle So can bottles, balls, Santa Claus, Easter bunnies or others Blow molds that can be filled with medium, then sealed and then demolded.

Especially It is advantageous that the shaped body during blow molding in the Emboss blow mold and / or decorate. By appropriate design of the blow mold, can be a motive mirror image transferred to the molding. In this way let yourself the surface of the molding make virtually any shape. For example, it can be opened like this the shaped body Information such as calibration marks, instructions for use, hazard symbols, Brands, weight, capacity, Apply expiration date, pictures, etc.

The Have walls of the molded body produced by blow molding a wall thickness from between 0.05-5 mm, preferably between 0.06-2 mm, preferably between 0.07 to 1.5 mm, more preferably from 0.08-1.2 mm, more preferably from between 0.09-1 mm and most preferably, between 0.1-0.6 mm.

The Filling opening of the hollow body after filling let yourself liquid-tight, preferably by material closure, preferably by means of thermal Treatment, particularly preferably by applying a melted spot, close. The filling opening or openings of the hollow body can also be advantageous by thermal treatment, preferably by fusing the walls adjacent to the opening, in particular by means of clamping jaws, liquid-tight close.

Especially It is preferred according to the invention, the blow molding as a BFS (blow-fill-seal) method to design so that the moldings produced are still filled in the blow mold and be closed. In this blow-mold / fill-seal technique, the particular shape desired first blown, then filled with the content and then in closed a process. Here, a hose is plasticized water-soluble Plastic material in an open Blow mold extruded into it, the blow mold closed and by generating a pressure gradient acting on the tube of this widened and for the formation of the container applied to the shaping wall of the blow mold.

In a preferred embodiment The present invention encompasses the washing or cleaning agent a water-soluble Packaging having a chamber. Preferably, packaging is used the two, three, four or five Have recording chambers and so the separation of the ingredients enable. Here it is particularly preferred that the rinse aids a '), a' ') and a' '') are not common filled in a receiving chamber are, but preferably in each case together with (a) sulfur-containing amino acid (s) present. Also the separation of amino acid (s) and rinse aid substances, the combination of selected ones Klarspülsubstanzen a) with each other both with and without amino acid (s), as well as the separation of the amino acids may be preferred.

The Washing according to the invention or detergent is preferably used as a dosing unit, for example as a tablet, wash ball or pouch, provided to the consumer. Preferably, such a dosing unit comprises 10 to 30 g, especially preferably 15 to 25 g and in particular 20 to 25 g or 10 to 40 ml, preferably 12 to 30 ml and preferably 14 to 30 ml. Also preferred dosage units are from 15 to 75 ml, preferably from 20 to 70 ml and especially from 30 to 60 ml. These come especially in less concentrated liquid or gelatinous Means for use.

Preferably is the longest Room diagonal of the dosing units smaller than 15 cm, preferably smaller than 10 cm, more preferably less than 8 cm, most preferably smaller than 6 cm and especially smaller than 5 cm.

at the spatial form is preferably a cuboid, since metering units this form the highest Space utilization in dosing chambers of washing machines and dishwashers to reach.

In a preferred embodiment, the agent according to the invention containing a) and b) is granulated or extruded. Granules are particularly preferred in which the rinse aid a) is applied to a solid, which consists partly or completely of builders, and thus as binders tel serve the subsequent granulation / serves. It is also preferred that only a part of the rinse aid is used as a binder, while the other part has already been mixed with the solid. The sulfur-containing amino acids can be present here in the solid or else in the binder.

The average particle size of the granules is preferably below 5000 .mu.m, preferably between 20 and 3000 .mu.m, more preferably between 40 and 2000 .mu.m, in particular between 50 and 1600 microns. As bulk density, average values of 350 to 1200 gl ^-1 , preferably of 500 to 900 gl ^-1 and in particular of 650 to 900 gl ^{-1 are} preferred.

The Granules can be made by mixing with other washing-or cleaning-active substances as part of a washing or cleaning agent used, as well as a concentrated drug combination for targeted application on silver surfaces. For this it is preferred enriched with other ingredients to ensure high adhesion to the To reach silverware.

Also the packaging of the granules is preferably water-soluble Packaging, which with the detergent or cleaning agent in the Dosing a washing or dishwasher can be given, or can be metered directly into the washroom.

in the The scope of this invention is also water-dispersible under water-soluble Understood. The use of water-soluble or water-dispersible Packaging allows the thorough Cleaning the items to be washed even at low temperatures, where water-insoluble packaging not yet soften and therefore not the washing or cleaning agent would release.

at Application of the washing However, cleaning agents at high temperatures may be advantageous be if the packaging consists of almost water-insoluble material. In In this case, the controlled release of the active ingredients in dependence the temperature control the cleaning process possible. As a result, it is preferable to use materials which are almost water-insoluble as the shell materials used. For these materials should be at a temperature of about 30 ° C the solubility in water do not exceed about 10 mg / l and preferably below 5 mg / l.

• a) mindestens eine Klarspülsubstanz aus der Gruppe a') der Hydroxymischether, a'') der Polymere mit kationischer Monomereinheit und a''') der Copolymere aus Sulfonsäure-haltigen Monomeren,
• b) mindestens eine schwefelhaltige Aminosäure und

umfassend eine nahezu wasserunlösliche Verpackung.The present invention is a washing or cleaning agent containing

• a) at least one rinse aid substance from the group a ') of the hydroxy mixed ethers, a'') of the polymers having a cationic monomer unit and a''') of the copolymers of sulfonic acid-containing monomers,
• b) at least one sulfur-containing amino acid and

comprising a nearly water-insoluble packaging.

to Preparation of water-insoluble Packaging can same techniques are used already related with the production of water-soluble Packaging were described.

The according to the invention and detergents are preferably for machine dishwashing used.

preferred Washing according to the invention or detergents contain in addition to the builders (Builder, Cobuilder), the rinse aid substances and the sulfur-containing amino acids furthermore one or more substances from the group of bleaching agents, Bleach activators, enzymes, dyes, fragrances, or another common Component of detergents and cleaners. Additionally, you can continue Polymers, surfactants and corrosion inhibitors contained in the agents be.

These Ingredients are described below.

builders

To the builders counting in particular the zeolites, silicates, carbonates, organic cobuilders and where no ecological Prejudices against their use exist - even the phosphates.

The finely crystalline, synthetic and bound water-containing zeolite used is preferably zeolite A and / or P. As zeolite P, zeolite ^MAP® (commercial product of Crosfield) is particularly preferred prefers. Also suitable, however, are zeolite X and mixtures of A, X and / or P. Commercially available and preferably usable in the context of the present invention is, for example, a cocrystal of zeolite X and zeolite A (about 80% by weight of zeolite X) ), which is sold by the company CONDEA Augusta SpA under the brand name VEGOBOND AX ^® and by the formula n Na ₂ O • (1-n) K ₂ O • Al ₂ O ₃ • (2-2.5) SiO ₂ • (3.5-5.5) H ₂ O can be described. The zeolite can be used both as a builder in a granular compound and for a kind of "powdering" of a granular mixture, preferably a mixture to be compressed, whereby usually both ways of incorporating the zeolite into the premix are used an average particle size of less than 10 microns (volume distribution, measuring method: Coulter Counter) and preferably contain 18 to 22 wt .-%, in particular 20 to 22 wt .-% of bound water.

Suitable crystalline layered sodium silicates have the general formula NaMSi _x O _{2x + 1} H ₂ O, where M is sodium or hydrogen, x is a number from 1.9 to 4 and y is a number from 0 to 20 and preferred values for x 2 , 3 or 4 are. Preferred crystalline layered silicates of the formula given are those in which M is sodium and x assumes the values 2 or 3. In particular, both β- and δ-sodium disilicates Na ₂ Si ₂ O ₅ .yH ₂ O are preferred.

With particular preference, in particular as a constituent of automatic dishwashing compositions, crystalline layer-form silicates of the general formula NaMSi _x O _{2x + 1} .yH ₂ O are used, in which M represents sodium or hydrogen, x is a number from 1.9 to 22, preferably from 1 , 9 to 4, and y is a number from 0 to 33. The crystalline layered silicates of the formula NaMSi _x O _{2x + 1} · y H ₂ O are sold for example by Clariant GmbH (Germany) under the trade name Na-SKS. Examples of these silicates are Na-SKS-1 (Na ₂ Si ₂₂ O ₄₅ .xH ₂ O, Kenyaite), Na-SKS-2 (Na ₂ Si ₁₄ O ₂₉ .xH ₂ O, magadiite), Na-SKS -3 (Na ₂ Si ₈ O ₁₇ .xH ₂ O) or Na-SKS-4 (Na ₂ Si ₄ O ₉ .xH ₂ O, Makatite).

Particularly suitable for the purposes of the present invention are crystalline phyllosilicates of the formula NaMSi _x O _{2x + 1} .yH ₂ O, in which x is 2. Of these, especially Na-SKS-5 (α-Na ₂ Si ₂ O ₅ ), Na-SKS-7 (β-Na ₂ Si ₂ O ₅ , Natrosilit), Na-SKS-9 (NaHSi ₂ O ₅ · H ₂ O), Na-SKS-10 (NaHSi ₂ O ₅ 3H ₂ O, kanemite), Na-SKS-11 (t-Na ₂ Si ₂ O ₅₎ and Na-SKS-13 (NaHSi ₂ O ₅ ), but especially Na-SKS-6 (δ-Na ₂ Si ₂ O ₅ ).

If the silicates are used as a constituent of automatic dishwasher detergents, these compositions preferably contain a weight fraction of the crystalline layered silicate of the formula NaMSi _x O _{2x + 1} .yH ₂ O of from 0.1 to 20% by weight of from 0.2 to 15% by weight .-% and in particular from 0.4 to 10 wt .-%, each based on the total weight of these agents. It is particularly preferred in particular if such automatic dishwashing agents have a total silicate content of less than 7% by weight, preferably less than 6% by weight, preferably less than 5% by weight, more preferably less than 4% by weight, most preferably less than 3% by weight % and in particular below 2.5 wt .-%, wherein it is in this silicate, based on the total weight of the silicate contained, preferably at least 70 wt .-%, preferably at least 80 wt .-% and in particular to At least 90 wt .-% is silicate of the general formula NaMSi _x O _{2x + 1} · y H ₂ O.

It is also possible to use amorphous sodium silicates with a Na ₂ O: SiO ₂ modulus of from 1: 2 to 1: 3.3, preferably from 1: 2 to 1: 2.8 and in particular from 1: 2 to 1: 2.6, which Delayed and have secondary washing properties. The dissolution delay compared with conventional amorphous sodium silicates may have been caused in various ways, for example by surface treatment, compounding, compaction / densification or by overdrying. In the context of this invention, the term "amorphous" is also understood to mean "X-ray amorphous". This means that the silicates do not yield sharp X-ray reflections typical of crystalline substances in X-ray diffraction experiments, but at most one or more maxima of the scattered X-rays which have a width of several degrees of diffraction angle. However, it may well even lead to particularly good builder properties if the silicate particles provide blurred or even sharp diffraction maxima in electron diffraction experiments. This is to be interpreted as meaning that the products have microcrystalline regions of the size of ten to a few hundred nm, with values of up to max. 50 nm and in particular up to max. 20 nm are preferred. Such so-called X-ray amorphous silicates also have a dissolution delay compared with the conventional water glasses. Particularly preferred are compacted / compacted amorphous silicates, compounded amorphous silicates and overdried X-ray amorphous silicates.

in the Within the scope of the present invention, it is preferred that this (s) Silicate (s), preferably alkali metal silicates, particularly preferably crystalline or amorphous alkali disilicates, in detergents or cleaners in amounts of from 10 to 60% by weight, preferably from 15 to 50% by weight and in particular from 20 to 40 wt .-%, each based on the weight of the washing or cleaning agent are included.

Of course it is also a use of the well-known phosphates as builders possible, if such use is not avoided for environmental reasons should be. This applies in particular to the use according to the invention or by inventive method prepared agent as a machine dishwashing detergent, which in the context the present application is particularly preferred. Among the multitude the commercially available Phosphates have the alkali metal phosphates with particular preference of pentasodium or pentapotassium triphosphate (sodium or potassium tripolyphosphate) in the washing and cleaning industry the greatest importance.

Alkali metal phosphates is the summary term for the alkali metal (especially sodium and potassium) salts of various phosphoric acids, in which one can distinguish metaphosphoric acids (HPO ₃ ) _n and orthophosphoric H ₃ PO _{4 in} addition to higher molecular weight representatives. The phosphates combine several advantages: they act as alkali carriers, prevent lime deposits on machine parts or lime incrustations in fabrics and also contribute to the cleaning performance.

Suitable phosphates are, for example, the sodium dihydrogen phosphate, NaH ₂ PO ₄ , in the form of the dihydrate (density 1.91 gcm ^-3 , melting point 60 °) or in the form of the monohydrate (density 2.04 gcm ^-3 ), the disodium hydrogen phosphate (secondary sodium phosphate) , Na ₂ HPO ₄ , which is anhydrous or 2 moles (density 2.066 gcm ^-3 , loss of water at 95 °), 7 moles (density 1.68 gcm ^-3 , melting point 48 ° with loss of 5 H ₂ O) and 12 moles of water (Density 1.52 gcm ^-3 , melting point 35 ° with loss of 5 H ₂ O) can be used, but especially the trisodium phosphate (tertiary sodium phosphate) Na ₃ PO ₄ , which as dodecahydrate, as decahydrate (corresponding 19-20% P ₂ O ₅ ) and in anhydrous form (corresponding to 39-40% P ₂ O ₅ ) can be used.

Another preferred phosphate is the tripotassium phosphate (tertiary or tribasic potassium phosphate), K ₃ PO ₄ . Also preferred are the tetrasodium diphosphate (sodium pyrophosphate), Na ₄ P ₂ O ₇ , which is in anhydrous form (density 2.534 gcm ^-3 , melting point 988 °, also indicated 880 °) and as decahydrate (density 1.815-1.836 gcm ^-3 , melting point 94 ° with loss of water), and the corresponding potassium salt potassium diphosphate (potassium pyrophosphate), K ₄ P ₂ O ₇ .

The technically important pentasodium triphosphate, Na ₅ P ₃ O ₁₀ (sodium tripolyphosphate), is an anhydrous or with 6 H ₂ O crystallizing, non-hygroscopic, colorless, water-soluble salt of the general formula NaO- [P (O) (ONa) -O] _n -Na with n = 3. The corresponding potassium salt pentapotassium triphosphate, K ₅ P ₃ O ₁₀ (potassium tripolyphosphate), for example, comes in the form of a 50% strength by weight solution (> 23% P ₂ O ₅ , 25% K ₂ O). in the trade. The potassium polyphosphates are widely used in the washing and cleaning industry. There are also sodium potassium tripolyphosphates which can also be used in the context of the present invention. These arise, for example, when hydrolyzed sodium trimetaphosphate with KOH: (NaPO ₃ ) ₃ + 2KOH → Na ₃ K ₂ P ₃ O ₁₀ + H ₂ O

These are exact according to the invention such as sodium tripolyphosphate, potassium tripolyphosphate or mixtures can be used from these two; also mixtures of sodium tripolyphosphate and sodium potassium tripolyphosphate or mixtures of potassium tripolyphosphate and sodium potassium tripolyphosphate or mixtures of sodium tripolyphosphate and potassium tripolyphosphate and sodium potassium tripolyphosphate used according to the invention.

Become in the context of the present application phosphates as washing or cleaning active Substances used in detergents or cleaners, so included preferred agents are said phosphate (s), preferably alkali metal phosphate (s), particularly preferably pentasodium or pentapotassium triphosphate (sodium or potassium tripolyphosphate), in amounts of 5 to 80 wt .-%, preferably from 15 to 75% by weight, in particular, from 20 to 70% by weight, respectively based on the weight of the washing or cleaning agent.

It is preferred in particular to use potassium tripolyphosphate and sodium tripolyphosphate in a weight ratio of more than 1: 1, preferably more than 2: 1, preferably more than 5: 1, more preferably more than 10: 1 and in particular more than 20: 1. It is particularly preferred, exclusively potassium tripot lyphosphate without admixtures of other phosphates use.

Further builders are the alkali carriers. As alkali carrier For example, alkali metal hydroxides, alkali metal carbonates, Alkali metal bicarbonates, alkali metal sesquicarbonates, the mentioned alkali metal silicates, alkali metal silicates, and mixtures of aforementioned substances, wherein for the purposes of this invention preferably the Alkali carbonates, especially sodium carbonate, sodium bicarbonate or sodium sesquicarbonate. Especially preferred is a builder system containing a mixture of tripolyphosphate and Sodium. Also particularly preferred is a builder system containing a mixture of tripolyphosphate and sodium carbonate and sodium disilicate. Because of their compared with other builders low chemical compatibility with the rest Ingredients of detergents or cleaning agents, the alkali metal hydroxides preferably only in small amounts, preferably in amounts below 10 Wt .-%, preferably below 6 wt .-%, more preferably below 4 wt .-% and in particular below 2% by weight, based in each case on the total weight of the washing or cleaning agent used. Particularly preferred are agents which based on their total weight less than 0.5 wt .-% and especially no alkali metal hydroxides included.

Especially preference is given to the use of carbonate (s) and / or bicarbonate (s), preferably alkali metal carbonate (s), more preferably sodium carbonate, in amounts of from 2 to 50% by weight, preferably from 5 to 40% by weight and in particular from 7.5 to 30 wt .-%, each based on the Weight of washing or cleaning agent. Particularly preferred Means, based on the weight of the detergent or cleaning agent less than 20% by weight, preferably less than 17% by weight, is preferred less than 13% by weight and in particular less than 9% by weight of carbonate (s) and / or bicarbonate (s), preferably alkali carbonate (s), especially preferably contain sodium carbonate.

When Organic co-builders are in particular polycarboxylates / polycarboxylic acids, polymers Polycarboxylates, aspartic acid, Polyacetals, dextrins, other organic cobuilders (see below) as well as phosphonates. These classes of substances are hereafter described.

useful organic builders For example, they can be used in the form of their sodium salts polycarboxylic where among polycarboxylic acids such carboxylic acids be understood that carry more than one acid function. For example these are citric acid, adipic acid, Succinic acid, Glutaric acid, malic acid, tartaric acid, maleic acid, fumaric acid, sugar acids, aminocarboxylic acids, nitrilotriacetic acid (NTA), if such an application for ecological reasons not is objectionable, as well as mixtures of these. Preferred salts are the salts of polycarboxylic acids like citric acid, adipic acid, Succinic acid, glutaric, Tartaric acid, sugar acids and mixtures of these.

Also the acids in itself can be used. The acids In addition to their builder effect, they also typically have the property an acidifying component and thus serve to set a lower and milder one pH value of detergents or cleaning agents. In particular, here are citric acid, Succinic acid, glutaric, adipic acid, gluconic and to name any mixtures of these.

Especially the use of citrate-containing builder systems is preferred, preferably Sodium citrate-containing systems. As sodium citrate come anhydrous Trisodium citrate or preferably trisodium citrate dihydrate into consideration. Trisodium citrate dihydrate can be used as a fine or coarse crystalline powder be used.

When builders are further polymeric polycarboxylates suitable, these are for example the alkali metal salts of polyacrylic acid or polymethacrylic acid, for example those with a molecular weight from 500 to 70000 g / mol.

For the purposes of this document, the molecular weights indicated for polymeric polycarboxylates are weight-average molar masses M _{w of the} respective acid form, which were determined in principle by means of gel permeation chromatography (GPC), a UV detector being used. The measurement was carried out against an external polyacrylic acid standard, which provides realistic molecular weight values due to its structural relationship with the polymers investigated. These data differ significantly from the molecular weight data, in which polystyrene sulfonic acids are used as standard. The molar masses measured against polystyrenesulfonic acids are generally significantly higher than the molecular weights specified in this document.

Suitable polymers are in particular polyacrylates, which preferably have a molecular weight of 2,000 to 20,000 g / mol. Because of their superior solubility, the short-chain polyacrylates, which have molar masses of from 2000 to 10000 g / mol, and particularly preferably from 3000 to 5000 g / mol, may again be preferred from this group.

Suitable are furthermore copolymeric polycarboxylates, especially those of acrylic acid with methacrylic acid and the acrylic acid or methacrylic acid with maleic acid. Particularly suitable are copolymers of acrylic acid with maleic which contain 50 to 90% by weight of acrylic acid and 50 to 10% by weight of maleic acid. Your molecular weight, based on free acids, is in general from 2000 to 70000 g / mol, preferably from 20,000 to 50,000 g / mol and in particular 30,000 to 40,000 g / mol.

The (co) polymeric polycarboxylates can be used either as a powder or as an aqueous solution. The content of detergents or cleaning agents on (co) polymeric polycarboxylates is preferably 0.5 to 20 wt .-%, in particular 3 to 10 wt .-%.

to Improvement of water solubility can the polymers also include allylsulfonic acids, such as allyloxybenzenesulfonic acid and methallylsulfonic acid, as Contain monomer.

Especially Biodegradable polymers of more than two are also preferred various monomer units, for example, those as monomers Salts of acrylic acid and maleic acid and vinyl alcohol or vinyl alcohol derivatives or as monomers Salts of acrylic acid and 2-alkylallyl sulfonic acid and sugar derivatives.

Further preferred copolymers are those which are preferably used as monomers Acrolein and acrylic acid / acrylic acid salts or acrolein and vinyl acetate.

As well are as further preferred builders polymeric aminodicarboxylic acids whose Salts or their precursors to call. Particular preference is given to polyaspartic acids or their salts.

Further Suitable builders are polyacetals, which by reaction of dialdehydes with polyol carboxylic acids containing 5 to 7 carbon atoms and at least 3 hydroxyl groups can be obtained. preferred Polyacetals are made from dialdehydes such as glyoxal, glutaraldehyde, terephthalaldehyde and mixtures thereof and from polyol carboxylic acids such as gluconic acid and / or glucoheptonic receive.

Further suitable organic builders are dextrins, for example Oligomers or polymers of carbohydrates by partial Hydrolysis of starches can be obtained. The hydrolysis can be carried out according to usual, for example acidic or enzyme-catalyzed processes. Preferably These are hydrolysis products with average molecular weights in the range from 400 to 500,000 g / mol. It is a polysaccharide with a Dextrose equivalent (DE) in the range from 0.5 to 40, in particular from 2 to 30 preferred where DE is a common one Measure of the reducing Effect of a polysaccharide compared to dextrose, which DE of 100 is. Useful are both maltodextrins with a DE between 3 and 20 and dry glucose syrup with a DE between 20 and 37 as well as so-called yellow dextrins and white dextrins with higher Molar masses in the range of 2000 to 30,000 g / mol.

at the oxidized derivatives of such dextrins are their reaction products with oxidants, which are able are at least one alcohol function of the saccharide ring to the carboxylic acid function to oxidize.

Also Oxydisuccinates and other derivatives of disuccinates, preferably Ethylenediamine disuccinate are other suitable cobuilders. there becomes ethylenediamine-N, N'-disuccinate (EDDS) preferably used in the form of its sodium or magnesium salts. Also preferred in this context are glycerol disuccinates and glycerol trisuccinates. Suitable amounts are zeolithhaltigen and / or silicate-containing formulations at 3 to 15 wt .-%.

Further useful organic cobuilders are, for example, acetylated hydroxy or their salts, which may also be present in lactone form can and which at least 4 carbon atoms and at least one hydroxy group and a maximum of two acid groups contain.

Furthermore can all compounds that are capable of complexes with alkaline earth ions train as builders be used.

surfactants

to Group of surfactants are the nonionic, the anionic, the cationic and the amphoteric surfactants counted.

As nonionic surfactants, it is possible to use all nonionic surfactants known to the person skilled in the art. Low-foaming nonionic surfactants are used as preferred surfactants. With particular preference, washing or cleaning agents, in particular automatic dishwashing detergents, comprise nonionic surfactants, in particular nonionic surfactants from the group of the alkoxylated alcohols. The nonionic surfactants used are preferably alkoxylated, advantageously ethoxylated, in particular primary, alcohols having preferably 8 to 18 carbon atoms and on average 1 to 12 moles of ethylene oxide (EO) per mole of alcohol, in which the alcohol radical can be linear or preferably methyl-branched in the 2-position or linear and methyl-branched radicals in the mixture can contain, as they are usually present in Oxoalkoholresten. In particular, however, alcohol ethoxylates with linear radicals of alcohols of natural origin having 12 to 18 carbon atoms, for example of coconut, palm, tallow or oleyl alcohol, and on average 2 to 8 moles of EO per mole of alcohol are preferred. The preferred ethoxylated alcohols include, for example, C _12-14 alcohols with 3 EO or 4 EO, C _9-11 alcohols with 7 EO, C _13-15 alcohols with 3 EO, 5 EO, 7 EO or 8 EO, C _12-18 alcohols with 3 EO, 5 EO or 7 EO and mixtures of these, such as mixtures of C _12-14 -alcohol with 3 EO and C _12-18 -alcohol with 5 EO. The stated degrees of ethoxylation represent statistical averages, which may correspond to a particular product of an integer or a fractional number. 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.

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

A another class of preferred nonionic surfactants, the 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 having 1 to 4 carbon atoms in the alkyl chain.

Also nonionic surfactants of the amine oxide type, for example N-cocoalkyl-N, N-dimethylamine oxide and N-tallow alkyl-N, N-dihydroxyethylamine oxide, and the fatty acid alkanolamide can 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 from that.

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

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

in der R für einen linearen oder verzweigten Alkyl- oder Alkenylrest mit 7 bis 12 Kohlenstoffatomen, R¹ für einen linearen, verzweigten oder zyklischen Alkylrest oder einen Arylrest mit 2 bis 8 Kohlenstoffatomen und R² für einen linearen, verzweigten oder zyklischen Alkylrest oder einen Arylrest oder einen Oxy-Alkylrest mit 1 bis 8 Kohlenstoffatomen steht, wobei C_1-4-Alkyl- oder Phenylreste bevorzugt sind und [Z] für einen linearen Polyhydroxyalkylrest steht, dessen Alkylkette mit mindestens zwei Hydroxylgruppen substituiert ist, oder alkoxylierte, vorzugsweise ethoxylierte oder propxylierte Derivate dieses Restes.The group of polyhydroxy fatty acid amides also includes compounds of the formula

R is a linear or branched alkyl or alkenyl radical having 7 to 12 carbon atoms, R ^{1 is} a linear, branched or cyclic alkyl radical or an aryl radical having 2 to 8 carbon atoms and R ^{2 is} a linear, branched or cyclic alkyl radical or an aryl radical or an oxy-alkyl radical having 1 to 8 carbon atoms, wherein C _1-4 alkyl or phenyl radicals are preferred and [Z] is a linear polyhydroxyalkyl radical whose alkyl chain having at least two hydroxyl groups substituted, or alkoxylated, preferably ethoxylated or propoxylated derivatives of this radical.

[Z] is preferably by reductive amination of a reduced sugar obtained, for example, glucose, fructose, maltose, lactose, galactose, Mannose or xylose. The N-alkoxy or N-aryloxy substituted Connections can by reaction with fatty acid methyl esters in the presence of an alkoxide as a catalyst in the desired Polyhydroxyfatty acid amides are transferred.

With Particular preference is furthermore given to using surfactants which have a or more tallow fatty alcohols with 20 to 30 EO in combination with a silicone defoamer contain.

nonionic surfactants from the group of alkoxylated alcohols, particularly preferably from the group of mixed alkoxylated alcohols and in particular from the group of EO-AO-EO-Niotenside, are also with special Preference used.

Especially preferred are nonionic surfactants which have a melting point above Have room temperature. Nonionic surfactant (s) having a melting point above 20 ° C, preferably above 25 ° C, more preferably between 25 and 60 ° C and especially between 26.6 and 43.3 ° C, is / are particularly preferred.

suitable nonionic surfactants, the melting or softening points in said Temperature range, for example, low-foaming nonionic Surfactants which may be solid or highly viscous at room temperature. Become Used nonionic surfactants which are highly viscous at room temperature, so it is preferred that this has a viscosity above 20 Pa · s, preferably above 35 Pa · s and in particular above 40 Pa · s. Also nonionic surfactants, which are waxy at room temperature, are preferred.

Prefers surfactants to be used which are solid at room temperature from the groups of the alkoxylated nonionic surfactants, in particular the ethoxylated primary Alcohols and mixtures of these surfactants with structurally complicated built-up surfactants such as polyoxypropylene / polyoxyethylene / polyoxypropylene ((PO / EO / PO) surfactants). Such (PO / EO / PO) nonionic surfactants stand out about it out by good foam control.

In a preferred embodiment The present invention is the nonionic surfactant having a Melting point above room temperature an ethoxylated nonionic surfactant, that from the reaction of a monohydroxyalkanol or alkylphenol with 6 to 20 carbon atoms, preferably at least 12 mol, more preferably at least 15 moles, in particular at least 20 moles of ethylene oxide per Mol alcohol or alkylphenol emerged.

A particularly preferred room temperature solid nonionic surfactant is obtained from a straight chain fatty alcohol having 16 to 20 carbon atoms (C _16-20 alcohol), preferably a C ₁₈ alcohol and at least 12 moles, preferably at least 15 moles and especially at least 20 moles of ethylene oxide. Of these, the so-called "narrow range ethoxylates" (see above) are particularly preferred.

Particular preference is therefore given to ethoxylated nonionic surfactants which consist of C ₆ _ ₂₀ monohydroxyalkanols or C ₆ _ ₂₀ -alkylphenols or C ₁₆ _ ₂₀ -fatty alcohols and more than 12 mol, preferably more than 15 mol and in particular more than 20 mol of ethylene oxide per mol Alcohol was used.

The nonionic surfactant solid at room temperature preferably additionally has propylene oxide units in the molecule. Preferably, such PO units make up to 25% by weight, especially preferably up to 20 wt .-% and in particular up to 15 wt .-% of total molecular weight of the nonionic surfactant. Especially preferred nonionic surfactants are ethoxylated monohydroxyalkanols or alkylphenols, the additional Having polyoxyethylene-polyoxypropylene block copolymer units. The alcohol or alkylphenol part of such nonionic surfactant molecules makes preferably more than 30% by weight, particularly preferably more than 50% by weight and more preferably more than 70% by weight of the total molecular weight of such Nonionic surfactants. Preferred agents are characterized in that they contain ethoxylated and propoxylated nonionic surfactants in which the Propylene oxide units in the molecule up to 25% by weight, preferably up to 20% by weight and in particular to to 15% by weight of the total molecular weight of the nonionic surfactant.

Further particularly preferred nonionic surfactants with melting points above room temperature contain from 40 to 70% of a polyoxypropylene / polyoxyethylene / polyoxypropylene block polymer blend, the 75% by weight of a reverse block copolymer of polyoxyethylene and polyoxypropylene with 17 moles of ethylene oxide and 44 moles of propylene oxide and 25% by weight of a block copolymer of polyoxyethylene and polyoxypropylene initiated with trimethylolpropane and containing 24 moles of ethylene oxide and 99 moles of propylene oxide per mole of trimethylolpropane, contains.

Nonionic surfactants that may be used with particular preference are available, for example under the name Poly Tergent ^® SLF-18 from Olin Chemicals.

As anionic surfactants, for example, those of the sulfonate type and sulfates are used. The surfactants of the sulfonate type are preferably C _9-13 -alkylbenzenesulfonates, olefinsulfonates, ie mixtures of alkene and hydroxyalkanesulfonates and disulfonates, as are obtained, for example, from C _12-18 -monoolefins having terminal or internal double bonds by sulfonation with gaseous sulfur trioxide and subsequent alkaline or acid hydrolysis of the sulfonation products into consideration. Also suitable are alkanesulfonates which are obtained from C _12-18 alkanes, for example by sulfochlorination or sulfoxidation with subsequent hydrolysis or neutralization. Likewise, the esters of α-sulfo fatty acids (ester sulfonates), for example the α-sulfonated methyl esters of hydrogenated coconut, palm kernel or tallow fatty acids are suitable.

Further Suitable anionic surfactants are sulfated fatty acid glycerol esters. Among fatty acid glycerol esters are to understand the mono-, di- and triesters and their mixtures, such as they are produced by esterification of a monoglycerol with 1 to 3 moles of fatty acid or in the transesterification of triglycerides with 0.3 to 2 moles of glycerol to be obtained. Preferred sulfated fatty acid glycerol esters are included the sulphonated products of saturated fatty acids with 6 to 22 carbon atoms, for example the caproic acid, caprylic acid, capric acid, myristic acid, lauric acid, palmitic acid, stearic acid or Behenic acid.

Alk (en) ylsulfates are the alkali metal salts and in particular the sodium salts of the sulfuric monoesters of C ₁₂ -C ₁₈ fatty alcohols, for example coconut fatty alcohol, tallow fatty alcohol, lauryl, myristyl, cetyl or stearyl alcohol or the C ₁₀ -C ₂₀ oxo alcohols and those half-esters of secondary alcohols of these chain lengths are preferred. Also preferred are alk (en) ylsulfates of said chain length, which contain a synthetic, produced on a petrochemical basis straight-chain alkyl radical, which have an analogous degradation behavior as the adequate compounds based on oleochemical raw materials. Of washing technology interest, the C ₁₂ -C ₁₆ alkyl sulfates and C ₁₂ -C ₁₅ alkyl sulfates and C ₁₄ -C ₁₅ alkyl sulfates are preferred. Also 2,3-alkyl sulfates, which can be obtained as commercial products of Shell Oil Company under the name DAN ^® , are suitable anionic surfactants.

The sulfuric acid monoesters of straight-chain or branched C _7-21 -alcohols ethoxylated with from 1 to 6 mol of ethylene oxide, such as 2-methyl-branched C _9-11- alcohols having on average 3.5 mol of ethylene oxide (EO) or C _12-18 . Fatty alcohols with 1 to 4 EO are suitable. Due to their high foaming behavior, they are only used in detergents in relatively small amounts, for example in amounts of from 1 to 5% by weight.

Further suitable anionic surfactants are also the salts of alkylsulfosuccinic acid, which are also referred to as sulfosuccinates or as sulfosuccinic acid esters and which are monoesters and / or diesters of sulfosuccinic acid with alcohols, preferably fatty alcohols and in particular ethoxylated fatty alcohols. Preferred sulfosuccinates contain C _8-18 fatty alcohol residues or mixtures of these. Particularly preferred sulfosuccinates contain a fatty alcohol residue derived from ethoxylated fatty alcohols, which by themselves are nonionic surfactants. Sulfosuccinates, whose fatty alcohol residues are derived from ethoxylated fatty alcohols with a narrow homolog distribution, are again particularly preferred. Likewise, it is also possible to use alk (en) ylsuccinic acid having preferably 8 to 18 carbon atoms in the alk (en) yl chain or salts thereof.

When other anionic surfactants are especially soaps into consideration. Suitable are saturated fatty acid soaps, like the salts of lauric acid, myristic, palmitic acid, stearic acid, hydrogenated erucic acid and behenic acid and in particular of natural fatty acids, e.g. Coconut, palm kernel or tallow derived soap mixtures.

The anionic surfactants, including the soaps, may be in the form of their sodium, potassium or ammonium salts and as soluble salts of organic bases, such as mono-, di- or triethanolamine. In front Preferably, the anionic surfactants are in the form of their sodium or potassium salts, especially in the form of the sodium salts.

are the anionic surfactants component of automatic dishwashing detergents, so is their content, based on the total weight of the funds preferably less than 4% by weight, preferably less than 2% by weight and most especially preferably less than 1% by weight. Automatic dishwashing detergents, which do not contain anionic surfactants are particularly preferred.

At Place of said surfactants or in conjunction with them may also cationic and / or amphoteric surfactants are used.

worin jede Gruppe R¹ unabhängig voneinander ausgewählt ist aus C_1-6-Alkyl-, -Alkenyl- oder -Hydroxyalkylgruppen; jede Gruppe R² unabhängig voneinander ausgewählt ist aus C_8-28-Alkyl- oder -Alkenylgruppen; R³ = R¹ oder (CH₂)_n-T-R²; R⁴ = R¹ oder R² oder (CH₂)_n-T-R²; T = -CH₂-, -O-CO- oder -CO-O- und n eine ganze Zahl von 0 bis 5 ist.As cationic active substances, for example, cationic compounds of the following formulas can be used:

wherein each R ^{1 group is} independently selected from C _1-6 alkyl, alkenyl or hydroxyalkyl groups; each R ^{2 group is} independently selected from C _8-28 alkyl or alkenyl groups; R ³ = R ¹ or (CH ₂ ) _n -TR ² ; R ⁴ = R ¹ or R ² or (CH ₂ ) _n -TR ² ; T = -CH ₂ -, -O-CO- or -CO-O- and n is an integer from 0 to 5.

In automatic dishwashing detergents, is the content of cationic and / or amphoteric surfactants preferably less than 6% by weight, preferably less than 4% by weight, very particularly preferably less than 2% by weight and in particular less than 1% by weight. Automatic dishwashing detergents, which contain no cationic or amphoteric surfactants particularly preferred.

bleach

The bleaching agents are a particularly preferred washing or cleaning substance. Among the compounds serving as bleaches in water H ₂ O ₂ , sodium percarbonate, sodium perborate tetrahydrate and sodium perborate monohydrate are of particular importance. Other useful bleaching agents are, for example, peroxypyrophosphates, citrate perhydrates and H ₂ O ₂ -forming peracidic salts or peracids, such as perbenzoates, peroxophthalates, diperazelaic acid, phthaloiminoperacid or diperdodecanedioic acid.

Furthermore, bleaching agents from the group of organic bleaching agents can also be used. Typical organic bleaches are the diacyl peroxides such as dibenzoyl peroxide. Other typical organic bleaches are the peroxyacids, examples of which include the alkyl peroxyacids and the aryl peroxyacids. Preferred representatives are (a) the peroxybenzoic acid and its ring-substituted derivatives, such as alkylperoxybenzoic acids, but also peroxy-α-naphthoic acid and magnesium monoperphthalate, (b) the aliphatic or substituted aliphatic peroxyacids, such as peroxylauric acid, peroxystearic acid, ε-phthalimidoperoxycaproic acid [phthaliminoperoxyhexanoic acid (PAP)] , o-Carboxybenzamidoperoxycapronsäure, N-Nonenylamidoperadipinsäure and N-Nonenylamidopersuccinate, and (c) aliphatic and Araliphatic peroxydicarboxylic acids such as 1,12-diperoxycarboxylic acid, 1,9-diperoxyazelaic acid, diperoxysebacic acid, diperoxybrassic acid, the diperoxyphthalic acids, 2-decyldiperoxybutane-1,4-diacid, N, N-terephthaloyl-di (6-aminopercapronate) can be used.

When Bleach can Chlorine or bromine releasing substances are used. Among the suitable chlorine or bromine releasing materials come for example, heterocyclic N-bromo- and N-chloroamides, for example trichloroisocyanuric acid, tribromoisocyanuric acid, dibromoisocyanuric acid and / or dichloroisocyanuric (DICA) and / or their salts with cations such as potassium and sodium into consideration. Hydantoin compounds, such as 1,3-dichloro-5,5-dimethylhydanthoin are also suitable.

According to the invention Washing or cleaning preparations, in particular automatic dishwashing detergents, preferably 1 to 35% by weight, preferably 2.5 to 30% by weight, particularly preferably from 3.5 to 20% by weight and in particular from 5 to 15 Wt .-% bleach, preferably sodium percarbonate.

Of the Active oxygen content of detergents or cleaners, in particular the automatic dishwashing detergent, is, in each case based on the total weight of the composition, preferably between 0.4 and 10 wt .-%, particularly preferably between 0.5 and 8 wt .-% and in particular between 0.6 and 5 wt .-%. Especially preferred Means have an active oxygen content above 0.3 wt .-%, preferably above 0.7 wt .-%, more preferably above 0.8 wt .-% and in particular above 1.0% by weight.

Bleach activators

Bleach activators are used in detergents or cleaning agents, for example, to improve cleaning at temperatures of 60 ° C and below To achieve bleaching effect. As bleach activators, compounds, which under perhydrolysis aliphatic peroxycarboxylic acids with preferably 1 to 10 C atoms, in particular 2 to 4 C atoms, and / or optionally substituted perbenzoic acid, are used. Suitable substances are the O- and / or N-acyl groups of the mentioned C atom number and / or optionally substituted benzoyl groups wear. Preference is given to polyacylated alkylenediamines, in particular Tetraacetylethylenediamine (TAED), acylated triazine derivatives, in particular 1,5-diacetyl-2,4-dioxohexahydro-1,3,5-triazine (DADHT), acylated glycolurils, especially tetraacetylglycoluril (TAGU), N-acylimides, especially N-nonanoylsuccinimide (NOSI), acylated Phenolsulfonates, especially n-nonanoyl or isononanoyloxybenzenesulfonate (n- or iso-NOBS), carboxylic acid anhydrides, in particular phthalic anhydride, acylated polyhydric alcohols, especially triacetin, ethylene glycol diacetate and 2,5-diacetoxy-2,5-dihydrofuran.

in der R¹ für -H, -CH₃, einen C_2-24-Alkyl- oder -Alkenylrest, einen substituierten C_2-24-Alkyl- oder -Alkenylrest mit mindestens einem Substituenten aus der Gruppe -Cl, -Br, -OH, -NH₂, -CN, einen Alkyl- oder Alkenylarylrest mit einer C_1-24-Alkylgruppe, oder für einen substituierten Alkyl- oder Alkenylarylrest mit einer C_1-24-Alkylgruppe und mindestens einem weiteren Substituenten am aromatischen Ring steht, R² und R³ unabhängig voneinander ausgewählt sind aus -CH₂-CN, -CH₃, -CH₂-CH₃, -CH₂-CH₂-CH₃, -CH(CH₃)-CH₃, -CH₂-OH, -CH₂-CH₂-OH, -CH(OH)-CH₃, -CH₂-CH₂-CH₂-OH, -CH₂-CH(OH)-CH₃, -CH(OH)-CH₂-CH₃, -(CH₂CH₂-O)_nH mit n = 1, 2, 3, 4, 5 oder 6 und X ein Anion ist.Further bleach activators preferably used in the context of the present application are compounds from the group of cationic nitriles, in particular cationic nitriles of the formula

in the R ^{1 is} -H, -CH ₃ , a C _2-24 alkyl or alkenyl radical, a substituted C _2-24 alkyl or alkenyl radical having at least one substituent from the group -Cl, -Br, - OH, -NH ₂ , -CN, an alkyl or alkenylaryl radical having a C _1-24 -alkyl group, or represents a substituted alkyl or alkenylaryl radical having a C _1-24 -alkyl group and at least one further substituent on the aromatic ring, R ² and R ^{3 are} independently selected from -CH ₂ -CN, -CH ₃ , -CH ₂ -CH ₃ , -CH ₂ -CH ₂ -CH ₃ , -CH (CH ₃ ) -CH ₃ , -CH ₂ - OH, -CH ₂ -CH ₂ -OH, -CH (OH) -CH ₃ , -CH ₂ -CH ₂ -CH ₂ -OH, -CH ₂ -CH (OH) -CH ₃ , -CH (OH) - CH ₂ -CH ₃ , - (CH ₂ CH ₂ -O) _n H where n = 1, 2, 3, 4, 5 or 6 and X is an anion.

in der R⁴, R⁵ und R⁶ unabhängig voneinander ausgewählt sind aus -CH₃, -CH₂-CH₃, -CH₂-CH₂-CH₃, -CH(CH₃)-CH₃, wobei R⁴ zusätzlich auch -H sein kann und X ein Anion ist, wobei vorzugsweise R⁵ = R⁶ = -CH₃ und insbesondere R⁴ = R⁵ = R⁶ = -CH₃ gilt und Verbindungen der Formeln (CH₃)₃N⁽⁺⁾CH₂-CN X (CH₃CH₂)₃N⁽⁺⁾CH₂-CN X^-, (CH₃CH₂CH₂)₃N⁽⁺⁾CH₂-CN X^-, (CH₃CH(CH₃))₃N⁽⁺⁾CH₂-CN X^-, oder (HO-CH₂-CH₂)₃N⁽⁺⁾CH₂-CN X^- besonders bevorzugt sind, wobei aus der Gruppe dieser Substanzen wiederum das kationische Nitril der Formel (CH₃)₃N⁽⁺⁾CH₂-CN X^-, in welcher X^- für ein Anion steht, das aus der Gruppe Chlorid, Bromid, Iodid, Hydrogensulfat, Methosulfat, p-Toluolsulfonat (Tosylat) oder Xylolsulfonat ausgewählt ist, besonders bevorzugt wird.Particularly preferred is a cationic nitrile of the formula

in which R ⁴ , R ⁵ and R ^{6 are} independently selected from -CH ₃ , -CH ₂ -CH ₃ , -CH ₂ -CH ₂ -CH ₃ , -CH (CH ₃ ) -CH ₃ , wherein R ⁴ additionally also -H may be and X is an anion, preferably R ⁵ = R ⁶ = -CH ₃ and in particular R ⁴ = R ⁵ = R ⁶ = -CH ₃ and compounds of the formulas (CH ₃ ) ₃ N ⁽⁺⁾ CH ₂ -CN X (CH ₃ CH ₂ ) ₃ N ⁽⁺⁾ CH ₂ -CN X ^- , (CH ₃ CH ₂ CH ₂ ) ₃ N ⁽⁺⁾ CH ₂ -CN X ^- , (CH ₃ CH (CH ₃ )) ₃ N ^{( +)} CH ₂ -CN X ^- , or (HO-CH ₂ -CH ₂ ) ₃ N ⁽⁺⁾ CH ₂ -CN X ^{- are} particularly preferred, wherein from the group of these substances turn the cationic nitrile of the formula (CH ₃ ) ₃ N ⁽⁺⁾ CH ₂ -CN X ^-, where X ^- is an anion selected from among chloride, bromide, iodide, hydrogen sulfate, methosulfate, p-toluene sulfonate (tosylate) or xylene sulfonate, is particularly preferred.

When Bleach activators can furthermore compounds which are aliphatic under perhydrolysis conditions peroxycarboxylic with preferably 1 to 10 C atoms, in particular 2 to 4 C atoms, and / or optionally substituted perbenzoic acid, can be used. Suitable substances are the O- and / or N-acyl groups of the mentioned C atom number and / or optionally substituted benzoyl groups. Preference is given to polyacylated alkylenediamines, in particular tetraacetylethylenediamine (TAED), acylated triazine derivatives, in particular 1,5-diacetyl-2,4-dioxohexahydro-1,3,5-triazine (DADHT), acylated glycolurils, especially tetraacetylglycoluril (TAGU), N-acylimides, especially N-nonanoylsuccinimide (NOSI), acylated Phenolsulfonates, especially n-nonanoyl or isononanoyloxybenzenesulfonate (n- or iso-NOBS), carboxylic acid anhydrides, in particular phthalic anhydride, acylated polyhydric alcohols, in particular triacetin, ethylene glycol diacetate, 2,5-diacetoxy-2,5-dihydrofuran, n-methyl-morpholinium-acetonitrile-methylsulfate (MMA) and acetylated sorbitol and mannitol or their Mixtures (SORMAN), acylated sugar derivatives, in particular pentaacetylglucose (PAG), Pentaacetylfruktose, Tetraacetylxylose and Octaacetyllactose and acetylated, optionally N-alkylated glucamine and gluconolactone, and / or N-acylated lactams, for example N-benzoyl-caprolactam. Hydrophilic substituted Acyl acetals and acyl lactams are also preferably used. Combinations of conventional bleach activators can also be used become.

Provided in addition to the Nitrilquats further bleach activators are used are preferred bleach activators from the group of multiple acylated alkylenediamines, especially tetraacetylethylenediamine (TAED), N-acylimides, in particular N-nonanoylsuccinimide (NOSI), acylated Phenolsulfonates, especially n-nonanoyl or isononanoyloxybenzenesulfonate (n- or iso-NOBS), n-methyl-morpholinium-acetonitrile-methyl sulfate (MMA), preferably in amounts of up to 10% by weight, in particular 0.1% by weight to 8 wt .-%, especially 2 to 8 wt .-% and particularly preferably 2 to 6 wt .-%, each based on the total weight of the bleach activator-containing Medium, used.

In addition to The conventional bleach activators or in their place may also so-called bleach catalysts are used. For these substances These are bleach-enhancing transition metal salts or transition metal complexes such as Mn, Fe, Co, Ru or Mo saline complexes or carbonyl complexes. Also Mn, Fe, Co, Ru, Mo, Ti, V and Cu complexes with N-containing tripod ligands and Co, Fe, Cu and Ru ammine complexes are useful as bleach catalysts.

Bleach-enhancing transition metal complexes, in particular with the central atoms Mn, Fe, Co, Cu, Mo, V, Ti and / or Ru, preferably selected from the group of manganese and / or cobalt salts and / or complexes, particularly preferably the cobalt (ammin) complexes, the cobalt (acetate) complexes, the cobalt (carbonyl) complexes, the chlorides of cobalt or manganese, manganese sulfate in usual Quantities, preferably in an amount up to 5 wt .-%, in particular from 0.0025 wt.% to 1 wt.%, and more preferably from 0.01 Wt .-% to 0.25 wt .-%, each based on the total weight of bleach activator-containing agent used. But in special cases can also more bleach activator can be used.

enzymes

To increase the washing or cleaning performance of detergents or cleaners enzymes can be used. These include in particular proteases, amylases, lipases, hemicellulases, cellulases or oxidoreductases, and preferably mixtures thereof. These enzymes are basically of natural origin; Starting from the natural molecules, improved variants are available for use in detergents and cleaners, which are preferably used accordingly. Detergents or cleaning agents contain enzymes preferably in total amounts of 1 × 10 ^-6 to 5 wt .-% based on active protein. The protein concentration can be determined by known methods, for example the BCA method or the biuret method.

Among the proteases, those of the subtilisin type are preferable. Examples thereof are the subtilisins BPN 'and Carlsberg, the protease PB92, the subtilisins 147 and 309, the alkaline protease from Bacillus lentus, subtilisin DY and the enzymes thermitase, proteinase K and the subtilases, but not the subtilisins in the narrower sense Proteases TW3 and TW7. Subtilisin Carlsberg is in further development ckelter form under the trade names Alcalase ^® from Novozymes A / S, Bagsvaerd, Denmark. The subtilisins 147 and 309 are sold under the trade names Esperase ^®, or Savinase ^® from Novozymes. From the protease from Bacillus lentus DSM 5483 derived under the name BLAP ^® variants are derived.

Other usable proteases are, for example, under the trade names Durarym ^®, relase ^®, Everlase® ^®, Nafizym, Natalase ^®, Kannase® ^® and Ovozymes ^® from Novozymes, under the trade names Purafect ^®, Purafect ^® OxP and Properase.RTM ^® by the company Genencor, that under the trade name Protosol® ^® from Advanced Biochemicals Ltd., Thane, India, under the trade name Wuxi ^® from Wuxi Snyder Bioproducts Ltd., China, under the trade names Proleather® ^® and protease P ^® by the company Amano Pharmaceuticals Ltd., Nagoya, Japan, and the enzyme available under the name Proteinase K-16 from Kao Corp., Tokyo, Japan.

Examples of amylases which can be used according to the invention are the α-amylases from Bacillus licheniformis, B. amyloliquefaciens or B. stearothermophilus and also their further developments improved for use in detergents and cleaners. The enzyme from B. licheniformis is available from Novozymes under the name Termamyl ^® and from Genencor under the name Purastar® ^® ST. Development products of this α-amylase are available from Novozymes under the trade names Duramyl ^® and Termamyl ^® ultra, from Genencor under the name Purastar® ^® OxAm and from Daiwa Seiko Inc., Tokyo, Japan, as Keistase ^®. The α-amylase of B. amyloliquefaciens is sold by Novozymes under the name BAN ^®, and variants derived from the a-amylase from B. stearothermophilus under the names BSG ^® and Novamyl ^®, also from Novozymes.

Furthermore are for this purpose the α-amylase from Bacillus sp. A 7-7 (DSM 12368) and cyclodextrin glucanotransferase (CGTase) from B. agaradherens (DSM 9948).

In addition, the enhancements available under the trade names Fungamyl.RTM ^® by Novozymes of α-amylase from Aspergillus niger and A. oryzae. Another commercial product is, for example, the amylase ^LT® .

Also usable according to the invention are lipases or cutinases, in particular because of their triglyceride-splitting activities, but also in order to generate in situ peracids from suitable precursors. These include, for example, the lipases originally obtainable from Humicola lanuginosa (Thermomyces lanuginosus) or further developed, in particular those with the amino acid exchange D96L. They are for example marketed by Novozymes under the trade names Lipolase ^®, Lipolase Ultra ^®, LipoPrime® ^®, Liporyme ^® and Lipex ^®. Furthermore, for example, the cutinases can be used, which were originally isolated from Fusarium solani pisi and Humicola insolens. Likewise useable lipases are available from Amano under the designations Lipase CE ^®, Lipase P ^®, Lipase B ^®, or lipase CES ^®, Lipase AKG ^®, Bacillis sp. ^Lipase® , Lipase ^AP® , Lipase M- ^AP® and Lipase ^{AML® are} available. From the company Genencor, for example, the lipases, or cutinases can be used, the initial enzymes were originally isolated from Pseudomonas mendocina and Fusarium solanii. Other important commercial products, the preparations originally sold by Gist-Brocades M1 Lipase ^® and Lipomax® ^® and the enzymes marketed by Meito Sangyo KK, Japan under the names Lipase MY-30 ^®, Lipase OF ^® and lipase PL ^® to mention also the product Lumafast® ^® from Genencor.

Furthermore, enzymes can be used, which are summarized by the term hemicellulases. These include, for example, mannanases, xanthan lyases, pectin lyases (= pectinases), pectin esterases, pectate lyases, xyloglucanases (= xylanases), pullulanases and β-glucanases. Suitable mannanases are available, for example under the name Gamanase ^® and Pektinex AR ^® from Novozymes, under the name Rohapec ^® B1 L from AB Enzymes and under the name Pyrolase® ^® from Diversa Corp., San Diego, CA, USA , The obtained from B. subtilis β-glucanase is available under the name Cereflo ^® from Novozymes.

Oxidoreductases, for example oxidases, oxygenases, catalases, peroxidases, such as halo, chloro, bromo, lignin, glucose or manganese peroxidases, dioxygenases or laccases (phenol oxidases, polyphenol oxidases) can be used according to the invention to increase the bleaching effect. Suitable commercial products Denilite® ^® 1 and 2 from Novozymes should be mentioned. Advantageously, it is additionally preferred to add organic, particularly preferably aromatic, compounds which interact with the enzymes in order to enhance the activity of the oxidoreductases in question (enhancers). or to ensure the flow of electrons in the case of greatly differing redox potentials between the oxidizing enzymes and the soiling (mediators).

The For example, enzymes are either originally derived from microorganisms, about the genera Bacillus, Streptomyces, Humicola, or Pseudomonas, and / or are used according to known biotechnological processes produced by suitable microorganisms, such as transgenic Expression hosts of the genera Bacillus or filamentous fungi.

The Purification of the enzymes concerned is preferably carried out by itself established methods, for example about precipitation, sedimentation, concentration, Filtration of the liquid Phases, microfiltration, ultrafiltration, exposure to chemicals, Deodorization or suitable combinations of these steps.

The Enzymes can used in any form established in the prior art become. These include for example, by granulation, extrusion or lyophilization obtained solid preparations or, especially in liquid or gelatinous Means, solutions the enzymes, advantageously as concentrated as possible, low in water and / or added with stabilizers.

alternative can the enzymes for both the solid as well for the liquid Dosage form can be encapsulated, for example by spray drying or extrusion of the enzyme solution together with a preferably natural polymer or in the form of capsules, for example those in which the enzymes are as in enclosed in a solidified gel or in those of the core-shell type, in which a enzyme-containing core coated with a water, air and / or chemical impermeable protective layer is. In superimposed layers additional active ingredients, For example, stabilizers, emulsifiers, pigments, bleach or Dyes are applied. Such capsules are after known methods, for example by shaking or Roll granulation or applied in fluid-bed processes. Advantageously Such granules, for example by applying polymeric film-forming agents, low in dust and storage-stable due to the coating.

Farther Is it possible, to assemble two or more enzymes together, making one individual granules has several enzyme activities.

One Protein and / or enzyme may be particularly harmful during storage against damage such as inactivation, denaturation or decay, for example through physical influences, Oxidation or proteolytic cleavage are protected. In microbial Obtaining the proteins and / or enzymes is inhibiting the Proteolysis particularly preferred, especially if the means Contain proteases. Detergents or cleaners can contain stabilizers for this purpose; the provision of such funds represents a preferred embodiment of the present invention.

A Group of stabilizers are reversible protease inhibitors. Become frequent Benzamidine hydrochloride, Borax, boric acids, boronic acids or their salts or esters, including derivatives in particular with aromatic groups, such as ortho-substituted, meta-substituted and para-substituted phenylboronic, or their salts or esters. As peptidic protease inhibitors include ovomucoid and leupeptin; a additional Option is the formation of fusion proteins from proteases and peptide inhibitors.

Other enzyme stabilizers are amino alcohols such as mono-, di-, triethanol- and -propanolamine and mixtures thereof, aliphatic carboxylic acids up to C ₁₂ , such as succinic acid, other dicarboxylic acids or salts of said acids. End-capped fatty acid amide alkoxylates are also suitable. Certain organic acids used as builders are additionally capable of stabilizing a contained enzyme.

low aliphatic alcohols, but especially polyols, such as Glycerine, ethylene glycol, propylene glycol or sorbitol are other often used enzyme stabilizers. Likewise, calcium salts are used such as calcium acetate or calcium formate, and magnesium salts.

Polyamide oligomers or polymeric compounds such as lignin, water-soluble vinyl copolymers or cellulose ethers, acrylic polymers and / or polyamides stabilize the enzyme preparation, inter alia, against physical influences or pH fluctuations. Polyamine N-oxide containing polymers act as enzyme stabilizers. Other polymeric stabilizers are the linear C ₈ -C ₁₈ polyoxyalkylenes. Alkyl polyglycosides can stabilize the enzymatic components and even increase their performance. Crosslinked N-containing compounds also act as enzyme stabilizers.

reducing agent and increase antioxidants the stability of the enzymes oxidative decay. A sulfur-containing reducing agent is, for example Sodium sulfite.

Prefers Kombinatonen be used by stabilizers, for example made of polyols, boric acid and / or borax, the combination of boric acid or borate, reducing Salts and succinic acid or other dicarboxylic acids or the combination of boric acid or borate with polyols or polyamino compounds and with reducing Salt. The effect of peptide-aldehyde stabilizers is through the combination with boric acid and / or boric acid derivatives and polyols increased and by the additional use of divalent Cations, such as calcium ions further amplified.

Prefers are one or more enzymes and / or enzyme preparations, preferably solid protease preparations and / or amylase preparations, in Amounts of 0.1 to 5 wt .-%, preferably from 0.2 to 4.5 wt .-% and in particular from 0.4 to 4 wt .-%, each based on the total enzyme-containing agents used.

Glass corrosion inhibitors

Glass corrosion inhibitors prevent the occurrence of cloudiness, Streaks and scratches but also iridescence of the glass surface of mechanically cleaned glasses. Preferred glass corrosion inhibitors come from the group of Magnesium and / or zinc salts and / or magnesium and / or zinc complexes.

A preferred class of compounds used to prevent glass corrosion can be used are insoluble Zinc salts.

Insoluble zinc salts in the context of this preferred embodiment are zinc salts which have a solubility of a maximum of 10 grams of zinc salt per liter of water at 20 ° C. Examples of particularly preferred insoluble zinc salts according to the invention are zinc silicate, zinc carbonate, zinc oxide, basic zinc carbonate (Zn ₂ (OH) ₂ CO ₃ ), zinc hydroxide, zinc oxalate, zinc monophosphate (Zn ₃ (PO ₄ ) ₂ ) and zinc pyrophosphate (Zn ₂ (P ₂ O ₇ )).

The mentioned zinc compounds are preferably used in amounts which has a content of the zinc ions of between 0.02 and 10% by weight, preferably between 0.1 and 5.0 wt .-% and in particular between 0.2 and 1.0 wt .-%, each based on the total glass corrosion inhibitor-containing Means, effect. The exact content of the agent on the zinc salt or The zinc salts are naturally dependent on the type of zinc salts - ever less soluble the zinc salt used is, the higher its concentration should be to be in the media.

There the insoluble Zinc salts during the Geschirreinigungsvorgangs mostly unchanged remain, is the particle size of the salts a criterion to be observed so that the salts do not affect glassware or attach machine parts. Here, agents are preferred in which the insoluble Zinc salts have a particle size below 1.7 millimeters.

If the maximum particle size of the insoluble Zinc salts below 1.7 mm are insoluble residues in the dishwasher not to be afraid. Preferably, this has insoluble Zinc salt has a mean particle size that is well below This value is in order to further minimize the risk of insoluble residues, for example a mean particle size smaller 250 μm. Again, this is even more true the less the zinc salt is soluble. In addition, the glass corrosion inhibiting effectiveness increases with decreasing Particle size. at very poorly soluble Zinc salts, the average particle size is preferably below 100 μm. For still poorly soluble Salts can be even lower; for example, that's for the very most poorly soluble Zinc oxide mean particle sizes below of 60 μm prefers.

A Another preferred class of compounds are magnesium and / or Zinc salt (s) of at least one monomeric and / or polymeric organic Acid. These do not cause the surfaces of glassware even with repeated use changed corrosively, in particular no clouding, Streaks or scratches but also no iridescence of the glass surfaces caused become.

Although all magnesium and / or zinc salt (s) of monomeric and / or polymeric organic acids can be used, the magnesium and / or zinc salts of monomeric and / or polymeric organic acids from the groups of unbranched saturated or unsaturated monocarboxylic acids, the branched saturated or unsaturated monocarboxylic acids, the saturated and unsaturated dicarboxylic acids, the aromatic mono-, di- and tricarboxylic acids, the sugar acids, the hydroxy acids, the oxo acids, the amino acids and / or the polymeric carboxylic acids are preferred.

The Spectrum of the invention preferred Zinc salts of organic acids, preferably organic carboxylic acids, ranges from salts that are heavy or insoluble in water, So a solubility below 100 mg / l, preferably below 10 mg / l, especially below 0.01 mg / l, to such salts which have a solubility in water above 100 mg / l, preferably above 500 mg / l, more preferably above 1 g / l and especially above 5 g / l (all solubilities at 20 ° C Water temperature). For example, the first group of zinc salts include the zinc citrate, the zinc oleate and the zinc stearate, to the group the soluble Zinc salts belong for example, zinc formate, zinc acetate, zinc lactate and the zinc gluconate.

With Particular preference is given as a glass corrosion inhibitor at least one Zinc salt of an organic carboxylic acid, more preferably in order a zinc salt from the group zinc stearate, zinc oleate, zinc gluconate, Zinc acetate, zinc lactate and / or zinc citrate used. Also zinc ricinoleate, Zinc-absate and zinc oxalate are preferred.

In the context of the present invention, the content of cleaning agents to zinc salt is preferably between 0.1 to 5 wt .-%, preferably between 0.2 to 4 wt .-% and in particular between 0.4 to 3 wt .-%, or the content of zinc in oxidized form (calculated as Zn ²⁺ ) is between 0.01 and 1% by weight, preferably between 0.02 and 0.5% by weight and in particular between 0.04 and 0.2% by weight. -%, in each case based on the total weight of the glass corrosion inhibitor-containing agent.

corrosion inhibitors

corrosion inhibitors serve the protection of the dishes or the machine, being particularly in the field of machine dishwashing Silver protectants have a special meaning. Can be used the known substances of the prior art. Generally, you can all silver protectants selected from the group of triazoles, benzotriazoles, bisbenzotriazoles, the aminotriazoles, the alkylaminotriazoles and the transition metal salts or complexes are used. Particularly preferable to use are benzotriazole and / or alkylaminotriazole. As examples of preferred according to the invention 3-amino-5-alkyl-1,2,4-triazoles to be used can be mentioned: propyl, Butyl, pentyl, heptyl, octyl, nonyl, decyl, undecyl, Dodecyl, isononyl, versatic-10-alkyl, -phenyl, -p-tolyl, - (4-tert-butylphenyl) -, - (4-methoxyphenyl) -, - (2-, -3-, -4-pyridyl) -, - (2-Thienyl) -, - (5-methyl-2-furyl) -, - (5-oxo-2-pyrrolidinyl) -, 3-amino-1,2,4-triazole. In dishwashing detergents are the alkyl-amino-1,2,4-triazoles or their physiologically acceptable Salts in a concentration of 0.001 to 10 wt .-%, preferably 0.0025 to 2 wt .-%, particularly preferably 0.01 to 0.04 wt .-% used. Preferred acids for the Salt formation are hydrochloric, sulfuric, phosphoric, carbonic, sulphurous Acid, organic carboxylic acids such as acetic, glycolic, citric, succinic acid. Very effective are 5-pentyl, 5-heptyl, 5-nonyl, 5-undecyl, 5-isononyl, 5-versatic-10-alkyl-3-amino-1,2,4-triazoles as well as mixtures of these substances.

you In addition, cleaning agent formulations often contain active chlorine Means that can significantly reduce the corrosion of the silver surface. In Chlorine-free cleaners are especially oxygen- and nitrogen-containing organic redox-active compounds, such as di- and trihydric phenols, e.g. Hydroquinone, pyrocatechol, hydroxyhydroquinone, gallic acid, phloroglucin, Pyrogallol or derivatives of these classes of compounds used. Also salt- and complex-like inorganic compounds, such as salts of Metals Mn, Ti, Zr, Hf, V, Co and Ce are often used. Prefers here are the transition metal salts, the selected are from the group of manganese and / or cobalt salts and / or complexes, particularly preferably the cobalt (ammin) complexes, the cobalt (acetate) complexes, the cobalt (carbonyl) complexes, the chlorides of cobalt or manganese and manganese sulfate. Also, zinc compounds for preventing the Corrosion on the items to be washed be used.

Instead of from or in addition to the silver protectants described above, for example the Benzotriazoles, can redox-active substances are used. These substances are preferably inorganic redox-active substances from the group Manganese, Titanium, Zirconium, Hafnium, Vanadium, Cobalt and Cerium salts and / or complexes, the metals preferably in one of the oxidation states II, III, IV, V or VI.

The metal salts or metal complexes used should be at least partially soluble in water. The counterions suitable for salt formation comprise all customary mono-, di- or tri-positively negatively charged inorganic anions, for example oxide, sulfate, nitrate, fluoride, but also organic anions such as stearate.

metal complexes in the context of the invention are compounds which consist of a central atom and one or more ligands and optionally in addition one or more of the o.g. Anions exist. The central atom is one the o.g. Metals in one of the above Oxidation states. The ligands are neutral molecules or anions which are monodentate or polydentate; the term "ligands" within the meaning of the invention is e.g. in "Römpp Chemie Lexicon, Georg Thieme Verlag Stuttgart / New York, 9th edition, 1990, Page 2507 " in a metal complex the charge of the central atom and the charge of the ligand (s) is not zero, so, depending on whether a cationic or an anionic charge excess is present, either one or more of the above. Anions or one or more Cations, e.g. Sodium, potassium, ammonium ions, for charge balance. Suitable complexing agents are e.g. Citrate, acetylacetonate or 1-hydroxyethane-1,1-diphosphonate.

The common in chemistry Definition for "oxidation state" is e.g. in "Römpp Chemie Lexikon, Georg Thieme Verlag Stuttgart / New York, 9th edition, 1991, page 3168 "reproduced.

Particularly preferred metal salts and / or metal complexes are selected from the group MnSO ₄ , Mn (II) citrate, Mn (II) stearate, Mn (II) acetylacetonate, Mn (II) - [1-hydroxyethane-1,1- diphosphonate], V ₂ O ₅ , V ₂ O ₄ , VO ₂ , TiOSO ₄ , K ₂ TiF ₆ , K ₂ ZrF ₆ , CoSO ₄ , Co (NO ₃ ) ₂ , Ce (NO ₃ ) ₃ , and mixtures thereof, such that the metal salts and / or metal complexes are selected from the group MnSO ₄ , Mn (II) citrate, Mn (II) stearate, Mn (II) acetylacetonate, Mn (II) - [1-hydroxyethane-1,1- diphosphonate], V ₂ O ₅ , V ₂ O ₄ , VO ₂ , TiOSO ₄ , K ₂ TiF ₆ , K ₂ ZrF ₆ , CoSO ₄ , Co (NO ₃ ) ₂ , Ce (NO ₃ ) _{3 are used} with particular preference ,

These metal salts or metal complexes are generally commercially available substances which can be used for the purpose of silver corrosion protection without prior purification in detergents or cleaners. Thus, for example, the mixture of pentavalent and tetravalent vanadium (V ₂ O ₅ , VO ₂ , V ₂ O ₄ ) known from the SO ₃ preparation (contact method) is suitable, as is the case by diluting a Ti (SO ₄ ) ₂ - Solution resulting titanyl sulfate, TiOSO ₄ .

The inorganic redox-active substances, in particular metal salts or metal complexes are preferably coated, i. completely with a waterproof, but easily soluble at the cleaning temperatures Material coated, to their premature decomposition or oxidation during storage too prevent. Preferred coating materials which, according to known methods, such as Sandwik's melt coating process from the food industry, are applied, paraffins, microwaxes, waxes are natural Origin like carnauba wax, candellila wax, beeswax, higher melting Alcohols such as hexadecanol, soaps or fatty acids. there is the solid at room temperature coating material in molten Condition applied to the material to be coated, e.g. by finely divided material to be coated in continuous stream through a likewise continuously generated spray zone of the molten coating material is spun. The melting point must be chosen be that the coating material during the silver treatment easily dissolves or melted quickly. The melting point should ideally be in the Range between 45 ° C and 65 ° C and preferably in the range 50 ° C up to 60 ° C lie.

The mentioned metal salts and / or metal complexes are in cleaning agents, preferably in an amount of 0.05 to 6 wt .-%, preferably 0.2 to 2.5 wt .-%, each based on the total corrosion inhibitor-containing Contain funds.

disintegration aid

Around the disintegration of prefabricated moldings to facilitate, it is possible Disintegration aids, so-called tablet disintegrants, in to incorporate these agents to reduce disintegration times. Under Tablet disintegrants or disintegrants are used according to Römpp (9. Auflage, Bd. 6, p. 4440) and Voigt "Textbook of Pharmaceutical Technology" (6th edition, 1987, Pp. 182-184) are excipients which are responsible for the rapid disintegration of tablets in water or gastric juice and for ensure the release of the pharmaceuticals in a resorbable form.

These substances, which are also referred to as "explosives" due to their effect, increase their volume upon ingress of water, on the one hand increasing the intrinsic volume (swelling), and on the other hand creating a pressure via the release of gases which can break the tablet into smaller particles decays. Well-known disintegration aids are, for example, carbonate / citric acid systems, wherein also which organic acids can be used. Swelling disintegration aids are, for example, synthetic polymers such as polyvinylpyrrolidone (PVP) or natural polymers or modified natural substances such as cellulose and starch and their derivatives, alginates or casein derivatives.

Prefers are disintegration aids in amounts of 0.5 to 10 wt .-%, preferably 3 to 7% by weight and in particular 4 to 6% by weight, respectively based on the total weight of the desintegrationshilfsmittelhaltigen By means of, used.

Preferred disintegrating agents used are cellulose-based disintegrating agents, so that preferred washing and cleaning agents contain such cellulose-based disintegrants in amounts of from 0.5 to 10% by weight, preferably from 3 to 7% by weight and in particular from 4 to 6% by weight. % contain. Pure cellulose has the formal gross composition (C ₆ H ₁₀ O ₅ ) _n and is formally a β-1,4-polyacetal of cellobiose, which in turn is composed of two molecules of glucose. Suitable celluloses consist of about 500 to 5000 glucose units and therefore have average molecular weights of 50,000 to 500,000. Cellulose-based disintegrating agents which can be used in the context of the present invention are also cellulose derivatives obtainable by polymer-analogous reactions of cellulose. Such chemically modified celluloses include, for example, products of esterifications or etherifications in which hydroxy hydrogen atoms have been substituted. Celluloses in which the hydroxy groups have been replaced by functional groups which are not bonded via an oxygen atom can also be used as cellulose derivatives. The group of cellulose derivatives includes, for example, alkali metal celluloses, carboxymethylcellulose (CMC), cellulose esters and ethers, and aminocelluloses. The cellulose derivatives mentioned are preferably not used alone as disintegrating agents based on cellulose, but used in admixture with cellulose. The content of these mixtures of cellulose derivatives is preferably below 50% by weight, particularly preferably below 20% by weight, based on the cellulose-based disintegrating agent. It is particularly preferred to use cellulose-based disintegrating agent which is free of cellulose derivatives.

The cellulose used as a disintegration aid is preferably not used in finely divided form, but converted into a coarser form, for example granulated or compacted, before it is added to the premixes to be tabletted. The particle sizes of such disintegrating agents are usually above 200 .mu.m, preferably at least 90 wt .-% between 300 and 1600 .mu.m and in particular at least 90 wt .-% between 400 and 1200 microns. The above and described in more detail in the documents cited coarser disintegration aids, are preferred as disintegration aids and are commercially available, for example under the name of Arbocel ^® TF-30-HG from Rettenmaier available in the present invention.

When another disintegrating agent based on cellulose or as an ingredient This component can be used microcrystalline cellulose. This microcrystalline cellulose is made by partial hydrolysis of Celluloses obtained under such conditions, only the amorphous ones Areas (about 30% of the total cellulose mass) of the celluloses attack and completely dissolve, the crystalline areas (about 70%) but leave undamaged. A subsequent disaggregation of the resulting from the hydrolysis microfine celluloses provide the microcrystalline celluloses, the primary particle sizes of approx. 5 μm and compactable, for example, to granules having an average particle size of 200 microns are.

preferred Disintegration aid, preferably a disintegration aid based on cellulose, preferably in granular, cogranulated or compact form, are in disintegrating agents in amounts of from 0.5 to 10% by weight, preferably from 3 to 7% by weight and in particular from 4 to 6 wt .-%, each based on the total weight of the disintegrant-containing agent.

According to the invention preferred can about that in addition, gas-evolving effervescent systems as tablet disintegration aids be used. The gas-developing effervescent system can from a consist of a single substance which releases a gas on contact with water. Among these compounds is in particular the magnesium peroxide to call, which releases oxygen on contact with water. Usually However, the gas-releasing effervescent system in turn from at least two components that are together under gas formation react. While here a variety of systems is thinkable and executable, for example Nitrogen, oxygen or hydrogen will release the both in the detergents and cleaners used effervescent system on the basis of economic as well as ecological Select points of view to let. Preferred effervescent systems consist of alkali metal carbonate and / or bicarbonate and an acidifier, the is suitable to release carbon dioxide from the alkali metal salts in aqueous solution.

at The alkali metal carbonates or bicarbonates are the sodium and potassium salts for cost reasons across from the other salts clearly preferred. Of course, not the relevant pure alkali metal carbonates or bicarbonates be used; rather, you can Mixtures of different carbonates and bicarbonates preferred be.

Prefers be used as effervescent 2 to 20 wt .-%, preferably 3 to 15 wt .-% and in particular 5 to 10 wt .-% of an alkali metal carbonate or hydrogen carbonate and 1 to 15, preferably 2 to 12 wt .-% and in particular from 3 to 10% by weight of an acidifying agent, respectively based on the total weight of the agent used.

Acidifying agents which release carbon dioxide from the alkali metal salts in aqueous solution include, for example, boric acid and alkali metal hydrogen sulfates, alkali metal dihydrogen phosphates and other inorganic salts. However, preference is given to using organic acidifying agents, the citric acid being a particularly preferred acidifying agent. However, it is also possible in particular to use the other solid mono-, oligo- and polycarboxylic acids. Tartaric acid, succinic acid, malonic acid, adipic acid, maleic acid, fumaric acid, oxalic acid and polyacrylic acid are again preferred from this group. Organic sulfonic acids such as sulfamic acid are also usable. A commercially available as an acidifier in the context of the present invention also preferably be used is Sokalan ^® DCS (trademark of BASF), a mixture of succinic acid (max. 31 wt .-%), glutaric acid (max. 50 wt .-%) and adipic acid ( at most 33% by weight).

Prefers are Acidifizierungsmittel in effervescent system from the group of organic Di-, tri- and oligocarboxylic acids or mixtures.

fragrances

When Perfume oils or Fragrances can in the context of the present invention, individual fragrance compounds, e.g. the synthetic products of the ester, ether, aldehyde, Ketones, alcohols and hydrocarbons are used. fragrance compounds the type of esters are e.g. Benzyl acetate, phenoxyethyl isobutyrate, p-tert-butylcyclohexyl acetate, linalyl acetate, dimethylbenzylcarbinyl acetate, Phenylethyl acetate, linalyl benzoate, benzyl formate, ethyl methyl phenyl glycinate, Allyl cyclohexyl propionate, styrallyl propionate and benzyl salicylate. Count to the Ethern for example, benzyl ethyl ether, to the aldehydes e.g. the linear ones Alkanals with 8-18 C atoms, citral, citronellal, citronellyloxyacetaldehyde, Cyclamenaldehyde, Hydroxycitronellal, Lilial and Bourgeonal, to the Ketones e.g. the ionone, α-isomethylionone and methyl cedryl ketone, to the alcohols anethole, citronellol, eugenol, Geraniol, linalool, phenylethyl alcohol and terpineol, to the hydrocarbons belong mainly the terpenes like limonene and pinene. However, mixtures of various are preferred Fragrances are used, which together create an appealing fragrance produce. Such perfume oils can also natural Fragrance mixtures as available from vegetable sources, e.g. Pine, citrus, jasmine, patchouly, rose or ylang-ylang oil. Also suitable are muscatel, sage oil, Chamomile oil, Clove oil, Balm oil, mint oil, Cinnamon leaf oil, lime blossom oil, juniper berry oil, vetiver oil, olbanum oil, galbanum oil and labdanum oil, as well as Orange blossom oil, neroliol, Orange peel oil and sandalwood oil.

The general description of the applicable perfumes (see above) provides in general the different substance classes of fragrances In order to be perceptible, a fragrance must be volatile, besides the nature of the functional groups and the structure the molecular weight of the chemical compound also plays an important role plays. So most perfumes have molecular weights up to about 200 Dalton, while Molar masses of 300 daltons and above rather an exception. Due to the different volatility changed by fragrances the smell of a compound of several fragrances perfumes or perfume during vaporizing, whereby the odor impressions in "top note", "middle note" body) and "base note" (end note or dry divided out). Because the smell perception to a large extent also on the smell intensity is based, the top note of a perfume or fragrance is not alone from volatile Connections while the base note for the most part from less volatile, i.e. adherent fragrances. When composing perfumes can be easier volatile For example, fragrances can be bound to specific fixatives. which prevents it from evaporating too quickly. At the following Classification of the fragrances in "lighter volatile or "adherent" fragrances So over the smell impression and about it, whether the corresponding perfume perceived as a head or middle note nothing is said.

Adhesive-resistant fragrances which can be used in the context of the present invention are, for example the essential oils such as angelica root oil, aniseed oil, arnica blossom oil, basil oil, bay oil, bergamot oil, champa blossom oil, fir pine oil, pinecone oil, elemi oil, eucalyptus oil, fennel oil, spruce needle oil, galbanum oil, geranium oil, ginger grass oil, guaiac wood oil, guriuri balm oil, helichrysum oil, ho oil, ginger oil, iris oil, Cajuput oil, calamus oil, chamomile oil, camphor oil, kanga oil, cardamom oil, cassia oil, pine oil, copaiba balsam, coriander oil, spearmint oil, caraway oil, cumin oil, lavender oil, lemongrass oil, lime oil, tangerine oil, lemon balm oil, musk kernel oil, myrrh oil, clove oil, neroli oil, niaouli oil, olibanum oil, orange oil, Origanum oil, Palmarosa oil, Patchouli oil, Peruvian balsam oil, Petitgrain oil, Pepper oil, Peppermint oil, Pimento oil, Pine oil, Rose oil, Rosemary oil, Sandalwood oil, Celery oil, Spik oil, Star aniseed oil, Turpentine oil, Thuja oil, Thyme oil, Verbena oil, Vetiver oil, Juniper berry oil, Vermouth oil, Wintergreen oil, Ylang Ylang oil, hyssop oil, cinnamon oil, Cinnamon leaf oil, lemon oil, lemon oil and cypress oil. But also the higher-boiling or solid fragrances of natural or synthetic origin can be used in the context of the present invention as adherent fragrances or fragrance mixtures, ie fragrances. These compounds include the following compounds and mixtures thereof: ambrettolide, α-amylcinnamaldehyde, anethole, anisaldehyde, anisalcohol, anisole, methyl anthranilate, acetophenone, benzylacetone, benzaldehyde, ethyl benzoate, benzophenone, benzyl alcohol, benzyl acetate, benzyl benzoate, benzyl formate, benzyl valerate, borneol , Bornyl acetate, α-bromostyrene, n-decyl aldehyde, n-dodecyl aldehyde, eugenol, eugenol methyl ether, eucalyptol, farnesol, fenchone, fenchyl acetate, geranyl acetate, geranyl formate, heliotropin, heptincarboxylic acid methyl ester, heptaldehyde, hydroquinone dimethyl ether, hydroxycinnamaldehyde, hydroxycinnamyl alcohol, indole, iron, isoeugenol , Isoeugenol methyl ether, isosafrole, jasmon, camphor, karvakrol, karvon, p-cresol methyl ether, coumarin, p-methoxyacetophenone, methyl n-amyl ketone, methyl anthranilate, p-methylacetophenone, methylchavikole, p-methylquinoline, methyl-β-naphthyl ketone, methyl-n nonylacetaldehyde, methyl n-nonyl ketone, Muskon, β-N aphtholethyl ether, β-naphthol methyl ether, nerol, nitrobenzene, n-nonylaldehyde, nonyl alcohol, n-octylaldehyde, p-oxyacetophenone, pentadecanolide, β-phenylethyl alcohol, phenylacetaldehyde dimethyacetal, phenylacetic acid, pulegone, safrole, isoamyl salicylate, methyl salicylate, hexyl salicylate, cyclohexyl salicylate, Santalol, skatole, terpineol, thymen, thymol, γ-undelactone, vaniline, veratrum aldehyde, cinnamaldehyde, cimat alcohol, cinnamic acid, cinnamic acid ethyl ester, cinnamic acid benzyl ester. The more volatile fragrances include in particular the lower-boiling fragrances of natural or synthetic origin, which can be used alone or in mixtures. Examples of more volatile fragrances are alkyl isothiocyanates (alkyl mustard oils), butanedione, limonene, linalool, linayl acetate and propionate, menthol, menthone, methyl-n-heptenone, phellandrene, phenylacetaldehyde, terpinyl acetate, citral, Zitranellal.

The Dufstoffe can can be processed directly, but it can also be beneficial to the Fragrances on carrier The slow release of fragrance for long-lasting Provide scent. As such carrier materials For example, cyclodextrins have proven useful, with the cyclodextrin-perfume complexes additionally still can be coated with other excipients.

dyes

preferred Dyes whose selection does not present any difficulty to the skilled person have a high storage stability and insensitivity to the rest Ingredients of the agents and against light and no pronounced substantivity to the with the dye-containing agents to be treated substrates such as for example textiles, glass, ceramics or plastic dishes, so as not to stain them.

When choosing the colorant, it must be taken into account that in the case of textile detergents, the colorants do not have too high an affinity for textile surfaces and, in particular, for synthetic fibers, whereas in the case of detergents an excessive affinity for glass, ceramic or plasticware must be avoided. Is ₂ eitig also have the choice of suitable coloring agents should be noted that colorant different stabilities with respect to oxidation. In general, water-insoluble colorants are more stable to oxidation than water-soluble colorants. Depending on the solubility and thus also on the sensitivity to oxidation, the concentration of the colorant in the detergents or cleaners varies. For highly soluble dyes, for example, the above-mentioned Basacid ^® Green or the above-mentioned Sandolan Blue ^®, are typically selected dye concentrations in the range of a few 10 ^-2 to 10 ^-3 wt .-%. In the due to their brilliance, particularly preferred, but are less readily water-soluble pigment dyes, for example the above-mentioned Pigmosol ^® ATTO-dyes, the appropriate concentration of the colorant is in washing or cleaning agents, however, typically a few 10 ^-3 to 10 ^-4 wt .-% ,

Dyeing agents which can be oxidatively destroyed in the washing process and mixtures thereof with suitable blue dyes, so-called blue toners, are preferred. It has proved to be advantageous to use colorants which are soluble in water or at room temperature in liquid organic substances are. Suitable examples are anionic colorants, for example anionic nitrosofarbstoffe. One possible dye is, for example, naphthol green (Color Index (CI) Part 1: Acid Green 1; Part 2: 10020)., That is as a commercial product, for example as Basacid ^® Green 970 from BASF, Ludwigshafen available, as well as mixtures thereof with suitable blue dyes. Further suitable colorants Pigmosol come ^® Blue 6900 (CI 74160), Pigmosol ^® Green 8730 (CI 74260), Basonyl ^® Red 545 FL (CI 45170), Sandolan® ^® rhodamine EB400 (CI 45100), Basacid® ^® Yellow 094 (CI 47005) Sicovit ^® Patentblau 85 e 131 (CI 42051), Acid Blue 183 (CAS 12217-22-0, CI Acidblue 183), pigment Blue 15 (CI 74160), Supranol Blue ^® GLW (CAS 12219-32-8, CI Acidblue 221 )), Nylosan Yellow ^® N-7GL SGR (CAS 61814-57-1, CI Acidyellow 218) and / or Sandolan ^® Blue (CI Acid Blue 182, CAS 12219-26-0) is used.

In addition to so far in detail described components can the detergents and cleaners contain other ingredients, which the application and / or aesthetic properties of this Improve funds further. Preferred agents include one or several substances from the group of electrolytes, pH adjusters, fluorescers, Hydrotopes, foam inhibitors, silicone oils, anti redeposition agents, optical brighteners, grayness inhibitors, anti-shrinkage agents, Anti-crease agents, color transfer inhibitors, antimicrobial agents, germicides, fungicides, antioxidants, Antistatic agents, ironing aids, Phobic and impregnating agents, Swelling and anti-slip agents as well as UV absorbers.

As electrolytes from the group of inorganic salts, a wide number of different salts can be used. Preferred cations are the alkali and alkaline earth metals, preferred anions are the halides and sulfates. From a manufacturing point of view, the use of NaCl or MgCl ₂ in the washing or cleaning agents is preferred.

Around the pH of detergents or cleaners in the desired The use of pH-adjusting agents may be indicated be. Can be used here all known acids or alkalis, provided that their use is not from application technology or ecological establish or for reasons consumer protection. Usually exceeds the amount of these adjusting agents 1 wt .-% of the total formulation not.

Suitable foam inhibitors are, inter alia, soaps, oils, fats, paraffins or silicone oils, which may optionally be applied to support materials. Suitable carrier materials are, for example, inorganic salts such as carbonates or sulfates, cellulose derivatives or silicates and mixtures of the abovementioned materials. In the context of the present application preferred agents include paraffins, preferably unbranched paraffins (n-paraffins) and / or silicones, preferably linear-polymeric silicones, which are constructed according to the scheme (R ₂ SiO) x and are also referred to as silicone oils. These silicone oils usually are clear, colorless, neutral, odorless, hydrophobic liquids having a molecular weight between 1,000 and 150,000, and viscosities between 10 and 1,000,000 mPa.s.

suitable Anti redeposition agent, also referred to as soil repellents are, for example, nonionic cellulose ethers such as methyl cellulose and methylhydroxypropylcellulose with a proportion of methoxy groups from 15 to 30% by weight and of hydroxypropyl groups from 1 to 15% by weight, in each case based on the nonionic cellulose ether and the known from the prior art polymers of phthalic acid and / or terephthalic acid or of their derivatives, in particular polymers of ethylene terephthalates and / or Polyethylene glycol terephthalates or anionic and / or nonionic modified derivatives of these. Especially preferred of these are the sulfonated derivatives of phthalic and terephthalic acid polymers.

optical Brighteners (so-called "whiteners") can Detergents or cleaners are added to graying and to eliminate yellowing of the treated textiles. These Substances attract to the fiber and cause a whitening and feigned Bleaching action by turning invisible ultraviolet radiation into visible length wavy Convert light, with the ultraviolet absorbed from sunlight Light as slightly bluish Fluorescence is emitted and with the yellow of the bated or yellowed laundry pure white results. Suitable compounds are derived, for example, from the substance classes 4,4'-diamino-2,2'-stilbenedisulfonic acids (flavonic acids), 4,4'-distyryl-biphenylene, Methylumbelliferones, coumarins, dihydroquinolinones, 1,3-diarylpyrazolines, naphthalic acid, Benzoxazole, benzisoxazole and benzimidazole systems and the by Heterocycles substituted pyrene derivatives.

Grayness inhibitors have the task of keeping the dirt detached from the fiber suspended in the liquor and thus preventing the dirt from being rebuilt. Water-soluble colloids of mostly organic nature are suitable for this purpose, for example the water-soluble salts of polymeric carboxylic acids, Glue, gelatin, salts of ether sulfonic acids or cellulose or salts of acidic sulfuric acid esters of cellulose or starch. Also, water-soluble polyamides containing acidic groups are suitable for this purpose. It is also possible to use soluble starch preparations and starch products other than those mentioned above, for example degraded starch, aldehyde starches etc. Polyvinylpyrrolidone is also useful. Also usable as graying inhibitors are cellulose ethers such as carboxymethylcellulose (sodium salt), methylcellulose, hydroxyalkylcellulose and mixed ethers such as methylhydroxyethylcellulose, methylhydroxypropylcellulose, methylcarboxymethylcellulose and mixtures thereof.

There textile fabrics, in particular of rayon, rayon, cotton and mixtures thereof, for Can tend to wrinkles, because the individual fibers against bending, bending, pressing and squeezing are sensitive to the grain direction, synthetic crease inhibitors be used. These include, for example synthetic products based on fatty acids, fatty acid esters, fatty acid amides, Alkylolestern, -alkylolamiden or fatty alcohols, usually with Ethylene oxide reacted or products based on lecithin or modified phosphoric acid ester.

phobicizing and impregnation method serve the equipment of textiles containing substances which are the deposit of dirt prevent or make it easier to wash out. Preferred phobic and impregnating agents are perfluorinated fatty acids, also in the form of their aluminum u. Zirconium salts, organic silicates, silicones, polyacrylate with perfluorinated alcohol component or with perfluorinated acyl or sulfonyl radical-coupled, polymerizable compounds. Also Antistatics can be included. The dirt-repellent finish with phobic and impregnating agents Often classified as an easy-care item. The intrusion the impregnating agent in the form of solutions or emulsions of the active substances in question can be made by adding Wetting agents that minimize the surface tension. One Another field of application of repellents and impregnating agents is the water-repellent equipment of textiles, tents, tarpaulins, leather, etc., in contrast for waterproofing the tissue pores are not closed, the fabric thus remains breathable (hydrophobing). The water repellent coat the water repellents used Textiles, leather, paper, wood, etc. with a very thin layer hydrophobic groups, such as longer Alkyl chains or siloxane groups. Suitable water repellents are e.g. Paraffins, waxes, metal soaps etc. with additives Aluminum or zirconium salts, quaternary ammonium compounds with long-chain Alkyl radicals, urea derivatives, fatty acid-modified melamine resins, Chromium complex salts, silicones, tin organic compounds and glutaric dialdehyde as well as perfluorinated compounds. The hydrophobized materials feel not greasy; nevertheless, similar to greasy substances, water drops drip at them without moistening. Thus, e.g. Silicone impregnated Textiles have a soft feel and are water and dirt repellent; Stains from ink, wine, fruit juices and the like are easier to remove.

to fight of microorganisms can antimicrobial agents are used. This is different depending on the antimicrobial spectrum and mechanism of action between Bacteriostats and bactericides, fungistats and fungicides etc .. Important substances from these groups are, for example, benzalkonium chlorides, Alkylarlylsulfonates, halophenols and Phenolmercuriacetat, wherein also completely on these compounds can be dispensed with.

Around unwanted, caused by oxygen and other oxidative processes changes on the detergents and / or the treated textiles to prevent the agents contain antioxidants. To this class of connection belong for example, substituted phenols, hydroquinones, catechols and aromatic amines and organic sulfides, polysulfides, dithiocarbamates, Phosphites and phosphonates.

One increased Comfort can come from the extra Use of antistatics will result. Antistatic agents increase the surface conductivity and allow thus an improved drainage formed charges. External antistatic agents are usually substances with at least one hydrophilic molecule ligand and give on the surfaces a more or less hygroscopic film. These mostly surface-active Antistatic agents can be converted into nitrogen-containing (amines, amides, quaternary ammonium compounds), phosphorus-containing (phosphoric acid ester) and sulfur-containing (alkyl sulfonates, alkyl sulfates) antistatic agents. lauryl (or stearyl) dimethylbenzylammonium chlorides are also suitable as antistatics for Textiles or as an additive to detergents, with an additional Avivageeffekt is achieved.

Softeners can be used to care for the textiles and to improve the textile properties such as a softer "handle" (avivage) and reduced electrostatic charge (increased wearing comfort). The active ingredients in softener formulations are "esterquats", quaternary ammonium compounds with two hydrophobic radicals, such as the Disteraryldimethylammoniumchlorid, but which is increasingly replaced because of its insufficient biodegradability by quaternary ammonium compounds containing ester groups in their hydrophobic residues as breaking points for biodegradation. Such "esterquats" with improved biodegradability are obtainable, for example, by esterifying mixtures of methyldiethanolamine and / or triethanolamine with fatty acids and then quaternizing the reaction products in a manner known per se with alkylating agents. Further suitable as a finish is dimethylolethyleneurea.

to Improvement of water absorbency, rewettability treated textiles and to facilitate ironing treated textiles can Silicone derivatives are used. These additionally improve that rinse behavior of detergents or cleaners by their foam-inhibiting Properties. Preferred silicone derivatives are, for example, polydialkyl or alkylaryl siloxanes in which the alkyl groups have one to five carbon atoms and are completely or partially fluorinated. Preferred silicones are polydimethylsiloxanes which may optionally be derivatized can and are then amino-functional or quaternized or Si-OH-, Si-H- and / or Si-Cl bonds. Other preferred silicones are the polyalkylene oxide-modified Polysiloxanes, ie polysiloxanes, which are, for example, polyethylene glycols and also the polyalkylene oxide-modified Dimetylpolysiloxane.

Finally, according to the invention, UV absorbers which are applied to the treated textiles and the light resistance improve the fibers. Compounds that have these desired properties are, for example, by radiationless deactivation effective compounds and derivatives of benzophenone with substituents in 2- and / or 4-position. Furthermore, substituted benzotriazoles, in the 3-position phenyl-substituted acrylates (cinnamic acid derivatives), optionally with cyano groups in the 2-position, salicylates, organic Ni complexes as well Natural substances such as umbelliferone and the body's own urocanic acid are suitable.

protein are due to their fiber care effect more in the context of present invention preferred active substances from the field of detergents and cleaners. Protein hydrolysates are product mixtures, by acid, base or enzymatically catalyzed degradation of Proteins (proteins) to be obtained. According to the invention, protein hydrolysates be used both of plant and animal origin. Animal protein hydrolysates are, for example, elastin, collagen, Keratin, silk and milk protein protein hydrolysates, too may be in the form of salts. According to the invention preferred is the use of protein hydrolysates of plant origin, e.g. Soy, almonds, rice, pea, potato and wheat protein hydrolysates. Although the use of protein hydrolysates is preferred as such is, can in their place, if appropriate, otherwise obtained amino acid mixtures or individual amino acids such as arginine, lysine, histidine or pyrroglutamic acid used become. Also possible is the use of derivatives of protein hydrolysates, for example in the form of their fatty acid condensation products.

To the non-aqueous Solvent, which used according to the invention can be count in particular the organic solvents, of which only the most important can be listed here: alcohols (methanol, ethanol, Propanols, butanols, octanols, cyclohexanol), glycols (ethylene glycol, Diethylene glycol), ethers and glycol ethers (diethyl ether, dibutyl ether, Anisole, dioxane, tetrahydrofuran, mono-, di-, tri-, polyethylene glycol ethers), Ketones (acetone, butanone, cyclohexanone), esters (acetic acid esters, Glycol esters), amides and other nitrogen compounds (dimethylformamide, Pyridine, N-methylpyrrolidone, acetonitrile), sulfur linkages (Carbon disulfide, dimethyl sulfoxide, sulfolane), nitro compounds (Nitrobenzene), halogenated hydrocarbons (dichloromethane, chloroform, carbon tetrachloride, Tri-, tetrachloroethene, 1,2-dichloroethane, chlorofluorocarbons), Hydrocarbons (gasolines, petroleum ethers, cyclohexane, methylcyclohexane, Decalin, terpene solvent, Benzene, toluene, xylenes). Alternatively, instead of pure solvents also their mixtures, which, for example, the solution properties of various solvent combine beneficial, be used. Such and in the Within the scope of the present application, a particularly preferred solvent mixture is, for example, benzene, a suitable for chemical cleaning Mixture of various hydrocarbons, preferably with one Content of C12 to C14 hydrocarbons above 60% by weight, especially preferably above 80% by weight and in particular above 90% by weight, in each case based on the total weight of the mixture, preferably with a boiling range of 81 to 110 ° C.

Example:

Not Soiled silver sink (Spoon) was in a Miele G 646-dishwasher at 65 ° C and a water hardness of 21 ° dH rinsed with the formulations A and B, respectively.

Of the flushing was repeated 30 times under the conditions described above. Subsequently the overall appearance of the dishes was calculated using the scale below assessed.

• Bewertungsscala: Note 5 = nicht angelaufen, unverändert; Note 4 = gering angelaufen; Note 3 = mittelstark angelaufen; Note 2 = stark angelaufen; Note 1 = sehr stark angelaufen

The results are given in the table below.

• Rating scale: grade 5 = not started, unchanged; Grade 4 = low started; Grade 3 = medium started; Grade 2 = strong start; Grade 1 = very strong

The Table shows that the machine dishwashing detergent according to the invention Under the conditions mentioned a significantly improved silver corrosion protection having.

Claims (21)

Washing or cleaning compositions comprising a) at least one rinse aid substance from the group a ') of the hydroxy mixed ethers, a '') of the polymers having a cationic monomer unit and a ''') of the copolymers of sulfonic acid-containing monomers and b) at least one sulfur-containing amino acid. Washing or cleaning agent according to claim 1, characterized in that the weight fraction of the final rinse substance a) 0.01 to 80 wt .-%, preferably 0.5 to 65 wt .-%, particularly preferably 0.8 to 50 wt .-%, most preferably 1.1 to 35 wt .-% and in particular from 1.4 to 20% by weight, based on the total agent, is. Washing or cleaning agent according to claim 1 or 2, characterized in that the weight fraction of the hydroxy mixed ether a ') preferably 0.5 to 15% by weight, preferably 1 to 12.5% by weight, more preferably 1.5 to 10 wt .-%, most preferably 2 to 8 wt .-% and in particular 2.5 to 6 wt .-%, based on the total agent is. Detergent or cleaner according to one of the claims 1 to 3, characterized in that the weight fraction of the polymers with cationic monomer unit a ") preferably 0.01 to 7.5% by weight, preferably 0.02 to 5% by weight, especially preferably 0.03 to 2.5 wt .-%, most preferably 0.04 to 1 wt .-% and in particular 0.05 to 1 wt .-%, based on the total Means, amounts. Detergent or cleaner according to one of the claims 1 to 4, characterized in that the weight fraction of the copolymers from sulfonic acid-containing Monomers a '' ') preferably 0.1 to 70 wt .-%, preferably 0.25 to 50 wt .-%, particularly preferably 0.5 to 35 wt .-%, completely particularly preferably 0.75 to 20 wt .-% and in particular 1 to 15 Wt .-%, based on the total agent is. Detergent or cleaner according to one of the claims 1 to 5, characterized in that the weight ratio of the hydroxy mixed ether a ') to the polymers with cationic monomer unit a ") preferably between 10: 1 and 200: 1, preferably between 12.5: 1 and 150: 1, more preferably between 15: 1 and 100: 1, most especially preferably between 17.5: 1 and 50: 1 and in particular between 20: 1 and 40: 1. Detergent or cleaner according to one of the claims 1 to 6, characterized in that the weight ratio of the hydroxy mixed ether a ') to the copolymers from sulfonic acid-containing Monomers a '' ') preferably between 1: 100 and 10: 1, preferably between 1:75 and 7.5: 1, more preferably between 1:50 and 5: 1, most preferably between 1:25 and 2.5: 1 and especially between 1:10 and 1: 1. Detergent or cleaner according to one of the claims 1 to 7, characterized in that the weight ratio of the polymers with cationic Monomer unit a ") to the copolymers with sulfonic acid-containing Monomers a '' ') preferably between 1: 700 and 1:10, preferably between 1: 500 and 1:30, more preferably between 1: 300 and 1:50 and in particular between 1: 150 and 1:50. Detergent or cleaner according to one of the claims 1 to 8, characterized in that the agent is hydroxy mixed ether (a ')) of the formula R ^{1 is} -O- [CH ₂ CH (R ³ ) O] _x - [CH ₂ CH (OH)] - R ² R ¹ and R ^{2 may be} different or the same, where R ^{1 is} a linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radical having 1 to 30 carbon atoms or mixtures thereof, R ^{2 is} a linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radical having 1 to 30 carbon atoms, which optionally contains up to 5 hydroxyl and / or up to 3 ether functions, R ^{3 is} H or a methyl, ethyl, n-propyl, iso Propyl, n-butyl, 2-butyl or 2-methyl-butyl radical, wherein each R ³ may be different at x ≥ 2 and x is greater than 1 stands. Washing or cleaning agent according to one of claims 1 to 9, characterized in that as polymers with cationic functional Group (a ") cationic polymers be used. Washing or cleaning agent according to one of claims 1 to 9, characterized in that as polymers with cationic functional Group (a ") amphoteric polymers be used. Washing or cleaning agent according to one of claims 1 to 11, characterized in that the weight fraction of the sulfur-containing amino acid 0.01 to 10 wt .-%, preferably 0.05 to 8 wt .-%, more preferably 0.10 to 6 wt .-%, particularly preferably 0.15 to 4 wt .-%, very particularly preferably 0.20 to 2% by weight and in particular 0.20 to 1% by weight, relative to the total mean. Washing or cleaning agent according to one of claims 1 to 12, characterized in that as the sulfur-containing amino acid at least one from the group methionine, cysteine and cystine is used. Detergent or cleaner according to one of the claims 1 to 13, characterized in that the weight ratio of Klarspülsubstanzen a) to the sulfur-containing amino acid b) preferably between 450: 1 and 1: 100, preferably between 350: 1 and 1:80, more preferably between 250: 1 and 1:60, most preferably between 200: 1 and 1:40 and especially between 100: 1 and 1:20. Washing or cleaning agent according to one of claims 1 to 14, characterized in that the weight ratio of Hydroxymix ether a ') to the sulfur-containing amino acid b) preferably between 55: 1 and 2: 1, preferably 50: 1 and 4: 1, especially preferably between 45: 1 and 6: 1, very particularly preferably between 40: 1 and 8: 1 and in particular between 35: 1 and 10: 1. Washing or cleaning agent according to one of claims 1 to 15, characterized in that the weight ratio of Polymers with cationic monomer unit a ") to the sulfur-containing amino acid (b) preferably between 30: 1 and 1: 100, preferably between 20: 1 and 1:80, more preferably between 10: 1 and 1:60, especially preferably between 5: 1 and 1:40 and in particular between 1: 1 and 1:20. Washing or cleaning agent according to one of claims 1 to 16, characterized in that the weight ratio of Copolymers of sulfonic acid-containing Monomers a '' ') to the sulfur-containing amino acid (b) between 250: 1 and 12: 1, preferably between 200: 1 and 13: 1, especially preferably between 150: 1 and 14: 1, most preferably between 100: 1 and 15: 1 and in particular between 50: 1 and 16: 1. Washing or cleaning agent according to one of claims 1 to 17, characterized in that the agent is a water-soluble packaging comprising, which in the form of a deep-drawn part and / or injection-molded part and / or Blow molding is present. Washing or cleaning agent according to one of claims 1 to 18, characterized in that the means in the form of a tablet is present. Washing or cleaning agent according to one of claims 1 to 19, characterized in that the agent in liquid form or as a gel. Use of a washing or cleaning agent accordingly one of the claims 1 to 20 as means for the machine dishwashing.