RU2597014C2 - Optional use of oxidised thioethers of alcohol alkoxylates in detergent and cleaning agents - Google Patents

Abstract

FIELD: chemistry.

SUBSTANCE: present invention relates to use (oxidised) thioesters of alcohol alkoxylates in detergent and cleaning agents, especially in dishwashing agents, and to detergent and cleaning agent, especially dishwashing agent containing (oxidised) thioester of alcohol alkoxylates. Said (oxidised) thioesters are suitable as surfactants with rinsing function to clean water. Described is use of compounds of formula R-O-[CH₂CH(R¹)-O]_l-[CH₂CH₂-O]_m-[CH₂CH(R²)-O]_n-CH₂CH₂-S(O)_x-R' (I), where R denotes alkyl with 8-24 carbon atoms, R′ is alkyl with 10-14 carbon atoms, R¹ and R², independently from each other and irrespective of their specific appearance, denote an alkyl with 1-5 carbon atoms, m denotes a number from 25 to 50, l and n equal to 0 and x equals 0 or 1.

EFFECT: absence of foaming, reducing staining on dishware during washing.

25 cl, 6 tbl

Description

The present invention relates to the use of (oxidized) alcohol alkoxylate thioethers in detergents and cleaners, especially dishwashing agents, and a detergent and detergent, especially a dishwasher, containing (oxidized) alcohol alkoxylates thioether. Moreover, these simple thioethers are particularly suitable as surfactants with the function of rinsing to clean water (surfactants rinsing to clean water). “Oxidized” refers to the sulfur atom in a simple thioether, which may be in the oxidized form as sulfoxide (SO) or sulfonyl (SO ₂ ).

Surfactants are substances that can reduce surface tension at the interface. Typically, surfactants have a characteristic structure and at least one hydrophilic and at least one hydrophobic functional group. If both parts of the molecule are in equilibrium with each other, then the substance accumulates at the interface and is oriented, that is, hydrophilic groups are sent, for example, to the aqueous phase, and hydrophobic groups are oriented in the direction of other solid, liquid or gaseous phases. Another feature of surfactants is the formation of larger aggregates, the so-called micelles. Their surfactant molecules are arranged in such a way that the polar groups, for example, form a spherical shell. Due to this, substances, such as dirt particles, become soluble in an aqueous solution during the formation of micelles. Therefore, surfactants are particularly suitable for cleaning surfaces and as an additive in detergents.

Surfactants containing hydrophobic and hydrophilic blocks are widespread. However, their tendency to foam makes them inapplicable or only conditionally applicable for many areas of use. Therefore, for those areas of use in which strong foaming is undesirable, nonionic surfactants containing a second hydrophobic block have been developed, which limits the volume of the foam.

The second hydrophobic block may, for example, come from fatty alcohols. However, the use of dishwashing detergents containing such a surfactant, especially the use of detergents for machine dishwashing, often leads to residues being washed on the dishes (deposit formation, the so-called “spotting”, in the case of formation of spot deposits or “filming” in the case of the formation of film-like deposits).

The second hydrophobic block may alternatively be derived from a fatty acid. Although dishwashers containing such surfactants have a problem of scale formation, they are susceptible to hydrolysis due to their ester group, which greatly limits their applicability in alkaline formulations and at high temperatures, especially during long washing processes .

Thioether alcohol alkoxylates and their oxidized form (that is, sulfoxides and sulfones) are, in principle, known, for example, from US Pat. No. 3,627,845. It describes the use of such compounds as a biologically active agent, for example, as fungicides, acaricides and anthelmintics as well as surfactants in agrochemical compositions and coating agents. No use is made of detergents or cleaners.

The present invention was to obtain compounds that do not have the disadvantages of surfactants of the prior art. In particular, the compounds should not have any foaming or any strong predisposition to foaming. They should leave a small precipitate, especially a precipitate in the form of spots on the dishes during washing and should not or should be as little as possible not subject to hydrolysis as surfactants based on fatty acid esters. But, especially, the compounds should have a melting point as high as possible so that solid detergents and cleaners can also be made from them.

This problem is solved by the use of compounds of the formula I:

RO- [CH ₂ CH (R ¹⁾ -O] _l - [CH ₂ CH ₂ -O] _m - [CH ₂ CH (R ²⁾ -O] _n -CH ₂ CH ₂ -S (O) _x -R '(I),

Where

R is alkyl with 8-24 carbon atoms,

R ′ means alkyl with 6-18 carbon atoms,

R ¹ and R ² , independently of each other and regardless of their specific representatives, mean alkyl with 1-5 carbon atoms,

m means a number from 10 to 100,

l and n, independently from each other, mean a number from 0 to 15 and

x is 0.1 or 2,

in detergents or cleaners, especially dishwashers.

In addition, the invention relates to a detergent or detergent, especially a dishwasher, containing at least one compound of formula I according to the above definition.

According to the present invention, alkyl with 1-5 carbon atoms means a straight-chain or branched alkyl radical with 1-5 carbon atoms. Examples thereof are methyl, ethyl, propyl isopropyl, n-butyl, sec. butyl, isobutyl, tert. butyl, pentyl and their location isomers.

Alkyl with 6-18 carbon atoms means a straight-chain or branched alkyl radical with 6-18 carbon atoms. Examples thereof are hexyl, heptyl, octyl, 2-ethylhexyl, nonyl, decyl, 2-propylheptyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl and their location isomers.

Alkyl with 8-24 carbon atoms means a straight-chain or branched alkyl radical with 8-24 carbon atoms. Examples thereof are octyl, 2-ethylhexyl, nonyl, decyl, 2-propylheptyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl nonadecyl, eicosyl, genicosile and dockyose, docile isose, and dockile.

Branched alkyl with 8-24 carbon atoms are octyl location isomers, such as 2-ethylhexyl, n-nonyl location isomers; n-decyl location isomers, such as 2-propylheptyl; isomers of the location of n-undecyl; isomers of the location of n-dodecyl; isomers of the location of n-tridecyl; isomers of the location of n-tetradecyl; isomers of the location of n-pentadecyl; isomers of the location of n-hexadecyl; isomers of the location of n-heptadecyl; n-octadecyl location isomers; isomers of the location of n-non-decyl; n-eicosyl location isomers; isomers of the location of n-genicosyl; n-docosyl location isomers; isomers of the location of n-tricosyl and isomers of the location of n-tetracosyl.

Alkyl with 10-14 carbon atoms is a straight-chain or branched alkyl radical with 10-14 carbon atoms. Examples thereof are decyl, 2-propylheptyl, undecyl, dodecyl, tridecyl, tetradecyl and their location isomers.

Branched alkyl of 10-14 carbon atoms are n-decyl location isomers, such as 2-propylheptyl; isomers of the location of n-undecyl; isomers of the location of n-dodecyl; isomers of the location of n-tridecyl; and isomers of the location of n-tetradecyl.

Alkyl with 10-15 carbon atoms is a straight-chain or branched alkyl radical with 10-15 carbon atoms. Examples thereof are decyl, 2-propylheptyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl and their location isomers.

Branched alkyl with 10-15 carbon atoms are n-decyl location isomers, such as 2-propylheptyl; isomers of the location of n-undecyl; isomers of the location of n-dodecyl; n-tridecyl location isomers, n-tetradecyl location isomers and n-pentadecyl location isomers.

Alkyl with 8-15 carbon atoms is a straight-chain or branched alkyl radical with 8-15 carbon atoms. Examples of it are the radicals mentioned above for alkyl radicals with 10-15 carbon atoms, as well as octyl, 2-ethylhexyl, nonyl and their location isomers.

Branched alkyl with 8-15 carbon atoms are octyl location isomers, such as 2-ethylhexyl, n-nonyl location isomers, n-decyl location isomers, such as 2-propylheptyl; isomers of the location of n-undecyl; isomers of the location of n-dodecyl; n-tridecyl location isomers, n-tetradecyl location isomers and n-pentadecyl location isomers.

C ₁₂ -alkyl is dodecyl and its location isomers.

The above descriptions of the preferred forms of carrying out the invention, especially the implementation of the preferred forms of the compounds of formula I, their use and the means containing them, refer to each of them individually, and to each possible combination with each other. The forms of carrying out the invention, unless otherwise indicated, relate both to the use according to the invention, as well as to the detergent and cleaning agent according to the invention.

Compounds I used according to the invention can be understood to mean chemically pure substances or mixtures of various compounds of formula I. As a rule, due to the method of their preparation and the starting reagents (educts) used for this, which can be technical products or product mixtures, we mean mixtures of various compounds I, differing, for example, by the values of the variables R, R ′, I, m, n and / or x.

In compounds I, R preferably means alkyl with 8-15 carbon atoms, particularly preferably alkyl with 10-15 carbon atoms and, especially, alkyl with 10-14 carbon atoms. In a particular embodiment of compounds I, the alkyl radical R is branched. Special examples of R are 2-propylheptyl, tridecyl and their positional isomers such as isotridecyl (i.e. branched radicals of tridecyl and mixtures thereof), n-dodecyl (lauryl), n-tetradecyl (myristyl) and mixtures thereof.

R ′ preferably means alkyl with 10-14 carbon atoms and, especially, alkyl with 12 carbon atoms (dodecyl), especially n-dodecyl.

R ′ and R ² , independently of one another, are preferably methyl.

m preferably means a number from 20 to 50, particularly preferably from 25 to 50, more preferably from 25 to 45, and especially from 25 to 40.

l and n, independently of one another, preferably mean a number from 0 to 5, and particularly preferably 0, 1, 2 or 3; l and n, in particular, mean 0.

If at least one of the coefficients I or n is 0, then the repeating units of ethylene oxide (-CH ₂ -CH ₂ -O-) and the repeating units that are different from them (-CH ₂ -CH (R ′) - O- ) and / or (-CH ₂ -CH (R ² ) -O-) can be distributed statistically or block, preferably block, that is, all I, if necessary, of the available repeating units -CH ₂ -CH (R ′) - O- form a block, followed by a block of ethylene oxide (-CH ₂ -CH ₂ -O-) _m , which in the form of a block ends all n, if necessary, the existing repeating units -CH ₂ -CH (R ² ) -O- .

x is preferably 0 or 1.

The compounds of formula I are characterized by a relatively high melting point. Their melting point is at least 35 ° C, for example, from 35 to 50 ° C, preferably from 35 to 47 ° C, and especially from 35 to 45 ° C; particularly preferably at least 38 ° C, for example, from 38 to 50 ° C, preferably from 38 to 47 ° C and, especially, from 38 to 45 ° C and, in particular, at least 40 ° C for example, from 40 to 50 ° C, preferably from 40 to 47 ° C, and especially from 40 to 45 ° C.

Methods for preparing compounds of formula I are, in principle, known, for example, from US Pat. No. 3,627,845. Thus, in the case where I is different from O, the R-OH alcohol is reacted with an epoxide

and then with ethylene oxide.

The resulting product, if n is other than 0, is then reacted with epoxide

This is followed by reaction with mercaptan R′-S-CH ₂ -CH ₂ -OH to form a compound of formula I. If x is 1 or 2, then the resulting thioether is then further oxidized.

The reaction of the epoxides is preferably carried out in an anhydrous medium in the presence of bases as a catalyst. The reaction is carried out preferably in an inert atmosphere, for example, nitrogen or argon. The interaction is preferably carried out in bulk material, that is, without another solvent. Suitable bases are, for example, inorganic bases, such as alkali metal hydroxides, for example lithium, sodium or potassium hydroxides; alkaline earth metal hydroxides, for example magnesium or calcium hydroxides; alkali metal carbonates, for example lithium, sodium or potassium carbonates, or alkaline earth metal carbonates, for example magnesium or calcium carbonates; sodium or potassium hydroxide is preferred. The reaction temperature is preferably from 50 to 200 ° C, particularly preferably from 100 to 150 ° C. The reaction is preferably carried out at elevated pressure, for example, at a pressure of 1.1 to 10 bar or 1.2 to 5 bar, whereby an inert gas and / or epoxide (especially ethylene oxide) is introduced into the structure of the compounds. In a preferred embodiment, an inert gas, typically nitrogen, is pre-pressurized before the epoxide is fed. This pre-pressure is preferably in the range from 1.1 to 5 bar, particularly preferably from 1.2 to 3 bar and, in particular, from 1.2 to 2 bar. The addition of epoxide (especially ethylene oxide) then leads, as a rule, to an additional increase in pressure. In the reaction process itself, the pressure is in the range of preferably from 1.2 to 10 bar, particularly preferably from 2 to 8 bar. After the reaction, the resulting mixture of products, if desired, can be neutralized.

Condensation with mercaptoethanol is preferably carried out in the presence of an acid catalyst. Suitable acids are, for example, p-toluenesulfonic acid, methanesulfonic acid, phosphoric acid and an acid ion exchanger. During the reaction, the reaction water formed is preferably removed, for example, by azeotropic distillation or by inert gas distillation. If the removal of the reaction water is to be carried out by azeotropic distillation, the condensation is preferably carried out in a solvent forming a minimum of an azeotrope with water, such as toluene or xylene. After the interaction, the resulting mixture of products can be subjected, if necessary, to neutralize.

The oxidation of the sulfur atom in the resulting thioether to sulfoxide (x = 1) or sulfone (x = 2) can be carried out using a conventional oxidizing agent such as hydrogen peroxide, pyrolusite, permanganate, m-chloroperbenzoic acid or perchlorate. Whether oxidation to sulfoxide or sulfone occurs can be determined, inter alia, by selecting an oxidizing agent, its concentration and reaction temperature.

According to the invention, compounds I can be used as a solution obtained during their synthesis. However, they are preferably isolated in the usual manner and, if necessary, purified.

The compounds of formula I, in principle, can be used in all commonly used detergents and cleaners.

Under the detergents in the framework of the present invention mean such agents that are used to clean elastic materials with high absorption capacity, for example, textile materials, while under the cleaners in the framework of the present invention mean agents that are used to clean materials with a closed surface, that is, with a surface not having pores or having only a small number of small pores, and therefore not having or having only a small absorption ability.

Examples of elastic materials with high absorption capacity are materials containing or consisting of natural, synthetic or semi-synthetic fibrous materials, and therefore, as a rule, are at least partially textile in nature. The fiber-containing or fiber-containing materials can, in principle, be in any form conventional in use or in the manufacture or processing. For example, the fibers can be in the disordered form of a flock or mass, in the ordered form of threads, yarn, twisted yarn or in the form of flat structures such as canvas, coarse cloth or felt, fabrics, knitwear of any possible kind of weave. By fibers is meant raw fibers or fibers of any processing stage. Examples thereof are protein or cellulose fibers, such as wool, silk, cotton, sisal, hemp or coconut fibers, or synthetic fibers, such as, for example, polyester, polyamide or polyacrylonitrile fibers.

Examples of materials that do not contain pores or contain few and small pores and that do not or have only a slight absorbent capacity are metal, glass, enamel or ceramic. Typical products made from these materials are, for example, metal washing tanks, tool kits, glass and porcelain dishes, bathtubs, washing tanks, tiles, tiles, cured synthetic resins, such as decorative melamine resin surfaces on kitchen furniture or lacquered metal surfaces such as refrigerators and cars, printed circuits, microchips, printed or varnished high-quality wood, such as parquet and wall cladding, window frames, doors, synthetic coatings ytiya such as floor coverings of PVC or hard rubber, or hard and soft foams largely closed surface.

Examples of cleaning agents containing compounds of Formula I include dishwashing detergents, such as dishwashing detergents or dishwashing detergents (i.e. dishwasher for dishwasher), metal degreasers, wiper, floor cleaner, universal cleaner , high-pressure cleaner, neutral cleaner, alkaline cleaner, acid cleaner, spray degreaser, milk cleaner, food processor cleaner, machine cleaner in industry, especially in the chemical industry, car wash cleaner and universal household cleaner.

The compounds of formula I are preferably used in dishwashing agents. Particularly preferably, they are used in dishwashing means for machine washing dishes. Among them, dishwashing agents are preferred, especially a dishwasher for machines with the function of rinsing to clean water. Detergents and cleaning agents containing compounds I that are solid at room temperature (20 ° C) are preferred.

As solid detergents and cleaners, powdered products or tablet products can be used. Preferably, tablet products are used. Particularly preferred are tablet dishwashers, especially tablet dishwashers for machines.

Tableted dishwashing agents can be simple tablets or also the so-called “2 in 1”, “3 in 1”, “5 in 1”, “7 in 1” products and the like (multifunctional products: usually “x in 1” products where x = integer). Details of such formulations are found in Hermann G. Hauthal, G. Wagner (Hrsg.), Reinigungs- und Pflegemittel im Haushalt, Verlag fur chemische Industrie, H. Ziolkowsky GmbH, Augsburg 2003, Kapitel 4.2, Seiten 161-184. Two-in-one products (2-in-1) contain, in addition to the usual components of dishwashing agents for machines, an additional brightening cleaner. Three-in-one products (3-in-1) also contain a water softener. Five in one products (5 in 1) contain, in addition, a glass protective agent and a cleaning amplifier. Seven in one products (7 in 1) contain, in addition, a means to brighten special (high-quality) steel and an anti-scale agent.

The compounds of formula I are preferably used in tableted multifunctional dishwashers for machines in which they completely or partially replace the usual means for rinsing to clean water.

The compounds of formula I have both a surface-active action and the action of a rinse to clean water. Therefore, the invention also relates to the use of compound I as a surfactant and / or as a means for rinsing to clean water. In particular, the invention relates to the use of compounds I as a surfactant with the effect of rinsing to clean water or as a surfactant to rinsing to clean water.

The compounds I used according to the invention are characterized by a particularly excellent deposition inhibitory effect when used in a rinse to clean water with a dishwashing agent for a machine agent. Moreover, they inhibit both inorganic and organic deposits. By inorganic deposits are meant especially phosphate, carbonate or silicate and / or calcium and magnesium phosphonate, which are formed in water containing calcium and magnesium salts and are formed in ordinary dishwashing agents containing complexing agents. By organic deposits are meant especially the pollution components from the washing solution, such as, for example, protein, starch and fat deposits. Compounds I used according to the invention are effective against the residues of water formed on the bottom of the dishwasher and other residues of the dishwasher, and possibly also on the residues of contamination generated during washing in a dishwasher (so-called Carry-Over deposits).

Another object of the invention is a detergent and a cleaning agent containing at least one compound of formula I. Regarding a suitable detergent and cleaning agent, reference can be made to the forms described above for their implementation.

With regard to detergents and cleaners, it is preferable to use detergents and cleaners for dishwashers, among which a dishwasher for machines is preferable. In particular, it is a dishwasher, especially a dishwasher for cars, with the function of rinsing to clean water.

The detergent and cleaner of the invention is preferably solid at room temperature (20 ° C). Regarding a suitable and preferred solid detergent and cleaning agent, reference can be made to the above embodiments. The detergent and cleaning agent according to the invention, in particular, is a tablet machine multifunctional dishwasher. In these agents, compounds I can be contained in clarifying clarifying grains. Preferably, they are contained, however, as a solid in a tableted dishwasher.

The dishwasher preferably contains the following components:

a) at least one compound of formula I;

b) at least one bilder (also called a sequestering agent, sclera, a complexing agent, a chelator, a chelating agent or a water hardness reducing agent);

c) if necessary, at least one enzyme;

d) if necessary, at least one bleach and

e) if necessary, at least one other additive selected, preferably, among surfactants other than component a), bases, corrosion inhibitors, antifoam agents, colorants, flavorings, fillers, tabletting aids, disintegrants, thickeners, dissolution aids, organic solvents and water.

These components are mainly contained in the dishwasher according to the invention in the following quantitative ratio:

a) at least one compound of formula I from 0.1 to 20 wt.%;

b) at least one complexing agent from 5 to 80 wt.%;

c) at least one enzyme from 0 to 8 wt.%;

d) at least one bleach from 0 to 30 wt.% and

e) at least one other additive from 0 to 50 wt.%.

Moreover, the data in mass percent refers to the total weight of the dishwasher. The mass content of the components from a) to e) in the amount of 100 wt.%.

Most preferably, the dishwasher according to the invention contains at least one enzyme.

It is especially preferred if the above components are contained in the dishwasher according to the invention in the following proportions:

a) at least one compound of formula I from 0.1 to 10 wt.%;

b) at least one complexing agent from 20 to 80 wt.%;

c) at least one enzyme from 0.1 to 6 wt.%;

d) at least one bleach from 0 to 30 wt.% and

e) at least one other additive from 0 to 50 wt.%.

Moreover, the data in mass percent refers to the total weight of the dishwasher. The mass content of the components from a) to e) in the amount of 100 wt.%.

Most preferably, the dishwasher of the invention further comprises bleach.

Most preferably, if these components are contained in the dishwasher according to the invention in the following quantitative ratio:

a) at least one compound of formula I - from 0.1 to 10 wt.%;

b) at least one complexing agent - from 20 to 80 wt.%;

c) at least one enzyme - from 0.1 to 6 wt.%;

d) at least one bleach - from 5 to 25 wt.%

e) at least one additive from 0 to 50 wt.%.

Moreover, the data in mass percent refers to the total weight of the dishwasher. The quantitative content of the components from a) to e) in the amount of 100 wt.%.

Relatively suitable and preferred compounds I can refer to the previously described forms of their embodiment.

A bilder, also called a sequester, a sclerizing agent, a complexing agent, a chelator, a chelating agent or a water hardness reducing agent, binds alkaline earth metals and other water-soluble metals without precipitation. It helps to destroy pollution, disperses dirt particles, helps dissolve dirt and, in part, has its own washing action. In addition, if it is solid and is used in powder formulations, it helps to maintain the powder in a loose state.

Suitable complexing agents may be both organic and inorganic substances. They can be, for example, aluminosilicates, carbonates, phosphates and polyphosphates, polycarboxylic acids, hydroxycarboxylic acids, phosphonic acids, for example hydroxyalkylphosphonic acids, phosphonates, aminopolycarboxylic acids and their salts and polymeric compounds with carboxylic acid groups and their salts.

Suitable inorganic complexing agents are, for example, crystalline or amorphous aluminosilicates with the properties of ion exchangers, such as zeolites. Various types of zeolites are suitable, especially zeolites A, X, B, P, MAP and HS in their sodium form or in forms in which sodium is partially exchanged for other cations, such as lithium, potassium, calcium, magnesium or ammonium. Suitable zeolites, for example, are zeolites described in US Pat. No. 4,404,224. Suitable crystalline silicates as complexing agents are, for example, disilicates or layered silicates such as 5-Na ₂ Si ₂ O ₅ or B-Na ₂ Si ₂ O ₅ (SKS 6 or SKS 7). Silicates can be used in the form of their alkaline, alkaline earth or ammonium salts, mainly in the form of silicates of sodium, lithium and magnesium. Amorphous silicates such as, for example, sodium metasilicate having a polymer structure or amorphous disilicate (Britesil® H 20, manufactured by Akzo) may also be used. Among these, sodium disilicate is preferred.

Suitable carbonate-based inorganic complexing agents are carbonates and bicarbonates. They can be used in the form of alkaline, alkaline earth or ammonium salts. Preferably, sodium, lithium and magnesium carbonates and bicarbonates are used, especially sodium carbonate and / or sodium bicarbonate.

Common phosphates used as the inorganic complexing agent are alkali metal orthophosphates and / or polyphosphates, such as, for example, pentasodium triphosphate.

Suitable organic complexing agents are, for example, di-, tri- and tetracarboxylic acids with 4-30 carbon atoms, such as succinic acid, propantricarboxylic acid, butantetracarboxylic acid, cyclopentantetracarboxylic acid and their alkyl and alkenyl succinic acid with alkyl containing 2-20 atoms carbon or with alkenyl radicals.

Suitable organic complexing agents are, in addition, hydroxycarboxylic acids and polyhydroxycarboxylic acids (sugar acids). These include hydroxycarboxylic acids with 4-20 carbon atoms, for example, such as malic acid, tartaric acid, gluconic acid, mucous acids, lactic acid, glutaric acid, citric acid, tartronic acid, glucoheptonic acid, lactobionic acid and sucrose mono-, di- and tricarboxylic acid. Among them, citric acid and its salts are preferred.

In addition, phosphonic acids such as hydroxyalkylphosphonic acids, aminophosphonic acids and their salts are suitable organic complexing agents. These include, for example, fosfonobutantrikarbonovaya acid aminotrismetilenfosfonovaya acid, ethylene-diaminotetraetilfosfonovaya acid, hexamethylenediamine-tetra-methylenephosphonic acid, dietilentriaminopentametilen-phospho-new acid, morpholinomethane diphosphonic acid, 1-hydroxy (C ₁ -C ₁₀₎ -alkyl-1, 1-diphosphonic acid, such as 1-hydroxyethane-1,1-di-phosphonic acid. Among them, preferred is 1-hydroxy-ethane-1,1-diphosphonic acid and its salts.

A suitable organic bilder is, in addition, nitrilotriacetic acid (NTA), nitrilomonoacetic dipropionic acid, nitrilotripropionic acid, β-alanine diacetic acid (β-ADA), ethylenediaminetetraacetic acid (EDTA), diethylenetriamine pentaacetic acid, 1,2-diethylenetriamine-pentaacetic acid propylene diamine aminetetraacetic acid, N- (alkyl) ethylenediamine triacetic acid, N- (hydroxyalkyl) ethylenediamine triacetic acid, ethylenediamine triacetic acid, cyclohexylene-1,2-diaminetetraacetic acid, iminodiyant rnaya acid etilendiaminodiyantarnaya acid serindiuksusnaya acid izoserindiuksusnaya acid, L-asparagindiuksusnaya acid, L-glutamindiuksusnaya acid metilglitsindiuksusnaya acid (MGDA) salts and aminopolikislot previously mentioned. Among them, preferred are L-glutamindiacetic acid, methylglycine diacetic acid and their salts.

Suitable organic complexing agents are, in addition, polymeric compounds containing carboxylic acid groups, such as homopolymers of acrylic acid. They preferably have a number average molecular weight ranging from 800 to 70,000 g / mol, particularly preferably from 900 to 50,000 g / mol, in particular from 1,000 to 20,000 g / mol, especially from 1,000 to 10,000 g / mol. The term “acrylic acid homopolymer” also includes polymers in which the carboxylic acid groups are partially or completely neutralized. These include homopolymers of acrylic acid, in which the carboxylic acid groups are partially or completely in the form of alkali metal salts or ammonium salts. Homopolymers of acrylic acid are preferred in which the carboxylic acid groups are protonated or in which they are partially or completely in the form of sodium salts.

Suitable polymeric compounds containing carboxylic acid groups are also oligomaleic acids, such as are described, for example, in European patents EP-A451508 and EP-A 396303.

Suitable polymeric compounds containing carboxylic acid groups are also terpolymers of unsaturated dicarboxylic acids with 4-8 carbon atoms, the copolymerized comonomers being monoethylenically unsaturated monomers, of which the monomers of the following group (i) can be copolymerized in an amount of up to 95 wt%; from group (ii) in an amount up to 60 wt.% and from group (iii) in an amount up to 20 wt.%. Suitable unsaturated dicarboxylic acids with 4-8 carbon atoms are, for example, maleic acid, fumaric acid, itaconic acid and citric acid. Maleic acid is preferred. Group (i) includes monoethylenically unsaturated monocarboxylic acids with 3-8 carbon atoms, such as acrylic acid, methacrylic acid, crotonic acid, and vinylacetic acid. Preferably, from group (i), acrylic acid and methacrylic acid are used. Group (ii) includes monoethylenically unsaturated olefins with 2-22 carbon atoms, vinylalkyl ether with alkyl groups containing 1-8 carbon atoms, styrene, vinyl carboxylic acid ether with 1-8 carbon atoms, (meth) acrylamide and vinylpyrrolidone. In group (ii), olefins with 2-6 carbon atoms, vinylalkyl ether with 1-4 carbon atoms, vinyl acetate and vinyl propionate are preferred. If the polymers contain a copolymerized vinyl ester from group (ii), then they can also be partially or completely hydrolyzed into the structural units of vinyl alcohol. Suitable co and terpolymers are, for example, the known polymers from US Pat. No. 3,887,806, as well as from German Patent Application DE-A 4,313,909. Group (iii) includes an ester of (meth) acrylic acid with alcohols containing from 1 to 8 atoms carbon, (meth) acrylonitrile, (meth) acrylamides of amines with 1-8 carbon atoms, N-vinylformamide and N-vinylimidazole.

Suitable polymeric compounds containing carboxylic acid groups are also homopolymers of monoethylenically unsaturated monocarboxylic acids with 3-8 carbon atoms, such as, for example, acrylic acid, methacrylic acid, crotonic acid and vinylacetic acid, especially acrylic acid and methacrylic acid; copolymers of dicarboxylic acids, such as, for example, copolymers of maleic acid and acrylic acid in a mass ratio of from 10:90 to 95: 5, particularly preferably in a mass ratio of from 30: 7 to 90:10 with a molecular weight of from 1000 to 150,000; terpolymers of maleic acid, acrylic acid and vinyl ester of carboxylic acid with 1-3 carbon atoms with a weight ratio of maleic acid: (acrylic acid + vinyl ester) 10: 90-95: 10, and the mass ratio of acrylic acid to vinyl ester can vary ranging from 30:70 to 70:30; copolymers of maleic acid with olefins containing 2-8 carbon atoms, with a mass ratio of from 40:60 to 80:20, with copolymers of maleic acid with ethylene, propylene or isobutene in a molar ratio of 50:50 being particularly preferred.

Suitable polymeric compounds containing carboxylic acid groups are, in addition, copolymers of 50-98 wt.% Ethylenically unsaturated weak carboxylic acids with 2-50 wt.% Ethylenically unsaturated sulfonic acids, such as, for example, as described in European patent application EP-A 0877002 Suitable weak ethylenically unsaturated carboxylic acids are, in particular, monocarboxylic acids with 3-6 carbon atoms, such as acrylic acid and methacrylic acid. Suitable ethylenically unsaturated sulfonic acids are 2-acetylamidomethyl-1-propanesulfonic acid, 2-methacrylamido-2-methyl-1-propanesulfonic acid, 2-methacrylamido-2-hydroxypropanesulfonic acid, allyl sulfonic acid, metal sulfonic acid, allyloxybenzenesulfonic acid, metal 2-hydroxy-3- (2-propenyloxy) propanesulfonic acid, 2-methyl-2-propane-1-sulfoxyl lot, styrene sulfonic acid, vinyl sulfonic acid, 3-sulfopropyl acrylate, 3-sulfopropyl methacrylate, sulfomethyl acrylamide, sulfomethyl methacrylamide and salts thereof by. The copolymers may also contain from 0 to 30 wt.% Ethylenically unsaturated dicarboxylic acids with 4-8 carbon atoms, such as maleic acid, as well as from 0 to 30 wt.%, At least one monomer copolymerizable with the previously mentioned monomers. The latter are, for example, an alkyl ester of (meth) acrylic acid with 1-4 carbon atoms in alkyl, a hydroxyalkyl ether of (meth) acrylic acid with 1-4 carbon atoms in alkyl, acrylamide substituted with alkyl acrylamide, N, N-dialkyl acrylamide , vinylphosphonic acid, vinyl acetate, allyl alcohol, sulfonated allyl alcohol, styrene and other vinyl aromatics, acrylonitrile, N-vinylpyrrolidone, N-vinyl formamide, N-vinylimidazole or N-vinylpyridine. The weight average molecular weight of these copolymers is in the range of 3,000 to 50,000. Particularly suitable are copolymers containing about 77 wt.%, At least one ethylenically unsaturated monocarboxylic acid with 3-6 carbon atoms and about 23 wt.%, At least one ethylenically unsaturated sulfo acid.

Grafted copolymers of unsaturated carboxylic acids based on low molecular weight carbohydrates or hydrogenated carbohydrates are also suitable (see US Pat. No. 5,227,446 and German Patent Applications DE-A 4,415,623 and DE-A 4,313,909). Suitable unsaturated carboxylic acids are, for example, maleic acid, fumaric acid, itaconic acid, citric acid, acrylic acid, methacrylic acid, crotonic acid and vinylacetic acid, as well as mixtures of acrylic and maleic acids, which are inoculated in an amount of from 40 to 95 wt.% based on the grafted component. For modification, up to 30 wt% (based on the graftable component) of other monoethylenically unsaturated monomers can be additionally copolymerized. Suitable modifying monomers are the above monomers from groups (ii) and (iii). The graft substrate is cleaved polysaccharides, such as, for example, acid or enzyme-cleaved starches, inulins or cellulose, protein hydrolysates, and reduced (hydrogenated or hydrogenating aminated) cleaved polysaccharides, such as mannitol, sorbitol, aminosorbite, and N-alkylglycalkylene, are also suitable weight average molecular weight M _w up to 5000, such as, for example, polyethylene glycols, block copolymers of ethylene oxide and propylene oxide, or ethylene oxide and butylene oxide, or ethylene oxide len, propylene oxide and butylene oxide and hydroxyalkylated monohydric or many atomic alcohols with 1-22 carbon atoms (see US patent A-5756456).

Polyglyoxylic acids are also suitable, such as, for example, those described in European patent publication EP-B-001004, US patent US-A 5399286, German patent application DE-A 4106355 and European patent application EP-A 656914. Polyglyoxylic end groups acids can have a different structure.

In addition, polyamidocarboxylic acids and modified polyamidocarboxylic acids are suitable. They are known, for example, from European patent application EP-A 454126, European patent publication EP-B-511037, from international application WO-A 94/01486 and European patent application EP-A 581452.

Polyaspartic acids or joint condensates of aspartic acid with other amine acids, mono- or dicarboxylic acids with 4-25 carbon atoms and / or mono- or diamines with 4-25 carbon atoms can also be used as polymeric compounds with carboxylic acid groups. Particularly preferably used are obtained in phosphorus-containing acids modified with mono- or dicarboxylic acids with 6-22 carbon atoms or mono- or diamines with 6-22 carbon atoms polyaspartic acids.

Among the polymeric compounds containing carboxylic acid groups, polyacrylic acids are also preferred in partially or fully neutralized form.

Suitable organic complexing agents are, in addition, iminoduccinic acid, hydroxydisuccinic acid, aminopolycarboxylates, alkylpolyaminocarboxylates, aminopolyalkylene phosphonates, polyglutamates, hydrophobically modified citric acids such as agaricinic acid, poly- [alpha] -hydroxydiethylacrythacrylacrylate, acetyl diacetylacrylated, ethylenediaminetetraacetic acid alkylamides such as EDTA-Talgamid.

In addition, oxidized starches can also be used as organic complexing agents.

As component b), a mixture of various complexing agents is preferably used.

The mixture of various complexing agents preferably contains at least two of the following components: at least one carbonate (eg sodium carbonate); at least one silicate (e.g., sodium silicate); at least one polymeric compound containing carboxylic acid groups, in which carboxylic acid groups can be partially or completely neutralized (for example, polyacrylic acid); at least one (poly) hydroxycarboxylic acid or a salt thereof (e.g. citric acid or citrate); at least one aminopolycarboxylic acid or its salt (for example, methyl glycine diacetic acid or its salt, for example, sodium salt); at least one phosphonic acid (e.g., 1-hydroxyethane- (1,1-diphosphonic acid), HEDP); at least one phosphate. It is particularly preferred if the mixture contains at least one carbonate, at least one silicate and at least one polymer compound containing carboxylic acid groups, optionally (partially) neutralized, and also, if necessary, at least one of the following components: at least one (poly) hydroxycarboxylic acid or a salt thereof; at least one phosphonic acid; at least one phosphate. In a special case, the mixture contains: at least one carbonate, at least one silicate, at least one polymer compound containing carboxylic acid groups, optionally partially or completely neutralized; at least one (poly) hydroxycarboxylic acid or its salt and at least one phosphonic acid, and also, if necessary, at least one phosphate.

In such a mixture, the components are preferably contained in the following amounts:

b1) at least one carbonate from 10 to 50 wt.%;

b2) at least one silicate from 1 to 10 wt.%;

b3) at least one polymer compound containing carboxylic acid groups, optionally partially or completely neutralized, from 5 to 20 wt.%;

b4) at least one (poly) hydroxycarboxylic acid or its salt from 0 to 50 wt.% and

b5) at least one aminopolycarboxylic acid or its salt from 0 to 60 wt.%;

b6) at least one phosphonic acid from 0.2 to 1 wt.%;

b7) at least one phosphate from 0 to 60 wt.%.

The data in mass percent, in this case, refers to the total mass of the complexing agent. The sum of the mass percent of the components from b1 to b7) is 100 wt.%.

Enzymes are preferably selected from hydrolases, such as proteases, esterases, glucosidases, lipases, amylases, cellulases, mannanases, other glycosyl hydrolases and mixtures of the above enzymes. All of these hydrolases contribute to the dissolution of pollution and the removal of protein, fatty or starchy contaminants. Oxyreductases may also be used for bleaching. Especially suitable are bacterial strains or fungi, such as producing Bacillus subtilis, Bacillus licheniformis, Streptomyceus griseus and Humicola insolens enzymatic biologically active substances.

Suitable hydrolases are, for example, α-glucosidases (EC-Nummer 3.2.1.20), proteases (Ovozyme® (von Novozymes); EC-Nummer 3.2.1.20), amylases (Purastar® (fon Genencor), Termamyl® (von Novozymes) , Duramyl® (von Novozymes)), mannanases (Purabrite® (fon Genencor), Mannastar® (fon Genencor), Mannaway® (von Novozymes)) and cellulases (Carezyme® (von Novozymes), Celluzyme® (von Novozymes), Endolase , Puradax® (fon Genencor)). Suitable amylases include, in particular, α-amylases (EC-Nummer 3.2.1.1), iso-amylases, pullulanases and pectinases. As cellulases, preferably, cellobiohydrolases, endoglucanases and β-glucosidases, also called cellobiases, or mixtures thereof, are used. Since different types of cellulase differ in their CMCase activity and the activity of aircellase, through the targeted mixing of cellulases, the desired activity can be obtained.

Suitable lipases are esterases such as Lipex and lipolase. Examples of lipolytically active enzymes are known cutinases.

In some cases, peroxidases or oxidases are also suitable.

The dishwashing agent of the invention preferably contains at least one protease and / or amylase.

Preferably, the dishwashing mixture contains a mixture of enzymes. Preferred are, for example, mixtures containing the following enzymes (or consisting of them):

- protease and amylase;

- protease and lipase (or lipolytically active enzymes);

- protease and cellulase;

- amylase, cellulase and lipase (or lipolytically active enzymes);

- protease, amylase and lipase (or lipolytically active enzymes);

- protease, lipase (or lipolytically active enzymes) and cellulase.

Especially preferred are protease and / or mixtures containing amylase. In the above mixtures, proteases of the species Subtilisin (Savinase, etc .; EC-Nummer 3.4.21.62) are preferred as proteases.

Enzymes can be absorbed on a carrier to protect against premature degradation.

The detergent and detergent according to the invention, if necessary, may also contain enzyme stabilizers, for example, calcium propionate, sodium formate or boric acid and their salts and / or oxidation inhibitor.

Bleachers d) are mainly bleaching systems containing, in addition to bleaches, bleach activators, bleach catalysts and / or bleach stabilizers, if necessary.

Suitable bleach are, for example, percarboxylic acid, such as diperoxodecandicarboxylic acid, phthalimidopercapaproic acid or monoperoxophthalic acid or monoperoxoterephthalic acid; salts of percarboxylic acids, for example sodium percarbonate, products of the addition of hydrogen peroxide to inorganic salts, for example, sodium perborate monohydrate, sodium perborate tetrahydrate, sodium carbonate perhydrate or sodium phosphate perhydrate; products of the addition of hydrogen peroxide to organic compounds, for example, urea perhydrate or inorganic peroxosols, for example, alkali metal persulfates or alkali metal peroxydisulfates.

Suitable whitening activators are, for example, polyacylated sugar, for example, pentaacetylglucose; acyloxy benzosulfonic acid and its salts with alkali and alkaline earth metals, for example, sodium p-nonanoyloxybenzenesulfate or sodium p-benzyloxybenzenesulfate; N, N-diacylated and N, N, N ′, N′-tetraacetylated amines, for example N, N, N ′, N′-tetraacetylmethylenediamine and α-ethylenediamine (TAED), N, N-diacetylaniline, N, N-diacetyltoluidine or 1,3-diacetylated hydantoins, such as 1,3-diacetyl-5,5-dimethyl-hydantoin, N-alkyl-N-sulfonylcarbonamide, for example, N-Memn-N-mesylacetamide or N-methyl-N-mesylbenzamide; N-acylated cyclic hydrazides; acylated triazoles or urazoles, for example monoacetylmaleic acid hydrazide; O, N, N-trisubstituted hydroxylamines, for example, O-benzoyl-N, N-succinylhydroxylamine, O-acetyl-N, N-succinylhydroxylamine or O, N, N-triacetylhydroxylamine, N, N′-diacetylsulfurylamides, for example, N, N′-dimethyl-N, N′-diacetylsulfurylamide or N, N′-diethyl-N, N′-dipropionylsulfurylamide; acylated lactams such as acetylcaprolactam, octanoyl-caprolactam, benzoylcaprolactam or carbonylbiscaprolactam; derivatives of anthranyl, such as 2-methylanthranyl or 2-phenyl-anthranyl; triacetyl cyanurates, for example triacetyl cyanurate or tribenzoyl cyanurate; oxime ester or bisxime ester, such as, for example, O-acetylacetonoxime or bisisopropyliminocarbonate; carboxylic acid anhydrides, for example, acetic anhydride, benzoic anhydride, m-chlorobenzoic acid anhydride or phthalic anhydride; enol ester, such as, for example, isopropenyl acetate; 1,3-diacyl-4,5-diacyloxy-imidazolines, for example, 1,3-diacetyl-4,5-diacetoxyimidazoline; tetra-acetyl glycoluryl and tetrapropionyl glycoluryl; diacylated 2,5-diketopiperazines, for example 1,4-diacetyl-2,5-diketopiperazine; ammonium substituted nitriles such as N-methylmorpholinium acetonitrile methyl sulfate; acylation products of propylene diurea and 2,2-dimethylpropylenediurea, for example, tetraacetylpropylene diurea; α-acyloxy polyacrylacyl malonamides, for example α-acetoxy-N, N′-diacetyl malonamide; diacyldioxyhexahydro-1,3,5-triazines, for example 1,5-diacetyl-2,4-dioxohexahydro-1,3,5-triazine; benz- (4H) -1,3-oxazin-4-ones with alkyl radicals, for example methyl, or with aromatic radicals, for example, phenyl in position 2.

The bleaching system of bleaches and bleach activators, if necessary, may also contain bleaching catalysts. Suitable bleaching catalysts are, for example, quaternary imines and sulfonimines, such as those described, for example, in US Pat. No. 5,360,569 and European Patent Application EP-A 453003. Especially effective bleaching catalysts are manganese complexes which are described, for example, in international application WO-A 94/21777. Such compounds, if used in detergents and cleaning compositions, are administered in a maximum of up to 1.5 wt.%, Especially up to 0.5 wt.%, And in the case of very active manganese complex compounds, in an amount of up to 0.1 wt.%. In addition to the described bleaching system of bleaches, bleaching activators and, if necessary, catalysts, it is also possible to use systems with the enzymatic release of peroxide or the use of photoactivated bleaching systems in the washing and cleaning agent according to the invention.

Surfactants from group e) that are different from component a) may be cationic, anionic, amphoteric or nonionic.

Suitable nonionic surfactants are, for example, hydroxyalkylated, preferably ethoxylated, especially primary alcohols, preferably with 8-18 carbon atoms and, on average, from 1-20, preferably 1-12 moles of ethylene oxide (EO) in an alcohol molecule in which the alcohol residue may be straight-chain or, preferably, branched methyl in position 2, or may contain straight-chain and branched methyl radicals in a mixture, such as are usually found in oxo-alcohol radicals. However, alcohol ethoxylates with straight-chain radicals of alcohols of native origin with 12-18 carbon atoms, for example coconut, palm, fatty alcohols of fat or oleyl alcohol, and containing on average from 2 to 8 units of ethylene oxide (EO) in the alcohol molecule, are particularly preferred. Preferred ethoxylated alcohols include, for example, alcohols with 12-14 carbon atoms and 3 EO, 4 EO or 7 EO; alcohol with 9-11 carbon atoms and with 7 EO; alcohols with 13-15 carbon atoms and with 3 EO, 4 EO, 7 EO or 8 EO; alcohols with 12-18 carbon atoms and with 3 EO, 4 EO or 7 EO and mixtures thereof, such as mixtures of alcohol with 12-14 carbon atoms and with 3 EO with alcohol with 12-18 carbon atoms and 7 EO. The indicated degrees of hydroxyethylation are the average value, which for special products can be an integer or fractional number. Alcohol ethoxylates with a narrow homologous distribution (narrow range of ethoxylates are also suitable. Fatty alcohols with more than 12 EO can also be used in addition to these nonionic surfactants. Examples are fatty alcohols with 14 EO, 25 EO or 30 EO. Can be used also nonionic surfactants containing both ethylene oxide (EO) groups and propylene oxide (PO) groups in the molecule. In this case, block copolymers with EO-PO block units or with PO-EO units, and t EO-PO-EO copolymers or PO-EO-PO copolymers. Of course, mixed alkoxylated nonionic surfactants can also be used in which the EO and PO units are not block but randomly distributed. These products are obtained by simultaneously acting on fatty alcohols ethylene oxide and propylene oxide.

In addition, alkyl glycosides of the general formula (1) are also used as other nonionic surfactants:

where R ^a is a primary straight chain or branched methyl, especially at position 2, an aliphatic radical with 8-22 carbon atoms, preferably 12-18 carbon atoms, and G represents a glycoside unit with 5-6 carbon atoms, preferably glucose. The degree of oligomerization of y, which determines the distribution of monoglycosides and oligoglycosides, is any number between 1 and 10 and, preferably, is from 1.2 to 1.4.

Another class of suitable nonionic surfactants that are used as the sole nonionic surfactant or in combination with other nonionic surfactants are hydroxyalkylated, preferably hydroxyethylated or ethoxylated and hydroxypropylated fatty acid esters, preferably with 1- 4 carbon atoms in the alkyl chain, especially methyl ester of a fatty acid, such as described, for example, in Japanese patent application JP 58/217598 il such as prepared, preferably, by the method described in the international application WO-A-90/13533.

Nonionic surfactants such as amine oxides, for example, N-cocosalkyl-N, N-dimethylamine oxide and N-fatty alkyl sala-N, N-dihydroxyethylamine oxide and fatty acid alkanolamides may also be suitable. The amount of these nonionic surfactants preferably does not exceed the amount of ethoxylated fatty alcohols, especially half of their amount.

Other suitable surfactants are amides of polyhydroxy fatty acids of the formula (2):

where R ^b C (= O) means an aliphatic acyl radical with 6-22 carbon atoms, R ^c means hydrogen, an alkyl or hydroxyalkyl radical with 1-4 carbon atoms and [Z] means a straight-chain or branched polyhydroxyalkyl radical with 3-10 carbon atoms and with 3-10 hydroxyl groups. Polyhydroxy fatty acid amides are known substances which can usually be obtained by reductive amination of sugars with reducing properties by ammonia, alkylamine or alkanolamine followed by acylation with fatty acids, fatty acid alkyl esters or fatty acid chlorides.

The amide groups of polyhydroxy fatty acids also include compounds of the formula (3):

where R ^e means a straight-chain or branched alkyl or alkenyl radical with 7-12 carbon atoms, a R ¹ means a straight-chain, branched or cyclic alkylene radical with 2-8 carbon atoms or an arylene radical with 6-8 carbon atoms, and R ^g means straight-chain , branched or cyclic alkyl radical or aryl radical or a hydroxyalkyl radical with 1-8 carbon atoms, preferably an alkyl radical with 1-4 carbon atoms or a phenyl radical, a [Z] ¹ denotes a straight-chain or polygenes roksialkilny radical whose alkyl chain is substituted by at least two hydroxyl groups, or alkoxylated, preferably ethoxylated or propoxylated derivatives of these radicals. [Z] ^{1 is} obtained, preferably, by reductive amination of a sugar, for example, glucose, fructose, maltose, lactose, galactose, mannose or xylose. N-alkoxy or N-aryloxy substituted compounds can then be converted to the desired amides of polyhydroxy fatty acids, for example, according to international application WO-A-95/07331 by reaction with fatty acid methyl esters in the presence of an alkoxide as a catalyst.

Suitable anionic surfactants are, for example, surfactants such as sulfonates and sulfates. In this case, surfactants such as sulfonates are preferably alkylbenzenesulfonates with 9-13 carbon atoms in alkyl, olefin sulfonates, that is, mixtures of alkene and hydroxyalkanesulfonates, as well as disulfonates, such as, for example, obtained from monoolefins with 12-18 carbon atoms with terminal or internally double bonds, sulfonation of gaseous sulfur trioxide followed by alkaline or acid hydrolysis of sulfonation products. Alkansulfonates which are obtained from alkanes with 12-18 carbon atoms, for example, sulfochlorination or sulfoxidation, followed by hydrolysis or neutralization, are also suitable. The α-sulfo fatty acid ester (ester sulfates) is also suitable, for example, the α-sulfonated methyl ester of hydrogenated coconut acids, palm kernel acids or fatty acids.

Other suitable anionic surfactants are sulfonated glycerol fatty acid esters. By glycerol esters of fatty acids are meant mono-, di- and triesters of glycerol, as well as mixtures thereof, which are obtained by esterification of monoglycerin with 1-3 moles of fatty acid or transesterification of triglycerides with 0.3-2 moles of glycerol. Preferred sulfonated glycerol fatty acid esters are sulfonated products of saturated fatty acids with 6-22 carbon atoms, for example, caproic acid, caprylic acid, capric acid, myristic acid, lauric acid, palmitic acid, stearic acid or behenic acid.

Alkyl enesulfates are preferably alkaline, especially sodium, salts of the half ester of sulfuric acid and a fatty alcohol with 12-18 carbon atoms, for example coconut fatty alcohol, fatty alcohol, fat, lauryl, myristyl, methyl or stearyl alcohol or oxoalcohols with 10 -20 carbon atoms and such a half ester of secondary alcohols with this chain length. In addition, chain-length alk (en) il sulphates containing a synthetic, petrochemical-derived straight chain alkyl radical with the same degradability as those of adequate compounds based on raw fat chemistry are preferred. Preferred from the point of view of the washing action are the alkyl sulfates of the C ₁₂ -C ₁₆ fraction and the alkyl sulfates of the C ₁₂ -C ₁₅ fraction, as well as the alkyl sulfates of the C ₁₄ -C ₁₅ fraction. Suitable anionic surfactants are also 2,3-alkyl sulfates, which are obtained, for example, according to US patents US 3234258 or US 5075041 and which can be obtained as a commercial product of Shell Oil Company under the name DAN®.

Sulfuric acid monoesters of ethoxylated 1-6 moles of ethylene oxide, straight or branched alcohols with 7-21 carbon atoms, such as branched at position 2 methyl, alcohols with 9-11 carbon atoms with an average degree of hydroxyethylation (EO) of 3.5 or fatty alcohols are also suitable. with 12-18 atoms and a degree of hydroxyethylation (EO) of 1-4. Due to their high foaming ability, they are used in cleaning products only in a relatively low amount, for example, in an amount of from 1 to 5 wt.%.

Other suitable anionic surfactants are also salts of alkyl sulfosuccinic acid, also called sulfosuccinates or esters of sulfosuccinic acid, and a monoester and / or diester of sulfosuccinic acid with alcohols, preferably fatty alcohols, and especially ethoxylated fatty alcohols. Preferred sulfosuccinates contain radicals of fatty alcohols with 8-18 carbon atoms or mixtures thereof. Particularly preferred sulfosuccinates contain a fatty alcohol residue derived from ethoxylated fatty alcohols. Especially preferred are again sulfosuccinates, the fatty alcohol radicals of which are derived from ethoxylated fatty alcohols with a narrow homologous distribution. You can also use alk (en) ylant acid, preferably with 8-18 carbon atoms in the alk (en) yl chain or their salts.

In addition, soaps are suitable anionic surfactants. Soaps of saturated and unsaturated fatty acids are suitable, such as salts of lauric acid, myristic acid, palmitic acid, stearic acid, (hydrogenated) erucanoic acid and behenic acid, and also, especially, a mixture of soaps derived from natural fatty acids, for example, fatty acids coconut, palm kernels, olive oil or lard.

Anionic surfactants, including soaps, can be in the form of sodium, potassium or ammonium salts, as well as in the form of water-soluble salts of organic bases, such as mono-, di- or triethanolamine. Preferably, the anionic surfactants are in the form of their sodium or potassium salts, especially in the form of a sodium salt.

Cationic surfactants are, for example, ammonium salts, dialkyl dimethyl ammonium halides with 8 to 16 carbon atoms in alkyl, dialkoxy dimethyl ammonium halides or imidazolinium salts with a long chain alkyl radical.

Amphoteric surfactants are, for example, derivatives of secondary or tertiary amines, such as, for example, alkyl betaines with 6-18 carbon atoms in alkyl or alkylsulfobetaines with 6-15 carbon atoms in alkyl or amine oxides, such as alkyl dimethyl amine oxides.

The solvent contained in component e) is selected, for example, from the group of mono- or polyhydric alcohols, alkanolamines or glycol ether. Preferably, they are selected from ethanol, n- or iso-propanol, butanols, glycol, propanediol or butanediol, glycerol, diglycol, propyldiglycol or butyldiglycol, hexylene glycol, ethylene glycol ethylene glycol ethylene glycol ethyl ether, glycol ethylene glycol ether diethylene glycol methyl ether, diethylene glycol ethyl ether, propylene glycol methyl, ethyl or propyl ether, dipropylene glycol monomethyl or ethyl ether, monomethyl or ethyl ether di-zopropylene glycol, methoxy, ethoxy or butoxytriglycol, isobutoxy-ethoxy-2-propanol, 3-methyl-3-methoxybutanol, tert. propylene glycol butyl ether, as well as mixtures of these solvents.

As foaming inhibitors or defoamers of component e), for example, soaps, paraffins or silicones are used, which can, if necessary, be applied to carrier materials.

Suitable bases of component e) are, especially, carbonates previously mentioned for complexing agents.

In an alternative preferred embodiment, the detergents and cleaners of the invention are gelled. Preferably, gel-like detergents and cleaners are gel-like dishwashing agents, among which dishwashing gel-like means for machines are particularly preferred. In particular, gel-like dishwashers, especially dishwashers for machines, with the function of rinsing to clean water are meant.

By gel-like detergents and cleaning agents is meant a liquid agent having a viscosity at room temperature (20 ° C) exceeding the viscosity of water, which, however, is still so fluid that it can be dispensed without problems with conventional auxiliary dosing agents. The gel detergents and cleaners according to the invention preferably have a viscosity of from 0.5 to 100 Pa · s at 20 ° C, particularly preferably from 0.5 to 50 Pa · s and, especially from 1 to 30 Pa · s.

The gel-like dishwasher of the invention preferably contains the following components:

a) at least one compound of formula I;

b) at least one bilder (also called a sequestering agent, sclera, a complexing agent, a chelator, a chelating agent or a water hardness reducing agent);

c) if necessary, at least one enzyme;

d) if necessary, at least one bleach;

e1) water;

e2) at least one thickener and

e3) if necessary, at least one other additive, preferably selected from surfactants other than component a), bases, corrosion inhibitors, antifoam agents, colorants, flavors, fillers, solubilizers, and organic solvents.

In a gel-like dishwasher according to the invention, these components are contained in the following proportion:

a) at least one compound of formula I from 0.1 to 20 wt.%;

b) at least one complexing agent from 5 to 80 wt.%;

c) at least one enzyme from 0 to 8 wt.%;

d) at least one bleach from 0 to 30 wt.%;

e1) water from 10 to 90 wt.%;

e2) at least one thickener from 0.1 to 8 wt.% and

e3) at least one other additive from 0 to 25 wt.%.

Moreover, the data in mass percent refers to the total weight of the dishwasher. The mass amount of components from a) to e 3) in total is 100 wt.%.

The dishwashing agent according to the invention, particularly preferably, contains at least one enzyme.

It is especially preferred if the above components are contained in the gel-like dishwasher of the invention in the following proportion:

a) at least one compound of formula I from 0.1 to 10 wt.%;

b) at least one complexing agent from 5 to 60 wt.%;

c) at least one enzyme from 0.1 to 6 wt.%;

d) at least one bleach from 0 to 30 wt.%;

e1) water from 10 to 90 wt.%;

e2) at least one thickener from 0.1 to 6 wt.% and

e3) at least one other additive from 0 to 25 wt.%.

Moreover, the data in mass percent refers to the total weight of the dishwasher. The mass amount of components from a) to e3) in total is 100 wt.%.

Most preferably, if the above components are contained in the gel-like dishwashing detergent according to the invention in the following quantitative ratio:

a) at least one compound of formula I from 0.1 to 10 wt.%;

b) at least one bilder from 5 to 40 wt.%;

c) at least one enzyme from 0.1 to 6 wt.%;

d) at least one bleach from 0 to 25 wt.%;

e1) water from 20 to 80 wt.%;

e2) at least one thickener from 0.3 to 5 wt.% and

e3) at least one other additive from 0 to 25 wt.%.

Data in mass percent refers to the total weight of dishwashing detergent. The mass amount of components from a) to e3) in total is 100 wt.%.

The thickener serves to impart the desired viscosity to the dishwasher of the invention.

In principle, any known thickeners (rheologically modifying agents) are suitable that do not adversely affect the effectiveness of the dishwasher. Thickeners of both natural and synthetic origin may be suitable.

Examples of naturally occurring thickeners are xanthan, carob flour, guar flour, carrageenan, agar, tragacanth, gum arabic, alginates, modified starches, such as hydroxyethyl starches, starch phosphate ester or starch acetates, dextrins, pectins and cellulose derivatives such as carbocellulose such as carbamide hydroxyethyl cellulose, hydroxypropyl cellulose, methyl cellulose and the like.

Inorganic thickeners are also inorganic thickeners, such as polysilicic acids and clay minerals, for example, layered silicates, as well as such silicates as are named for complexing agents.

Examples of synthetic thickeners are polyacrylic and polymethacrylic compounds, such as (partially) crosslinked acrylic acid homopolymers, e.g. sucrose allyl ether or pentaerythritol or propylene crosslinked acrylic acid homopolymers (carbomer), e.g. Carbopol®, BF Goodridge (e.g. Carbopol®76 940, 941, 934 and the like) or Polygel®, 3V Sigma grades (e.g. Polygel® DA); copolymers of ethylenically unsaturated mono- or di-carboxylic acids, such as terpolymers of acrylic, methacrylic or maleic acid with methyl or ethyl acrylate and (meth) acrylate, a derivative of long chain ethoxylated alcohols, for example, Acusol®, Rohm & Haas (e.g. Acusol® 820 or 1206 A); copolymers of two or more monomers selected from acrylic acid, methacrylic acid and their alkyl esters with 1-4 carbon atoms in alkyl, for example, copolymers of methacrylic acid, butacrylic acid and methyl methacrylate or butyl acrylate and methyl methacrylate, for example, Aculyn® and Acusol®, Rohm & Haas (e.g. Aculyn® 22, 28 or 33 and Acusol® 810, 823 and 830) or crosslinked high molecular weight acrylic acid copolymers, e.g. sucrose or pentaerythritol allyl ester, 10-30 carbon alkyl acrylate copolymers with one or several somo Omer selected from acrylic acid, methacrylic acid and their alkyl esters with 1-4 carbon atoms (e.g., Carbopol® ETD 2623, Carbopol® 1382 and Carbopol® AQUA 30, Rohm & Haas).

Examples of synthetic thickeners are, in addition, the products of the interaction of maleic acid polymers with ethoxylated long chain alcohols, for example, the Sulfonic L series, Texaco Chemical Co. or Gantrez AN-119, ISP; polyethylene glycols, polyamides, poly-imines and polycarboxylic acids.

Mixtures of the above thickeners are also suitable.

Preferred thickeners are xanthan gums and the aforementioned polyacrylic and polymethacrylic compounds.

As for the suitable and preferred components a) to d) and e3), one can refer to the above forms of their implementation.

Compounds I used according to the invention are characterized in comparison with conventional surfactants from the prior art by a high melting point, which allows them to be used in solid detergents and cleaners. They do not have or do not have a very strong predisposition to foaming, have a good deposition inhibitory effect during the washing of dishes with their use, especially in relation to staining, and are not unstable to hydrolysis.

The claimed invention is illustrated in more detail by the following examples, but not limiting its scope.

Examples

1. Synthesis Examples General Procedure

1.1. Preparation of alkoxyethylene glycol dodecyl mercaptoethanol

1.1.1. Obtaining ethoxylates of alcohols

In 2 liter Mettler autoclaves, alkoxylated alcohol (isotridecanol, 2-propylheptanol or alcohol fraction 12/14; 1.0 eq.) Is mixed with an aqueous solution of potassium hydroxide containing 50 wt.% Potassium hydroxide. The amount of potassium hydroxide is 0.2 wt.% Of the resulting product. The mixture was dehydrated with stirring at 100 ° C and a pressure of 20 mbar for 2 hours. Then it is purified three times with nitrogen, a preliminary pressure of nitrogen is set at about 1.3 bar and the temperature is increased to 120 ° C. Dose ethylene oxide (n mol equiv.) So that the temperature remains between 125 and 135 ° C. Then it is additionally stirred for 5 hours at a temperature of 125 ° C, purified with nitrogen, cooled to 70 ° C and the reactor is unloaded. The crude product is degassed in a rotary evaporator for 2 hours at 100 ° C (vacuum <20 mbar). This basic crude product can be deionized with conventional commercial magnesium silicates, which are then filtered off. Alternatively, neutralization by means of acetic acid can also be carried out. The light product is characterized by ¹ H-NMR spectrum in CDCl ₃ and gel permeation chromatography, as well as by determining the hydroxyl number and determine the yield (> 98%).

1.1.2. Interactions with dodecyl mercaptoethanol

The alkoxylate from Example 1.1.1 (1 mol equiv.), Paratoluenesulfonic acid (0.005 mol equiv.) And toluene are placed in a 500 ml equipment with a circulation circuit with water discharge. The reaction mixture is heated to a reverse flow. Dodecyl mercaptoethanol (x mol equiv.) Is added dropwise. The resulting water is removed overnight through a circulation circuit with a drain of water. The reaction mixture is cooled, neutralized with sodium carbonate (0.005 mol equiv.), Filtered and the solvent completely removed at a temperature of 100 ° C and a pressure of 6 mbar. A white solid is obtained. Using TAI-NMR determine the structure (percentage of reacted hydroxyl groups). The method of gel permeation chromatography (GC) was determined by the residual amount of toluene (always <0.5%) and dodecyl-mercaptoethanol.

Name Structure n x The degree of interaction [%] * The residual amount of dodecyl mercaptoethanol I [%] ** AT iC ₁₃ -35EO - dodecyl mercaptoethanol 35 1.0 93 0.1 FROM 2RN-35EO - dodecyl mercaptoethanol 35 1.2 94 0.1 E C ₁₂ / C ₁₄ Alkohol-27EO - dodecyl mercaptoethanol 27 1.2 94 0.1 F iC ₁₃ -40EO - dodetsilmerkaptoetanol 40 1.0 84 0.1 * according to TAI-NMR ** according to quantity Gc i-C ₁₃ = ′ ′ isotridecanol ′ ′; a mixture of various isomers of tridecanol EO = ethylene oxide PO = propylene oxide 2PH = 2-propylheptanol TAI = trichloroacetyl isocyanate.

1.2. Oxidation of product C to the corresponding sulfoxide D

71.6 g of the above product C (40 mmol, 1 mol equiv.) Were melted in 250 ml flasks, placed in water and heated to a temperature of 70 ° C. hydrogen peroxide (50%) (4.1 g, 60 mmol, 1.5 mol equiv) was added dropwise. The reaction mixture was then stirred for 2 hours at 70 ° C, after which it was cooled and concentrated at 100 ° C and given 6 mbar. 69.2 g (96% yield) of a yellow solid are obtained. The absence of hydrogen peroxide was proved by IR, and the yield (100%) was determined by ¹ H-NMR.

Description of the method of TAI-NMR

или $$C{l}_{3}CC(O)NHC(O)-\underset{\_}{OCH}-RR\text{'}$$

имеют в ¹H-ЯМР спектре различные типичные смещения для ОСН₂ и OCHRR′. Типичные области смещения для «первичных карбаматов» находятся в пределах от 4,0 до 4,5 ч. на млн.ч., в то время как для «вторичных карбаматов» области смещения находятся в пределах от 5,0 до 5,3 частей на млн.In order to determine (quantitatively) superimposed signals of primary and / or secondary alcohols in a ¹ H-NMR spectrum, the sample in CDCI _{3 is} mixed with an excess of TAI (trichloroacetyl isocyanate). In this case, the isocyanate immediately reacts with alcohol groups to form carbamate. The resulting compounds $$C{l}_{3}CC(O)NHC(O)-\underset{\_}{OC{H}_2}R$$

or $$C{l}_{3}CC(O)NHC(O)-\underset{\_}{OCH}-RR\text{'}\text{'}$$

in ¹ H-NMR spectrum have various typical biases for OCH ₂ and OCHRR ′. Typical displacement regions for “primary carbamates” range from 4.0 to 4.5 parts per million parts, while for “secondary carbamates” ranges of displacement range from 5.0 to 5.3 parts per million

2. Examples of use

Various surfactants were tested with their use. A is a polymer for comparison.

Name Surface-active substance BUT C ₆ -C ₁₀ - alcohol -1РО-20ЕО-1 DeO (according to the international patent application WO 94/22800) AT i-C ₁₃ - 35EO-dodecylmercaptoethanol FROM 2RN - 35EO - dodecyl mercaptoethanol D 2PH - 35EO - dodecyl mercaptoethanol oxidized to sulfide E C ₁₂ / C ₁₄ alcohol - 27EO - dodetsilmerkaptoetanol F iC ₁₃ - 40EO - dodetsilmerkaptoetanol.

PO = propylene oxide;

EO = ethylene oxide;

DeO = 1,2-decenoxide;

iC ₁₃ = ′ ′ isotridecanol ′ ′; a mixture of various isomers of tridecanol;

2PH = 2-propylheptanol.

2.1. Melting point determination

The solidification point was determined by DSC (differential scanning calorimetry).

Surface-active substance BUT AT FROM D E F Melting point [° C] 33.1 40.1 41.8 41.1 44.1 44.9

2.2. Foam volumes in the dishwasher

The volumes of the foam were determined directly by measuring the foaming through the rotation speed of the spray arm of the dishwasher. To do this, 10 ml of mixed chicken egg, 19 g of the main dishwashing detergent (48 parts of sodium metasilicate hydrate × 5H ₂ O, 45 parts of sodium triphosphate, 5 parts of sodium carbonate) and 1 g of surfactant (A-F) are added to washer (Miele Desinfector G7735 CD MCU; Programm - Steurgerät MCU - Version S04.01). Then, at different temperatures, the rotation speed of the spray beam was measured. At a high level of foam, the spray beam is inhibited, and at a low level of foam, it functions at the highest possible speed (about 125 rpm). The rotation speed of the dishwasher head is usually about 125 rpm in the absence of foam. The maximum rotation speed of the dishwasher was set artificially in this test (by means of drilled holes in the spray arm to obtain a wider range so that products can be better distinguished.

The rotation speed was determined at a temperature of 40 ° C, 50 ° C and 60 ° C. The table below shows the rotor speed (in rpm) at different temperatures.

Temperature BUT AT FROM D E F 40 [° C] 119 99 128 122 84 89 50 [° C] 121 111 131 122 106 90 60 [° C] 122 117 122 122 117 101

2.3. Test washing with rinses to clean water

All examples were carried out with the main composition of the following composition:

1 parts by weight proteases (Ovozyme® 64T),

0.2 parts by weight amylases (Stainzyme® 12T),

3.0 parts by weight surfactant

10 parts by weight polyacrylic acid with a molecular weight of 4000 g / mol (Sokalan® PA 25 CI),

10.5 parts by weight sodium percarbonate,

4 parts by weight tetraacetylethylenediamine,

2 parts by weight sodium disilicate (Britesil® H 265 LC),

18.8 parts by weight sodium carbonate

33 parts by weight sodium citrate dihydrate,

15 parts by weight trisodium salt of methylglycine diacetic acid (Trilon® M),

0.5 parts by weight 1-hydroxyethane- (1,1-diphosphonic acid) (HEDP; Cublen® K 8514 GR).

Ovozyme® and Stainzyme® are brand names of Novozymes; Sokalan® and Trilon® are BASF SE brand names; Britesil® is a brand name of PQ Corp .; Cublen® is a brand name of the Zschimmer & Schwarz Mohsdorf GmbH & Co KG.

All tests of washing dishes with rinsing to clean water were carried out in a Miele dishwasher (Tour G 1222 SCL). In this case, a program with a temperature of 50 ° C (R-time 2) was selected for the washing cycle and 65 ° C for the washing cycle with rinsing to clean water. The tests were carried out with hard water with a hardness of 21 ° dH (Ca / Mg): HCO ₃ (3: 1): 1.35. Separate rinse aid was not added to clean water. And the integrated water softener (ion exchanger) was not regenerated by means of a regenerating salt. The above composition was dosed twice in 21 g. For each washing process, 100 g of ballast contamination, consisting of fat, protein and starch, was added. In each washing process, a knife made of cromargan, a blue melamine plate, a glass and a plate of porcelain served as test dishes. Between washing cycles, in each case, one hour was expected, of which 10 minutes - with the door closed and 50 minutes - with the door open.

After the sixth washing cycle, the dishes were visually compared with a reference in a darkened chamber under the action of light through a diaphragm with holes and evaluated on a rating scale from 1 (large sediment) to 10 (absence of sediment) relative to the presence of spots, streaks and film-like deposits.

Marked spotting BUT AT FROM D E F Knife one 5 2 2 5 2 Glass one 2 one 2 one one Melamine plate one 3 2 2 2 3 Total 3 10 5 6 8 6 Marked Film Formation BUT AT FROM D E F Knife 6 6 5 6 5 6 Glass 6 5 5 7 5 5 Melamine plate 6 7 7 9 7 7 Total eighteen eighteen 17 22 17 eighteen

2.4. Usability Stability Test

The test was carried out similarly to 2.2. The rotation speed was measured at a maximum temperature (57 ° C-70 ° C for 2 hours. The table below shows the rotation speed in rpm. The exact temperature at the rotation speed is shown in square brackets.

Time [min] 10 twenty thirty 40 fifty 60 70 80 90 one hundred 110 120 BUT 129 [60] 127 [61] 128 [62] 125 [64] 127 [64] 127 [65] 127 [67] 127 [68] 126 [68] 126 [68] 124 [68] 122 [69] AT 119 [57] 121 [58] 122 [59] 118 [60] 117 [61] 117 [62] 116 [63] 114 [64] 111 [65] 108 [66] 104 [67] 97 [68] FROM 114 [58] 115 [60] 118 [61] 117 [62] 122 [63] 126 [64] 125 [65] 125 [66] 126 [67] 123 [68] 124 [69] 125 [70] D 117 [58] 119 [60] 118 [61] 120 [62] 120 [64] 122 [65] 122 [66] 120 [67] 120 [68] 121 [68] 119 [69] 120 [70] E 123 [59] 124 [60] 122 [61] 122 [63] 121 [64] 119 [65] 119 [66] 115 [67] 113 [68] 113 [69] 109 [70] 111 [70] F 103 [58] 97 [58] 97 [59] 99 [60] 104 [61] 102 [62] 105 [63] 104 [64] 104 [65] 105 [63] 104 [66] 102 [67]

Claims (25)

1. The use of compounds of formula I:
RO- [CH ₂ CH (R ¹⁾ -O] _l - [CH ₂ CH ₂ -O] _m - [CH ₂ CH (R ²⁾ -O] _n -CH ₂ CH ₂ -S (O) _x -R '(I),
Where
R is alkyl with 8-24 carbon atoms,
R ′ means alkyl with 10-14 carbon atoms,
R ¹ and R ² , independently of each other and regardless of their specific appearance, mean alkyl with 1-5 carbon atoms,
m means a number from 25 to 50,
l and n are 0 and
x means 0 or 1,
in detergents or detergents, and detergents and detergents selected from dishwashers. 2. The use according to claim 1, wherein the detergents and cleaners are selected from machine dishwashers. 3. The use according to claim 1, wherein the detergents and cleaners are selected among dishwashers with a rinse function. 4. The use according to claim 1, wherein the detergents and cleaners are solid. 5. The use according to claim 1, wherein the detergents and cleaners are gel-like. 6. The use according to claim 1, wherein compounds I are used as surfactants. 7. The use according to claim 1, wherein Compound I is used as a rinsing surfactant. 8. The use according to claim 1, wherein R is alkyl with 10-15 carbon atoms. 9. The use according to claim 1, wherein R ′ is alkyl with 12 carbon atoms. 10. The use according to claim 1, wherein R ¹ and R ² , independently of each other and regardless of their specific appearance, mean methyl. 11. The use according to one of paragraphs. 1-10, and the melting temperature of compounds I is at least 35 ° C, preferably at least 38 ° C. 12. A detergent or detergent, which is a dishwasher, containing at least one compound of formula I according to the definition of one of claims. 1 and from 8 to 11. 13. The detergent or detergent according to claim 12, which is a machine dishwasher. 14. The detergent or detergent according to claim 12, which is a dishwasher with a rinse function. 15. The detergent or detergent according to claim 12, which is solid at room temperature. 16. A detergent or cleaning agent according to claim 13, containing the following components:
a) at least one compound of formula I;
b) at least one complexing agent;
c) if necessary, at least one enzyme;
d) if necessary, at least one bleach and
e) if necessary, at least one additional additive selected from surfactants other than component a), bases, corrosion inhibitors, antifoam agents, colorants, flavorings, fillers, tabletting aids, disintegrating agents, thickeners, promoting solubility, organic solvents and water. 17. A detergent or cleaning agent according to claim 16, containing the following components:
a) at least one compound of formula I from 0.1 to 20 wt.%;
b) at least one complexing agent from 5 to 80 wt.%;
c) at least one enzyme from 0 to 8 wt.%;
d) at least one bleach from 0 to 30 wt.% and
e) at least one additional additive from 0 to 50 wt.%
calculated on the total weight of the detergent or detergent. 18. A detergent or cleaner according to claim 16, comprising the following components:
a) at least one compound of formula I from 0.1 to 10 wt.%;
b) at least one complexing agent from 20 to 80 wt.%;
c) at least one enzyme from 0.1 to 6 wt.%;
d) at least one bleach from 0 to 30 wt.% and
e) at least one additional additive from 0 to 50 wt.%.
calculated on the total weight of the detergent or detergent. 19. A detergent or cleaning agent according to claim 16, containing the following components:
a) at least one compound of formula I from 0.1 to 10 wt.%;
b) at least one complexing agent from 20 to 80 wt.%;
c) at least one enzyme from 0.1 to 6 wt.%;
d) at least one bleach from 5 to 25 wt.% and
e) at least one additional additive from 0 to 50 wt.%
calculated on the total weight of the detergent or detergent. 20. The detergent or detergent according to claim 16, which as component b) contains a mixture of various complexing agents containing at least two of the following components: at least one carbonate, at least one silicate, at least , one polymeric compound containing carboxylic acid groups, or at least one polymeric compound containing carboxylic acid groups, in which the carboxylic acid groups are partially or completely neutralized, at least one (poly) hydroxy-carbon nd acid or its salt, at least one aminopolycarboxylic acid or salt thereof, at least one phosphonic acid, at least one phosphate. 21. Detergent or cleaner according to one of paragraphs. from 12 to 14 and from 16 to 20, which is gel-like at room temperature. 22. A detergent or detergent according to claim 21, containing the following components:
a) at least one compound of formula I;
b) at least one complexing agent;
c) if necessary, at least one enzyme;
d) if necessary, at least one bleach;
e1) water;
e2) at least one thickener and
e3) if necessary, at least one additional additive selected from surfactants other than component a), bases, corrosion inhibitors, antifoam agents, colorants, flavors, fillers, solubilizers, and organic solvents. 23. A detergent or cleaner according to claim 22, comprising the following components:
a) at least one compound of formula I from 0.1 to 20 wt.%;
b) at least one complexing agent from 5 to 80 wt.%;
c) at least one enzyme from 0 to 8 wt.%;
d) at least one bleach from 0 to 30 wt.%;
e1) water from 10 to 90 wt.%;
e2) at least one thickener from 0.1 to 8 wt.% and
e3) at least one additional additive from 0 to 25 wt.%
calculated on the total weight of the detergent or detergent. 24. A detergent or cleaning agent according to claim 22, containing the following components:
a) at least one compound of formula I from 0.1 to 10 wt.%;
b) at least one complexing agent from 5 to 60 wt.%;
c) at least one enzyme from 0.1 to 6 wt.%;
d) at least one bleach from 0 to 30 wt.%;
e1) water from 10 to 90 wt.%;
e2) at least one thickener from 0.1 to 6 wt.% and
e3) at least one additional additive from 0 to 25 wt.%
calculated on the total weight of the detergent or detergent. 25. Detergent or cleaning agent according to one of paragraphs. from 22 to 24, containing the following components:
a) at least one compound of formula I from 0.1 to 10 wt.%;
b) at least one complexing agent from 5 to 40 wt.%;
c) at least one enzyme from 0.1 to 6 wt.%;
d) at least one bleach from 0 to 25 wt.%;
e1) water from 20 to 80 wt.%;
e2) at least one thickener from 0.3 to 5 wt.% and
e3) at least one additional additive from 0 to 25 wt.%
calculated on the total weight of the detergent or detergent.