EP3218462B1 - Detergent and cleaning agents having improved performance - Google Patents

Description

The present invention relates to the use of dihydroxy terephthalic acid derivatives in detergents and cleaning agents to improve the washing or cleaning performance.

While the formulation of powdered detergents and cleaning agents containing bleach now no longer poses any problems, the formulation of stable liquid detergents and cleaning agents containing bleach continues to be a problem. Because of the usually lack of bleach in liquid detergents and cleaning agents, such Soiling, which is normally removed in particular due to the bleaching agent contained, is correspondingly frequently only removed in an inadequate manner. A similar problem also exists for bleach-free color detergents in which the bleach is omitted in order to protect the dyes in the textile and prevent them from fading. In the absence of bleach, it is aggravated that instead of removing the so-called bleachable stains, which are normally at least partially removed by the use of bleaching agents based on peroxygen, on the contrary, the washing process often leads to an intensification and / or deterioration in the removability of the stain, This should not least be attributed to initiated chemical reactions, which may consist, for example, in the polymerisation of certain dyes contained in the soiling.

Such problems occur in particular with soiling which contain polymerizable substances. The polymerizable substances are mainly polyphenolic dyes, preferably flavonoids, in particular from the class of anthocyanidins or anthocyanins. The soiling can in particular have been caused by food products or beverages that contain the corresponding colorants. The soiling can be, in particular, stains from fruits or vegetables or also red wine stains, which in particular contain polyphenolic dyes, especially those from the class of anthocyanidins or anthocyanins.

From the international patent application WO 2011/023716 A1 the use of gallic acid esters such as propyl gallate in detergents and cleaning agents for improved removal of soils which contain polymerizable substances is known.

The international patent application WO 2013/092263 A1 relates to the improvement of the performance of detergents and cleaning agents through the use of oligohydroxybenzoic acid amides.

Surprisingly, it was found that the use of dihydroxy terephthalic acid and / or dihydroxy terephthalic acid esters and / or amides can significantly improve the washing or cleaning performance of washing or cleaning agents, particularly with regard to bleachable soiling.

in der R¹ und R² unabhängig voneinander für NR³R⁴ oder OR⁵ stehen sowie R³, R⁴ und R⁵ unabhängig voneinander für H oder einen cyclischen oder acyclischen, geradkettigen oder verzweigtkettigen, aliphatischen oder aromatischen Kohlenwasserstoffrest mit 1 bis 20, vorzugsweise 1 bis 10 Kohlenstoffatomen, dessen Gerüst durch ein oder mehrere nicht benachbarte Heteroatome, insbesondere ausgewählt aus O und/oder N, durchbrochen sein kann und/oder der an nicht mit Heteroatomen verbundenen C-Atomen mit OH-Gruppen oder NH₂-Gruppen substituiert sein kann, stehen, in Wasch- oder Reinigungsmitteln zur Verbesserung der Wasch- oder Reinigungsleistung gegenüber bleichbaren Anschmutzungen.A first object of the present invention is therefore the use of compounds of the general formula (I)

in which R ¹ and R ² independently of one another are NR ³ R ⁴ or OR ⁵ and R ³ , R ⁴ and R ⁵ independently of one another are H or a cyclic or acyclic, straight-chain or branched-chain, aliphatic or aromatic hydrocarbon radical having 1 to 20, preferably 1 to 10 carbon atoms, the backbone of which may be broken by one or more non-adjacent heteroatoms, in particular selected from O and / or N, and / or which is substituted on the C atoms not connected with heteroatoms with OH groups or NH ₂ groups can be, in detergents or cleaning agents to improve the washing or cleaning performance compared to bleachable stains.

As mentioned above, bleachable stains are those which are at least partially removed by using bleaching agents based on peroxygen, for example sodium percarbonate in combination with tetraacetylethylene diamine. The bleachable soils usually contain polymerizable substances, in particular polymerizable dyes, the polymerizable dyes preferably being polyphenolic dyes, in particular flavonoids, especially anthocyanidins or anthocyanins or oligomers of these compounds. In addition to the removal of soiling in the colors green, yellow, red or blue, there is also the possibility of soiling in intermediate colors, in particular violet, purple, brown, purple or pink, and also soiling which is green, yellow, red, violet , purple, brown, purple, pink or blue tint without essentially consisting entirely of this color. The colors mentioned can in particular also be light or dark. These are preferably soiling, in particular stains on grass, fruits or vegetables, in particular also soiling through food products such as spices, sauces, chutneys, curries, purees and jams, or beverages such as coffee, tea, wines and juices, the corresponding green, yellow, red, violet, purple, brown, purple, pink and / or contain blue dyes.

The soiling to be removed according to the invention can in particular be caused by cherry, morelle, grape, apple, pomegranate, aronia, plum, sea buckthorn, açai, kiwi, mango, grass, or berries, especially red or black currants, elderberries, blackberries, raspberries , Blueberries, cranberries, cranberries, strawberries or blueberries, through coffee, tea, red cabbage, blood orange, eggplant, tomato, carrot, beetroot, spinach, bell pepper, red-fleshed or blue-fleshed potato, or red onion.

Preferred compounds of the general formula (I) are those in which R ¹ and R ^{2 are} identical. R ³ is preferably H, and R ⁴ and R ⁵ are, independently of one another, preferably alkyl groups, such as methyl, ethyl, n-propyl or i-propyl, alkoxyalkyl groups, such as methoxyethyl, methoxypropyl, (2-methoxy) ethoxyethyl, ethoxyethyl, ethoxypropyl or (2-ethoxy) ethoxyethyl, hydroxyalkyl groups such as hydroxyethyl, hydroxypropyl, 2-hydroxypropyl, 1,2-dihydroxypropyl, 2-hydroxyethoxyethyl, (N-hydroxyethyl) aminoethyl, (N-methoxyethyl) aminoethyl or (N-ethoxyethyl) -Aminoethyl, or aromatic groups, such as phenyl or benzyl.

The use of the compound of the general formula (I) according to the invention is preferably carried out in detergents or cleaning agents by adding them in an amount of 0.001% by weight to 20% by weight, in particular in an amount of 0.01% by weight. % to 10% by weight is used, the details of "% by weight" here and below refer to the weight of the entire detergent or cleaning agent. The invention therefore furthermore relates to a washing or cleaning agent comprising nonionic, anionic, cationic and / or amphoteric surfactants and 0.001% by weight to 20% by weight, in particular 0.01% by weight to 10% by weight. % of compound of the general formula (I), the preferred embodiments described above or below in connection with the use according to the invention also applying to this subject of the invention, and conversely the preferred embodiments described in connection with agents according to the invention also apply to the use aspect of the invention .

The washing or cleaning agent can be present in any dosage form established according to the prior art and / or in any expedient form. These include, for example, solid, powder, liquid, gel or pasty dosage forms, possibly also consisting of several phases; this also includes, for example: extrudates, granules, tablets or pouches, both in large containers and packaged in portions.

In a preferred embodiment, the use according to the invention takes place in a washing and cleaning agent which contains no bleaching agents. This is to be understood to mean that the agent does not contain any bleaching agents in the narrower sense, that is to say hypochlorites, hydrogen peroxide or substances providing hydrogen peroxide; it preferably also has no bleach activators and / or bleach catalysts.

In a particularly preferred embodiment, the detergent is a liquid textile detergent.

In a further particularly preferred embodiment, the detergent is a powdery or liquid color detergent, that is to say a textile detergent for colored textiles.

The detergents and cleaning agents can furthermore contain customary other constituents of detergents or cleaning agents, in particular textile detergents, in particular selected from the group of builders, polymers, enzymes, disintegration aids, fragrances and perfume carriers.

The builders include, in particular, the zeolites, silicates, carbonates, organic cobuilders and - if there are no ecological prejudices against their use - also the phosphates.

The finely crystalline, synthetic and bound water-containing zeolite is preferably zeolite A and / or zeolite P. As zeolite P, for example, zeolite MAP® (commercial product from Crosfield) is suitable. However, zeolite X and mixtures of zeolite A, X and / or P are also suitable. Commercially available and usable in the context of the present invention is, for example, a co-crystallizate of zeolite X and zeolite A (approx. 80% by weight zeolite X ) 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 as a kind of "powdering" of a granular mixture, preferably a mixture to be compressed, usually using both ways of incorporating the zeolite into the premix. Zeolites can have an average particle size of less than 10 μm (volume distribution; measurement method: Coulter Counter) and preferably contain 18% by weight to 22% by weight, in particular 20% by weight to 22% by weight, of bound water.

Crystalline layered silicates of the general formula NaMSi _x O _{2x + 1} .y H ₂ O can also be used, in which M represents sodium or hydrogen, x is a number from 1.9 to 22, preferably from 1.9 to 4, where are particularly preferred values for x 2, 3 or 4, and y is a number from 0 to 33, preferably from 0 to 20. 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, Kenyait), 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).

Preference is given to crystalline sheet silicates of the formula NaMSi _x O _{2x + 1} .y H ₂ O, in which x represents 2. In particular, both β- and δ-sodium disitikates are Na ₂ Si ₂ O ₅ .y H ₂ O and, above all, Na-SKS-5 (α-Na ₂ Si ₂ O ₅ ), Na-SKS-7 (β-Na ₂ Si ₂ O ₅ , natrosilite), Na-SKS-9 (NaHSi ₂ O ₅ · H ₂ O), Na-SKS-10 (NaHSi ₂ O ₅ · 3 H ₂ O, Kanemit), Na-SKS-11 ( t-Na ₂ Si ₂ O ₅ ) and Na-SKS-13 (NaHSi ₂ O ₅ ), but in particular Na-SKS-6 (δ-Na ₂ Si ₂ O ₅ ) are preferred. Detergents or cleaning agents preferably contain a proportion _by weight of the crystalline layered silicate of the formula NaMSi _x O _{2x + 1} .yH ₂ O from 0.1% by weight to 20% by weight, preferably from 0.2% by weight to 15% by weight and in particular from 0.4% by weight to 10% by weight.

Amorphous sodium silicates with a modulus Na ₂ O: SiO ₂ of 1: 2 to 1: 3.3, preferably from 1: 2 to 1: 2.8 and in particular from 1: 2 to 1: 2.6, can also be used are preferably delayed release and have secondary washing properties. The delay in dissolution compared to conventional amorphous sodium silicates can be caused in various ways, for example by surface treatment, compounding, compacting / compression or by overdrying. The term "amorphous" is understood to mean that the silicates in X-ray diffraction experiments do not provide sharp X-ray reflections, as are typical for crystalline substances, but at most produce one or more maxima of the scattered X-rays, which have a width of several degree units of the diffraction angle.

As an alternative or in combination with the aforementioned amorphous sodium silicates, X-ray amorphous silicates can be used, the silicate particles of which deliver washed-out or even sharp diffraction maxima in electron diffraction experiments. This is to be interpreted as meaning that the products have microcrystalline areas with a size of ten to a few hundred nm, values up to max. 50 nm and in particular up to max. 20 nm are preferred. X-ray amorphous silicates of this type also have a delay in dissolution compared to conventional water glasses. Compacted / compacted amorphous silicates, compounded amorphous silicates and over-dried X-ray amorphous silicates are particularly preferred.

These silicate (s), preferably alkali silicates, particularly preferably crystalline or amorphous alkali disilicates, are, if present, in detergents or cleaning agents in amounts of 3% by weight to 60% by weight, preferably 8% by weight. Contain% to 50 wt .-% and in particular from 20 wt .-% to 40 wt .-%.

It is also possible to use the generally known phosphates as builder substances, provided that such use should not be avoided for ecological reasons. Of the large number of commercially available phosphates, the alkali metal phosphates, with particular preference for pentasodium and pentapotassium triphosphate (sodium and potassium tripolyphosphate), have the greatest importance in the detergent and cleaning agent industry.

Alkali metal phosphates is the general term for the alkali metal (especially sodium and potassium) salts of the various phosphoric acids, in which one can distinguish between metaphosphoric acids (HPO ₃ ) _n and orthophosphoric acid H ₃ PO _{4 in} addition to higher molecular weight representatives. The phosphates combine several advantages: They act as alkali carriers, prevent limescale deposits on machine parts and lime incrustations in tissues and also contribute to cleaning performance. Technically particularly important phosphates are pentasodium triphosphate, Na ₅ P ₃ O ₁₀ (sodium tripolyphosphate) and the corresponding potassium salt pentapotassium triphosphate, K ₅ P ₃ O ₁₀ (potassium tripolyphosphate). The sodium potassium tripolyphosphates are also preferably used. If phosphates are used in washing or cleaning agents, preferred agents contain these phosphate (s), preferably alkali metal phosphate (s), particularly preferably pentasodium or pentapotassium triphosphate (sodium or potassium tripolyphosphate), in amounts of 5% by weight. % to 80% by weight, preferably from 15% by weight to 75% by weight and in particular from 20% by weight to 70% by weight.

Alkali carriers can also be used. Examples of alkali carriers include alkali metal hydroxides, alkali metal carbonates, alkali metal hydrogen carbonates, alkali metal sesquicarbonates, the alkali silicates mentioned, alkali metal silicates, and mixtures of the abovementioned substances, the alkali metal carbonates, in particular sodium carbonate, sodium hydrogen carbonate or sodium sesquicarbonate, preferably being used. A builder system containing a mixture of tripolyphosphate and sodium carbonate can be particularly preferred. Because of their low chemical compatibility with the other ingredients of detergents or cleaning agents compared to other builder substances, the alkali metal hydroxides are usually only used in small amounts, preferably in amounts below 10% by weight, preferably below 6% by weight, particularly preferably below 4 % By weight and in particular below 2% by weight. Agents which contain less than 0.5% by weight and in particular no alkali metal hydroxides, based on their total weight, are particularly preferred. Preference is given to using carbonate (s) and / or hydrogen carbonate (s), preferably alkali carbonate (s), particularly preferably sodium carbonate, in amounts from 2% by weight to 50% by weight, preferably from 5% by weight to 40% by weight and in particular from 7.5% by weight to 30 % By weight.

Organic builders include, in particular, polycarboxylates / polycarboxylic acids, polymeric polycarboxylates, aspartic acid, polyacetals, dextrins and phosphonates. For example, the polycarboxylic acids which can be used in the form of the free acid and / or their sodium salts can be used, polycarboxylic acids being understood as meaning those carboxylic acids which 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), as long as such use is not objectionable for ecological reasons, and mixtures of these. In addition to their builder action, the free acids typically also have the property of an acidifying component and thus also serve to set a lower and milder pH of detergents or cleaning agents. Citric acid, succinic acid, glutaric acid, adipic acid, gluconic acid and any mixtures thereof can be mentioned in particular. Polymeric polycarboxylates are also suitable as builders, for example the alkali metal salts of polyacrylic acid or polymethacrylic acid, for example those with a relative molecular weight of 500 g / mol to 70,000 g / mol. Particularly suitable are polyacrylates, which preferably have a molecular weight of 2,000 g / mol to 20,000 g / mol. Because of their superior solubility, the short-chain polyacrylates which have molar masses from 2000 g / mol to 10000 g / mol, and particularly preferably from 3000 g / mol to 5000 g / mol, can in turn be preferred from this group. Also suitable are copolymeric polycarboxylates, in particular those of acrylic acid with methacrylic acid and of acrylic acid or methacrylic acid with maleic acid. Copolymers of acrylic acid with maleic acid which contain 50% by weight to 90% by weight of acrylic acid and 50% by weight to 10% by weight of maleic acid have proven to be particularly suitable. Their relative molecular weight, based on free acids, is generally from 2000 g / mol to 70,000 g / mol, preferably from 20,000 g / mol to 50,000 g / mol and in particular from 30,000 g / mol to 40,000 g / mol. To improve water solubility, the polymers can also contain allylsulfonic acids, such as, for example, allyloxybenzenesulfonic acid and methallylsulfonic acid, as monomers. The (co) polymeric polycarboxylates can be used as a solid or in aqueous solution. The content of (co) polymeric polycarboxylates in washing or cleaning agents is preferably 0.5% by weight to 20% by weight and in particular 3% by weight to 10% by weight.

Also particularly preferred are biodegradable polymers composed of more than two different monomer units, for example those which contain salts of acrylic acid and maleic acid as well as vinyl alcohol or vinyl alcohol derivatives as monomers or those which contain salts of acrylic acid and 2-alkylallylsulfonic acid and sugar derivatives as monomers . Further preferred copolymers are those which, as monomers, acrolein and acrylic acid / acrylic acid salts or acrolein and Have vinyl acetate. Also to be mentioned as further preferred builder substances are polymeric aminodicarboxylic acids, their salts or their precursor substances. Polyaspartic acids and / or their salts are particularly preferred.

Another class of substances with builder properties are the phosphonates. These are the salts of, in particular, hydroxyalkane or aminoalkanephosphonic acids. Among the hydroxyalkanephosphonic acids, 1-hydroxyethane-1,1-diphosphonic acid (HEDP) is of particular importance. It is used in particular as the sodium salt, the disodium salt reacting neutrally and the tetrasodium salt in an alkaline manner. Particularly suitable aminoalkanephosphonic acids are ethylenediaminetetramethylenephosphonic acid (EDTMP), diethylenetriaminepentamethylenephosphonic acid (DTPMP) and their higher homologs. They are used in particular in the form of the neutral sodium salts, for example as the hexasodium salt of EDTMP or as the hepta- and octa-sodium salt of DTPMP. Mixtures of the phosphonates mentioned can also be used as organic builders. The aminoalkanephosphonates in particular also have a pronounced ability to bind heavy metals.

Other suitable builder substances are polyacetals, which can be obtained by reacting dialdehydes with polyolcarboxylic acids which have 5 to 7 carbon atoms and at least 3 hydroxyl groups. Preferred polyacetals are obtained from dialdehydes such as glyoxal, glutaraldehyde, terephthalaldehyde and their mixtures and from polyol carboxylic acids such as gluconic acid and / or glucoheptonic acid.

Other suitable organic builder substances are dextrins, for example oligomers or polymers of carbohydrates, which can be obtained by partial hydrolysis of starches. The hydrolysis can be carried out by customary, for example acid or enzyme-catalyzed, processes. They are preferably hydrolysis products with average molecular weights in the range from 400 g / mol to 500000 g / mol. A polysaccharide with a dextrose equivalent (DE) in the range from 0.5 to 40, in particular from 2 to 30, is preferred, DE being a customary measure of the reducing action of a polysaccharide compared to dextrose, which has a DE of 100 , is. Both maltodextrins with a DE between 3 and 20 and dry glucose syrups with a DE between 20 and 37 as well as so-called yellow dextrins and white dextrins with higher molar masses in the range from 2000 g / mol to 30000 g / mol can be used. The oxidized derivatives of such dextrins are their reaction products with oxidizing agents which are capable of oxidizing at least one alcohol function of the saccharide ring to the carboxylic acid function.

Oxydisuccinates and other derivatives of disuccinates, preferably ethylenediamine disuccinate, are further suitable cobuilders. Ethylene diamine N, N'-disuccinate (EDDS) is preferably used in the form of its sodium or magnesium salts. Are further preferred in this Connection also glycerol disuccinate and glycerol trisuccinate. If desired, suitable amounts used are, in particular in formulations containing zeolite and / or silicate, from 3% by weight to 15% by weight.

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

In addition, all compounds that are able to form complexes with alkaline earth metal ions can be used as builders.

Detergents and cleaning agents contain nonionic, anionic, cationic and / or amphoteric surfactants.

All nonionic surfactants known to the person skilled in the art can be used as nonionic surfactants. Washing or cleaning agents particularly preferably contain 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 an average of 1 to 12 moles of ethylene oxide (EO) per mole of alcohol, in which the alcohol radical can be linear or preferably methyl-branched in the 2-position or may contain linear and methyl-branched radicals in the mixture, as are usually present in oxo alcohol radicals. However, alcohol ethoxylates with linear residues of alcohols of native origin with 12 to 18 carbon atoms, for example from coconut, palm, tallow fat or oleyl alcohol, and an average of 2 to 8 moles of EO per mole of alcohol are particularly preferred. The preferred ethoxylated alcohols include, for example, C _12-14 alcohols with 3 EO or 4 EO, C _9-11 alcohol with 7 EO, C _13-15 alcohols with 3 EO, 5 EO, 7 EO or 8 EO, C _12-18 alcohols with 3 EO, 5 EO or 7 EO and mixtures thereof, such as mixtures of C _12-14 alcohol with 3 EO and C _12-18 alcohol with 5 EO. The degrees of ethoxylation given represent statistical mean values which can correspond to an integer or a fractional number for a specific product. Preferred alcohol ethoxylates have a narrow homolog distribution (narrow range ethoxylates, NRE).

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

Another class of preferably used nonionic surfactants, which are used either as the sole nonionic surfactant or in combination with other nonionic surfactants, are alkoxylated, preferably ethoxylated or ethoxylated and propoxylated fatty acid alkyl esters, preferably with 1 to 4 carbon atoms in the alkyl chain.

Nonionic surfactants of the amine oxide type, for example N-cocoalkyl-N, N-dimethyla-minoxide and N-tallow alkyl-N, N-dihydroxyethylamine oxide, and the fatty acid alkanolamides can also be used. The amount of these nonionic surfactants is preferably not more than that of the ethoxylated fatty alcohols, in particular not more than half of them.

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 nachfolgender Acylierung mit einer Fettsäure, einem Fettsäurealkylester oder einem Fettsäurechlorid erhalten werden können. Zur Gruppe der Polyhydroxyfettsäureamide gehören auch Verbindungen der Formel

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 propoxylierte Derivate dieses Restes. [Z] wird vorzugsweise durch reduktive Aminierung eines reduzierten Zuckers erhalten, beispielsweise Glucose, Fructose, Maltose, Lactose, Galactose, Mannose oder Xylose. Die N-Alkoxy- oder N-Aryloxy-substituierten Verbindungen können durch Umsetzung mit Fettsäuremethylestern in Gegenwart eines Alkoxids als Katalysator in die gewünschten Polyhydroxyfettsäureamide überführt werden.Other suitable surfactants are polyhydroxy fatty acid amides of the formula

in which R stands for an aliphatic acyl radical with 6 to 22 carbon atoms, R ¹ for hydrogen, an alkyl or hydroxyalkyl radical with 1 to 4 carbon atoms and [Z] for a linear or branched polyhydroxyalkyl radical with 3 to 10 carbon atoms and 3 to 10 hydroxyl groups. The polyhydroxy fatty acid amides are known substances which can usually be obtained by reductive amination of a reducing sugar with ammonia, an alkylamine or an alkanolamine and subsequent acylation with a fatty acid, a fatty acid alkyl ester or a fatty acid chloride. The group of polyhydroxy fatty acid amides also includes compounds of the formula

in which R represents a linear or branched alkyl or alkenyl radical having 7 to 12 carbon atoms, R ^{1 represents} a linear, branched or cyclic alkyl radical or an aryl radical having 2 to 8 carbon atoms and R ^{2 represents} a linear, branched or cyclic alkyl radical or an aryl radical or an oxy-alkyl radical having 1 to 8 carbon atoms, C _1-4 -alkyl or phenyl radicals being preferred and [Z] being a linear polyhydroxyalkyl radical, the alkyl chain of which has at least two hydroxyl groups is substituted, or alkoxylated, preferably ethoxylated or propoxylated derivatives of this radical. [Z] is preferably obtained by reductive amination of a reduced sugar, for example glucose, fructose, maltose, lactose, galactose, mannose or xylose. The N-alkoxy- or N-aryloxy-substituted compounds can be converted into the desired polyhydroxy fatty acid amides by reaction with fatty acid methyl esters in the presence of an alkoxide as catalyst.

Cleaning agents include 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 nonionic surfactants, or PO / AO / PO nonionic surfactants, especially PO / EO / PO nonionic surfactants are particularly preferred. Such PO / EO / PO nonionic surfactants are characterized by good foam control.

Anionic surfactants used are, for example, those of the sulfonate and sulfate type. Preferred surfactants of the sulfonate type are C _9-13- alkylbenzenesulfonates, olefin sulfonates, ie mixtures of alkene and hydroxyalkanesulfonates, and disulfonates such as are obtained, for example, from C _12-18 monoolefins with a terminal or internal double bond by sulfonating with gaseous sulfur trioxide and subsequent alkaline or acidic hydrolysis of the sulfonation products. Also suitable are alkanesulfonates obtained from C _12-18 alkanes, for example by sulfochlorination or sulfoxidation with subsequent hydrolysis or neutralization. The esters of α-sulfofatty acids (ester sulfonates), for example the α-sulfonated methyl esters of hydrogenated coconut, palm kernel or tallow fatty acids, are also suitable.

Other suitable anionic surfactants are sulfonated fatty acid glycerol esters. Fatty acid glycerol esters are to be understood as meaning the mono-, di- and triesters and their mixtures, as obtained in the production 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. Preferred sulfated fatty acid glycerol esters are the sulfonation products of saturated fatty acids having 6 to 22 carbon atoms, for example caproic acid, caprylic acid, capric acid, myristic acid, lauric acid, palmitic acid, stearic acid or behenic acid.

Alk (en) yl sulfates are the alkali and in particular the sodium salts of the sulfuric acid half esters of C ₁₂ -C ₁₈ fatty alcohols, for example from coconut oil alcohol, tallow fatty alcohol, lauryl, myristyl, cetyl or stearyl alcohol or the C ₁₀ -C ₂₀ oxo alcohols and those half-esters of secondary alcohols of this chain length are preferred. Also preferred are alk (en) yl sulfates of the chain length mentioned, which have a synthetic, straight-chain, petrochemical-based Contain alkyl radicals that have a degradation behavior similar to that of the adequate compounds based on oleochemical raw materials. The C ₁₂ -C ₁₆ alkyl sulfates and C ₁₂ -C ₁₅ alkyl sulfates as well as C ₁₄ -C ₁₅ alkyl sulfates are preferred from the point of view of washing technology.

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

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

Soaps are particularly suitable as further anionic surfactants. Saturated fatty acid soaps are suitable, such as the salts of lauric acid, myristic acid, palmitic acid, stearic acid, hydrogenated erucic acid and behenic acid, and in particular from natural fatty acids, e.g. Coconut, palm kernel or tallow fatty acids, derived soap mixtures.

The anionic surfactants, including the soaps, can be in the form of their sodium, potassium or ammonium salts and also as soluble salts of organic bases, such as mono-, di- or triethanolamine. The anionic surfactants are preferably in the form of their sodium or potassium salts, in particular in the form of the sodium salts.

Instead of the surfactants mentioned or in combination with them, cationic and / or amphoteric surfactants can also be 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.Cationic compounds of the following formulas, for example, can be used as cationic active substances:

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.

Textile softening compounds can be used to care for the textiles and to improve the textile properties, such as a softer "feel (finish) and reduced electrostatic charging (increased wearing comfort). The active ingredients of these formulations are quaternary ammonium compounds with two hydrophobic residues, such as, for example, the disteraryldimethylammonium chloride, which however Because of its insufficient biodegradability, it is increasingly being replaced by quaternary ammonium compounds, which contain ester groups in their hydrophobic residues as predetermined breaking points for biodegradation.

Such "esterquats" with improved biodegradability can be obtained, for example, by esterifying mixtures of methyldiethanolamine and / or triethanolamine with fatty acids and then quaternizing the reaction products with alkylating agents in a manner known per se. Dimethylolethylene urea is also suitable as a finish.

Enzymes can be used to increase the performance of detergents or cleaning agents. These include in particular proteases, amylases, lipases, hemicellulases, cellulases, perhydrolases or oxidoreductases, and preferably their mixtures. In principle, these enzymes are of natural origin; Based on the natural molecules, improved variants are available for use in detergents and cleaning agents, which are accordingly preferred. Washing or cleaning agents preferably contain enzymes in total amounts of 1 x 10 ^-6 wt .-% to 5 wt .-% based on active protein. The protein concentration can be determined using known methods, for example the BCA method or the biuret method.

Among the proteases, those of the subtilisin type are preferred. Examples of this are the subtilisins BPN 'and Carlsberg and their further developed forms, the protease PB92, the subtilisins 147 and 309, the alkaline protease from Bacillus lentus, subtilisin DY and the enzymes thermitase which can no longer be assigned to the subtilisins in the narrower sense, Proteinase K and the proteases TW3 and TW7.

Examples of usable amylases are the α-amylases from Bacillus licheniformis, from B. amyloliquefaciens, from B. stearothermophilus, from Aspergillus niger and A. oryzae, and the further developments of the aforementioned amylases, which have been improved for use in detergents and cleaning agents. Furthermore, the α-amylase from Bacillus sp. A 7-7 (DSM 12368) and the cyclodextrin glucanotransferase (CGTase) from B. agaradherens (DSM 9948).

Lipases or cutinases can be used because of their triglyceride-cleaving activity. These include, for example, the lipases originally obtainable from Humicola lanuginosa (Thermomyces lanuginosus) or developed further therefrom, in particular those with the amino acid exchange D96L. Furthermore, the cutinases, which were originally isolated from Fusarium solani pisi and Humicola insolens , can also be used. Lipases and / or cutinases whose starting enzymes were originally isolated from Pseudomonas mendocina and Fusarium solanii can also be used.

Furthermore, enzymes can be used, which are summarized under the term hemicellulases. These include, for example, mannanases, xanthan lyases, pectin lyases (= pectinases), pectin esterases, pectate lyases, xyloglucanases (= xylanases), pullulanases and β-glucanases.

If desired, oxidoreductases, for example oxidases, oxygenases, catalases, peroxidases, such as halo-, chloro-, bromo-, lignin, glucose or manganese peroxidases, dioxygenases or laccases (phenoloxidases, polyphenoloxidases) can be used to increase the bleaching effect. Advantageously, organic, particularly preferably aromatic, compounds interacting with the enzymes are additionally added in order to increase the activity of the oxidoreductases in question (enhancers) or to ensure the flow of electrons (mediators) in the case of very different redox potentials between the oxidizing enzymes and the soiling.

The enzymes can be used in any form established according to the prior art. These include, for example, the solid preparations obtained by granulation, extrusion or lyophilization or, in particular in the case of liquid or gel form agents, solutions of the enzymes, advantageously as concentrated as possible, low in water and / or with stabilizers. Alternatively, the enzymes can be encapsulated both for the solid and for the liquid administration form, 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 enclosed as in a solidified gel or those of the core-shell type, in which an enzyme-containing core is coated with a protective layer impermeable to water, air and / or chemicals. Additional active ingredients, for example stabilizers, emulsifiers, pigments, bleaching agents or dyes, can additionally be applied in layers. Capsules of this type are applied by methods known per se, for example by shaking or roll granulation or in fluid-bed processes. Such granules are advantageously low in dust, for example by applying polymeric film formers, and are stable on storage due to the coating. Furthermore, it is possible to assemble two or more enzymes together, so that a single granulate has several enzyme activities.

One or more enzymes and / or enzyme preparations, preferably protease preparations and / or amylase preparations, are preferred in amounts from 0.1% by weight to 5% by weight, preferably from 0.2% by weight to 4 , 5 wt .-% and in particular from 0.4 wt .-% to 4 wt .-%, used.

Individual perfume compounds, for example synthetic products of the ester, ether, aldehyde, ketone, alcohol and hydrocarbon type, can be used as perfume oils or fragrances. However, preference is given to using mixtures of different fragrances which together produce an appealing fragrance. Perfume oils of this type can also contain natural fragrance mixtures such as are obtainable from plant sources, for example pine, citrus, jasmine, patchouly, rose or ylang-ylang oil. In order to be perceptible, a fragrance must be volatile, whereby in addition to the nature of the functional groups and the structure of the chemical compound, the molecular weight also plays an important role. Most odoriferous substances have molar masses of up to about 200 g / mol, while molar masses of 300 g / mol and more are an exception. Due to the different volatility of odoriferous substances, the smell of a perfume or fragrance composed of several odoriferous substances changes during evaporation, whereby the odor impressions are expressed in "top note", "heart or middle note" (middle note or body) and "base note" (end note or dry out). Since the smell is largely based on the intensity of the smell, the top note of a perfume or fragrance does not consist solely of volatile compounds, while the base note largely consists of less volatile, ie non-stick fragrances. When composing Perfumes can bind more volatile fragrances to certain fixatives, for example, which prevents them from evaporating too quickly. In the subsequent classification of the fragrances into "more volatile" or "adherent" fragrances, nothing is said about the odor impression and whether the corresponding fragrance is perceived as a top or heart note. The fragrances can be processed directly, but it can also be advantageous to apply the fragrances to carriers which ensure a long-lasting fragrance due to a slower fragrance release. Cyclodextrins, for example, have proven useful as such carrier materials, and the cyclodextrin-perfume complexes can additionally be coated with further auxiliaries.

When choosing the colorant, it must be borne in mind that the colorants can have a high storage stability and insensitivity to light and not too strong an affinity for textile surfaces and especially synthetic fibers. At the same time, it should also be taken into account that colorants can have different stabilities against 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 washing or cleaning agents varies. In the case of readily water-soluble colorants, colorant concentrations in the range from a few 10 ^-2 % by weight to 10 ^-3 % by weight are typically selected. In contrast, in the case of the pigment dyes which are particularly preferred on account of their brilliance but are less readily water-soluble, the suitable concentration of the colorant in washing or cleaning agents is typically a few 10 ^-3 % by weight to 10 ^-4 % by weight. Colorants which can be oxidatively destroyed in the washing process and mixtures thereof with suitable blue dyes, so-called blue toners, are preferred. It has proven to be advantageous to use colorants which are soluble in water or in liquid organic substances at room temperature. For example, anionic colorants, for example anionic nitroso dyes, are suitable.

In addition to the components mentioned so far, the detergents or cleaning agents can contain further ingredients which further improve the application technology and / or aesthetic properties of these agents. Preferred agents contain one or more substances from the group of electrolytes, pH adjusting agents, fluorescent agents, hydrotopes, foam inhibitors, silicone oils, anti-redeposition agents, optical brighteners, graying inhibitors, anti-shrink agents, anti-crease agents, color transfer inhibitors, antimicrobial agents, germicides, anti-fungal agents, antioxidants, antioxidants, antioxidants , Phobing and impregnating agents, swelling and sliding resistant agents as well as UV absorbers.

A wide number of different salts can be used as electrolytes from the group of inorganic salts. 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.

In order to bring the pH value of washing or cleaning agents into the desired range, the use of pH adjusting agents can be indicated. All known acids or alkalis can be used here, provided that their use is not prohibited for application-related or ecological reasons or for reasons of consumer protection. The amount of these adjusting agents usually does not exceed 1% by weight of the total formulation.

Suitable foam inhibitors are soaps, oils, fats, paraffins or silicone oils, which can optionally be applied to carrier materials. Suitable carrier materials are, for example, inorganic salts such as carbonates or sulfates, cellulose derivatives or silicates and mixtures of the aforementioned materials. Agents preferred in the context of the present application contain paraffins, preferably unbranched paraffins (n-paraffins) and / or silicones, preferably linear-polymeric silicones, which are structured according to the scheme (R ₂ SiO) _x and are also referred to as silicone oils. These silicone oils are usually clear, colorless, neutral, odorless, hydrophobic liquids with a molecular weight between 1000 g / mol and 150,000 g / mol and viscosities between 10 mPas and 1,000,000 mPas.

Suitable anti-redeposition agents are, for example, nonionic cellulose ethers such as methyl cellulose and methyl hydroxypropyl cellulose with a proportion of methoxy groups of 15 to 30% by weight and of hydroxypropyl groups of 1 to 15% by weight, in each case based on the nonionic cellulose ether.

The soil repellents are the polymers of phthalic acid and / or terephthalic acid or their derivatives known from the prior art, in particular polymers of ethylene terephthalate and / or polyethylene glycol terephthalate or anionically and / or nonionically modified derivatives thereof. Of these, the sulfonated derivatives of phthalic acid and terephthalic acid polymers are particularly preferred.

Optical brighteners can in particular be added to the detergents in order to eliminate graying and yellowing of the treated textiles. These substances absorb on the fiber and bring about a brightening and fake bleaching effect by converting invisible ultraviolet radiation into visible longer-wave light, whereby the ultraviolet light absorbed from the sunlight is emitted as a slightly bluish fluorescence and pure with the yellow tone of the grayed or yellowed laundry White results. Suitable compounds originate, for example, from the substance classes of 4,4'-diamino-2,2'-stilbenedisulfonic acids (flavonic acids), 4,4'-distyryl-biphenyls, methylumbelliferones, coumarins, dihydroquinolinones, 1,3-diarylpyrazolines, Naphthalic acid imides, benzoxazole, benzisoxazole and benzimidazole systems as well as the pyrene derivatives substituted by heterocycles.

Graying inhibitors have the task of keeping the dirt detached from the fiber suspended in the liquor and thus preventing the dirt from being re-absorbed. 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 of starch or cellulose or salts of acidic sulfuric acid esters of cellulose or starch. Water-soluble polyamides containing acidic groups are also suitable for this purpose. Soluble starch preparations can also be used, for example degraded starch and / or aldehyde starches. Polyvinyl pyrrolidone can also be used. Also usable as graying inhibitors are cellulose ethers such as carboxymethyl cellulose (sodium salt), methyl cellulose, hydroxyalkyl cellulose and mixed ethers such as methyl hydroxyethyl cellulose, methyl hydroxypropyl cellulose, methyl carboxymethyl cellulose and mixtures thereof.

Since textile fabrics, in particular rayon, rayon, cotton and their mixtures, can tend to wrinkle because the individual fibers are sensitive to bending, kinking, pressing and squeezing transversely to the fiber direction, synthetic anti-crease agents can be used. These include, for example, synthetic products based on fatty acids, fatty acid esters, fatty acid amides, alkylol esters, alkylolamides or fatty alcohols, which are mostly reacted with ethylene oxide, or products based on lecithin or modified phosphoric acid esters.

Phobing and impregnation processes are used to finish textiles with substances that prevent dirt from accumulating or make it easier to wash out. Preferred waterproofing and impregnating agents are perfluorinated fatty acids, also in the form of their aluminum and. Zirconium salts, organic silicates, silicones, polyacrylic acid esters with perfluorinated alcohol component or polymerizable compounds coupled with perfluorinated acyl or sulfonyl radical. Antistatic agents can also be included. The dirt-repellent finish with phobing and impregnating agents is often classified as an easy-care finish. The penetration of the impregnating agents in the form of solutions or emulsions of the active substances in question can be facilitated by adding wetting agents which reduce the surface tension. Another area of application for waterproofing and impregnating agents is the water-repellent finishing of textile goods, tents, tarpaulins, leather, etc., which, in contrast to waterproofing, does not close the fabric pores, which means that the fabric remains breathable (hydrophobic). The hydrophobizing agents used for the hydrophobizing coat textiles, leather, paper, wood etc. with a very thin layer of hydrophobic groups, such as longer alkyl chains or siloxane groups. Suitable water repellents are, for example, paraffins, waxes, metal soaps etc. with additions of aluminum or zirconium salts, quaternary ammonium compounds with long-chain alkyl residues, Urea derivatives, fatty acid-modified melamine resins, chromium complex salts, silicones, organic tin compounds and glutardialdehyde as well as perfluorinated compounds. The hydrophobized materials do not feel greasy; nevertheless - similar to greased substances - water drops roll off them without wetting them. For example, 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.

Antimicrobial agents can be used to control microorganisms. Depending on the antimicrobial spectrum and mechanism of action, a distinction is made between bacteriostatics and bactericides, fungistatics and fungicides. Substances from these groups are, for example, benzalkonium chlorides, alkylarlyl sulfonates, halophenols and phenol mercuric acetate, although these compounds can also be dispensed with entirely.

In order to prevent undesirable changes in the detergents and cleaning agents and / or the treated textiles caused by atmospheric oxygen and other oxidative processes, the agents can contain antioxidants. This class of compounds includes, for example, substituted phenols, hydroquinones, pyrocatechols and aromatic amines as well as organic sulfides, polysulfides, dithiocarbamates, phosphites and phosphonates.

Increased comfort can result from the additional use of antistatic agents. Antistatic agents increase the surface conductivity and thus enable the flow of charges that have formed to improve. External antistatic agents are generally substances with at least one hydrophilic molecular ligand and give a more or less hygroscopic film on the surfaces. These mostly surface-active antistatic agents can be divided into nitrogen-containing (amines, amides, quaternary ammonium compounds), phosphorus-containing (phosphoric acid esters) and sulfur-containing (alkyl sulfonates, alkyl sulfates) antistatic agents. Lauryl (or stearyl) dimethylbenzylammonium chlorides are also suitable as antistatic agents for textiles or as an additive to detergents, with an additional finishing effect.

Silicone derivatives can be used in textile detergents to improve the water absorption capacity, the rewettability of the treated textiles and to facilitate ironing of the treated textiles. These additionally improve the rinsing behavior of detergents or cleaning agents due to their foam-inhibiting properties. Preferred silicone derivatives are, for example, polydialkyl or alkylarylsiloxanes in which the alkyl groups have one to five carbon atoms and are completely or partially fluorinated. Preferred silicones are polydimethylsiloxanes, which can optionally be derivatized and are then amino-functional or quaternized or have Si-OH, Si-H and / or Si-Cl bonds. Other preferred silicones are the polyalkylene oxide-modified polysiloxanes, ie polysiloxanes which have, for example, polyethylene glycols, and the polyalkylene oxide-modified dimethylpolysiloxanes.

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

Due to their fiber-caring effect, protein hydrolyzates are other suitable active substances. Protein hydrolyzates are product mixtures that are obtained by acidic, basic or enzymatically catalyzed breakdown of proteins (proteins). Protein hydrolysates of both vegetable and animal origin can be used. Animal protein hydrolyzates are, for example, elastin, collagen, keratin, silk and milk protein protein hydrolyzates, which can also be in the form of salts. Preference is given to using protein hydrolysates of plant origin, for example soy, almond, rice, pea, potato and wheat protein hydrolyzates. Although the use of the protein hydrolysates as such is preferred, amino acid mixtures or individual amino acids, such as arginine, lysine, histidine or pyroglutamic acid, which have otherwise been obtained, can optionally be used in their place. It is also possible to use derivatives of the protein hydrolyzates, for example in the form of their fatty acid condensation products.

Examples Example 1: Synthesis of 2,3-dihydroxy-N, N'-bis (2-methoxyethyl) terephthalamide (S1) a) Preparation of dimethyl 2,3-dihydroxyterephthalate

96% sulfuric acid (3.14 g, 32 mmol) was slowly added dropwise to a suspension of 2,3-dihydroxyterephthalic acid (9.39 g, 45 mmol) in methanol (500 mL) with stirring. The reaction mixture was heated to 65 ° C. and stirred under reflux for 70 h. The reaction solution was then cooled to room temperature and the solvent was removed under reduced pressure. The residue was taken up in aqueous saturated NaHCO ₃ solution (300 mL) and extracted with dichloromethane (3 x 400 mL). The organic phase was dried with magnesium sulfate, filtered and the solvent removed under reduced pressure. Dimethyl 2,3-dihydroxyterephthalate (5.9 g, 26.1 mmol, 58%) was obtained as a beige solid.

b) Preparation of 2,3-dihydroxy-N, N'-bis (2-methoxyethyl) terephthalamide

2,3-Dihydroxyterephthalatesimimylester (0.68 g, 3.0 mmol) from step a) was suspended in 2-methoxyethylamine (5.46 g, 72.0 mmol) and the reaction solution was in the microwave (PowerMax®, T = 100 ° C, t = 4 h , Power = 300 W) reacted. Excess 2-methoxyethylamine was then removed under reduced pressure (2 mbar at 60 ° C). The residue was recrystallized from ethyl acetate (50 mL). The ethyl acetate was decanted off; the precipitated solid was washed with a little cold ethyl acetate and dried under reduced pressure. 2,3-Dihydroxy-N, N'-bis (2-methoxyethyl) terephthalamide S1 was obtained as a beige solid (0.801 g, 2.56 mmol, 85%).

Example 2: Synthesis of 2,3-dihydroxy-N, N'-diethylterephthalamide (S2)

2,3-Dihydroxyterephthalic acid methyl ester (0.90 g, 4.0 mmol) from Example 1 step a) was suspended in ethylamine (44 mL, 88 mmol, 2M in THF) and the reaction mixture was heated in a pressure reactor (T = 100 ° C. , t = 24 h, pressure: 2.6 bar, stirrer: 250 rpm). The excess ethylamine and tetrahydrofuran were decanted off and the beige solid residue was dissolved in methanol (70 ml) in the reactor. The methanol was removed under reduced pressure and the residue was recrystallized from ethyl acetate (25 mL). The ethyl acetate was decanted off; the precipitated solid was washed with a little cold ethyl acetate and dried under reduced pressure. 2,3-Dihydroxy-N, N'-diethyl terephthalamide S2 was obtained as a beige solid (0.207 g, 0.82 mmol, 21%).

Example 3: Synthesis of the comparative substance 2,3-dihydroxy-N- (2-methoxyethyl) benzamide (V1)

2,3-Dihydroxybenzoic acid methyl ester (0.77 g, 4.5 mmol) was dissolved in 2-methoxyethylamine (4.10 g, 54 mmol) and the reaction solution was reacted in the microwave (PowerMax®, T = 100 ° C., t = 4 h, Power = 300 W). Excess 2-methoxyethylamine was then removed under reduced pressure (2 mbar at 60 ° C). The residue was purified by column chromatography (ethyl acetate); 2,3-dihydroxy-N- (2-methoxyethyl) benzamide V1 (0.91 g, 4.31 mmol, 96%) was obtained.

Example 4: Synthesis of the reference substance 2,3-dihydroxy-N-ethylbenzamide (V2)

2,3-Dihydroxybenzoic acid methyl ester (1.50 g, 8.74 mmol) was suspended in ethylamine (55.6 mL, 110.12 mmol, 2M in THF) and the reaction mixture was heated in a pressure reactor (T = 100 ° C., t = 4 h, pressure: 2.5 bar, stirrer: 250 rpm). The reaction solution was concentrated under reduced pressure. The slightly viscous residue was taken up in ethyl acetate (50 ml) and washed with 1 M HCl (100 ml); after drying with magnesium sulfate and filtration, the solvent was removed from the organic phase under reduced pressure. The crude product was purified by column chromatography (CH ₂ Cl ₂ / methanol 9: 1). 2,3-Dihydroxy-N-ethylbenzamide V2 was obtained as a brown, viscous residue (0.81 g, 4.47 mmol, 51%).

Example 5: Cleaning performance

Washing tests were carried out at 40 ° C. as a triple determination on standardized soiling on cotton given in Table 1, using a bleach-free aqueous liquid detergent (containing 5.5% by weight of 7-fold ethoxylated C _12/14 fatty alcohol, 5. 3% by weight sodium C _9-13 alkylbenzenesulfonate, 4.9% by weight sodium C _12/14 fatty alcohol ether sulfate with 2 EO, 1.8% by weight citric acid, 3% by weight C _{12- 18} -Fatty acid, 0.1 wt .-% diethylenetriaminepenta (methylenephosphonic acid) -hepta sodium salt, 1.3 wt .-% NaOH, 3.6 wt .-% ethanol / glycerol) used with pH 8.5 and thus used wash liquors , consisting of 69.3 g of the liquid detergent or 69.3 g of the liquid detergent and 1.39 g of one of the compounds listed in Table 1 from Examples 1 to 4 in 17 l of water at 16 ° dH. The evaluation was carried out by measuring the color distance in accordance with the L * a * b * values and the Y values calculated therefrom as a measure of the brightness. The following table shows the dY values which resulted from the difference Y (after washing) - Y (before washing). Table 1: dY values Soiling / connection - S1 S2 V1 V2 red wine 25.1 38.8 37.5 27.9 28.9 Red grape 21.6 34.8 37.2 23.4 24.4 bilberry 22.2 36.3 37.3 26.7 23.5 cherry 16.8 36.1 39.6 18th 21.1 Blackcurrant 16.3 27.3 28.6 15.9 15.7

The dY values when using the substances essential to the invention were significantly greater than those which result from using only the liquid detergent or the comparison substances, which corresponds to a higher degree of whiteness and thus improved stain removal.

Claims (10)

1. A use of compounds of general formula (I),

   

   in which R¹ and R² independently of one another represent NR³R⁴ or OR⁵ and R³, R⁴ and R⁵ independently of one another represent H or a cyclic or acyclic, straight-chain or branched-chain, aliphatic or aromatic hydrocarbon functional group having 1 to 20 carbon atoms, the backbone of which may be interrupted by one or more non-adjacent heteroatoms, in particular selected from O and/or N, and/or which may be substituted by OH groups or NH₂ groups on C atoms not bonded to heteroatoms, in washing or cleaning agents in order to improve the washing or cleaning performance against bleachable stains.
2. The use according to claim 1, characterized in that the stains contain polymerizable substances, selected from polyphenolic dyes, in particular flavonoids, more particularly from dyes from the class of anthocyanidins or anthocyanins or oligomers of said compounds.
3. The use according to claim 1 or 2, characterized in that the improved washing or cleaning performance consists in improved removal of green, yellow, red, blue, violet, lilac, brown, purple or pink stains, in particular marks caused by grass, fruits or vegetables, in particular stains caused by food products, such as spices, sauces, chutneys, curries, purees and jams, or beverages, such as coffee, tea, wines and juices, which contain corresponding green, yellow, red, violet, lilac, brown, purple, pink, and/or blue dyes.
4. The use according to one of claims 1 to 3, characterized in that the stains are selected from stains caused by cherries, morellos, grapes, apples, pomegranates, chokeberries, plums, sea buckthorns, açai berries, kiwis, mangoes, grass or berries, in particular caused by redcurrants, blackcurrants, elderberries, blackberries, raspberries, blueberries, lingonberries, cranberries, strawberries or bilberries, or by coffee, tea, red cabbage, blood orange, eggplant, tomato, carrot, beetroot, spinach, bell pepper, red or blue potato or red onion.
5. The use according to one of claims 1 to 4, characterized in that, in the compounds of general formula (I), R¹ and R² are the same.
6. The use according to one of claims 1 to 5, characterized in that, in the compounds of general formula (I), R³ is H.
7. The use according to one of claims 1 to 5, characterized in that, in the compounds of general formula (I), R⁴ and R⁵ are independently of one another alkyl groups such as methyl, ethyl, n-propyl or i-propyl, alkoxyalkyl groups such as methoxyethyl, methoxypropyl, (2-methoxy)ethoxyethyl, ethoxyethyl, ethoxypropyl or (2-ethoxy)ethoxyethyl, hydroxyalkyl groups such as hydroxyethyl, hydroxypropyl, 2-hydroxypropyl, 1,2-dihydroxypropyl, 2-hydroxyethoxyethyl, (N-hydroxyethyl)aminoethyl, (N-methoxyethyl)aminoethyl or (N-ethoxyethyl)aminoethyl, or aromatic groups such as phenyl or benzyl.
8. Washing or cleaning agent containing nonionic, anionic, cationic and/or amphoteric surfactants and 0.001 wt.% to 20 wt.%, in particular 0.01 wt.% to 10 wt.% of compound of general formula (I),

   

   in which R¹ and R² independently of one another represent NR³R⁴ or OR⁵ and R³, R⁴ and R⁵ independently of one another represent H or a cyclic or acyclic, straight-chain or branched-chain, aliphatic or aromatic hydrocarbon functional group having 1 to 20 carbon atoms, the backbone of which may be interrupted by one or more non-adjacent heteroatoms, in particular selected from O and/or N, and/or which may be substituted by OH groups or NH₂ groups on C atoms not bonded to heteroatoms.
9. The agent according to claim 8, characterized in that it does not contain bleaching agents in the narrower sense, i.e. hypochlorites, hydrogen peroxide or substances that yield hydrogen peroxide.
10. The agent according to claim 8 or 9, characterized in that it is a liquid textile-washing agent or a powdered or liquid color washing agent, i.e. a textile-washing agent for dyed textiles.