ANTHRACENE-9,10-DIONE DERIVATIVES AS PHOTOACTIVATORS IN DETERGENTS

Description

[0001] The present invention relates to the use of alkyloxy-substituted anthracene-9,10-diones as photobleaching agents for removing soils from textile materials, and to washing compositions containing such photobleaching agents, as well as to a process for removing soils from textile materials using alkyloxy-substituted anthracene-9,10-diones in an aqueous washing liquid under light irradiation.

[0002] In addition to removing odors and, if necessary, scenting the textiles, the primary purpose of textile washing is usually to remove a wide variety of soiling. This cleaning effect is supported by the use of bleaching agents, surfactants, and builders in the wash liquor, with the bleaching agent playing a significant role in removing colored soiling in particular. In addition to reductive bleaching, which plays only a minor role, peroxygen compounds are generally used as bleaching agents. Their oxidative bleaching power is conventionally enhanced by so-called bleach activators, which, for example, form percarboxylic acids such as peracetic acid through perhydrolysis of carboxylic acid derivatives such as TAED. These acids have a higher oxidative capacity than the original peroxygen compound. A variety of metal complexes are also capable of enhancing the bleaching power of peroxygen compounds.

[0003] Alternatively, it has been proposed to form bleach-active species during the washing process by irradiating compounds that, upon irradiation, enter photoexcited states that are more reactive than the ground state. For example, it is known from WO 98 / 32826 A1 and the prior art cited therein that certain water-soluble phthalocyanine, naphthocyanine, and metallocyanine compounds can be used as photobleaching agents.

[0004] WO 2004 / 072217 A1 discloses alkyl-substituted anthraquinones as photobleaching agents in textile cleaning.

[0005] A disadvantage of some such photobleaching agents, which are also synonymously referred to as photoactivators, is the requirement of exposure to high-energy electromagnetic radiation such as UV radiation in order for the bleaching-active species to form.

[0006] Surprisingly, it was found that certain anthracene-9,10-dione derivatives are capable of this when irradiated with visible light.

[0007] A first aspect of the invention is the use of alkyloxy-substituted anthracene-9,10-diones of the general formula (I), in which R 1< and R 2< independently of one another represent H, SO 3 -< M +< or an optionally substituted linear or branched alkyl radical having 1 to 20 C atoms, preferably 8 to 16 C atoms, with the proviso that at least one of the radicals R 1< or R 2< is an optionally substituted linear or branched alkyl radical having 1 to 20 C atoms, preferably 8 to 6 C atoms, X represents H or SO 3 -< M +< and M +< represents a proton, an alkali metal ion or an ammonium ion or mixtures thereof, as a photobleaching agent for removing soiling from textile materials.

[0008] The soils are preferably those that contain polymerizable substances, in particular polymerizable dyes, where the polymerizable dyes are preferably polyphenolic dyes, in particular flavonoids, especially anthocyanidins or anthocyanins or oligomers of these compounds. The soils are also preferably those that contain carotenoids and / or chlorophylls, i.e. dyes based on the porphyrin ring, as dyes. In addition to the removal of soils in the colors green, yellow, red or blue, the removal of soils in intermediate colors, in particular violet, purple, brown, purple or pink, and also of soils that have a green, yellow, red, violet, purple, brown, purple, pink or blue tint without themselves consisting essentially entirely of this color.The colors mentioned can, in particular, also be light or dark. These preferably refer to soiling, especially stains from grass, fruit, or vegetables, and especially also to soiling from food products such as spices, sauces, chutneys, curries, purees, and jams, or beverages such as coffee, tea, wine, and juices containing corresponding green, yellow, red, violet, purple, brown, purple, pink, and / or blue dyes.The soiling to be removed according to the invention can be caused in particular by cherries, morello cherries, grapes, apples, pomegranates, chokeberries, plums, sea buckthorn, açai, kiwi, mangoes, grass, or berries, especially by red or black currants, elderberries, blackberries, raspberries, blueberries, cranberries, blackberries, strawberries or blueberries, by coffee, tea, red cabbage, blood orange, eggplant, tomato, carrot, beetroot, spinach, peppers, red-fleshed or blue-fleshed potatoes, or red onions.

[0009] If in the compounds of the general formula (I) a radical R 1< and / or R 2< is substituted, it preferably carries substituents selected from -OH, -COO -< M +< , -SO 3 -< M +< , -OSO 3 -< M +< , -N +< (CH 2 CH 3 ) 3 Hal -< and mixtures thereof, where Hal -< stands for Cl -< , Br -< , J -< , F -< and mixtures thereof and M +< and Hal -< can also be absent if -COO -< , -SO 3 -< , -OSO 3 -< and -N +< (CH 2 CH 3 ) 3 are present in a charge-balancing amount; it is also preferred if at least 1 substituent is terminal.

[0010] The above-mentioned alkyloxy-substituted anthracene-9,10-diones can be used according to the invention as such or in the form of detergents containing them and optionally other conventional detergent ingredients.

[0011] A second aspect of the invention is therefore a detergent comprising a nonionic, anionic, cationic and / or amphoteric surfactant and an alkyloxy-substituted anthracene-9,10-dione as defined above. The detergent preferably contains 0.00001% to 1% by weight, in particular 0.001% to 0.1% by weight, of alkyloxy-substituted anthracene-9,10-dione.

[0012] A further subject matter is a process for removing soiling from textile materials using the above-defined alkyloxy-substituted anthracene-9,10-diones in an aqueous washing liquid in which the soiled textile materials requiring washing are located, by irradiating the aqueous washing liquid with visible light.

[0013] Visible light is understood here to mean electromagnetic radiation visible to the human eye, the wavelength of which is in the range from 400 nm to 780 nm. Within the scope of the present invention, light in the wavelength range from 400 nm to 600 nm, in particular from 450 nm to 525 nm, is preferably used. This can be daylight or sunlight, or artificially generated light, the latter preferably being generated with the aid of an LED light source. Within the scope of the method according to the invention, the light acts on the washing liquid in which the soiled textile materials requiring washing and the alkyloxy-substituted anthracene-9,10-dione are present. This can be done, for example, by carrying out the washing process manually in an open container whose opening is exposed to natural daylight or sunlight.The use of a conventional washing machine is also possible if it has a so-called porthole through which light penetrates the interior of the machine and the washing liquid contained therein. The use of alternative light sources, such as LEDs, is also possible. When using a washing machine, the light source is preferably arranged inside the machine in such a way that it illuminates the washing liquid at least temporarily, for example, when it is being pumped around. With the latter variant, it is also possible to operate the light source not for the entire washing process, but only for part of it, so that oxidative bleaching only takes place during this partial period.

[0014] Within the scope of the use according to the invention and the process according to the invention, it is preferred to use the said alkyloxy-substituted anthracene-9,10-dione in concentrations in the range from 0.0001 mmol / l to 0.1 mmol / l, in particular from 0.001 mmol / l to 0.01 mmol / l in aqueous washing liquors.

[0015] The detergent can be in any dosage form established according to the state of the art and / or any suitable. These include, for example, solid, powder, liquid, gel, or paste-like dosage forms, optionally also consisting of several phases; furthermore, they include, for example, extrudates, granules, tablets, or pouches, both in bulk and packaged in portions. In a preferred embodiment, the detergent is liquid.

[0016] The process according to the invention is carried out and the use according to the invention is carried out in a respective preferred embodiment by using a washing and cleaning agent according to the invention that does not contain bleaching agents. This means that the agent does not contain bleaching agents in the narrower sense, i.e., hypochlorites or peroxygen compounds. In a particularly preferred embodiment, the washing agent is a liquid textile detergent.

[0017] Detergents according to the invention can contain, in addition to the alkyloxy-substituted anthracene-9,10-dione and surfactant essential to the invention, other usual constituents of textile detergents, in particular selected from the group of builders, polymers, enzymes, fragrances and perfume carriers.

[0018] The builders include in particular zeolites, silicates, carbonates, organic cobuilders and - provided there are no ecological concerns about their use - also phosphates.

[0019] The finely crystalline, synthetic zeolite containing bound water is preferably zeolite A and / or zeolite P. Zeolite MAP ®< (a commercial product from Crosfield), for example, can be used as zeolite P. However, zeolite X and mixtures of zeolite A, X and / or P are also suitable. A co-crystallizate of zeolite X and zeolite A (approx. 80% by weight of zeolite X), which can be described 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, is also commercially available and can be used in the context of the present invention. The zeolite can be used both as a builder in a granular compound and as a kind of "dusting" of a granular mixture, preferably a mixture to be pressed, whereby both methods are usually used to incorporate 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 wt.% to 22 wt.%, in particular 20 wt.% to 22 wt.% of bound water.

[0020] It is also possible to use crystalline layered silicates of the general formula NaMSi x O2 x+1 y H 2 O, in which M is sodium or hydrogen, x is a number from 1.9 to 22, preferably from 1.9 to 4, with particularly preferred values ​​for x being 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 O2 x+1 y H 2 O are marketed, 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 · x H 2 O, Kenyaite), Na-SKS-2 (Na 2 Si 14 O 29 · x H 2 O, magadiite), Na-SKS-3 (Na 2 Si 8 O 17 · x H 2 O) or Na-SKS-4 (Na2Si4O9 · x H2O, Makatite).

[0021] Preference is given to crystalline layered silicates of the formula NaMSi x O2 x+1 y H 2 O, in which x is 2. In particular, both ß- and δ-sodium disilicates Na 2 Si 2 O 5 y H 2 O and also, above all, Na-SKS-5 (α-Na 2 Si 2 O 5 ), Na-SKS-7 (ß-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, kanemite), 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 preferably contain a weight fraction of the crystalline layered silicate of the formula NaMSi x O2 x+1 · y H 2 O of 0.1 wt.% to 20 wt.%, preferably of 0.2 wt.% to 15 wt.% and in particular of 0.4 wt.% to 10 wt.%.

[0022] Amorphous sodium silicates with a Na2O:SiO2 modulus of 1:2 to 1:3.3, preferably 1:2 to 1:2.8, and especially 1:2 to 1:2.6, can also be used. These preferably have delayed dissolution and secondary washing properties. The delayed dissolution compared to conventional amorphous sodium silicates can be caused in various ways, for example, by surface treatment, compounding, compaction / densification, or overdrying. The term "amorphous" refers to the fact that the silicates do not produce sharp X-ray reflections in X-ray diffraction experiments, as is typical for crystalline substances, but at most produce one or more maxima of the scattered X-ray radiation, which have a width of several degrees of the diffraction angle.

[0023] Alternatively, or in combination with the aforementioned amorphous sodium silicates, X-ray amorphous silicates can be used. Their silicate particles produce blurred or even sharp diffraction maxima in electron diffraction experiments. This can be interpreted as meaning that the products exhibit microcrystalline regions ranging in size from tens to several hundred nm, with values ​​up to a maximum of 50 nm and especially up to a maximum of 20 nm being preferred. Such X-ray amorphous silicates also exhibit a dissolution delay compared to conventional water glasses. Particularly preferred are densified / compacted amorphous silicates, compounded amorphous silicates, and overdried X-ray amorphous silicates.

[0024] These silicate(s), preferably alkali silicates, particularly preferably crystalline or amorphous alkali disilicates, are, when present, contained in detergents in amounts of from 3% by weight to 60% by weight, preferably from 8% by weight to 50% by weight and in particular from 20% by weight to 40% by weight.

[0025] The use of commonly known phosphates as builder substances is also possible, provided that such use is not to be avoided for ecological reasons. Of the numerous commercially available phosphates, alkali metal phosphates, with particular preference for pentasodium and pentapotassium triphosphate (sodium and potassium tripolyphosphate), are the most important in the detergent and cleaning agent industry. Alkali metal phosphate is the collective name for the alkali metal (particularly sodium and potassium) salts of the various phosphoric acids, which include metaphosphoric acids (HPO3)n and orthophosphoric acid H3PO4, as well as higher molecular weight representatives. Phosphates combine several advantages: They act as alkali carriers, prevent limescale deposits on machine parts and limescale incrustations in fabrics, and also contribute to cleaning performance.Particularly important phosphates from an industrial perspective 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). Sodium potassium tripolyphosphates are also preferred. If phosphates are used in detergents, preferred detergents contain these phosphate(s), preferably alkali metal phosphate(s), particularly preferably pentasodium or pentapotassium triphosphate (sodium or potassium tripolyphosphate), in amounts of 5% to 80% by weight, preferably 15% to 75% by weight, and in particular 20% to 70% by weight.

[0026] Alkali carriers can also be used. Examples of alkali carriers include alkali metal hydroxides, alkali metal carbonates, alkali metal bicarbonates, alkali metal sesquicarbonates, the aforementioned alkali silicates, alkali metasilicates, and mixtures of the aforementioned substances, with preference being given to using alkali carbonates, in particular sodium carbonate, sodium bicarbonate or sodium sesquicarbonate. A builder system comprising a mixture of tripolyphosphate and sodium carbonate can be particularly preferred. Due to their low chemical compatibility with the other ingredients of detergents compared with other builder substances, 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. Particular preference is given to agents which, based on their total weight, contain less than 0.5% by weight.-% and in particular no alkali metal hydroxides. Preference is given to using carbonate(s) and / or bicarbonate(s), preferably alkali metal carbonate(s), particularly preferably sodium carbonate, in amounts of 2 wt.% to 50 wt.%, preferably 5 wt.% to 40 wt.%, and in particular 7.5 wt.% to 30 wt.%.

[0027] Organic builders include, in particular, polycarboxylates / polycarboxylic acids, polymeric polycarboxylates, aspartic acid, polyacetals, dextrins, and phosphonates. Examples of suitable builders are polycarboxylic acids in the form of the free acid and / or their sodium salts, whereby polycarboxylic acids are understood to be carboxylic acids that carry more than one acid function. These include, for example, citric acid, adipic acid, succinic acid, glutaric acid, malic acid, tartaric acid, maleic acid, fumaric acid, sugar acids, aminocarboxylic acids, nitrilotriacetic acid (NTA), provided such use is not objectionable on ecological grounds, and mixtures thereof. In addition to their builder effect, the free acids typically also possess the property of an acidifying component and thus also serve to adjust a lower and milder pH value of detergents.Particularly suitable builders are citric acid, succinic acid, glutaric acid, adipic acid, gluconic acid, and any mixtures thereof. Polymeric polycarboxylates are also suitable, 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. Polyacrylates, which preferably have a molecular weight of 2,000 g / mol to 20,000 g / mol, are particularly suitable. Due to their superior solubility, the short-chain polyacrylates, which have molecular weights of 2,000 g / mol to 10,000 g / mol, and particularly preferably of 3,000 g / mol to 5,000 g / mol, may be preferred from this group. Copolymeric polycarboxylates are also suitable, 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 containing 50 wt.-% to 90 wt.% acrylic acid and 50 wt.% to 10 wt.% maleic acid. Their relative molecular mass, based on free acids, is generally 2000 g / mol to 70 000 g / mol, preferably 20 000 g / mol to 50 000 g / mol and in particular 30 000 g / mol to 40 000 g / mol. To improve water solubility, the polymers can also contain allylsulfonic acids, such as allyloxybenzenesulfonic acid and methallylsulfonic acid, as monomer. The (co)polymeric polycarboxylates can be used as a solid or in aqueous solution. The content of (co)polymeric polycarboxylates in detergents is preferably 0.5 wt.% to 20 wt.% and in particular 3 wt.% to 10 wt.%.

[0028] Biodegradable polymers composed of more than two different monomer units are also particularly preferred, for example those containing, as monomers, salts of acrylic acid and maleic acid, as well as vinyl alcohol or vinyl alcohol derivatives, or those containing, as monomers, salts of acrylic acid and 2-alkylallylsulfonic acid, as well as sugar derivatives. Further preferred copolymers are those containing, as monomers, acrolein and acrylic acid / acrylic acid salts, or acrolein and vinyl acetate. Likewise, further preferred builder substances include polymeric aminodicarboxylic acids, their salts, or their precursors. Polyaspartic acids and / or their salts are particularly preferred.

[0029] Phosphonates represent another class of substances with builder properties. 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 primarily as the sodium salt, with the disodium salt being neutral and the tetrasodium salt being alkaline. Suitable aminoalkanephosphonic acids include, in particular, ethylenediaminetetramethylenephosphonic acid (EDTMP), diethylenetriaminepentamethylenephosphonic acid (DTPMP), and their higher homologues. They are used primarily in the form of the neutral sodium salts, for example, the hexasodium salt of EDTMP or the hepta- and octa-sodium salt of DTPMP. Mixtures of the aforementioned phosphonates can also be used as organic builders. Aminoalkanephosphonates, in particular, also possess a pronounced heavy metal binding capacity.

[0030] Other suitable builder substances are polyacetals, which can be obtained by reacting dialdehydes with polyolcarboxylic acids containing 5 to 7 carbon atoms and at least 3 hydroxyl groups. Preferred polyacetals are obtained from dialdehydes such as glyoxal, glutaraldehyde, terephthalaldehyde, and mixtures thereof, and from polyolcarboxylic acids such as gluconic acid and / or glucoheptonic acid.

[0031] Other suitable organic builders 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 conventional processes, for example, acid- or enzyme-catalyzed processes. These are preferably hydrolysis products with average molecular weights in the range from 400 g / mol to 500,000 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, where DE is a common measure of the reducing effect of a polysaccharide compared to dextrose, which has a DE of 100. 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 molecular weights in the range of 2000 g / mol to 30000 g / mol are suitable.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.

[0032] Oxydisuccinates and other derivatives of disuccinates, preferably ethylenediamine disuccinate, are also suitable cobuilders. Ethylenediamine N,N'-disuccinate (EDDS) is preferably used in the form of its sodium or magnesium salts. Glycerol disuccinates and glycerol trisuccinates are also preferred in this context. Suitable amounts used, if desired, are between 3% and 15% by weight, particularly in zeolite- and / or silicate-containing formulations.

[0033] Other useful organic cobuilders are, for example, acetylated hydroxycarboxylic acids or their salts, which may optionally also be present in lactone form and which contain at least 4 carbon atoms and at least one hydroxy group and a maximum of two acid groups.

[0034] In addition, all compounds that are able to form complexes with alkaline earth ions can be used as builders.

[0035] Detergents and cleaning agents according to the invention must contain nonionic, anionic, cationic and / or amphoteric surfactants. A detergent according to the invention preferably contains nonionic and / or anionic surfactant.

[0036] All nonionic surfactants known to those skilled in the art can be used as nonionic surfactants. Detergents particularly preferably contain nonionic surfactants from the group of alkoxylated alcohols. The nonionic surfactants used are preferably alkoxylated, advantageously ethoxylated, in particular primary alcohols with preferably 8 to 18 C atoms and an average of 1 to 12 mol 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 can contain linear and methyl-branched radicals in a mixture, as are usually found in oxo alcohol radicals. In particular, however, alcohol ethoxylates with linear radicals from alcohols of native origin with 12 to 18 C atoms, e.g., from coconut, palm, tallow, or oleyl alcohol, and an average of 2 to 8 mol of EO per mole of alcohol are preferred.Preferred ethoxylated alcohols include, for example, C12-14 alcohols with 3 EO or 4 EO, C9-11 alcohols with 7 EO, C13-15 alcohols with 3 EO, 5 EO, 7 EO, or 8 EO, C12-18 alcohols with 3 EO, 5 EO, or 7 EO, and mixtures thereof, such as mixtures of C12-14 alcohols with 3 EO and C12-18 alcohols with 5 EO. The stated degrees of ethoxylation represent statistical averages, which for a specific product can correspond to a whole or fractional number. Preferred alcohol ethoxylates have a narrow homolog distribution (narrow range ethoxylates, NRE).

[0037] Alternatively or in addition to these nonionic surfactants, fatty alcohols with more than 12 EO can also be used. Examples of these are tallow fatty alcohol with 14 EO, 25 EO, 30 EO, or 40 EO. 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 2-methyl-branched, aliphatic radical having 8 to 22, preferably 12 to 18, carbon atoms, and G is the symbol representing a glycose unit with 5 or 6 carbon atoms, preferably glucose. The degree of oligomerization x, which indicates the distribution of monoglycosides and oligoglycosides, is any number between 1 and 10; preferably, x is between 1.2 and 1.4.

[0038] 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.

[0039] Nonionic surfactants of the amine oxide type, for example N-cocoalkyl-N,N-dimethylamine oxide and N-tallowalkyl-N,N-dihydroxyethylamine oxide, and fatty acid alkanolamides can also be used. The amount of these nonionic surfactants is preferably no more than that of the ethoxylated fatty alcohols, in particular no more than half that amount.

[0040] Other suitable surfactants are polyhydroxy fatty acid amides of the formula, in which R represents an aliphatic acyl radical having 6 to 22 carbon atoms, R 1< represents hydrogen, an alkyl or hydroxyalkyl radical having 1 to 4 carbon atoms, and [Z] represents a linear or branched polyhydroxyalkyl radical having 3 to 10 carbon atoms and 3 to 10 hydroxyl groups. Polyhydroxy fatty acid amides are known substances that can usually be obtained by reductive amination of a reducing sugar with ammonia, an alkylamine, or an alkanolamine, followed by 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 oxyalkyl radical having 1 to 8 carbon atoms, with C 1-4 alkyl or phenyl radicals being preferred and [Z] represents a linear polyhydroxyalkyl radical whose alkyl chain is substituted by at least two hydroxyl groups, 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 a catalyst.

[0041] In cleaning agents, non-ionic surfactants from the group of alkoxylated alcohols, particularly preferably from the group of mixed alkoxylated alcohols and especially from the group of EO / AO / EO non-ionic surfactants, or PO / AO / PO non-ionic surfactants, especially PO / EO / PO non-ionic surfactants, are particularly preferred. Such PO / EO / PO non-ionic surfactants are characterized by good foam control.

[0042] Examples of anionic surfactants used include sulfonates and sulfates. Sulfonate-type surfactants that are preferred are C9-13 alkylbenzenesulfonates, olefinsulfonates, i.e. mixtures of alkene and hydroxyalkanesulfonates, and disulfonates, such as those obtained, for example, from C12-18 monoolefins with a terminal or internal double bond by sulfonation with gaseous sulfur trioxide and subsequent alkaline or acidic hydrolysis of the sulfonation products. Also suitable are alkanesulfonates obtained from C12-18 alkanes, for example, by sulfochlorination or sulfoxidation with subsequent hydrolysis or neutralization. Esters of α-sulfofatty acids (estersulfonates), e.g., the α-sulfonated methyl esters of hydrogenated coconut, palm kernel, or tallow fatty acids, are also suitable.

[0043] Other suitable anionic surfactants are sulfated fatty acid glycerol esters. Fatty acid glycerol esters are understood to be the mono-, di-, and triesters, as well as mixtures thereof, as obtained by esterification of a monoglycerol with 1 to 3 mol of fatty acid or by transesterification of triglycerides with 0.3 to 2 mol of glycerol. Preferred sulfated fatty acid glycerol esters are the sulfonation products of saturated fatty acids with 6 to 22 carbon atoms, for example, caproic acid, caprylic acid, capric acid, myristic acid, lauric acid, palmitic acid, stearic acid, or behenic acid.

[0044] Preferred alk(en)yl sulfates are the alkali metal salts, especially the sodium salts, of the sulfuric acid half-esters of C 12 -C 18 fatty alcohols, for example, coconut fatty alcohol, tallow fatty alcohol, lauryl, myristyl, cetyl, or stearyl alcohol, or of C 10 -C 20 oxo alcohols, and those half-esters of secondary alcohols with these chain lengths. Also preferred are alk(en)yl sulfates of the stated chain length that contain a synthetic, petrochemically produced straight-chain alkyl radical, which exhibit degradation behavior similar to that of equivalent compounds based on oleochemical raw materials. For washing purposes, C 12 -C 16 alkyl sulfates and C 12 -C 15 alkyl sulfates, as well as C 14 -C 15 alkyl sulfates, are preferred.

[0045] Sulfuric acid monoesters of 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 also suitable. Due to their high foaming behavior, they are used in cleaning agents only in relatively small amounts, for example, in amounts of 1 wt.% to 5 wt.%.

[0046] Other suitable anionic surfactants include the salts of alkyl sulfosuccinic acid, also known as sulfosuccinates or sulfosuccinic acid esters, 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 derived from ethoxylated fatty alcohols, which, considered individually, are nonionic surfactants. 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, preferably with 8 to 18 carbon atoms in the alk(en)yl chain, or salts thereof.

[0047] Other anionic surfactants that may be considered include soaps. Suitable examples include saturated fatty acid soaps, such as the salts of lauric acid, myristic acid, palmitic acid, stearic acid, hydrogenated erucic acid, and behenic acid, as well as soap mixtures derived from natural fatty acids, such as coconut, palm kernel, or tallow fatty acids.

[0048] The anionic surfactants, including soaps, can be present in the form of their sodium, potassium, or ammonium salts, as well as soluble salts of organic bases, such as mono-, di-, or triethanolamine. The anionic surfactants are preferably present in the form of their sodium or potassium salts, especially in the form of the sodium salts.

[0049] Instead of the surfactants mentioned or in combination with them, cationic and / or amphoteric surfactants can also be used.

[0050] Cationic compounds of the following formulas can be used as cationic active substances: wherein each group R 1< is independently selected from C 1-6 alkyl, alkenyl or hydroxyalkyl groups; each group R 2< 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.

[0051] Fabric softening compounds can be used to care for textiles and improve their properties, such as a softer feel (softening) and reduced electrostatic charge (increased comfort). The active ingredients in these formulations are quaternary ammonium compounds with two hydrophobic residues, such as disteraryldimethylammonium chloride. However, due to its insufficient biodegradability, this compound is increasingly being replaced by quaternary ammonium compounds that contain ester groups in their hydrophobic residues as predetermined breaking points for biodegradation.

[0052] Such "esterquats" with improved biodegradability can be obtained, for example, by esterifying mixtures of methyldiethanolamine and / or triethanolamine with fatty acids and subsequently quaternizing the reaction products with alkylating agents in a conventional manner. Dimethylolethyleneurea is also suitable as a finish.

[0053] Enzymes can be used to enhance the performance of detergents. These include, in particular, proteases, amylases, lipases, hemicellulases, cellulases, perhydrolases, or oxidoreductases, and preferably mixtures thereof. These enzymes are essentially of natural origin; based on the natural molecules, improved variants are available for use in detergents and cleaning agents and are therefore used preferentially. Detergents 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.

[0054] Among the proteases, those of the subtilisin type are preferred. Examples include subtilisins BPN' and Carlsberg, as well as their more advanced forms, protease PB92, subtilisins 147 and 309, alkaline protease from Bacillus lentus, subtilisin DY, and the enzymes thermitase, proteinase K, and proteases TW3 and TW7, which are classified as subtilases but no longer as subtilisins in the narrower sense.

[0055] Examples of usable amylases include the α-amylases from Bacillus licheniformis, B. amyloliquefaciens, B. stearothermophilus, Aspergillus niger, and A. oryzae, as well as the improved versions of the aforementioned amylases for use in detergents and cleaning agents. Other examples of amylases suitable for this purpose include the α-amylase from Bacillus sp. A 7-7 (DSM 12368) and the cyclodextrin glucanotransferase (CGTase) from B. agaradherens (DSM 9948).

[0056] Lipases or cutinases can be used due to their triglyceride-cleaving activity. These include, for example, those originally obtained from Humicola lanuginosa (Thermomyces lanuginosus) or those developed from these, particularly those with the amino acid substitution D96L. Cutinases 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.

[0057] Enzymes collectively referred to as hemicellulases can also be used. These include, for example, mannanases, xanthan lyases, pectin lyases (=pectinases), pectinesterases, pectate lyases, xyloglucanases (=xylanases), pullulanases, and β-glucanases.

[0058] To enhance the bleaching effect, oxidoreductases, for example, oxidases, oxygenases, catalases, peroxidases such as halo-, chloro-, bromo-, lignin-, glucose-, or manganese-peroxidases, dioxygenases, or laccases (phenol oxidases, polyphenol oxidases) can be used if desired. Advantageously, organic compounds, particularly aromatic ones, that interact with the enzymes are also added to enhance the activity of the respective oxidoreductases (enhancers) or to ensure electron flow in the event of significantly different redox potentials between the oxidizing enzymes and the soils (mediators).

[0059] The enzymes can be used in any form established according to the state of the art. These include, for example, solid preparations obtained by granulation, extrusion, or lyophilization or, particularly in the case of liquid or gel-like preparations, solutions of the enzymes, advantageously as concentrated as possible, with a low water content, and / or containing stabilizers. Alternatively, the enzymes can be encapsulated for both solid and liquid dosage forms, 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 if in a solidified gel, or in 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, such as stabilizers, emulsifiers, pigments, bleaching agents, or dyes, can be applied in superimposed layers. Such capsules are applied using conventional methods, for example, by shaking or rolling granulation or in fluid-bed processes. Such granules, for example, through the application of polymeric film-forming agents, are advantageously low in dust and, thanks to the coating, are storage-stable. Furthermore, it is possible to package two or more enzymes together, so that a single granule exhibits multiple enzyme activities.

[0060] Preferably, one or more enzymes and / or enzyme preparations, preferably protease preparations and / or amylase preparations, are used in amounts of from 0.1 wt% to 5 wt%, preferably from 0.2 wt% to 4.5 wt% and in particular from 0.4 wt% to 4 wt%.

[0061] Individual odorant compounds, e.g. synthetic products such as esters, ethers, aldehydes, ketones, alcohols and hydrocarbons, can be used as perfume oils or fragrances. However, mixtures of different odorants are preferred, as they together create an appealing scent. Such perfume oils can also contain natural odorant mixtures, such as those obtainable from plant sources, e.g. pine, citrus, jasmine, patchouli, rose or ylang-ylang oil. In order to be perceptible, an odorant must be volatile, and in addition to the nature of the functional groups and the structure of the chemical compound, the molar mass also plays an important role. Most odorants have molar masses of up to around 200 g / mol, while molar masses of 300 g / mol and above are rather rare. Due to the varying volatility of odorants, the smell of a perfume or fragrance composed of several odorants changes depending on the fragrance.Fragrance during evaporation, whereby the olfactory impressions are divided into "top note," "middle note" or body," and "base note" (end note or dry out). Since olfactory perception is largely based on odor intensity, the top note of a perfume or fragrance does not consist solely of highly volatile compounds, while the base note consists largely of less volatile, i.e., more persistent odorants. In perfume composition, more volatile odorants can, for example, be bound to certain fixatives, which prevents them from evaporating too quickly. The following classification of odorants into "more volatile" and "more persistent" odorants therefore says nothing about the olfactory impression or whether the corresponding odorant is perceived as a top or heart note.The fragrances can be processed directly, but it can also be advantageous to apply them to carriers that ensure a long-lasting fragrance through slower fragrance release. Cyclodextrins, for example, have proven to be effective carrier materials, although the cyclodextrin-perfume complexes can also be coated with other excipients.

[0062] When selecting a dye, it is important to ensure that the dyes have a high level of storage stability and are insensitive to light, as well as a low affinity for textile surfaces, particularly synthetic fibers. At the same time, it is also important to consider that dyes can exhibit varying degrees of stability towards oxidation. In general, water-insoluble dyes are more stable towards oxidation than water-soluble dyes. The concentration of the dye in the detergents varies depending on the solubility and thus also on the sensitivity to oxidation. For highly water-soluble dyes, dye concentrations in the range of a few 10 -2 < wt.% to 10 -3 < wt.% are typically selected.In contrast, for pigment dyes, which are particularly preferred due to their brilliance but are less water-soluble, the suitable concentration of the colorant in detergents is typically between a few 10 -3% and 10 -4% by weight. Colorants that can be destroyed by oxidation during the washing process, as well as mixtures thereof with suitable blue dyes, so-called blue tinters, are preferred. It has proven advantageous to use colorants that are soluble in water or, at room temperature, in liquid organic substances. Suitable examples include anionic colorants, such as anionic nitroso dyes.

[0063] In addition to the components mentioned above, the detergents may contain other ingredients that further improve their performance and / or aesthetic properties. Preferred detergents contain one or more substances from the group of electrolytes, pH adjusters, fluorescent agents, hydrotopes, foam inhibitors, silicone oils, anti-redeposition agents, optical brighteners, graying inhibitors, shrinkage inhibitors, crease inhibitors, dye transfer inhibitors, antimicrobial agents, germicides, fungicides, antioxidants, antistatic agents, ironing aids, anti-staining and waterproofing agents, swelling and slip-resistant agents, and UV absorbers.

[0064] A wide variety of salts from the group of inorganic salts can be used as electrolytes. Preferred cations are alkali and alkaline earth metals, and preferred anions are halides and sulfates. From a manufacturing perspective, the use of NaCl or MgCl2 in detergents is preferred.

[0065] To bring the pH value of detergents into the desired range, the use of pH adjusters may be indicated. All known acids and alkalis can be used, provided their use is not prohibited for technical, environmental, or consumer protection reasons. The amount of these adjusters typically does not exceed 1% by weight of the total formulation.

[0066] Suitable foam inhibitors include soaps, oils, fats, paraffins, or silicone oils, which may optionally be applied to carrier materials. Suitable carrier materials include, for example, inorganic salts such as carbonates or sulfates, cellulose derivatives or silicates, and mixtures of the aforementioned materials. Preferred agents 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 mPa s and 1,000,000 mPa s.

[0067] Suitable antiredeposition agents are, for example, non-ionic cellulose ethers such as methylcellulose and methylhydroxypropylcellulose with a proportion of methoxy groups of 15 to 30 wt.% and of hydroxypropyl groups of 1 to 15 wt.%, in each case based on the non-ionic cellulose ether.

[0068] Suitable 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.

[0069] Optical brighteners can be added to detergents, in particular, to eliminate graying and yellowing of treated textiles. These substances absorb into the fibers and cause a brightening effect and simulated bleaching by converting invisible ultraviolet radiation into longer-wavelength visible light. The ultraviolet light absorbed from sunlight is emitted as a faint bluish fluorescence, which, along with the yellow tone of the grayed or yellowed laundry, produces pure white. Suitable compounds include, for example, 4,4'-diamino-2,2'-stilbenedisulfonic acids (flavonic acids), 4,4'-distyrylbiphenyls, methylumbelliferones, coumarins, dihydroquinolinones, 1,3-diarylpyrazolines, naphthalimides, benzoxazole, benzisoxazole, and benzimidazole systems, as well as heterocyclic-substituted pyrene derivatives.

[0070] The purpose of graying inhibitors is to keep the soil detached from the fiber suspended in the liquor, thus preventing it from reabsorbing. Suitable for this purpose are water-soluble colloids, usually of an organic nature, such as the water-soluble salts of polymeric carboxylic acids, glue, gelatin, salts of ethersulfonic 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, such as degraded starch and / or aldehyde starches. Polyvinylpyrrolidone is also suitable. Other graying inhibitors that can be used include cellulose ethers such as carboxymethylcellulose (sodium salt), methylcellulose, hydroxyalkylcellulose, and mixed ethers such as methylhydroxyethylcellulose, methylhydroxypropylcellulose, methylcarboxymethylcellulose, and mixtures thereof.

[0071] Since textile fabrics, especially those made of rayon, viscose staple fiber, cotton, and their blends, can tend to crease because the individual fibers are sensitive to bending, kinking, pressing, and crushing across the fiber direction, synthetic crease protection agents can be used. These include, for example, synthetic products based on fatty acids, fatty acid esters, fatty acid amides, fatty alkylol esters, fatty alkylolamides, or fatty alcohols, which are usually reacted with ethylene oxide, or products based on lecithin or modified phosphoric acid esters.

[0072] Repellent and impregnating processes are used to finish textiles with substances that prevent the deposition of dirt or facilitate its washout. Preferred repellent and impregnating agents are perfluorinated fatty acids, including in the form of their aluminum and zirconium salts, organic silicates, silicones, polyacrylic acid esters with perfluorinated alcohol components, or polymerizable compounds coupled with perfluorinated acyl or sulfonyl radicals. Antistatic agents may also be included. Dirt-repellent finishing with repellent and impregnating agents is often classified as easy-care finishing. The penetration of the impregnating agents in the form of solutions or emulsions of the active ingredients in question can be facilitated by adding wetting agents that reduce surface tension. Another area of ​​application for repellent and impregnating agents is the water-repellent finishing of textiles, tents, tarpaulins, leather, etc., in which, in contrast to waterproofing, the fabric pores are not closed, so the material remains breathable (hydrophobicization). The hydrophobic agents used for hydrophobicization coat textiles, leather, paper, wood, etc. with a very thin layer of hydrophobic groups, such as longer alkyl chains or siloxane groups. Suitable hydrophobic agents include paraffins, waxes, metal soaps, etc. with added aluminum or zirconium salts, quaternary ammonium compounds with long-chain alkyl radicals, urea derivatives, fatty acid-modified melamine resins, chromium complex salts, silicones, organotin compounds, glutaraldehyde, and perfluorinated compounds. The hydrophobized materials do not feel greasy; nevertheless, similar to greased fabrics, water droplets roll off them without wetting. 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.

[0073] Antimicrobial agents can be used to combat microorganisms. Depending on their antimicrobial spectrum and mechanism of action, a distinction is made between bacteriostatics and bactericides, and fungistatics and fungicides. Substances from these groups include benzalkonium chlorides, alkylarylsulfonates, halophenols, and phenolmercuriacetate, although these compounds can also be omitted entirely.

[0074] To prevent undesirable changes to the detergents and cleaning agents and / or the treated textiles caused by atmospheric oxygen and other oxidative processes, the agents may 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.

[0075] Increased wearing comfort can result from the additional use of antistatic agents. Antistatic agents increase surface conductivity, thus enabling a better dissipation of generated charges. External antistatic agents are generally substances with at least one hydrophilic molecular ligand and form a more or less hygroscopic film on 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, where they also provide a softening effect.

[0076] Silicone derivatives can be used in textile detergents to improve the water absorption capacity, the rewettability of treated textiles, and to facilitate ironing of treated textiles. These derivatives also improve the rinsing behavior of detergents through 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 fully or partially fluorinated. Preferred silicones are polydimethylsiloxanes, which can optionally be derivatized and are then amino-functional or quaternized, or contain Si-OH, Si-H, and / or Si-Cl bonds. Other preferred silicones are polyalkylene oxide-modified polysiloxanes, i.e., polysiloxanes containing, for example, polyethylene glycols, and polyalkylene oxide-modified dimethylpolysiloxanes.

[0077] Finally, UV absorbers can also be used, which absorb onto the treated textiles and improve the lightfastness of the fibers. Compounds that exhibit these desired properties include compounds and derivatives of benzophenone with substituents in the 2- and / or 4-position, which are effective through radiationless deactivation. Also suitable are substituted benzotriazoles, 3-phenyl-substituted acrylates (cinnamic acid derivatives), optionally with cyano groups in the 2-position, salicylates, organic Ni complexes, and natural substances such as umbelliferone and the body's own urocanic acid.

[0078] Protein hydrolysates are other suitable active substances due to their fiber-conditioning effect. Protein hydrolysates are product mixtures obtained by acidic, alkaline, or enzymatically catalyzed degradation of proteins. Protein hydrolysates of both plant and animal origin can be used. Animal protein hydrolysates include, for example, elastin, collagen, keratin, silk, and milk protein hydrolysates, which can also be present in the form of salts. The use of protein hydrolysates of plant origin is preferred, e.g., soy, almond, rice, pea, potato, and wheat protein hydrolysates. Although the use of protein hydrolysates as such is preferred, amino acid mixtures obtained from other sources or individual amino acids, such as arginine, lysine, histidine, or pyroglutamic acid, can also be used instead.The use of derivatives of protein hydrolysates, for example in the form of their fatty acid condensation products, is also possible.

[0079] The detergents can be in the form of tablets. To facilitate the disintegration of such prefabricated tablets, it is possible to incorporate disintegration aids, so-called tablet disintegrants, into these tablets to shorten disintegration times. Tablet disintegrants or disintegration accelerators are understood to be adjuvants that ensure the rapid disintegration of tablets in water or other media and the rapid release of the active ingredients. Disintegration aids can preferably be used in amounts of 0.5 to 10 wt.%, preferably 3 to 7 wt.%, and in particular 4 to 6 wt.%, in each case based on the total weight of the tablet containing the disintegration aid.

[0080] The detergents described herein can be pre-packaged in dosing units. These dosing units preferably contain the amount of detergent required for one wash cycle. Preferred dosing units have a weight between 10 g and 50 g, preferably between 15 g and 40 g. The volume of the aforementioned dosing units and their spatial shape are particularly preferably selected to ensure that the pre-packaged units can be dosed via the dosing chamber of a washing machine. The volume of the dosing unit is therefore preferably between 10 and 35 ml, preferably between 12 and 30 ml.

[0081] The detergents, in particular the prefabricated dosing units, particularly preferably have a water-soluble casing. The water-soluble casing is preferably formed from a water-soluble film material selected from the group consisting of polymers or polymer blends. The casing can be formed from one or two or more layers of the water-soluble film material. The water-soluble film material of the first layer and the additional layers, if present, can be the same or different. Films that can be glued and / or sealed, for example, to form packaging such as tubes or pillows after they have been filled with a detergent are particularly preferred.

[0082] The water-soluble packaging may have one or more compartments. The agent may be contained in one or more compartments, if present, of the water-soluble wrapper.

[0083] It is preferred that the water-soluble coating contains polyvinyl alcohol or a polyvinyl alcohol copolymer. Water-soluble coatings containing polyvinyl alcohol or a polyvinyl alcohol copolymer exhibit good stability with sufficiently high water solubility, particularly cold water solubility. Suitable water-soluble films for producing the water-soluble coating are preferably based on a polyvinyl alcohol or a polyvinyl alcohol copolymer whose molecular weight is in the range from 10,000 g / mol to 1,000,000 g / mol, preferably from 20,000 g / mol to 500,000 g / mol, particularly preferably from 30,000 g / mol to 100,000 g / mol, and in particular from 40,000 g / mol to 80,000 g / mol. Polyvinyl alcohol is usually produced by hydrolysis of polyvinyl acetate, since the direct synthesis route is not possible. The same applies to polyvinyl alcohol copolymers, which are made from polyvinyl acetate copolymers.It is preferred if at least one layer of the water-soluble casing comprises a polyvinyl alcohol whose degree of hydrolysis is from 70 mol% to 100 mol%, preferably from 80 mol% to 90 mol%, particularly preferably from 81 mol% to 89 mol%, and in particular from 82 mol% to 88 mol%. A polymer selected from the group comprising (meth)acrylic acid-containing (co)polymers, polyacrylamides, oxazoline polymers, polystyrenesulfonates, polyurethanes, polyesters, polyethers, polylactic acid, or mixtures of the above polymers can additionally be added to a polyvinyl alcohol-containing film material suitable for producing the water-soluble casing. A preferred additional polymer is polylactic acid. Preferred polyvinyl alcohol copolymers comprise, in addition to vinyl alcohol, dicarboxylic acids as further monomers. Suitable dicarboxylic acids are itaconic acid, malonic acid, succinic acid, and mixtures thereof, with itaconic acid being preferred.Likewise preferred polyvinyl alcohol copolymers comprise, in addition to vinyl alcohol, an ethylenically unsaturated carboxylic acid, its salt, or its ester. Particularly preferably, such polyvinyl alcohol copolymers contain, in addition to vinyl alcohol, acrylic acid, methacrylic acid, acrylic acid esters, methacrylic acid esters, or mixtures thereof. It may be preferred for the film material to contain further additives. The film material may, for example, contain plasticizers such as dipropylene glycol, ethylene glycol, diethylene glycol, propylene glycol, glycerin, sorbitol, mannitol, or mixtures thereof. Further additives include, for example, release aids, fillers, crosslinking agents, surfactants, antioxidants, UV absorbers, antiblocking agents, anti-adhesive agents, or mixtures thereof.Suitable water-soluble films for use in the water-soluble wrappers of the water-soluble packages according to the invention are films sold by MonoSol LLC, for example, under the designation M8630, C8400, or M8900. Other suitable films include films designated Solublon®< PT, Solublon®< GA, Solublon®< KC, or Solublon®< KL by Aicello Chemical Europe GmbH, or VF-HP films by Kuraray. Examples Example 1: Preparation of substituted anthracenediones a) Synthesis of 1,2-bis(octyloxy)anthracene-9,10-dione

[0084]

[0085] Based on published procedures (X. Chen, K. Ding, L. Jun, Synthesis, identification and application of aldehyde reactive dyes, Dyes and Pigments 2015, 123, 404-412 and loannis Drivas, Richard S. Blackburn, Christopher M. Rayner, Natural anthraquinonoid colorants as platform chemicals in the synthesis of sustainable disperse dyes for polyesters, Dyes and Pigments 2011, 88, 7-17), a mixture of 30 ml of dimethylacetamide, 2.00 g of alizarin (8.30 mmol), and 3.50 g of potassium carbonate (25 mmol) was heated to 80°C in a round-bottom flask and reacted for 30 min. Subsequently, 4.80 g of 1-bromooctane (25 mmol) were added, and the reaction mixture was stirred for a further 16 h. To quench the reaction, the mixture was cooled to room temperature and dimethylacetamide was added. The mixture was filtered, and the residue was washed with dimethylacetamide until a yellow solid was obtained. The residue was then dried under reduced pressure.1,2-Bis(octyloxy)anthracene-9,10-dione (M1) was obtained as a yellow solid in 94% yield. b) Preparation of further 1,2-bis(alkyloxy)anthracene-9,10-diones

[0086] Analogous to the procedure described in a), 1,2-bis(decyloxy)anthracene-9,10-dione (M2), 1,2-bis(dodecyloxy)anthracene-9,10-dione (M3) and 1,2-bis(hexadecyloxy)anthracene-9,10-dione (M4) were prepared. Example 2: Degradation of lycopene

[0087] Using a simplified model reaction, the decolorization of the red tomato pigment lycopene was visualized and characterized using a UV / VIS spectrum. Equal volumes of a solution of 0.01 mM lycopene in chloroform and a solution of 0.0001 mM of each compound prepared in Example 1 in chloroform were mixed in a cuvette. The cuvette was placed in a Specord S600 spectrometer from Analytik Jena; the wavelength was 480 nm. The kinetics of the degradation of the lycopene pigment were determined with the distance between the cuvette and a blue LED lamp (450 nm) as small as possible. The data presented in Table 1 below were obtained. Table 1: Degradation of lycopene, pseudo 1st order reaction Photoactivator K [min -1< ] t 1 / 2 [min] Absorption maximum (t = 0 min) [au] Absorption maximum (t = 5 min) [au] Reduction [%] - 0,006 107 1,00 0,98 2 M1 0,28 2,5 1,00 0,40 60 M2 0,28 2,5 1,00 0,47 53 M3 0,28 2,5 1,00 0,51 49 M4 0,28 2,5 1,00 0,53 47 Example 3: Degradation of β-carotene

[0088] Example 2 was repeated using the yellow pigment β-carotene, which is derived from carrots, instead of lycopene and a measurement wavelength of 463 nm. The data shown in Table 2 below were obtained. Table 2: Degradation of β-carotene, pseudo 1st order reaction Photoactivator K [min -1< ] t 1 / 2 [min] Absorption maximum (t = 0 min) [au] Absorption maximum (t = 5 min) [au] Reduction [%] - 0,027 29 1,00 0,87 13 M1 0,31 2 1,00 0,17 83 M2 0,31 2 1,00 0,20 80 M3 0,31 2 1,00 0,22 78 M4 0,31 2 1,00 0,27 73

Claims

1. Use of alkyloxy-substituted anthracene-9,10-diones of the general formula (I), in which R1 and R2 independently of one another represent H, SO3- M+ or an optionally substituted linear or branched alkyl radical having 1 to 20 carbon atoms, with the proviso that at least one of the radicals R1 or R2 is an optionally substituted linear or branched alkyl radical having 1 to 20 carbon atoms, X is H or SO3- M+ and M+ is a proton, an alkali metal ion or an ammonium ion or mixtures thereof, as a photo-bleaching agent for removing soiling from textile materials.

2. Detergent containing alkyloxy-substituted anthracene-9,10-dione of the general formula (I), in which R1 and R2 independently of one another represent H, SO3-M+ or an optionally substituted linear or branched alkyl radical having 1 to 20 carbon atoms, with the proviso that at least one of the radicals R1 or R(2) dis an optionally substituted linear or branched alkyl radical having 1 to 20 carbon atoms, X is H or SO3-M+ and M+ is a proton, an alkali metal ion or an ammonium ion or mixtures thereof, and a nonionic, anionic, cationic and / or amphoteric surfactant.

3. Agent according to claim 2, characterized in that it contains 0.00001 wt% to 1 wt%, in particular 0.001 wt% to 0.1 wt%, of alkyloxy-substituted anthracene-9,10-dione of the general formula (I).

4. Agent according to claim 2 or 3, characterized in that it is liquid.

5. Agent according to any of claims 2 to 4, characterized in that it does not contain bleaching agents in the form of hypochlorites or peroxygen compounds.

6. Agent according to any of claims 2 to 5, characterized in that it is available as a prefabricated dosing unit with a water-soluble coating.

7. Method for removing soiling from textile materials using alkyloxy-substituted anthracene-9,10-diones of the general formula (I), in which R1 and R2 independently of one another represent H, SO3-M+ or an optionally substituted linear or branched alkyl radical with 1 to 20 carbon atoms, with the proviso that at least one of the radicals R1 or R2 is an optionally substituted linear or branched alkyl radical having 1 to 20 carbon atoms, X is H or SO3-M+ and M+ represent a proton, an alkali metal ion or an ammonium ion or mixtures thereof, in an aqueous washing liquid in which the soiled textile materials requiring washing are present, while irradiating the aqueous washing liquid with visible light.

8. Method according to claim 7, characterized in that light in the wavelength range from 400 nm to 600 nm, in particular from 450 nm to 525 nm, is used.

9. Use according to claim 1 or process according to claim 7 or 8, characterized in that the alkyloxy-substituted anthracene-9,10-dione of the general formula (I) is used in concentrations in the range from 0.0001 mmol / I to 0.1 mmol / l, in particular from 0.001 mmol / I to 0.01 mmol / l, in aqueous washing lyes.

10. Use, agent or process according to one of the preceding claims, characterized in that in formula (I) R1 and R2 independently of one another represent a linear or branched alkyl radical with 1 to 20 carbon atoms, which may be substituted, and / or that the radical R1 and / or R2 is substituted and substituents are selected from -OH, -COO- M+ , -SO3-M+, -OSO3-M+, -N+(CH2CH3)3Hal- and mixtures thereof, wherein M+ represent a proton, an alkali metal ion, an ammonium ion and mixtures thereof, and Hal- represents Cl-, Br ,J-, F- and mixtures thereof, and M+ and Hal- may also be absent if -COO- ,-SO3-, -OSO3- and -N+(CH2CH3)3 are present in charge-balancing amounts.