Use and method for freezing soiling with washing or cleaning agents containing bleach precursor

Abstract

The invention relates to a water and surfactant-containing liquid detergent or cleaning agent containing a hydrophobic precursor compound in microemulsified form from which a peroxocarboxylic acid or salts thereof can be released by UV irradiation. The invention also relates to methods for washing textiles and cleaning hard surfaces with the aid of such precursor compounds.

Description

[0001] Liquid detergents are well-known in the art and have become increasingly popular with consumers in recent years, offering several advantages over solid detergents. These include easier dosing and generally faster dissolution in the wash. Additionally, they are often perceived as safer and less aggressive to fabrics and the environment.

[0002] However, liquid detergents have the disadvantage that not all ingredients that are established in solid detergents and cleaning agents, whose performance users rely on, can be readily incorporated into them in a stable manner. In particular, the incorporation of an effective bleaching system, which in solid detergents usually consists of a peroxidic bleaching agent and a bleach activator that forms a peroxycarboxylic acid under perhydrolysis conditions, into liquid detergents is problematic because, especially in water-based detergents, the stability of the bleach activator against hydrolytic attack cannot usually be adequately guaranteed. Furthermore, the presence of oxidative bleaching agents can impair the stability of other detergent and cleaning agent ingredients, such as dyes, fragrances, or enzymes.It has therefore been proposed on various occasions to separate the components of liquid products which are not very compatible with one another by providing multi-compartment packaging for the corresponding components of the finished product, for example multi-chamber bottles from which the components are dosed together, or multi-chamber bags made of water-soluble film material from whose individual chambers the components are released simultaneously or successively by dissolving the chamber walls.

[0003] Another known embodiment of the separation principle involves coating at least one of the problematic ingredients with a protective layer. This layer surrounds the ingredient during the production and storage of the liquid agent and prevents contact with the negatively interacting other ingredients. However, under application conditions, it breaks open and releases the ingredient, allowing it to contribute the desired amount to the washing or cleaning result of the agent. In this case, concentration differences between the liquid agent and the washing or cleaning liquid are generally exploited to dissolve the coating layer only under application conditions of the agent. EP0744462A2 discloses microemulsions of liquid peracid precursors used in washing and cleaning agents.

[0004] In contrast to the known release mechanisms based essentially on water concentration or pH differences, the present invention uses a targeted energy input to produce a reactive active ingredient from an ingredient that is stable during storage of the liquid agent.

[0005] The invention relates to the use of a combination of an aqueous microemulsion of a hydrophobic precursor compound selected from selected peroxoesters and mixtures thereof, from which a peroxocarboxylic acid or its salt can be released by UV irradiation, and UV radiation for removing soiling when washing textiles or cleaning hard surfaces. The microemulsion mentioned here can be a washing or cleaning agent according to the invention, but it can also be devoid of conventional components of washing and cleaning agents; preferably, the microemulsion used according to the invention contains from 2% to 12% by weight, in particular from 4% to 10% by weight, of the hydrophobic precursor compound, from 2% to 40% by weight, in particular from 4% to 35% by weight, of microemulsifier, and 100% by weight of water.

[0006] The invention further relates to a washing or cleaning process in which a textile surface requiring washing or a hard surface requiring cleaning is brought into contact with a surfactant-containing aqueous washing or cleaning liquid containing a hydrophobic precursor compound in microemulsified form, which is selected from selected peroxoesters and mixtures thereof, and from which a peroxocarboxylic acid or its salt can be released by UV irradiation, and UV radiation is allowed to act on the liquid. Such a process can be carried out manually or mechanically, for example with the aid of a washing machine or a dishwasher, wherein the washing machine or dishwasher has a device for UV irradiation or the washing or cleaning liquid, particularly when the process is carried out manually, is manually exposed to a UV radiation source.Washing machines and dishwashers that have a UV radiation source are well known. The process according to the invention can be carried out at temperatures even below room temperature, particularly when cold water is used to prepare the surfactant-containing aqueous washing or cleaning liquid, or is preferably carried out at temperatures in the range of 5°C to 60°C, in particular 10°C to 40°C.

[0007] If desired, the liquid can be exposed to UV radiation shortly before it comes into contact with the object to be cleaned. It is preferred if the UV radiation exposure occurs during contact between the washing or cleaning liquid and the textile to be washed or the hard surface to be cleaned. The UV radiation need not be applied for the entire contact period, which is generally 1 minute to 2 hours, especially 2 minutes to 1 hour. However, the exposure can begin before contact if desired.

[0008] UV radiation is known to be electromagnetic radiation with a spectrum comprising wavelengths from 100 nm to 380 nm. Preferably, UV radiation is used according to the invention with wavelengths in the range from 100 nm to 300 nm, in particular from 240 nm to 270 nm, with the maximum intensity of the UV radiation also being preferred within the range mentioned. The particularly preferred range from 240 nm to 270 nm lies in the UVC range and is not covered by sunlight, since its UVC component is filtered out by the atmosphere before reaching the earth's surface. For example, mercury vapor lamps or light-emitting diodes (LEDs) can be used to generate the UV radiation essential to the invention. UV irradiation times in the range from 5 minutes to 40 minutes, in particular from 6 minutes to 30 minutes, are normally entirely sufficient.Energy densities of UV radiation in the range of 150 mJ / cm 2< to 400 mJ / cm 2< , in particular from 200 mJ / cm 2< to 300 mJ / cm 2< , measured on the surface of the washing or cleaning liquid, are normally completely sufficient.

[0009] Hydrophobic in the context of the precursor compound means that it has an n-octanol-water partition coefficient log K ow at 20 °C of at least 0.5, preferably in the range from 1 to 30, and in particular from 2 to 20.

[0010] The hydrophobic precursor compounds are used in microemulsified form. "Microemulsified," as used herein, refers to the generally accepted chemical meaning of this term and indicates that at least one liquid is dispersed within another with average droplet diameters in the single-digit to double-digit micrometer range, and the normally immiscible liquids are present without visible demixing. The preferred (o / w) microemulsions according to the invention contain the precursor finely dispersed in water, stabilized with the aid of a microemulsifier; they are optically isotropic, microstructured, and thermodynamically stable.Useful microemulsifiers include alkyl glycol ethers, alkoxylated fatty alcohols, alkoxylated oxo alcohols, alkoxylated fatty acid alkyl esters, fatty acid amides, alkoxylated fatty acid amides, polyhydroxy fatty acid amides, alkylphenol polyglycol ethers, amine oxides, alkyl (poly)glucosides, sulfonates, especially alkylbenzenesulfonates and / or secondary alkanesulfonates, and mixtures thereof. Alkyl glycol ethers, sulfonates, and mixtures thereof are particularly preferred. Such microemulsifiers are preferably present in the compositions according to the invention in amounts of 0.01 wt.% to 60 wt.%, in particular 1 wt.% to 50 wt.%.

[0011] The precursor compounds which can be used according to the invention are prepared from the peroxoesters of one of the general formulas (I) to (VI), in which R stands for a linear or branched-chain alkyl group having 1 to 30 C atoms, in particular 2 to 20 C atoms, R' stands for a linear or branched-chain alkyl group having 1 to 30 C atoms, in particular 2 to 20 C atoms, R" stands for a linear or branched-chain alkylene group having 1 to 30 C atoms, in particular 2 to 20 C atoms, R‴ stands for an m-valent linear or branched-chain alkyl group having 2 to 9 C atoms, in particular 3 to 5 C atoms, A stands for an alkylene group having 2 to 4 C atoms, m stands for a number from 2 to 6, in particular 3 or 4, and n stands for a number from 2 to 30, in particular from 3 to 15, and mixtures thereof.Without wishing to be bound by this theory, these peroxoesters presumably form radical intermediates under the influence of UV radiation, which react directly with colored soils on the surfaces to be cleaned or in the washing or cleaning liquid, or can react with water, for example, to form peroxo acids, which exert their bleaching power. Such peroxoesters are commercially available under the name Luperox®.

[0012] A further advantage of the invention is that when using such microemulsified hydrophobic precursor compounds, the stability of enzymes, for example proteases, in liquid agents during storage is just as high as when the precursor compound is omitted, whereas the use of the same molar amount of H 2 O 2 or phthalimidoperoxohexanoic acid instead of the precursor compound leads to noticeable decreases in enzyme activity.

[0013] "Liquid," when used in reference to the agent used in the washing or cleaning process, includes all compositions that flow under standard conditions (20°C, 1013 mbar) and, in particular, also encompasses gels and pasty compositions. In particular, the term also includes non-Newtonian liquids that have a yield point. The amounts stated in connection with the components of the liquid agent described herein refer, unless otherwise stated, to wt.%, each based on the total weight of the agent. Furthermore, quantities referring to at least one component always refer to the total amount of that component contained in the agent, unless explicitly stated otherwise.This means that such quantities, for example in connection with "at least one non-ionic surfactant", refer to the total amount of non-ionic surfactants contained in the product.

[0014] "At least one," as used herein, refers to 1 or more, for example, 1, 2, 3, 4, 5, 6, 7, 8, 9, or more. In the context of components of the compositions described herein, this statement does not refer to the absolute amount of molecules but to the type of component. "At least one nonionic surfactant" therefore means, for example, one or more different nonionic surfactants, i.e., one or more different types of nonionic surfactants. Together with quantities, the quantities refer to the total amount of the correspondingly designated type of component, as already defined above.

[0015] The liquid washing or cleaning agent used in the washing or cleaning process preferably contains 1 wt.% to 60 wt.%, preferably 5 wt.% to 45 wt.% and, in particular when it is a washing agent, 15 wt.% to 40 wt.% of at least one surfactant.

[0016] Usable nonionic surfactants include all known nonionic surfactants commonly used in washing or cleaning agents, in particular those selected from the group consisting of alkyl glycol ethers, alkoxylated fatty alcohols, alkoxylated oxo alcohols, alkoxylated fatty acid alkyl esters, fatty acid amides, alkoxylated fatty acid amides, polyhydroxy fatty acid amides, alkylphenol polyglycol ethers, amine oxides, alkyl (poly)glucosides, and mixtures thereof. In a preferred embodiment of the invention, the agents contain, as nonionic surfactant, at least one fatty alcohol alkoxylate of the following formula R 1< -O-(AO) m -H, in which R 1< is a linear or branched, substituted or unsubstituted alkyl radical, AO is an ethylene oxide (EO) or propylene oxide (PO) group, and m is an integer from 1 to 50.In a preferred embodiment of the present invention, R 1< is a linear or branched alkyl radical having 5 to 30 C atoms, preferably having 7 to 25 C atoms, and in particular having 10 to 19 C atoms. Preferred radicals R 1< are selected from decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl radicals, and mixtures thereof, with preference given to representatives with an even number of C atoms. Particularly preferred radicals R 1< are derived from fatty alcohols having 12 to 19 C atoms, for example from coconut fatty alcohol, tallow fatty alcohol, lauryl, myristyl, cetyl, or stearyl alcohol, or from oxo alcohols having 10 to 19 C atoms. AO is an ethylene oxide (EO) or propylene oxide (PO) moiety, preferably an ethylene oxide moiety. The index m is an integer from 1 to 50, preferably 2 to 20, and more preferably 2 to 10. In particular, m is 3, 4, 5, 6, or 7.The agent according to the invention can contain mixtures of nonionic surfactants having different degrees of ethoxylation. Surfactants with degrees of alkoxylation / ethoxylation of at least 5 are preferred. In summary, particularly preferred fatty alcohol alkoxylates are those of the formula . with k = 9 to 17, m = 3, 4, 5, 6, or 7. Very particularly preferred representatives are fatty alcohols with 10 to 18 C atoms and with 7 EO (k = 11-17, m = 7). Such fatty alcohol ethoxylates are available under the trade names Dehydol ®< LT7 (BASF SE), Lutensol ®< AO7 (BASF SE), Lutensol ®< M7 (BASF SE), and Neodol ®< 45-7 (Shell Chemicals). The above-mentioned fatty alcohol ethoxylates preferably have degrees of ethoxylation of at least 5, preferably 7. Such fatty alcohol ethoxylates can be used alone, as mixtures of such fatty alcohol ethoxylates, or as mixtures with lower-ethoxylated fatty alcohol ethoxylates, such as, for example, Lutensol ®< AO3 (BASF). In such mixtures, it is preferred that the fatty alcohol ethoxylates with degrees of ethoxylation of at least 5, preferably 7, constitute at least 50% by weight, preferably at least 75% by weight of the total amount of fatty alcohol ethoxylates.

[0017] Further nonionic surfactants that may be present in the compositions according to the present invention include, but are not limited to, alkyl (poly)glycosides, alkoxylated fatty acid alkyl esters, fatty acid alkanolamides, hydroxy mixed ethers, sorbitan fatty acid esters, and polyhydroxy fatty acid amides. Suitable alkyl (poly)glycosides are, for example, those of the formula R 2< O-[G] p , in which R 2< is a straight-chain or branched alkyl having 12 to 16 carbon atoms, G is a sugar residue having 5 or 6 carbon atoms, in particular glucose, and the index p is 1 to 10. These can be present in the composition, for example, in amounts of up to 5% by weight.

[0018] Furthermore, the liquid agent used in the washing or cleaning process according to the present invention preferably contains 1 wt.% to 30 wt.%, in particular 2 wt.% to 20 wt.%, and particularly preferably at least 10 wt.% of at least one anionic surfactant. The anionic surfactants are preferably surfactants from the group of sulfonates, in particular alkylbenzenesulfonates and / or secondary alkanesulfonates. In one embodiment, the agent according to the invention comprises at least one secondary alkanesulfonate. The at least one secondary alkanesulfonate can be any known secondary alkanesulfonate suitable for the purpose of the invention. Secondary refers to the generally known chemical meaning of this term and indicates that the carbon atom to which the sulfonate group is covalently bonded further has two covalent bonds to two organic radicals and one covalent bond to a hydrogen atom.Together with the carbon atom to which they are bonded, the two organic radicals form a linear or branched alkyl group having 1 to 50 carbon atoms. To balance the negative charge of the sulfonate group, the alkanesulfonate further comprises any cation, preferably selected from the group consisting of Na +< , K +< , NH 4 +< , ½ Zn 2+< , ½ Mg 2+< , ½ Ca 2+< , ½ Mn 2+< and mixtures thereof, particularly preferably Na +< . Alternatively, in various embodiments, the corresponding acid can also be used, i.e. the cation is H +< .In a preferred embodiment of the present invention, the at least one secondary alkanesulfonate has the formula R 1< CH(SO 3 -< X +< )R 2<, where each R 1< and R 2< is independently a linear or branched alkyl having 1 to 20 carbon atoms and forms a linear or branched alkyl group with the carbon atom to which they are bonded, preferably having 10 to 30 carbon atoms, more preferably having 10 to 20 carbon atoms, and X +< is selected from the group Na +< , K +< , NH 4 +< , ½ Zn 2+< , ½ Mg 2+< , ½ Ca 2+< , ½ Mn 2+< and mixtures thereof, preferably Na +< . As already mentioned above, in various embodiments X +< can also be H +<. In yet another preferred embodiment, the at least one secondary alkanesulfonate has the following formula H 3 C-(CH 2 ) n -CH(SO 3 -< X +< )-(CH 2 ) m -CH 3 , where m and n are independently an integer between 0 and 20.Preferably, m + n is an integer between 7 and 17, more preferably 10 to 14, and X +< is selected from the group Na +< , K +< , NH 4 +< , ½ Zn 2+< , ½ Mg 2+< , ½ Ca 2+< , ½ Mn 2+< and mixtures thereof, preferably Na +< . As already mentioned above, in various embodiments, X +< can also be H +<. In a particularly preferred embodiment, the at least one secondary alkanesulfonate is secondary C 14-17 sodium alkanesulfonate or the corresponding acid. Such a secondary C 14-17 sodium alkanesulfonate is marketed, for example, by Clariant under the trade name "Hostapur SAS60". It should be expressly pointed out at this point that the agent described herein can contain several secondary alkanesulfonates.

[0019] Furthermore, in various embodiments, the agent used in the washing or cleaning process contains other anionic surfactants that can be used alternatively or in addition to the secondary alkanesulfonates. Preferably, such anionic surfactants include alkylbenzenesulfonates. Alkylbenzenesulfonates are preferably selected from linear or branched alkylbenzenesulfonates of the formula in which R' and R" are independently hydrogen or alkyl and together contain 9 to 19, preferably 9 to 15 and in particular 9 to 13 carbon atoms. A very particularly preferred representative is sodium dodecylbenzenesulfonate or the corresponding acid (HLAS). In other embodiments, Na +< can be replaced by a cation selected from K +< , NH 4 +< , ½ Zn 2+< , ½ Mg 2+< , ½ Ca 2+< , ½ Mn 2+< and mixtures thereof or by H +< (corresponding acid). In preferred embodiments, the secondary alkanesulfonates and alkylbenzenesulfonates described above are used in combination, in particular in a weight ratio of 2:1 to 1:2, preferably 1:1. It is particularly preferred to use the alkylbenzenesulfonates in the acid form.

[0020] Finally, the agents used in the washing or cleaning process can also contain other anionic surfactants, such as, for example, alkyl ether sulfates. Preference is given to fatty alcohol ether sulfates of the following formula R 4< -O-(AO) n -SO 3 -< X +< (V), where R 4< is a linear or branched, substituted or unsubstituted alkyl group having 5 to 30 carbon atoms, preferably having 7 to 25 carbon atoms, and more preferably having 10 to 19 carbon atoms. Furthermore, AO in the above formula represents an ethylene oxide (EO) or propylene oxide (PO) group, preferably an ethylene oxide (EO) group, and n is an integer from 1 to 50, preferably from 1 to 20, and more preferably from 2 to 10. X +< is any cation and is preferably selected from the group Na +< , K +< , NH 4 +< , ½ Zn 2+< ,½ Mg 2+< ,½ Ca 2+< ,½ Mn 2< and mixtures thereof, particularly preferably Na +< .In a preferred embodiment, R 4< is a linear or branched alkyl radical having 5 to 30 carbon atoms, preferably having 7 to 25 carbon atoms and in particular having 10 to 19 carbon atoms. Preferred radicals R 4< are selected from decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl radicals and mixtures thereof, with the representatives with an even number of carbon atoms being preferred. Particularly preferred radicals R 4< are derived from fatty alcohols having 12 to 19 carbon atoms, for example from coconut fatty alcohol, tallow fatty alcohol, lauryl, myristyl, cetyl or stearyl alcohol or from oxo alcohols having 10 to 19 carbon atoms. The agent can contain mixtures of surfactants having various degrees of alkoxylation n. The fatty alcohol ether sulfate used can also be one of the formula . where k = 11 to 19, n = 2, 3, 4, 5, 6, 7 or 8. Very particularly preferred representatives are Na fatty alcohol ether sulfates having 12 to 18 carbon atoms and 2 EO (k = 11 to 13, n = 2). The stated degree of ethoxylation n represents a statistical mean, which can be a whole or fractional number for a specific product. In general, the stated degrees of alkoxylation represent statistical mean, which can be a whole or fractional number for a specific product. Preferred alkoxylates / ethoxylates have a narrow homolog distribution (narrow range ethoxylates, NRE).

[0021] Furthermore, the liquid agent, particularly if it is a detergent, may contain at least one fatty acid. The term "fatty acid" as used herein refers to branched or unbranched carboxylic acids and their salts, the so-called soaps, having 6 to 22, preferably 12 to 18, carbon atoms. The fatty acid soaps may be in the form of their sodium, potassium, magnesium, or ammonium salts. In saponified form, they are preferably in the form of their sodium and / or ammonium salts. Amines that can be used for neutralization are preferably choline, triethylamine, monoethanolamine, diethanolamine, triethanolamine, methylethylamine, or a mixture thereof, with monoethanolamine being preferred. In various embodiments, the fatty acids are used as such, i.e., unsaponified.For example, they can be dissolved in one or more components of the product, preferably the at least one non-ionic surfactant, and combined in this dissolved form with the other components of the product. The fatty acid can be emulsified in the final product.

[0022] Furthermore, preferred liquid detergents used in the washing or cleaning process contain water as a solvent. In embodiments of the invention, the detergents used in the washing or cleaning process contain 4% to 25% by weight, in particular 6% to 15% by weight, of water; in other embodiments of the invention, the detergents contain more than 25% and up to 90% by weight, in particular 35% to 65% by weight, of water. The liquid detergents used in the washing or cleaning process can additionally contain one or more non-aqueous organic solvents. Suitable non-aqueous solvents include mono- or polyhydric alcohols, alkanolamines, or glycol ethers.The solvents are preferably selected from ethanol, n-propanol, i-propanol, butanols, glycol, propanediol, butanediol, methylpropanediol, glycerol, glycols such as diglycol, propyl diglycol, butyl diglycol, hexylene glycol, ethylene glycol methyl ether, ethylene glycol ethyl ether, ethylene glycol propyl ether, ethylene glycol mono-n-butyl ether, diethylene glycol methyl ether, diethylene glycol ethyl ether, propylene glycol methyl ether, propylene glycol ethyl ether, propylene glycol propyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, methoxytriglycol, ethoxytriglycol, butoxytriglycol, 1-butoxyethoxy-2-propanol, 3-methyl-3-methoxybutanol, propylene glycol t-butyl ether, di-n-octyl ether and low molecular weight Polyalkylene glycols, such as PEG 400, and their mixtures.In a preferred embodiment, the non-aqueous solvent is selected from the group consisting of ethanol, n-propanol, i-propanol, butanols, glycol, propanediol, butanediol, methylpropanediol, glycerin, and mixtures thereof. In a preferred embodiment, the non-aqueous solvent contains 1,2-propanediol, glycerin, or a mixture thereof, most preferably glycerin.

[0023] The agents used in the washing or cleaning process preferably have a viscosity (Brookfield rotational viscometer; spindle adapted to the viscosity range) in the range from 1 mPa.s to 1000 mPa.s, in particular from 5 mPa.s to 500 mPa.s. Furthermore, an agent used in the washing or cleaning process is preferably translucent, in particular transparent, i.e., it has no visually perceptible turbidity.

[0024] In general, the pH of the liquid detergent used in the washing or cleaning process according to the invention can be adjusted by means of conventional pH regulators and is preferably in the range from pH 5 to pH 10, in particular from pH 7 to pH 9; these relate to the pH of a 1% (wt.%) solution of the detergent in distilled water at 30°C.

[0025] Suitable pH adjusters include acids and / or alkalis. Suitable acids are organic acids such as acetic acid, glycolic acid, lactic acid, succinic acid, adipic acid, malic acid, tartaric acid, and gluconic acid, or even amidosulfonic acid. In addition, the mineral acids hydrochloric acid, sulfuric acid, and nitric acid, or mixtures thereof, can also be used. Suitable bases come from the group of alkali and alkaline earth metal hydroxides and carbonates, particularly alkali metal hydroxides, of which potassium hydroxide and especially sodium hydroxide are preferred. Volatile alkali can also be used, for example in the form of ammonia and / or alkanolamines, which can contain up to 9 carbon atoms per molecule. The alkanolamine is preferably selected from the group consisting of mono-, di-, triethanolamine, and propanolamine, and mixtures thereof.

[0026] In addition, the agent used in the washing or cleaning process may contain other ingredients that improve its performance and / or aesthetic properties. Within the scope of the present invention, the detergent preferably additionally contains one or more substances from the group of enzymes, builders, complexing agents, electrolytes, perfumes, perfume carriers, fluorescent agents, dyes, hydrotropes, foam inhibitors, silicone oils, anti-redeposition agents, graying inhibitors, shrinkage inhibitors, crease inhibitors, dye transfer inhibitors, antimicrobial agents, germicides, fungicides, antioxidants, preservatives, corrosion inhibitors, antistatic agents, bittering agents, ironing aids, phobic and waterproofing agents, swelling and slip-resistant agents, softening components, and UV absorbers.

[0027] The agents used in the washing or cleaning process preferably contain at least one enzyme. The at least one enzyme can be any enzyme known in the art that can exhibit catalytic activity in a washing or cleaning agent and includes, but is not limited to, proteases, amylases, lipases, cellulases, hemicellulases, mannanases, pectin-cleaving enzymes, tannases, xylanases, xanthanases, ß-glucosidases, carrageenases, perhydrolases, oxidases, oxidoreductases, and mixtures thereof. In a preferred embodiment, the at least one enzyme is selected from the group consisting of proteases, amylases, lipases, cellulases, and mixtures thereof. These enzymes are, in principle, of natural origin; however, improved variants based on the natural molecules are available for use in washing or cleaning agents, which are accordingly used with preference.

[0028] Among the proteases, those of the subtilisin type are preferred. Examples are the subtilisins BPN' and Carlsberg, the protease PB92, the subtilisins 147 and 309, the alkaline protease from Bacillus lentus, Subtilisin DY and the enzymes Thermitase, Proteinase K, and the proteases TW3 and TW7, which are classified as subtilases but no longer as subtilisins in the narrower sense. Subtilisin Carlsberg is available in a further developed form under the trade name Alcalase ®< from Novozymes A / S, Bagsvaerd, Denmark. Subtilisins 147 and 309 are marketed under the trade names Esperase ®< and Savinase ®< by Novozymes, respectively. The protease from Bacillus lentusThe protease variants known under the name BLAP ®< are derived from DSM 5483. Other useful proteases are, for example, the enzymes available under the trade names Durazym ®< , Relase ®< , Everlase ®< , Nafizym ®< , Natalase ®< , Kannase ®< and Ovozyme ®< from Novozymes, the enzymes available under the trade names Purafect ®< , Purafect ®< OxP, Purafect ®< Prime, Excellase ®< and Properase ®< from Genencor, the enzyme available under the trade name Protosol ®< from Advanced Biochemicals Ltd., Thane, India, the enzyme available under the trade name Wuxi ®< from Wuxi Snyder Bioproducts Ltd., China, the enzyme available under the trade names Proleather ®< and Protease P ®< from Amano Pharmaceuticals Ltd., Nagoya, Japan, and the enzyme available under the name Proteinase K-16 from Kao Corp., Tokyo, Japan. The proteases from Bacillus gibsonii and Bacillus pumilus.

[0029] Examples of amylases are the α-amylases from Bacillus licheniformis,from B. amyloliquefaciens or from B. stearothermophilus and their improved further developments for use in detergents and cleaning agents. The enzyme from B. licheniformis is available from Novozymes under the name Termamyl ®< and from Genencor under the name Purastar ®< ST. Further developments of this α-amylase are available from Novozymes under the trade names Duramyl ®< and Termamyl ®< ultra, from Genencor under the name Purastar ®< OxAm, and from Daiwa Seiko Inc., Tokyo, Japan, as Keistase ®<. The α-amylase from B. amyloliquefaciens is marketed by Novozymes under the name BAN ®<, and derived variants of the α-amylase from B. stearothermophilus under the names BSG ®< and Novamyl ®< , also from Novozymes. Furthermore, the α-amylase from Bacillus sp. A 7-7 (DSM 12368) and the cyclodextrin glucanotransferase (CGTase) from B. agaradherens(DSM 9948) are particularly noteworthy. Fusion products of all of the above-mentioned molecules can also be used. Furthermore, the further developments of α-amylase from Novozymes, available under the trade name Fungamyl ®<, are also suitable. Aspergillus niger and A. oryzae suitable. Other commercial products that can be used advantageously include Amylase-LT ® and Stainzyme ® or Stainzyme ultra ® or Stainzyme plus ® , the latter also from Novozymes. Variants of these enzymes obtained through point mutations can also be used according to the invention.

[0030] Examples of usable lipases or cutinases, which are included particularly for their triglyceride-splitting activities, are those originally from Humicola lanuginosa (Thermomyces lanuginosus)Available or further developed lipases, especially those with the amino acid exchange D96L. They are marketed, for example, by Novozymes under the trade names Lipolase ®< , Lipolase ®< Ultra, LipoPrime ®< , Lipozyme ®< and Lipex ®<. Furthermore, cutinases, for example, which were originally derived from Fusarium solani pisi and Humicola insolens have been isolated. Equally useful lipases are available from Amano under the names Lipase CE ®< , Lipase P ®< , Lipase B ®< , or Lipase CES ®< , Lipase AKG ®< , Bacillus sp. Lipase ®< , Lipase AP ®< , Lipase M-AP ®< and Lipase AML ®< are available. For example, the lipases and cutinases from Genencor can be used, whose starting enzymes were originally derived from Pseudomonas mendocina and Fusarium solaniiOther important commercial products include the preparations M1 Lipase ®< and Lipomax ®< originally marketed by Gist-Brocades and the enzymes marketed by Meito Sangyo KK, Japan, under the names Lipase MY-30 ®< , Lipase OF ®< and Lipase PL ®<, as well as the product Lumafast ®< from Genencor.

[0031] Depending on their purpose, cellulases can be present as pure enzymes, as enzyme preparations, or in the form of mixtures in which the individual components advantageously complement each other with regard to their various performance aspects. These performance aspects include, in particular, the cellulase's contribution to the primary washing performance of the agent (cleaning performance), the secondary washing performance of the agent (anti-redeposition effect or graying inhibition), the finishing (fabric effect), or the exertion of a "stonewashing" effect. A useful fungal, endoglucanase (EG)-rich cellulase preparation, or its further developments, is offered by Novozymes under the trade name Celluzyme ® . The products Endolase ® and Carezyme ® , also available from Novozymes, are based on the 50 kD EG and the 43 kD EG, respectively, from H. insolensDSM 1800. Other commercial products from this company are Cellusoft ®< , Renozyme ®< and Celluclean ®< . Also suitable are, for example, the 20 kD EG from Melanocarpus, which is available from AB Enzymes, Finland, under the trade names Ecostone ®< and Biotouch ®<. Other commercial products from AB Enzymes are Econase ®< and Ecopulp ®< . Other suitable cellulases are available from Bacillus sp. CBS 670.93 and CBS 669.93, with the Bacillus sp. CBS 670.93 is available from Genencor under the trade name Puradax ®. Other commercial products from Genencor are "Genencor detergent cellulase L" and IndiAge ® Neutra. Variants of these enzymes obtained by point mutations can also be used according to the invention. Particularly preferred cellulases are Thielavia terrestris Cellulase variants, cellulases from Melanocarpus, in particular Melanocarpus albomyces, EGIII-type cellulases from Trichoderma reesei or variants available from it.

[0032] Furthermore, other enzymes can be used, which are collectively referred to as hemicellulases, particularly for the removal of certain problematic soils. These include, for example, mannanases, xanthan lyases, xanthanases, xyloglucanases, xylanases, pullulanases, pectin-cleaving enzymes, and β-glucanases. Bacillus subtilisThe β-glucanase obtained is available under the name Cereflo® from Novozymes. Particularly preferred hemicellulases according to the invention are mannanases, which are marketed, for example, under the trade names Mannaway® by Novozymes or Purabrite® by Genencor.The pectin-cleaving enzymes also include, within the scope of the present invention, enzymes with the names pectinase, pectate lyase, pectin esterase, pectin demethoxylase, pectin methoxylase, pectin methylesterase, pectase, pectin methylesterase, pectin esterase, pectin pectyl hydrolase, pectin depolymerase, endopolygalacturonase, pectolase, pectin hydrolase, pectin polygalacturonase, endo-polygalacturonase, poly-α-1,4-galacturonide glycanohydrolase, endogalacturonase, endo-D-galacturonase, galacturan 1,4-α-galacturonidase, exopolygalacturonase, poly(galacturonate) hydrolase, exo-D-galacturonase, exo-D-galacturonanase, Exopoly-D-galacturonase, exo-poly-α-galacturonosidase, exopolygalacturonosidase or exopolygalacturanosidase.Examples of enzymes suitable in this regard are available under the names Gamanase ®< , Pektinex AR ®< , X-Pect ®< or Pectaway ®< from Novozymes, under the names Rohapect UF ®< , Rohapect TPL ®< , Rohapect PTE100 ®< , Rohapect MPE ®< , Rohapect MA plus HC, Rohapect DA12L ®< , Rohapect 10L ®< , Rohapect B1L ®< from AB Enzymes and under the name Pyrolase ®< from Diversa Corp., San Diego, CA, USA.

[0033] The liquid agents used in the washing or cleaning process preferably contain the at least one enzyme in total amounts established in the prior art. Thus, the at least one enzyme can be present in a total amount of 1 × 10 -8 to 5 wt.% based on active protein, or in a total amount of 0.001 to 3 wt.%, or 0.01 to 1.5 wt.%, or 0.05 to 1.25 wt.%. The stated amounts are to be understood as meaning that each enzyme present can be present in the stated amounts. The enzymes are preferably used as liquid enzyme formulation(s).

[0034] The at least one enzyme present in a washing or cleaning agent used in the washing or cleaning process supports the cleaning performance of the agent on specific soils or stains. Particularly preferably, an agent used in the washing or cleaning process contains several enzymes, whereby the enzymes may belong to the same or different enzyme classes. Particularly preferably, the enzymes exhibit synergistic effects with regard to their effectiveness against specific soils or stains, i.e., the enzymes contained in the composition support each other in their performance.

[0035] Terephthalate-PEG-based polymers are particularly suitable as antiredeposition agents. Alternatively, (co)polymers based on polyethyleneimine, polyvinyl acetate, and polyethylene glycol can also be used.

[0036] Organic builders are particularly suitable as builders, for example polycarboxylic acids, which can be used in the form of their sodium salts or as acids. Polycarboxylic acids are understood to be carboxylic acids that carry more than one acid function. Examples include adipic acid, succinic acid, glutaric acid, malic acid, tartaric acid, maleic acid, fumaric acid, sugar acids, aminocarboxylic acids, in particular glutamic acid-N,N-diacetic acid (GLDA) and methylglycine-N,N-diacetic acid (MGDA), as well as mixtures thereof. Polymeric polycarboxylates are also suitable as builders. These include, for example, the alkali metal salts of polyacrylic acid or polymethacrylic acid, for example, those with a relative molecular weight of 600 to 750,000 g / mol. Suitable polymers are, in particular, polyacrylates, which preferably have a molecular weight of 1,000 to 15,000 g / mol.Due to their superior solubility, short-chain polyacrylates, which have molecular weights of 1,000 to 10,000 g / mol, and particularly preferably 1,000 to 5,000 g / mol, may be preferred from this group. Copolymeric polycarboxylates are also suitable, especially those of acrylic acid with methacrylic acid and of acrylic acid or methacrylic acid with maleic acid. To improve water solubility, the polymers can also contain allylsulfonic acids, such as allyloxybenzenesulfonic acid and methallylsulfonic acid, as monomers. Soluble builders, such as acrylic polymers with a molecular weight of 1,000 to 5,000 g / mol, are preferred in liquid detergents.

[0037] The agents used in the washing or cleaning process may additionally contain phosphonates, such as HEDP (1-hydroxyethane-1,1-diphosphonic acid) or DTPMP (diethylenetriamine penta(methylenephosphonate), as builders and complexing agents.

[0038] The liquid washing and cleaning agents used in the washing or cleaning process can be produced using processes analogous to those known in the prior art. They can be filled into a water-soluble casing and thus be part of a water-soluble package. If the agent is packaged in a water-soluble casing, it is preferred that the water content is less than 10% by weight, based on the total agent, and that the anionic surfactants are present in the form of their ammonium salts or as free acids. A water-soluble package contains, in addition to the agent, a water-soluble casing. The water-soluble casing is preferably formed from a water-soluble film material. Such water-soluble packages can be produced either by vertical form-fill-seal (VFFS) or thermoforming processes.The thermoforming process generally involves forming a first layer of a water-soluble film material to form recesses for receiving a composition therein, filling the composition into the recesses, covering the composition-filled recesses with a second layer of a water-soluble film material, and sealing the first and second layers together at least around the recesses. The water-soluble enclosure is preferably formed from a water-soluble film material selected from the group consisting of polymers or polymer blends. The enclosure may be formed from one or two or more layers of the water-soluble film material.

[0039] The water-soluble film material of the first layer and the further layers, if present, can be the same or different. The water-soluble package comprising the agent and the water-soluble wrapper can have one or more compartments. The liquid agent can be contained in one or more compartments, if present, of the water-soluble wrapper. The amount of liquid agent preferably corresponds to the full or half dose required for one washing or cleaning cycle. It is preferred that the water-soluble wrapper contains polyvinyl alcohol or a polyvinyl alcohol copolymer. 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. A film material suitable for producing the water-soluble wrapping can additionally have polymers selected from the group comprising acrylic acid-containing polymers, polyacrylamides, oxazoline polymers, polystyrenesulfonates, polyurethanes, polyesters, polyethers, polylactic acid, and / or mixtures of the above polymers added to it. 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. Such polyvinyl alcohol copolymers particularly preferably contain, in addition to vinyl alcohol, acrylic acid, methacrylic acid, acrylic acid esters, methacrylic acid esters or mixtures thereof.Suitable water-soluble films for use in the wrappers of the water-soluble packages according to the invention are films marketed by MonoSol LLC, for example, under the designation M8630, C8400, or M8900. Other suitable films include films with the designation Solublon®< PT, Solublon®< GA, Solublon®< KC, or Solublon®< KL from Aicello Chemical Europe GmbH, or the VF-HP films from Kuraray. The water-soluble packages can have a substantially dimensionally stable spherical and pillow-shaped configuration with a circular, elliptical, square, or rectangular basic shape. The water-soluble package can have one or more chambers for storing one or more agents.If the water-soluble packaging has two or more chambers, at least one chamber contains a liquid agent, whereby the other chambers can each contain a solid or a differently composed liquid agent, or the contents of the individual chambers together form a liquid agent. Examples:

[0040] By simply shaking the mixing vessel, microemulsions were prepared from 10 parts by weight of one of the peroxoesters A, B and C listed below, 10 parts by weight of 4-fold ethoxylated C 10 -Guerbet alcohol (Lutensol ®< XL40) and 75 parts by weight of water at room temperature.

[0041] Non-microemulsified preparations of otherwise identical composition served as references, which, like the preparations according to the invention, were used with or without UV irradiation. For this purpose, white cotton swabs (4 cm × 4 cm) coated with a standardized blueberry soil were each filled with 10 ml of the test formulation and irradiated for 15 minutes with a UV-C lamp at a wavelength of 253.7 nm and an energy density of 221.4 mJ / cm² at a distance of 3 cm, or left in a light-tight box for the same time ("unirradiated"). After irradiation, the swabs were rinsed with water, dried, and their brightness measured. The difference in the L values ​​before and after treatment is shown in the table below; negative values ​​mean that the soil became darker, positive values ​​mean that the soil became lighter. Table: Brightness differences Peroxoester unirradiated irradiated A microemulsified -4,18 15,25 A not emulsified -7,21 -5,21 B microemulsified -3,85 16,55 B not emulsified -9,25 -2,87 C microemulsified nb 16,55 C not emulsified -7,41 -2,68 nb: not determined

Claims

1. Use of a combination of an aqueous microemulsion of a hydrophobic precursor compound consisting of the peroxo esters of one of the general formulae (I) to (VI), in which R represents a linear or branched-chain alkyl group having 1 to 30 carbon atoms, in particular 2 to 20 carbon atoms, R' represents a linear or branched-chain alkyl group having 1 to 30 carbon atoms, in particular 2 to 20 carbon atoms, R" represents a linear or branched-chain alkylene group having 1 to 30 carbon atoms, in particular 2 to 20 carbon atoms, R‴ represents a m-bonded linear or branched-chain alkyl group having 2 to 9 carbon atoms, in particular 3 to 5 carbon atoms, A in particular 2 to 20 carbon atoms, R‴ is an m-bonded linear or branched-chain alkylene group having 2 to 9 carbon atoms, in particular 3 to 5 carbon atoms, A is an alkylene group having 2 to 4 carbon atoms, m is a number from 2 to 6, in particular 3 or 4, and n is a number from 2 to 30, in particular from 3 to 15, and mixtures thereof, and from which a peroxocarboxylic acid or its salt can be released by UV irradiation, and UV radiation for removing soiling when washing textiles or cleaning hard surfaces2. Use according to claim 1, characterized in that the microemulsion contains 2% by weight to 12% by weight, in particular from 4% by weight to 10% by weight of the hydrophobic precursor compound, 2% by weight to 40% by weight, in particular from 4% by weight to 35% by weight of microemulsifier and to 100% by weight of water.

3. A washing or cleaning process in which a textile surface requiring washing or a hard surface requiring cleaning is brought into contact with a surfactant-containing aqueous washing or cleaning liquid which contains a hydrophobic precursor compound in microemulsified form which consists of the peroxo esters of one of the general formulae (I) to (VI), in which R represents a linear or branched-chain alkyl group having 1 to 30 carbon atoms, in particular 2 to 20 carbon atoms, R' represents a linear or branched-chain alkyl group having 1 to 30 carbon atoms, in particular 2 to 20 carbon atoms, R" represents a linear or branched-chain alkylene group having 1 to 30 carbon atoms, in particular 2 to 20 carbon atoms, R‴ represents a m-bonded linear or branched-chain alkyl group having 2 to 9 carbon atoms, in particular 3 to 5 carbon atoms, A in particular 2 to 20 carbon atoms, R‴ is an m-bonded linear or branched-chain alkylene group having 2 to 9 carbon atoms, in particular 3 to 5 carbon atoms, A is an alkylene group having 2 to 4 carbon atoms, m is a number from 2 to 6, in particular 3 or 4, and n is a number from 2 to 30, in particular from 3 to 15, and mixtures thereof, from which a peroxocarboxylic acid or its salt can be released by UV irradiation, and UV radiation is allowed to act on the liquid4. Process according to claim 3, characterized in that it is carried out at temperatures still below room temperature or at temperatures in the range from 5 °C to 60 °C, in particular from 10 °C to 40 °C.

5. Process according to claim 3 or 4, characterized in that the contact of the washing or cleaning liquid with the textile to be washed or the hard surface to be cleaned takes place for a duration of 1 minute to 2 hours, in particular 2 minutes to 1 hour, and / or in that the UV irradiation time is in the range from 5 minutes to 40 minutes, in particular from 6 minutes to 30 minutes, and / or in that the energy density of the UV radiation is in the range from 150 mJ / cm2 to 400 mJ / cm2 , in particular from 200 mJ / cm2 to 300 mJ / cm2 .

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