WO2010097245A1 - Gentle decoloring of colored dirt on hard and/or soft surfaces - Google Patents

Abstract

The invention relates to how to successfully control the problem of colored dirt on hard and/or soft surfaces, for example, textiles, which can be extremely adherent and therefore hard to remove and which at the same time even in small amounts can lead to highly visible, disturbing spots, in a manner in which the inherent coloring of the surface to be cleaned is maintained, by using electromagnetic radiation having wavelengths of 380-800 nm.

Description

 Gentle discoloration of paint dirt on hard and / or soft surfaces

The present invention relates to a process for decolorization of colored stains on hard and / or soft surfaces (in particular textile and / or tableware), in which the stain to be decolored is irradiated with electromagnetic radiation having wavelengths between 380-800 nm.

Furthermore, it relates to the use of radiation sources which emit electromagnetic radiation with wavelengths between 380-800 nm, in particular LED, in washing, rinsing or cleaning machines and in machine dryers to assist the removal of colored soiling from the hard to be cleaned and / or or soft surfaces. Furthermore, it relates to a suitable for use for decolorization of colored stains on hard and / or soft surfaces kit comprising a radiation source, a (pre-) treatment agent and optionally an instruction manual.

Finally, it relates to a washing, cleaning or dishwasher as well as a machine dryer, each containing one or more radiation sources, which are capable of emitting electromagnetic radiation having wavelengths between 380-800 nm, preferably 440 to 480 nm.

An important goal in the washing and cleaning of hard and soft surfaces is in addition to the creation of a hygienic condition in the removal of colored stains or stains, as these, even if they are harmless from a hygienic point of view, at least the aesthetic sensibility of the consumer sensitive can affect.

Particularly problematic is e.g. the removal of colored soiling of textiles, because they can adhere to the great annoyance of the consumer extremely firmly on the textile fiber and even in small quantities to clearly visible stains.

Against this background, the object of the present invention was to provide a possibility for decolorization of colored stains on hard and / or soft surfaces.

The object of the invention lies in a process for decolorization of colored stains on hard and / or soft surfaces (in particular textile and / or tableware and / or cellulose) in which the stain to be decolored is irradiated with electromagnetic radiation having wavelengths between 380-800 nm. One advantage of this method is, inter alia, that it offers a very mild and gentle way of decolorizing colored stains.

The intrinsic color of the substance to be cleaned (or the hard and / or soft surfaces) is retained, so that the present invention is very advantageous, especially with regard to colored textiles. A good material protection of the substance to be cleaned (or the hard and / or soft surfaces) is guaranteed. Upon the use of common bleaching agents, e.g. Sodium perborate, sodium percarbonate, hydrogen peroxide or Natriumhypochlord can be dispensed with or their amount can be at least reduced. The use of high temperatures in washing processes is not necessary to obtain the desired cleaning performance.

The term "colored stains" refers to stains such as those from

Natural dyes, e.g. in coffee, tea, chocolate and cocoa, fruit, red wine, grass, juices, e.g. Elderberry juice or tomato juice, curry, mustard are included, or, for example, of technical

Dyes, e.g. from cosmetics, color pencils and inks, originate on hard or soft

Surfaces visible stains form.

Known natural dyes are e.g. Curcumin (e.g., in curry and mustard), lycopene (e.g., in tomatoes),

Carotenes (e.g., in carrots), betanidine (e.g., in beetroot), or quercetin (e.g., many

Fruits, especially berries).

Typical colored stains are e.g. yellow mustard patch, green grass patch or red

Wine stains.

The term "decolorization of colored stains" means any color change of the stain to lighter colors, ie, the partial discoloration of the stain, more specifically, it means reducing the color intensity of the stain or stain so that the stain In particular, this term in the optimal case, of course, includes the complete removal of the color of a stain.

The term "hard and / or soft surfaces" encompasses in particular all textiles and / or crockery. Textiles are primarily used to refer to sheetlike structures such as felts, woven fabrics, knitted fabrics, nonwovens, but especially to the apparel industry (such as underwear) , In addition, also home textiles such as carpets, blankets, curtains and curtains and so-called technical textiles.With dishes are mainly dinner and cookware (ie plates, cups, pots, pans, etc.), glasses, cutlery and the like meant more.

If the electromagnetic radiation used according to the invention has wavelengths between 400-700 nm, preferably 400 to 480 nm, in particular 440 to 480 nm, then there is one preferred embodiment of the invention. In particular, the wavelengths of the radiation lie exclusively in the stated range.

As a radiation source, in particular light-emitting diodes (LED), called light-emitting diodes for short, can be used. This corresponds to a preferred embodiment of the invention. Other radiation sources can be used in principle.

The construction and the operating principle of preferably usable light-emitting diodes are known and widely described in the literature, so that it is possible to dispense with further explanations here.

The light emission of light-emitting diodes is based on the recombination of electron-hole pairs (excitons) in the transition region of a forward-biased pn junction (semiconductor). The size of the band gap and thus the color of the radiation can be controlled by the chemical composition of the semiconductor. For example, the semiconductor GaAs has a direct band gap of 1.4 eV, corresponding to a wavelength of 885 nm.

As a result of the targeted selection of the semiconductor materials of an LED and of the doping, the properties of the light generated can consequently be varied so that in particular the spectral range (that is to say the color which corresponds to the visible range) and the efficiency can be influenced. Below are some examples.

Aluminum gallium arsenide (AIGaAs) and gallium aluminum arsenide (GaAIAs) can emit red light. Gallium arsenide phosphide (GaAsP) and aluminum indium gallium phosphide (AlInGaP) can emit red, orange and yellow light. Gallium phosphide (GaP) can emit green light. Silicon carbide (SiC) and zinc selenide (ZnSe) can emit blue light. Indium gallium nitride (InGaN) / gallium nitride (GaN) can emit blue and green light.

With sufficiently strong carrier inversion, population inversion and stimulated emission can be achieved. A light emitting diode then becomes a laser diode (diode laser, semiconductor laser). These are also possible sources of radiation within the meaning of the invention

A preferred embodiment of the invention is when the spectral half-width of the spectral curves (half-width of the spectral light output of the emitted radiation) in the range of 4 to 100 nm, preferably 5-40 nm, in particular 10-20 nm.

The duration of the irradiation should be at least 30 seconds, with longer irradiation times leading to improved stain removal according to the invention. It therefore corresponds to a preferred embodiment of the invention if the duration of the irradiation is 30 seconds to 5 hours, preferably 1 minute to 2 hours, in particular 5 minutes to 1 hour.

The distance between the radiation source and the irradiated object should preferably be <1 meter, advantageously <50 cm, more advantageously <30 cm, even more advantageously <20 cm, for example <10 cm or even <5 cm.

The irradiance is advantageously in the range of 10 mW / cm ² to 200 W / cm ² , preferably in the range of 1 to 10 W / cm ² . This corresponds to a preferred embodiment of the invention.

If the pulse duration of the radiation is 5 ns to continuous wave, preferably 100 ns to continuous wave, then another preferred embodiment of the invention is present.

According to a further preferred embodiment of the invention, it may be provided that the regulation of the brightness of the LED is effected by pulse width modulation (PWM), preferably in the ratio 1: 100-100: 1, in particular 1:10 to 10: 1.

The process according to the invention is generally suitable for decolorization of colored soils on hard and / or soft surfaces and in particular it is suitable for decolorization of colored soils which contain yellow to orange dyes, preferably curcuma dyes, e.g. Curry and mustard, in particular curcumin include, in particular using blue light emitting radiation sources, in particular corresponding LED.

The method according to the invention is likewise suitable for decolorization of colored stains comprising carotenoids, in particular carotenes and / or xanthophylls.

In particular, good results have been achieved in the decolorization of colored soils resulting from soiling with egg yolk or egg yolk, preferably comprising dyes such as carotenoids, zeaxanthin, lutein, xanthophylls, canthaxanthin, astaxanthin, apocarotenoids, cryptoxanthins and / or .beta.-carotene, in particular with respect to Removal of soiling of textile and / or tableware.

The inventive method is also suitable for decolorization of colored soils, which include anthocyanins and / or anthocyanidins. The anthocyanins are glycosides whose actual chromophores are their aglycones, the anthocyanidins. The inventive method is also suitable for decolorization of colored soils, which include chlorophylls.

The process according to the invention is generally suitable for decolorization of colored stains comprising color impressions from the range of purple, green, greenish-yellow, red, orange, yellow, brown, yellow-green, green, blue-green (cyan), blue and / or violet.

In a preferred embodiment of the invention, the process according to the invention is provided for decolorization of colored stains comprising yellow to orange dyes, such as, preferably, curcuma dyes, e.g. of curry and mustard, which in particular comprise curcumin, and / or which comprise dyes which may be present in egg yolks or egg yolks, preferably comprising colorants such as carotenoids, zeaxanthin, lutein, xanthophylls, canthaxanthin, astaxanthin, apocarotenoids, cryptoxanthins and / or Carotene.

The present invention also includes the possibility of carrying out processes according to the invention for decolorization of colored stains on hard and / or soft surfaces, in which the stain to be decolorized is irradiated with electromagnetic radiation having wavelengths between 380 and 800 nm, such that the respective stains to be decolored colored soiling is irradiated with light of the complementary color, ie e.g. a blue-appearing spot is irradiated with orange light (wavelength 590 nm), a violet appearing spot with yellow-green light (wavelength 530 nm), etc. In particular, it is preferable to have yellow to dark orange appearing spots with blue light (wavelength preferably 400 nm to preferably 490 nm).

A decolouring performance occurs both in the dry and in the wet state of the object to be cleaned. However, it is more preferable for the colored soil to be irradiated in the wet (or wet) state. This corresponds to a preferred embodiment of the invention.

The irradiation can be carried out with a corresponding radiation source in principle at any location. However, it is particularly preferred if the irradiation is carried out in a washing, rinsing or cleaning machine or in a machine dryer, preferably before and / or during and / or after a mechanical washing, rinsing or cleaning process or during a drying process.

The ambient temperature during the irradiation may preferably be at room temperature, which, depending on the climatic conditions, is generally in the range of approximately 18 ° C to 35 ° C. The ambient temperature during irradiation may also be increased, for example, lie at 40 ° or at 60 ⁰ C or in the field, particularly when the irradiation in a washing, Rinsing or cleaning machine or in a machine dryer, preferably before and / or during and / or after a mechanical washing, rinsing or cleaning process or during a drying process.

Suitable washing, rinsing or cleaning machines are e.g. conventional automatic washing machines for textile washing and e.g. usual dishwasher.

Likewise, it corresponds to a preferred embodiment of the invention, when the irradiation in a machine-type clothes dryer, which are able to dry the textiles moist after textile washing, in particular with the supply of warm air mechanically in a short time, takes place. Suitable devices for this purpose are e.g. the so-called exhaust air dryer, condensation dryer, dryer with heat pump and the washer dryer, which represent a combination of the dryer with a washing machine in a device.

Another object of the present invention is the use of radiation sources which emit electromagnetic radiation having wavelengths between 380-800 nm, preferably 400-700 nm, in particular 440-480 nm, in particular LED, in washing, rinsing or cleaning machines or tumble dryers to aid in the removal of colored stains from the hard and / or soft surfaces to be cleaned.

The radiation sources can be part of the machines, they can also be added separately to the machines.

"Supporting the removal of colored stains" here means the contribution that is made by "discoloring" coloring substances of the stains, so that at least a color change of stain or stain to brighter colors is made possible.Accordingly, the reduction of color intensity so that the stain or soiling becomes less visible to the human eye, in particular, in the optimal case, this term includes, of course, the complete removal of stain staining up to the complete removal of the stains concerned.

The use of the invention makes it possible to increase the water solubility of the colored stains and thus the removability of the stain is facilitated. Thus, if the use according to the invention for promoting the removal of colored stains from the hard or soft surfaces to be cleaned is accompanied by an increase in the water solubility of the colored stains or the removal of colored stains is promoted by increasing the water solubility of the colored stains, so is a preferred embodiment of the invention.

The use according to the invention makes it possible to reduce the dirt adhesion of the colored soil on the surface to be cleaned.

A use according to the invention for assisting the removal of colored stains from the hard or soft surfaces to be cleaned by reducing the dirt adhesion of the colored stains on the surface to be cleaned therefore corresponds to a preferred embodiment of the invention.

Another object of the present invention is a washing, cleaning or dishwashing machine, which contains one or more radiation sources, which is capable of emitting electromagnetic radiation having wavelengths between 380-800 nm, preferably 400-700 nm, in particular 440-480 nm. Another object of the invention is therefore a washing, cleaning or rinsing method using a just mentioned a washing, cleaning or dishwasher, which thus contains one or more radiation sources, which for emitting electromagnetic radiation having wavelengths between 380-800 nm, preferably 400-700 nm, in particular 440-480 nm is capable. With regard to preferred embodiments of this subject, reference is also made to the preceding and to the following description.

The radiation sources which can be used in this case should preferably be capable of emitting electromagnetic radiation having such wavelengths which lies in the absorption region of the soil to be removed.

Yet another object of the present invention is a mechanical clothes dryer, in particular exhaust air dryer, condensation dryer, heat pump dryer and washer dryer (ie a combination of the dryer with a washing machine in a device), which contains one or more radiation sources, which for emitting electromagnetic radiation having wavelengths between 380-800 nm, preferably 400 to 700 nm, in particular 440 to 480 nm is capable. Another object of the invention is also a drying method using a just-mentioned machine dryer, which thus contains one or more radiation sources, which is capable of emitting electromagnetic radiation having wavelengths between 380-800 nm, preferably 440 to 480 nm. With regard to preferred embodiments of this subject, reference is also made to the preceding and to the following description. Another object of the invention is a kit, suitable for use for decolorization of colored stains on hard and / or soft surfaces, comprising

(A) a radiation source, preferably comprising light emitting diodes (LED) and

(B) a (pre-) treatment agent, preferably in liquid form, and optionally (c) a user manual for the consumer about the right handling of the kit and its applications.

Suitable radiation sources in the sense of this kit and the invention are thus light-emitting diodes, in particular those as previously described, preferably in the preferred embodiments of the invention.

A suitable (pre-) treatment agent in the sense of this invention may e.g. any textile treatment agent, such as e.g. a laundry detergent or e.g. any hard surface treating agent, e.g. Dishwashing or general cleaning agent. The treating agent may also be a pre- or after-treatment agent. In its simplest embodiment, the (pre) treatment agent can also be desalinated water.

The (pre) treatment agent may in particular be in the form of a homogeneous solution or as a suspension, but may also be in the form of a powdery solid, e.g. also in post-compacted particle form.

The instructions for use, which may optionally be included in the kit, teach the consumer how to handle the kit and its uses. This is advantageous because such kits are not yet available on the market and the consumer therefore still has no wealth of experience regarding the use of the kit, in particular the radiation source.

To enhance the decolorization performance obtainable according to the invention, it is possible to use photocatalytically active materials in the (pre) treatment agent, such as (optionally modified or doped) TiO ₂ , CeO ₂ , ZnO or other photocatalytically active semiconductor materials.

It is particularly advantageous to use finely divided materials, e.g. with an average size of the primary particles (measured by transmission electron microscopy) in the range of 5 to 2000 nm, preferably in the range of 10 to 200 nm, in particular 15 to 100 nm, e.g. correspondingly finely divided (modified) titanium dioxide.

For example, it is possible to use a fine-particle, carbon-containing photocatalyst based on titanium dioxide. Applicable semiconductor materials are described, for example, in US 2005/0226761 A1 and in US 2005/0227854 A1. The size of the bandgap usable photocatalytically active materials should preferably in the range of 1, 2 to 3.3 eV, in particular 2.535 to 2.95 eV lie. In particular, it is advantageous if the band gap of the optionally usable semiconductor material is tuned to the wavelength of the radiation of the radiation source, preferably LED.

A suitable (pre) treatment agent may thus be e.g. an aqueous composition containing photocatalytically active materials as described above, e.g. in dispersed form, e.g. also other ingredients such. Thickeners, organic solvents and surfactants and possibly other optional ingredients may be included.

The (pre) treatment agent of the invention may e.g. also contain biocidal compounds, fragrances, surfactants and other ingredients, especially those which further improve the performance and / or aesthetic properties of the (pre) treatment agent.

In the context of the present invention, it is therefore possible to use preferred (pre) treatment agents, e.g. one or more substances from the group of softening components, thickeners, builders, electrolytes, non-aqueous (preferably water-miscible) organic solvents, pH regulators, fluorescers, dyes, hydrotopes, foam inhibitors, silicone oils, anti-redeposition agents, optical brighteners, grayness inhibitors, Sequestering agents, shrinkage inhibitors, enzymes, anti-crease agents,

Color transfer inhibitors, antioxidants, preservatives, corrosion inhibitors, antistatic agents, bittering agents (in particular based on organic and / or inorganic peroxygen compounds), bleach activators ironing auxiliaries, bleaching agents, repellents and impregnating agents, swelling and anti-slip agents, skin care compounds and UV absorbers.

The (pre-) treatment agents according to the invention may contain in particular one or more surfactants, preferably anionic surfactants, nonionic surfactants and mixtures thereof, but also cationic, zwitterionic and amphoteric surfactants.

Suitable optional nonionic surfactants are in particular alkyl glycosides and ethoxylation and / or propoxylation of alkyl glycosides or linear or branched alcohols each having 12 to 18 carbon atoms in the alkyl moiety and 3 to 20, preferably 4 to 10 alkyl ether groups. Also suitable are ethoxylation and / or propoxylation products of N-alkylamines, vicinal diols, fatty acid esters and fatty acid amides which correspond to said long-chain alcohol derivatives with respect to the alkyl moiety, and of alkylphenols having 5 to 12 C atoms in the alkyl radical. As optional nonionic surfactants it is preferred to use alkoxylated, advantageously ethoxylated, in particular primary, alcohols having preferably 8 to 18 C atoms and on average 1 to 12 moles of ethylene oxide (EO) per mole of alcohol, in which the alcohol radical is linear or preferably in the 2-position may be methyl branched or contain linear and methyl-branched radicals in the mixture, as they are usually present in Oxoalkoholresten. In particular, however, alcohol ethoxylates with linear radicals of alcohols of natural origin having 12 to 18 carbon atoms, for example of coconut, palm, tallow or oleyl alcohol, and on average 2 to 8 EO per mole of alcohol are preferred. The preferred ethoxylated alcohols include, for example, C ₁₂ -C ₁₄ -alcohols with 3 EO or 4 EO, C ₉ -C ₁₁ -alkyl with 7 EO, C ₁₃ -C ₁₅ -alcohols with 3 EO, 5 EO, 7 EO or 8 EO, C ₁₂ -C ₁₈ -alcohols with 3 EO, 5 EO or 7 EO and mixtures of these, such as mixtures of C ₁₂ -C ₁₄ -alcohol with 3 EO and C ₁₂ -C ₁₈ -alcohol with 7 EO. The degrees of ethoxylation given represent statistical means which, for a particular product, may be an integer or a fractional number. Preferred alcohol ethoxylates have a narrow homolog distribution (narrow rank ethoxylates, NRE). In addition to these nonionic surfactants, fatty alcohols with more than 12 EO can also be used. Examples of these are (TaIg) fatty alcohols with 14 EO, 16 EO, 20 EO, 25 EO, 30 EO or 40 EO. In particular, agents for use in mechanical processes usually extremely low-foam compounds are used. These include preferably C ₁₂ -C ₁₈ -Alkylpolyethylen- glycol-polypropylene glycol ethers, each with at 8 mol ethylene oxide and propylene oxide in the molecule. However, it is also possible to use other known low-foam nonionic surfactants, such as, for example, C ₁₂ -C ₁₈ -alkylpolyethyleneglycol-polybutylene glycol ethers having up to 8 mol of ethylene oxide and butylene oxide units in the molecule as well as end-capped alkylpolyalkylene glycol mixed ethers. Also particularly preferred are the hydroxyl-containing alkoxylated alcohols, as described in European Patent Application EP 0 300 305, so-called hydroxy mixed ethers. The optionally usable nonionic surfactants also include alkyl glycosides of the general formula RO (G) _x , in which R is 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 represents a glycose unit having 5 or 6 C atoms, preferably glucose. The degree of oligomerization x, which indicates the distribution of monoglycosides and oligoglycosides, is an arbitrary number - which, as a variable to be determined analytically, may also assume fractional values - between 1 and 10; preferably x is 1, 2 to 1, 4. Also suitable are polyhydroxy fatty acid amides of the formula (III) in which R ^{1 is} CO for an aliphatic acyl radical having 6 to 22 carbon atoms, R ^{2 is} hydrogen, an alkyl or hydroxyalkyl radical having 1 to 4 carbon atoms and [Z] is a linear or branched polyhydroxyalkyl radical having 3 to 10 carbon atoms and 3 to 10 hydroxyl groups: R ²

I

R ¹ -CO-N- [Z] (IM)

The polyhydroxy fatty acid amides are preferably derived from reducing sugars having 5 or 6 carbon atoms, in particular from glucose. The group of polyhydroxy fatty acid amides also includes compounds of the formula (IV)

R ⁴ -OR ⁵

(IV)

R -CO-N- [Z]

in the R ^{3 is} a linear or branched alkyl or alkenyl radical having 7 to 12 carbon atoms, R ^{4 is} a linear, branched or cyclic alkylene radical or an arylene radical having 2 to 8 carbon atoms and R ^{5 is} a linear, branched or cyclic alkyl radical or a Aryl radical or an oxyalkyl radical having 1 to 8 carbon atoms, wherein Ci-C ₄ alkyl or phenyl radicals are preferred, and [Z] is a linear polyhydroxyalkyl radical whose alkyl chain is substituted with at least two hydroxyl groups, or alkoxylated, preferably ethoxylated or propoxylated derivatives of this group. [Z] is also obtained here preferably by reductive amination of a sugar such as glucose, fructose, maltose, lactose, galactose, mannose or xylose. The N-alkoxy- or N-aryloxy-substituted compounds can then be converted into the desired polyhydroxy fatty acid amides, for example by reaction with fatty acid methyl esters in the presence of an alkoxide as catalyst. Another class of preferably usable nonionic surfactants, which are used either as the sole nonionic surfactant or in combination with other nonionic surfactants, in particular together with alkoxylated fatty alcohols and / or alkyl glycosides, are alkoxylated, preferably ethoxylated or ethoxylated and propoxylated fatty acid alkyl esters, preferably with 1 to 4 carbon atoms in the alkyl chain, especially fatty acid methyl ester. Nonionic surfactants of the amine oxide type, for example N-cocoalkyl-N, N-dimethylamine oxide and N-tallowalkyl-N, N-dihydroxyethylamine oxide, and the fatty acid alkanolamides may also be suitable. The amount of these nonionic surfactants is preferably not more than that of the ethoxylated fatty alcohols, especially not more than half thereof. Other suitable surfactants are so-called gemini surfactants. These are generally understood as meaning those compounds which have two hydrophilic groups per molecule. These groups are usually separated by a so-called "spacer". This spacer is typically a carbon chain that should be long enough for the hydrophilic groups to be spaced sufficiently apart for them to act independently of each other. Such surfactants are generally characterized by an unusually low critical micelle concentration and the ability to greatly reduce the surface tension of the water. In exceptional cases are understood by the term gemini surfactants not only such "dimer", but also according to "trimeric" surfactants. Suitable gemini surfactants are, for example, sulfated hydroxy mixed ethers or dimer alcohol bis- and trimer tris sulfates and ether sulfates. End-capped dimeric and trimeric mixed ethers are characterized in particular by their bi- and multi-functionality. Thus, the end-capped surfactants mentioned have good wetting properties and are low foaming, so that they are particularly suitable for use in machine washing or cleaning processes. However, it is also possible to use gemini polyhydroxy fatty acid amides or polyoxy hydroxy fatty acid amides. Also suitable are the sulfuric acid monoesters of the straight-chain or branched C ₇ -C ₂ -substituted alcohols ethoxylated with from 1 to 6 mol of ethylene oxide, such as 2-methyl-branched C ₉ -C ₁₁ -alcohols having on average 3.5 mol of ethylene oxide (EO) or C ₁₂ C ₁₈ fatty alcohols with 1 to 4 EO.

Examples of anionic surfactants which can preferably be used are soaps, alkylbenzenesulfonates, alkanesulfonates, methyl ester sulfonates and α-olefin sulfonates, alkyl sulfates, for example fatty alcohol sulfates, sulfosuccinates and alkyl ether sulfates. Preferred anionic surfactants include the salts of alkylsulfosuccinic acid, also referred to 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 to C ₁₈ fatty alcohol residues or mixtures of these. Particularly preferred sulfosuccinates contain a fatty alcohol residue derived from ethoxylated fatty alcohols, which by themselves are nonionic surfactants. Sulfosuccinates, whose fatty alcohol residues are derived from ethoxylated fatty alcohols with a narrow homolog distribution, are again particularly preferred. Likewise, it is also possible to use alk (en) ylsuccinic acid having preferably 8 to 18 carbon atoms in the alk (en) yl chain or salts thereof. Suitable further anionic surfactants are fatty acid derivatives of amino acids, for example N-methyltaurine (Tauride) and / or N-methylglycine (sarcosides). Particularly preferred are the sarcosides or the sarcosinates and here especially sarcosinates of higher and optionally monounsaturated or polyunsaturated fatty acids such as oleyl sarcosinate. As further anionic surfactants are particularly soaps into consideration. Particularly suitable are saturated fatty acid soaps, such as the salts of lauric acid, myristic acid, palmitic acid, stearic acid, hydrogenated erucic acid and behenic acid and, in particular, soap mixtures derived from natural fatty acids, for example coconut, palm kernel or tallow fatty acids. Together with these soaps or as a substitute for soaps, it is also possible to use the known alkenylsuccinic acid salts.

The anionic surfactants, including soaps, may be in the form of their sodium, potassium or ammonium salts and as soluble salts of organic bases, such as mono-, di- or triethanolamine. The anionic surfactants are preferably present in the form of their sodium or potassium salts, in particular in the form of the sodium salts. Examples of cationic surfactants which can be used are quaternary ammonium compounds having one or two hydrophobic alkyl radicals and quaternary phosphonium salts or tertiary sulfonium salts. Quaternary ammonium salts having a hydrophobic radical, for example dodecylbenzylammonium chloride, have a biocidal action, those having two hydrophobic groups, in particular those which additionally have an ester bond (so-called esterquats), are particularly preferred as active ingredients with a softener function.

Surfactants may optionally be present in (pre-) treatment agents according to the invention in proportions of preferably> 0.1% by weight, advantageously from 5% by weight to 50% by weight, in particular from 8% by weight to 30% by weight. be included. Combinations of anionic and nonionic surfactants, e.g. the combination of linear alkyl benzene sulfonates and fatty alcohol alkoxylates are particularly preferred. Also, pretreatment agents containing only small amounts of surfactants, e.g. 0.05 wt .-% to <5 wt .-%, or even surfactant-free.

A (pre-) treatment agent according to the invention may preferably contain at least one water-soluble and / or water-insoluble, organic and / or inorganic builder. The water-soluble organic builder substances include polycarboxylic acids, in particular citric acid and sugar acids, monomeric and polymeric aminopolycarboxylic acids, in particular methylglycinediacetic acid, nitrilotriacetic acid and ethylenediaminetetraacetic acid and polyaspartic acid, polyphosphonic acids, in particular aminotris (methylenephosphonic acid), ethylenediaminetetrakis (methylenephosphonic acid) and 1-hydroxyethane-1, 1-diphosphonic acid, polymeric hydroxy compounds such as dextrin and polymeric (poly) carboxylic acids, in particular the accessible by oxidation of polysaccharides or dextrins polycarboxylates, polymeric acrylic acids, methacrylic acids, maleic acids and copolymers thereof, which also small amounts of polymerizable substances without carboxylic acid functionality may contain polymerized. The molecular weight of the homopolymers of unsaturated carboxylic acids is generally between 3,000 and 200,000, of the copolymers between 2,000 and 200,000, preferably 30,000 to 120,000, each based on the free acid. A particularly preferred acrylic acid-maleic acid copolymer has a molecular weight of from 30,000 to 100,000. Commercially available products are, for example, Sokalan® CP 5, CP 10 and PA 30 from BASF. Suitable, although less preferred, compounds of this class are copolymers of acrylic acid or methacrylic acid with vinyl ethers, such as vinylmethyl ethers, vinyl esters, ethylene, propylene and styrene, in which the proportion of the acid is at least 50% by weight. It is also possible to use terpolymers which contain two unsaturated acids and / or salts thereof as monomers and also vinyl alcohol and / or an esterified vinyl alcohol or a carbohydrate as the third monomer as water-soluble organic builder substances. The first acidic monomer or its salt is derived from a monoethylenically unsaturated C ₃ -C ₈ carboxylic acid and preferably from a C ₃ -C ₄ monocarboxylic acid, in particular from (meth) acrylic acid. The second acidic monomer or its salt may be a derivative of a C ₄ -C ₈ -dicarboxylic acid, with maleic acid being particularly preferred, and / or a derivative of an allylsulfonic acid substituted in the 2-position with an alkyl or aryl radical. Such polymers generally have a molecular weight between 1,000 and 200,000. Further preferred copolymers are those which preferably have as monomers acrolein and acrylic acid / acrylic acid salts or vinyl acetate. The organic builder substances can be used, in particular for the preparation of liquid agents, in the form of aqueous solutions, preferably in the form of 30 to 50 percent by weight aqueous solutions. All of the acids mentioned are generally used in the form of their water-soluble salts, in particular their alkali metal salts.

If desired, such organic builder substances may be present in amounts of up to 40% by weight, in particular up to 25% by weight and preferably from 1% by weight to 8% by weight. Quantities close to the stated upper limit are preferably used in paste-form or liquid, in particular water-containing, agents according to the invention.

Suitable water-soluble inorganic builder materials are, in particular, alkali metal silicates, alkali metal carbonates and alkali metal phosphates, which may be in the form of their alkaline, neutral or acidic sodium or potassium salts. Examples of these are trisodium phosphate, tetra sodium diphosphate, disodium dihydrogen diphosphate, pentasodium triphosphate, so-called sodium hexametaphosphate, oligomeric trisodium phosphate with degrees of oligomerization of from 5 to 1000, in particular from 5 to 50, and the corresponding potassium salts or mixtures of sodium and potassium salts.

As water-insoluble, water-dispersible inorganic builder materials, in particular crystalline or amorphous alkali metal aluminosilicates, in amounts of up to 50 wt .-%, preferably not more than 40 wt .-% and in liquid agents, in particular from 1 wt .-% to 5 wt .-%, be used. Among these, preferred are the detergent grade crystalline sodium aluminosilicates, particularly zeolite A, P and optionally X, alone or in mixtures, for example in the form of a cocrystal of zeolites A and X (Vegobond® AX, a commercial product of Condea Augusta SpA) , Amounts near the above upper limit are preferably used in solid, particulate agents. In particular, suitable aluminosilicates have no particles with a particle size greater than 30 .mu.m and preferably consist of at least 80% by weight of particles having a size of less than 10 .mu.m.

Suitable substitutes or partial substitutes for the said aluminosilicate are crystalline alkali silicates which may be present alone or in a mixture with amorphous silicates. The alkali silicates useful as builders in the compositions according to the invention preferably have one molar ratio of alkali metal oxide to SiO ₂ below 0.95, in particular from 1: 1, 1 to 1: 12 and may be present in amorphous or crystalline form. Preferred alkali metal silicates are the sodium silicates, in particular the amorphous sodium silicates, with a molar ratio of Na ₂ O: SiO ₂ of 1: 2 to 1: 2.8. The crystalline silicates which may be present alone or in admixture with amorphous silicates, are crystalline layer silicates with the general formula Na ₂ Si _x O _{2x + I} y H ₂ O are used in which x, known as the modulus, an integer of 1, 9 to 22, in particular 1, 9 to 4 and y is a number from 0 to 33 and preferred values for x are 2, 3 or 4. Preferred crystalline phyllosilicates are those in which x in the abovementioned general formula assumes the values 2 or 3. In particular, both β- and δ-sodium disilicates (Na ₂ Si ₂ O ₅ y H ₂ O) are preferred. Also prepared from amorphous alkali silicates, practically anhydrous crystalline alkali silicates of the abovementioned general formula in which x is a number from 1, 9 to 2.1, can be used in inventive compositions. In a further preferred embodiment of the composition according to the invention, a crystalline sodium layer silicate with a modulus of 2 to 3 is used, as can be prepared from sand and soda. Crystalline sodium silicates with a modulus in the range of 1.9 to 3.5 are used in a further preferred embodiment of compositions according to the invention. Crystalline layer-form silicates of formula (I) given above are sold by Clariant GmbH under the trade name Na-SKS, eg Na-SKS-1 (Na ₂ Si ₂₂ O ₄₅ XH ₂ O, Kenyaite), Na-SKS-2 (Na ₂ Si ₁₄ O ₂₉ XH ₂ O, magadiite), Na-SKS-3 (Na ₂ Si ₈ O ₁₇ XH ₂ O) or Na-SKS-4 (Na ₂ Si ₄ O ₉ XH ₂ O, makatite). Of these, especially Na SKS-5 ((Na-X are ₂ Si ₂ O _5), Na-SKS-7 (.beta.-Na ₂ Si ₂ 0 _5, natrosilite), Na-SKS-9 (NaHSi ₂ O ₅ 3H ₂ O), Na-SKS-10 (NaHSi ₂ O ₅ 3H ₂ O, kanemite), Na-SKS-11 (t-Na ₂ Si ₂ 0 ₅₎ and Na-SKS-13 (NaHSi ₂ O ₅₎ , but in particular Na-SKS-6 (5-Na ₂ Si ₂ O _5). In a preferred embodiment of inventive compositions, a granular compound of crystalline layered silicate and citrate, of crystalline layered silicate and the above-mentioned (co) polymeric polycarboxylic acid, or from alkali metal silicate and alkali carbonate, as it is commercially available, for example under the name Nabion® 15.

Builder substances may preferably be present in the compositions according to the invention in amounts of up to 75% by weight, in particular 5% by weight to 50.

As for the use in agents according to the invention suitable peroxygen compounds are in particular organic peracids or pers acid salts of organic acids, such as phthalimidopercaproic acid, perbenzoic acid or salts of diperdodecanedioic acid, hydrogen peroxide and under the washing conditions hydrogen peroxide donating inorganic salts, which include perborate, percarbonate, persilicate and / or persulfate Caroat belong into consideration. If solid peroxygen compounds are to be used, they can be used in the form of powders or granules, which can also be enveloped in a manner known in principle. If an agent according to the invention contains peroxygen compounds, they are present in amounts of preferably up to 50% by weight, in particular from 5% by weight to 30% by weight. The addition Small amounts of known bleach stabilizers such as phosphonates, borates or metaborates and metasilicates and magnesium salts such as magnesium sulfate may be useful.

As bleach activators, it is possible to use compounds which, under perhydrolysis conditions, give aliphatic peroxycarboxylic acids having preferably 1 to 10 C atoms, in particular 2 to 4 C atoms, and / or optionally substituted perbenzoic acid. Suitable substances are those which carry O- and / or N-acyl groups of the stated C atom number and / or optionally substituted benzoyl groups. Preference is given to polyacylated alkylenediamines, in particular tetraacetylethylenediamine (TAED), acylated triazine derivatives, in particular 1,5-diacetyl-2,4-dioxohexahydro-1,3,5-triazine (DADHT), acylated glycolurils, in particular tetraacetylglycoluril (TAGU), N- Acylimides, in particular N-nonanoylsuccinimide (NOSI), acylated phenolsulfonates, in particular n-nonanoyl or isononanoyloxybenzenesulfonate (n- or iso-NOBS), carboxylic anhydrides, in particular phthalic anhydride, acylated polyhydric alcohols, in particular triacetin, ethylene glycol diacetate, 2,5-diacetoxy- 2,5-dihydrofuran and enol esters and also acetylated sorbitol and mannitol or their described mixtures (SORMAN), acylated sugar derivatives, in particular pentaacetylglucose (PAG), pentaacetylfruktose, tetraacetylxylose and octaacetyllactose as well as acetylated, optionally N-alkylated glucamine and gluconolactone, and / or N- acylated lactams, for example N-benzoyl-caprolactam. The hydrophilic substituted acyl acetals and the acyl lactams are also preferably used. Combinations of conventional bleach activators can also be used. Such bleach activators can, in particular in the presence of the abovementioned hydrogen peroxide-supplied bleach, in the usual amount range, preferably in amounts of from 0.5 wt .-% to 10 wt .-%, in particular 1 wt .-% to 8 wt .-%, based on However, total agent, be included, missing when using percarboxylic acid as the sole bleach, preferably completely.

In addition to the conventional bleach activators or in their place, sulfone imines and / or bleach-enhancing transition metal salts or transition metal complexes may also be present as so-called bleach catalysts.

Suitable enzymes which can be used in the compositions are those from the class of amylases, proteases, lipases, cutinases, pullulanases, hemicellulases, cellulases, oxidases, laccases and peroxidases and mixtures thereof. Particularly suitable are from fungi or bacteria, such as Bacillus subtilis, Bacillus licheniformis, Bacillus lentus, Streptomyces griseus, Humicola lanuginosa, Humicola insolens, Pseudomonas pseudoalcaligenes, Pseudomonas cepacia or Coprinus cinereus derived enzymatic agents. The enzymes may be adsorbed to carriers and / or embedded in encapsulating substances to prevent premature inactivation protect. They are preferably present in the compositions according to the invention in amounts of up to 5% by weight, in particular from 0.2% by weight to 4% by weight. If the agent of the invention contains protease, it preferably has a proteolytic activity in the range of about 100 PE / g to about 10,000 PE / g, in particular 300 PE / g to 8000 PE / g. If several enzymes are to be used in the agent according to the invention, this can be carried out by incorporation of the two or more separate or in a known manner separately prepared enzymes or by two or more enzymes formulated together in a granule.

Among the solvents according to the invention, in particular when they are in liquid or pasty form, organic solvents which can be used in addition to water include alcohols having 1 to 4 C atoms, in particular methanol, ethanol, isopropanol and tert-butanol, diols having 2 to 4 C -Ato- men, in particular ethylene glycol and propylene glycol, and mixtures thereof and derived from the said classes of compounds ethers. Such water-miscible solvents are preferably present in the compositions according to the invention in amounts of not more than 30% by weight, in particular from 6% by weight to 20% by weight.

In order to establish a desired pH, which does not naturally result from the mixture of the other components, the compositions according to the invention may contain system and environmentally acceptable acids, in particular citric acid, acetic acid, tartaric acid, malic acid, lactic acid, glycolic acid, succinic acid, glutaric acid and / or adipic acid, but also mineral acids, in particular sulfuric acid, or bases, in particular ammonium or alkali metal hydroxides. Such pH regulators are present in the compositions according to the invention in amounts of preferably not more than 20% by weight, in particular from 1.2% by weight to 17% by weight.

Graying inhibitors have the task of keeping suspended from the textile fiber dirt suspended in the fleet. Water-soluble colloids of mostly organic nature are suitable for this purpose, for example starch, glue, gelatin, salts of ether carboxylic acids or ether sulfonic acids of starch or of cellulose or salts of acidic sulfuric acid esters of cellulose or starch. Also, water-soluble polyamides containing acidic groups are suitable for this purpose. Furthermore, other than the above-mentioned starch derivatives can be used, for example aldehyde starches. Preference is given to using cellulose ethers, such as carboxymethylcellulose (Na salt), methylcellulose, hydroxyalkylcellulose and mixed ethers, such as methylhydroxyethylcellulose, methylhydroxypropylcellulose, methylcarboxymethylcellulose and mixtures thereof, for example in amounts of from 0.1 to 5% by weight, based on the compositions ,

Compositions according to the invention may contain as optical brighteners, for example, derivatives of diaminostilbenedisulfonic acid or their alkali metal salts, although they are suitable for the use as a color detergent preferably free of optical brighteners. For example, salts of 4,4'-bis (2-anilino-4-morpholino-1, 3,5-triazinyl-6-amino) stilbene-2,2'-disulphonic acid or compounds of similar construction which are used instead of the morpholino Group carry a diethanolamino group, a methylamino group, an anilino group or a 2-methoxyethylamino group. Further, brighteners of the substituted diphenylstyrene type may be present, for example, the alkali salts of 4,4'-bis (2-sulfostyryl) -diphenyl, 4,4'-bis (4-chloro-3-sulfostyryl) -diphenyl, or 4 - (4-chlorostyryl) -4 '- (2-sulfostyryl). Mixtures of the aforementioned optical brightener can be used.

In particular, when used in mechanical processes, it may be advantageous to add conventional foam inhibitors to the compositions. As foam inhibitors are, for example, soaps of natural or synthetic origin, which have a high proportion of Ci ₈ -C ₂₄ fatty acids. Suitable non-surfactant foam inhibitors are, for example, organopolysiloxanes and mixtures thereof with microfine, optionally silanized silica and paraffins, waxes, microcrystalline waxes and mixtures thereof with silanated silicic acid or bis-fatty acid alkylenediamides. It is also advantageous to use mixtures of various foam inhibitors, for example those of silicones, paraffins or waxes. Preferably, the foam inhibitors, in particular silicone and / or paraffin-containing foam inhibitors, are bound to a granular, water-soluble or dispersible carrier substance. In particular, mixtures of paraffins and bistearylethylenediamide are preferred.

The preparation of employable solid agents presents no difficulty and can be accomplished in a known manner, for example by spray-drying or granulation, with enzymes and any other thermally-sensitive ingredients such as bleaching agents optionally being added separately later. For the preparation of inventive compositions having an increased bulk density, in particular in the range from 650 g / l to 950 g / l, a process comprising an extrusion step is preferred.

For the preparation of compositions in tablet form, which may be monophasic or multiphase, monochromatic or multicolor and in particular consist of one or more layers, in particular two layers, the procedure is preferably such that all components - optionally one layer at a time - in a mixer mixed together and the mixture by means of conventional tablet presses, such as eccentric or rotary presses, pressed with compressive forces in the range of about 50 to 100 kN, preferably at 60 to 70 kN. Particularly in the case of multilayer tablets, it may be advantageous if at least one layer is pre-compressed. This is preferably carried out at pressing forces between 5 and 20 kN, in particular at 10 to 15 kN. You get so easily unbreakable and yet under application conditions, sufficiently fast-dissolving tablets with breaking and bending strengths of normally 100 to 200 N, but preferably above 150 N. Preferably, a tablet thus produced has a weight of 10 g to 50 g, in particular from 15 g to 40 g. The spatial form of the tablets is arbitrary and can be round, oval or angular, with intermediate forms are also possible. Corners and edges are advantageously rounded. Round tablets preferably have a diameter of 30 mm to 40 mm. In particular, the size of rectangular or cuboid-shaped tablets, which are introduced predominantly via the metering device, for example the dishwasher, is dependent on the geometry and the volume of this metering device. Exemplary preferred embodiments have a base area of (20 to 30 mm) x (34 to 40 mm), in particular of 26x36 mm or 24x38 mm.

Liquid or pasty compositions in the form of conventional solvent-containing solutions are usually prepared by simply mixing the ingredients, which can be added in bulk or as a solution in an automatic mixer.

A preferred agent for the purposes of this invention may e.g. Ingredients include selected from anionic surfactants, such as preferably alkylbenzenesulfonate and / or alkylsulfate, nonionic surfactants such as, preferably, fatty alcohol polyglycol ethers, alkylpolyglucoside and / or fatty acid glucamide, builders such as preferably zeolite, polycarboxylate and / or sodium citrate, alkalis such as preferably sodium carbonate, alcohols, preferably Ethanol and / or glycerol, bleaches, preferably sodium perborate or sodium percarbonate, bleach activators, preferably tetraacetylethylenediamine (TAED or p-nonanoyloxybenzenesulfonate (NOBS), corrosion inhibitors, preferably sodium silicate, stabilizers, preferably phosphonates, foam inhibitors, preferably soap, silicone oils and / or or paraffins, enzymes, such as preferably proteases, amylases, cellulases and / or lipases, grayness inhibitor, such as preferably carboxymethyl cellulose, discoloration inhibitor, such as preferably polyvinylpyrrolidone derivatives or polyimidazoles, Sch Mutzabweiser, such as preferably soil-release polymers, such as in particular soluble oligomeric terephthalic acid esters, adjusting agents, such as preferably sodium sulfate, fragrances, optical brighteners, such as preferably stilbene derivative and / or biphenyl derivative and water.

Claims

claims: 1. A method for decolorization of colored stains on hard and / or soft surfaces, characterized in that the stain to be discolored is irradiated with electromagnetic radiation having wavelengths between 380-800 nm. 2. The method according to claim 1, characterized in that electromagnetic radiation having wavelengths between 400-700 nm, preferably 400 to 480 nm is used. 3. The method according to claim 1 or 2, characterized in that light emitting diodes (LED) are used as the radiation source. 4. The method according to any one of claims 1 to 3, characterized in that the spectral half-width of the spectral curves (half-width of the spectral light power) in the range of 4 to 100 nm, preferably 5-40 nm, in particular 10-20 nm. 5. The method according to any one of claims 1 to 4, characterized in that the duration of the irradiation 30 seconds to 5 hours, preferably 1 minute to 2 hours, in particular 5 minutes to 1 hour. 6. The method according to any one of claims 1 to 5, characterized in that the irradiance is 10 mW / cm ² to 200 W / cm ² , preferably 1 to 10 W / cm ² . 7. The method according to any one of claims 1 to 6, characterized in that the pulse duration is 5 ns to continuous wave, preferably 100 ns to continuous wave. 8. The method according to any one of claims 1 to 7, characterized in that the regulation of the brightness of the LED is effected by pulse width modulation. A process according to any one of claims 1-8, characterized in that the colored soils comprise yellow to orange dyes, such as preferably curcuma dyes, e.g. of curry and mustard, which in particular comprise curcumin, and / or preferably dyes which may be present in egg yolk or egg yolk, preferably comprising colorants such as carotenoids, zeaxanthin, lutein, xanthophylls, canthaxanthin, astaxanthin, apocarotenoids, cryptoxanthins and / or Carotene. 10. The method according to any one of claims 1 to 9, characterized in that the colored soiling is irradiated in the wet state. 11. The method according to any one of claims 1 to 10, characterized in that the irradiation is carried out in a washing, rinsing or cleaning machine or in a machine dryer, preferably before and / or during and / or after a mechanical washing, rinsing or cleaning process or machine drying process. 12. The use of radiation sources which emit electromagnetic radiation having wavelengths between 380-800 nm, in particular LED, in washing, rinsing or - cleaning machines or in machine dryers to assist the removal of colored stains from the hard and / or soft to be cleaned Surfaces. 13. Use according to claim 12 for promoting the removal of colored stains from the hard or soft surfaces to be cleaned by increasing the water solubility of the colored stains. 14. Kit, suitable for use for decolorization of colored stains on hard and / or soft surfaces, comprising (A) a radiation source, preferably comprising light emitting diodes (LED) and (B) a (pre-) treatment agent, preferably in liquid form, and optionally (c) a user manual for the consumer about the right handling of the kit and its applications. 15. Washing, cleaning or dishwasher or machine dryer, characterized in that it contains one or more radiation sources, which is capable of emitting electromagnetic radiation having wavelengths between 380-800 nm, preferably 400 to 480 nm.