EP2550389B1 - Electrochemical textile-washing aparatus, method, combination and e-bleach ball - Google Patents

Description

The present invention relates to a washing machine with electrochemical cell, a method for the electrochemical cleaning of fibers, detergents for the electrochemical cleaning of fibers and the thus cleaned fibers, a corresponding method, a combination and an e-bleach ball. In recent years, the awareness of the population for the influence of man on the environment has grown steadily. The prevention of harmful waste as well as methods of reduction and recycling are in the foreground and are becoming increasingly important. A large proportion of private-sector emissions are associated with textile cleaning and care using complex detergent blends. Since some components of these detergents can have a negative impact on the environment in the long term, there is an increasing demand for detergents that are less environmentally hazardous. However, the reduction of the ingredients should not lead to a reduced washing performance. A solution lies in special detergents for certain colors or fibers, but this leads to an increased number of detergents in households and thus is less consumer friendly.

Alternatively, the functionality of the washing machines can be increased.

In particular, the bleach-active compounds present a challenge. Today's detergents contain bleach catalysts or bleach precursors and a source of peroxide, so that the bleaching is activated only during the washing process.

A challenge in formulating a detergent is to protect the delicate components of the detergent (e.g., enzymes, perfumes) from the bleaching components.

One way to do this is to protect the sensitive components from the influence of bleach by encapsulation. This is particularly difficult in liquid detergents, where the reaction medium water is already available in the formulation. A separation of bleaching components and sensitive substances often succeed here only with the help of storage containers, which have elaborately designed and less user-friendly multi-chamber systems. Furthermore, it must be ensured that the bleaching is formed exclusively during the washing process and not before, since bleaching-active substances, such as. As hydrogen peroxide are unstable under the alkaline conditions typically present and decompose to form gas. Furthermore, many bleaching components used in powder detergents are not sufficiently soluble in liquid detergents.

One way of overcoming the described limitations is to generate in situ generation of bleach-active substances in the washing machine. It is known that hydrogen peroxide are formed by electrolysis ( US 6,387,238 ) and with TAED (tetraacetylethylenediamine) to peracetic acid, known to be a bleach-active compound. In US 2002 / 0,166,177 a washing machine is described, which is equipped with a unit for producing peroxide. In EP 1 739 207 an electrolysis unit for in situ production of peroxide and the application in the field of textile bleaching is claimed. The use of diamond electrodes in divided cells in conjunction with textile washing is in JP 2003 211 104 described. The diamond electrodes serve in this case, the electrochemical treatment of the wash water at the end of the wash cycle in terms of wastewater treatment (TOC degradation). In another aspect, acid (anolyte) and basic (catholyte) water are formed by electrolysis to achieve a better washing result by sequential and repeated use of these wash solutions. However, all systems are based on a split electrolysis cell. A divided electrolysis cell requires not only a membrane but also additional containers and pumps in order to be able to operate the different circuits (anolyte and catholyte) separately from one another. The material flows through permeation and electroosmosis, ie by transport of solvent molecules, which are carried through the membrane as a solvation shell and by a friction effect with the ions, must be compensated accordingly. In places with a high flow velocity, the membrane can erode and even be destroyed by "hot spots" when locally increased current densities occur. Direct contact of the (flexible) membranes with the electrodes, in particular the anode, is permanently detrimental and must be prevented by technical measures. After assembly, the membranes must not dry up, as, among other things, cracks can form. If sparingly soluble salts are present in the electrolyte (wash water, wash liquor), the free acids or bases in the membrane may crystallize under certain circumstances and thus lead to holes and cracks. Due to the increasing complexity of the system, not only the purchase price (investment) for the end user, but also the maintenance costs and the energy consumption increase due to the additional pumps, components and control units. A technical realization of the frequently used gas diffusion electrodes in the private sector and the often very limited life span of the membranes (risk of hairline cracks, loss of permselectivity) prevent a widespread use of the systems. In addition, the commonly used gas diffusion electrode consumes oxygen for the generation of hydrogen peroxide. However, oxygen has only a limited solubility in water (especially at elevated temperature) and must be permanently replenished by introducing air. Surfactant-containing washing solutions tend to foam, which is further enhanced by additional injection of air and can damage the machine.

The use of diamond electrodes in the context of a bleach activation, however, is described in WO 2009/06 7838. Boron-doped diamond electrodes have traditionally been used in wastewater treatment (TOC degradation), where the aggressive OH radicals, which are formed at this electrode, attack organic material and oxidize to CO ₂ . When used in textile washing machines thus significant color and fiber damage were expected.

Basically, electrochemical processes are used in a number of applications. The most common applications are those in which individual chemical substances are specifically converted into others. By electrochemical means z. B. bond cleavages, dimerizations, couplings, etc. are performed.

In the field of textile washing, electrochemical processes have hitherto not been used commercially. Among other things, this is due to the fact that not all parameters required by the apparatus have been researched, hitherto heavy-metal electrodes have been used which always lead to a heavy metal entry into the wash liquor and because no detergent formulations developed specifically for such washing processes have hitherto existed.

It is therefore an object of the present invention to provide a system for the purification of fibers - and in particular textiles - which meets the technical requirements as well as the chemical.

This is surprisingly achieved by the washing machine according to claims 1 to 4, the method according to claims 5 to 9, the detergent according to claim 10 and the fibers according to claim 11, because it has surprisingly been found that boron-doped diamond electrodes can be used for textile bleaching even though these electrodes, which are usually used in wastewater treatment (TOC degradation), were to be subject to considerable damage to the color and fibers,
a pre-electrolysis of the water (before the addition of detergent, bleach activator and textile fabric) for bleach activation is sufficient, so that in this way the energy consumption can be significantly reduced (10 min pre-electrolysis over 30 min - 60 min continuous electrolysis during the washing process), and also sensitive Components of laundry detergent and clothing need not be unnecessarily exposed to the electrodes / OH radicals,
an integration of an electrolysis cell in the external water supply is possible, the electrochemical bleach activation is also combined with liquid detergents, an undivided cell can be used, which is very simple and low maintenance and thus compared to divided cells very low in construction, with no additional Containers, pumps, membranes etc are necessary, even at low washing temperatures (<40 ° C) good bleaching results can be achieved and
the use of the electrode in the washing machine has hygienic advantages.

The subject of the present invention is a washing machine according to claim 1.

Preference is given to a washing machine, in which the applicable current strength in the range of 0.1 to 16 A and more preferably 0.3 to 10 A is.

And a washing machine is preferred in which the current is applied during the filling and / or washing process.

The current can vary over time. Inventive preferred embodiments have a constant current or a variable current intensity.

The type of washing machine covers all types of washing machines, ie both washing machines for household and washing machines for industrial fiber and especially textile cleaning. Washing machines are often described, for. In EP 2 098 627 and EP 2 098 628 ,

As electrode materials, in particular as anode materials, in the electrochemical cell are preferably used materials with which one can achieve a high oxygen overvoltage, for example noble metals such as platinum or metal oxides such as ruthenium, chromium or lead oxide or mixed oxides of the type RuO _x TiO _x or per se known dimensionally stable anodes (DSA) or diamond electrodes.

Preferably, the electrode is selected from the group consisting of graphite electrode, diamond electrode, steel electrode, and platinum electrode.

Diamond electrodes are claimed. They are created by applying one or more diamond layers to a substrate. Possible support materials are niobium, silicon, tungsten, titanium, silicon carbide, tantalum, graphite or ceramic supports such as titanium suboxide. However, a support of niobium, titanium or silicon is preferred for the method according to the invention, very particular preference is given to a support of niobium, if a diamond electrode is used.

Preferably, the anode is a diamond electrode, wherein the diamond electrode may also be doped with other elements. Boron and nitrogen are preferred as doping elements. Very particularly preferred is the claimed method with a boron-doped diamond electrode (BDD electrode) as the anode.

For the electrolysis any known to the expert electrolysis cells can be used from the said electrodes - such as divided or undivided flow cell, Capillary gap cell or plate stack cell. Particularly preferred is the undivided flow cell. To achieve optimum space-time yields, a bipolar arrangement of several electrodes is advantageous.

It has now further been found that diamond electrodes behave similar to heavy metal electrodes under the conditions of fiber and especially textile washing.

An advantage of the inventive method according to claim 3 is that no metal ions in the electrolyte (ie, the wash liquor) and thus reach the environment, since in the corrosion of the diamond layer of the BDD electrode heavy metal ions can not arise.

It can be used diamond electrodes, which have been prepared by the CVD method (chemical vapor deposition). Such electrodes are commercially available, for example from manufacturers: Condias, Itzehoe (Germany) and Adamant Technologies, La-Chaux-de-Fonds (Switzerland).

Lower cost diamond electrodes made by the HTHP method (high temperature high pressure: industrial diamond powder is mechanically introduced into the surface of a carrier sheet) are also suitable.

HTHP-BDD electrodes are commercially available from pro aqua, Niklasdorf (Austria), their properties are from A Cieciwa, R. Wüthrich and Ch. Comninellis in Electrochem. Commun. 8 (2006) 375-382 described.

Of the electrode type, therefore, a washing machine in which the electrode is a diamond electrode is preferred.

As cathode materials, unless the polarity of the electrode is to be reversed, for example iron, steel, stainless steel or nickel, otherwise also precious metals such as platinum and diamond electrodes come into consideration. Preferably, however, boron-doped diamond electrodes are used as the cathode.

For the inventive method according to claim 3, the cathode is a diamond electrode. This diamond electrode contains a diamond layer applied to a carrier material, wherein the carrier material is selected from the group of niobium, silicon, tungsten, titanium, silicon carbide, tantalum, graphite or ceramic carriers such as titanium suboxide. Particular preference is given to niobium or silicon as support material. The diamond layer on the carrier may be doped with other elements. Boron- or nitrogen-doped diamond electrodes are preferred. Particularly preferred are boron-doped diamond electrodes.

Very particularly preferred is the combination of boron-doped diamond electrode as an anode with steel as the cathode, wherein in particular the washing machine housing made of steel acts as a cathode. In particular stainless steel is used as steel.

In another preferred embodiment, the washing machine comprises two diamond electrodes, which are connected as anode and cathode.

If the anode (s) and the cathode (s) are diamond electrodes, the electrolysis can also be carried out at intervals and, if necessary, the polarity of the electrodes exchanged (short-term electrolysis, washing process, short-term electrolysis, washing process, etc.). An advantage of this interval circuit is that sensitive components of the detergent would only briefly be exposed to possible degradation at the electrodes (primarily by OH radicals).

The method according to the invention is advantageous if the polarity in the diamond electrodes is reversed in the range from 0.1 to 200 minutes or from wash cycle to wash cycle to avoid electrode deposits (fouling).

The individual electrodes have a certain size, which has an influence on the effect. A washing machine is preferred in which the individual electrode has an effective surface area of 0.5 to 1000 cm ² , preferably 1 to 500 cm ² and particularly preferably 2 to 100 cm ² . In this case, the electrode size refers to the surface of the single electrode, which is connected during the electrolysis as the anode and facing the cathode. If an anode is located between two cathodes, the electrode size of the anode results from the sum of the front and the back. The effective electrode area of the single electrode is the electrode area of the anode, which comes in contact with the electrolyte during electrolysis and faces the cathode (s).
If two electrodes are connected in such a way that they can alternately act as an anode or as a cathode, twice as large values for the total electrode area result.

The effective areas of the anode (s) and cathode (s) are preferably the same size, - this is particularly preferred when both anode (s) and cathode (s) are diamond electrodes. The electrodes are arranged at a certain distance from each other. Preference is given to a distance of 0.1-20 mm, preferably 1-10 mm, more preferably 2-5 mm

An electrolytic cell in this case comprises a pair of electrodes, which are preferably not separated from each other by a membrane. To optimize the space-time yields, a bipolar arrangement of several electrodes is advantageous. Within the washing machine, the cell is installed in the flooded area of the washing tub, preferably outside the washing drum. The cell can also be installed in the supply line inside or outside the washing machine. The cell can be a permanently installed component of the washing machine or a separate component (eg in the fresh water inlet between faucet and washing machine or as an e-bleach ball with its own energy supply in the drum). Such a kit of parts comprising a washing machine and an electrolysis cell which can be connected to the water inlet constitutes a further subject matter of the present invention. Another embodiment according to the invention consists in integrating the electrolysis cell into an additional water circulation within the machine.

An e-bleach ball comprising a mains independent power supply, a diamond anode and a cathode arranged so that the electrodes can contact the electrolyte when the e-bleach ball is in the washing drum of a washing machine during the washing process is a further subject of the present invention.

For the inventive method, an electrolyte is selected which is selected from the group consisting of water, methanol and ethanol. Particularly preferred is water.

In the process according to the invention, the pH is in the range from 2 to 13, preferably from 3 to 12, particularly preferably in the range from 6 to 11.

The temperature for the inventive method is in the range of 10 to 95 ° C, preferably in the range of 15 to 90 ° C, more preferably in the range of 20 to 60 ° C and most preferably in the range of 25 to 40 ° C, such as eg 30 ° C.

Other general parameters of such a method are for example the EP 2 088 231 refer to.

Further preferred is a method in which the diamond electrode having an effective surface area of 0.5 to 1000 cm ² , preferably from 1 to 500 cm ² and more preferably from 2 to 100 cm ² .

A process in which, in addition to the OH radicals (or its secondary products such as hydrogen peroxide and ozone) at least one compound selected from the group consisting of builder, surfactant, enzyme used for purification, represents a preferred variant.

These are preferably contained in the detergent according to the invention. Non-exhaustive examples of builders, surfactants and enzymes are listed there.

Furthermore, a method is preferred which is carried out at a temperature up to 60 ° C, preferably up to 40 ° C, particularly preferably up to 30 ° C.

A method as described above having a soil removal rate for bleachable stains (e.g., tea) of at least 20% is another aspect of the present invention.

The degree of soil removal is determined as follows:

Alle Wäschen werden dabei zwei Mal durchgeführt und es wird dann der Mittelwert gebildet.
Die Remissionsmessungen werden mit einem Spectrophotometer der Marke Gretag Macbeth, Typ Spectrolino unter den folgenden Bedingungen durchgeführt: Beobachterwinkel 10°, Lichtart D65, UV-Filter.The determination is made by first soiling a white cotton test fabric and subjecting it to a reflection measurement at 460 nm before and after the method has been carried out, ie before and after the wash. The soil removal is determined from the remission values R before and after the method and the remission value of a white reference cotton fabric according to the following formula in%: $$\mathrm{Soil\; removal\; degree}\left[\%\right]=\frac{\mathrm{R}\left(\mathrm{after\; the\; wash}\right)-\mathrm{R}\left(\mathrm{before\; the\; wash}\right)}{\mathrm{R}\left(\mathrm{white\; cotton}\right)-\mathrm{R}\left(\mathrm{before\; the\; wash}\right)}\mathrm{x}\mathrm{100}$$

All washes are done twice, and then the average is formed.
The reflectance measurements are carried out with a Spectrophotometer Gretag Macbeth, type Spectrolino under the following conditions: observer angle 10 °, illuminant D65, UV filter.

A detergent, in particular a heavy-duty detergent, comprising bleach activator (s) and / or bleach catalyst (s) and less than 1% by mass of hydrogen peroxide or hydrogen peroxide-releasing compounds is a further constituent of the present invention.

Likewise, a liquid detergent containing bleach activator (s) and / or bleach catalyst (s) is the subject of the present invention. The liquid detergent contains the bleach activator in an amount of at least 0.01 to 10% by mass, preferably from 0.1 to 5% by mass, more preferably from 0.5 to 3% by mass. The bleach activator is preferably selected from the below-mentioned suitable bleach activators. Particularly preferred is the bleach activator TAED. Pre-washing agent (prespotter) containing bleach activator (s) and / or bleach catalyst (s) is a further subject of the present invention. The prewash agent contains the bleach activator in an amount of at least 0.01 to 50% by mass, preferably from 0.1 to 30% by mass, particularly preferably from 0.5 to 10% by mass. The bleach activator is preferably selected from the below-mentioned suitable bleach activators. Particularly preferred is the bleach activator TAED.

• polyacylierte Zucker, z. B. Pentaacetylglucose;
• Acyloxybenzolsulfonsäuren und deren Alkali- und Erdalkalimetallsalze, z. B. Natrium-p-isononanoyloxy-benzolsulfonat oder Natrium-p-benzoyloxyenzolsulfonat;
• Acyloxybenzoesäuren und deren Alkali- und Erdalkalimetallsalze, z. B. Natrium-p-nonanoyloxy-benzoesäure oder Natrium-p- decanoyloxy-benzoesäure;
• N,N-diacylierte und N,N,N',N'-tetraacylierte Amine, z. B. N,N,N',N'-Tetra-acetyl-methylendiamin und -ethylendiamin (TAED), N,N-Diacetylanilin, N,N-Diacetyl-p-toluidin oder 1,3-diacylierte Hydantoine wie 1,3-Diacetyl-5,5-dimethylhydantoin;
• N-Alkyl-N-sulfonyl-carbonamide, z. B. N-Methyl-N-mesyl-acetamid oder N-Methyl-N-mesylbenzamid;
• N-acylierte cyclische Hydrazide, acylierte Triazole oder Urazole, z. B. Monoacetylmaleinsäurehydrazid;
• O,N,N-trisubstituierte Hydroxylamine, z. B. O-Benzoyl-N,N-succinylhydroxylamin, O-Acetyl-N,N-succinyl-hydroxylamin oder O,N,N-Triacetylhydroxylamin;
• N,N'-Diacyl-sulfurylamide, z. B. N,N'-Dimethyl-N,N'-diacetylsulfurylamid oder N,N'-Diethyl-N,N'-dipropionyl-sulfurylamid;
• Triacylcyanurate, z.B. Triacetylcyanurat oder Tribenzoylcyanurat;
• Carbonsäureanhydride, z. B. Benzoesäureanhydrid, m-Chlorbenzoesäureanhydrid oder Phthalsäureanhyrid;
• 1,3-Diacyl-4,5-diacyloxy-imidazoline, z. B. 1,3-Diacetyl-4,5-diacetoxyimidazolin;
• Tetraacetylglycoluril und Tetrapropionylglycoluril;
• diacylierte 2,5-Diketopiperazine, z. B. 1,4-Diacetyl-2,5-diketopiperazin;
• Acylierungsprodukte von Propylendiharnstoff und 2,2-Dimethylpropylendiharnstoff, z. B. Tetraacetylpropylendiharnstoff;
• α-Acyloxy-polyacyl-malonamide, z. B. α-Acetoxy-N,N'-diacetylmalon-amid;
• Diacyl-dioxohexahydro-1,3,5-triazine, z. B. 1,5-Diacetyl-2,4-dioxohexahydro-1,3,5-triazin;
• Ammoniumnitrile, z.B. N-Methylmorpholiniumacetonitril-Hydrogensulfat oder Trimethylammoniumacetonitril-Hydrogensulfat;
• Benz-(4H)1,3-oxazin-4-one mit Alkylresten, z. B. Methyl, oder aromatischen Resten z.B. Phenyl, in der 2-Position.

Suitable bleach activators are:

• polyacylated sugars, e.g. For example, pentaacetylglucose;
• Acyloxybenzolsulfonsäuren and their alkali and alkaline earth metal salts, eg. Sodium p-isononanoyloxy-benzenesulfonate or sodium p-benzoyloxy-cenzenesulfonate;
• Acyloxybenzoic acids and their alkali and alkaline earth metal salts, e.g. Sodium p-nonanoyloxybenzoic acid or sodium p-decanoyloxybenzoic acid;
• N, N-diacylated and N, N, N ', N'-tetraacylated amines, e.g. N, N, N ', N'-tetra-acetyl-methylenediamine and -ethylenediamine (TAED), N, N-diacetylaniline, N, N-diacetyl-p-toluidine or 1,3-diacylated hydantoins such as 1,3 diacetyl-5,5-dimethylhydantoin;
• N-alkyl-N-sulfonyl-carboxamides, eg. N-methyl-N-mesyl-acetamide or N-methyl-N-mesylbenzamide;
• N-acylated cyclic hydrazides, acylated triazoles or urazoles, e.g. Monoacetylmaleic hydrazide;
• O, N, N-trisubstituted hydroxylamines, e.g. O-benzoyl-N, N-succinylhydroxylamine, O-acetyl-N, N-succinyl-hydroxylamine or O, N, N-triacetylhydroxylamine;
• N, N'-diacyl-sulfurylamides, e.g. N, N'-dimethyl-N, N'-diacetylsulfurylamide or N, N'-diethyl-N, N'-dipropionyl-sulfurylamide;
• Triacylcyanurates, eg triacetyl cyanurate or tribenzoyl cyanurate;
• Carboxylic anhydrides, eg. Benzoic anhydride, m-chlorobenzoic anhydride or phthalic anhydride;
• 1,3-diacyl-4,5-diacyloxy-imidazolines, e.g. B. 1,3-diacetyl-4,5-diacetoxyimidazoline;
• Tetraacetylglycoluril and tetrapropionylglycoluril;
• diacylated 2,5-diketopiperazines, e.g. For example, 1,4-diacetyl-2,5-diketopiperazine;
• Acylation products of propylene diurea and 2,2-dimethylpropylenediurea, e.g. For example, tetraacetylpropylenediurea;
• α-acyloxy-polyacyl malonamides, e.g. For example, α-acetoxy-N, N'-diacetylmalonamide;
• Diacyl-dioxohexahydro-1,3,5-triazines, e.g. For example, 1,5-diacetyl-2,4-dioxohexahydro-1,3,5-triazine;
• Ammonium nitriles, eg N-methylmorpholinium acetonitrile hydrogen sulfate or trimethyl ammonium acetonitrile hydrogen sulfate;
• Benz (4H) 1,3-oxazin-4-ones with alkyl radicals, eg. As methyl, or aromatic radicals such as phenyl, in the 2-position.

The detergent used may optionally contain bleach catalysts. Suitable bleach catalysts are, for example, quaternized imines and sulfonimines, which are described, for example, in US Pat US-A 5,360,569 and EP-A 0 453 003 , Particularly effective bleach catalysts are manganese complexes which are described, for example, in US Pat WO-A 94/21777 are described. In the case of their use in detergents, such compounds are incorporated at most in amounts of up to 1.5% by weight, in particular up to 0.5% by weight. Other suitable metal catalysts are, for example, in Angew. Chem. 2006, 118, 212-229 called.

For the better conductivity of the base electrolyte, conductive salts can be added during the process and most simply as a component of the detergent. As conductive salts z. B. quaternary, preferably bisquaternary ammonium salts are used. The conducting salts are particularly preferably selected from the group of the bis-N, N '- (tri C ₁ - to C ₈ -alkyl) -substituted tri-, tetra-, penta-, hexa etc. - methylenediammonium salts such as hexamethylenebis (dibutylethylammonium ) phosphate or hydroxide. Very particular preference is given to using hexamethylenebis (dibutylethylammonium) phosphate or hydroxide as the conductive salt. Optionally, the electrolyte, preferably by adding to the detergent according to the invention, also certain additives such as EDTA or triethanolamine to prevent the cathodic deposition of iron, which would have a detrimental effect on the desired high hydrogen overvoltage of the cathode. Borates such as disodium diborate or orthoboric acid may be added as anode corrosion inhibitors.

Builder

Suitable inorganic builders (A ') are, above all, crystalline or amorphous aluminosilicates having ion-exchanging properties, in particular zeolites. Various types of zeolites are suitable, in particular zeolites A, X, B, P, MAP and HS in their Na form or in forms in which Na is partially exchanged with other cations such as Li, K, Ca, Mg or ammonium. Suitable zeolites are described, for example, in EP-A 0 038 591 . EP-A 0 021 491 . EP-A 0 087 035 . US-A 4,604,224 . GB-A 2 013 259 . EP-A 0 522 726 . EP-A 0 384 070 and WO-A 94/24251 ,

Suitable crystalline silicates (A ') are, for example, disilicates or layered silicates, for. B. SKS-6 (manufacturer: Hoechst). The silicates may be used in the form of their alkali metal, alkaline earth metal or ammonium salts, preferably as Na, Li and Mg silicates.

Amorphous silicates such as sodium metasilicate, which comprises a polymeric structure, or Britesil ^® H20 (manufactured by Akzo) are also useful.

Suitable inorganic builders based on carbonate are carbonates and bicarbonates. These can be used in the form of their alkali metal, alkaline earth metal or ammonium salts. Preference is given to using Na, Li and Mg carbonates or bicarbonates, in particular sodium carbonate and / or sodium bicarbonate.

Usual phosphates as inorganic builders are polyphosphates such. B. pentasodium triphosphate.

The stated components (A ') can be used individually or in mixtures with one another. Of particular interest as inorganic builder component is a mixture of aluminosilicates and carbonates, in particular of zeolites, especially zeolite A, and alkali metal carbonates, especially sodium carbonate, in a weight ratio of 98: 2 to 20: 80, in particular from 85: 15 to 40:60. In addition to this mixture, other components (A ') may be present.

In a preferred embodiment, the detergent contains 0.1 to 20 wt .-%. in particular from 1 to 12% by weight of organic cobuilders (B ') in the form of low molecular weight, oligomeric or polymeric carboxylic acids, in particular polycarboxylic acids, or phosphonic acids or their salts, in particular sodium or potassium salts.

• C₄-C₂₀-Di-, -Tri- und -Tetracarbonsäuren wie z.B. Bernsteinsäure, Propantricarbonsäure, Butantetracarbonsäure, Cyclopentantetracarbonsäure und Alkyl- und Alkenylbernsteinsäuren mit C₂-C₁₆-Alkyl- bzw. -Alkenyl-Resten;
• C₄-C₂₀-Hydroxycarbonsäuren wie z.B. Äpfelsäure, Weinsäure, Gluconsäure, Glutarsäure, Citronensäure, Lactobionsäure und Saccharosemono-, -di- und -tricarbonsäure;
• Aminopolycarbonsäuren wie z.B. Nitrilotriessigsäure, β-Alanindiessigsäure, Ethylendiamintetraessigsäure, Serindiessigsäure, Isoserindiessigsäure, Methylglycindiessigsäure und Alkylethylendiamintriacetate;
• Salze von Phosphonsäuren wie z.B. Hydroxyethandiphosphonsäure.

Suitable low molecular weight carboxylic acids or phosphonic acids for (B ') are, for example:

• C ₄ -C ₂₀ di-, tri- and tetracarboxylic acids such as succinic acid, propane tricarboxylic acid, butanetetracarboxylic acid, cyclopentanetetracarboxylic acid and alkyl and alkenyl succinic acids with C ₂ -C ₁₆ alkyl or alkenyl radicals;
• C ₄ -C ₂₀ -hydroxycarboxylic acids such as, for example, malic acid, tartaric acid, gluconic acid, glutaric acid, citric acid, lactobionic acid and sucrose mono-, di- and tricarboxylic acid;
• Aminopolycarboxylic acids such as nitrilotriacetic acid, β-alaninediacetic acid, ethylenediaminetetraacetic acid, serinediacetic acid, isoserinediacetic acid, methylglycinediacetic acid and alkylethylenediamine triacetates;
• Salts of phosphonic acids such as hydroxyethanediphosphonic acid.

• Oligomaleinsäuren, wie sie beispielsweise in EP-A 451 508 und EP-A 396 303 beschrieben sind;
• Co- und Terpolymere ungesättigter C₄-C₈-Dicarbonsäuren, wobei als Comonomere monoethylenisch ungesättigte Monomere
• aus der Gruppe (i) in Mengen von bis zu 95 Gew.-%,
• aus der Gruppe (ii) in Mengen von bis zu 60 Gew.-% und
• aus der Gruppe (iii) in Mengen von bis zu 20 Gew.-%
• einpolymerisiert sein können.
• Als ungesättigte C₄-C₈-Dicarbonsäuren sind hierbei beispielsweise Maleinsäure, Fumarsäure, Itaconsäure und Citraconsäure geeignet. Bevorzugt ist Maleinsäure.

Suitable oligomeric or polymeric carboxylic acids for (B ') are, for example:

• Oligomaleeinsäuren, as used for example in EP-A 451 508 and EP-A 396 303 are described;
• Co- and terpolymers of unsaturated C ₄ -C ₈ -dicarboxylic acids, wherein as comonomers monoethylenically unsaturated monomers
• from the group (i) in amounts of up to 95% by weight,
• from the group (ii) in amounts of up to 60 wt .-% and
• from group (iii) in amounts of up to 20% by weight
• can be polymerized.
• Examples of suitable unsaturated C ₄ -C ₈ -dicarboxylic acids are maleic acid, fumaric acid, itaconic acid and citraconic acid. Preference is given to maleic acid.

The group (i) comprises monoethylenically unsaturated C ₃ -C ₈ monocarboxylic acids such as acrylic acid, methacrylic acid, crotonic acid and vinylacetic acid. Preferably, from group (i), acrylic acid and methacrylic acid are used.

Group (ii) comprises monoethylenically unsaturated C ₂ -C ₂₂ -olefins, vinylalkyl ethers having C ₁ -C ₈ -alkyl groups, styrene, vinyl esters of C ₁ -C ₈ -carboxylic acids, (meth) acrylamide and vinylpyrrolidone. C ₂ -C ₆ -olefins, vinylalkyl ethers having C ₁ -C ₄ -alkyl groups, vinyl acetate and vinyl propionate are preferably used from group (ii).

Group (iii) comprises (meth) acrylic esters of C ₁ -C ₈ -alcohols, (meth) acrylonitrile, (meth) acrylamides of C ₁ -C ₈ -amines, N-vinylformamide and vinylimidazole.

If the polymers of group (ii) contain copolymerized vinyl esters, these may also be partially or completely hydrolyzed to vinyl alcohol structural units. Suitable copolymers and terpolymers are for example US-A 3,887,806 such as DE-A 43 13 909 known.

• Copolymere von Maleinsäure und Acrylsäure im Gewichtsverhältnis 10 : 90 bis 95 : 5, besonders bevorzugt solche im Gewichtsverhältnis 30 : 70 bis 90 : 10 mit Molmassen von 100.000 bis 150.000;
• Terpolymere aus Maleinsäure, Acrylsäure und einem Vinylester einer C₁-C₃-Carbonsäure im Gewichtsverhältnis 10 (Maleinsäure) : 90 (Acrylsäure + Vinylester) bis 95 (Maleinsäure) : 10 (Acrylsäure + Vinylester), wobei das Gewichtsverhältnis von Acrylsäure zum Vinylester im Bereich von 30 : 70 bis 70 : 30 variieren kann;
• Copolymere von Maleinsäure mit C₂-C₈-Olefinen im Molverhältnis 40:60 bis 80:20, wobei Copolymere von Maleinsäure mit Ethylen, Propylen oder Isobuten im Molverhältnis 50:50 besonders bevorzugt sind.

Suitable copolymers of dicarboxylic acids for (B ') are preferably:

• Copolymers of maleic acid and acrylic acid in a weight ratio of 10:90 to 95: 5, more preferably those in a weight ratio of 30: 70 to 90: 10 with molecular weights of 100,000 to 150,000;
• Terpolymers of maleic acid, acrylic acid and a vinyl ester of a C ₁ -C ₃ carboxylic acid in a weight ratio of 10 (maleic acid): 90 (acrylic acid + vinyl ester) to 95 (maleic acid): 10 (acrylic acid + vinyl ester), wherein the weight ratio of acrylic acid to vinyl ester in Range may vary from 30: 70 to 70: 30;
• Copolymers of maleic acid with C ₂ -C ₈ olefins in a molar ratio of 40:60 to 80:20, with copolymers of maleic acid with ethylene, propylene or isobutene in the molar ratio 50:50 are particularly preferred.

Graft polymers of unsaturated carboxylic acids on low molecular weight carbohydrates or hydrogenated carbohydrates, cf. US Pat. No. 5,227,446 . DE-A 44 15 623 and DE-A 43 13 909 , are also suitable as (B ').

Examples of suitable unsaturated carboxylic acids are maleic acid, fumaric acid, itaconic acid, citraconic acid, acrylic acid, methacrylic acid, crotonic acid and vinylacetic acid and also mixtures of acrylic acid and maleic acid which are grafted in amounts of from 40 to 95% by weight, based on the component to be grafted.

For modification, in addition up to 30% by weight, based on the component to be grafted, of further monoethylenically unsaturated monomers may be present in copolymerized form. Suitable modifying monomers are the above-mentioned monomers of groups (ii) and (iii).

Degraded polysaccharides such as, for example, acidic or enzymatically degraded starches, inulins or cellulose, protein hydrolysates and reduced (hydrogenated or hydrogenated aminated) degraded polysaccharides such as mannitol, sorbitol, aminosorbitol and N-alkylglucamine are suitable as well as polyalkylene glycols having molecular weights of up to M _w = 5,000 such as polyethylene glycols, ethylene oxide / propylene oxide or ethylene oxide / butylene oxide or ethylene oxide / propylene oxide / butylene oxide block copolymers and alkoxylated mono- or polyhydric C ₁ -C ₂₂ -alcohols, cf. US Pat. No. 5,756,456 ,

Grafted degraded or degraded reduced starches and grafted polyethylene oxides are preferably used from this group, with from 20 to 80% by weight of monomers, based on the grafting component, being used in the graft polymerization. For grafting, a mixture of maleic acid and acrylic acid in a weight ratio of 90:10 to 10:90 is preferably used.

As (B ') suitable polyglyoxylic acids are described, for example, in EP-B 001 004 . US Pat. No. 5,399,286 . DE-A 41 06 355 and EP-A 0 656 914 , The end groups of the polyglyoxylic acids can have different structures.

As (B ') suitable polyamidocarboxylic acids and modified polyamidocarboxylic acids are known, for example from EP-A 454 126 . EP-B 511,037 . WO-A 94/01486 and EP-A 581 452 ,

In particular, polyaspartic acids or cocondensates of aspartic acid with further amino acids, C ₄ -C ₂₅ -mono- or -dicarboxylic acids and / or C ₄ -C ₂₅ -mono- or -diamines are also used as (B '). Particular preference is given to using polyaspartic acids prepared in phosphorus-containing acids and modified with C ₆ -C ₂₂ -mono- or dicarboxylic acids or with C ₆ -C ₂₂ -mono- or -diamines.

Suitable (B ') condensation products of citric acid with hydroxycarboxylic acids or polyhydroxy compounds are known, for example WO-A 93/22362 and WO-A 92/16493 , Such condensates containing carboxyl groups usually have molecular weights of up to 10,000, preferably up to 5,000.

Also suitable as (B ') are ethylenediamine disuccinic acid, oxydisuccinic acid, aminopolycarboxylates, aminopolyalkylene phosphonates and polyglutamates.

Furthermore, oxidized starches may be used as organic co-builders in addition to (B ').

surfactants

Suitable anionic surfactants (C) are, for example, fatty alcohol sulfates of fatty alcohols having 8 to 22, preferably 10 to 18 carbon atoms, for. C ₉ -C ₁₁ alcohol sulfates, C ₁₂ -C ₁₄ alcohol sulfates, cetyl sulfate, myristyl sulfate, palmityl sulfate, stearyl sulfate and tallow fatty alcohol sulfate.

Other suitable anionic surfactants are alkanesulfonates such as C ₈ -C ₂₄ -, preferably C ₁₀ -C ₁₈ -Alkansulfonate and soaps such as the Na and K salts of C ₈ -C ₂₄ carboxylic acids.

Further suitable anionic surfactants are C ₉ -C ₂₀ linear alkyl benzene sulphonates (LAS) and alkyl toluenesulphonates.

Also suitable as anionic surfactants (C) are C ₈ -C ₂₄ -olefinsulfonates and -disulfonates, which may also be mixtures of alkene and hydroxyalkanesulfonates or disulfonates, alkyl ester sulfonates, sulfonated polycarboxylic acids, alkyl glycerol sulfonates, fatty acid glycerol ester sulfonates, alkylphenol polyglycol ether sulfates, paraffin sulfonates with ca From about 20 to about 50 carbon atoms (based on paraffin or paraffin mixtures obtained from natural sources), alkyl phosphates, acyl isethionates, acyltaurates, acylmethyltaurates, alkylsuccinic acids, alkenylsuccinic acids or their half-esters or hemiamides, alkylsulfosuccinic acids or their amides, mono- and diesters of sulfosuccinic acids, acylsarcosinates, sulfated alkyl polyglucosides, alkyl polyglycol carboxylates and hydroxyalkyl sarcosinates.

The anionic surfactants are preferably added to the fiber and textile treatment agent in the form of salts. Suitable cations in these salts are alkali metal ions such as sodium, potassium and lithium and ammonium salts such as hydroxyethylammonium, di (hydroxyethyl) ammonium and tri (hydroxyethyl) ammonium salts.

The component (C) is preferably present in the fiber and textile treatment agent in an amount of 3 to 30 wt .-%, in particular 5 to 20 wt .-% before. If C ₉ -C ₂₀ linear alkylbenzenesulfonates (LAS) are also used, they are usually used in an amount of up to 25% by weight, in particular up to 20% by weight. Only one class of anionic surfactants can be used alone, for example only fatty alcohol sulfates or only alkylbenzenesulfonates, but it is also possible to use mixtures of different classes, eg. B. a mixture of fatty alcohol sulfates and alkylbenzenesulfonates. Within the individual classes of anionic surfactants it is also possible to use mixtures of different species.

Another class of suitable surfactants are nonionic surfactants D, in particular alkylphenol alkoxylates such as alkylphenol ethoxylates with C ₆ -C ₁₄ -alkyl chains and 5 to 30 mol of alkylene oxide units.

Another class of nonionic surfactants are alkyl polyglucosides or hydroxyalkyl polyglucosides having from 8 to 22, preferably 10 to 18, carbon atoms in the alkyl chain. These compounds usually contain 1 to 20, preferably 1.1 to 5, glucoside units. Another class of nonionic surfactants are N-alkylglucamides with C ₆ -C ₂₂ alkyl chains. Such compounds are obtained, for example, by acylation of reducing aminated sugars with corresponding long-chain carboxylic acid derivatives.

Also suitable as nonionic surfactants (D) are block copolymers of ethylene oxide, propylene oxide and / or butylene oxide (Pluronic®) and Tetronic®) brands from BASF), polyhydroxy or polyalkoxy fatty acid derivatives such as polyhydroxy fatty acid amides, N-alkoxy or N-aryloxy polyhydroxy fatty acid amides, fatty acid amide ethoxylates, in particular end-capped, and fatty acid alkanolamide alkoxylates.

The component (D) is present in the fiber and textile treatment agent according to the invention preferably in an amount of 1 to 20 wt .-%, in particular 3 to 12 wt .-% before. Only one class of nonionic surfactants can be used alone, in particular only alkoxylated C ₈ -C ₂₂ -alcohols, but it is also possible to use mixtures of different classes. Within the individual classes of nonionic surfactants, mixtures of different species can also be used.

Since the balance between the surfactant types mentioned is of importance for the effectiveness of the fiber and textile treatment agents according to the invention, anionic surfactants (C) and nonionic surfactants (D) are preferably in a weight ratio of 95: 5 to 20:80, especially 80 : 20 to 50: 50. In this case, the surfactant constituents of the surfactant mixture according to the invention are to be considered.

Furthermore, cationic surfactants (E) can also be present in the fiber and textile treatment agents according to the invention.

Suitable cationic surfactants are, for example, ammonium-containing surface-active compounds such as, for example, alkyldimethylammonium halides and compounds of the general formula

RR'R "R"'N ⁺ X-

in which the radicals R to R "'are alkyl, aryl radicals, alkylalkoxy, arylalkoxy, hydroxyalkyl (alkoxy), hydroxyaryl (alkoxy) groups and X is a suitable anion.

Optionally, the fiber and textile treatment agents may also contain ampholytic surfactants (F), such as aliphatic derivatives of secondary or tertiary amines containing an anionic group in one of the side chains, alkyldimethylamine oxides or alkyl or alkoxymethylamine oxides.

Components (E) and (F) may contain up to 25%, preferably 3-15% in the fiber and textile treatment agents.

enzymes

In a further preferred embodiment, the fiber and textile treatment agent additionally contains 0.05 to 4% by weight of enzymes (J). Preferably used in fiber and textile treatment agents enzymes are proteases, amylases, lipases and cellulases. Of the enzymes preferably amounts of 0.1 to 1.5 wt .-%, particularly preferably 0.2 to 1.0 wt .-%, of the formulated enzyme is added. Suitable proteases are, for. Savinase and Esperase (manufacturer: Novo Nordisk). A suitable lipase is e.g. Lipolase (manufacturer: Novo Nordisk). A suitable cellulase is for example Celluzym (manufacturer: Novo Nordisk). The use of peroxidases to activate the bleaching system is also possible. You can use individual enzymes or a combination of different enzymes. Optionally, the textile detergent formulation according to the invention can still enzyme stabilizers, z. As calcium propionate, sodium formate or boric acids or their salts, and / or oxidation inhibitors.

A fiber treated according to the claimed method or in contact with a detergent constitutes a further subject of the present invention. The fibers may be both natural and synthetic fibers. Non-inclusive examples of natural fibers are: cotton, wool, linen and viscose. Fibers, non-exhaustive examples of synthetic fibers are: polypropene, polyamide, polyester, nylon, perlon, Teflon®, Lycra®, fibers.

The fibers are preferably woven, knitted, spun, knitted, knotted, laceed.

The present invention is explained in more detail below by the non-limiting example of the invention:

Examples: experimental setup

1000 mL jacketed vessel made of glass with mechanical stirrer (IKA stirring motor with glass stirrer and movable PTFE stirring blade) and liquid circuit (Iwaki magnetic pump MD6-230GS01, 80-90 L / h) and an electrolysis cell with boron-doped diamond electrodes (Adamant miniDiaCell, diamond on silicon, 12.5 cm ² electrode area). The test fabrics were placed in the jacketed vessel at the start of the experiment.

Fig. 1: Schematic representation of the experimental apparatus

• ECE98
• AATCC1993

For the evaluation of the results of the electrochemical bleaching reference experiments were carried out with a comparison system of hydrogen peroxide (H ₂ O ₂ ) and tetraacetylethylenediamine (TAED) without electrolysis. The selected concentration ranges correspond to those of commercial detergents in which TAED is currently widely used. The reference system is a mixture of H ₂ O ₂ and TAED in the ratio 4: 1 (mmol / L).
For the reference experiments solutions of H ₂ O ₂ and TAED were prepared in deionized water and pumped without electrolysis at 40 ° C. After 30 minutes, the swatches were removed, rinsed thoroughly with demineralised water, dried under exclusion of light, and the reflectance values measured as a measure of soil removal.
The wash liquor of reference experiment R 3 has the following composition: 700 g DI water, 10 g NaHCO ₃ , 0.32 g H ₂ O ₂ solution (30% H ₂ O ₂ in water), 0.16 g TAED (4: 1 mmol / L).
The wash liquor for the active electrolysis experiments typically has the following composition: 700 g DI water, 10 g NaHCO ₃ , 0.16 g TAED.
The possibility of combining the process according to the invention with commercially available detergents was tested by way of example with reference to the following standard formulations (wfk Research Institute for Cleaning Technology):

• ECE98
• AATCC1993

These exemplary detergents were dosed in deionized water as follows: 4.8 g / L detergent, 0.67 g / L sodium percarbonate, 0.15 g / L TAED. The total volume of the wash solution is 300 mL, unless stated otherwise.

Dirt removal was determined by subjecting the test fabric to a reflectance measurement at 460 nm before and after the wash. The stain removal was determined from the remission values R before and after the laundry and the remission value of a white reference cotton fabric according to the following formula in%: $$\mathrm{soil\; removal}\left[\%\right]=\frac{\mathrm{R}\left(\mathrm{after\; the\; wash}\right)-\mathrm{R}\left(\mathrm{before\; the\; wash}\right)}{\mathrm{R}\left(\mathrm{white\; cotton}\right)-\mathrm{R}\left(\mathrm{before\; the\; wash}\right)}\mathrm{x}\mathrm{100}$$

All washes were done twice. The soil removal values listed for the wash results in the tables are the average of the measurements obtained under the same conditions.
The remission measurements were made with a Spectrophotometer Gretag Macbeth, type Spectrolino under the following conditions: observer angle 10 °, illuminant D65, UV filter.

Reference Example R 1 and Example 1

Reference Example R 1 describes the soil removal achieved solely by the wash solution (700 g deionized water, 10 g NaHCO ₃ ). This test is a reference for determining the achieved dirt removal.
Example 1 describes the bleaching effect achieved by electrolysis of the wash solution (700 g deionized water, 10 g NaHCO ₃ ) on boron-doped diamond electrodes without the addition of a bleach activator or bleach precursor such as TAED. Compared to the reference experiment R 1, a significant increase in soil removal can be observed. Table 1: Dirt removal using the example of test fabric EMPA 167 (tea on cotton). Dirt removal in% at 40 ° C (remission measurement at 460 nm) example electrolysis time 30 min R1 --- ^a 12 1 30 min ^b 26 ^a : 700 g demineralized water, 10 g NaHCO ₃
^b : 30 minutes electrolysis at 1.2 A (700 g demineralized water, 10 g NaHCO ₃ ).

Example 2 to 6:

Examples 2 to 6 show the soil removal (test fabric EMPA 167, tea on cotton), which is achieved as a function of the current strength using the method according to the invention in the presence of the bleach activator TAED. Table 2: Influence of the current on the removal of dirt (tea on cotton, EMPA 167). Dirt removal in% at 40 ° C ^a (remission measurement at 460 nm) example amperage Electrolysis time 30 min 2 0.06 A 29 3 0.12 A 47 4 0.6A 49 5 1.2 A 59 6 6.0A 67 ^a : The electrolyte used (washing liquid) typically has the following composition: 700 g of deionized water, 10 g of NaHCO ₃ , 0.16 g of TAED

The results reflect the influence of the current on the removal of dirt. It has been found that the dirt removal achieved increases with increasing current intensity.

Reference Examples R 2 to R 4:

Reference examples R 2 to R 4 represent the results of bleaching with a system of H ₂ O ₂ and TAED in different compositions. Thus, the washing solution with an addition of H ₂ O ₂ / TAED in a concentration ratio of 4: 1 (mmol / l) a commonly used in commercial powder detergents composition. Table 3: Influence of the composition of H <sub> 2 </ sub> O <sub> 2 </ sub> / TAED on soil removal on the example of test fabric EMPA 167 (tea on cotton). Dirt removal in% at 40 ° C (remission measurement at 460 nm) example H ₂ O ₂ / TAED [mmol / L] Test duration 30 min R2 8.1 72 R3 4.1 64 R4 4 / 0.5 59

As expected, it has been found that increasing the H ₂ O ₂ concentration to 8/1 (R 2) results in greater soil removal because the formation of peracetic acid from TAED is favored. It has also been found that the degree of soil removal also depends on the amount of TAED available. So leads one Halved the TAED concentration from 4/1 (R 3) to 4 / 0.5 (R 4) to decrease the dirt removal from 64% to 59%.
A comparison of the soil removal by the electrochemical bleach activation with the results of the reference experiments shows that the electrochemical process can achieve a soil removal comparable to the H ₂ O ₂ / TAED 4: 1 (mmol / l) system (about 60% soil removal after 30 Minutes at 40 ° C, see Ex 5).

Examples 7 and 8:

Examples 7 and 8 describe the difference between sequential splitting of the two steps (example 7) and parallelization of electrolysis and cleaning process (example 8) on the result of dirt removal. Table 4: Influence of the duration of the electrolysis on the removal of dirt (test fabric EM-PA 167). Dirt removal in% at 40 ° C (remission measurement at 460 nm) example Pre-electrolysis [min] / electrolysis [min] 30 minutes after TAED 7 10/0 46 8th 10/30 61

By default, throughout the duration of the test, the wash solution passed the electrodes at 1.2 A and achieved very good soil removal (Ex. 5). Surprisingly, a very good soil removal was also achieved when the wash solution was pumped for 10 minutes at 1.2 A before adding TAED and test fabric. After switching off the power source, TAED and test tissue were added and pumped for 30 minutes without further current application (example 7). This effect is very advantageous because a very good dirt removal can be achieved with a lower current input. Dirt removal can be increased to 61% if the wash solution is pumped at 1.2 A for 10 minutes prior to the addition of TAED and test tissue, and the electrolysis is continued for 30 minutes after addition of TAED and test tissue (Ex 8).

Examples 9 to 12 and Reference Examples R 5 and R 6:

Examples 9 to 12 and the reference examples R 5 and R 6 describe the treatment of various types of stains with the method according to the invention for electrochemical bleach activation.
The results show that the dirt removal achieved is as expected different degrees of severity with respect to various soils. Comparative Examples R 5 and R 6 each describe the pure washing action in the absence of TAED and without electrolysis. Accordingly, both with respect to red wine (Ex 9 and 10) and to blueberry juice (Ex 11 and 12), good soil removal is achieved by the method according to the invention. Table 5: Dirt removal on the example of test fabric EMPA 114 (red wine on cotton). Dirt removal in% at 40 ° C (remission measurement at 460 nm) example Current [A] Duration of test after addition of TAED or test tissue: 30 min 9 1.2 ^a 55 10 1.2 ^b 64 R 5 --- ^c 39 ^a : 30 min electrolysis at 1.2 A without addition of TAED.
^b : 10 min pre-electrolysis at 1.2 A, then addition of TAED (1 mmol / L based on the total volume of the washing solution), 30 min pumping without further electrolysis at 40 ° C. ^c : 30 min pump-circulation at 40 ° C without electrolysis (700 g DI water, 10 g NaHCO ₃ ) Dirt removal in% at 40 ° C (remission measurement at 460 nm) example Current [A] Duration of test after addition of TAED or test tissue: 30 min 11 1.2 ^a 84 12 1.2 ^b 83 R 6 --- ^c 53 ^a : 30 min electrolysis at 1.2 A without addition of TAED.
^b : 10 min pre-electrolysis at 1.2 A, then addition of TAED (1 mmol / L based on the total volume of the wash solution), 30 min pump-over without further electrolysis at 40 ° C. ^c : 30 min pump circulation at 40 ° C. without electrolysis ( 700 g demineralized water, 10 g NaHCO ₃ ).

Examples 13 to 26 and Reference Examples R 7 to R 20

Examples 13-26 and reference examples R 7-R 20 describe the treatment of various textile dyes with the method according to the invention for electrochemical bleach activation. For this purpose, a solution of 15.4 g of sodium bicarbonate in 1084 g of deionized water for 10 minutes at 40 ° C and 1.2 A electrolyzed. Subsequently, 0.25 g of TAED and the color monitors were added and pumped without current for 45 minutes. After each wash, the color monitors were rinsed briefly with deionized water and after every 5 wash cycles a remission measurement at 460 nm to determine the degree of color removal. In total, 15 wash cycles (3 x 5) were performed per color monitor. As shown in Table 7, surprisingly no significant color damage is observed by the method according to the invention within the scope of the measurement accuracy. An exception is the fabric dyed with Sulfur Black 1 (AISE-1) (Example 13), which already tends to discolour or bleed the dye in a wash liquor without bleach and without electrolysis. Table 7: Studies on the color damage by the inventive method using selected color monitors after 15 washing cycles. Color removal in% example color monitor 5 washing cycles 10 washing cycles 15 washing cycles 13 AISE 1 3% 7% 13% 14 AISE 3 -3% -3% -3% 15 AISE 5 -4% -5% -5% 16 AISE 8 -1% -1% -1 % 17 AISE 16 -1% -1% -1 % 18 AISE 20 1% 1% 3% 19 AISE 21 0% 0% 1% 20 AISE-22 1% 2% 3% 21 AISE 24 -22% -20% -17% 22 AISE 26 3% 3% 5% 23 AISE 27 -1% 0% 0% 24 AISE 29 0% 0% 0% 25 AISE 33 0% 0% 0% 26 AISE 39 0% 0% 0%

The results of the method according to the invention were compared with a simplified reference system. For the color removal of selected textile dyes, the color monitors were set up in a system of 15.4 g sodium bicarbonate, 1085 g deionized water, 0.25 g TAED and 0.44 g hydrogen peroxide solution (30% H ₂ O ₂ in water) for 45 minutes at 40 ° C touched. The results of the reference experiments are summarized in Table 8. Again, as described above, in the case of the color monitor colored with Sulfur Black 1 (AISE-1), a very large change can be detected (R 7). The comparison of the remaining data shows that the reference system generally leads to a more pronounced color damage than the method according to the invention. Table 8: Color damage analysis by a reference system using selected color monitors after 15 washing cycles. Color removal in% example color monitor 5 wash cycles 10 wash cycles 15 washing cycles R7 AISE 1 9% 21% 32% R8 AISE 3 -4% -4% -4% R9 AISE 5 -4% -5% -6% R10 AISE 8 -1% -1% -1 % R11 AISE 16 -1% -1% -1 % R12 AISE 20 3% 5% 8th% R13 AISE 21 1% 2% 3% R14 AISE-22 3% 7% 11% R15 AISE 24 -26% -23% -22% R16 AISE 26 4% 6% 8th% R17 AISE 27 -1% 0% 0% R18 AISE 29 0% 1% 1% R19 AISE 33 0% 0% 0% R20 AISE 39 0% 0% 0%

Reference Examples R 21 to R 24

Reference Examples 21 to 24 show the soil removal (test fabric EMPA 167, tea on cotton) achieved by the detergent formulations in the presence and absence of sodium percarbonate and TAED at 40 ° C within 30 min. The protective distance in the absence of sodium percarbonate and TAED thus shows the pure washing effect, which is not due to chemical bleaching operations (Reference Examples 21 and 23). Table 9: Effect of detergent composition on soil removal (tea on cotton, EMPA 167, 40 ° C). Dirt removal in% at 40 ° C ^a (remission measurement at 460 nm) example amperage Duration of test after addition of TAED or test tissue: 30 min R21 - - - 29 ^a R22 - - - 51 ^b R23 - - - 33 ^c R24 - - - 50 ^{d a} : ECE98 in deionised water
^b : ECE98 in deionized water, sodium percarbonate, TAED
^c : AATCC1993 in deionized water
^d : AATCC1993 in deionized water, sodium percarbonate, TAED

Example 27 to 30

Examples 27 to 30 describe the result of the sequential splitting of the two steps (electrolysis and cleaning process) on the result of dirt removal. In Examples 27 and 29, the solution of the respective detergent was subjected to pre-electrolysis for 10 minutes prior to the addition of the textile samples. It turns out that the dirt removal of the pure detergent solutions is not significantly influenced by the pre-electrolysis (see also reference examples R21 and R23). In Examples 28 and 30, after a 10 minute pre-electrolysis of the respective wash solution, both the fabric samples and TAED were added. Accordingly, a significant increase in soil removal is already found after 10 minutes pre-electrolysis (at 1.2 A). The inventive method is thus compatible with complex detergent formulations. Table 10: Dirt removal by pre-electrolysis of detergent formulations (test fabric EMPA 167). Dirt removal in% at 40 ° C (remission measurement at 460 nm) example Pre-electrolysis [min] / current [A] Duration of test after addition of TAED or test tissue: 30 min 27 10 min / 1.2 A 28 ^a 28 10 min / 1.2 A 38 ^b 29 10 min / 1.2 A 27 ^c 30 10 min / 1.2 A 35 ^{d a} : ECE98 in deionized water, pre-electrolysis for 10 min, then test tissue addition
^b : ECE98 in deionized water, pre-electrolysis for 10 min, then TAED and test tissue addition
^c : AATCC1993 in deionized water, 10 min pre-electrolysis, then test tissue addition
^d : AATCC1993 in deionized water, pre-electrolysis for 10 min, then TAED and test tissue addition

Example 31 to 34

Examples 31 to 34 describe the result of the parallel execution of the two steps (electrolysis and cleaning process) on the result of dirt removal. In Examples 31 and 33, the detergent solution was subjected to electrolysis for 30 minutes after the textile samples had been added. It turns out that the dirt removal of the pure detergent solutions is only slightly influenced by the continuous electrolysis (see Reference Examples R21 and R23 and Examples 27 and 29). For Examples 32 and 34, both textile samples and TAED were added to the detergent solution. The dirt removal achieved by the continuous electrolysis (Examples 32 and 34) is expected to be slightly higher (see Example 28) or comparable (see Example 30) to the dirt removal achieved by short-term (but energy-saving) pre-electrolysis.

The inventive method is thus compatible with complex detergent formulations. Table 11: Dirt removal by continuous electrolysis of detergent formulations (test fabric EMPA 167). Dirt removal in% at 40 ° C (remission measurement at 460 nm) example Electrolysis [min] / current [A] Duration of test after addition of TAED or test tissue: 30 min 31 30 min / 1.2 A 32 ^a 32 30 min / 1.2 A 42 ^b 33 30 min / 1.2 A 26 ^c 34 30 min / 1.2 A 34 ^{d a} : ECE98 in deionized water, 30 min electrolysis after test tissue addition
^b : ECE98 in deionized water, 30 min electrolysis according to TAED and test tissue addition
^c : AATCC1993 in deionized water, 30 min electrolysis after test tissue addition
^d : AATCC1993 in deionised water, 30 min electrolysis according to TAED and test tissue addition

Claims (10)

1. A washing machine comprising an electrode and a closed-loop control unit, wherein a current strength in the range from 0.02 to 30 A can be applied to the electrode during the washing operation, wherein the electrode is a diamond electrode, and the poling of the diamond electrode is interchanged in the range from 0.1 to 200 min or from wash to wash to avoid electrode fouling.
2. The washing machine according to claim 1 wherein the electrode has an effective surface area in the range from 0.5 to 1000 cm².
3. A process for cleaning fibers, which comprises generating free OH radicals and/or H₂O₂ in aqueous solution by applying a current strength in the range from 0.02 to 30 A to an electrode, wherein the electrode is a diamond electrode, and the poling of the diamond electrode is interchanged in the range from 0.1 to 200 min or from wash to wash to avoid electrode fouling.
4. The process according to claim 3 wherein the electrode is a diamond electrode having an effective surface area in the range from 0.5 to 1000 cm².
5. The process according to claim 3 or 4 wherein at least one compound selected from the group consisting of builder, surfactant and enzyme is used for cleaning as well as the free OH radicals (or descendent products).
6. The process according to any one of claims 3 to 5 carried out at a temperature of up to 60°C.
7. The process according to any one of claims 3 to 6 having an at least 20% degree of soil removal for bleachable stains.
8. A method of using a washing machine according to claim 1 or 2 and a laundry detergent comprising bleach activator(s) and/or bleach catalyst(s) and less than 1% by mass of hydrogen peroxide or of hydrogen peroxide releaser compounds, or
   a laundry detergent, selected from the group consisting of fully built laundry detergent, liquid laundry detergent, color detergent and wool detergent.
9. A kit of parts, comprising a washing machine and an electrolytic cell connectable upstream of the water inlet, wherein the electrode is a diamond electrode, and the poling of the diamond electrode is interchanged in the range from 0.1 to 200 min or from wash to wash to avoid electrode fouling.
10. An e-bleach ball comprising a power supply independent of the electricity grid, a diamond anode and a cathode, which are arranged such that the electrodes are able to come into contact with the electrolyte when the e-bleach ball is in the washing drum of a washing machine during the washing operation.

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