JP2013524868A - Electrochemical textile washing method - Google Patents

Abstract

  The present invention relates to a washing machine having an electrochemical cell, a method for electrochemically cleaning fibers, a detergent for electrochemically cleaning fibers, and thus cleaned fibers.

Description

  The present invention relates to a washing machine having an electrochemical cell, a method for electrochemically cleaning fibers, a detergent for electrochemically cleaning fibers, and thus cleaned fibers.

  In recent years, residents' awareness of the impact on humans on the environment has constantly grown. Methods of avoiding hazardous waste and reducing and reusing hazardous waste are of interest and are always important. Most of the release within the private range is associated with the cleaning and care of the fabric, for which complex detergent mixtures are used. Since some components of the detergents can have adverse consequences for the environment, there is an increasing demand for detergents that do not substantially harm the environment. However, in this case, reducing the content material should not result in reduced washing efficiency. One solution is in special detergents for specific colors or fibers, but this increases the number of detergents in the home and thus is not very favorable to consumers.

  Apart from that, the functionality of the washing machine can be improved.

  In particular, bleach activating compounds are one challenge. Modern detergents contain a bleach catalyst or bleach precursor and a peroxidation source, so that bleaching is only activated during the laundry operation.

  One challenge in formulating detergents is to protect the detergent's sensitive ingredients (eg, enzymes, perfumes) from bleaching ingredients.

  To that end there is one possibility to protect sensitive components by encapsulation before the effects of bleaching. This is particularly difficult in liquid detergents where the reaction medium water is already free in the formulation. Here, the separation of bleaching components and sensitive materials is often successful only with storage containers having a multi-chamber system that is costly configured and hardly user-friendly. Furthermore, it must be ensured that the bleaching is formed exclusively during the washing operation, and not even prior. This is because bleach actives such as hydrogen peroxide are unstable under typical alkaline conditions and decompose under gas formation. Furthermore, many bleaching ingredients used in powder detergents are not sufficiently soluble in liquid detergents.

  One possibility to overwhelm the described limit is the in-situ regeneration of the bleaching active in the washing machine. It is known that hydrogen peroxide can be formed by electrolysis (US Pat. No. 6,387,238), reacted with TAED (tetraacetylethylenediamine) and converted to peracetic acid, a known bleaching active compound. US 2002/0166177 describes a washing machine equipped with a unit for generating hydrogen peroxide. EP 1739207 claims patent protection for use within the scope of electrolysis units and textile bleaching to produce peroxides in-situ. The use of diamond electrodes in divided cells in connection with textile washing is described in JP 2003-211104. In this case, the diamond electrode is used for the electrochemical treatment of the wash water at the final stage of the wash cycle within the range of post-drain treatment (TOC decomposition). In another view, acidic water (anolyte) and basic water (catholyte) are formed by electrolysis, and relatively good washing results are achieved by continuous and repeated use of the washing liquid. .

  However, all systems are based on split electrolysis cells. Divided electrolysis cells require additional vessels and pumps with membranes, and different circuits (anolyte and catholyte) may be operated separately from each other. The material flow by osmosis and electroosmosis, i.e. by transport of solvent molecules pulled through the membrane by the frictional effect with ions as solvates must be compensated accordingly. At locations with high flow rates, the membrane can erode and is rather destroyed by “hot spots” if a locally increased current density occurs. Direct contact between the (flexible) membrane and the electrode, in particular the anode, is indefinite and must be avoided by technical means. The membrane should no longer dry after installation. This is especially because cracks can form. If a sparingly soluble salt is contained in the electrolyte (washing water, washing solution), free acid or free base may crystallize out in the film, thus leading to pores and cracks. Thus, the increased complexity of the system increases not only the purchase price (investment amount) for the end user, but also the maintenance costs and the energy consumption by additional pumps, components and control units. The industrial realization of gas diffusion electrodes often used within the private range and often very limited lifetimes of membranes (risk of hair cracking, loss of palm oil selectivity) hinder large expansion of the system . Furthermore, often used gas diffusion electrodes consume oxygen due to the generation of hydrogen peroxide. However, oxygen has only limited solubility in water (especially at elevated temperatures) and must be permanently supplied by the introduction of air. Surfactant-containing laundry fluids have a tendency to foam, which can still be strengthened by the additional blowing of air and damage the mechanical device.

On the other hand, the use of diamond electrodes in the context of bleach activation has not been described so far. Boron-doped diamond electrodes are conventionally used in wastewater treatment, where the aggressive OH radicals formed on the electrode attack the organic material and oxidize to CO ₂ (TOC decomposition). Therefore, significant color damage and fiber damage could be expected when used in a textile washing machine.

  In principle, electrochemical methods are used for a range of applications. The most frequent use is to intentionally convert individual chemicals to other chemicals. For example, bond breaking, sizing, coupling, etc. may be performed by electrochemical methods.

  Within the fabric wash, electrochemical methods have not been used commercially so far. This is especially the case in that heavy metal electrodes have been used that have always led to the introduction of heavy metals into the washing liquid and that no detergent formulations have been developed so far for this type of laundry process. All the parameters that are required by the public have not been studied.

  The object of the present invention is therefore to provide a system for cleaning fibers, in particular textiles, which satisfies the industrial preconditions as well as the chemical preconditions.

Surprisingly, this is the washing machine according to any one of claims 1 to 4, the method according to any one of claims 5 to 9, the detergent according to claim 10, and the claim. In the case of boron-doped diamond electrodes, even if the use of electrodes with significant color damage and fiber damage is considered in the case of boron-doped diamond electrodes, Boron-doped diamond electrodes can be used for textile bleaching, and prior electrolysis of water (before addition of detergents, bleach activators and textile fabrics) is sufficient for bleach activation and thus energy consumption The amount can be reduced significantly (10 minutes pre-electrolysis compared to 30-60 minutes continuous electrolysis during the washing operation), in this case, in addition, detergent Need not sensitive component and clothing is exposed unnecessarily to the electrode / OH radicals,
Enables the incorporation of an electrolytic cell into an external water supply tube, can combine electrochemical bleach activation with a liquid detergent, and can use one undivided cell, which has a structure In this respect, the maintenance is very simple and it is extremely advantageous compared with the divided cell, and in this case, no additional container, pump, membrane, etc. are required.
This is because good bleaching results can be achieved even at low washing temperatures (below 40 ° C.) and the use of electrodes in the washing machine has hygienic advantages.

  Thereafter, the subject of the present invention is a washing machine comprising one electrode and one adjustment unit, in which case a current intensity of 0.02 to 30 A can be applied to the electrode during the washing operation.

  Preference is given in this case to washing machines with an applicable current intensity in the range from 0.1 to 16 A, particularly preferably in the range from 0.3 to 10 A.

  A washing machine in which the current intensity is applied during filling and / or washing operations is preferred.

  In this case, the current intensity can vary over several hours. Preferred embodiments according to the invention have a constant current intensity or a variable course of current intensity.

  In this case, the types of washing machines include all types of washing machines, i.e. household washing machines as well as washing machines for industrial textile cleaning, in particular textile cleaning. Various washing machines are described, for example, in European Patent No. 2098627 and European Patent No. 2098628.

As an electrode material, in particular as an anode material, the electrochemical cell has a material that can achieve a particularly high oxygen overvoltage, such as a noble metal, such as platinum or a metal oxide, such as ruthenium oxide, chromium oxide or lead oxide, or type RuO. _x A mixed oxide of TiO _x or a dimensionally stable anode (DSA) or diamond electrode known per se is used.

  In particular, the electrodes are selected from the group consisting of graphite electrodes, diamond electrodes, steel electrodes and platinum electrodes.

  A diamond electrode is preferred. This diamond electrode is produced by applying one or more diamond layers on a support material. Niobium, silicon, tungsten, titanium, silicon carbide, tantalum, graphite or ceramic supports such as titanium suboxide are suitable as possible support materials. However, when diamond electrodes are used, preferred for the process according to the invention are supports made from niobium, titanium or silicon, particularly preferred are supports made from niobium.

  Preferably, the anode is a diamond electrode, in which case the diamond electrode may still be doped with other elements. Boron and nitrogen are preferred as doping elements. The process according to the invention with a boron-doped diamond electrode (BDD electrode) as anode is particularly preferred.

  In this case, electrolysis may be used for each electrolysis cell known to the person skilled in the art consisting of the described electrodes, for example divided or undivided flow-through cells, capillary gap cells or panel stack cells. Particularly preferred are non-divided once-through cells. In order to achieve an optimal space time yield, a dipole arrangement with multiple electrodes is preferred.

  By the way, it has further been found that the diamond electrode behaves similarly to the heavy metal electrode under the conditions of textile washing, especially textile washing.

  Therefore, it is preferred for the method according to the present invention that the metal ions do not reach the electrolyte solution (ie, the washing solution), and hence the environment at all, because the heavy metal ions when the diamond layer of the BDD electrode is corroded. This is because it cannot occur.

  A diamond electrode manufactured by CVD (chemical vapor deposition) may be used. Such electrodes are commercially available, for example, from the manufacturer: Condias, Itzehoe (Germany) or Adamant Technologies, La-Chaux-de-Fonds (Switzerland).

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

  The HTHP-BDD method is commercially available from pro aqua, Niklassdorf (Austria), and is characterized by A.D. Cieciwa, R .; Wuerthrich and Ch. By Cominellis, Electrochem. Commun. 8 (2006) 375-382.

  Accordingly, preferred from the electrode type is a washing machine in which the electrode is a diamond electrode.

  Examples of cathode materials include iron, steel, special steel or nickel, as well as other precious metals such as platinum and diamond electrodes, as long as the electrode polarity is not mixed. However, preferably a boron doped diamond electrode is used as the cathode.

  For the process according to the invention, the cathode is in particular a diamond electrode. The diamond electrode includes a diamond layer applied on a support material, in which case the support material is from the group of niobium, silicon, tungsten, titanium, silicon carbide, tantalum, graphite or a ceramic support, such as a titanium suboxide. Selected. Niobium or silicon is particularly preferred as the support material. The diamond layer on the support may be further doped with other elements. Boron doped or nitrogen doped diamond electrodes are preferred. A boron-doped diamond electrode is particularly preferred.

  The combination of a boron-doped diamond electrode as anode and steel as cathode is particularly preferred, in which case a washing machine casing, especially made of steel, functions as cathode. In this case, special steel is used as the steel.

  In one other preferred embodiment, the washing machine includes two diamond electrodes connected as an anode and a cathode.

  If the anode or anodes and the cathode or cathodes are diamond electrodes, the electrolysis may be performed at intervals and in some cases the polarity of the electrodes may be exchanged (for a short time). Electrolysis, washing operation, short-time electrolysis, washing operation, etc.). One advantage of switching this interval switch is that the sensitive components of the detergent are exposed to possible degradation at the electrode (first by OH radicals) in a very short time.

  In order to avoid electrode membranes (fouling), the method according to the present invention can be used when the polarity at the diamond electrode is switched within the range of 0.1 to 200 minutes or is switched from a washing operation to a washing operation. ,preferable.

Individual electrodes have certain dimensions that have one effect on action. Preference is given to washing machines in which the individual electrodes have an effective surface area of 0.5 to 1000 cm ² , in particular 1 to 500 cm ² , particularly preferably ² to 100 cm ² . In this case, the electrode dimensions relate to the area of the individual electrode that is connected as the anode during electrolysis and faces the cathode. If an anode is present between the two cathodes, the anode electrode dimensions are derived from the sum of the front and back surfaces. The effective electrode area of an individual electrode is the electrode area of the anode that contacts the electrolyte during electrolysis and faces one or more cathodes.

  If the two electrodes are connected in such a way that they can function alternately as anodes or cathodes, the result is a correspondingly double value for the total electrode area.

  The effective surface area of the anode or anodes and the cathode or cathodes is advantageously of the same size, which is particularly preferred when the anode or anodes and the cathode or cathodes are diamond electrodes. The electrodes are arranged at regular intervals. In this case, a distance of 0.1 to 20 mm, preferably 1 to 10 mm, particularly preferably 2 to 5 mm is preferred.

  The electrolysis cell according to the invention comprises a pair of electrodes according to the invention, in particular not separated from each other by a membrane. In order to optimize the space time yield, a dipole arrangement with a plurality of electrodes is preferred.

  The cell is mounted on the inside of the washing machine within the area where the washing basket is submerged, in particular on the outside of the washing drum. However, the cell may be mounted in a supply conduit outside or inside the washing machine. The cell can be a rigidly attached component or a separate component of the washing machine (eg, in a fresh water supply pipe between the water cock and the washing machine, or in the drum) E-bleach-ball with its own energy supply). This kind of parts kit comprising an electrolysis cell that can be pre-connected to a washing machine and a water supply pipe is another object of the present invention. Another embodiment according to the invention is to incorporate an electrolysis cell into the additional water circuit inside the machine.

  Current supply independent of current grid, diamond arranged so that both electrodes can make contact with the electrolyte when an e-breach ball is present in the washing drum of the washing machine during the washing operation An e-breach ball comprising an anode and a cathode is another subject of the present invention.

Furthermore, the object of the present invention is a method for cleaning fibers in which OH radicals and H ₂ O ₂ are generated in an aqueous solution by applying a current intensity of 0.02 to 30 A to one electrode. .

  For the method according to the invention, an electrolyte selected from the group consisting of water, methanol and ethanol is selected. Water is particularly preferred.

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

  The temperature of the process according to the invention is in the range from 10 to 95 ° C., preferably in the range from 15 to 90 ° C., particularly preferably in the range from 20 to 60 ° C., particularly preferably in the range from 25 to 40 ° C. For example, 30 ° C.

  Furthermore, the general parameters of such a method can be confirmed, for example, from the description in EP 2088231.

Furthermore, a method is preferred in which the electrode is a diamond electrode having an effective surface area of 0.5 to 1000 cm ² , in particular 1 to 500 cm ² , particularly preferably ² to 100 cm ² .

  The method in which at least one compound selected from the group consisting of builders, surfactants, enzymes, together with OH radicals (or derivatives thereof such as hydrogen peroxide and ozone) is used for cleaning is one preferred variant. It is.

  Said compound is contained in particular in the detergent according to the invention. Simple examples of builders, surfactants and enzymes are described therein.

  Furthermore, processes which are carried out at temperatures up to 60 ° C., in particular up to 40 ° C., particularly preferably up to 30 ° C. are preferred.

  Methods as described above having a degree of decontamination for at least 20% of bleachable stains (eg tea) are another subject of the present invention.

Decontamination is measured as described below:
Measurements are made by first soiling a white test cotton fabric and subjecting it to a reflection measurement at 460 nm before and after carrying out the method, ie before and after washing. Soil removal is calculated in% from the reflectance R before and after the method and from the reflectance of the white reference cotton cloth according to the following formula:

  In this case, all washings are performed twice, and an average value is formed.

  The reflectance measurement is carried out using a spectrophotometer of Mark Gretag Maxbeth, type Spectrolino under the following conditions: viewing angle 10 °, light source D65, UV filter.

  Detergents, in particular heavy duty detergents, containing one or more bleach activators and / or one or more bleach catalysts and hydrogen peroxide or hydrogen peroxide releasing compounds of less than 1% by weight, are another feature of the invention. It is an ingredient.

  Similarly, liquid detergents containing one or more bleach activators and / or one or more bleach catalysts are the subject of the present invention. In this case, the liquid detergent contains at least 0.01 to 10% by weight, in particular 0.1 to 5% by weight, particularly preferably 0.5 to 3% by weight, of bleach activators. In this case, the bleach activator is selected from among the suitable bleach activators specifically described. The bleach activator TAED is particularly preferred.

  Pre-detergents (pre-stain remover prespotter) containing one or more bleach activators and / or one or more bleach catalysts are another subject of the present invention. In this case, the preliminary detergent contains at least 0.01 to 50% by weight, in particular 0.1 to 30% by weight, particularly preferably 0.5 to 10% by weight, of bleach activators. In this case, the bleach activator is selected from among the suitable bleach activators specifically described. The bleach activator TAED is particularly preferred.

The following are preferred as bleach activators:
A polyacylated sugar, such as pentaacetylglucose;
-Acyloxybenzenesulfonic acid and its alkali metal salts and alkaline earth metal salts thereof, such as sodium-p-isononanoyloxybenzenesulfonate or sodium-p-benzoyloxybenzenesulfonate;
-Acyloxybenzoic acid and its alkali metal salts and alkaline earth metal salts thereof such as sodium-p-nonanoyloxybenzoic acid or sodium-p-decanoyloxybenzoic acid;
N, N-diacylated amines and N, N, N ′, N′-tetraacylated amines such as N, N, N ′, N′-tetraacetylmethylenediamine and N, N, N ′, N′-tetraacetylethylenediamine (TAED), N, N-diacetylaniline, N, N-diacetyl-p-toluidine or 1,3-diacylated hydantoin, such as 1,3-diacetyl-5,5-dimethylhydantoin ;
-N-alkyl-N-sulfonyl-carbonamide, such as N-methyl-N-mesyl-acetamide or N-methyl-N-mesylbenzamide;
-N-acylated cyclic hydrazides, acylated triazoles or urazoles, such as monoacetylmaleic hydrazide;
-O, N, N-trisubstituted hydroxylamines such as O-benzoyl-N, N-succinylhydroxylamine, O-acetyl-N, N-succinyl-hydroxylamine or O, N, N-triacetylhydroxylamine;
-N, N'-diacyl-sulfuramide, such as N, N'-dimethyl-N, N'-diacetylsulfuramide or N, N'-diethyl-N, N'-dipropionyl-sulfuramide;
-Triacyl cyanurates, such as triacetyl cyanurate or tribenzoyl cyanurate;
A carboxylic anhydride, such as benzoic anhydride, m-chlorobenzoic anhydride or phthalic anhydride;
1,3-diacyl-4,5-diacyloxy-imidazoline, such as 1,3-diacetyl-4,5-diacetoxyimidazoline;
-Tetraacetyl glycoluril and tetrapropionyl glycoluril;
Diacylated 2,5-diketopiperazine, such as 1,4-diacetyl-2,5-diketopiperazine;
-Acylation products of propylene diurea and 2,2-dimethyl-propylene diurea, such as tetraacetylpropylene diurea;
An α-acyloxy-polyacyl-malonamide, such as α-acetoxy-N, N′-diacetylmalon-amide;
Diacyl-dioxohexahydro-1,3,5-triazine, such as 1,5-diacetyl-2.4-dioxohexahydro-1,3,5-triazine;
An ammonium nitrile, such as N-methylmorpholinium acetonitrile hydrogen sulfate or trimethyl ammonium acetonitrile hydrogen sulfate;
-Benz- (4H) -1,3-oxazin-4-one having an alkyl group, for example methyl, or an aromatic group, for example phenyl, in the 2-position.

  The detergent according to the invention can optionally further contain a bleach catalyst. Suitable bleach catalysts are, for example, quaternized imines and sulfonimines as described in US Pat. No. 5,360,569 A and EP-A-0453003. A particularly effective bleach catalyst is, for example, the manganese complex described in WO-A 94/21777. Such compounds are incorporated in amounts up to 1.5% by weight, in particular up to 0.5% by weight, when used in detergents. Furthermore, suitable metal catalysts are described, for example, in Angew. Chem. 2006, 118, 212-229.

Due to the relatively good conductivity of the basic electrolyte, the conductive salt may most easily be added as a detergent component during processing. As conductive salts, for example, quaternary ammonium salts, preferably bis quaternary ammonium salts, may be used. Bis -N, N '- (tri C ₁ -C ₈ alkyl) substituted tri -, tetra -, penta -, hexa - equal - methylenedioxyphenyl ammonium salts, such as hexamethylene bis - (di-butyl-ethyl ammonium) phosphate or hexa Particularly preferred are conductive salts selected from the group of methylene bis- (dibutylethylammonium) hydroxide. Very particular preference is given to using hexamethylene-bis (dibutylethylammonium) phosphate or hexamethylene-bis (dibutylethylammonium) hydroxide as the conductive salt. In some cases, in order to prevent the cathode deposition of iron, which has a detrimental effect on the desired high hydrogen overvoltage of the cathode, the electrolyte is preferably further added with certain additives by addition to the detergent according to the invention. For example, EDTA or triethanolamine is added. As anodic corrosion inhibitors, borates such as disodium diborate or orthoboric acid may be added.

Builders Suitable inorganic builders (A ′) are inter alia crystalline or amorphous aluminosilicates with ion exchange properties, such as in particular zeolites. Zeolite A, X, B, P, MAP and HS are preferred, which are various types of zeolites, especially in the form of Na or Na partially replaced by other cations such as Li, K, Ca, Mg or ammonium. is there. Suitable zeolites are, for example, European Patent Application Publication No. 0038591, European Patent Application Publication No. 0021491, European Patent Application Publication No. 0087035, US Pat. No. 4,604,224, British Patent No. 2013259. , European Patent Application Publication No. 0522726, European Patent Application Publication No. 0384070 and WO-A 94/24251.

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

  Amorphous silicates such as sodium metasilicate having a polymer structure or Britesil® H20 (manufacturer: Akzo) can likewise be used.

  Suitable inorganic builder materials based on carbonate are carbonates and bicarbonates. These carbonates and bicarbonates may be used in the form of their alkali metal salts, alkaline earth metal salts or ammonium salts. Preferably, Na carbonate, Li carbonate and Mg carbonate, or Na bicarbonate, Li bicarbonate and Mg bicarbonate, in particular sodium carbonate and / or sodium bicarbonate, are used.

  A common phosphate as an inorganic builder is a polyphosphate, such as pentasodium triphosphate.

  Said component (A ') may be used alone or in a mixture of components with one another. As an inorganic builder component, a mixture of aluminosilicates and carbonates in a mass ratio of 98: 2 to 20:80, in particular 85:15 to 40:60, in particular zeolites, in particular zeolite A and alkali metal carbonates, in particular Mixtures with sodium carbonate are particularly important. In addition to the mixture, further components (A ') may be present.

  In a preferred embodiment, the detergent according to the invention comprises from 0.1 to 20% by weight, in particular from 1 to 12% by weight, of organic auxiliary builders (B ′), low molecular weight, oligomeric or polymeric carboxylic acids, in particular polycarboxylic acids, or It is contained in the form of phosphonic acid or a salt thereof, particularly Na salt or K salt.

Suitable low molecular weight carboxylic or phosphonic acids for (B ′) are, for example:
C ₄ -C ₂₀ -di-, -tri- and -tetracarboxylic acids, such as succinic acid, propanetricarboxylic acid, butanetetracarboxylic acid, cyclopentanetetracarboxylic acid and C ₂ -C ₁₆ -alkyl- or -alkenyl groups Alkyl- and alkenyl-succinic acids having:
C ₄ -C ₂₀ -hydroxycarboxylic acids such as malic acid, tartaric acid, gluconic acid, glutaric acid, citric acid, lactobionic acid and saccharose mono-, -di- and -tricarboxylic acids;
Aminopolycarboxylic acids such as nitrilotriacetic acid, β-alanine diacetic acid, ethylenediaminetetraacetic acid, serine diacetic acid, isoserine diacetic acid, methylglycine diacetic acid and alkylethylenediamine triacetate;
Salts of phosphonic acids such as hydroxyethanediphosphonic acid.

Suitable oligomeric or polymeric carboxylic acids for (B ′) are, for example:
For example, oligomaleic acid as described in EP-A-451508 and EP-A-396303;
Unsaturated C ₄ -C ₈ dicarboxylic acids copolymers and terpolymers, as comonomers in this case,
From group (i) in an amount up to 95% by weight,
Monoethylenically unsaturated monomers from group (ii) in an amount up to 60% by weight and from group (iii) in an amount up to 20% by weight may be polymerised.

In this case, as the unsaturated C ₄ -C ₈ -dicarboxylic acid, for example, maleic acid, fumaric acid, itaconic acid and citraconic acid are suitable. Maleic acid is preferred.

Group (i) monoethylenically unsaturated C ₃ -C ₈ - including monocarboxylic acids, such as acrylic acid, methacrylic acid, crotonic acid and vinyl acetate. Preferably, acrylic acid and methacrylic acid from group (i) are used.

Group (ii) monoethylenically unsaturated C ₂ -C ₂₂ - olefins, C ₁ -C ₈ - vinyl alkyl ethers having alkyl group, styrene, C ₁ -C ₈ - vinyl esters of carboxylic acids, (meth) Contains acrylamide and vinyl pyrrolidone. Preferably, C ₂ -C ₆ -olefins, vinyl alkyl ethers having a C ₁ -C ₄ -alkyl group, vinyl acetate and vinyl propionate are used from group (ii).

Group (iii) is, C ₁ -C ₈ - including (meth) acrylamide amine, N- vinylformamide and vinylimidazole - alcohol (meth) acrylic esters, (meth) acrylonitrile, C ₁ -C _8.

  When the polymer of group (ii) contains a vinyl ester introduced by polymerization, the polymer may be present partially or completely hydrolyzed into vinyl alcohol structural units. Suitable copolymers and terpolymers are known, for example, from U.S. Pat. No. 3,887,806 and from German Offenlegungsschrift 4,313,909.

As copolymers of dicarboxylic acids, the following are preferred with regard to (B ′):
A copolymer of maleic acid and acrylic acid having a molecular weight of 100,000 to 150,000 in a mass ratio of 10:90 to 95: 5, particularly preferably in a mass ratio of 30:70 to 90:10;
Mass ratio of maleic acid, acrylic acid and vinyl ester of C ₁ -C ₃ -carboxylic acid: 10 (maleic acid): 90 (acrylic acid + vinyl ester) to 95 (maleic acid): 10 (acrylic acid + vinyl The weight ratio of acrylic acid to vinyl ester may vary within the range of 30:70 to 70:30;
Copolymers of maleic acid and C ₂ -C ₈ -olefins in a molar ratio of 40:60 to 80:20, in this case copolymers of maleic acid and ethylene, propylene or isobutene in a molar ratio of 50:50 are particularly preferred.

  Graft polymers of unsaturated carboxylic acids on low molecular weight or hydrogenated carbohydrates (see US Pat. No. 5,227,446, German Offenlegungsschrift 4,415,623 and German Offenlegungsschrift 4,313,909). ) Is also suitable as (B ′).

  Suitable unsaturated carboxylic acids in this case are, for example, maleic acid, fumaric acid, itaconic acid, citraconic acid, acrylic acid, methacrylic acid, crotonic acid and vinyl acetate, and mixtures of acrylic acid and maleic acid. The acid and maleic acid are grafted in an amount of 40 to 95% by weight with respect to the component to be grafted.

  Due to the modification, other monoethylenically unsaturated monomers can be present polymerized up to 30% by weight with respect to the components to be grafted. Suitable modifying monomers are the above monomers of groups (ii) and (iii).

Graft backbones include degraded polysaccharides such as acid or enzymatically degraded starch, inulin or cellulose, protein hydrolysates and reduced (hydrogenated or hydrogenated aminated) degraded polysaccharides such as mannitol, sorbitol Aminosorbitol and N-alkylglucamine, and polyalkylene glycols having a molecular weight up to M _w = 5000, such as polyethylene glycol, ethylene oxide / propylene oxide- or ethylene oxide / butylene oxide or ethylene oxide / propylene oxide / butylene oxide-block copolymers and Also suitable are alkoxylated mono- or polyvalent C ₁ -C ₂₂ -alcohols (see US Pat. No. 5,756,456).

  Preference is given to using starch that has been grafted or degraded and reduced from said group and grafted polyethylene oxide, with 20 to 80% by weight of monomers being used in the graft polymerization, based on the grafting component. The For the grafting, a mixture of maleic acid and acrylic acid, preferably in a mass ratio of 90:10 to 10:90, is used.

  Polyglyoxylic acids suitable as (B ′) are, for example, European Patent No. 00001004, US Pat. No. 5,399,286, German Patent Publication No. 4106355 and European Patent Application No. 0656914. It is described in. The end groups of polyglyoxylic acid can have different structures.

  Polyamide carboxylic acids and modified polyamide carboxylic acids suitable as (B ′) are, for example, European Patent Application Publication No. 454126, European Patent No. 511037, WO-A 94/01486 and European Patent No. 581452. It is known from the description.

As (B ′), in particular polyaspartic acid or co-condensates of aspartic acid with other amino acids, C ₄ -C ₂₅ -mono- or -dicarboxylic acid and / or C ₄ -C ₂₅ -mono- or -diamine Also used. Particularly preferably, be prepared in phosphorus-containing acids, C ₆ -C ₂₂ - mono - or - dicarboxylic acid or C ₆ -C ₂₂ - mono - or - modified polyaspartic acids are used in a diamine.

  Condensation products of citric acid with hydroxycarboxylic acids or polyhydroxy compounds suitable as (B ′) are known, for example, from WO-A 93/22362 and WO-A 92/16493. Such carboxyl group-containing condensation products usually have a molecular weight of up to 10,000, in particular up to 5000.

  Further, (B ′) is preferably ethylenediamine disuccinic acid, oxydisuccinic acid, aminopolycarboxylate, aminopolyalkylenephosphonate and polyglutamate.

  Furthermore, in addition to (B '), oxidized starch may be used as an organic auxiliary builder.

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

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

Other suitable anionic surfactants are C ₉ -C ₂₀ -linear alkyl benzene sulfonate (LAS) and C ₉ -C ₂₀ -linear alkyl toluene sulfonate.

In addition, as anionic surfactants (C), there are still C ₈ -C ₂₄ -olefin sulfonates and C ₈ -C ₂₄ -olefin disulfonates, which are alkene sulfonates and hydroxyalkane sulfonates or alkene disulfonates and hydroxyalkanes. It may be a mixture of candisulfonates, alkyl ester sulfonates, sulfonated polycarboxylic acids, alkyl glycerol sulfonates, fatty acid glycerol ester sulfonates, alkylphenol polyglycol ether sulfates, about 20 to about 50 C atoms. Paraffin sulfonates (based on paraffin or paraffin mixtures obtained from natural sources), alkyl phosphates, acyl isethionates, acyl esters Acrylates, acylmethyl taurates, alkyl succinic acids, alkenyl succinic acids or their half esters or half amides, alkyl sulfosuccinic acids or their amides, monoesters and diesters of sulfosuccinic acid, acyl sarcosineates, sulfated alkyl polyglucosides Alkyl polyglycol carboxylates as well as hydroxyalkyl sarcosinates are suitable.

  These anionic surfactants are added to the fiber and fabric treating agents, in particular in the form of salts. Suitable cations in said salts are alkali metal ions such as sodium, potassium and lithium salts and ammonium salts such as hydroxyethylammonium salt, di (hydroxyethyl) ammonium salt and tri (hydroxyethyl) ammonium salt.

Component (C) is present in the fiber- and textile treatment agents according to the invention in particular in amounts of 3 to 30% by weight, in particular 5 to 20% by weight. When C ₉ -C ₂₀ -linear alkylbenzene sulfonate (LAS) is used in combination, it is 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 fatty alcohol sulfate only, or only alkylbenzene sulfonate, but mixtures from various classes, such as fatty alcohol sulfate It is also possible to use a mixture of benzene and alkylbenzenesulfonate. Within the individual classes of anionic surfactants, mixtures of different species can also be used.

Classes of another preferred surfactants, non-ionic surfactants D, especially alkylphenol alkoxylates, e.g., C ₆ -C ₁₄ - alkylphenol ethoxylates having an alkyl chain and from 5 to 30 moles of alkylene oxide units include It is done.

Another type of nonionic surfactant is an alkyl polyhydroxyside or hydroxyalkyl polyglucoside having 8 to 22, in particular 10 to 18 carbon atoms in the alkyl chain. The compounds often contain 1-20, in particular 1.1-5, glucoside units. Another class of nonionic surfactants, C ₆ ~C ₂₂ - is N- alkylglucamides having an alkyl chain. Such compounds are obtained, for example, by acylating a reductively aminated sugar with a corresponding long-chain carboxylic acid derivative.

  Furthermore, nonionic surfactants (D) may still be block copolymers from ethylene oxide, propylene oxide and / or butylene oxide (trademark Pluronic® and Tetronic® from BASF), polyhydroxy fatty acid derivatives Or polyalkoxy fatty acid derivatives such as polyhydroxy fatty acid amides, N-alkoxy-polyhydroxy fatty acid amides or N-aryloxy-polyhydroxy fatty acid amides, fatty acid amide ethoxylates, especially end-capped, and fatty acid alkanolamide alkoxylates Is preferred.

Component (D) is present in the fiber and fabric treating agents according to the invention in particular in an amount of 1 to 20% by weight, in particular 3 to 12% by weight. Only one class of nonionic surfactants can be used alone, C ₈ -C _22, especially alkoxylated - Alcohol only can be used, to use mixtures of various classes You can also Within the individual classes of nonionic surfactants, mixtures of different species can also be used.

  Since the balance between the surfactant species is important for the action of the fiber- and fabric treatment agents according to the invention, anionic surfactants (C) and nonionic surfactants (D) are in particular 95: It is present in a mass ratio of 5 to 20:80, in particular 80:20 to 50:50. Here, the surfactant component of the surfactant mixture according to the invention must also be taken into account.

  Furthermore, a cationic surfactant (E) may also be included in the fiber and fabric treatment agents according to the present invention.

Cationic surfactants include, for example, ammonium group-containing surfactant compounds such as alkyldimethylammonium halides and the general formula RR′R ″ R ′ ″ N ⁺ X ⁻
Wherein the groups R to R ′ ″ represent an alkyl group, an aryl group, an alkylalkoxy group, an arylalkoxy group, a hydroxyalkyl (alkoxy) group, a hydroxyaryl (alkoxy) group, and X is a suitable anion. Are suitable.

  The fiber- and fabric treatment agents according to the invention are optionally amphoteric surfactants (F), for example secondary amines containing an anionic group in one of the side chains or aliphatic derivatives of tertiary amines, alkyldimethylamine oxides. Alternatively, alkylmethylamine oxide or alkoxymethylamine oxide may be contained.

  Components (E) and (F) may be contained in the fiber and fabric treatment agents up to 25%, in particular 3-15%.

Enzymes In another preferred embodiment, the fiber- and fabric treatment agents according to the invention additionally contain 0.05 to 4% by weight of enzyme (J). In particular, the enzymes used in fiber- and fabric treatment agents are proteases, amylases, lipases and cellulases. Among the enzymes, the prepared enzyme is added in an amount of 0.1 to 1.5% by mass, particularly preferably 0.2 to 1.0% by mass. Suitable proteases are, for example, savinase and Esperase (manufacturer: Novo Nordisk). A suitable lipase is for example lipolase (manufacturer: Novo Nordisk). A suitable cellulase is, for example, Celluxym (manufacturer: Novo Nordisk). It is also possible to use peroxidases for the activation of the bleaching system. Individual enzymes or combinations of different enzymes can be used. Optionally, the textile detergent formulations according to the invention can still contain enzyme stabilizers such as calcium propionate, sodium formate or boric acid or their salts, and / or antioxidants.

  Fibers treated by the method according to the invention or contacted with the detergent according to the invention are another subject of the invention. The fibers can be natural fibers as well as synthetic fibers. Simple examples of natural fibers are: cotton, wool, linen and viscose. Simple examples of synthetic fibers are: polypropene fibers, polyamide fibers, polyester fibers, nylon fibers, perion fibers, Teflon® fibers, Lycra® fibers.

  The fibers are in particular woven, knitted, spun, knitted and woven, knotted or bobbin lace knitted.

1 is a schematic diagram showing a test apparatus.

  In the following, the present invention is illustrated by examples which do not limit the subject of the present invention:

Example:
Test setup Equipped with mechanical stirrer (IKA stirrer motor with glass stirrer and movable PTFE stirrer blades) and liquid circuit (Iwaki magnet pump MD6-230GS01, 80-90 L / h) and boron doped diamond electrode 1000 mL glass double-jacketed vessel with an electrolysis cell (Adamant miniDiaCell, diamond on silicon, electrode surface area 12.5 cm ² ). The test fabric was introduced into the double jacket container at the start of the test.

In order to evaluate the results of electrochemical bleaching, a reference test with a comparative system consisting of hydrogen peroxide (H ₂ O ₂ ) and tetraacetylethylenediamine (TAED) was carried out without electrolysis. The concentration range selected corresponds to the concentration range of commercial detergents, in which TAED is currently widely used. As a reference system, a mixture of H ₂ O ₂ and TAED in a ratio of 4: 1 (mmol / L) is used.

For reference testing, a solution of H ₂ O ₂ and TAED in deionized water was prepared and circulated at 40 ° C. without electrolysis. After 30 minutes, the fabric specimen was removed, washed thoroughly with deionized water, dried while blocking the light, and the reflectance was measured as a reference for removing soil.

The wash liquid of Reference Test R3 had the following composition: 700 g deionized water, 10 g NaHCO ₃ , H ₂ O ₂ solution (30% H ₂ O _{2 in} water), 0.16 g TAED (4: 1 mmol / L).

Laundry fluid for testing according to the present invention with active electrolysis typically has the following composition: 700 g deionized water, 10 g NaHCO ₃ , 0.16 g TAED.

The possibility of combining the method according to the invention with a commercial detergent was exemplarily tested for the following standard formulation (wfk-Forschungstitut for Reinigstetechnology e.V.):
-ECE98
-AATCC 1993

  This exemplary detergent was metered into deionized water as follows: detergent 4.8 g / L, sodium percarbonate 0.67 g / L, TAED 0.15 g / L. The total volume of the washing liquid is 300 mL unless otherwise stated.

Soil removal was measured by subjecting the test fabric to reflection measurements at 460 nm before and after washing. The stain removal rate or color removal rate was calculated in% from the reflectance R before and after washing and the reflectance of the white reference cotton cloth according to the following formula:

  All washing was performed twice. The value for soil removal listed in the table during the washing results corresponds to the average of the measured values obtained under the same conditions.

  Reflectance measurements were performed using a spectrophotometer of Mark Gretag Maxbeth, type Spectrolino, under the following conditions: 10 ° viewing angle, light source D65, UV filter.

Reference Example R1 and Example 1
Reference Example R1 describes soil removal that is achieved only with a wash solution (700 g of deionized water, NaHCO ₃ ). This test is one reference example for measuring the intended soil removal.

Example 1 shows the bleaching action achieved without the addition of a bleach activator or bleach precursor, such as TAED, by electrolysis of a wash liquor (700 g deionized water, 10 g NaHCO ₃ ) at a boron doped diamond electrode. Have been described. Compared with the reference test R1, a significant increase in the soil removal rate can be observed.

Examples 2-6:
Examples 2-6 show the soil removal achieved in the presence of the bleach activator TAED using the method according to the invention, depending on the current intensity (test fabric EMPA 167, tea on cotton).

  This result reflects the influence of the current intensity on the removal of dirt. It was found that as the current intensity increased, the intended soil removal rate increased.

Reference examples R2 to R4:
Reference examples R2 to R4 represent the results of bleaching in a system from H ₂ O ₂ and TAED in different compositions. That is, a wash liquor having an addition amount of H ₂ O ₂ / TAED at a concentration ratio of 4: 1 (mmol / l) often corresponds to the composition used in commercial powder detergents.

As expected, it has been found that increasing the H ₂ O ₂ concentration to 8/1 (R2) provides a relatively high soil removal rate. This is because the formation of peracetic acid from TAED is promoted. Similarly, the degree of soil removal was found to depend on the available amount of TAED as well. That is, halving the TAED concentration from 4/1 (R3) to 4 / 0.5 (R4) leads to a reduction in the stain removal rate from 64% to 59%.

Comparison of soil removal rate by electrochemical bleaching activation and reference test results is achieved by electrochemical method, achieving soil removal rate comparable to system H ₂ O ₂ / TAED 4: 1 (mmol / l) (Soil removal rate after about 30 minutes at 40 ° C., about 60%, see Example 5).

Examples 7 and 8:
Examples 7 and 8 describe the differences between the two-step continuous disassembly for soil removal results (Example 7) and the comparison of electrolysis and cleaning operations for soil removal results (Example 8). Has been.

  According to the standard method, the wash liquor moved through the electrode at 1.2 A during the entire test time and achieved a very good soil removal rate (Example 5). Surprisingly, a very good soil removal rate was achieved as well when the wash liquor was pumped at 1.2 A for 10 minutes prior to the addition of TAED and test fabric. After switching off the current source, TAED and test fabric were added and pumped through for 30 minutes without application of further current (Example 7). This effect is very favorable. This is because a very good dirt removal rate can be achieved with a small current input. If the wash liquor is pumped at 1.2A for 10 minutes before addition of TAED and test fabric and electrolysis is continued for 30 minutes after addition of TAED and test fabric, the soil removal rate can be increased to 61%. (Example 8).

Examples 9-12 and Reference Examples R5 and R6:
Examples 9-12 and reference examples R5 and R6 describe the treatment of various stain types with the process according to the invention for electrochemical bleaching activation.

  This result shows that the intended soil removal rate is significant at different intensities as expected for various stains. Comparative examples R5 and R6 each describe a pure laundry effect without electrolysis in the absence of TAED. According to it, good soil removal rates for red wine (Examples 9 and 10) and for blueberry juice (Examples 11 and 12) are achieved by the method according to the invention.

Examples 13 to 26 and Reference Examples R7 to R20
Examples 13 to 26 and reference examples R7 to R20 describe the treatment of various fabric colors with the process according to the invention for electrochemical bleaching activation. To that end, a solution of 15.4 g of sodium bicarbonate in 1084 g of deionized water was electrolyzed at 40 ° C. and 1.2 A for 10 minutes. Subsequently, 0.25 g TAED and a color monitor were added and the pump was circulated for 45 minutes with no current. After each wash operation, the color monitor was rinsed briefly with deionized water and subjected to reflectance measurements at 460 nm after each wash cycle to determine the degree of color removal. A total of 15 washing cycles (3 × 5) were performed per color monitor. As shown in Table 7, unexpectedly significant color damage cannot be confirmed within the range of measurement accuracy by the method according to the invention. One exception is a fabric colored with Sulfur Black 1 (AISE-1) (Example 13), which already loses color or bleeds in the laundry solution without bleach and without electrolysis. Have a tendency to lose.

The results of the method according to the invention were compared with a simplified reference system. For testing for color removal of selected fabric colors, from 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) In this system, the color monitor was stirred at 40 ° C. for 45 minutes. The results of the reference test are listed in Table 8. Also in this case, as described above, in the case of a color monitor colored with Sulfur Black 1 (AISE-1), extremely remarkable discoloration can be confirmed (R7). Comparison of the remaining data shows that the reference system generally causes significantly more color damage than the method according to the invention.

Reference examples R21 to R24
Reference Examples 21-24 show the soil removal achieved in 30 minutes at 40 ° C. by detergent formulations in the presence or absence of sodium percarbonate and TAED (test fabric EMPA 167, tea on cotton). Thereby, soil removal in the absence of sodium percarbonate and TAED exhibits a pure laundering effect not attributable to chemical bleaching operations.

Examples 27-30
Examples 27 and 30 describe the results of continuous degradation of two steps (electrolysis and cleaning operations) on the results of soil removal. In Examples 27 and 29, each detergent solution was subjected to a 10 minute pre-electrolysis prior to the addition of the fabric specimen. It turns out that the soil removal of a pure detergent solution is not significantly affected by pre-electrolysis (see also Reference Examples R21 and R23). In Examples 28 and 30, the fabric specimen and TAED were added after a 10 minute pre-electrolysis of the respective wash liquor. Therefore, a significant increase in soil removal is found already after 10 minutes of pre-electrolysis (at 1.2A). The method according to the invention is therefore also compatible with complex detergent formulations.

Examples 31-34
Examples 31-34 describe the results of the simultaneous implementation of two steps (electrolysis and cleaning operations) on the result of soil removal. In Examples 31 and 33, the detergent solution was subjected to electrolysis for 30 minutes after addition of the fabric specimen. It turns out that the soil removal of a pure detergent solution is influenced only slightly by continuous electrolysis (see also Reference Examples R21 and R23 and Examples 27 and 29). For Examples 32 and 34, fabric specimens and TAED were added to the detergent solution. The intended soil removal by continuous electrolysis (Examples 32 and 34) is, as expected, slightly less than the soil removal achieved by a short (but energy saving) pre-electrolysis. Only high (see Example 28) or comparable (see Example 30).

  The method according to the invention is therefore also compatible with complex detergent formulations.

Claims (15)

  A washing machine comprising one electrode and one adjustment unit, wherein a current intensity of 0.02 to 30 A can be applied to the electrode during a washing operation.   The washing machine according to claim 1, wherein the electrode is selected from the group consisting of a lead electrode, a diamond electrode, a special steel electrode, a platinum electrode and a tin oxide electrode.   The washing machine according to claim 2, wherein the electrode is a diamond electrode. Electrode has an effective surface area of 0.5~1000cm ^2, the washing machine according to any one of claims 1 to 3. A method of cleaning fibers, in which OH radicals and H ₂ O ₂ are generated in an aqueous solution by applying a current intensity of 0.02 to 30 A to one electrode. 6. The method of claim 5, wherein the electrode is a diamond electrode having an effective surface area of 0.5 to 1000 cm < ² >.   7. A method according to claim 5 or 6, wherein at least one compound selected from the group consisting of builders, surfactants, enzymes with OH radicals (or derivative products) is used for cleaning.   The process according to claim 1, wherein the process is carried out at a temperature up to 60 ° C.   9. A method according to any one of claims 5 to 8, having a degree of soil removal with respect to at least 20% of the bleachable stain.   A detergent containing less than 1% by weight of one or more bleach activators and / or one or more bleach catalysts and hydrogen peroxide or hydrogen peroxide releasing compound.   A detergent selected from the group consisting of heavy duty detergents, liquid detergents, color detergents and wool detergents.   A method of using the washing machine according to any one of claims 1 to 4 and the detergent according to claim 10 or 11.   A fiber treated by the method of any one of claims 5 to 9 or claim 12 or contacted with a detergent according to claim 10 or 11.   Parts kit including one electrolytic cell that can be connected in advance to one washing machine and a water supply pipe.   Current supply independent of current grid, diamond arranged so that both electrodes can make contact with the electrolyte when an e-breach ball is present in the washing drum of the washing machine during the washing operation E bleach ball including anode and cathode.

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