EP2550389B1 - Electrochemical textile-washing aparatus, method, combination and e-bleach ball - Google Patents
Electrochemical textile-washing aparatus, method, combination and e-bleach ball Download PDFInfo
- Publication number
- EP2550389B1 EP2550389B1 EP11709743.6A EP11709743A EP2550389B1 EP 2550389 B1 EP2550389 B1 EP 2550389B1 EP 11709743 A EP11709743 A EP 11709743A EP 2550389 B1 EP2550389 B1 EP 2550389B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- electrode
- wash
- diamond
- washing
- electrolysis
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- 238000000034 method Methods 0.000 title claims description 46
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- 239000000835 fiber Substances 0.000 claims description 26
- 239000002689 soil Substances 0.000 claims description 24
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- 239000003792 electrolyte Substances 0.000 claims description 9
- 239000004094 surface-active agent Substances 0.000 claims description 9
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- 235000019254 sodium formate Nutrition 0.000 description 1
- 235000019795 sodium metasilicate Nutrition 0.000 description 1
- URLJMZWTXZTZRR-UHFFFAOYSA-N sodium myristyl sulfate Chemical compound CCCCCCCCCCCCCCOS(O)(=O)=O URLJMZWTXZTZRR-UHFFFAOYSA-N 0.000 description 1
- 229950005425 sodium myristyl sulfate Drugs 0.000 description 1
- 229910052911 sodium silicate Inorganic materials 0.000 description 1
- 235000019832 sodium triphosphate Nutrition 0.000 description 1
- NJWINEJWPSVGQC-UHFFFAOYSA-M sodium;4-(7-methyloctanoyloxy)benzenesulfonate Chemical compound [Na+].CC(C)CCCCCC(=O)OC1=CC=C(S([O-])(=O)=O)C=C1 NJWINEJWPSVGQC-UHFFFAOYSA-M 0.000 description 1
- 238000007614 solvation Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000000600 sorbitol Substances 0.000 description 1
- 239000004759 spandex Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 235000011044 succinic acid Nutrition 0.000 description 1
- 239000005720 sucrose Substances 0.000 description 1
- 150000003871 sulfonates Chemical class 0.000 description 1
- 239000003760 tallow Substances 0.000 description 1
- 239000011975 tartaric acid Substances 0.000 description 1
- 235000002906 tartaric acid Nutrition 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- 150000000000 tetracarboxylic acids Chemical class 0.000 description 1
- KQTIIICEAUMSDG-UHFFFAOYSA-N tricarballylic acid Chemical compound OC(=O)CC(C(O)=O)CC(O)=O KQTIIICEAUMSDG-UHFFFAOYSA-N 0.000 description 1
- 239000001226 triphosphate Substances 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Images
Classifications
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06F—LAUNDERING, DRYING, IRONING, PRESSING OR FOLDING TEXTILE ARTICLES
- D06F35/00—Washing machines, apparatus, or methods not otherwise provided for
- D06F35/003—Washing machines, apparatus, or methods not otherwise provided for using electrochemical cells
Definitions
- 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.
- the functionality of the washing machines can be increased.
- 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.
- 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).
- 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.
- 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 membrane 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.
- 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.
- 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.
- 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.
- the subject of the present invention is a washing machine according to claim 1.
- 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.
- 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.
- EP 2 098 627 and EP 2 098 628 are often described, for.
- 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.
- 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.
- 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.
- 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.
- BDD electrode boron-doped diamond electrode
- 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.
- 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.
- 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).
- 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.
- the 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.
- precious metals such as platinum and diamond electrodes come into consideration.
- boron-doped diamond electrodes are used as the cathode.
- 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.
- 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.
- the washing machine housing made of steel acts as a cathode.
- stainless steel is used as steel.
- the washing machine comprises two diamond electrodes, which are connected as anode and cathode.
- 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 .
- 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.
- 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).
- 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.
- an electrolyte is selected which is selected from the group consisting of water, methanol and ethanol. Particularly preferred is water.
- 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.
- 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.
- 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:
- 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 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.
- 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.
- 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.
- 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.
- conductive salts can be added during the process and most simply as a component of the detergent.
- conductive salts z.
- 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.
- 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.
- EDTA EDTA
- 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.
- Suitable inorganic builders (A ') are, above all, crystalline or amorphous aluminosilicates having ion-exchanging properties, in particular zeolites.
- 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 .
- GB-A 2 013 259 EP-A 0 522 726 .
- EP-A 0 384 070 and WO-A 94/24251 are, above all, crystalline or amorphous aluminosilicates having ion-exchanging properties.
- 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.
- the stated components (A ') can be used individually or in mixtures with one another.
- 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.
- other components (A ') may be present.
- 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.
- 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.
- the group (i) comprises monoethylenically unsaturated C 3 -C 8 monocarboxylic acids such as acrylic acid, methacrylic acid, crotonic acid and vinylacetic acid.
- 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.
- 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.
- 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.
- Suitable modifying monomers are the above-mentioned monomers of groups (ii) and (iii).
- 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.
- a mixture of maleic acid and acrylic acid in a weight ratio of 90:10 to 10:90 is preferably used.
- suitable polyamidocarboxylic acids and modified polyamidocarboxylic acids are known, for example from EP-A 454 126 .
- WO-A 94/01486 and EP-A 581 452 are known, for example from EP-A 454 126 .
- 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.
- (B ') are ethylenediamine disuccinic acid, oxydisuccinic acid, aminopolycarboxylates, aminopolyalkylene phosphonates and polyglutamates.
- oxidized starches may be used as organic co-builders in addition to (B ').
- 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.
- 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.
- anionic surfactants are C 9 -C 20 linear alkyl benzene sulphonates (LAS) and alkyl toluenesulphonates.
- 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 amide
- 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.
- LAS linear alkylbenzenesulfonates
- 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.
- nonionic surfactants D 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.
- 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.
- nonionic surfactants 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.
- Pluronic® propylene oxide and / or butylene oxide
- Tetronic® Tetronic®
- 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.
- 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.
- the surfactant constituents of the surfactant mixture according to the invention are to be considered.
- 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.
- 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.
- 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.
- F ampholytic surfactants
- Components (E) and (F) may contain up to 25%, preferably 3-15% in the fiber and textile treatment agents.
- the fiber and textile treatment agent additionally contains 0.05 to 4% by weight of enzymes (J).
- enzymes are proteases, amylases, lipases and cellulases.
- 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.
- 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.
- Fig. 1 Schematic representation of the experimental apparatus
- 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.
- 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).
- 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
- 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.
- 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
- 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
- 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).
- 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.
- 0.25 g of TAED and the color monitors were added and pumped without current for 45 minutes.
- 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.
- 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% 0% R18 AISE 29 0% 1% 1% R19 AISE 33 0% 0% 0% 0% 0% R20 AISE 39 0% 0% 0% 0% 0% 0% 0% 0% 0% 0% 0% 0% 0% 0% 0% R20 AISE 39 0% 0% 0% 0%
- 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).
- 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.
- 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).
- 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
- 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.
- 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).
- both textile samples and TAED were added to the detergent solution.
- the dirt removal achieved by the continuous electrolysis 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.
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- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Detergent Compositions (AREA)
- Accessory Of Washing/Drying Machine, Commercial Washing/Drying Machine, Other Washing/Drying Machine (AREA)
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Description
Die vorliegende Erfindung betrifft eine Waschmaschine mit elektrochemischer Zelle, ein Verfahren zur elektrochemischen Reinigung von Fasern, Waschmittel zur elektrochemischen Reinigung von Fasern und die so gereinigten Fasern, ein entsprechendes Verfahren, eine Kombination und einen e-bleach ball. In den vergangenen Jahren ist das Bewusstsein der Bevölkerung für den Einfluss des Menschen auf die Umwelt stetig gewachsen. Die Vermeidung von schädlichen Abfällen ebenso wie Verfahren zur Reduzierung und Wiederaufbereitung (Recycling) stehen im Vordergrund und werden immer wichtiger. Ein großer Teil der Emissionen im privaten Bereich ist mit der Textilreinigung und -pflege verbunden, für die komplexe Waschmittelmischungen eingesetzt werden. Da einige Bestandteile dieser Waschmittel langfristig negative Auswirkungen auf die Umwelt haben können, steigt die Nachfrage nach Waschmitteln, die weniger umweltgefährdend sind. Die Reduktion der Inhaltsstoffe soll dabei jedoch nicht zu einer verminderten Waschleistung führen. Eine Lösung liegt in speziellen Waschmitteln für bestimmte Farben oder Fasern, was aber zu einer erhöhten Anzahl von Waschmitteln in den Haushalten führt und somit wenig verbraucherfreundlich ist.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.
Alternativ kann die Funktionalität der Waschmaschinen erhöht werden.Alternatively, the functionality of the washing machines can be increased.
Insbesondere die bleichaktiven Verbindungen stellen eine Herausforderung dar. Heutige Waschmittel enthalten Bleichkatalysatoren oder Bleichvorläufer und eine Peroxidquelle, so dass die Bleiche erst während des Waschvorgangs aktiviert wird.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.
Eine Herausforderung bei der Formulierung eines Waschmittels besteht darin, die empfindlichen Bestandteile des Waschmittels (z.B. Enzyme, Parfüme) vor den Bleichkomponenten zu schützen.A challenge in formulating a detergent is to protect the delicate components of the detergent (e.g., enzymes, perfumes) from the bleaching components.
Eine Möglichkeit dazu besteht darin, die empfindlichen Bestandteile durch Verkapselung vor dem Einfluss der Bleiche zu schützen. Besonders schwierig gestaltet sich dies in Flüssigwaschmitteln, wo das Reaktionsmedium Wasser bereits in der Formulierung zur Verfügung steht. Eine Trennung von Bleichkomponenten und empfindlichen Substanzen gelingt hier oft nur mit Hilfe von Vorratsbehältern, die aufwändig gestaltete und wenig benutzerfreundliche Mehrkammersysteme aufweisen. Ferner muss gewährleistet werden, dass die Bleiche ausschließlich während des Waschvorgangs und nicht schon vorher gebildet wird, da bleichaktive Substanzen, wie z. B. Wasserstoffperoxid unter den typischerweise vorliegenden alkalischen Bedingungen instabil sind und sich unter Gasbildung zersetzen. Weiterhin sind viele in Pulverwaschmitteln eingesetzte Bleichkomponenten in Flüssigwaschmitteln nicht ausreichend löslich.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.
Eine Möglichkeit, die beschriebenen Einschränkungen zu überkommen, stellt die in situ Generierung von bleichaktiven Substanzen in der Waschmaschine dar. Es ist bekannt, dass Wasserstoffperoxid durch Elektrolyse gebildet werden (
Die verwendung von Diamantelektroden im Kontext einer Bleichaktivierung ist hingegen in der WO 2009/06 7838 beschrieben. Bor-dotierte Diamantelektroden werden bisher üblicherweise in der Abwasserbehandlung eingesetzt (TOC Abbau), wo die aggressiven OH-Radikale, die an dieser Elektrode gebildet werden, organisches Material attackieren und bis zu CO2 oxidieren. Beim Einsatz in Textilwaschmaschinen sind somit erhebliche Farb- und Faserschädigung zu erwarten gewesen.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.
Grundsätzlich werden elektrochemische Verfahren in einer Reihe von Anwendungen eingesetzt. Am häufigsten sind Anwendungen, in denen gezielt einzelne chemische Stoffe in andere umgesetzt werden. Auf elektrochemischem Wege können z. B. Bindungsspaltungen, Dimerisierungen, Kupplungen usw. durchgeführt werden.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.
Im Bereich der Textilwäsche sind elektrochemische Verfahren bisher nicht kommerziell zum Einsatz gekommen. Dies liegt unter anderem daran, dass nicht alle apparativ notwendigen Parameter erforscht sind, bisher Schwermetallelektroden verwendet wurden, die stets zu einem Schwermetalleintrag in die Waschflotte führen und daran, dass bisher keine für derartige Waschprozesse gezielt entwickelten Waschmittelformulierungen existieren.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.
Es ist daher Aufgabe der vorliegenden Erfindung ein System zur Reinigung von Fasern - und insbesondere Textilien - bereitzustellen, das die technischen Voraussetzungen ebenso erfüllt, wie die chemischen.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.
Dies ist überraschend gelungen durch die Waschmaschine gemäß Ansprüchen 1 bis 4, das Verfahren gemäß Ansprüchen 5 bis 9, das Waschmittel gemäß Anspruch 10 sowie die Fasern gemäß Anspruch 11, denn es wurde überraschend gefunden, dass Bor-dotierte Diamantelektroden für die Textilbleiche eingesetzt werden können, obwohl bei diesen üblicherweise in der Abwasserbehandlung (TOC Abbau) Verwendung findenden Elektroden mit erheblicher Farb- und Faserschädigung zu rechnen war,
eine Vorelektrolyse des Wassers (vor der Zugabe von Waschmittel, Bleichaktivator und Textilgewebe) zur Bleichaktivierung ausreichend ist, so dass auf diese Weise der Energieverbrauch erheblich verringert werden kann (10 min Vorelektrolyse gegenüber 30 min - 60 min Dauerelektrolyse während des Waschvorgangs), wobei zudem empfindliche Bestandteile von Waschmittel und Kleidung nicht unnötig den Elektroden / OH Radikalen ausgesetzt werden müssen,
eine Integration einer Elektrolyse-Zelle in den externen Wasserzulauf möglich ist, die elektrochemische Bleichaktivierung auch mit Flüssigwaschmitteln kombinierbar ist, eine ungeteilte Zelle verwendet werden kann, die in ihrem Aufbau sehr einfach und wartungsarm und somit gegenüber geteilten Zellen sehr günstig ist, wobei auch keine zusätzlichen Behälter, Pumpen, Membranen etc notwendig sind, auch bei niedrigen Waschtemperaturen (< 40 °C) gute Bleichergebnisse erzielt werden können und
der Einsatz der Elektrode in der Waschmaschine hygienische Vorteile hat.This is surprisingly achieved by the washing machine according to
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.
Gegenstand der vorliegenden Erfindung ist danach eine Waschmaschine nach Anspruch 1.The subject of the present invention is a washing machine according to
Bevorzugt ist dabei eine Waschmaschine, bei der die anlegbare Stromstärke im Bereich von 0,1 bis 16 A und besonders bevorzugt 0,3 bis 10 A liegt.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.
Und es ist eine Waschmaschine bevorzugt, bei der die Stromstärke während des Befüll- und/oder Waschvorgangs angelegt wird.And a washing machine is preferred in which the current is applied during the filling and / or washing process.
Die Stromstärke kann dabei über die Zeit variieren. Erfindungsgemäße bevorzugte Ausführungsformen weisen eine konstante Stromstärke oder einen variablen Verlauf der Stromstärke auf.The current can vary over time. Inventive preferred embodiments have a constant current or a variable current intensity.
Die Art der Waschmaschine umfasst dabei alle Arten von Waschmaschinen, d.h. sowohl Waschmaschinen für den Haushalt als auch Waschmaschinen für die industrielle Faser- und insbesondere Textilreinigung. Waschmaschinen sind vielfach beschrieben, z. B. in
Als Elektrodenmaterialien, insbesondere als Anodenmaterialien, in der elektrochemischen Zelle verwendet man vorzugsweise Materialien, mit denen man eine hohe Sauerstoffüberspannung erreichen kann, beispielsweise Edelmetalle wie Platin oder Metalloxide wie Ruthenium-, Chrom- oder Bleioxid oder Mischoxide des Typs RuOxTiOx oder an sich bekannte dimensionsstabile Anoden (DSA) oder Diamantelektroden.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.
Vorzugsweise ist die Elektrode ausgewählt aus der Gruppe bestehend aus Graphitelektrode, Diamantelektrode, Stahlelektrode, und Platinelektrode.Preferably, the electrode is selected from the group consisting of graphite electrode, diamond electrode, steel electrode, and platinum electrode.
Diamantelektroden sind beansprucht. Sie entstehen in dem man auf ein Trägermaterial ein oder mehrere Diamantschichten aufbringt. Als mögliche Trägermaterialien eignen sich Niob, Silizium, Wolfram, Titan, Siliziumcarbid, Tantal, Graphit oder keramische Träger wie Titansuboxid. Bevorzugt für das erfindungsgemäße Verfahren ist jedoch ein Träger aus Niob, Titan oder Silizium, ganz besonders bevorzugt ist ein Träger aus Niob, wenn eine Diamantelektrode eingesetzt wird.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.
Bevorzugt ist die Anode eine Diamantelektrode, wobei die Diamantelektrode auch noch mit weiteren Elementen dotiert sein kann. Als Dotierungselemente sind Bor und Stickstoff bevorzugt. Ganz besonders bevorzugt ist das beanspruchte Verfahren mit einer bordotierten Diamantelektrode (BDD-Elektrode) als Anode.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.
Für die Elektrolyse können dabei jegliche dem Fachmann bekannte Elektrolysezellen aus den genannten Elektroden eingesetzt werden - wie geteilte oder ungeteilte Durchflusszelle, Kapillarspaltzelle oder Plattenstapelzelle. Besonders bevorzugt ist die ungeteilte Durchflusszelle. Zur Erzielung optimaler Raum-Zeit-Ausbeuten ist eine bipolare Anordnung mehrerer Elektroden vorteilhaft.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.
Es wurde nun weiter gefunden, dass sich Diamantelektroden unter den Bedingungen der Faser- und insbesondere der Textilwäsche ähnlich wie Schwermetallelektroden verhalten.It has now further been found that diamond electrodes behave similar to heavy metal electrodes under the conditions of fiber and especially textile washing.
Vorteilhaft an dem erfindungsgemäßen Verfahren nach Anspruch 3 ist, dass keine Metallionen in den Elektrolyten (also die Waschflotte) und somit die Umwelt gelangen, da bei der Korrosion der Diamantschicht der BDD-Elektrode keine Schwermetallionen entstehen können.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.
Es können Diamantelektroden eingesetzt werden, die nach dem CVD-Verfahren (chemical vapour deposition) hergestellt worden sind. Solche Elektroden sind kommerziell verfügbar wie zum Beispiel bei Hersteller: Condias, Itzehoe (Deutschland) bzw. Adamant Technologies, La-Chaux-de-Fonds (Schweiz).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).
Preisgünstigere Diamantelektroden, die nach dem HTHP-Verfahren (high temperature high pressure: Industriediamantpulver wird mechanisch in die Oberfläche eines Trägerbleches eingebracht) hergestellt wurden, sind ebenso geeignet.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-Elektroden sind kommerziell von pro aqua, Niklasdorf (Österreich) erhältlich, ihre Eigenschaften werden von
Vom Elektrodentyp her bevorzugt ist daher eine Waschmaschine, bei der die Elektrode eine Diamantelektrode ist.Of the electrode type, therefore, a washing machine in which the electrode is a diamond electrode is preferred.
Als Kathodenmaterialien kommen, sofern die Elektrodenpolarität nicht vertauscht werden soll, beispielsweise Eisen, Stahl, Edelstahl oder Nickel, ansonsten auch Edelmetalle wie Platin sowie Diamantelektroden in Betracht. Bevorzugt verwendet man aber bordotierte Diamantelektroden als Kathode.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.
Für das erfindungsgemäße Verfahren nach Anspruch 3 ist die Kathode eine Diamantelektrode. Diese Diamantelektrode enthält eine auf ein Trägermaterial aufgebrachte Diamantschicht, wobei das Trägermaterial ausgewählt ist aus Gruppe von Niob, Silizium, Wolfram, Titan, Siliziumcarbid, Tantal, Graphit oder keramische Trägern wie Titansuboxid. Besonders bevorzugt ist als Trägermaterial Niob oder Silizium. Die Diamantschicht auf dem Träger kann noch mit weiteren Elementen dotiert sein. Bevorzugt sind bor- oder stickstoffdotierte Diamantelektroden. Besonders bevorzugt sind bordotierte Diamantelektroden.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.
Ganz besonders bevorzugt ist die Kombination von bordotierter Diamantelektrode als Anode mit Stahl als Kathode, wobei insbesondere das Waschmaschinengehäuse aus Stahl als Kathode fungiert. Als Stahl wird dabei insbesondere Edelstahl verwendet.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 einer anderen bevorzugten Ausführungsform umfasst die Waschmaschine zwei Diamantelektroden, die als Anode und Kathode geschaltet sind.In another preferred embodiment, the washing machine comprises two diamond electrodes, which are connected as anode and cathode.
Sind Anode(n) und Kathode(n) Diamantelektroden, so kann die Elektrolyse auch in Intervallen durchgeführt und ggf. die Polarität der Elektroden vertauscht werden (kurzzeitige Elektrolyse, Waschvorgang, kurzzeitige Elektrolyse, Waschvorgang, usw.). Ein Vorteil dieser Intervallschaltung ist, dass empfindliche Bestandteile des Waschmittels nur kurzzeitig einem möglichen Abbau an den Elektroden (in erster Linie durch OH Radikale) ausgesetzt wären.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).
Vorteilhaft ist das erfindungsgemäße Verfahren, wenn die Polung bei der Diamantelektroden im Bereich von 0,1 bis 200 min oder von Waschgang zu Waschgang zu Vermeidung von Elektrodenbelägen (Fouling) vertauscht wird.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).
Die einzelnen Elektroden haben eine bestimmte Größe, die einen Einfluss auf die Wirkung hat. Bevorzugt ist eine Waschmaschine, bei der die einzelne Elektrode eine wirksame Oberfläche von 0,5 bis 1000 cm2, vorzugsweise 1 bis 500 cm2 und besonders bevorzugt 2 bis 100 cm2 hat. Dabei bezieht sich die Elektrodengröße auf die Fläche der Einzelelektrode, die während der Elektrolyse als Anode geschaltet und der Kathode zugewandt ist. Befindet sich eine Anode zwischen zwei Kathoden, so ergibt sich die Elektrodengröße der Anode aus der Summe von Vorder- und Rückseite. Die wirksame Elektrodenfläche der Einzelelektrode ist die Elektrodenfläche der Anode, die während der Elektrolyse mit dem Elektrolyten in Kontakt kommt und der (den) Kathode(n) zugewandt ist.
Sind zwei Elektroden so geschaltet, dass sie im Wechsel als Anode oder als Kathode fungieren können, ergeben sich entsprechend doppelt so große Werte für die Gesamtelektrodenfläche.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.
Die wirksamen Flächen der Anode(n) und Kathode(n) sind bevorzugt gleich groß, - dies ist besonders bevorzugt, wenn es sich sowohl bei Anode(n) als auch bei Kathode(n) um Diamantelektroden handelt. Die Elektroden sind in einem bestimmten Abstand zueinander angeordnet. Bevorzugt ist dabei ein Abstand von 0.1-20 mm, bevorzugt 1-10 mm, besonders bevorzugt 2-5 mmThe 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
Eine Elektrolysezelle umfasst vorliegend ein Paar Elektroden, die vorzugsweise nicht durch eine Membran voneinander getrennt sind. Zur Optimierung der Raum-Zeit-Ausbeuten ist eine bipolare Anordnung mehrerer Elektroden vorteilhaft. Innerhalb der Waschmaschine wird die Zelle im gefluteten Bereich des Waschbottichs, vorzugsweise außerhalb der Waschtrommel eingebaut. Die Zelle kann aber auch in der Zulaufleitung innerhalb oder außerhalb der Waschmaschine angebracht werden. Die Zelle kann ein fest eingebauter Bestandteil der Waschmaschine oder ein separates Bauteil sein (z.B. im Frischwasserzulauf zwischen Wasserhahn und Waschmaschine oder als e-bleach-ball mit eigener Energieversorgung in der Trommel). Ein derartiges Kit of Parts umfassend eine Waschmaschine und eine am Wasserzulauf vorschaltbare Elektrolysezelle stellt einen weiteren Gegenstand der vorliegenden Erfindung dar. Eine weitere erfindungsgemäße Ausführungsform besteht darin, die Elektrolysezelle in einen zusätzlichen Wasserkreislauf innerhalb der Maschine zu integrieren.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.
Ein e-bleach-ball, umfassend eine stromnetzunabhängige Stromversorgung, eine Diamantanode und eine Kathode, die so angeordnet sind, dass die Elektroden mit dem Elektrolyten in Kontakt treten können, wenn sich der e-bleach-ball während des Waschvorganges in der Waschtrommel einer Waschmaschine befindet, stellt einen weiteren Gegenstand der vorliegenden Erfindung dar.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.
Für das erfindungsgemäße Verfahren wird ein Elektrolyt gewählt, der ausgewählt ist aus der Gruppe bestehend aus Wasser, Methanol und Ethanol. Besonders bevorzugt ist Wasser.For the inventive method, an electrolyte is selected which is selected from the group consisting of water, methanol and ethanol. Particularly preferred is water.
Bei dem erfindungsgemäßen Verfahren liegt der pH-Wert im Bereich von 2 bis 13, bevorzugt von 3 bis 12, besonders bevorzugt im Bereich von 6 bis 11.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.
Die Temperatur für das erfindungsgemäße Verfahren liegt im Bereich von 10 bis 95 °C, bevorzugt im Bereich von 15 bis 90°C, besonders bevorzugt im Bereich von 20 bis 60 °C und ganz besonders bevorzugt im Bereich von 25 bis 40 °C, wie z.B. 30 °C.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.
Weitere allgemeine Parameter eines solchen Verfahrens sind z.B. der
Weiter bevorzugt ist ein Verfahren, bei dem die Diamantelektrode mit einer wirksamen Oberfläche von 0,5 bis 1000 cm2, vorzugsweise von 1 bis 500 cm2 und besonders bevorzugt von 2 bis 100 cm2 ist.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 .
Ein Verfahren, bei dem neben den OH-Radikalen (bzw. seinen Folgeprodukten wie Wasserstoffperoxid und Ozon) mindestens eine Verbindung ausgewählt aus der Gruppe bestehend aus Builder, Tensid, Enzym zur Reinigung verwendet wird, stellt eine bevorzugte Variante dar.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.
Diese sind vorzugsweise in dem erfindungsgemäßen Waschmittel enthalten. Nichtabschließende Beispiele für Builder, Tenside und Enzyme sind dort aufgeführt.These are preferably contained in the detergent according to the invention. Non-exhaustive examples of builders, surfactants and enzymes are listed there.
Weiterhin ist ein Verfahren bevorzugt, das bei einer Temperatur bis 60 °C, vorzugsweise bis 40 °C besonders bevorzugt bis 30 °C durchgeführt wird.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.
Ein Verfahren wie oben beschrieben mit einem Schmutzentfernungsgrad für bleichbare Anschmutzungen (z.B. Tee) von mindestens 20 % stellt einen weiteren Gegenstand der vorliegenden Erfindung dar.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.
Die Bestimmung erfolgt, indem ein weißes Baumwoll-Testgewebe zunächst angeschmutzt wird und vor und nach Durchführung des Verfahrens, also vor und nach der Wäsche, einer Reflexionsmessung bei 460 nm unterzogen wird. Die Schmutzentfernung wird aus den Remissionswerten R vor und nach Durchführung des Verfahrens sowie dem Remissionswert eines weißen Referenz-Baumwollgewebes gemäß der folgenden Formel in % ermittelt:
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%:
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.
Ein Waschmittel, insbesondere ein Vollwaschmittel, enthaltend Bleichaktivator(en) und/oder Bleichkatalysator(en) und weniger als 1 Massen% Wasserstoffperoxid oder wasserstoffperoxidfreisetzende Verbindungen ist ein weiterer Bestandteil der vorliegenden Erfindung.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.
Ebenso ist ein Flüssigwaschmittel enthaltend Bleichaktivator(en) und/oder Bleichkatalysator(en) Gegenstand der vorliegenden Erfindung. Das Flüssigwaschmittel enthält dabei den Bleichaktivator in einer Menge von mindestens 0,01 bis 10 Massen%, vorzugsweise von 0,1 bis 5 Massen%, besonders bevorzugt von 0,5 bis 3 Massen%. Der Bleichaktivator ist dabei vorzugsweise ausgewählt aus den unten genannten geeigneten Bleichaktivatoren. Besonders bevorzugt ist der Bleichaktivator TAED. Vorwaschmittel (prespotter) enthaltend Bleichaktivator(en) und/oder Bleichkatalysator(en)ist ein weiterer Gegenstand der vorliegenden Erfindung. Das Vorwaschmittel enthält dabei den Bleichaktivator in einer Menge von mindestens 0,01 bis 50 Massen%, vorzugsweise von 0,1 bis 30 Massen%, besonders bevorzugt von 0,5 bis 10 Massen%. Der Bleichaktivator ist dabei vorzugsweise ausgewählt aus den unten genannten geeigneten Bleichaktivatoren. Besonders bevorzugt ist der Bleichaktivator TAED.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.
Als Bleichaktivatoren eignen sich:
- 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.
- 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.
Das verwendete Waschmittel kann gegebenenfalls noch Bleichkatalysatoren enthalten. Geeignete Bleichkatalysatoren sind beispielsweise quaternierte Imine und Sulfonimine, die beispielsweise beschrieben sind in
Für die bessere Leitfähigkeit des Grundelektrolyten können während des Verfahrens und am einfachsten als Bestandteil des Waschmittels Leitsalze hinzugefügt werden. Als Leitsalze können z. B. quartäre, bevorzugt bisquartäre Ammoniumsalze eingesetzt werden. Besonders bevorzugt sind die Leitsalze ausgewählt aus der Gruppe der bis-N,N'-(tri C1- bis C8-Alkyl)-substituierten Tri-, Tetra-, Penta-, Hexa- etc. - methylendiammoniumsalze wie Hexamethylenbis-(dibutylethylammonium)-phosphat oder -hydroxid. Ganz besonders bevorzugt werden Hexamethylenbis(dibutylethylammonium)phosphat oder -hydroxid als Leitsalz eingesetzt. Gegebenenfalls setzt man dem Elektrolyten, bevorzugt durch Zusatz zu dem erfindungsgemäßen Waschmittel, auch noch bestimmte Additive, wie EDTA oder Triethanolamin zu, um die kathodische Abscheidung von Eisen zu unterbinden, welche einen nachteiligen Effekt auf die angestrebte hohe Wasserstoffüberspannung der Kathode hätte. Als Anodenkorrosionsinhibitoren können Borate wie Dinatriumdiborat oder Orthoborsäure zugesetzt werden.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.
Geeignete anorganische Builder (A') sind vor allem kristalline oder amorphe Alumosilicate mit ionenaustauschenden Eigenschaften wie insbesondere Zeolithe. Verschiedene Typen von Zeolithen sind geeignet, insbesondere Zeolithe A, X, B, P, MAP und HS in ihrer Na-Form oder in Formen, in denen Na teilweise gegen andere Kationen wie Li, K, Ca, Mg oder Ammonium ausgetauscht ist. Geeignete Zeolithe sind beispielsweise beschrieben in
Geeignete kristalline Silicate (A') sind beispielsweise Disilicate oder Schichtsilicate, z. B. SKS-6 (Hersteller: Hoechst). Die Silicate können in Form ihrer Alkalimetall-, Erdalkalimetall- oder Ammoniumsalze eingesetzt werden, vorzugsweise als Na-, Li- und Mg-Silicate.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.
Amorphe Silicate wie beispielsweise Natriummetasilicat, welches eine polymere Struktur aufweist, oder Britesil® H20 (Hersteller: Akzo) sind ebenfalls verwendbar.Amorphous silicates such as sodium metasilicate, which comprises a polymeric structure, or Britesil ® H20 (manufactured by Akzo) are also useful.
Geeignete anorganische Buildersubstanzen auf Carbonat-Basis sind Carbonate und Hydrogencarbonate. Diese können in Form ihrer Alkalimetall-, Erdalkalimetall oder Ammoniumsalze eingesetzt werden. Vorzugsweise werden Na, Li- und Mg-Carbonate bzw. -Hydrogencarbonate, insbesondere Natriumcarbonat und/oder Natriumhydrogencarbonat, eingesetzt.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.
Übliche Phosphate als anorganische Builder sind Polyphosphate wie z. B. Pentanatriumtriphosphat.Usual phosphates as inorganic builders are polyphosphates such. B. pentasodium triphosphate.
In einer bevorzugten Ausführungsform enthält das Waschmittel 0,1 bis 20 Gew.-%. insbesondere 1 bis 12 Gew.-% organische Cobuilder (B') in Form von niedermolekularen, oligomeren oder polymeren Carbonsäuren, insbesondere Polycarbonsäuren, oder Phosphonsäuren oder deren Salzen, insbesondere Na- oder K-Salzen.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.
Geeignete niedermolekulare Carbonsäuren oder Phosphonsäuren für (B') sind beispielsweise:
- 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.
- 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.
Geeignete oligomere oder polymere Carbonsäuren für (B') sind beispielsweise:
- Oligomaleinsäuren, wie sie beispielsweise in
EP-A 451 508 EP-A 396 303 - 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.
- Oligomaleeinsäuren, as used for example in
EP-A 451 508 EP-A 396 303 - 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.
Die Gruppe (i) umfasst monoethylenisch ungesättigte C3-C8-Monocarbonsäuren wie z.B. Acrylsäure, Methacrylsäure, Crotonsäure und Vinylessigsäure. Bevorzugt werden aus der Gruppe (i) Acrylsäure und Methacrylsäure eingesetzt.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.
Die Gruppe (ii) umfasst monoethylenisch ungesättigte C2-C22-Olefine, Vinylalkylether mit C1-C8-Alkylgruppen, Styrol, Vinylester von C1-C8-Carbonsäuren, (Meth)acrylamid und Vinylpyrrolidon. Bevorzugt werden aus der Gruppe (ii) C2-C6-Olefine, Vinylalkylether mit C1-C4-Alkylgruppen, Vinylacetat und Vinylpropionat eingesetzt.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).
Die Gruppe (iii) umfasst (Meth)acrylester von C1-C8-Alkoholen, (Meth)acrylnitril, (Meth)acrylamide von C1-C8-Aminen, N-Vinylformamid und Vinylimidazol.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.
Falls die Polymeren der Gruppe (ii) Vinylester einpolymerisiert enthalten, können diese auch teilweise oder vollständig zu Vinylalkohol-Struktureinheiten hydrolysiert vorliegen. Geeignete Co- und Terpolymere sind beispielsweise aus
Als Copolymere von Dicarbonsäuren eignen sich für (B') vorzugsweise:
- 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.
- 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.
Pfropfpoiymere ungesättigter Carbonsäuren auf niedermolekulare Kohlenhydrate oder hydrierte Kohlenhydrate, vgl.
Geeignete ungesättigte Carbonsäuren sind hierbei beispielsweise Maleinsäure, Fumarsäure, Itaconsäure, Citraconsäure, Acrylsäure, Methacrylsäure, Crotonsäure und Vinylessigsäure sowie Mischungen aus Acrylsäure und Maleinsäure, die in Mengen von 40 bis 95 Gew.-%, bezogen auf die zu pfropfende Komponente, aufgepfropft werden.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.
Zur Modifizierung können zusätzlich bis zu 30 Gew.-%, bezogen auf die zu pfropfende Komponente, weitere monoethylenisch ungesättigte Monomere einpolymerisiert vorliegen. Geeignete modifizierende Monomere sind die oben genannten Monomere der Gruppen (ii) und (iii).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).
Als Pfropfgrundlage sind abgebaute Polysaccharide wie z.B. saure oder enzymatisch abgebaute Stärken, Inuline oder Zellulose, Eiweißhydrolysate und reduzierte (hydrierte oder hydrierend aminierte) abgebaute Polysaccharide wie z.B. Mannit, Sorbit, Aminosorbit und N-Alkylglucamin geeignet sowie auch Polyalkylenglycole mit Molmassen mit bis zu Mw = 5.000 wie z.B. Polyethylenglycole, Ethylenoxid/Propylenoxid- bzw. Ethylenoxid/Butylenoxid- bzw. Ethylenoxid/Propylenoxid/Butylenoxid-Blockcopolymere und alkoxylierte ein- oder mehrwertige C1-C22-Alkohole, vgl.
Bevorzugt werden aus dieser Gruppe gepfropfte abgebaute bzw. abgebaute reduzierte Stärken und gepfropfte Polyethylenoxide eingesetzt, wobei 20 bis 80 Gew.-% Monomere, bezogen auf die Pfropfkomponente, bei der Pfropfpolymerisation eingesetzt werden. Zur Pfropfung wird vorzugsweise eine Mischung von Maleinsäure und Acrylsäure im Gewichtsverhältnis von 90 : 10 bis 10 : 90 eingesetzt.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.
Als (B') geeignete Polyglyoxylsäuren sind beispielsweise beschrieben in
Als (B') geeignete Polyamidocarbonsäuren und modifizierte Polyamidocarbonsäuren sind beispielsweise bekannt aus
Als (B') verwendet man insbesondere auch Polyasparaginsäuren oder Cokondensate der Asparaginsäure mit weiteren Aminosäuren, C4-C25-Mono- oder -Dicarbonsäuren und/oder C4-C25-Mono- oder -Diaminen. Besonders bevorzugt werden in phosphorhaltigen Säuren hergestellte, mit C6-C22-Mono- oder Dicarbonsäuren bzw. mit C6-C22-Mono- oder - Diaminen modifizierte Polyasparaginsäuren eingesetzt.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.
Als (B') geeignete Kondensationsprodukte der Zitronensäure mit Hydroxycarbonsäuren oder Polyhydroxyverbindungen sind z.B. bekannt aus
Als (B') eignen sich weiterhin Ethylendiamindibernsteinsäure, Oxydibernsteinsäure, Aminopolycarboxylate, Aminopolyalkylenphosphonate und Polyglutamate.Also suitable as (B ') are ethylenediamine disuccinic acid, oxydisuccinic acid, aminopolycarboxylates, aminopolyalkylene phosphonates and polyglutamates.
Weiterhin können zusätzlich zur (B') oxidierte Stärken als organische Cobuilder verwendet werden.Furthermore, oxidized starches may be used as organic co-builders in addition to (B ').
Geeignete anionische Tenside (C) sind beispielsweise Fettalkoholsulfate von Fettalkoholen mit 8 bis 22, vorzugsweise 10 bis 18 Kohlenstoffatomen, z. B. C9-C11-Alkoholsulfate, C12-C14-Alkoholsulfate, Cetylsulfat, Myristylsulfat, Palmitylsulfat, Stearylsulfat und Talgfettalkoholsulfat.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.
Weitere geeignete anionische Tenside sind Alkansulfonate wie C8-C24-, vorzugsweise C10-C18-Alkansulfonate sowie Seifen wie beispielsweise die Na- und K-Salze von C8-C24-Carbonsäuren.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.
Weitere geeignete anionische Tenside sind C9-C20-linear-Alkylbenzolsulfonate (LAS) und -Alkyltoluolsulfonate.Further suitable anionic surfactants are C 9 -C 20 linear alkyl benzene sulphonates (LAS) and alkyl toluenesulphonates.
Weiterhin eignen sich als anionische Tenside (C) noch C8-C24-Olefinsulfonate und - disulfonate, welche auch Gemische aus Alken- und Hydroxyalkansulfonaten bzw. - disulfonate darstellen können, Alkylestersulfonate, sulfonierte Polycarbonsäuren, Alkylglycerinsulfonate, Fettsäureglycerinestersulfonate, Alkylphenolpolyglykolethersulfate, Paraffinsulfonate mit ca. 20 bis ca. 50 C-Atomen (basierend auf aus natürlichen Quellen gewonnenem Paraffin oder Paraffingemischen), Alkylphosphate, Acylisethionate, Acyltaurate, Acylmethyltaurate, Alkylbernsteinsäuren, Alkenylbernsteinsäuren oder deren Halbester oder Halbamide, Alkylsulfobernsteinsäuren oder deren Amide, Monound Diester von Sulfobernsteinsäuren, Acylsarkosinate, sulfatierte Alkylpolyglucoside, Alkylpolyglykolcarboxylate sowie Hydroxyalkylsarkosinate.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.
Die anionischen Tenside werden dem Faser- und Textilbehandlungsmittel vorzugsweise in Form von Salzen zugegeben. Geeignete Kationen in diesen Salzen sind Alkalimetallionen wie Natrium, Kalium und Lithium und Ammoniumsalze wie zum Beispiel Hydroxyethylammonium-, Di(hydroxyethyl)ammonium- und Tri(hydroxyethyl)ammoniumsalze.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.
Die Komponente (C) liegt in dem Faser- und Textilbehandlungsmittel vorzugsweise in einer Menge von 3 bis 30 Gew.-%, insbesondere 5 bis 20 Gew.-% vor. Werden C9-C20-linear-Alkylbenzolsulfonate (LAS) mitverwendet, kommen diese üblicherweise in einer Menge bis zu 25 Gew.-%, insbesondere bis zu 20 Gew.-%, zum Einsatz. Es kann nur eine Klasse an anionischen Tensiden allein eingesetzt werden, beispielsweise nur Fettalkoholsulfate oder nur Alkylbenzolsulfonate, man kann aber auch Mischungen aus verschiedenen Klassen verwenden, z. B. eine Mischung aus Fettalkoholsulfaten und Alkylbenzolsulfonaten. Innerhalb der einzelnen Klassen an anionischen Tensiden können auch Mischungen unterschiedlicher Species zum Einsatz gelangen.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.
Eine andere Klasse nichtionischer Tenside sind Alkylpolyglucoside oder Hydroxyalkylpolyglucoside mit 8 bis 22, vorzugsweise 10 bis 18 Kohlenstoffatomen in der Alkylkette. Diese Verbindungen enthalten meist 1 bis 20, vorzugsweise 1,1 bis 5 Glucosideinheiten. Eine andere Klasse nichtionischer Tenside sind N-Alkylglucamide mit C6-C22-Alkylketten. Derartige Verbindungen erhält man beispielsweise durch Acylierung von reduzierend aminierten Zuckern mit entsprechenden langkettigen Carbonsäurederivaten.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.
Weiterhin eignen sich als nichtionische Tenside (D) noch Blockcopolymere aus Ethylenoxid, Propylenoxid und/oder Butylenoxid (Pluronic®)- und Tetronic®)-Marken der BASF), Polyhydroxy- oder Polyalkoxyfettsäurederivate wie Polyhydroxyfettsäureamide, N-Alkoxy- oder N-Aryloxy-polyhydroxyfettsäureamide, Fettsäureamidethoxylate, insbesondere endgruppenverschlossene, sowie Fettsäurealkanolamidalkoxylate.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.
Die Komponente (D) liegt in dem erfindungsgemäßen Faser- und Textilbehandlungsmittel vorzugsweise in einer Menge von 1 bis 20 Gew.-%, insbesondere 3 bis 12 Gew.-% vor. Es kann nur eine Klasse an nichtionischen Tensiden allein eingesetzt werden, insbesondere nur alkoxylierte C8-C22-Alkohole, man kann aber auch Mischungen aus verschiedenen Klassen verwenden. Innerhalb der einzelnen Klassen an nichtionischen Tensiden können auch Mischungen unterschiedlicher Species zum Einsatz gelangen.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.
Da die Balance zwischen den genannten Tensidsorten von Bedeutung für die Wirksamkeit der erfindungsgemäßen Faser- und Textilbehandlungsmittel ist, stehen anionische Tenside (C) und nichtionische Tenside (D) vorzugsweise im Gew.-Verhältnis von 95 : 5 bis 20 : 80, insbesondere von 80 : 20 bis 50 : 50. Hierbei sind auch die Tensidbestandteile des erfindungsgemäßen Tensidgemisches zu berücksichtigen.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.
Des Weiteren können auch kationische Tenside (E) in den erfindungsgemäßen Faserund Textilbehandlungsmitteln enthalten sein.Furthermore, cationic surfactants (E) can also be present in the fiber and textile treatment agents according to the invention.
Als kationische Tenside eignen sich beispielsweise Ammoniumgruppen enthaltende grenzflächenaktive Verbindungen wie z.B. Alkyldimethylammoniumhalogenide und Verbindungen der allgemeinen Formel
RR'R"R"'N+ X-
in denen die Rest R bis R"' für Alkyl-, Arylreste, Alkylalkoxy-, Arylalkoxy-, Hydroxyalkyl(alkoxy)-, Hydroxyaryl(alkoxy)-Gruppen stehen und X ein geeignetes Anion ist.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.
Die Faser- und Textilbehandlungsmittel können gegebenenfalls auch ampholytische Tenside (F) enthalten, wie z.B. aliphatische Derivate von sekundären oder tertiären Aminen, die in einer der Seitenketten eine anionische Gruppe enthalten, Alkyldimethylaminoxide oder Alkyl- oder Alkoxymethylaminoxide.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.
Komponenten (E) und (F) können bis 25%, vorzugsweise 3-15 % in der Faser- und Textilbehandlungsmittel enthalten sein.Components (E) and (F) may contain up to 25%, preferably 3-15% in the fiber and textile treatment agents.
In einer weiteren bevorzugten Ausführungsform enthält das Faserund Textilbehandlungsmittel zusätzlich 0,05 bis 4 Gew.-% Enzyme (J). Vorzugsweise in Faser- und Textilbehandlungsmitteln eingesetzte Enzyme sind Proteasen, Amylasen, Lipasen und Cellulasen. Von den Enzymen werden vorzugsweise Mengen von 0,1 - 1,5 Gew.-%, insbesondere vorzugsweise 0,2 bis 1,0 Gew.-%, des konfektionierten Enzyms zugesetzt. Geeignete Proteasen sind z. B. Savinase und Esperase (Hersteller: Novo Nordisk). Eine geeignete Lipase ist z.B. Lipolase (Hersteller: Novo Nordisk). Eine geeignete Cellulase ist zum Beispiel Celluzym (Hersteller: Novo Nordisk). Auch die Verwendung von Peroxidasen zur Aktivierung des Bleichsystems ist möglich. Man kann einzelne Enzyme oder eine Kombination unterschiedlicher Enzyme einsetzen. Gegebenenfalls kann die erfindungsgemäße Textilwaschmittel-Formulierung noch En-zymstabilisatoren, z. B. Calciumpropionat, Natriumformiat oder Borsäuren oder deren Salze, und/oder Oxidationsverhinderer enthalten.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.
Eine Faser, behandelt nach dem beanspruchten Verfahren oder in Kontakt gebracht mit einem Waschmittel stellt einen weiteren Gegenstand der vorliegenden Erfindung dar. Bei den Fasern kann es sich sowohl um natürliche als auch um synthetische Fasern handeln. Nichtabschließende Beispiele für natürliche Fasern sind: Baumwoll-, Woll-, Leinen- und Viskose. Fasern, nicht abschließende Beispiele für synthetische Fasern sind: Polypropen-, Polyamid-, Polyester-, Nylon-, Perlon, Teflon®-, Lycra®-, Fasern.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.
Die Fasern sind vorzugsweise gewebt, gestrickt, gesponnen, gewirkt, geknüpft, geklöppelt.The fibers are preferably woven, knitted, spun, knitted, knotted, laceed.
Die vorliegende Erfindung wird im Folgenden durch die den Gegenstand der Erfindung nicht einschränkenden Beispiele näher erläutert:The present invention is explained in more detail below by the non-limiting example of the invention:
1000 mL Doppelmantelgefäß aus Glas mit mechanischem Rührer (IKA Rührmotor mit Glasrührer und beweglichem PTFE Rührblatt) und Flüssigkreislauf (Iwaki Magnetpumpe MD6-230GS01, 80-90 L / h) und einer Elektrolysezelle mit Bor-dotierten Diamantelektroden (Adamant miniDiaCell, Diamant auf Silizium, 12.5 cm2 Elektrodenfläche). Die Testgewebe wurden bei Versuchsbeginn in das Doppelmantelgefäß eingebracht.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.
Zur Bewertung der Ergebnisse der elektrochemischen Bleiche wurden Referenzversuche mit einem Vergleichssystem aus Wasserstoffperoxid (H2O2) und Tetraacetylethylendiamin (TAED) ohne Elektrolyse durchgeführt. Die gewählten Konzentrationsbereiche entsprechen denen von handelsüblichen Waschmitteln, in denen TAED derzeit verbreitet Anwendung findet. Als Bezugssystem dient eine Mischung von H2O2 und TAED im Verhältnis 4 : 1 (mmol/L).
Für die Referenzversuche wurden Lösungen von H2O2 und TAED in VE-Wasser hergestellt und ohne Elektrolyse bei 40°C umgepumpt. Nach 30 Minuten wurden die Stoffproben entnommen, gründlich mit VE-Wasser gespült, unter Lichtausschluss getrocknet und die Remissionswerte als Maß für die Schmutzentfernung gemessen.
Die Waschflüssigkeit des Referenzversuches R 3 hat die folgende Zusammensetzung: 700 g VE-Wasser, 10 g NaHCO3, 0.32 g H2O2-Lösung (30% H2O2 in Wasser), 0.16 g TAED (4 : 1 mmol / L).
Die Waschflüssigkeit für die Versuche mit aktiver Elektrolyse hat typischerweise die folgende Zusammensetzung: 700 g VE-Wasser, 10 g NaHCO3, 0.16 g TAED.
Die Möglichkeit der Kombination des erfindungsgemäßen Verfahrens mit handelüblichen Waschmitteln wurde beispielhaft anhand der folgenden Standardformulierungen getestet (wfk-Forschungsinstitut für Reinigungstechnologie e.V.):
- ECE98
- AATCC1993
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
Diese exemplarischen Waschmittel wurden in VE-Wasser wie folgt dosiert: 4.8 g/L Waschmittel, 0.67 g/L Natriumpercarbonat, 0,15 g/L TAED. Das Gesamtvolumen der Waschlösung beträgt, sofern nicht anders angegeben, 300 mL.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.
Die Schmutzentfernung wurde bestimmt, indem das Testgewebe vor und nach der Wäsche einer Reflexionsmessung bei 460 nm unterzogen wurde. Die Schmutz- bzw. Farbentfernung wurde aus den Remissionswerten R vor und nach der Wäsche sowie dem Remissionswert eines weißen Referenz-Baumwollgewebes gemäß der folgenden Formel in % ermittelt:
Alle Wäschen wurden 2 x durchgeführt. Die bei den Waschergebnissen in den Tabellen aufgeführten Werte für die Schmutzentfernung entsprechen dem Durchschnitt der unter den gleichen Bedingungen erhaltenen Messwerte.
Die Remissionsmessungen wurden mit einem Spectrophotometer der Marke Gretag Macbeth, Typ Spectrolino unter den folgenden Bedingungen durchgeführt: Beobachterwinkel 10°, Lichtart D65, UV-Filter.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.
Referenzbeispiel R 1 beschreibt die Schmutzentfernung, die allein durch die Waschlösung (700 g VE-Wasser, 10 g NaHCO3) erzielt wird. Dieser Versuch stellt eine Referenz zur Bestimmung der erzielten Schmutzentfernung dar.
Beispiel 1 beschreibt die Bleichwirkung, die durch Elektrolyse der Waschlösung (700 g VE-Wasser, 10 g NaHCO3) an Bor-dotierten Diamantelektroden ohne den Zusatz eines Bleichaktivators oder Bleichvorläufers wie z.B. TAED erzielt wird. Gegenüber dem Referenzversuch R 1 ist eine signifikante Steigerung der Schmutzentfernung zu beobachten.
b: 30 min Elektrolyse bei 1.2 A (700 g VE-Wasser, 10 g NaHCO3).
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
b : 30 minutes electrolysis at 1.2 A (700 g demineralized water, 10 g NaHCO 3 ).
Beispiele 2 bis 6 zeigen die Schmutzentfernung (Testgewebe EMPA 167, Tee auf Baumwolle), die in Abhängigkeit von der Stromstärke unter Verwendung des erfindungsgemäßen Verfahrens in Gegenwart des Bleichaktivators TAED erzielt wird.
Die Ergebnisse spiegeln den Einfluss der Stromstärke auf die Schmutzentfernung wider. Es wurde gefunden, dass mit zunehmender Stromstärke die erzielte Schmutzentfernung zunimmt.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.
Referenzbeispiele R 2 bis R 4 stellen die Ergebnisse der Bleiche mit einem System aus H2O2 und TAED in unterschiedlicher Zusammensetzung dar. So entspricht die Waschlösung mit einem Zusatz von H2O2 / TAED im Konzentrationsverhältnis 4 : 1 (mmol /l) einer häufig in handelsüblichen Pulverwaschmitteln eingesetzten Zusammensetzung.
Erwartungsgemäß wurde gefunden, dass durch eine Erhöhung der H2O2 Konzentration auf 8 / 1 (R 2) eine stärkere Schmutzentfernung erhalten wird, da die Bildung von Peressigsäure aus TAED begünstigt wird. Ebenso wurde gefunden, dass der Grad der Schmutzentfernung ebenfalls von der verfügbaren Menge TAED abhängt. So führt eine Halbierung der TAED Konzentration von 4/1 (R 3) auf 4/0.5 (R 4) zu einer Abnahme der Schmutzentfernung von 64% auf 59%.
Ein Vergleich der Schmutzentfernung durch die elektrochemische Bleichaktivierung mit den Ergebnissen der Referenzversuche zeigt, dass durch das elektrochemische Verfahren eine zum System H2O2 / TAED 4 : 1 (mmol /l) vergleichbare Schmutzentfernung erzielt werden kann (ca. 60 % Schmutzentfernung nach 30 Minuten bei 40 °C, siehe Bsp 5).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).
Beispiele 7 und 8 beschreiben den Unterschied zwischen sequentieller Aufspaltung der beiden Schritte (Bsp. 7) und Parallelisierung von Elektrolyse und Reinigungsvorgang (Bsp. 8) auf das Ergebnis der Schmutzentfernung.
Standardmäßig wurde während der gesamten Versuchsdauer die Waschlösung an den Elektroden bei 1.2 A vorbeigeführt und eine sehr gute Schmutzentfernung erzielt (Bsp. 5). Überraschenderweise wurde ebenfalls eine sehr gute Schmutzentfernung erzielt, wenn die Waschlösung vor Zugabe von TAED und Testgewebe für 10 Minuten bei 1.2 A umgepumpt wurde. Nach Ausschalten der Stromquelle wurden TAED und Testgewebe hinzugegeben und für 30 Minuten ohne weitere Stromaufgabe umgepumpt (Bsp. 7). Dieser Effekt ist sehr vorteilhaft, da eine sehr gute Schmutzentfernung mit einem geringeren Stromeintrag erreicht werden kann. Die Schmutzentfernung kann auf 61% gesteigert werden, wenn die Waschlösung vor Zugabe von TAED und Testgewebe für 10 Minuten bei 1.2 A umgepumpt und die Elektrolyse nach der Zugabe von TAED und Testgewebe für 30 Minuten fortgesetzt wird (Bsp. 8).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).
Beispiele 9 bis 12 sowie die Referenzbeispiele R 5 und R 6 beschreiben die Behandlung verschiedener Fleckenarten mit dem erfindungsgemäßen Verfahren zur elektrochemischen Bleichaktivierung.
Die Ergebnisse zeigen, dass die erzielte Schmutzentfernung gegenüber verschiedenen Anschmutzungen erwartungsgemäß unterschiedlich stark ausgeprägt ist. Vergleichsbeispiele R 5 und R 6 beschreiben jeweils die reine Waschwirkung in Abwesenheit von TAED und ohne Elektrolyse. Demnach wird sowohl gegenüber Rotwein (Bsp. 9 und 10) als auch gegenüber Heidelbeersaft (Bsp. 11 und 12) eine gute Schmutzentfernung durch das erfindungsgemäße Verfahren erreicht.
b: 10 min Vorelektrolyse bei 1.2 A, dann Zugabe von TAED (1 mmol/L bez. auf Gesamtvolumen der Waschlösung), 30 min Umpumpen ohne weitere Elektrolyse bei 40°C c: 30 min Umpumpen bei 40°C ohne Elektrolyse (700 g VE-Wasser, 10 g NaHCO3)
b: 10 min Vorelektrolyse bei 1,2 A, dann Zugabe von TAED (1 mmol/L bez. auf Gesamtvolumen der Waschlösung), 30 min Umpumpen ohne weitere Elektrolyse bei 40°C c: 30 min Umpumpen bei 40°C ohne Elektrolyse (700 g VE-Wasser, 10 g NaHCO3).
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.
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 )
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 ).
Beispiele 13 - 26 sowie Referenzbeispiele R 7 - R 20 beschreiben die Behandlung verschiedener Textilfarben mit dem erfindungsgemäßen Verfahren zur elektrochemischen Bleichaktivierung. Dazu wurde eine Lösung von 15.4 g Natriumhydrogencarbonat in 1084 g VE-Wasser für 10 Minuten bei 40°C und 1,2 A elektrolysiert. Anschließend wurden 0.25 g TAED und die Farbmonitore zugegeben und 45 Minuten stromlos umgepumpt. Nach jedem Waschgang wurden die Farbmonitore kurz mit VE-Wasser abgespült und nach jeweils 5 Waschcyclen einer Remissionsmessung bei 460 nm unterzogen, um den Grad der Farbentfernung zu bestimmen. Insgesamt wurden pro Farbmonitor 15 Waschcyclen (3 x 5) durchgeführt. Wie in Tabelle 7 gezeigt, ist durch das erfindungsgemäße Verfahren im Rahmen der Messgenauigkeit überraschenderweise keine signifikante Farbschädigung festzustellen. Eine Ausnahme stellt das mit Sulphur Black 1 (AISE-1) eingefärbte Gewebe dar (Beispiel 13), welches bereits in einer Waschflotte ohne Bleichmittel und ohne Elektrolyse zum Abfärben bzw. Ausbluten des Farbstoffs neigt.
Die Ergebnisse des erfindungsgemäßen Verfahrens wurden mit einem vereinfachten Referenzsystem verglichen. Für die Untersuchungen zur Farbentfernung ausgewählter Textilfarben wurden die Farbmonitore dazu in einem System aus 15.4 g Natriumhydrogencarbonat, 1085 g VE-Wasser, 0.25 g TAED und 0.44 g Wasserstoffperoxid Lösung (30% H2O2 in Wasser) für 45 Minuten bei 40°C gerührt. Die Ergebnisse der Referenzversuche sind in Tabelle 8 zusammengefasst. Auch hier ist wie oben beschrieben im Fall des mit Sulphur Black 1 (AISE-1) eingefärbten Farbmonitors eine sehr starke Veränderung feststellbar (R 7). Der Vergleich der übrigen Daten zeigt, dass das Referenzsystem im Allgemeinen zu einer stärker ausgeprägten Farbschädigung führt als das erfindungsgemäße Verfahren.
Referenzbeispiele 21 bis 24 zeigen die Schmutzentfernung (Testgewebe EMPA 167, Tee auf Baumwolle), die durch die Waschmittelformulierungen in Gegenwart bzw. Abwesenheit von Natriumpercarbonat und TAED bei 40°C innerhalb von 30 min erreicht wird. Die Schutzentfernung in Abwesenheit von Natriumpercarbonat und TAED zeigt somit die reine Waschwirkung, die nicht auf chemische Bleichvorgänge zurückzuführen ist (Referenzbeispiele 21 und 23).
b: ECE98 in VE-Wasser, Natriumpercarbonat, TAED
c: AATCC1993 in VE-Wasser
d: AATCC1993 in VE-Wasser, Natriumpercarbonat, TAED
b : ECE98 in deionized water, sodium percarbonate, TAED
c : AATCC1993 in deionized water
d : AATCC1993 in deionized water, sodium percarbonate, TAED
Beispiele 27 bis 30 beschreiben das Ergebnis der sequentiellen Aufspaltung der beiden Schritte (Elektrolyse und Reinigungsvorgang) auf das Ergebnis der Schmutzentfernung. In den Beispielen 27 und 29 wurde die Lösung des jeweiligen Waschmittels vor Zugabe der Textilproben einer 10 minütigen Vorelektrolyse unterzogen. Es zeigt sich, dass die Schmutzentfernung der reinen Waschmittellösungen nicht signifikant durch die Vorelektrolyse beeinflusst wird (s. auch Referenzbeispiele R21 und R23). In den Beispielen 28 und 30 wurden nach einer 10 minütigen Vorelektrolyse der jeweiligen Waschlösung sowohl die Textilproben als auch TAED hinzugegeben. Demnach wird bereits nach einer 10 minütigen Vorelektrolyse (bei 1.2 A) eine signifikante Steigerung der Schmutzentfernung gefunden. Das erfindungsgemäße Verfahren ist somit auch mit komplexen Waschmittelformulierungen kompatibel.
b: ECE98 in VE-Wasser, 10 min Vorelektrolyse, dann TAED- und Testgewebe Zugabe
c: AATCC1993 in VE-Wasser, 10 min Vorelektrolyse, dann Testgewebe Zugabe
d: AATCC1993 in VE-Wasser, 10 min Vorelektrolyse, dann TAED- und Testgewebe Zugabe
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
Beispiele 31 bis 34 beschreiben das Ergebnis der parallelen Ausführung der beiden Schritte (Elektrolyse und Reinigungsvorgang) auf das Ergebnis der Schmutzentfernung. In den Beispielen 31 und 33 wurde die Lösung des Waschmittels nach Zugabe der Textilproben einer 30 minütigen Elektrolyse unterzogen. Es zeigt sich, dass die Schmutzentfernung der reinen Waschmittellösungen nur geringfügig durch die Dauerelektrolyse beeinflusst wird (s. Referenzbeispiele R21 und R23 sowie Beispiele 27 und 29). Für die Beispiele 32 und 34 wurden sowohl Textilproben als auch TAED zur Waschmittellösung gegeben. Die erzielte Schmutzentfernung durch die Dauerelektrolyse (Beispiele 32 und 34) ist erwartungsgemäß geringfügig höher (s. Beispiel 28) oder vergleichbar (s. Beispiel 30) zu der durch kurzzeitige (aber energiesparende) Vorelektrolyse erzielten Schmutzentfernung.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.
Das erfindungsgemäße Verfahren ist somit auch mit komplexen Waschmittelformulierungen kompatibel.
b: ECE98 in VE-Wasser, 30 min Elektrolyse nach TAED und Testgewebe Zugabe
c: AATCC1993 in VE-Wasser, 30 min Elektrolyse nach Testgewebe Zugabe
d: AATCC1993 in VE-Wasser, 30 min Elektrolyse nach TAED und Testgewebe Zugabe
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)
- 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.
- The washing machine according to claim 1 wherein the electrode has an effective surface area in the range from 0.5 to 1000 cm2.
- 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.
- 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.
- 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).
- The process according to any one of claims 3 to 5 carried out at a temperature of up to 60°C.
- The process according to any one of claims 3 to 6 having an at least 20% degree of soil removal for bleachable stains.
- 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. - 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.
- 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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EP11709743.6A EP2550389B1 (en) | 2010-03-25 | 2011-03-24 | Electrochemical textile-washing aparatus, method, combination and e-bleach ball |
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EP10157748 | 2010-03-25 | ||
PCT/EP2011/054542 WO2011117350A1 (en) | 2010-03-25 | 2011-03-24 | Electrochemical textile-washing method |
EP11709743.6A EP2550389B1 (en) | 2010-03-25 | 2011-03-24 | Electrochemical textile-washing aparatus, method, combination and e-bleach ball |
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EP2550389B1 true EP2550389B1 (en) | 2014-05-07 |
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EP (1) | EP2550389B1 (en) |
JP (2) | JP2013524868A (en) |
CN (1) | CN102906325A (en) |
BR (1) | BR112012023991A2 (en) |
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WO2013111788A1 (en) * | 2012-01-23 | 2013-08-01 | シャープ株式会社 | Water purification system and apparatus for producing antiseptic solution |
DE102014109623B4 (en) * | 2014-07-09 | 2023-01-05 | Miele & Cie. Kg | Method for operating a water-carrying electrical device and water-carrying electrical device |
DE102021132611A1 (en) | 2021-12-10 | 2023-06-15 | Miele & Cie. Kg | Cleaning device, control device and method for treating items to be cleaned |
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