CN101874133B - Laundry system for sensitive fabrics - Google Patents

Laundry system for sensitive fabrics Download PDF

Info

Publication number
CN101874133B
CN101874133B CN2008801177849A CN200880117784A CN101874133B CN 101874133 B CN101874133 B CN 101874133B CN 2008801177849 A CN2008801177849 A CN 2008801177849A CN 200880117784 A CN200880117784 A CN 200880117784A CN 101874133 B CN101874133 B CN 101874133B
Authority
CN
China
Prior art keywords
washing
composition
washing system
water
hydrogen peroxide
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.)
Active
Application number
CN2008801177849A
Other languages
Chinese (zh)
Other versions
CN101874133A (en
Inventor
R·哈格
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Unilever IP Holdings BV
Original Assignee
Unilever NV
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Unilever NV filed Critical Unilever NV
Publication of CN101874133A publication Critical patent/CN101874133A/en
Application granted granted Critical
Publication of CN101874133B publication Critical patent/CN101874133B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

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
    • 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
    • D06F2101/00—User input for the control of domestic laundry washing machines, washer-dryers or laundry dryers
    • 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
    • D06F2105/00—Systems or parameters controlled or affected by the control systems of washing machines, washer-dryers or laundry dryers
    • D06F2105/58—Indications or alarms to the control system or to the user
    • D06F2105/60—Audible signals
    • 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
    • D06F34/00—Details of control systems for washing machines, washer-dryers or laundry dryers
    • D06F34/04—Signal transfer or data transmission arrangements
    • D06F34/05—Signal transfer or data transmission arrangements for wireless communication between components, e.g. for remote monitoring or control
    • 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
    • D06F34/00—Details of control systems for washing machines, washer-dryers or laundry dryers
    • D06F34/28—Arrangements for program selection, e.g. control panels therefor; Arrangements for indicating program parameters, e.g. the selected program or its progress

Abstract

A washing system for washing multiple fabric items including one or more sensitive fabric items in a washing machine with a detergent composition comprising 5-99.9% surfactant, the washing system comprising: an in situ hydrogen peroxide generating system (4); a pH regulating device (2) a tag communicating device which reads a laundering instruction contained in an electronic tag attached to any sensitive fabric item, a controller in communication with the tag communicating device to control the laundry machine (9) to adjust the hydrogen peroxide generation system according to bleach and/or pH sensitivity of the fabric item.

Description

The clothes washing system of sensitive fabrics
The present invention relates to the system of protection sensitive fabrics product (item) in the automation washing process.
Known is automatically to control arranging of washing machine suitably to wash various fabric products.The U.S. Patent No. 5,388,299 that is issued to Lee discloses the washing control system that has be used to the Information Read-Out parts that read washing information.Each fabric product is one by one manual input on the front at read-out element before putting into clothes in the rinsing maching.
US 5715555 discloses laundering process and system, and contained instruction is attached to each material product (material items) in electronic tag (tags) in this system.When material product was within washing machine, these instructions all can read.
The improvement laundering process that the purpose of this invention is to provide pH/ bleaching sensitiveness fabric product.
Therefore, in one aspect, the invention provides the washing system that washs the many fabric products that comprise one or more sensitive fabrics products with the composition of detergent that comprises the 5-99.9% surfactant in washing machine, this washing system comprises:
Peroxidating hydrogen generation system on the spot;
The pH adjusting device;
Tag communication apparatus, it reads in laundry instruction contained in the electronic tag that is attached to any sensitive fabrics product;
With the controller that the tag communication apparatus realization is communicated by letter, its control washing machine being drifted and/or pH sensitiveness adjusting peroxidating hydrogen generation system according to fabric product.
Providing of on-the-spot peroxidating hydrogen generation system is provided, it can be controlled by the existence of the sensitive fabrics product of mark.This means that washing system need not bleach system added in the composition and all advantages of bleach system can be provided, meanwhile the sensitive product of mark considers that this type of sensitiveness automatically improves this system.The pure existence of the product of at least a mark can trigger this system and improve pH/ bleaching level.The user need not to differentiate that by this washing load (wash load) classification this type of sensitive product-they automatically differentiate they oneself before each washing.
Significant advantage of the present invention is that the clothes of only limited quantity needs mark.Therefore infiltration rate will be higher.In addition, the producer can add this label, and it is special sensitiveness clothes to need not to warn the consumer.This information is hidden on the label now.Another possible advantage is also to provide/sell label to the consumer, if the clothes of very responsive (according to consumer's suggestion) is arranged, then the consumer can own come mark with label, thereby realizes the fully control of this process.
Whole percentage is w/w percentage, except as otherwise noted.The number range of expressing with form " from x to y " is understood to include x and y.When describing a plurality of preferred scope for specific feature with form " from x to y ", should be understood that the four corner that different end points are combined also needs to consider.
Electronic tag can be introduced within the element of fabric product, as within the button of clothes product, seam, lining etc.Additionally this label can be the general type that is attached to any fabric product.
This label is separable in order to be attached on the fabric temporarily, and for example it gets on and then separate after washing process in attaching before the washing process.Advantageously, this label can attaching on the sensitive fabrics product, then in washing, dry and use (if it is clothes, when putting on) whole process situ to keep.This label in addition can be in the manufacturing of sensitive fabrics product, packaging process attaching on the sensitive fabrics product.Because more permanent connection is arranged, the improvement of above washing process automatically occurs at every turn when described product is included in the washing load.
This electronic tag can be stored by programming the authentication information of fabric product, differentiates that it is responsive to bleaching and/or high pH.
Preferably, sensitive fabrics product attaching the electronic tag of tape program, then these products are put in the washing machine in the clothes washing system.
Each washing machine has the controller of its operation of control.Tag communication apparatus is embedded in the washing machine and reads in laundry instruction contained in the electronic tag in fabric product is in washing machine the time.In case this label reads, this controller improves this peroxidating hydrogen generation system to reduce pH and/or bleaching level.
The present invention advantageously is the modification by pH, and the bleaching agent that uses in many known washing agent will inactivation.Under low pH (7-8), will there be peracid to discharge and H 2O 2Can not activate.
This H 2O 2The generation system improves can have the sound and/or visual alarm in advance to notify user/consumer.When the consumer does not need washing process to improve, override facility will be arranged.
The combination of the on the spot generation of hydrogen peroxide and pH conditioning equipment in washing process is so that be implemented in the on the spot generation of hydrogen peroxide in the washing machine and form the bleaching component from hydrogen peroxide and for example bleach precursor under high pH, simultaneously so that under the pH that reduces, carry out the washing of fabric, but need not to add chemicals, and so that allow automatically to improve by tag system.
This peroxidating hydrogen-generating apparatus can comprise from the electrochemical cell of from the beginning water and air production hydrogen peroxide, and be suitable in this washing machine when this washer operation.This pH conditioning equipment can comprise electrochemical cell, and this electrochemical cell comprises one or more negative electrodes and the anode electrode for the production of acid and alkaline water, does not therefore need to add chemicals when this equipment operating.
This composition of detergent can comprise bleach precursor.This can be added in the washing machine when operation.
In the fabric cleaning method of today, usually form peracid by the bleach precursor from Betengent product and hydrogen peroxide and obtain bleaching.
Additionally or in addition, can obtain bleaching by all being present in hydrogen peroxide in the Betengent product and the combination of bleach catalysts.
Term peracid or peracid bleaching agent here are defined as by general formula 1 defined any peracid.
ROOH (1)
Preferred one group peracid is the type of general formula 2.
Figure GPA00001141513100031
The peracid of another preferred group is the type of general formula 3.
Figure GPA00001141513100032
R contains 1 alkylidene or substituted alkylene to about 20 carbon atoms, chooses wantonly to have internal amide linkages; Or phenylene or substituted phenylene; With Y be hydrogen, halogen, alkyl, aryl, imino group aromatics or non-aromatic group, COOH or C=O (OOH) group or quaternary ammonium group.
The corresponding persalt of general formula 1,2 and 3 peracid is also included within the scope of the present invention, alkali and alkaline earth metal ions persalt especially, preferred sodium and potassium persalt.The existence of peracid in alkaline solution of removing protonated form within this patent also.
In order effectively to be used for washing process, in the time of in being diluted to this final washing lotion, the water that contains hydrogen peroxide preferably has 0.1-15mmol/l, more preferably 2-12mmol/l, the more more preferably concentration of hydrogen peroxide of 3-10mmol/l.The water that contains hydrogen peroxide can be directly used in this washing process, or with more concentrated form production, stores and be diluted to when needed predetermined concentration in washing machine.When producing with denseer form, this concentration is preferably between 1-500mmol/l, more preferably between 50-200mmol/l.When this hydrogenperoxide steam generator is stored the longer time in washing machine, for bin stability, be preferred at the pH that is equal to or less than 7, more preferably be equal to or less than 6, more preferably be equal to or less than 5 again.
Do not wish to be subjected to any particular theory to fetter, the reaction by water and oxygen forms hydrogen peroxide in battery.Oxygen is converted to hydrogen peroxide or hydrogen peroxide ions at negative electrode, general following carrying out:
O 2+ 2H ++ 2e -→ H 2O 2Under acid condition, or
O 2+ H 2O+2e -→ HO 2 -+ OH -Under alkali condition.
Hydrogen peroxide anion and proton (H +) or the water reaction, form hydrogen peroxide.At the anodic formation proton.This proton is formed by following reaction:
2H 2O→O 2+4H ++4e -
This hydrogen peroxide produces reaction does not need to add chemicals, only needs water and air.Because secure context preferably should be avoided hydrogen (H 2) formation.When chlorine is present in this make-up water, but the chlorine dioxide of also production small amount of this peroxidating hydrogen-generating apparatus.Chlorine dioxide also is suitable bleaching agent.
This hydrogen peroxide produces battery preferably can be by the electrochemical cell that comprises one or more negative electrodes and anode electrode of DC potential charging.This electrode can for example be the form of plate or rods, is preferably plate.Negative electrode is gas-diffusion electrode preferably.Negative electrode preferably includes the catalyst that is incorporated on the cathode surface.Negative electrode can comprise conductive material such as carbon (for example graphite, the carbon of CNT and other form), metal or conducting polymer or their combination.Preferred metallic catalyst is transition metal, transition metal oxide or transition metal macrocyclic.Preferred transition metal comprises gold, metal such as nickel and cobalt that mercury and oxide cover.Preferred metal oxide comprises nickel oxide, cobalt oxide and spinels.Preferred transition metal macrocyclic comprises: CoTsPc ((phthalocyanine tetrasulfonic acid) cobalt) and CoTMPP (tetramethoxy phenyl porphyrine).Anode is the anode of dimensionally stable type preferably, and it is preferably from conductive material such as metal, carbon or conducting polymer or their combined structure.
Some transition metal are not preferred, platinum especially, platinum alloy, platinum family metal, palladium, and silver.Also have not preferably perovskite and pyrochlore, such as the plumbous transition metal oxide of ruthenic acid, and encircle greatly FeTsPc (tetrasulfonic acid root FePC).
Size and standard that hydrogen peroxide produces battery depend on predetermined purposes.If when this hydrogen peroxide was stored in the interior surge tank of washing machine, the slow system (a for example night) that produces hydrogen peroxide was suitable.Yet, when in washing process, producing hydrogen peroxide, need fast production system.The battery of generation hydrogen peroxide of the present invention preferably includes at least 10cm 2, more preferably 50cm at least 2, even more preferably 100cm at least 21000cm at the most 2, more preferably 500cm at the most 2, even more preferably 400cm at the most 2, more preferably 300cm at the most again 2Total cathode area; This area depends on required throughput rate.Surface area is preferably distributed in 1 and 25, more preferably between 1 and 10 negative electrode.Hydrogen peroxide produce speed typically 0.1 and 2000mmol/h between.This actual speed rate depends on the surface area of negative electrode and the type of operation.In the system that the hydrogen peroxide hold-up tank is arranged, it is preferred producing slowly speed, typically from 0.1 to 200mmol/ hour, and and then in water absorption process, producing in the system of hydrogen peroxide, produce speed preferably 200 and 2000mmol/ hour between.Soon, the efficient of the hydrogen peroxide of this type generation battery is 50-100%, typically 60-95% preferably when the beginning that hydrogen peroxide produces or after the beginning.
The total surface area of anode is between the 10-100% of total surface area of negative electrode.
These electrodes are optional to be separated by pellicle.
As for the substituting of buffer, bronsted lowry acids and bases bronsted lowry, the pH of fabric washing lotion by the pH conditioning equipment make regulate, this equipment can be electrochemical and be described among the EP1841697.
As noted before, preferably under high pH, carry out from the bleaching agent peracid reaction of formation of hydrogen peroxide and bleach precursor generation, and bleaching action is more effective under low pH.Typically, the pH of peracid reaction of formation is higher than 9, preferably is higher than 9.5.This pH preferably is equal to or less than 13, more preferably is equal to or less than 12, more preferably is equal to or less than 11 again, is equal to or less than ideally 10.5.Use on the other hand the bleaching action of peracid preferably being equal to or less than 9.5, more preferably be equal to or less than 9, more preferably be equal to or less than again under 8.5 the pH and carry out.The pH of bleaching action is higher than 7, preferably is higher than 7.5, is higher than ideally 8.
Other of Betengent product that buffer, salt, bronsted lowry acids and bases bronsted lowry that be used for to regulate the pH of washing lotion consisted of today helps washes (bulky) composition.Yet the use of pH-meter allows the adjusting of pH in washing lotion in the situation of not adding chemicals, and this provides larger convenience for the consumer.
PH-meter of the present invention is for example to use electrolytic tank make-up water stream to be divided into the equipment of acid and basic stream thigh.PH-meter can feeding running water or demineralized water.The part of basic stream thigh can be used for the bleaching agent reaction of formation.In addition, the part of this acidity and basic stream thigh can be used for this washing process.The pH of acid water is preferably between 1 and 6, more preferably between 1 and 3.The pH of basic stream thigh is typically between 9 and 13, preferably between 10 and 12.Be used for equipment of the present invention the volume ratio between the alkaline water that produces and the acid water preferably between 1: 20 and 20: 1, more preferably between 1: 10 and 10: 1.
From the acid water of pH-meter also can be used for the regenerating electrochemical cell of this peroxidating hydrogen-generating apparatus.
In brief, pH-meter can be used for the production of acid water and alkaline water.This acid water can be used for the regeneration of electrochemical cell and be used for washing process.This alkaline water can be used for this bleaching agent reaction of formation and this washing process.This can improve bleaching characteristic and the fastness of electrochemical cell, reduce electrochemical cell regeneration usefulness institute's water requirement and do not need to add chemicals.
PH-meter is the electrochemical cell that comprises one or more negative electrodes and anode electrode.This electrode can for example be the form of plate or rods, is preferably plate.This plate and conductive surface onboard can be from conductive material such as metal, carbon or conducting polymer or their combined structures.
PH-meter preferably has between 1-500l/hr, more preferably total throughput rate of the total alkaline water between 2-300l/hr and acid water.
In order effectively to be used for the fabric washing process, for example do not adopt those of builder, the water hardness in the water in being added to washing process preferably is lower than 5 °F of H, preferably is lower than 2 °F of H and more preferably less than 1 °F of H.The reduction of the water hardness is in order to prevent the deposition of calcium soap in dirt (soil), prevent the precipitation of anion surfactant, at utmost improve colloidal stability and minimizing calcium-dirt-base material interaction and dirt-dirt interaction and therefore improve soil release desirable.
The attendant advantages of using the demineralized water of water softening plant production of the present invention be hydrogen peroxide in demineralized water than more stable in running water for example.
Modal Betengent product comprises the builder material so that chelating comes from the hardness ions of running water.The builder material is present in the composition of detergent with the concentration of 15-80% usually.Usually known builder is water-soluble phosphate such as sodium tripolyphosphate (stpp) or zeolite.Phosphate is considered to cause the eutrophication of surface water, and zeolite causes insoluble substance in sanitary wastewater.Owing to the amount of builder material character and its existence, it is opposed in Betengent product more and more, especially laundry detergent product.
As the replacement scheme of the use of builder material, known in the state of the art have different water softening plants.These equipment all come from hardness ions such as the Ca of running water by chelating 2+And Mg 2+, for example utilize ion exchange, produce soft water.Described a kind of system in WO-01/30229, it adopts the ion exchange system that embeds to remove calcium and magnesium ion from supply water.Yet this ion exchange material needs regular regeneration.Because be used for the automatic washing machine of common type, a large amount of for example salting liquids will be that the regeneration of ion-exchanger is needed, therefore offset the minimizing of builder chemicals in washing agent and used the effect of bringing.Another shortcoming of ion-exchange is the limited operating life of ion exchange resin and/or is used for the needed resin volume of generation in the required soft water amount of washing machine.
Another water softening method is electronics deionization (EDI), and it has taken into account ion-exchange and electrodialysis, as described in the EP 04076353.4 of unexamined.Although this method does not need the chemicals of regenerating, another shortcoming relevant with the use of ion exchange resin still exists, as mentioned above.In addition, EDI is complicated technology, and it is difficult to turn round in firm mode in the needed time in family expenses equipment.
Another water softening method is to use the disclosed capacitive deionization effect of flowing through formula capacitor (FTC) in the EP 05075218.7 of unexamined.The method comprises the use for the reproducible electrochemical cell of electrical way of capacitive deionization effect and electrochemistry purification, and the regeneration that comprises the electrode of two end plates (at each end of battery).By with battery polarization, ion is removed from electrolyte and is retained in the electric double layer (electric double layer) on the electrode.This battery can be with electrical way (partly) regeneration so that this type of ion of removing in advance of desorb.This regeneration can be carried out in the situation of not adding chemical substance.
This flows through formula capacitor (FTC) and comprises the plate with conductive surface.This plate can become chargeable in response to the DC electromotive force that applies.These plates are separated by non-conductive dividing plate each other.This plate and conductive surface onboard can from conductive material such as metal, carbon or conducting polymer or their combined structure, also be described among WO01/66217 or the WO02/86195 by Andelman.
Another kind of main component is the chemicals that pH improves usefulness in common microgranular Betengent product.For purpose of the present invention, the term chemicals of usefulness " pH improve " is used for describing by improving, reduce or keeping this pH affects pH in certain level composition in meaning.Typical example includes, but not limited to salt such as acetate, borate, carbonate, (two) silicate, acids such as boric acid, phosphoric acid, sulfuric acid, organic acid such as citric acid, inorganic base and organic base.
In common Betengent product, the chemicals of builder and pH improvement usefulness accounts for the at the most 70wt% of composition.Should be pointed out that for purpose of the present invention, even surfactant-some surfactants have the chemicals that some pH improved actions-be not considered to pH improves usefulness.
LEIP according to a preferred embodiment of the invention (low environmental impact product) is substantially free of the chemicals that pH improves usefulness.The chemicals that is substantially free of pH improvement usefulness is used for description in meaning and comprises that the pH of 5wt% improves the product of using chemicals at the most.Preferred this LEIP comprises the weight 0-3wt% based on total LEIP composition, more preferably 0-1wt%, the most preferably chemicals of the pH of 0wt% improvement usefulness.
According to a preferred embodiment of the invention, composition of detergent does not contain builder.
According to a preferred embodiment of the invention, composition of detergent does not contain hydrogen peroxide, SODIUM PERCARBONATE, and the sodium perborate monohydrate, sodium perborate tetrahydrate, or hydrogen peroxide produces the oxidizing ferment of usefulness.
Common detergent product usually contains acidic components, for example anion surfactant such as LAS (linear alkylbenzene sulfonate (LAS)).For these acid that neutralize, composition can randomly comprise neutralizer.These neutralizers are organic base or inorganic base preferably.This alkali preferably is selected from NaOH, KOH, list-monoethanolamine (MEA) and three-monoethanolamine (TEA).Neutralizer is to exist to the concentration of the molar concentration of the component of the needs neutralization of 200%mol with 50%mol.
Wish for rinsing maching one or more Betengent product containers to be housed, Betengent product can automatically measure distribution like this.This LEIP can according to dosage add from single container.Additionally, according to described in the EP-A-0419036, each composition that consists of LEIP can according to dosage add from independent container.Therefore automatically according to dosage add from least a composition of LEIP in a preferred embodiment.The advantage of LEIP can be that these compositions of consumption of the kind quantity that reduces and/or minimizing are so that Betengent product has much smaller volume.This means that in practice the consumer recharges this container not needing to resemble usually or this container can be less, therefore when use equipment of the present invention so that automatic batching system is more feasible.When adopting automatic batching system, preferably bleach precursor or activator (catalyst) are stored individually with other component of Betengent product.
Although hydrogen peroxide (H 2O 2) be good bleaching agent, but because dynamics and only obtain slowly oxidizing process slowly, and therefore bleaching process slowly.For some fabric, preferably has the more strong oxidizer of show activity under low temperature and concentration.
The common known method of improving bleaching be the use of bleaching catalyst with the activity of improved oxide, and/or the use of mistake acid substitution peroxide; This peracid preferably forms from hydrogen peroxide and bleach precursor on the spot.
The bleaching agent production method can carry out in washing machine drum or in the mixing device of or off-line online at.When using mixing device, mixing device is selected from static mixer, dynamic mixer, agitator tank or storage tank or their combination.
Peracid can form by the cross hydrolysis of following reaction by acid bleaching agent precursor:
Figure GPA00001141513100081
Dissimilar precursors, for example the CATION nitrile has different reaction equations, but is also included within the scope of the present invention.
The low environmental impact product (LEIP) that is used for method of the present invention can comprise one or more bleach precursors.
The organic peroxy acid precursors can be suitable as peroxy bleaching compound.After crossing hydrolysis, this type of material has following general formula usually:
Figure GPA00001141513100091
Wherein R contains about 20 carbon atoms of 1-, optional alkylidene or substituted alkylene with internal amide linkages; Or phenylene or substituted phenylene; With Y be hydrogen, halogen, alkyl, aryl, imino group aromatics or non-aromatic group, COOH or
Figure GPA00001141513100092
Group or quaternary ammonium group.
Here spendable typical single peroxyacid precursor comprises, for example:
(i) benzylhydroperoxide and nuclear substituted benzylhydroperoxide, for example peroxide-α-naphthoicacid;
(ii) aliphatic replaces aliphatic and aryl alkyl list peroxy acid, for example crosses laurate, perstearic acid and N, and N-phthalyl amido is crossed caproic acid; With
(iii) 6-octyl group amido-6-oxo-mistake caproic acid.
Here spendable typical two peracid precursors comprise, for example:
(iv) 1,12-diperoxy dodecanedioic acid (DPDA);
(v) 1, the 9-diperoxyazelaic acid;
(vi) diperoxy tridecandioic acid; Diperoxy decanedioic acid and diperoxy M-phthalic acid;
(vii) 2-decyl diperoxy butane-Isosorbide-5-Nitrae-dioctyl phthalate (2-decyldiperoxybutane-1,4-dioticacid); With
(viii) 4, the two benzoyl hydroperoxides of 4 '-sulfonyl.
Peroxyacid bleach precursor is known and describes in the literature fully, such as BP 836988; 864,798; 907,356; 1,003,310 and 1,519,351; Deutsche Bundespatent 3,337,921; EP-A-0185522; EP-A-0174132; EP-A-0120591; With US Patent No 1,246,339; 3,332,882; 4,128,494; 4,412,934 and 4,675,393.
The peroxyacid bleach precursor of another kind of useful type be cationic those, i.e. quaternary ammonium-substituted peroxyacid precursor, as at US patent No 4,751,015 and 4,397,757, at EP-A0284292 and EP-A-331, disclosed in 229.The example of the peroxyacid bleach precursor of this class is:
2-(N, N, N-trimethyl ammonium) ethyl sodium-4-sulfo group benzol carbonate chloride (SPCC);
N-octyl group-N, N-dimethyl-N10-carbonyl phenoxy group decyl ammonium chloride (ODC);
3-(N, N, N-trimethyl ammonium) propyl group sodium-4-sulfo group phenyl carboxylate; With
N, N, N-trimethyl ammonium tolyl oxygen base benzene sulfonate.
The bleach precursor of other specific type forms by the CATION nitrile, as at EP-A-303, in 520 and disclosed in European patent specification No 458,396 and 464,880.
Any can be used among the present invention in these peroxyacid bleach precursors is although wherein some may be than other more preferably.
In the bleach precursor of above type, preferred type is ester, comprises Acylphenol sulfonate and acyl group alkyl phenol sulfonate; Acyl group-acid amides; Peroxyacid precursor with the quaternary ammonium-substituted that comprises the CATION nitrile.
The example of preferred peroxyacid bleach precursor or activator is 4-benzoyloxy benzene sulfonic acid sodium salt (SBOBS); N, N, N ', N '-tetra acetyl ethylene diamine (TAED); 1-methyl-2-benzoyloxy benzene-4-sodium sulfonate; 4-methyl-3-benzoyloxy Sodium Benzoate; SPCC; Tolyl oxygen base benzene sulfonic acid trimethyl ammonium; Pelargonyl group oxygen base benzene sulfonic acid sodium salt (SNOBS); 3,5,5-trimethyl acetyl base-oxygen base benzene sulfonic acid sodium salt (STHOBS); With the CATION nitrile that replaces.
The bleach precursor of spendable other kind of the present invention can find from WO0015750, for example 6-(the amino caproyl of nonanoyl) oxygen base benzene sulfonate.
This precursor can be with the at the most 12wt% of composition, and the amount of preferred 2-10wt% is used.
Form with reaction and can obtain in the washing lotion in washing machine drum or in the mixer of off-line from the peroxide of washing agent and the peracid of bleach precursor.The advantage of latter event is that this peracid can form and can be diluted in the washing machine drum with acid water with conc forms under required pH, therefore reduces the pH of washing process, causes better bleaching activity.
Low environmental impact Betengent product of the present invention (LEIP) preferably includes in molar ratio between 1: 2 and 25: 1, more preferably the peroxide between 2: 1 and 10: 1: the bleach precursor of precursor ratio.
Form with reaction and can obtain in the washing lotion in washing machine drum or in the mixer of off-line from the peroxide of washing agent and the peracid of bleach precursor.The advantage of latter event is that this peracid can form and can be diluted in the washing machine drum with acid water with conc forms under required pH, therefore reduces the pH of washing process, causes better bleaching activity.
Low environmental impact Betengent product of the present invention (LEIP) preferably includes in molar ratio between 1: 2 and 25: 1, more preferably the peroxide between 2: 1 and 10: 1: the bleach precursor of precursor ratio.
The bleaching characteristic of improved hydrogen oxide, to allow the use of lower temperature and/or use another approach of less peroxide be the use of bleach catalysts.
Bleaching catalyst is defined as here that reduction by the activation energy of bleaching action comes the activity of improved oxide but any material of not participating in (namely consuming) reaction.The use of bleaching catalyst in decontamination developed and can be used among the present invention recent years.The example of spendable transition-metal catalyst for example can be at WO-01/48298, WO-00/60045, and WO-02/48301 finds among WO-00/29537 and the WO-00/12667.This catalyst can provide as free ligand in addition, just with water in the transition metal that exists form on the spot complex.Generally, this catalyst contains at least in part the transition metal with the covalent keyed jointing, and keyed jointing at least a part thereon.
Generally, here the transition metal bleach catalyst comprises and is selected from following transition metal in these: Mn (II), Mn (III), Mn (IV), Mn (V), Fe (II), Fe (III), Fe (IV), Co (I), Co (II), Co (III), Ni (I), Ni (II), Ni (III), Cu (I), Cu (II), Cu (III), Cr (II), Cr (III), Cr (IV), Cr (V), Cr (VI), V (III), V (IV), V (V), Mo (IV), Mo (V), Mo (VI), W (IV), W (V), W (VI), Pd (II), Ru (II), Ru (III) and Ru (IV).Preferred transition metal in transition metal bleach catalyst of the present invention comprises manganese, iron and copper, preferred Mn (II), Mn (III), Mn (IV), Fe (II), Fe (III), Cu (I), Cu (II), Cu (III).
Generally, " part " that here use is any structure division that can directly be bonded in metal ion with covalent bond.Part can be charged or neutral.Part can comprise that simple monovalence is to body class (such as chlorine) or simple amine, they form and are connected to metal, are connected to single coordinate bond and the single point of attachment of oxygen, or comprise ethene, therefore this ethene can form three-membered ring with metal and be considered to have two potential being connected to than the point of contact of macrostructure part such as ethylenediamine or nitrogen heterocyclic ring class, and these have formed the singly-bound on one or more metals of being connected to of maximum quantity that the quantity by the lone pair of the room on the metal and free ligand or other keyed jointing site allows.A lot of parts can form the key except simple donor bond, and can have a plurality of tie points.
Additionally, organic bleaching catalyst also can use.General organic bleaching catalyst has the activation imines, it with cross acid reaction after obtain oxaziridine (oxaziridine).Nonrestrictive, preferred compound comprises 3,4-dihydro-isoquinoline salt, as giving an example in WO/9513352.Other organic bleaching catalyst can be at EP0728181, EP0728182, EP0728183, EP0775192, US4,678,792, US 5,045,223, and US 5,047,163, US 5,360,568, and US 5,360,569, US 5,370,826, and US 5,442,066, US 5,478,357, and US 5,550,256, US 5,653, and 910, US 5,710,116, and US 5,760,222, US 5,785,886, and US 5,952,282, US 6,042, and 744, US2007173428, WO95/13351, WO95/13353, WO97/10323, WO98/16614, WO00/42151, WO00/42156, WO01/16110, WO01/16263, WO01/16273, WO01/16274, WO01/16275, WO01/16276, WO01/16277 finds among the WO07/087258.
Low environmental impact Betengent product of the present invention (LEIP) preferably includes according to mol ratio at 100: 1 and 100,000: between 1, more preferably at the peroxide of 500: 1 and 5000: 1: the bleaching catalyst of catalyst ratio.
Composition according to the present invention contains one or more surface active cpds (surfactant), and it is selected from soap and non-soap anionic, CATION, nonionic, both sexes and zwitterionic surface active cpd and their mixture.Many suitable surface active cpds are obtainable and fully describe in the literature, as be described in " Surface-Active Agents andDetergents ", I and II volume, Schwartz, Perry and Berch.
Preferred other detergent-active compounds that can use is soap and synthetic non-soap anionic, nonionic and cationic surfactant.Each some examples in the middle of these are described now.
Preferably there is anion surfactant.It for example is selected from one or more alkylbenzenesulfonates, alkylsulfonate, primary and secondary alkyl sulfate (with free acid and/or salt form).Aromatic alkyl sulfonic acid surfactant preferably accounts for the 0.5wt%-99.9wt% of total anionic surfactant concentration of composition, preferred 1wt%-80wt%, more preferably 10wt%-60wt%, especially 15wt%-50wt%, more specifically 25wt%-45wt%.
Composition according to the present invention is passable, for example contains 0.1%-70%, preferred 1%-40%, more preferably 2%-30%, especially the alkyl benzene sulphonate surfactant of 3%-20% (with free acid and/or salt form).
When hope further strengthens calcium not during tolerance, any anion surfactant except the aromatic alkyl surfactant in composition can comprise (preferably with the 70wt% of total anion surfactant or higher level) or only be comprised of one or more calcium tolerance non-soap anionic surfactants.
If the employing water softening plant, then the Ca-sensitiveness of surfactant is not too crucial.
Here " calcium tolerance " anion surfactant of mentioning is to be 200ppm calcium carbonate for the calcium concentration up to 20 °F of H (French hardness), at (with under the ion concentration of 1: 1 salting liquid of 0.040M) non-setting a kind of anion surfactant under the surfactant concentration of 0.4g/l.
The non-soap calcium tolerance anion surfactant that can be used for the preferred addition type in the composition of the present invention comprises alpha-alkene sulfonate.
The calcium tolerance anion surfactant of another preferred type comprises the material of the middle branching of chain, these have been disclosed in WO-A-97/39087, WO-A-97/39088, WO-A-97/39089, WO-A-97/39090, WO-A-98/23712, WO-A-99/19428, WO-A-99/19430, WO-A-99/19436, WO-A-99/19437, WO-A-99/19455, WO-A-99/20722, WO-A-99/05082, WO-A-99/05084, WO-A-99/05241, WO-A-99/05242, WO-A-99/05243, WO-A-99/05244 and WO-A-99/07656.
The calcium tolerance anion surfactant of another kind of adequate types comprises alkyl ether sulfate (i.e. (many) alkoxylated alkyl sulphate) again.
The another kind of suitable calcium tolerance anion surfactant that uses of combining comprises alpha-alkene sulfonate and the alkyl ether sulfate according to 5: 1 to 1: 15 weight ratio.Spendable other calcium tolerance anion surfactant be alkyl ethoxy carboxylate surfactant (for example, the Neodox of Shell (Trade Mark)), fatty acid ester sulfonate (for example, FAES MC-48 and the ML-40 of Stepan), alkyl xylene or toluene fulfonate, dialkyl sulfosuccinate, alkylamide sulfate, sophorolipid (sorpholipid), the alkali metal of alkyl glycoside sulfate and saturated or unrighted acid (for example sodium) salt.
Outside the deliming tolerance anion, other suitable anion surfactant is that those technical staff in this area are known.Example comprises primary and secondary alkyl sulfate, especially C 8-C 15Primary alkyl sulphates; And dialkyl sulfosuccinate.
Sodium salt generally is preferred.
Optional, soap also can exist.Suitable soap comprises having C 12To C 20Those of chain length, they are mainly saturatedly and optional contains limited amount 1 or 2 unsaturated bond, and derives from natural oil ﹠ fat, for example: (sclerosis or non-sclerosis) butter, cocounut oil, or palm oil.
In solid-state preparaton, the amount of optional soap is the 0.1wt%-10wt% of composition weight, more preferably 0.1wt%-5wt% preferably.In fluid composition, the level of optional soap is the 0.1wt%-20wt% of composition weight, more preferably 5wt%-15wt% preferably.
Other optional surfactant comprises nonionic surface active agent, cationic surfactant (being used for washing strengthens and/or fabric-softening), both sexes and zwitterionic surfactant.
If necessary, non-ionic surface active agent also can comprise.The amount that these materials amount to preferably is the 0.01%-50% of composition by weight, preferred 0.1%-35%, more preferably 0.5%-25%, more preferably 0.7%-20% again, even more preferably 0.8%-15%, especially 1%-10% and even 1%-7% more specifically.
Preferred nonionic surface active agent is to have 2 to 12, more preferably the aliphatic alcohol of 3 to 10 average degree of ethoxylation.Preferably, this aliphatic alcohol is C 8-C 16, more preferably C 10-C 15
The hydrophobe type nonionic that is disclosed in the middle branching of chain among the WO-A-98/23712 is the suitable nonionic surface active agent of another type.
Other suitable non-ethoxylated nonionic surface active agent comprises alkyl poly glucoside, glycerol monoethers, and polyhydroxy amides (glucamide).
Optional, can comprise 0.05%-10% by weight according to composition of the present invention, preferred 0.1%-5%, more preferably 0.25%-2.5%, the especially cationic surfactant of 0.5%-1%.
Suitable cationic fabric soften compound is to comprise having more than or equal to C 20The single alkyl of average chain length degree or the basically water-insoluble quaternary material of alkenyl long-chain or, more preferably, comprise the polar head group and have more than or equal to C 14Two alkyl of average chain length degree or the compound of alkenyl chain.Preferred this fabric softening compound has two chain alkyls or alkenyl chain, has more than or equal to C separately 16The average chain length degree.Most preferably, at least 50% this chain alkyl or alkenyl have C 18Or C 18Above chain length.If the chain alkyl of fabric softening compound or alkenyl mainly are linear, then be preferred.
Quaternary ammonium compound with two long-chain aliphatic group, for example, VARISOFT TA100 and two (hardened tallow alkyl) alkyl dimethyl ammonium chloride has been widely used in the commodity rinse conditioner composition.Other example of these cationic compounds can be at " Surfactants Science Series ", Richmond 1990 editors' 34 volumes find in Rubingh 1991 editors' 37 volumes and Cross andSinger 1994 editors' 53 volumes (Marcel Dekker Inc.New York).
Also might comprise some monoalkyl cationic surfactant, these can be used in their washing.
The cationic surfactant that can be used for this purpose comprises general formula R 1R 2R 3R 4N +X -Quaternary ammonium salt, wherein the R group is long or short hydrocarbon chain, typically alkyl, hydroxyalkyl or ethoxylated alkyl, and X is counter ion counterionsl gegenions (for example, such compounds: R wherein 1C 8-C 22Alkyl, preferred C 8-C 10Or C 12-C 14Alkyl, R 2Methyl, and R 3And R 4(identical or different) is methyl or hydroxyethyl groups); And cationic ester (for example cholinester).
Composition of the present invention also can contain one or more builders, and still, if comprise water softening plant, then the content of these builders is lower than the corresponding content in the common system.The total amount of builder typically is the 1%-50wt% of total composition by weight in composition, preferred 2%-30wt%, more preferably 4%-20%.
The inorganic builders that can exist comprises sodium carbonate, combines with the crystallization seed of calcium carbonate if necessary, as disclosed in GB-A-1 437 950; Crystal and amorphous aluminosilicate, disclosed zeolite in GB-A-1 473 201 for example, disclosed amorphous aluminosilicate and be disclosed in mixed crystal/amorphous aluminosilicate among the GB-A-1 470 250 in GB-A-1 473 202; And be disclosed in phyllosilicate among the EP-A-164 514.Inorganic phosphate builders, sodium orthophosphate for example, sodium pyrophosphate and sodium tripolyphosphate (STP) also are suitably for used herein.
Composition of the present invention preferably contains alkali metal, preferred sodium, aluminosilicate builder.Sodium aluminosilicate generally is that the amount of preferred 20-50wt% is introduced into 10-70% (by anhydrous) by weight.
When aluminosilicate was zeolite, preferred maximum amount was 30% by weight.
This alkali metal aluminosilicate can be crystal or amorphous or their mixture, has general formula: 0.8-1.5Na 2O.Al 2O 3.0.8-6SiO 2
These materials contain some and have at least calcium ion-exchanged capacity of 50mg Ca/g in conjunction with water and requirement.Preferred sodium aluminosilicate contains 1.5-3.5 SiO 2Unit (in above general formula).Amorphous and crystalline material both can easily prepare by the reaction between sodium metasilicate and sodium aluminate, and this fully describes in the literature.Suitable crystalline aluminium sodium metasilicate ion-exchange builder for example is described among the GB-A-1 429 143.The preferred sodium aluminosilicate of this type is well-known Wessalith CS and the X of being purchased, and their mixture.
This zeolite can be to be widely used in now to be purchased zeolite 4A in the cloth-washing detergent powder.Yet according to the preferred embodiments of the invention, the zeolite builders that is introduced in the composition of the present invention is the maximum aluminium zeolite P (zeolite MAP) that is described among the EP-A-384 070 and comes requirement as right.Zeolite MAP is defined as to have and is no more than 1.33 silicon and aluminum ratio, preferably in the 0.90-1.33 scope, and the more preferably alkali metal aluminosilicate of the zeolite P type in the 0.90-1.20 scope.
Especially preferred is to have to be no more than 1.07, more preferably from about the zeolite MAP of 1.00 silicon and aluminum ratio.The calcium binding capacity of zeolite MAP generally equals at least anhydrous material of the every gram of 150mg CaO/.
The organic washing-assisting detergent that can exist comprises polycarboxylate polymer such as polyacrylate, acrylic acid/maleic acid, and acrylic acid phosphinate; Monomer multi-carboxylate such as citrate, gluconate, oxygen base disuccinate, the glycerine list-, two and three succinates, carboxymethyl oxygen base succinate, carboxyl methyl oxygen propylmalonic acid salt, two pyrrole dicarboxylates, hydroxyethyliminodia,etates, alkyl-and alkenyl malonate and succinate; With the alpha-sulfonated fatty hydrochlorate.This tabulation is not exhaustive.
Especially preferred organic washing-assisting detergent is citrate, and suitable consumption is 2-30wt%, preferred 5-25wt%; And acrylic polymer, acrylic acid/maleic acid more particularly, suitable consumption is 0.5-15wt%, preferred 1-10wt%.
Builder (inorganic and organic) preferably exists with the form of alkali metal salt (especially sodium salt).
When composition be contain bleaching agent or bleaching agent generation type the time, they advantageously also contain one or more heavy metal chelants.This reduces the damaging action that bleaching agent brings.Generally, be adapted at chelating agent used herein and can be selected from aminocarboxylate, amino phosphonates do, the aromatic chelating agent that polyfunctional group replaces and their mixture.Be not wishing to be bound by theory, the benefit that can believe these materials is partly removed the ability of heavy metal ion from cleaning solution owing to their outstanding formation of passing through the soluble chelating thing; Other benefit comprises that inoranic membrane or dirt prevent (scaleprevention) effect.Being adapted at other suitable chelating agent used herein is to be purchased DEQUESTO series, and Monsanto, DuPont and Nalco, the chelating agent of Inc.
The aminocarboxylate that can be used as optional chelating agent comprises edetate, the N-hydroxyethyl-ethylenediamine triacetate, nitrilotriacetic acid(NTA) salt, ethylenediamine tetrapropionic acid salt, triethylenetetraaminehexaacetic acid salt, diethylentriamine pentacetate, and ethanol Diglycocol, their alkali metal, ammonium and substituted ammonium salt and their mixture.
When allowing low-level at least total phosphorus and comprise ethylenediamine tetraacetic (methylene phosphonic acid salt) in composition of detergent, amino phosphonates do also is suitable as the chelating agent in the composition of the present invention.Preferably, these amino phosphonates do do not contain alkyl or the alkenyl that has greater than about 6 carbon atoms.
The aromatic chelating agent of multifunctional replacement also can be used among the present invention.Referring to United States Patent (USP) 3,812,044.The preferred compound of this type of acid form is the dihydroxy disulfobenzene, such as 1,2-dihydroxy-3, and the 5-disulfobenzene.
The chelating agent that here uses is ethylenediamine two succinates (" EDDS "), and especially (but being not limited to) is described in United States Patent (USP) 4,704, [S, the S] isomers in 233.This trisodium salt is preferred, although other form such as magnesium salts also can use.
If you are using, it is about 10% that the selective sequestering agent of these chelating agents or transition metal preferably accounts for about 0.001%-of bleaching composition described here by weight, and more preferably from about 0.05%-about 1%.
Laundry according to the present invention also can contain one or more enzymes with cleaning compositions.This fermentoid can provide cleaning characteristics, fabric nursing and/or hygienic benefit.Suitable enzyme comprises the protease that can be used for being introduced in the composition of detergent, amylase, and cellulase, lipase, oxidizing ferment/oxidoreducing enzyme, transferase, hydrolase is crossed oxygenase, lyase, isomerase and ligase.
The suitable member of these enzyme classes is described in Enzyme nomenclature 1992:recommendations of the Nomenclature Committee of the InternationalUnion of Biochemistry and Molecular Biology on; The nomenclature and classification of enzymes, 1992, ISBN 0-12-227165-3, Academic Press.
The example of hydrolase is the carboxylic ester hydrolases that acts on the ester bond, mercaptan ester hydrolase, orthophosphoric ester monohydrolase, and phosphodiester hydrolase; Act on the glycosidase on the O-glycosyl compound; The glycosylase of hydrolyzing N-glycosyl compound acts on the thioether hydrolase on the ehter bond; And act on expeptidase and endopeptidase on the peptide bond.Carboxylic ester hydrolases preferably in the middle of them, glycosidase and expeptidase and endopeptidase.The specific examples of suitable hydrolase comprises (1) expeptidase such as aminopeptidase, carboxypeptidase A and B and endopeptidase such as pepsin, pepsin (pepsin B), renin (chymosin), trypsase, chymotrypsin, elastoser, enterokinase, cathepsin B (cathepsin B), papain (papain), chymopapain, ficin (ficain), fibrin ferment, fibrinolysin, renin, subtilopeptidase A, Aspergillus proteinase (aspergillopepsin), clostridiopetidase A, clostripain, kallikrein, gastricsin, cathepsin D, bromelain, chymotrypsin C, urokinase, cucumber protease, oryzenin enzyme (oryzin), Proteinase K, thermomycolin, thermolysin (thermitase), casease (lactocepin), thermolysin, hay bacillus metalloproteinases (bacillolysin).Subtilopeptidase A preferably in them; (2) glucosidase such as α-amylase, Q-amylase, glucoamylase, isoamylase, cellulase, inscribe-1,3 (4)-dextranase, zytase, dextranase, polygalacturonase (pectase), lysozyme, invertase, hyaluronidase, amylopectase, new amylopectase (neopullulanase), chitinase, arabinosidase, exocellobiohydrolase (exocellobiohydrolase), hexosaminidase, mycodextranase, inscribe-Isosorbide-5-Nitrae-mannase (hemicellulase), xyloglucanase enzymes (xyloglucanase), inscribe-galactosidase (keratan sulfate enzyme (keratanase)), mannase and other carbohydrate gum digestive enzyme that is described among the WO-A-99/09127.
Preferably α-amylase and cellulose carboxylic ester hydrolases in the middle of them, comprising carboxy-lesterase, lipase, phosphatidase, pectinesterase, cholesterase, chlorophyllase, tannase and wax-ester hydrolase.Lipase preferably in the middle of them.
The example of transferase and ligase is the Xyloglucan endotransglycosylase (xyloglycan endotransqlycosylase) that is described in glutathione s-transferase and the acid-mercaptan ligase among the WO-A-98/59028 and is described in WO-A-98/38288.
The example of lyase is the hyaluronic acid ester lyases, pectate lyase, the beautiful lipase (lipex) of sending, chondroitinase (chondroitinase), pectin lyase, alginase II.Especially preferred is pectin lyase (pectolyase), and it is the mixture of pectase and pectin lyase.
The example of oxidoreducing enzyme is oxidizing ferment such as glucose oxidase, methanol oxidase, bilirubin oxidase, catechol-oxydase, laccase, cross oxygenase such as ligninase and those enzymes that are described among the WO-A-97/31090, monooxygenase, dioxygenase such as lipoxygenase are urged bleach system with the cytochromes type enzyme that is described in other oxygenase among WO-A-99/02632, WO-A-99/02638, the WO-A-99/02639 and be described among the WO-A-99/02641.
The activity of oxidoreducing enzyme (especially Phenol oxidase) can strengthen by some organic compound of interpolation (being called reinforcing agent) in the method for the spot of bleaching on fabric and/or the dyestuff in solution and/or in antimicrobial treatment.The example of reinforcing agent is 2,2 '-azo-two-(3-ethyl benzo-thiazoline-6-sulfonate (ABTS) and phenthazine-10-propionic ester (PTP).More reinforcing agent is described in WO-A-94/12619, WO-A-94/12620, WO-A-94/12621, WO-A-97/11217, WO-A-99/23887.Reinforcing agent generally is to add with the level of the 0.01%-5% of composition of detergent weight.
Preferred proteolytic enzyme (protease) is the catalytic activity protein material, the spot of its degraded or change protein type when existing in the textile stains in hydrolysis.They can be any suitable sources, such as plant, and animal, bacterium or yeast source.
Various amounts and source and in the various pH scopes of 4-12 the activated proteolytic enzyme of tool or protease be commercially available and can be used among the present invention.The example of suitable proteolytic enzyme is the subtilopeptidase A from the special bacterial strain acquisition of B.Subtilis B.licheniformis, as by Gist Brocades N.V., Delft, Holland supply be purchased subtilopeptidase A Maxatase (trade mark), with by Novo Industri A/S, Copenhagen, the Alcalase (trade mark) of Denmark supply.
Specially suitable is the protease that obtains from the bacillus strain that has maximum activity the pH of 8-12 scope, and it is commercially available, for example is commercially available with registration mark Esperase (trade mark) and Savinase (trade mark) from Novo Industri A/S.The preparation of these and isoenzymes is described in GB-A-1243 785.Other is purchased protease is the Kazusase trade mark of company (Japanese Showa-Denko), Optimase (trade mark of West Germany Han Nuocheng city Miles Kali-Chemie company), and Superase (trade mark of U.S. Pfizer company).
The amount of the about 3.0wt% of the normally about 0.1-of detersive enzyme is used with granular form.Yet the enzyme of any suitable physical form can use.Adoptable suitable and preferred endonuclease capable finds in WO03/104378.
Composition of the present invention can contain alkali metal, and preferred sodium carbonate is in order to improve clean result and workability.Sodium carbonate is suitable to 1-60wt%, and the amount of preferred 2-40wt% exists.Yet the composition that contains hardly sodium carbonate also is within the scope of the invention.
Powder flowbility can be by a small amount of mealy structure agent, aliphatic acid (or fatty acid soaps) for example, and sugar, acrylate or acrylate/maleate copolymer, or the introducing of sodium metasilicate improves.A kind of preferred mealy structure agent is fatty acid soaps, and the amount with 1-5wt% exists aptly.
More again other material that can exist in composition of detergent of the present invention comprises sodium metasilicate; Anti redeposition agent such as cellulosic polymer; Inorganic salts such as sodium sulphate; Play suds controlling agent or the promoter of foaming (depending on the circumstances); Dyestuff; Painted stigma grain (colored speckle); Aromatic; Foam controller; Fluorescent whitening agent and the linked polymer of uncoupling.This tabulation is not exhaustive.
Composition of the present invention for example provides as solid composite, and such as powder or tablet, or inventive non-solid compositions is such as basically water-based or basically nonaqueous liquid, gel or slurry.Randomly, fluid composition can provide in water-soluble pouch.Non-solid (for example liquid) composition can have the composition different from solid composite and for example can comprise 5%-60% by weight, the anion surfactant of preferred 10%-40% (wherein at least some yes aromatic alkyl sulfonic acid surfactant), 2.5%-60% by weight, the non-ionic surface active agent of preferred 5%-35% and the water of 2%-99% by weight.
Randomly, fluid composition can for example contain 0.1%-20% by weight, the soap of preferred 5%-15%.
Non-solid (for example liquid) composition also can (contain of the present invention any aspect in any eliminating or any precondition expressed) comprise one or more hydrotropic agents, especially when the isotropic composition of needs.This type of hydrotropic agent can for example be selected from arylsulphonate, benzene sulfonate for example, in them any randomly on aryl rings or member ring systems independently by one or more C 1-6(C for example 1-4) the alkyl replacement, benzoic acid, salicylic acid, naphthoic acid, C 1-6(preferred C 1-4) the poly glucoside, single-, two-and triethanolamine.Any in these compounds be with acid or salt (no matter organic or inorganic, such as sodium) when form exists, and anyly all can use, and precondition is compatible with the remaining ingredient of preparaton.
The preparation of composition
Composition of the present invention can prepare by any suitable method.
The selection of processing approach can be partly can obtained form be decided by the stability of the surfactant that involves or heat sensitivity and they.
For microgranular product, add after the procedure of processing that the composition that adds separately traditionally such as enzyme, bleach additive composition, sequestering agent, polymer and aromatic (enzyme that for example adds as the rear metering of pellet form, the aromatic of spraying) can be listed below.
Suitable method comprises:
(1) drum dried of main component, the optional rear metering of carrying out after this granulation or supplementary element is added;
(2) whole compositions in high-speed mixer/granulator (for example, Fukae (trade mark) FS series blender) non-tower granulation in, preferably use at least a surfactant of slurry form, the water in the surfactant slurry is as binding agent like this;
(3) at a high speed/non-tower granulation in medium speed's comminutor coupling apparatus, film flash dryer/evaporimeter or the fluidized bed pelletizer.
The narration of non-limiting embodiments of the present invention
Can more clearly understand the present invention from narration below some accompanying drawings, the embodiments more of the present invention that only provide in the mode of embodiment, in the accompanying drawings:
Fig. 1 has shown as H 2O 2The flow chart of the preferred embodiment of the electrolytic tank of generation equipment;
Fig. 2 a-2b has shown that view and Fig. 2 c in hydrogen peroxide generation pond have shown the pH conditioning equipment;
Fig. 3 is the block diagram according to the embodiment of intelligent clothes washing system of the present invention;
Fig. 4 is the schematic diagram of having introduced the pH/ bleaching agent sensitive fabrics product (upper garment) of label in button;
Fig. 5 is the block diagram for the embodiment of the electronic tag of embodiment of the present invention;
Fig. 6 is the block diagram for the embodiment of the tag communication apparatus of embodiment of the present invention;
Fig. 7 is the flow chart of the method that communicates with a plurality of electronic tags;
Fig. 8 is the flow chart of the electronic tag method of communicating by letter with tag communication apparatus; With
Fig. 9 is the block diagram for the embodiment of the label programming device of embodiment of the present invention.
In Fig. 1, be imported into pH from the running water 1 of Trunk Line and improve in the pond 2, water is separated into acidity and alkaline water therein.Acid water is stored in the storage container 6, and alkaline water is stored in the storage container 5.Alkaline water from container 5 is imported in the hydrogen peroxide generation pond 4.Then the water that contains hydrogen peroxide of high pH be imported into bleaching agent and produce in the container 7, and this hydrogen peroxide and bleach precursor 8a react and the formation peracid therein.The solution that contains peracid produces the container 7 from bleaching agent subsequently and is input in the washing machine 9.This hydrogen peroxide and peracid precursors react in producing container.Produce container and also can contain bleaching catalyst, therefore formed bleaching catalyst+H 2O 2Mixture.In addition, this hydrogen peroxide can directly join in the washing machine that contains LEIP.This LEIP preparaton can not comprise the peracid bleach precursor and also not contain catalyst, or it can contain the peracid bleach precursor, or it can contain bleaching catalyst or it can contain both.
Can directly join in the washing machine 9 from the alkalescence of container 5 separately and 6 and/or the part of acid water.Be directly inputted in the washing machine from the residue detergent component 8b in the Betengent product.
In addition, the running water from main pipeline at first is imported in the water softener FTC-pond 3.Then demineralized water is imported into pH and improves in the pond 2, then according to such processing explained above.Regenerative wastewater (the stream thigh of dotted line) and washing machine wastewater from whole electrochemical cells discharge 10 together.This battery is for example used the acid water regeneration from container 6; In order to keep clear, these stream thighs do not show in the accompanying drawings.
Fig. 2 a has shown the hydrogen peroxide pond 4 of seeing from appearance, and Fig. 2 b has shown the work of each assembly in the exploded view of battery.This battery 4 comprises gas diffusion cathode 17 that tunicle 18 separates and the anode 19 of dimensionally stable, and they form the chamber together.Reactant namely from the oxygen of air, enters into this chamber via entrance 11, and air can leave this chamber from exporting 12 when equipment operating.Catholyte, namely water is transfused to via entrance 13, and the water that contains hydrogen peroxide when equipment operating is removed from exporting 14, therefore produces hydrogen peroxide.Similarly, this anolyte is respectively via mouth 15 and 16 inputs and discharge; Water is imported in this pond and draws from anode with water-soluble proton when equipment operating.
Fig. 2 c has shown the work that improves the electrolytic tank of device as pH.In Fig. 2 c, described to be suitable as the electrolytic tank that pH improves device with schematic diagram.Water 123 is transfused in this pond.Two negative electrodes 125 and anode 124 of being opened in 126 minutes by non-conductive partition (spacer) arranged in the inside, pond of Fig. 2 c.When operation, produce alkaline water 110 and produce acid water 115 at anode at negative electrode.
Electronic tag attaching according to the present invention is in a plurality of fabric products, and wherein some are bleaching agent sensitiveness, and wherein some are pH sensitiveness, and some whiles in them all are pH and bleaching agent sensitiveness.In the time of in product is in washing machine, the identifying information on label is read.As a result, when fabric product was loaded in the washing machine, this pH/ bleaching agent modify instruction can be obtained.Therefore, user of the present invention does not need to expend extra effort and sorts out laundry product in order to find sensitive product and non-or wash dividually than the hyposensitivity product with other.
Fig. 3 is the block diagram according to the preferred embodiment of clothes washing system of the present invention.Clothes washing system is utilized to wash multiple bleaching agent/pH sensitive product 20 and non-sensibility product 21.
In bleaching agent/pH sensitive fabrics product 20 each has the electronic tag 22 of attaching.Electronic tag 22 for good and all is introduced within the element (button 23-as shown in Figure 4 here) of a product 20.Other bleaching agent/pH sensitive fabrics product carries temporary transient general electronic tag 22 (not shown)s.Other bleaching agent/pH sensitive fabrics product is introduced in the washing load, but can not carry any label.
The electronic tag that is used for present embodiment is to programme in advance with various information.Yet they also can carry out programming by label programming device 24.This label programming device 24 can read and/or be written in electronic tag 22 interior canned datas through operation, such as identifying information, and other laundry indication, and the laundry of material product 20 counting (laundering count).This label programming device 24 can be used in identifies this material product 20 and/or detection each product 20 in clothes washing system.This label can determine that this fabric product is pH responsive type and/or bleaching agent responsive type or both.The dyestuff that bleaching agent brings if fabric suffers fades/damages, and then but pH there is no need to regulate H 2O 2Generation will need to regulate/stop.Some woollen fabrics product can be labeled as pH-sensitivity (so pH maintains lower level).
Each washing machine has the controller of its operation of control.In the embodiment of Fig. 3, washing machine 26 is controlled by controller 32, and the latter provides many control modes with many control positions or settings (comprise relevant with peroxidating hydrogen generation system on the spot those).
Tag communication apparatus 38 be embedded in the washing machine and the washing load that comprises bleaching agent/pH sensitive fabrics product 20 be in the washing machine time and electronic tag 22 exchange messages.Only the existence of a label 22 enough transmits information and regulate the peroxidating hydrogen generation system in controller.This system regulates according to bleaching agent and/or pH sensitiveness.According to the label 22 of attaching, H 2O 2Generation can fully stop and/or pH reduces.If pH and bleaching agent sensitiveness are all determined, then both regulate/restriction.In additional embodiment, tag communication apparatus/controller can comprise the virtual display unit of authentication information, in order to allow the overload of user's control example such as this protection system.
Fig. 5 is the schematic diagram of the example of the electronic tag 22 that comprises in the button 23 of Fig. 4, and this electronic tag 22 can be used in embodiment of the present invention.This electronic tag 22 comprises internal memory 70, and the latter has stored the information of pH/ bleaching agent sensitive fabrics product.This information comprises pH-sensitiveness and H 2O 2-sensitive information.Preferably, this internal memory 70 is non-volatile, therefore can preserve this storage information in the situation that it is not applied power supply.
A series of program steps carried out by processor 72 so that exchange message between the tag communication apparatus in internal memory 70 and clothes washing system.This processor 72 can for example be microprocessor, custom integrated circuit, programmable logic array, or the form of special IC.Comprise that also receiver 74 receives the information that passes out from tag communication apparatus.Provide transmitter 76 to come emission information to tag communication apparatus.Preferably, receiver 74 and transmitter 76 are by using the radiofrequency signal exchange message.Receiver 74 and transmitter 76 all be connected in processor 72 in case with internal memory 70 exchange messages.As a result, this transmitter 76 operates explicitly with internal memory 70, reads for the outside in order to launch information.
Circuit in electronic tag provides power by electromagnetic power receiver 78.Electromagnetic power receiver 78 receives and is transmitted to its electromagnetic power, and electromagnetic power is transformed into the DC voltage of the power circuit (that is, internal memory 70, processor 72, receiver 74, and transmitter 76) in electronic tag.
This electronic tag is for steam, high temperature, and laundry solution is all implemented sealing.This electronic tag still less with flat, therefore inconspicuous when for good and all being attached to a product.According to these preferred technical parameters, this electronic tag can be constructed according to the method for the transponder beacon of disclosed production environment sealing in US5420757.
Fig. 6 is the schematic diagram for the embodiment of the tag communication apparatus of embodiment of the present invention.This tag communication apparatus comprises processor 80, and the latter carries out a series of program step and comes and electronic tag 22 exchange messages.The same with processor 72, processor 80 can be microprocessor, custom integrated circuit, programmable logic array, or the form of special IC.This processor 80 is communicated by letter with internal memory 81, so that the information of storage and electronic tag 22 exchanges.
Tag communication apparatus comprises electromagnetic power transmitter 82 in order to the electromagnetic power signal is transmitted to the supply power of the circuit in the electronic tag 22.This electromagnetic power transmitter 82 will be activated in response to the order that processor 80 provides and stop.Transmitter 84 launch produced by processor 80 and/or in internal memory 81 canned data in order to received by the receiver 74 in the electronic tag.Receiver 86 receives the information by transmitter 76 emissions in the electronic tag.The information of these receiver 86 these receptions of exchange is in this processor 80.Processor 80 is processed the information of these receptions so that for arranging or verifying the control mode on this controller or the warning user is set signal is provided for incorrect.
Fig. 7 is the flow chart of the method that communicates with a plurality of electronic tags.The method can be adopted to read in a plurality of laundry indications of storing in a plurality of electronic tags that comprise in the washing machine by tag communication apparatus.Should be noted that, in the washing methods within the scope of the invention, a plurality of clothes contain label, so that pH and/or the responsive clothes of bleaching agent have been informed in communication, the responsive clothes of single pH, the responsive clothes of single bleaching agent, the existence of the responsive clothes of single pH and bleaching agent, or do not have responsive clothes to exist.If there is not responsive clothes to exist, then the flow process of back is not moved.If at least a clothes is with the mark of warning pH sensitiveness and/or bleaching agent sensitiveness, then the sequence of back will be used.The method is that to adopt the transmitter 84 in tag communication apparatus be starting point with the step that sequence signal 130 is transmitted into electronic tag 22.This sequence signal by the electronic tag of each be used to determine it with sequence that tag communication apparatus is communicated by letter in the position.In preferred embodiments, sequence signal comprises the demonstration of sequence length, and this sequence length is used to determine at random in this sequence its position by each electronic tag.This sequence length can be selected according to the capacity of washing machine.Shown as module 132, the initialized step of operation counter.Counter is used for indicating the current location at this communication sequence.This counter typically initializes and is stored within processor 80 or the internal memory 81 with processor 80.Then, the transmitter 84 in tag communication apparatus is launched information inquiry signal, shown in module 134.Information inquiry signal requires to have the electronic tag emission information of current location to tag communication apparatus in this sequence.Shown in module 136, the receiver 86 in tag communication apparatus is answered the label signal from one or more electronic tags.If label signal receives from the Single Electron label, then processor 80 checks, shown in module 138.If label signal receives from the Single Electron label, then contained information is stored in the internal memory 81 of tag communication apparatus, shown in module 140 in label signal.In order to confirm the reception of label signal, transmitter 84 sends confirmation signal, shown in module 142.
If it is pointed out that and then receive label signal from the Single Electron label if do not launch label signal or two or more label signals are launched.If two or more label signals are launched, then clash, therefore can't be from each label signal acquired information.After in module 142, sending confirmation signal, if or in module 138, from the Single Electron label, do not receive label signal, then measure the step whether this counter has reached predetermined threshold, shown in module 144.This predetermined threshold is the indication of the sequence length be scheduled to, and it preferably is contained in by within the sequence signal of launching in the step shown in the module 130.
If this counter does not reach predetermined threshold, the step of this counter that then gains is shown in module 146.Afterwards, the flow process of method is directed getting back to module 134 and communicates by letter with another electronic tag in order to launch another request signal.If this counter has reached this predetermined threshold, then carry out these steps to determine whether information successfully receives and store from whole electronic tags.At first, launch the step of label request signal unconfirmed and undertaken by transmitter 84, shown in module 148.Then this receiver 86 answers the signal that is produced by any label unconfirmed, shown in module 150.Shown in module 152, this processor 80 determines whether to receive from label unconfirmed the step of signal.
If receive signal from unacknowledged label, then the flow process of the method is directed getting back to module 130, launches therein new sequence signal.Preferably, new sequence signal comprises that the expression of sequence length of shortening is in order to contact with label communication unconfirmed.If do not receive signal from label unconfirmed, the method for then communicating by letter with electronic tag just finishes.
Should be noted that, in the washing methods within the scope of the invention, a plurality of clothes contain label, so that pH and/or the responsive clothes of bleaching agent have been informed in communication, the responsive clothes of single pH, the responsive clothes of single bleaching agent, the existence of the responsive clothes of single pH and bleaching agent, or do not have responsive clothes to exist.If there is not responsive clothes to exist, then the flow process of back is not moved.If at least a clothes.
Fig. 8 is the flow chart of the embodiment of the electronic tag method of communicating by letter with tag communication apparatus.Shown in module 160, the step that receives the sequence signal of being launched by tag communication apparatus is to be undertaken by the receiver 74 in electronic tag.Preferably, sequence signal comprises the expression of the integer indicated value of predetermined sequence length.Shown in module 162, the processor 72 in electronic tag produces random digit and determines its position in this communication sequence.This random digit be disperse and take predetermined probability distribution (being probability mass function or probability function) for the basis generation.Preferably, this probability distribution depends on the expression of predetermined sequence length contained in sequence signal.In one embodiment, this random digit is from 1 expression to the integer of sequence length.This random digit produces with the discrete basis that evenly is distributed as, and wherein similarly may be selected from 1 each integer to sequence length.Receiver 74 in electronic tag is answered any signal by the tag communication apparatus emission, shown in module 164.Shown in module 166, processor 72 determines based on random digit whether information inquiry signal is that electronic tag receives.If information inquiry signal is received by electronic tag, then launch the step of information signal, shown in module 168.
Behind this information signal of emission, this receiver 74 is answered confirmation signal from tag communication apparatus, shown in the step of module 170.If confirmation signal is received in module 172, then information signal is successfully received by tag communication apparatus, and then the execution of the method just finishes.If confirmation signal does not receive, if or similarly receive rub-out signal, then the flow process of the method is directed getting back to module 164.It is pointed out that if information inquiry signal by the tag communication apparatus of another electronic tag emission, if or label request signal unconfirmed be launched, then electronic tag does not receive information inquiry signal in module 166.
If electronic tag does not receive information inquiry signal in module 166, then determine whether received step of label request signal unconfirmed by module 174.If label request signal unconfirmed is not received, then the flow process of the method is directed getting back to module 164.If label request signal unconfirmed is received, then send the step of the signal of expression label unconfirmed, shown in module 176.Then the flow process of the method is directed getting back to module 160 to receive another sequence signal.
Fig. 9 is the block diagram for the embodiment of the label programming device of embodiment of the present invention.This label programming device comprises processor 180, and the latter carries out a series of program step and comes and electronic tag 22 exchange messages.This processor 180 can for example be microprocessor, custom integrated circuit, programmable logic array, or the form of special IC.This processor 180 is communicated by letter with internal memory 182, so that the information of storage and electronic tag 22 exchanges.
Provide electromagnetic power transmitter 184 in order to launch the electromagnetic power signal to the supply power of the circuit in the electronic tag.This electromagnetic power transmitter 184 will be activated in response to the order that processor 180 provides and stop.Provide input equipment 186 and processor 180 to write to each other.Input equipment 186 can be taked the form of one or more buttons, keyboard, touch pad or touch-screen, and its permission information and/or instruction are input by a user in the label programming device.This processor 180 is processed these information and instruction and is formed signal, and the latter is applied to transmitter 188.Transmitter 188 is launched the signal that is received by the receiver 74 in the electronic tag.This signal can be the indication that is stored in the information inquiry in the electronic tag, such as the inquiry of the currency of the inquiry of the identifying information of material product or counting.This signal can be the indication of canned data in electronic tag also, such as identifying information, and laundry instruction, and water treatment instruction.Receiver 190 receives the information by transmitter 76 emissions in the electronic tag.The information of these receiver 190 these receptions of exchange is in this processor 180.This processor 180 is processed the information of this reception, and the signal that drives display device 192 is provided.This display device 192 provides the means that show the information of being inquired about by the user, such as the currency of identifying information and counting.Preferably this display device 192 can show digital information or alphanumeric information.Itself, this display device 192 can be based on light emitting diode or liquid crystal technology.
Major advantage of the present invention is that the clothes of only limited quantity need to tag.Like this, the speed that penetrates is higher.In addition, the producer can add this label, need not to warn the consumer that this is responsive especially clothes.This information is hidden on the label now.Another possible advantage provides/sells mark to the consumer, if the clothes of very responsive (according to consumer's suggestion) is arranged then the consumer can own mark, has therefore realized the fully control of this process.
It is evident that those technical staff in this area that disclosed invention can be improved and it is contemplated that other the many embodiments except the above preferred form of specifically listing and describing in many ways.

Claims (11)

1. comprise the washing system of the various fabrics product of one or more sensitive fabrics products in washing machine with the composition of detergent washing that comprises the 5-99.9% surfactant, this washing system comprises:
Peroxidating hydrogen generation system on the spot;
The pH conditioning equipment;
Tag communication apparatus, it reads in the laundry instruction that comprises in the electronic tag of attaching in any sensitive fabrics product;
The controller of communicating by letter with tag communication apparatus, its control washing machine is regulated the peroxidating hydrogen generation system according to bleaching agent and/or the pH sensitiveness of fabric product.
2. according to claim 1 washing system, wherein the peroxidating hydrogen generation system comprises the electrochemical cell that produces hydrogen peroxide from water and air from the beginning.
3. according to claim 1 washing system, wherein the pH conditioning equipment comprises having for one or more negative electrodes of the production of acid water and alkaline water and the electrochemical cell of anode electrode, does not therefore need to add chemicals when equipment operating.
4. according to claim 1 washing system, wherein composition of detergent comprises bleach precursor.
5. according to claim 1 washing system, wherein composition of detergent comprises bleaching catalyst.
6. according to claim 1 washing system, wherein composition of detergent comprises bleach precursor and bleaching catalyst.
7. according to claim 1 washing system further comprises water softener.
8. according to claim 7 washing system, wherein water softener comprises ion-exchanger and/or electrodialysis plant and/or capacitive deionization equipment and/or flows through the formula capacitor.
9. the washing system of any one according to claim 1-8, wherein composition of detergent comprises based on the weight of total composition that the pH of 5wt% improves at the most and uses chemicals.
10. the washing system of any one according to claim 1-8, wherein composition of detergent does not contain builder.
11. the washing system of any one according to claim 1-8, wherein composition of detergent does not contain hydrogen peroxide, SODIUM PERCARBONATE, and the sodium perborate monohydrate, sodium perborate tetrahydrate, or hydrogen peroxide produces the oxidizing ferment of usefulness.
CN2008801177849A 2007-11-27 2008-11-24 Laundry system for sensitive fabrics Active CN101874133B (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
EP07121660.0 2007-11-27
EP07121660 2007-11-27
PCT/EP2008/066061 WO2009068496A1 (en) 2007-11-27 2008-11-24 Laundry system for sensitive fabrics

Publications (2)

Publication Number Publication Date
CN101874133A CN101874133A (en) 2010-10-27
CN101874133B true CN101874133B (en) 2013-03-27

Family

ID=39472451

Family Applications (1)

Application Number Title Priority Date Filing Date
CN2008801177849A Active CN101874133B (en) 2007-11-27 2008-11-24 Laundry system for sensitive fabrics

Country Status (6)

Country Link
EP (1) EP2220282B1 (en)
CN (1) CN101874133B (en)
BR (1) BRPI0819794B1 (en)
ES (1) ES2580131T3 (en)
WO (1) WO2009068496A1 (en)
ZA (1) ZA201003053B (en)

Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2017035246A1 (en) 2015-08-24 2017-03-02 Kohler Co. Toilet with dispenser for chemical compound
DE102020103651A1 (en) * 2020-02-12 2021-08-12 Miele & Cie. Kg Method for operating a water-bearing electrical device and water-bearing electrical device
DE102020103662A1 (en) * 2020-02-12 2021-08-12 Miele & Cie. Kg Water-bearing electrical device
DE102020103632A1 (en) * 2020-02-12 2021-08-12 Miele & Cie. Kg Use of a component as an electrolyte for an electrochemical cell, method for operating a water-bearing electrical device and water-bearing electrical device
DE102020103641A1 (en) * 2020-02-12 2021-08-12 Miele & Cie. Kg Method for operating a water-bearing electrical device and water-bearing electrical device

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5388299A (en) * 1993-04-06 1995-02-14 Goldstar Co., Ltd. Washing control system of a washing machine
US5715555A (en) * 1995-09-12 1998-02-10 Motorola Inc. Smart laundry system and methods therefor
CN1961111A (en) * 2004-07-21 2007-05-09 Lg电子株式会社 Transmitting/receiving device for washing machine and apparatus and method thereof
WO2007128960A2 (en) * 2006-04-11 2007-11-15 Dyson Technology Limited Electrolytic cells

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5388299A (en) * 1993-04-06 1995-02-14 Goldstar Co., Ltd. Washing control system of a washing machine
US5715555A (en) * 1995-09-12 1998-02-10 Motorola Inc. Smart laundry system and methods therefor
CN1961111A (en) * 2004-07-21 2007-05-09 Lg电子株式会社 Transmitting/receiving device for washing machine and apparatus and method thereof
WO2007128960A2 (en) * 2006-04-11 2007-11-15 Dyson Technology Limited Electrolytic cells

Also Published As

Publication number Publication date
EP2220282B1 (en) 2016-05-04
ES2580131T3 (en) 2016-08-19
ZA201003053B (en) 2011-07-27
EP2220282A1 (en) 2010-08-25
BRPI0819794B1 (en) 2019-07-09
BRPI0819794A2 (en) 2015-05-05
CN101874133A (en) 2010-10-27
WO2009068496A1 (en) 2009-06-04

Similar Documents

Publication Publication Date Title
CN101874133B (en) Laundry system for sensitive fabrics
US20060288743A1 (en) Peroxide generating device and method
ES2224169T3 (en) DETERGENTS THAT UNDERSTAND CELLS.
US5601750A (en) Enzymatic bleach composition
ES2274024T3 (en) COMPOSITION AND METHOD FOR WHITENING A SUBSTRATE.
CN102803458B (en) Comprise polyethylene glycol polymer and diastatic compositions
ES2387518T3 (en) Metal complexes of siderophores used as bleaching catalysts
US10781407B2 (en) Laundry method, use of polypeptide and detergent composition
ES2386650T3 (en) Bleaching systems coated with polymers
CN102131922A (en) Cleaning and/or treatment compositions
CN102933699A (en) Solid detergent composition comprising lipase of bacterial origin
JP2000515204A (en) Method for removing stains on fabric with detergent composition containing bleach
JP2012532246A (en) Catalytic laundry detergent composition comprising a relatively low concentration of a water-soluble electrolyte
BR112020011352A2 (en) fungal cellulase variants
WO2017001471A1 (en) Laundry method, use of polypeptide and detergent composition
CN108350400B (en) Laundry washing method, use of polypeptides and detergent compositions
DE19639603A1 (en) Transition metal complex activator for per:oxygen compounds
US20030008797A1 (en) Ligand and complex for catalytically bleaching a substrate
CN110499613A (en) Control method, control system and the device for clothing processing of device for clothing processing
EP1027416A2 (en) Peroxynitrite based bleaching systems
AU701937B2 (en) Enzymatic bleach booster compositions
JPS6377999A (en) Enzyme bonded builder
US20170114305A1 (en) Novel washing method with electrochemically activatable mediator compound
WO2012140413A1 (en) Coated fabric care agent
WO2019111000A1 (en) Methods of treatment comprising modified polymeric beads

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
C14 Grant of patent or utility model
GR01 Patent grant
TR01 Transfer of patent right
TR01 Transfer of patent right

Effective date of registration: 20210826

Address after: Rotterdam

Patentee after: Unilever Intellectual Property Holdings Ltd.

Address before: Rotterdam

Patentee before: Netherlands Unilever Co.,Ltd.