CN1292062C - Bleaching detergent compositions - Google Patents

Abstract

The invention relates to compositions comprising a peroxyacid bleach precursor, a peroxide source, at least 15 % by weight of a carbonate source, which may comprise the hydrogen peroxide source or part thereof, and at least 7 % by weight of an organic carboxylic acid whereby a 1 % solution of the composition in demineralised water provides a pH from 8.8 to 9.9. The compositions are useful to provide sanitisation of fabrics, in particular to reduce the activity of certain bacteria groups.

Description

Bleach detergent compositions

Technical field

The invention provides the method for special cleaning (sanitising) composition and improvement clean fabric.

Background of invention

Traditional hard surface cleaner contains SYNTHETIC OPTICAL WHITNER as clean-out system and sterilizing agent.They contain high-load chlorine bleach usually to reach needed cleaning and sterilization property.

Studies show that the hydrogen peroxide bleaching in laundry and dishwashing detergent also has disinfection, and detergent manufacturers is very interested in these washing composition sterilization property aspects recently.The also known sterilization functions that provides of peroxyacid bleach precursor.

Yet not all bleach system with enough sterilization character all is suitable for washing composition, and always for example enzyme is not compatible with other detergent component for SYNTHETIC OPTICAL WHITNER, and in addition, it is too high and can damage fabric to reach the needed bleach levels of sterilization.

The inventor finds: peroxyacid bleach precursor can be the preferred SYNTHETIC OPTICAL WHITNER material that clean fabric is provided during washing.; they find that using the problem of these bleach precursors is that they form peroxyacid bleach under high alkalinity pH condition; but under such high alkalinity pH condition; this peroxy acid (it is found to be the active substance that provides cleaning benefit) resolves into the form of non-activity, therefore causes spatter property to reduce.

Also preferably bleaching component in washing composition is percarbonate.Percarbonate makes that solution is very strong alkalescence, and when purpose was the high-load active substance of maintenance (being peroxy acid itself), it was unfavorable as mentioned above, and therefore its sterilization ability also is unfavorable.A lot of washing assistants are in the suds alkaline pH also are provided, and when seeking effective cleaning, it is unfavorable.

In addition, a lot of detergent components are in the suds and also require high alkalinity pH, and it is inconsistent with the preferred pH that washing needs high-load peroxy acid.

Therefore, difficulty is: prepare washing composition by this way, it makes a spot of peroxyacid bleach precursor that effective cleaning is provided, and reaches fabulous cleaning simultaneously.

The inventor has had now found that and a kind ofly provides effective sterilization ability and/or spatter property, but reached the method for good cleaning bleach spot and No bleach spot simultaneously.They find: as the pH of control washing composition in washing water liquid, be 8.8-9.9, preferred 9.0 or 9.2-9.85 or 9.8, when particularly realizing with optional buffer reagent by the bronsted lowry acids and bases bronsted lowry component of using certain content, fabulous spatter property and cleaning have been obtained, simultaneously only need limited amount precursor, thereby make that composition stores is more stable and it is safer to use.So they find these detergent composition even can contain percarbonate bleach.

Particular composition of the present invention is preferred for providing effectively clean fabric, or makes microorganism deactivatedly effectively, particularly makes the bacterium that is difficult to inactivation, and for example E.Hirae particularly also has S.Aureus, E Coli and Ps Aeruginosa inactivation.

Summary of the invention

The present invention relates to laundry or dishwashing detergent composition, said composition contains the carbonate source and the bleach system of at least 15% (weight), this bleach system contains at least 2.5% (weight) peroxyacid bleach precursor and hydrogen peroxide cource (this hydrogen peroxide cource can comprise percarbonate, so it can be the part of carbonate source); The acid of at least 7% (weight), preferred organic acid more preferably comprises organic carboxyl acid, it is characterized in that said composition stirs the mixture of 1% (weight) that obtains after 10 minutes and provides under the speed at 200rpm in 20 ℃ of softening waters pH is 8.8-9.9.

The invention still further relates to and during washing, use the present composition method of cleaning to be provided and to make E.Hirae, S.Aureus, the method for E Coli and Ps Aeruginosa inactivation.

The inventor also finds: when laundry of the present invention and dishwashing compositions are used for automatic clothes washing method, when the rotary drum that said composition directly provided (for example using distribution device) give washing machine, reached improved fabric sterilization ability or spatter property.Therefore one embodiment of the invention relate to the washing methods of laundering of textile fabrics, wherein by put composition of the present invention into distribution device before adding washing water it are joined in the rotary drum of washing machine.

Detailed Description Of The Invention

Composition of the present invention is preferably such, and the pH that 1% the mixture that it makes said composition stir under the speed at 200rpm in 20 ℃ of softening waters to obtain after 10 minutes provides is 9.0-9.85, and even 9.2-9.85 or 9.8, so that 9.4-9.8.This pH stirs this mixture to measure with conventional pH measuring method after 10 minutes under constant temperature.

Term " 1% mixture " refers to the mixture of composition in the softening water of 99 weight unit of 1 weight unit, dispersion liquid or solution, therefore should understand: if not fully dissolving of said composition after 10 minutes, that measure so is the such mixture or the pH of dispersion liquid.

When using in this article, " reduction microbic activity " comprise as at CEN method prEN1276,1993, and the active reduction that defines among (Comit é Europ é en de Normalisation) and the CEN method prEN1650.Wherein should reduce preferably and reduce at least 10 with specific microorganism or bacterium ⁵, more preferably at least 2 * 10 ⁵And even, 3 * 10 ⁵Represent.

When using in this article, reduce the reduction that microbic activity comprises any process that microorganism carries out, comprise that the product excretory reduces, but the preferably reduction of microorganism growth.

The present invention also provides the reduction microorganism, or the active method of preferred specific bacteria, this method comprises following step: microorganism is contacted with containing the liquid, aqueous of the present composition, make the peroxy acid that provided by (peroxy acid) precursor with in this liquid per 10 ⁶The microorganism content of 100ppm at least exists.

Preferably, said composition is such, and it makes the activity of E.Hirae at least, but more preferably also has S.Aureus, and the activity of E Coli and Ps Aeruginosa reduces at least 10 ⁵, preferably at least 2 * 10 ⁵And even, 3 * 10 ⁵(measuring) with above-mentioned CEN method.

Especially, this activity reduction is carried out in washing process.Therefore, composition of the present invention can contact with the specified microorganisms of solid form, but preferably this SYNTHETIC OPTICAL WHITNER is present in the liquid and contacts with microorganism.

Specific microorganism, preferred specific bacterium may reside in will cleaning and clean Surface and fabric on, for example be present in the laundry processes and will be cleaned on the fabric.This bacterium also may reside in and is used for cleaning or the liquid of cleaning method, or is present in the equipment (for example washing machine or distribution device) that is used for this method.

Composition of the present invention is useful especially making the inefficacy aspect with microorganism, particularly gram-positive bacteria (it may reside in the dirt or spot on fabric or surface, particularly in the human body dirt) of containing relative high-content peptidoglycan cell walls.

The amount that reaches the active needed composition of effective reduction specified microorganisms depends on multiple factor: the microbial biomass of Cun Zaiing for example, clean or the condition of purging method, and comprise other compound of existence and the temperature of purging method.

In the method for the invention, the liquid of use preferably contains per 10 ⁶Microorganism is 100ppm at least, more preferably 200ppm at least, and even the peroxy acid of 250ppm.

Having the active reduction of the specified microorganisms that contains the peptidoglycan cell walls can use as measuring at Petrocci described in the JOAC1981 and Clarke method, but for purpose of the present invention, preferably use CEN method prEN1276 for bacterium, 1993 measure, and preferably measure with CEN method prEN1650 for yeast.

Above-mentioned CEN method comprises: for example, according to CEN method the 7th page of preparation gram-positive bacteria inoculum and the further solution for preparing the hydrophobic bleach agent that contains 250ppm content, test according to the CEN method, coiled 24 hours at 36 ℃ of inoculation TSA; Then the bacterial colony on the dish is counted.

For the duration of contact that limits, the reduction that itself and reference result were compared and calculated bacterial growth.

Acid

Said composition contains one or more acid of at least 7% (weight), and preferred organic acid preferably comprises organic carboxyl acid at least.Its accurately content depend on other component of detergent composition and its alkalescence, regulate this sour content needed pH be provided thereby cause.

Preferably, the amount that this acid exists is at least 8% of a composition weight, and even at least 9%, so that at least 10%, upper limit amount is preferably 30% of composition weight, and even 20%.

The suitable acid that is used for the present invention comprises and not only helps to provide prescription needed pH, and also have the material that second function for example plays sequestrant, washing assistant and/or the effect of effervesce source in composition.Useful mineral acid comprises: boric acid, bisul-phite, preferably its sodium salt.

This acid preferably comprises organic carboxyl acid at least.That such acid comprises is single-or poly carboxylic acid, optimization citric acid, hexanodioic acid, pentanedioic acid, 3 chetoglutaric acid, citromalic acid, tartrate, toxilic acid, fumaric acid, oxysuccinic acid, succsinic acid, propanedioic acid also has polymeric or oligomeric poly carboxylic acid, for example acrylate copolymer or toxilic acid polymkeric substance, or toxilic acid and acrylic acid multipolymer.

Most preferred herein organic carboxyl acid comprises the toxilic acid by composition weight meter at least 7%, oxysuccinic acid or citric acid, or its mixture.

Preferably use the mixture of organic carboxyl acid and mineral acid, for example its ratio is 1: 1-10: 1, and even 2: 1-5: 1.

This acid can be used as separated portion of the present invention and exists, or is present in the solids composition of the present invention, can will should acid join in (washing composition) particle with other detergent component.In the latter case, preferably this acid is particulate material, wherein by volume, at least 75%, preferably at least 85%, and even at least 90%, so that at least 95%, particle diameter until at least 99% is the 1-500 micron, more preferably 1-350 micron, further preferably at least 60%, and even at least 75%, so that at least 85% particle diameter is the 1.0-250 micron, and even the 1.0-150 micron.

These particle diameters can be used methods known in the art, particularly laser light scattering or diffractive technology, for example use Malvem 2600 or Sympatec Helos laser light scattering device (or diffractometer) to measure.

When this acid was present in the solids composition of the present invention as isolating component, as mentioned below, this size distribution and median size preferred class were similar to the size distribution and the median size of other component of composition.

The salt of mineral acid and/or the salt of organic carboxyl acid or ester also can be used as additional component and exist, particularly because it is of value to composition is buffered in needed pH.For example, preferably said composition contains citric acid, toxilic acid, oxysuccinic acid, pentanedioic acid or tartaric salt or barate salt, or its mixture.

Carbonate source

Composition of the present invention contains the carbonate source of at least 15% (weight).Preferred carbonate source comprises carbonate, supercarbonate and percarbonate, and this carbonate source preferably contains the mixture of these 3 kinds of salt.

Should understand: when percarbonate existed, it formed as defined herein carbonate source part and hydrogen peroxide cource part.Therefore, in an embodiment preferred of the present invention, said composition contains percarbonate so that provide hydrogen peroxide and carbonate.For example, when said composition contained at least 10% (weight) as the percarbonate of hydrogen peroxide cource and carbonate source, said composition also contained other carbonate source of at least 5% (weight).

The content of carbonate source depends on the character of this washing composition.In addition, if use percarbonate, so also can only need other carbonate source of reduction amount as hydrogen peroxide cource.Said composition preferably contains the mixture of carbonate source, preferably includes carbonate, supercarbonate and percarbonate.So, said composition preferably contains the carbonate of at least 5% (weight), the percarbonate of the supercarbonate and at least 8% of at least 2% (weight) (weight), the carbonate that more preferably contains at least 7% (weight), the percarbonate of the supercarbonate and at least 15% of at least 4% (weight) (weight).Or described carbonate source contains the basic metal or the alkaline earth metal carbonate of at least 5% weight, the basic metal or the alkali metal bicarbonates of the basic metal of at least 8% weight or alkaline-earth metal percarbonate and at least 2% weight by composition weight meter.

The suitable carbonate that is used for the present invention comprises carbonate and the supercarbonate or the acid carbonate of alkaline-earth metal or basic metal and sodium and potassium.The inventor finds: it is useful especially that supercarbonate is included in the composition, provides buffered pH because have been found that supercarbonate near forming the needed pH of peroxy acid from precursor (for example as the TAED hereinafter).

In the preferred embodiment of the invention, press composition weight meter, said composition contains at least 1%, preferably at least 2%, and even at least 4% the basic metal or the supercarbonate of alkaline-earth metal, preferred sodium bicarbonate.The amount that this salt can exist reaches as high as any amount, presses composition weight meter, preferably is up to 20%, more preferably is up to 15%, and even is up to 10%.

Carbonate herein, supercarbonate and percarbonate can be used as isolating grain fraction and exist, and perhaps can join in the detergent particles with other detergent component.

When it was present in other detergent particles, the volume median diameter of this carbonate and supercarbonate material was preferably the 1-500 micron, wherein by volume, preferably at least 60%, preferably at least 70%, and even at least 80%, so that at least 90% particle diameter is the 0.5-1180 micron.More preferably, the volume median diameter of this carbonate or supercarbonate (volumemedian particle size) is the 10-375 micron, wherein by volume, preferably at least 60%, preferably at least 70%, and even at least 80%, so that at least 90% particle diameter is the 1-850 micron; Even more preferably, the volume median diameter is the 10-250 micron, wherein by volume, preferably at least 60%, preferably at least 70%, and even at least 80%, so that at least 90% particle diameter is the 5-425 micron.

Can be preferably:, randomly then select the required particle diameter of this material to obtain this carbonate and/or the supercarbonate of required particle diameter by any suitable method by grinding the greater particle size material.

Preferably by this way this carbonate source is joined in the composition, thereby it makes it possible to provide effervesce with acid-respons when contacting with water.

Hydrogen peroxide cource

Composition of the present invention contains hydrogen peroxide cource.Preferably supersalt, percarbonate for example, perborate, superphosphate, peroxide list persulphate and persilicate.This inorganic perhydrate salt generally is an alkali metal salt.Percarbonic acid, an alkali metal salt of peroxyboric acid, or its mixture is the preferred inorganic perhydrate salt that is used for the present invention.Preferred perborate is that chemical formula is respectively NaBO ₂H ₂O ₂And NaBO ₂H ₂O ₂.3H ₂The Sodium peroxoborate of the monohydrate of O or tetrahydrate form.Other suitable oxygen bleaching agent comprises persulphate, particularly Potassium Persulphate K ₂S ₂O ₈With Sodium Persulfate Na ₂S ₂O ₈

It is most preferred that an alkali metal salt of percarbonic acid, preferred SPC-D, it also forms above-mentioned carbonate source part.

By composition total weight, composition of the present invention generally contains the hydrogen peroxide cource of 5-50%, preferred 10%-45%, and more preferably 15%-35%, and even 17% or 19%-30% or 25%.

This supersalt can be used any coated material, preferably contains vitriol for example sal epsom or preferably sulfuric acid sodium, carbonate or supercarbonate, or its mixture applies.

Preferred supersalt and its preparation method are described in: for example, WO97/35951, WO96/14388, WO97/19890, WO94/02568, EP891417-A is among the EP681557A.

Bleach precursor

Particulate composition herein contains peroxyacid bleach precursor.Preferably, press composition weight meter, the amount that this peroxyacid bleach precursor exists is 2.5-10%, even 3-10%, and even 3.5-8%, so that 4-6%.

Peroxyacid bleach precursor is the compound that forms peroxy acid in crossing hydrolysis reaction with hydroperoxidation.Usually peroxyacid bleach precursor can be expressed as

Wherein L is a leavings group, and X is any functional group basically, causes the structure of the peroxy acid that produces when crossing hydrolysis to be

Suitable peroxyacid bleach precursor compound generally contains one or more N-or O-acyl group, and this precursor can be selected from broad variety.Suitable type comprises: the acyl derivative of acid anhydrides, ester, imide, lactan and imidazoles and oxime.The example of useful materials is disclosed among the GB-A-1586789 in these types.Suitable ester be disclosed in GB-A-836988,864798,1147871,2143231 and EP-A-0170386 in.

Leavings group, L group hereinafter must its reactivity be enough in the time period (for example wash(ing)cycle) in the best hydrolysis reaction take place., if the L reactivity is too strong, will be difficult to stablize for being used for this activator of bleaching composition so.

Preferred L group is selected from following these groups and its mixture:

R wherein ¹Be alkyl, aryl or the alkaryl that contains 1-14 carbon atom, R ³Be the alkyl chain that contains 1-8 carbon atom, R ⁴Be H or R ³, Y is H or solubilizing group.Any R ¹, R ³And R ⁴Basically can be replaced by any functional group, these functional groups comprise: for example alkyl, hydroxyl, alkoxyl group, halogen, amine, nitrosyl radical, acid amides and ammonium or alkyl ammonium group.

Preferred solubilizing group is-SO ₃ ^-M ⁺,-CO ₂ ^-M ⁺,-SO ₄ ^-M ⁺,-N ⁺(R ³) ₄X ^-And O＜--N (R ³) ₃, most preferably-SO ₃ ^-M ⁺With-CO ₂ ^-M ⁺, R wherein ³Be the alkyl chain that contains 1-4 carbon atom, M is the positively charged ion that solvability is offered this bleach-activating agent, and X is the negatively charged ion that solvability is offered this bleach-activating agent.Preferably, M is basic metal, ammonium or replacement ammonium cation, and sodium and potassium are most preferred, and X is halogenide, oxyhydroxide, methylsulfate or acetate anion.

The preferred example of compound is a tetra acetyl ethylene diamine like this; (TAED); 3; 5; 5-trimethyl acetyl oxygen base benzene sulfonic acid sodium salt; the pelargonamide of peroxide hexanodioic acid and positive nonanoly acyloxy benzene sulfonate (NOBS); the last of the ten Heavenly stems acyloxy benzene sulfonate; dodecanoyl oxygen base benzene sulfonate and ethanoyl trimethylammonium Citrate trianion (ATC); phenolsulfonate; N-nonanoyl-6-aminocaprolc acid ester has the aliphatics diacyl peroxy acid (DAP) of general formula R-C (O)-O-O-(O) C-R1, and wherein R and R1 can be the identical or different straight or branched aliphatic groups with 6-20 carbon atom.

Also particularly preferably be the N-acyl caprolactam; be selected from: replace or unsubstituted benzoyl caprolactam capryloyl hexanolactam, nonanoyl hexanolactam; the caproyl hexanolactam; the decanoyl hexanolactam, undecylene acyl caprolactam, formyl radical hexanolactam; the ethanoyl hexanolactam; the propionyl hexanolactam, butyryl radicals hexanolactam, pentanoyl hexanolactam.

The example of other suitable combination thing is disclosed in GB1586769, and GB2143231 is among US4818425 and the US4259201.

The alkyl peroxy acids precursor compound that acid amides replaces also is suitable, comprises those compounds with following general formula:

R wherein ¹Be alkyl with 1-14 carbon atom, R ²Be the alkylidene group that contains 1-14 carbon atom, R ⁵Be H or the alkyl that contains 1-10 carbon atom, L can be any leavings group basically, preferred oxidation Phenylsulfonic acid base (oxybenzene sulfonate).The bleach activating immunomodulator compounds that this class acid amides replaces is described among the EP-A-0170386.Nonanoyl amido caproyl Oxybenzene sulfonate, sodium-salt form preferably, NACA-OBS is such preferred precursor.

Very preferably bleach precursor is TAED among the present invention, NACA-OBS, DOBS and/or NOBS.Composition herein can contain the mixture of described bleach-activating agent, can cause improved spatter property because have been found that this.It is most preferred that TAED and be selected from NOBS, the mixture of DOBS or NACA-OBS precursor.Have been found that: when using such mixing precursor systems, particularly as TAED and NOBS, the ratio of DOBS or NACA-OBS is 1: 2-2:, reached further improved spatter property at 1 o'clock.

This precursor can be isolating detergent particles form, and it can be coated, or also contains the detergent particles form of other detergent active.Preferably exist to have with similar size distribution of other detergent particles and average size particles component form.

The inventor also finds: when this precursor and hydrogen peroxide cource closely mixing existence each other, be useful when for example being present in the particle.This mixture or particle preferably do not have organic acid basically.

Should understand: for purpose of the present invention, the peroxy acid that this precursor forms is not the part of present composition acid constituents.

Laundry and wash up method

Machine washing clothes washing method herein generally comprises in washing machine with dissolving therein or having disperseed the wash water solution of the machine detergent composition of the present invention of significant quantity to handle dirt clothes or tableware.Especially, imagined the laundry washing methods herein.For example, the laundry detergent composition of significant quantity generally is meant the product dissolving of 10-300g or is dispersed in the washing soln of 5-65 liter that this is normally used common product dosage and a washing soln volume in the machine washing clothes washing method of routine.Dosage depends on for example dirt degree of water hardness and dirty substrate of certain conditions.

At low temperature, be up to 60 ℃, and even be up to 45 ℃, so that under about 30 ℃ condition, in washing methods, preferably machine washing or when hand washing, be present in the reduction of the microorganism active on the dirty fabric of washing neutralization.

Detergent composition can distribute from the drawer divider of for example washing machine, perhaps can be sprinkling upon on the dirty substrate that is placed in the washing machine.

Aspect a use very preferably, in washing methods, use distribution device so that the present composition is introduced directly in the rotating cylinder of washing machine.Have been found that and reached improved spatter property.

Can use any distribution device, comprise that the preferred distribution device that uses with the present composition is disclosed in the following patent: GB-B-2157717, GB-B-2157718, EP-A-0201376, EP-A-0288345 and EP-A-0288346, WO94/11562.

Detergent composition

Composition of the present invention can be prepared into different bulk densities, 300-1200g/l preferably, preferred 500-1100g/l, and even 550-900g/l.These compositions are solids composition preferably, preferred solid laundry washing composition, and it can comprise doing and mix with various several different methods known in the art, spraying drying, extruding, roll-in, the combination of agglomeration and these methods prepares.This solids composition can be any type of, preferred granular or sheet or strips.

Can be preferably: said composition prepares by following step: mix all or part of particle, comprise those particles, thereby then add tackiness agent and mix or this particle of agglomeration and tackiness agent form preferred agglomerant detergent particles by the preparation of agglomeration or spraying drying.They can be needed particle diameters or their screenings are obtained needed particle diameter.

In highly preferred embodiment, acid or its a part of and carbonate source or its part are present in each other the intimate mixture (intimate mixture), preferably in particle,, this means the preferably mixing equably of this acid plus carbonate source for purpose of the present invention.For the best effervescent effect in water-bearing media, the acid in this intimate mixture or effervescent granule and the weight ratio of carbonate source be 0.1-10 preferably, preferred 0.5-2.5, more preferably 1-2.

By this particulate gross weight, the amount that this acid preferably is present in the above-mentioned particle is 5-85%, preferred 10-75%, more preferably 15-60%, most preferably 10-50%.

By this particulate gross weight, the amount that this carbonate source preferably is present in the above-mentioned particle is 5-90%, preferred 10-80%, more preferably 20-75%, most preferably 30-65%.

This particle does not preferably have water basically, does not promptly add entry or does not have the moisture of non-raw material itself.By this intimate mixture or particulate gross weight, water-content generally is lower than 5%, preferably is lower than 3%, more preferably less than 1.5%.

Can be preferably: in this intimate mixture or particle, exist siccative, the inorganic and organic salt of super-dry for example, the silicate of anhydrous salt, particularly super-dry and silico-aluminate, anhydrous silicate and/or vitriol.

This particle preferably obtains by following method, and this method comprises granulation step, preferably includes dry powder compacting or the agglomerant step of pressure.Although in the pressure agglomeration all adhesion mechanisms can take place, the bounding force between the solid particulate promptly should acid, the bounding force between carbonate source and the optional tackiness agent plays particularly important.This is because the pressure agglomeration, particularly the high pressure agglomeration be a kind of (promptly should acid by applying external force from solid particulate, supercarbonate, carbonate source and optional tackiness agent) form the method for exsiccant basically of novel entities (being the exsiccant effervescent granule), thereby increase the density that limits accumulation material or volume and between solid particulate, form adhesion mechanism by applying external force, intensity is provided for new entity, the high external force that promptly applies closely flocks together solid particulate.

This effervescent granule can randomly comprise tackiness agent or its mixture.By this particulate gross weight, this particle generally contains and is up to 50%, preferably is up to 35, more preferably is up to 20% tackiness agent or its mixture.Be used for herein suitable binder and be well known by persons skilled in the art those, comprise that anion surfactant is as C6-C20 alkyl or alkylaryl sulfonate or vitriol, preferred C8-C20 alkylbenzene sulfonate, derivatived cellulose is carboxymethyl cellulose for example, poly carboxylic acid or its salt with homopolymerization or copolymerization, nonionogenic tenside, preferred every mol of alcohol contains the C10-C20 alcohol ethoxylate of 5-100 moles of ethylene oxide, and more preferably every mol of alcohol contains the C15-C20 primary alcohol ethoxylate of 20-100 moles of ethylene oxide.In the middle of them, every mol of alcohol is preferred with the tallow alcohol of 25 moles of ethylene oxide (TAE25) or 50 moles of ethylene oxide (TAE50) ethoxylation.Other preferred adhesive comprises that polymeric material is that polyvinylpyrrolidone and the molecular-weight average of 12000-700000 is the polyoxyethylene glycol of 600-10000 as molecular-weight average.Maleic anhydride and ethene, ethylene methacrylic ether, methacrylic acid or acrylic acid multipolymer are other examples of polymeric tackiness agent.Other tackiness agent also comprises C10-C20 single and two glyceryl ethers and C10-C20 lipid acid.

This effervescent granule can have any particle diameter, and preferred particle diameter depends on this particulate purposes and component.

The inventor finds: this acid herein and this precursor and preferred any other bleaching components that exists comprise hydrogen peroxide cource, comprise that it is useful that percarbonate (if present) separates cleaning and cleaning performance.Therefore, above-mentioned effervescent granule does not preferably comprise percarbonate as carbonate source, but preferably contains carbonate and/or supercarbonate.

In preferred embodiments, said composition preferably contains such particle, wherein by weight, at least 60%, more preferably at least 80% has the median size of 400-1400 micron, the median size of more preferably 500-1100 micron, and even 750-1000 micron.Can be preferably: by the weight of grain fraction, said composition contains and is lower than 20%, and even is lower than 10%, is lower than 300 microns so that be lower than 5% particle diameter, and even is lower than 425 microns, so that be lower than 600 microns; Can also be preferably: by the weight of composition, said composition contains and is lower than 20%, and even is lower than 10%, so that be lower than 5% particle diameter greater than 1700 microns, and even greater than 1400 microns, so that greater than 1180 microns grain fraction.

Therefore, said composition can contain different grain fractions, and every kind of component has top particle diameter and requires and have similar size distribution and a median size.

The inventor finds: when said composition contains spices with high fabric substantivity (fabricsubstantivity) or perfume composition, reached improved spatter property.It is believed that this is owing to stay and be washed on the fabric face and provide thus due to the spice oil of spatter property between the follow-up usage period of fabric.

So preferred perfume particle of encapsulate (encapsulated) spice oil is described in the autre action pendante european patent application 98870137.1.The preferred content of perfume particle depends on the wherein amount of spice oil, but presses composition weight meter, and its content is generally about 0.05-8%, and even 0.5-5%, so that 0.8-3%.In addition, said composition preferably also contains the perfume composition of non-encapsulated fragrances oil particles form, but preferably is sprayed to the perfume composition form on the said composition detergent particles.

Composition herein preferably contains one or more additional detergent components, it is selected from: tensio-active agent, bleaching catalyst, additional washing assistant, additional organic polymer, enzyme, suds suppressor, lime soap dispersing agent, dirt suspends and anti redeposition agent, dirt release agent, whitening agent, optical white and additional corrosion inhibitor.

Should understand: the content of detergent component is chosen such that it makes the pH of composition of 1% (weight) in softening water for as defined above.For example, can be preferably: when using crystalline layered silicate or amorphous silicic salt, its content be up to 12% (weight), and even is up to 10% (weight).

Tensio-active agent

Detergent composition herein preferably contains one or more tensio-active agents.This tensio-active agent can comprise any tensio-active agent known in the art, and it is selected from: negatively charged ion, nonionic, positively charged ion, both sexes and zwitterionics and its mixture.

Be appreciated that for purpose of the present invention, this detergent composition can contain tensio-active agent, it is not present in the intimate mixture with crystalline layered silicate, but is present in other detergent component.

Anion surfactant

Composition of the present invention preferably contains anion surfactant.Basically anyly can be included in this detergent composition washing purpose useful anion surfactant.They can comprise: the salt of anion sulfate, sulfonate, carboxylate salt and sarcosinate surfactant (comprise, for example, sodium, potassium, ammonium and the ammonium salt that replaces be for example single-, two-and triethanolamine salt).Anion sulfate and sulfonate are preferred.

It is most preferred that and contain sulfonate and sulfate surfactant that preferably straight or branched alkylbenzene sulfonate and alkyl ethoxy sulfate as described herein are preferably with the surfactant system of cats product combination as described herein.

It is most preferred that the anion sulfoacid salt surfactant herein.Be used for that the present invention is specially suitable to be comprised: C ₅-C ₂₀The straight or branched alkylbenzene sulfonate, also have alkyl ester sulfonate, C ₆-C ₂₂Uncle or secondary paraffin sulfonate, C ₆-C ₂₄Alkene sulfonate, sulfonated poly carboxylic acid, alkyl glycerol sulfonate, fatty acyl group glycerol sulfonate, fatty oil acyl group (fattyoleyl) glycerol sulfonate and its any mixture.C most preferably ₉-C ₁₄Linear alkylbenzene sulfonate.

Be applicable to that anion sulfate tensio-active agent herein comprises: the uncle of straight or branched or secondary alkyl sulfate, alkyl ethoxy sulfate, fatty oil acylglycerol vitriol, alkyl phenol epoxy ethane ether salt, C ₅-C ₁₇Acyl group-N-(C ₁-C ₄Alkyl) and-N-(C ₁-C ₂Hydroxyalkyl) vitriol of glucosamine sulfate and the alkyl polysaccharide vitriol of alkyl polyglucoside (compound of described herein nonionic non-sulfuric acidization) for example.

Alkyl sulfate surfactant is preferably selected from the uncle C of straight chain and side chain ₁₀-C ₁₈Alkyl-sulphate, more preferably side chain C ₁₁-C ₁₅Alkyl-sulphate and straight chain C ₁₂-C ₁₄Alkyl-sulphate.

Alkyl ethoxy sulfate surfactant is preferably selected from the C of per molecule with the ethoxylation of 0.5-20 moles of ethylene oxide ₁₀-C ₁₈Alkyl-sulphate.More preferably, this alkyl ethoxy sulfate surfactant is a per molecule 0.5-7 mole, the C of preferred 1-5 moles of ethylene oxide ethoxylation ₁₁-C ₁₈, C most preferably ₁₁-C ₁₅Alkyl-sulphate.

The present invention uses particularly preferred aspect the mixture of preferred alkyl-sulphate and/or sulfonate and alkyl ethoxy sulfate surfactant.Such mixture is disclosed among the PCT patent application WO93/18124.

Herein very preferably, particularly for improved surfactant properties is provided, be the alkyl chain of following formula, medium chain branched chain surfactant compound:

Wherein the total number of carbon atoms in this formula branched primary alkyl moiety part (comprises R, R ¹And R ²Side chain) is 13-19, R, R ¹And R ²Be selected from hydrogen and C independently of one another ₁-C ₃Alkyl (preferable methyl), condition is R, R ¹And R ²Not hydrogen and when z is 0 entirely, R or R at least ¹Not hydrogen; W is the integer of 0-13; X is the integer of 0-13; Y is the integer of 0-13; Z is the integer of 0-13; With w+x+y+z be 7-13.

The most preferred medium chain branched chain surfactant compound that is used for this paper detergent composition is medium chain branched primary alkyl moiety sulfonate, more preferably sulfate surfactant.Should understand: for purpose of the present invention, preferably this surfactant system contains the mixture of two or more medium chain chain primary alkyl sulfates or sulfosalt surfactant.

Preferred medium chain chain primary alkyl sulfate tensio-active agent is the compound of following formula:

These tensio-active agents have linear primary alkyl-sulphate chain main chain (promptly the longest straight chain carbochain, it comprises Sulfated carbon atom), it preferably has 12-19 carbon atom and its branched primary alkyl moiety part preferably contains sum at least 14 and preferably is not more than 20 carbon atoms.In the surfactant system that contains more than a kind of these sulfate surfactants, average the total number of carbon atoms of branched primary alkyl moiety part is preferably in about 17.5 the scope greater than 14.5-.Therefore, this surfactant system preferably contains at least a chain primary alkyl sulfate surfactant compounds, it has the long linear carbochain that is no less than 12 carbon atoms or no more than 19 carbon atoms, with the total number of carbon atoms that comprises side chain must be at least 14, and further, average the total number of carbon atoms of branched primary alkyl moiety part is in about 17.5 the scope greater than 14.5-.

R, R ¹And R ²Be selected from hydrogen and C independently of one another ₁-C ₃Alkyl (preferred hydrogen or C ₁-C ₂Alkyl, more preferably hydrogen or methyl, and most preferable), condition is R, R ¹And R ²Not hydrogen entirely.In addition, when z is 1, R or R at least ¹Not hydrogen.

Preferred list-methyl branch primary alkyl sulphates is selected from: 3-methyl pentadecylic alcohol vitriol, 4-methyl pentadecylic alcohol vitriol, 5-methyl pentadecylic alcohol vitriol, 6-methyl pentadecylic alcohol vitriol, 7-methyl pentadecylic alcohol vitriol, 8-methyl pentadecylic alcohol vitriol, 9-methyl pentadecylic alcohol vitriol, 10-methyl pentadecylic alcohol vitriol, 11-methyl pentadecylic alcohol vitriol, 12-methyl pentadecylic alcohol vitriol, 13-methyl pentadecylic alcohol vitriol, 3-methyl cetyl alcohol sulfate, 4-methyl cetyl alcohol sulfate, 5-methyl cetyl alcohol sulfate, 6-methyl cetyl alcohol sulfate, 7-methyl cetyl alcohol sulfate, 8-methyl cetyl alcohol sulfate, 9-methyl cetyl alcohol sulfate, 10-methyl cetyl alcohol sulfate, 11-methyl cetyl alcohol sulfate, 12-methyl cetyl alcohol sulfate, 13-methyl cetyl alcohol sulfate, 14-methyl cetyl alcohol sulfate and its mixture.

Preferred two-methyl branch primary alkyl sulphates is selected from: 2, and 3-methyl tetradecanol vitriol, 2,4-methyl tetradecanol vitriol, 2,5-methyl tetradecanol vitriol, 2,6-methyl tetradecanol vitriol, 2,7-methyl tetradecanol vitriol, 2,8-methyl tetradecanol vitriol, 2,9-methyl tetradecanol vitriol, 2,10-methyl tetradecanol vitriol, 2,11-methyl tetradecanol vitriol, 2,12-methyl tetradecanol vitriol, 2,3-methyl pentadecylic alcohol vitriol, 2,4-methyl pentadecylic alcohol vitriol, 2,5-methyl pentadecylic alcohol vitriol, 2,6-methyl pentadecylic alcohol vitriol, 2,7-methyl pentadecylic alcohol vitriol, 2,8-methyl pentadecylic alcohol vitriol, 2,9-methyl pentadecylic alcohol vitriol, 2,10-methyl pentadecylic alcohol vitriol, 2,11-methyl pentadecylic alcohol vitriol, 2,12-methyl pentadecylic alcohol vitriol, 2,13-methyl pentadecylic alcohol vitriol and their mixture.

Oxyalkylated nonionogenic tenside

Basically any oxyalkylated nonionogenic tenside all is suitable among the present invention.Ethoxylation and propenoxylated nonionogenic tenside are preferred.

The tensio-active agent of preferred alkoxylated can be selected from: the nonionic condenses of alkylphenol, the alcohol of nonionic ethoxylation, the Fatty Alcohol(C12-C14 and C12-C18) of nonionic ethoxylated/propoxylated, the condensation product of the polycondensate of nonionic ethoxylate/propoxylated glycerine and propylene glycol and nonionic ethoxylate and propylene oxide/ethylenediamine adduct.

Nonionogenic tenside may reside in the detergent composition.Can be preferably: by this mixture weight, the amount of ethoxylated non-ionic surface active agent in this intimate mixture be lower than 10%, preferably is lower than 5%.

The condensation product of Fatty Alcohol(C12-C14 and C12-C18) and 1-25 mole alkylene oxide, particularly oxyethane and/or propylene oxide be applicable to of the present invention.The alkyl chain of this Fatty Alcohol(C12-C14 and C12-C18) is a straight or branched, the uncle or the second month in a season, and contain 6-22 carbon atom usually.Particularly preferably be and have the alcohol that contains 8-20 carbon atom alkyl and the condensation product of every mol of alcohol 2-10 moles of ethylene oxide.

Cats product

The suitable cationic surfactants that is used for herein comprises quaternary surfactant.Preferred quaternary surfactant is single C ₆-C ₁₆, preferred C ₈-C ₁₄N-alkyl or alkenyl ammonium surfactant, wherein remaining N position is replaced by methyl, hydroxyethyl or hydroxypropyl.The amine tensio-active agent of monoalkoxyization and bis-alkoxyization further preferably.

The another kind of suitable cationic surfactants that can be used for this paper detergent composition or component is the cationic ester tensio-active agent.This cationic ester tensio-active agent is, preferably water is dispersible, has surfactant properties and comprises at least one ester (compound of key and at least one positively charged ion charged group promptly-COO-).

For example, suitable cationic ester tensio-active agent comprises the cholinesterase tensio-active agent, is for example disclosing among USP 4228024, USP 4239660 and the USP 4260529.

Bleaching catalyst

Composition herein can contain the bleaching catalyst of transition metal.

The bleaching catalyst that one class is suitable is disclosed among the USP 4430243.

The bleaching catalyst of other type comprises the manganese basigamy compound that is disclosed among USP 5246621 and the USP 5244594.The preferred example of these catalyzer comprises: Mn ^IV ₂(u-O) ₃(1,4,7-trimethylammonium-1,4,7-7-triazacyclononane) ₂-(PF ₆) ₂, Mn ^III ₂(u-O) ₁(u-OAc) ₂(1,4,7-trimethylammonium-1,4,7-7-triazacyclononane) ₂-(ClO ₄) ₂, Mn ^IV ₄(u-O) ₆(1,4, the 7-7-triazacyclononane) ₄-(ClO ₄) ₄, Mn ^IIIMn ^IV ₄(u-O) ₁(u-OAc) ₂(1,4,7-trimethylammonium-1,4,7-7-triazacyclononane) ₂-(ClO ₄) ₃, and its mixture.Being described in the European patent application published numbers 549272 of other.Be applicable to that other ligand herein comprises: 1,5,9-trimethylammonium-1,5,9-triazododecane, 2-methyl isophthalic acid, 4,7-7-triazacyclononane, 1,2,4,7-tetramethyl--1,4,7-7-triazacyclononane and its mixture.

Also can select useful bleaching catalyst as the suitable component of the present invention herein.The example of suitable bleaching catalyst is seen USP 4246612 and USP 5227084.Referring to USP5194416, it discloses for example Mn (1,4,7-trimethylammonium-1,4,7-7-triazacyclononane) (OCH of monokaryon manganese (IV) title complex ₃) ₃(PF ₆).

Another kind of bleaching catalyst, disclosed as USP 5114606, be manganese (III) and/or (IV) and water-soluble complexes with non-carboxylate salt polyol ligand of at least 3 consecutive C-OH groups.Preferred ligand comprises: sorbyl alcohol, iditol, dulsitol, mannitol, Xylitol, arabitol, admitol (adonitol), meso tetrahydroxybutane, meso-inositol, lactose and its mixture.

USP 5114611 discloses a kind of bleaching catalyst, and it contains the title complex that transition metal comprises Mn, Co, Fe or Cu and non--(greatly)-ring ligand.Described ligand is the following formula material:

R wherein ¹, R ², R ³And R ⁴Can be selected from H independently of one another, the alkyl of replacement and aryl make each R ¹-N=C-R ²And R ³-C=N-R ⁴Form 5 or 6 Yuans rings.Described ring can further be substituted.B is that abutment is selected from O, S, CR ⁵R ⁶, NR ⁷And C=O, wherein R ⁵, R ⁶And R ⁷Can be H independently of one another, alkyl or aryl comprises replacement or unsubstituted group.Preferred ligand comprises: pyridine, pyridazine, pyrimidine, pyrazine, imidazoles, pyrazoles and triazole ring.Randomly, described ring can be with substituting group alkyl for example, aryl, and alkoxyl group, halogen and nitro replace.Particularly preferably be part 2,2 '-two pyridyl amine.Preferred bleaching catalyst comprises Co, Cu, Mn, Fe ,-two pyridyl methane and-two pyridyl amine complexes.Catalyzer very preferably comprises Co (2,2 '-two pyridyl) Cl ₂, two (isocyanide sulfenyl) two pyridyl amine-cobalts (II), three (bipyridyl amine)-cobalt (II) perchlorate, Co (2, the two pyridyl amine of 2-) ₂O ₂ClO ₄, two (2,2 '-two pyridyl amine) copper (II) perchlorate, three (two-2-pyridyl amine) iron (II) perchlorate) and its mixture.

Other example comprises the double-core Mn title complex with four-N-dentate and two-N-dentate, comprises N ₄Mn ^III(u-O) ₂Mn ^IVN ₄) ⁺[Bipy ₂Mn ^III(u-O) ₂Mn ^IVBipy ₂]-(ClO ₄) ₃

Other suitable bleaching catalyst is described in: European patent application publication No. 408131 (cobalt complex catalyzer) for example, European patent application publication No. 384503 and 306089 (catalysis of metalloporphyrin agent), U54728455 (manganese/polygamy position polymerization of olefin using catalyst body catalyst), US4711748 and European patent application publication No. 224952 (manganese is adsorbed on catalyzer on the silico-aluminate), US4601845 (aluminosilicate carrier) with manganese and zinc or magnesium salts, US4626373 (manganese/ligand catalyst), US4119557 (high ferro composition catalyst), German Patent 2054019 (cobalt sequestrant catalyzer), Canadian patent application 866191 (containing transition metal salt), among US4430243 (sequestrant) and the US4728455 (manganese gluconate catalyzer) with manganese positively charged ion and on-catalytic metallic cation.

The washing assistant material

Except the organic carboxyl acid that can play the washing assistant effect with play the carbonate of washing assistant effect, detergent composition of the present invention preferably also contains additional water-soluble and/or water-insoluble washing assistant material.Preferably silicate, silico-aluminate, crystalline layered silicate and phosphoric acid salt.

For example, said composition can contain phosphatic washing assistant material, preferably contains tetrasodium pyrophosphate, more preferably anhydrous sodium tripolyphosphate, and the amount of its existence is 0.5-60%, more preferably 5-50%, most preferably 8-40%.

Suitable water soluble detergency promoter compound comprises water-soluble (many) carboxylate salts and borate.Carboxylate salt or multi-carboxy acid salt washing agent can be monomer or oligomeric, although owing to the reason monomer multi-carboxylate of cost and performance is normally preferred.

Can be preferably: press composition weight meter, should (many) carboxylate salts and/or the amount of polymeric or the existence of oligomeric (many) carboxylate salts be lower than 5%, preferably be lower than 3%, and even be lower than 2%, down to 0%.

Basically the example of insoluble washing assistant comprises sodium silicoaluminate.Suitable aluminosilicate zeolite has structure cell formula Na _z[(AlO ₂) _z(SiO ₂) _y] .xH ₂O, wherein z and y are at least 6, and the mol ratio of z and y is 1.0-0.5, and x is at least 5, preferred 7.5-276, more preferably 10-264.This alumino-silicate materials be hydrated form and crystalline preferably, contain 10-28%, more preferably the water of the bonding scheme of 18-22%.

This aluminosilicate zeolite can be naturally occurring material, but preferably synthetic obtaining.Synthetic crystal aluminosilicate ion-exchange material can title zeolite A, zeolite B, zeolite P, X zeolite, zeolite HS and its mixture obtain.Zeolite A has following formula:

Na ₁₂[AlO ₂) ₁₂(SiO ₂) ₁₂].xH ₂O

Wherein x is 20-30, particularly 27.X zeolite has formula Na ₈₆[(AiO ₂) ₈₆(SiO ₂) ₁₀₆] .276H ₂O.

Another preferred aluminosilicate zeolite is a zeolite MAP builder.Zeolite MAP is described among the EP384070A (Unilever).It is defined as having silica alumina ratio and is not more than 1.33, preferably in the 0.9-1.33 scope and the more preferably zeolite P type alkali metal aluminosilicate in the 0.9-1.2 scope.

Composition herein also can contain additional silicate material, comprises the amorphous silicic salt material, and metasilicate preferably is the material that the crystalline layered silicate material is for example sold with trade(brand)name SKS-6 at least.Press composition weight meter, the amount that this silicate material preferably exists is to be lower than 20%, preferably is lower than 15%, and even is lower than 10%.

Heavy metal ion chelating agent

Heavy metal ion chelating agent also is useful herein annexing ingredient.Referred to the component of sequester (chelating) heavy metal ion effect herein about " heavy metal ion chelating agent ".These components also can have calcium and magnesium sequestering power, but preferably they demonstrate for example selectivity of iron, manganese and copper of bonding heavy metal.

In the weight of composition, heavy metal ion chelating agent is usually with 0.005-10%, preferred 0.1-5%, and more preferably 0.25-7.5%, most preferably the amount of 0.5-2% exists.

The suitable heavy metal ion chelating agent that is used for herein comprises: organic phosphonate is poly-(alkylene phosphonic acids salt), basic metal ethane 1-hydroxyl diphosphonate of amino alkylidenyl, nitrilo trimethylene phosphonic salt for example.

Preferably diethylenetriamine five (methylene phosphonic acid salt), quadrol three (methylene phosphonic acid salt), hexamethylene-diamine four (methylene phosphonic acid salt) and hydroxy ethylene 1 in the above-mentioned substance, 1 diphosphonate, 1,1 hydroxyl ethane di 2 ethylhexyl phosphonic acid and 1,1 hydroxyl ethane dimethylene phosphonic acids.

Other the suitable heavy metal ion chelating agent that is used for herein comprises: nitrilotriacetic acid(NTA) and polyamino carboxylic acid be the amino tetraacethyl of ethylene, ethylenediamine disuccinic acid, ethylene diamine two valeric acids, 2-hydroxy propylidene diamines disuccinic acid for example, or its any salt.

The iminodiacetic acid derivatives that is used for herein other suitable heavy metal ion chelating agent and is being described in EP-A-317542 and EP-A-399133 is 2-hydroxyethyl oxalic acid or glyceryl iminodiethanoic acid for example.Iminodiethanoic acid-N-2-hydroxypropyl the sulfonic acid and the aspartic acid N-carboxymethyl N-2-hydroxypropyl-3-sulfonic acid sequestrant that are described among the EP-A-516102 also are suitable for herein.Be described in the β-An Jibingsuan-N among the EP-A-509382, N '-oxalic acid, aspartic acid-N, single acetate of N '-oxalic acid, aspartic acid-N-and imino-diacetic succsinic acid sequestrant also are suitable.

EP-A-476257 has described the suitable sequestrant based on amino.EP-A-510331 has described from collagen protein, Keratin sulfate or casein derived suitable sequestrant.EP-A-528859 has described suitable alkyl imino oxalic acid sequestrant.Two pyridine carboxylic acids and 2-phosphinylidyne butane-1,2,4-tricarboxylic acid also are suitable.G-NH2-N, N '-disuccinic acid (GADS), quadrol-N, N '-two pentanedioic acid (EDDG) and 2-hydroxyl propylene diamine-N, N '-disuccinic acid (HPDDS) also is suitable.

Particularly preferably be diethylene triaminepentaacetic acid(DTPA), quadrol-N, N '-disuccinic acid (EDDS) and 1,1-hydroxyl ethane di 2 ethylhexyl phosphonic acid or its basic metal, alkaline-earth metal, ammonium or substituted ammonium salt, or its mixture.

Enzyme

Another useful herein preferred ingredient is one or more additional enzymes.

Preferred additional enzyme material comprises the lipase the detergent composition of being routinely added to that can buy from market, at, amylase, neutrality and Sumizyme MP, cellulase, endoenzyme, esterase, polygalacturonase, Sumylact L and peroxidase.Suitable enzyme has been discussed in USP3519570 and USP3533139.

Preferably the proteolytic enzyme that can buy from market comprises by Novo Industries A/S (Denmark) with trade(brand)name Alcalase, Savinase, Primase, those enzymes that Durazym and Esperase sell, by Gist-Brocades with trade(brand)name Maxatase, those enzymes that Maxacal and Maxapem sell are by those enzymes of Genencor International sale and those enzymes of being sold with trade(brand)name Opticlean and Optimase by Solvay Enzymes.Proteolytic enzyme can be joined in the composition of the present invention, press composition weight meter, its amount is the 0.0001-4% organized enzyme.

Additional organic polyhydroxyl compound

The additional organic polyhydroxyl compound of non-carboxylic acid is the preferred annexing ingredient of composition or agglomerate herein herein, and here they can play a part such as the agglomerate component is bonded together.

About " organic polyhydroxyl compound ", refer to herein and in detergent composition, be used as tackiness agent basically usually, dispersion agent, any organic polyhydroxyl compound of antiredeposition and soil-suspending agent, comprise herein that as the described any high molecular organic polyhydroxyl compound of clay flocculating agent (gathering) the amine clay soil removal/anti that comprises quaternized ethoxylation among the present invention is deposition agent again.

Press composition weight meter, organic polyhydroxyl compound is generally with 0.01-30%, preferred 0.1-15%, and most preferably the amount of 0.5-10% joins in the detergent composition of the present invention.

The organic polyhydroxyl compound that is suitable for adding in this paper detergent composition comprises derivatived cellulose for example methylcellulose gum, Xylo-Mucine, Vltra tears and Natvosol.The carboxymethyl cellulose that also has the acid amides modification very preferably and the Mierocrystalline cellulose of acid amides modification, or derivatives thereof.

Other useful organic polyhydroxyl compound is a polyoxyethylene glycol, particularly molecular weight 1000-10000, more preferably 2000-8000, most preferably from about those polyoxyethylene glycol of 4000.

The suds suppressor system

Detergent composition of the present invention can contain the suds suppressor system when being mixed with the composition that is used to machine-wash, press composition weight meter, and its amount is 0.01-15%, preferred 0.02-10%, most preferably 0.05-3%.

The suitable suds suppressor system that is used for herein can comprise any basically known anti-foam compound, comprising: for example anti-foam compound of siloxanes and 2-alkyl chain triacontanol (2-alkylalcanol) are prevented the foam compound.

The clay softening agent

Composition herein can be the washing composition that soft effect is provided by washing.Preferably said composition contains the clay softening agent, and preferably also contains flocculation agent.

The object lesson of suitable smectic clays (smectite clays) comprises and is selected from montmorillonite, hectorite, volchonskoites, nontronite (nontronites), those materials of talcum powder and sauconites particularly have those materials of basic metal or alkaline-earth metal ions in crystalline network.Sodium or Ca-montmorillonite are particularly preferred.POLARGEL NF preferably.

Preferably conduct clay flocculating agent herein is that molecular-weight average is 100000-10000000, preferred 150000-5000000, the more preferably organic polymer materials of 200000-2000000.

Suitable organic polymer materials comprises homopolymer or multipolymer, and it contains and is selected from following monomeric unit: alkylene oxide, particularly oxyethane, acrylamide, vinylformic acid, vinyl alcohol, vinyl pyrrolidone, and azacyclopropane.Especially, oxyethane and acrylamide and acrylic acid homopolymer are preferred.

European patent EP-A-299575 and EP-A-313146 (Procter and GambleCompany) have described the preferred organic polymer clay flocculating agent that is used for herein.

Other optional components

Other the optional components that is suitable for being included in the present composition comprises: the spices of the encapsulate that spices is for example above-mentioned, and whitening agent, colored small-particle comprises pigment and dyestuff, filling salt, sodium sulfate are preferred filling salts.

In addition, the neutralization reagent that also can have a small amount of (for example being lower than about 20% weight), additional buffer reagent, phase modifier, hydrotropic agent, enzyme stabilizers, polyacid, foaming regulator, opalizer, antioxidant, sterilant and dyestuff, those described in the USP4285841 (document is incorporated herein through quoting) that issues in 25 days Augusts in 1981 of people such as Barrat.

The dummy suffix notation that uses among the embodiment

LAS: straight chain C _11-13Sodium alkyl benzene sulfonate

TAS: tallow alkyl sodium sulfate

CxyAS: C _1x-C _1ySodium alkyl sulfate

C46SAS: C ₁₄-C ₁₆Secondary (2,3) sodium alkyl sulfate

CxyEzS: with the C of z moles of ethylene oxide condensation _1x-C _1ySodium alkyl sulfate

CxyEz: with the C of z moles of ethylene oxide condensation _1x-C _1yBasically the primary alconol of straight chain

QAS ：R ₂·N ⁺(CH ₃) ₂(C ₂H ₄OH)，R ₁＝C ₁₂-C ₁₄

QAS ：R ₂·N ⁺(CH ₃) ₂(C ₂H ₄OH)，R ₁＝C ₈-C ₁₁

Soap: the straight-chain alkyl carboxylic acid who obtains from 80/20 tallow and coconut oil blend

Sodium

STS: toluenesulfonic acid sodium salt

STPP: anhydrous sodium tripolyphosphate

Zeolite A: formula Na ₁₂(AlO ₂SiO ₂) ₁₂.27H ₂The primary particle diameter of O is that 0.1-10 is little

The hydrated sodium aluminosilicate (representing weight) of rice by moisture-free basis

NaSKS-6: median size is 25 microns formula d-Na ₂Si ₂O ₅Crystalline layered silicon

Hydrochlorate

Carbonate: anhydrous sodium carbonate

Supercarbonate: anhydrous sodium bicarbonate

Silicate: amorphous silicic sodium (SiO ₂: Na ₂O is than=2.0: 1)

Vitriol: anhydrous sodium sulphate

Sal epsom: anhydrous magnesium sulfate

Citrate trianion: citrate trisodium dihydrate

MA/AA: toxilic acid/acrylic copolymer of 1: 4, weight-average molecular weight about 70000

AA: weight-average molecular weight is 4500 polyacrylic acid sodium polymer

CMC: Xylo-Mucine

Ether of cellulose: the polymerization degree that obtains from Shin Etsu Chemicals is 650 first

The base ether of cellulose

Proteolytic enzyme: sell with trade(brand)name Savinase by NOVO Industries A/S

Decomposition of protein enzyme with 3.3% weight organized enzyme, or as WO

Described in 95/10591, sell by Genencor Int.Inc.

Decomposition of protein enzyme with 4% weight organized enzyme

Amylase: by NOVO Industries A/S with trade(brand)name Termamyl 120T

The amylolytic enzyme of selling with 1.6% weight organized enzyme

Lipase: sell with trade(brand)name Lipolase by NOVO Industries A/S

Lipolytic enzyme with 2.0% weight organized enzyme, or by NOVO

Industries A/S sells with trade(brand)name Lipolase Ultra

Lipolytic enzyme with 2.0% weight organized enzyme

PB4: contain nominal formula (nominal formula) and be NaBO ₂.3H ₂O

The particle of sodium perborate tetrahydrate, its weight average particle diameter (weight

Average particle size) be 950 microns, 85% particle

Particle diameter is the 850-950 micron

PB1: containing nominal formula is NaBO ₂.H ₂O ₂The anhydrous sodium perborate SYNTHETIC OPTICAL WHITNER

Particle, its weight average particle diameter is 800 microns, 85% grain diameter

Be the 750-950 micron

Percarbonate: containing nominal formula is 2Na ₂CO ₃.3H ₂O ₂SPC-D

Grain, its weight average particle diameter is the 550-850 micron, 5% or lower

The grain particle diameter be lower than 300 microns and 7% or lower grain diameter greater than

1180 microns

NOBS: contain the particle of sodium-salt form nonanoly acyloxy benzene sulfonate, its weight average grain

The footpath is the 550-900 micron

NAC-OBS: contain the particle of (6-nonanoyl amido caproyl) oxygen base benzene sulfonate, its

Weight average particle diameter is the 550-900 micron

TAED1: contain the particle of tetra acetyl ethylene diamine, its weight average particle diameter is 550-900

Micron

DTPA: diethylene triaminepentaacetic acid(DTPA)

DTPMP: by the two inferior second of Monsanto with trade(brand)name Dequest 2060 sale

Base triamine five (methylene phosphonic acid salt)

Photoactivation: be encapsulated in the sulfonated zinc in SYNTHETIC OPTICAL WHITNER (1) the soluble dextrins polymkeric substance

Phthalocyanine

Photoactivation: be encapsulated in the sulfonated aluminium in SYNTHETIC OPTICAL WHITNER (2) the soluble dextrins polymkeric substance

Phthalocyanine (alumino phthlocyanine)

Whitening agent: 4,4 '-two (2-sulfo group styryl) biphenyl disodium, or 4,4 '-two [(4-

Anilino-6-morpholino-1,3,5-triazines-2-yl) amino] stilbene-2,2 '-

The disulfonic acid disodium

EDDS: quadrol-N, N '-disuccinic acid sodium, [S, S] isomer

HEDP: 1,1-hydroxyl ethane di 2 ethylhexyl phosphonic acid

PEGx: molecular-weight average is the polyoxyethylene glycol of x (being generally 4000)

PEO: molecular-weight average is 50000 polyethylene oxide

TEPAE: tetren ethoxylate

PVI: molecular-weight average is 20000 polyethylene pyrroles (Polyvinyl

imidosole)

PVP: molecular-weight average is 60000 polyvinylpyrrolidone

PVNO: molecular-weight average is 50000 polyvinyl pyridine N oxide polymer

PVPVI: molecular-weight average is 20000 polyvinylpyrrolidone and vinyl miaow

The multipolymer of azoles

QEA: two ((C ₂H ₅O) (C ₂H ₄O) _n) (CH ₃)- ^N+- _C6H ₁₂-N ⁺-(CH ₃) two

((C ₂H ₅O)-(C ₂H ₄O)) _n, wherein=20-30

SRP: the end capped polyester of negatively charged ion

Siloxanes is anti-: the siloxanes oxyalkylene copolymers is as the polydimethylsiloxane of dispersion agent

Foam agent or press down Foam Control, described Foam Control and described dispersion agent it

The infusion ratio is 10: 1-100: 1

In the following embodiments, all content are all represented with the weight % of composition.

Table 1

Following composition is according to composition of the present invention, and is about 9.4-9.85 with the pH in washings that defined method is herein measured.

	A	B	C	D	E	F	G	H	I	J	K
												Spraying drying Particle
LAS	8.0	10.0	15.0	5.0	5.0	10.0	-	-	-
												TAS	-	1.0	-	0.5	0.5		-	-	-
MBAS	4.0	-		5.0	-		-	-	-
												C 45AS	-	-	1.0		5.0	2.0	-	-	-
C 45AE 3S	-	-		1.0	1.0		-	-	-
												QAS			1.0	1.0	1.0	1.0	-	-	-
DTPA, HEDP and/or EDDS	0.3	0.3	0.5	0.3	0.4	-	-	-	-
												MgSO4	0.5	0.5	0.1	0.1	0.1		-	-	-
Yellow soda ash	3.0	7.0	5.0	4.0	-	3.0	-	-	-
												Sodium sulfate	-	-	-	-	5.0	3.0	-	-	-
Water glass 1.6R	-	-	-	0.3	2.0		-	-	-
												STPP	-	-	-	-	-	16.0
Zeolite A	16. 0	18.0	20.0	20. 0	10. 0	-	-	-	-
												SKS-6	8.0	-	-		5.0	-	-	-	-
MA/AA or AA	1.0	2.0	-	-	-	2.0	-	-	-
												PEG4000	-	2.0	-		-	1.0	-	-	-

QEA	1.0	-	-	1.0	1.0	-	-	-	-
												Whitening agent	0.0 5	0.05	0.05	-	0.0 5	-	-	-	-
Silicone oil	0.0 1	0.01	0.01	-	-	0.01	-	-	-
												Agglomerate
TAS								0.5	0.5	-	0.8
												LAS	3.0		-	-	-	-	6.0	2.0	8.0	-	-
MBAS			-	-	-	-	2.0	-	1.0	14.0	8.0
												C 45AS			-	-	-	-	-	4.0	-	-	4.0
C45AE 3			-	-	-	-	1.0	1.0	0.5	-	1.0
												Carbonate	1.0		-	-	-	-	6.0	7.0	5.0	-	3.0
Trisodium Citrate	2.0		-	-	-	-	-	-	5.0
												Citric acid	2.0		-	-	-	-	-	-	-	9.0	-
QEA			-	-	-	-	2.0	1.0	-	1.0	-
												SRP			-	-	-	-	1.0	0.2	-	-	-
Zeolite A	2.0		-	-	-		20. 0	15. 0	18. 0	15.0	25.0
												Water glass			-	-	-	-	-	0.5	0.5	-	-
PEG	-	-	-	-	-	-	2.0	-	-	-	-
												MA/AA or AA	-	-	-	-	-	-	3.0	4.0	1.0	1.0	0.8
Washing assistant Agglomerate
												SKS-6	6.0	-	-	-	-	3.0	-	7.0	-	-	-
LAS	4.0	-	-	-	-	3.0	-	6.0	-	-	-

Dried adding Grain fraction
												Carbonate/citric acid is 1: 1: 1 a effervescent granule	10. 0	15.0	15.0	-	-	12.0	2.0	-	15. 0	12.0
Sodium bicarbonate	-	-	4.0	2.0	4.0	2.0	7.0	8.0	3.0	4.0	5.0
												Yellow soda ash	3.0	-	2.0	2.0	-	-	-	-	-	5.0
NOBS	3.0	3.0	4.5	-	-	-	-	-	5.0	-	-
												TAED	2.5	2.0	-	6.0	3.0	5.0	-	4.5	-	5.0	-
NACA-OBS	-	-	-	-	2.5	-	-	-	-		4.5
												Citric acid	5.0	5.0	3.0	-	8.0	-	10. 0	7.0	-	7.0	10.0
Toxilic acid	-	-	-	10. 0		10.0
												Citrate trianion	-	-	-	-	-	-	3.0	-	-	-	2.0
Percarbonate	15. 0	6.0	6.0	20. 0	-	-	14. 0	18. 0	20. 0	10.0	16.0
												PB1 and/or PB4	-	6.0	-	-	10. 0	18.0	-	-	-
Optical white	0.0 2	0.02	0.02	0.1	0.0 5	-	0.3	-	0.0 3

Enzyme (amylase, proteolytic enzyme, lipase)	1.3	-	0.5	0.2	0.8	2.0	0.8	1.0	0.2	0.7	-
												Spices (encapsulate)	-	0.5	0.5	-	0.3	0.8	0.2	0.5	-	1.0	2.0
Suds suppressor	1.0	0.6	0.3	-	0.1 0	0.5	1.0	0.3	1.2	0.5	0.9
												Soap	0.5	0.2	0.3	3.0	0.5	-	-	0.3	-	-	-
SKS-6	-	-	-	4.0	-	-	-	6.0	-	-	-
												POLARGEL NF	-	-	-	-	8.0	-	-	-	10. 0	-	-
Painted carbonate (blueness, green)	0.5	0.5	1.0	2.0	-	0.5	0.5	0.5	1.0	1.0	-
												In the spraying
Whitening agent	0.2	0.2	0.3	0.1	0.2	0.1	-	0.6	0.3
												Dyestuff	-	-	-	0.3	0.0 5	0.1	-	-	-
C25AE5	-	-	-	-	-	0.5	-	0.7	-
												Spices	1.0	0.5	1.1	0.8	0.3	0.5	0.3	0.5	0.8	0.5	1.0
Total amount to 100%

Claims (12)

1. do washing or the dishwashing detergent composition for one kind, it contains bleach system, this bleach system contains the hydrogen peroxide cource of 5-50% weight, it is selected from percarbonate, perborate, superphosphate, peroxide list persulphate and persilicate, with at least two kinds of peroxyacid bleach precursors of 2.5%-10% weight, wherein a kind of described peroxyacid bleach precursor is TAED, and second kind of peroxyacid bleach precursor is NOBS, DOBS or NACA-OBS; The carbonate source of at least 15% weight, it is selected from basic metal or alkaline earth metal carbonate, alkali metal percarbonate and basic metal or alkali metal bicarbonates; The acid of 7%-30% weight; Wherein the said composition pH that stirs the mixture of 1% weight that obtains after 10 minutes under the speed at 200rpm provide in 20 ℃ of softening waters is 8.8-9.9, and the ratio of TAED and second kind of bleach precursor is 1: 2 to 2: 1.

2. according to the composition of claim 1, wherein said acid is organic acid, described carbonate source contains the basic metal or the alkaline earth metal carbonate of at least 5% weight, the basic metal or the alkali metal bicarbonates of the alkali metal percarbonate of at least 8% weight and at least 2% weight by composition weight meter.

3. according to the composition of claim 2, wherein said organic acid is a carboxylic acid.

4. according to the composition of claim 3, wherein said carboxylic acid is citric acid, toxilic acid, oxysuccinic acid or its mixture.

5. according to the composition of claim 1, wherein press composition weight meter, the amount that described peroxyacid bleach precursor exists is a 3-10% weight, and wherein said composition contains the hydrogen peroxide cource of 10-45% weight.

6. according to the composition of claim 5, wherein said hydrogen peroxide cource is a percarbonate, and it has formed the part of described carbonate source.

7. according to the composition of claim 1, wherein said pH is 9.2-9.85.

8. according to the composition of claim 1, it contains and comprises described acid or its part and belong to carbonate in the described carbonate source and/or the particle of supercarbonate.

9. composition according to Claim 8, wherein said acid and carbonate and/or supercarbonate with each other closely the form of uniform mixture exist.

10. the washing methods of a laundering of textile fabrics in washing machine, this method comprises:

(A) provide a kind of composition, said composition contains bleach system, this bleach system contains the hydrogen peroxide cource of 5-50% weight, it is selected from percarbonate, perborate, superphosphate, peroxide list persulphate and persilicate, with at least two kinds of peroxyacid bleach precursors of 2.5%-10% weight, wherein a kind of described peroxyacid bleach precursor is TAED, and second kind of peroxyacid bleach precursor is NOBS, DOBS or NACA-OBS; The carbonate source of at least 15% weight, it is selected from basic metal or alkaline earth metal carbonate, alkali metal percarbonate and basic metal or alkali metal bicarbonates; The acid of 7%-30% weight; Wherein the said composition pH that stirs the mixture of 1% weight that obtains after 10 minutes under the speed at 200rpm provide in 20 ℃ of softening waters is 8.8-9.9, and the ratio of TAED and second kind of bleach precursor is 1: 2 to 2: 1,

(B) described composition is joined in the distribution device,

(C) this distribution device is put into washing machine rotary drum and

(D) in described washing machine, add washing water.

11. according to the method for claim 10, wherein said fabric washing has reduced microbic activity, wherein said microorganism is E Coli, E.Hirae, S.Aureus or PsAruginosa.

12. according to the method for claim 10, wherein said bacterium contacts with liquid, aqueous, this is liquid, aqueous to contain a certain amount of described composition, makes peroxy acid that described peroxyacid bleach precursor provides with in this liquid per 10 ⁶The microorganism content of 100ppm at least exists.