CN1191349C - Delivery systems - Google Patents

Abstract

Glassy particles containing agents useful for laundry and cleaning products (preferably perfumes, bleaching agents, soil release polymers), and laundry and cleaning products containing these glassy particles. The particles comprise a glass derived from one or more at least partially water-soluble hydroxylic compounds, such as sucrose, glucose, and maltodextrin. The glassy particle also has a hygroscopicity value of less than about 80 %.

Description

Delivery system

Invention field

The present invention relates to comprise can be used for doing washing with and the glass particles of the reagent of Clean-product and comprise the laundry usefulness and the Clean-product of these glass particles.This particle comprises a kind of glassy mass, this glassy mass be derived from one or more to small part be water miscible oxy-compound, for example sucrose, glucose and Star Dri 5.The water absorbability value that this glass particles has is less than about 80%.From these particles, carry, can be used for doing washing with and the reagent of Clean-product comprise, for example, spices reagent, SYNTHETIC OPTICAL WHITNER, removal dirt polymkeric substance and their mixture.

Background of invention

Laundry is used and Clean-product continues to evolve so that not only better cleaning but also how good performance, for example color and fabric nursing and attractive in appearance to be provided.Can develop the novel agent that such effect is provided, still, the stability of product inside or the removeability through washing usually also are a difficult problem concerning their use.Various carrier systems that the scope of having developed is very wide and coating process are to satisfy these needs.Such system is not universally useful usually.

For example, people seeking effectively always and efficiently from laundry with the method and composition that the liquid spices is carried to fabric face.As the field that relates to later from this paper see, developed the whole bag of tricks of delivery spices.United States Patent (USP) 4,096,072 people such as Brock, that be disclosed on June 20th, 1978 proposes a kind of method, and this method comprises the fabric conditioner of spices via a kind of fatty quaternary ammonium salt delivery by washing and dry recycle.United States Patent (USP) people such as Schnoring, that be disclosed in September 6 nineteen eighty-three 4,402,856 proposes a kind of microencapsulation technology, and this technology comprises a kind of shell-type material pref, and said preparation only allows spices to spread from micro-capsule to come at a certain temperature.United States Patent (USP) 4,152,272 Young, that be disclosed on May 1st, 1979 proposes spices is sneaked into wax shape particle, protects spices by being stored in the neutralization of exsiccant composition by clothes washing method.This spices is dispersed on the fabric certainly by wax in moisture eliminator.United States Patent (USP) 5 people such as Walley, that be disclosed on November 19th, 1991; 066,419 proposes spices to be disperseed with water-fast, non-polymeric solid support material and use microencapsulation in the protectiveness shell by coating a kind of water-fast, frangible coating material.United States Patent (USP) 5,094,761 people such as Trinh, that be disclosed on March 10th, 1992 proposes a kind of spices/beta-cyclodextrin composition by the clay protection, and this title complex is provided to spices on the partially wetted at least fabric.

The another kind of method that delivers spices in cycles of washing comprises mixes spices with a kind of emulsifying agent and water-soluble polymers, make this mixture forming particle, and they are added in the laundry composition, this method is described in the following patent: United States Patent (USP) 4 Whyte, that be disclosed on June 24th, 1980,209,417; United States Patent (USP) 4,339,356 Whyte, that be disclosed in July 13 nineteen eighty-two; With U.S. Patent No.s 3,576,760 people, that be disclosed on April 27th, 1971 such as Gould.

Spices also can be attracted on the porous solid support material, for example is described in a kind of polymeric material in the English Patents 2,066,839 people, that be disclosed on July 15th, 1981 such as Bares.Spices also has been attracted on clay or the zeolitic material, then this clay and zeolitic material is sneaked in the particle cleaning composition.Usually, preferred zeolite is the zeolite of nominal pore size for the A type of average 4 dusts or 4A type.Believe that now on A type or 4A type zeolite, spices is attracted to this zeolite surface and does not almost have spices in fact to be adsorbed on the zeolite pore the inside.Though perhaps the absorption of spices on zeolite or polymeric carrier compared some improvement with pure spices is sneaked in the cleaning composition, but industry member is still in the improvement of seeking aspect following: the characteristics that do not lose spices, the length of the period of storage of cleaning composition passes to the time that aroma strength on the fabric or quantity and fragrance are retained in the fabric face of nursing one's health.

The mixture that the X type of spices and macropore and y-type zeolite are formed also proposes in this area usually.Be disclosed in the Deutsches Wirtschafts Patent No.248 on August 12nd, 1987,508 relate to spices dispersion agent (for example, air freshener), and this dispersion agent comprises a kind of faujasite (for example, X type zeolite and y-type zeolite) that is loaded with spices.The scf molecule diameter of perfume molecules it is said between the 2-8 dust.Be disclosed in the Deutsches Wirtschafts Patent No.137 on September 12nd, 1979,599 also propose to be used for the composition of powder washing reagent, discharge so that spices carries out temperature regulation.A type, X type and y-type zeolite are used for these compositions.These zeolites that early propose repeat the European patent No.535 that is disclosed on April 7th, 1993 in recent submission, 942 and European patent No.536 UnileverPLC, that be disclosed on April 14th, 1993,942 and United States Patent (USP) 5 people, that be disclosed on August 9th, 1994 such as Garner-Gray, in 336,665.

Effectively spices delivery composition is at Procter ﹠amp; Be suggested among the world patent WO 94/28107 Gamble company, that be disclosed on December 8th, 1994.These compositions comprise that zeolite that tool foraminous size is at least 6 dusts (for example, X type or y-type zeolite), wrap in releasable spices and a kind of a kind of matrix that is coated on the zeolite that is loaded with spices in the zeolite pore, this matrix comprises a kind of water miscible (washing removable) composition, and spices is insoluble in the said composition substantially.Said composition comprises from the 0% at least a solid polyalcohol to about 80% (weight), this polyvalent alcohol comprises more than 3 hydroxylic moiety with from about 20% a kind of liquid glycol or polyvalent alcohol to about 100% (weight), and spices is insoluble to wherein substantially and solid polyalcohol dissolves in wherein substantially.

United States Patent (USP) 5 people such as Kamel, that be disclosed on November 2nd, 1993,258,132 and be disclosed in the United States Patent (USP) 5 on July 27th, 1993,230,822 what relate to is the solid core particle of microencapsulation in the single layer coating of paraffin, this paraffin have from about 40 ℃ to about 50 ℃ fusing point and contained solid matter 40 ℃ the time from about 100 to about 35%, in the time of 50 ℃ from 0 to about 15%.The particle that this coating allegedly can prolong microencapsulation keeps the active time in aqueous environment.United States Patent (USP) 5,141,664 people such as Corring, that be disclosed on August 25th, 1992 relates to cleaning compositions, and said composition comprises a kind of transparent adhesive tape, and the opaque uniform particles of active material is disperseed and is suspended in this transparent adhesive tape.Active material by a kind of protective substance for example the microencapsulation layer be surrounded.

United States Patent (USP) 2,809,895 Swisher, that be disclosed in October 15 nineteen fifty-seven relates to solid essence oil, and this volatile oil comprises the suitable composition of making a kind of composition in various foods, medicine, spices, soap and the makeup.It is said that this patent relates to generation a kind of homodisperse volatile oil-maize treacle emulsion, this emulsion is cured and further handles to obtain the oxidation resistant volatile oil product of a kind of particulate.Described method relates to a kind of volatile oil that has added antioxidant and dispersion agent of emulsification in corn-syrup solids solution, generates a kind of granular solids emulsion.

Although these effort are arranged, still need the particle delivery system, laundry usefulness and cleaning composition, especially granulous cleaning composition and granulous automatic bowl can be sneaked into in the cleaning composition with reagent with the laundry of wide range by this system.It is desirable to such particle especially: very stable under the storage requirement of high temperature and high humidity.And preferred use also is such composition is not subjected to harmful level of water to the reagent of water sensitive with protection influence.

Background technology

United States Patent (USP) 4,539,135 people such as Ramachandran, that be disclosed on September 3rd, 1985 discloses the granular laundry compound, and this compound comprises a kind of clay or zeolitic material that delivers spices.United States Patent (USP) 4,713,193 Tai, that be disclosed on December 15th, 1987 discloses a kind of free flowing granule detergent additive, and this additive comprises and has the aqueous of a kind of zeolitic material or oily additive.Japanese Patent HEI 4 (1992)-218583 Nishishiro, that be disclosed on August 10th, 1992 discloses release controllable material, and this material comprises that spices adds zeolite.United States Patent (USP) 4,304,675 people such as Corey, that be disclosed on December 8th, 1981 has proposed a kind of method and composition, and said composition comprises the zeolite that can remove foul smell.Be disclosed in the Deutsches Wirtschafts Patent No.248 on August 12nd, 1987,508; Be disclosed in the Deutsches Wirtschafts Patent No.137 on September 12nd, 1979,599; European patent application No.535 Unilever PLC, that be disclosed on April 7th, 1993, on April 14th, 942 and 1993 disclosed patent No.536,942; United States Patent (USP) 5,336,665 people such as Garner-Gray, that be disclosed on August 9th, 1994; Be disclosed in the world patent WO 94/28107 on December 8th, 1994; United States Patent (USP) 5,258,132 people such as Kamel, that be disclosed on November 2nd, 1993 and the United States Patent (USP) 5,230,822 that is disclosed on July 27th, 1993; United States Patent (USP) 5,141,664 people such as Corring, that be disclosed on August 25th, 1992; With United States Patent (USP) 2,809,895 Swisher, that be disclosed in October 15 nineteen fifty-seven.

Summary of the invention

The present invention relates to a kind of laundry and use or cleaning composition, said composition comprises:

(a) a kind of glass particles, this particle comprise be selected from following material can be used for do washing with or the reagent of cleaning composition: spices, SYNTHETIC OPTICAL WHITNER, bleach boosters, the bleaching accelerator, bleaching catalyst, sequestrant, the card synthetic fibre agent (antiscalants) of anti-department, limit inhibitor, dye transfer inhibitor, optical bleaching agent, enzyme, catalytic antibody, whitening agent, the fabric substantive dyestuff, mycocide, biocide, wormer, the de-sludging polymkeric substance, fabric softener, dye-fixing agent, pH transition system and their mixture (those reagent that preferably can low-levelly be used for cleaning composition); With

(b) the detergent active material of at least a non-soap;

Wherein said glass particles comprises from one or more to small part it being water miscible oxy-compound deutero-glassy mass.At least a in the wherein said oxy-compound have about 0 ℃ or higher of a glass transition temp Tg anhydrous, non-plasticizing;

And the moisture absorptivity value that wherein further described glass particles has is less than about 80%.

The present invention also relates to can be used for to do washing with and the glass particles of cleaning composition, composition wherein comprises:

(a) be selected from following material can be used for do washing with or the reagent of cleaning composition: spices, SYNTHETIC OPTICAL WHITNER, bleach boosters, the bleaching accelerator, bleaching catalyst, sequestrant, the card synthetic fibre agent of anti-department, limit inhibitor, dye transfer inhibitor, optical bleaching agent, enzyme, catalytic antibody, whitening agent, the fabric substantive dyestuff, mycocide, biocide, wormer, the de-sludging polymkeric substance, fabric softener, dye-fixing agent, the mixture of pH transition system and they (the spices reagent in Zeolite support preferably; SYNTHETIC OPTICAL WHITNER; The de-sludging polymkeric substance; Optical bleaching agent; Enzyme); With

(b) be a kind of glassy mass of water miscible oxy-compound deutero-from one or more to small part, at least a in the wherein said oxy-compound have about 0 ℃ or higher of a glass transition temp Tg anhydrous, non-plasticizing;

The moisture absorptivity value that wherein said glass particles has is less than about 80%.

And wherein when described reagent was spices reagent, so described glass particles further comprised at least a fragrance carrier material (being preferably X type or y-type zeolite).

In sum, the invention provides a kind of laundry and use or cleaning composition, said composition comprises:

(A) calculate by said composition weight, from 0.1% to 10% glass particles and

(B) calculate by said composition weight, non-the soaping of one or more of from 0.1% to 90% washed active material;

From 1 to 500 micron of the mean particle size that wherein said glass particles has, and comprise the spices that is adsorbed on the zeolite and is encased by the glassy mass of sugar, the scope of the Tg that described glassy mass has is from 50 ℃ to 200 ℃;

The composition of wherein said glass particles, the listed as parts by weight of pressing composition recently is expressed as follows with the percentage that accounts for the glass particles total amount:

(a) calculate by weight from 2% to 40% described spices;

(b) from 2% to 95% described zeolite, the surface-area that described zeolite has is 50m2/g or higher;

(c) from 12% to 96% sugar that is selected from sucrose, Star Dri 5, lactose and their mixture; With

(d) from 0.05% to 35% water or softening agent;

Its condition be each component concentration per-cent and must be 100%.

A kind of embodiment is that wherein said spices comprises and calculates by weight from 50% to 100% delivered reagent.

A kind of embodiment is that said composition has cloth-washing detergent, laundry with the form of detergent additive or fabric softener, and the sugar that wherein forms described glassy mass can be processed as extrudable liquid when 60 ℃ to 160 ℃ of temperature ranges; 40% spices of no more than described spices total amount dissociates out from described fragrance carrier material; The moisture no more than 7% that the described glass particles that is prepared into is contained.

Unless otherwise indicated, otherwise all per-cent, ratio and the ratios of this paper all are by weight calculation.The full content of the document of all references is all included this paper in as a reference.

Detailed description of the invention

The present invention relates to a kind of glass particles delivery system, this system comprise can be used for doing washing with or Clean-reagent.This glassy mass be derived from one or more to small part be water miscible oxy-compound, at least a in the wherein said oxy-compound have glass transition temp Tg anhydrous, non-plasticizing and be about 0 ℃ or higher.Glass particles also has the moisture absorptivity value less than about 80% in addition.These delivery systems especially can be used in the granular detergent compositions, especially can be used for delivering low-level following laundry usefulness and Clean-reagent of great use in composition.

Can be used for of the present invention to small part be the material that water miscible oxy-compound is preferably selected from following type:

1. carbohydrate, this compounds can be any of following material or their mixture: i) monose (simple sugar) (or monose (monosaccharide)); Ii) oligose (being defined as the carbohydrate chain that contains 2-10 monose molecule); Iii) glycan (being defined as the carbohydrate chain that contains at least 35 monose molecules); Iv) starch.

Can use the carbohydrate chain of linear and side chain.In addition, also can use chemical modification starch and poly--/oligomeric-sugar.Typical modification comprises the interpolation of the hydrophobic part of forms such as alkyl, aryl, and identical with in tensio-active agent is to give some surfactivitys to these compounds.

2. all are natural or synthetic is gummy, for example alginate esters, carrageenin, agar, pectic acid and for example natural gum of Sudan Gum-arabic, Tragacanth and kuteera gum.

3. chitin and chitosan.

4. Mierocrystalline cellulose and derivatived cellulose.Example comprises: i) rhodia and acetate phthalic acid Mierocrystalline cellulose (CAP); Ii) Vltra tears (HPMC); Iii) carboxymethyl cellulose (CMC); Iv) all enterics /aquateric coating and their mixture.

5. silicate, phosphoric acid salt and borate.

6. polyvinyl alcohol (PVA).

7. polyoxyethylene glycol (PEG).

The material of these types be not to small part be water miscible and the glass transition temp Tg that has be lower than the present invention about 0 ℃ than lower bound.The material that belongs to these types is being useful under the following situation only: when with such amount when can be used for oxy-compound of the present invention and mix, this oxy-compound has required higher glass transition temp Tg, and therefore the glass particles of preparation has required moisture absorptivity value less than about 80%.

Usually the glass transition temp of being abbreviated as " Tg " is known, and glassy material is the character that is easy to measure.This conversion is described as a kind of material and changes into liquid equivalent liquification from vitreous state when being heated to the Tg zone.It is not a kind of conversion of phase, for example melts, evaporates or distil.(referring to " the scanning calorimetry summary of ' what Tg is ' gamma transition " (" ' What is a Tg? ' the A review of thescanning calorimetry of the glass transition ") of William P.Brennan, hot analytical applications research #7 (Thermal Analysis Application Study # 7), Perkin-Elmer company limited, in March, 1973.) measurement of Tg is easy to obtain by using differential scanning calorimeter.

To achieve the object of the present invention, the Tg of oxy-compound is for the anhydrous compound that do not contain any plasticizer (this softening agent may influence the Tg observed value of oxy-compound).Glass transition temp also is described in detail among P.Peyser's " glass transition temp of polymkeric substance " (" Glass Transition Temperatures of Polymers "), The polymkeric substance hand Volume(P Olymer Handbook), The third edition, J.Brandrup and E.H.Immergut (Wiley-Interscience; 1989), pp.VI/209-VI/277.

Can be used for having at least a kind of Tg anhydrous, non-plasticizing that must have to be at least 0 ℃ in the oxy-compound of glass particles of the present invention, for the particle that does not have moisture protection plaster, Tg is at least about 20 ℃, preferably at least about 40 ℃, more preferably at least 60 ℃, most preferably at least about 100 ℃.These compounds preferably low temperature are machinable, and preferred range is from about 50 ℃ to about 200 ℃, and preferred scope is from about 60 ℃ to about 160 ℃.Preferred such oxy-compound comprises sucrose, glucose, lactose and Star Dri 5.

The moisture level that " moisture absorptivity value " used herein meaning is absorbed by glass particles is the per-cent that the particle weight measured under following testing method increases.The required moisture absorptivity value of glass particles of the present invention by under the condition of 90 and relative humidity 80% with the 2 gram particle (particles of about 500 microns sizes; Without any dampproof coating) put into 4 weeks of an open container Petri dish and measure.The per-cent that four stars after date particle weight increases is exactly the particle moisture absorptivity value that the present invention uses.The moisture absorptivity value that preferred particle has is more preferably less than about 10% less than about 50%.

Glass particles of the present invention typically comprise from about 10% to about 99.99% to small part be water miscible oxy-compound, preferably from about 20% to about 90%, more preferably from about 20% to about 75%.Glass particles of the present invention also typically comprise from about 0.01% to about 90% can be used for do washing with or the reagent of cleaning composition, preferably from about 10% to about 80%, more preferably from about 25% to about 80%.

The method for preparing glass particles of the present invention derives out from the sugaring field.Such method comprises, for example is described in the method in the United States Patent (USP) 2,809,895 Swisher, that be disclosed in October 15 nineteen fifty-seven.

Can be used for doing washing with or the reagent of cleaning composition

According to the present invention, can be used for doing washing with or the reagent of cleaning composition be selected from following material: spices, SYNTHETIC OPTICAL WHITNER, bleach boosters, bleaching accelerator, bleaching catalyst, sequestrant, the card synthetic fibre agent of anti-department, limit inhibitor, dye transfer inhibitor, optical bleaching agent, enzyme, catalytic antibody, whitening agent, fabric substantive dyestuff, mycocide, biocide, wormer, de-sludging polymkeric substance, fabric softener, dye-fixing agent, pH transition system and their mixture.Just as pointed out in the present invention, can be used for doing washing with or these reagent of cleaning composition, wherein said composition be incorporated in the glass particles of the present invention can be used to prepare the laundry that contains glass particles with or those reagent of the excess of cleaning composition identical or different.For example, this glass particles can comprise a kind of spices reagent, and (identical or different) this reagent also can be sneaked in the final composition with the glass particles that contains spices.Select these required reagent according to the type of composition prepared, such composition for example, granular laundry with cleaning composition, granular automatic bowl with composition or hard surface cleaner.

Can be used for doing washing with and various types of reagent of cleaning composition be described in the back of this paper.The composition that comprises glass particles can be chosen wantonly and comprise that one or more other washing adds material or other material (for example, spices, tinting material, dyestuff etc.) that helps or strengthen clean-up performance, help or strengthen the processing of the substrate that will clean or improve the aesthetic property of cleaning composition.

Spices

Term used herein " spices " be used to refer to any odorous, subsequently be discharged into contain in the water-bath or with it the contact fabric on material.What spices was the most common at ambient temperature is liquid.The very wide various chemical of known range can be used as spices and use, and comprise for example material of aldehyde, ketone and ester.More common is naturally occurring plant and animal oil and comprise the exudate of the complex mixture of known various chemical ingredientss as spices.The composition of spices of the present invention can be simple relatively or contain the very complicated mixture of natural and synthetic chemical ingredients that the spices of all selections is for required smell is provided.Typical spices can comprise that for example, comprise the wooden/soil property alkali of special material, this special material is santal oil, civet oil and patchouli oil for example.Spices can have light flowery odour, for example the smell of rose extract, violet extract and Syringa oblata Lindl..This spices also can be formulated into can provide the fruit smell, for example, and bitter orange, lemon and orange.The compatible material of any chemistry that can distribute pleasant or required smell can both be used in the flavor compositions of the present invention.

Spices also comprises and helps pastil, for example, acetal help pastil, ketal help pastil, ester help pastil (for example, succsinic acid two-geraniol ester), hydrolyzable inorganic-machine aided pastil and their mixture arranged.These help pastil to discharge spices by simple hydrolysis, maybe can be cause that pH changes help pastil (for example, the pH drops), maybe can be enzyme catalysis discharge help pastil.

Can be used for preferred spices reagent of the present invention defines hereinafter.

Be exposed to the purpose of laundry with the moisture media in the washing methods for reaching the present composition, the several characteristic parameter of identifying and define perfume molecules is very important: their the longest and the wideest useful range; The zone of cross section; Molecular volume; And molecular surface area.These values use the CHEMX program (available from Chemical Design, Ltd.) one perfume molecules is calculated, this procedural application is in the molecule of the least energy configuration of measuring for how much by the standard of having optimized in CHEMX, and used the van der Waals radius of standard atom.Parameter is defined as follows:

" the longest ": interatomic ultimate range (dust) in the molecule that increases owing to the van der Waals radius of atom.

" the wideest ": interatomic ultimate range is perpendicular to the planar molecule projection (dust) on molecule " the longest " axle in the molecule that increases owing to the van der Waals radius of atom.

" cross section area ": in the zone that is full of perpendicular to the planar molecule projection on the major axis (dust square).

" molecular volume ": the volume that is full of at the molecule of its least energy configuration (dust square).

" molecular surface area ": unit be dust square arbitrarily big small area (in order to calibrate, the surface-area observed value that methyl betanaphthyl ketone, Whitfield's ointment benzene methyl and camphor xanthan molecule have is respectively 128 ± 3,163.5 ± 3 and 122.5 ± 3 units).

The shape of molecule also is very important to sneaking into.For example, an ideal symmetrical, enough little do not have preferred orientation so that be impregnated in the globular molecule of zeolite pipeline, in any direction all can sneak into.Yet,, " entering the orientation " that preferably is impregnated in is just arranged for the molecule of length above the size in hole.The calculating of molecule volume/surface-area ratio is used to this paper to represent " form parameter " of a molecule.This value is high more, and molecule is bordering on sphere more.

To achieve the object of the present invention, spices reagent is impregnated in the Capability Categories of zeolite pore according to them, and therefore, also the one-tenth that is utilized according to them assigns to classify, and this composition carries from Zeolite support by aqueous environment.Be impregnated in the ability of zeolite according to these reagent, with the ratio of volume/surface-area these reagent being divided on cross section area plane can be easily with these reagent classification.Specifically, according to the present invention, to X type and y-type zeolite carrier, if reagent is lower than the lower limit (being called " mixing line " at this) of the definition that established an equation down, then they just are impregnated in:

y＝-0.01068x+1.497

Wherein x is the cross section area, and y is volume/surface-area ratio.Be lower than the reagent that mixes line and be called " can deliver reagent " in the present invention; Be higher than those reagent that mix line and be called " can not deliver reagent " in the present invention.

For the inclusion that is in the suds, can deliver reagent owing to their affinities to carrier are retained in the Zeolite support.Affinity is influenced by molecular size, wetting ability, functionality, volatility etc., and can be affected by the interaction between the delivered reagent in Zeolite support.These interactions can impel by washing the inclusion that can deliver reagent mixture mixes.Specifically, to the present invention, have one dimension at least closely and the use of the delivered reagent that is complementary of Zeolite support hole dimension slowed down that other can deliver the loss of reagent in the aqueous cleaning environment.Zuo Yong delivered reagent is referred to herein as " retardance reagent " by this way, and is restricted to those delivered reagent molecules that are lower than " mixing line " (as above-mentioned definition) but are higher than the line (this paper is called " delay line ") of the definition that establishes an equation down in to the cross section area at volume/surface-area ratio:

y＝-0.01325x+1.46

Wherein, x is the cross section area, and y is volume/surface-area ratio.

For the present composition that utilizes X type and y-type zeolite as carrier, all delivered reagent under " mixing line " can be delivered, and discharge from the present composition, and said composition has those preferred materials of being lower than " delay line ".Preferred reagent also is that retarding agent can deliver the mixture of reagent with other.Can be used for the present invention laundry and comprise from about 5% to about 100% (preferably from about 25% to about 100% with the spices reagent mixture with the particulate laundry; More preferably from about 50% to about 100%) delivered reagent; With preferably include from about 0.1% retarding agent to about 100% (preferably from about 0.1% to about 50%), calculate with reagent mixture weight by laundry.

For the present composition, be combined the obviously thing delivery of spices reagent, the benefit that can see needs human consumer's perception delicately.For flavor compositions of the present invention, can be used for the significance lower bound that most preferred spices reagent of the present invention has (being described in detail in the smell calibrating lower bound of measuring under the GC condition of careful control of this paper back (" ODT ")) per million and be less than or equal 10 parts (" ppb ").The reagent of ODT between 10ppb and per 1,000,000 parts (" ppm ") is less preferred.ODT preferably avoids using greater than the reagent of 1ppm.Can be used for laundry of the present invention with particulate laundry with the spices reagent mixture preferably include from about 0% to about 80%, the delivered reagent and from about 20% to about 100% (preferably from about 30%% to about 100% of ODT 10ppb and 1ppm; More preferably from about 50% to about 100%), ODT is less than or equal to the delivered reagent of 10ppb.

Preferred spices also is the spices that is delivered by washing methods, and is released to the spices in the exsiccant fabric ambient air (for example, the space around the fabric in storage process) thereafter.This need shift out spices from zeolite pore, be assigned to subsequently in the fabric ambient air.Therefore, preferred spices reagent is further identified according to their volatility.Boiling point is used as volatile measuring at this, and the boiling point that preferable material has is less than 300 ℃.Can be used for the present invention laundry with the particulate laundry with the spices reagent mixture preferably include at least about 50%, boiling point less than 300 ℃ delivered reagent (preferably at least about 60%; More preferably at least about 70%).

In addition, the present invention preferably does washing and comprises composition with particle, and wherein " the ClogP value " that at least about 80%, more preferably has at least about 90% delivered reagent is greater than about 1.0.The following acquisition of ClogP value.

The calculating of ClogP:

These fragrance components are characterised in that their octanol/water partition ratio P.A kind of octanol/water partition ratio of fragrance component is its equilibrium state concentration in octanol and the ratio between the equilibrium state concentration in the water.Because the partition ratio of most of fragrance components is very big, so partition ratio provides for the logarithm logP form at the end more easily in order to 10.

The logP of many fragrance components is in the news; For example, purchase in the Pomona92 database of daylight Chemical Information System company limited (Daylight Chemical Information Systems, Inc. (DaylightCIS)) and comprise many logP, pointed out the source of original simultaneously.

But, calculate logP value most convenient by " CLOGP " program, this program also can be purchased in Daylight CIS.When can obtain the logP value in the Pomona92 database time, this program has also been listed the experimental value of this logP." logP of calculating " (ClogP) be sheet phase method by Hansch and Leo determine (referring to, A.Leo, in Comprehensive MedicinalChemistry, Vol.4, C.Hansch, P.G.Sammens, J.B.Taylor and C.A.Ramsden, Eds., p.295, Pergamon publishes, and 1990).This sheet phase method is based on the chemical structure of each fragrance component, and considers the number and the type of the associativity and the chemical bond of atom, atom.The most reliable and be widely used in the CLogP value of estimating this physicochemical property can substitute logP when selecting fragrance component experimental value use.

The mensuration of smell calibrating lower bound

Gas-chromatography is characterised in that with concentration known and chain length distribution standard hydrocarbon polymer measures the accurate volume of the material that injects by syringe, accurate splitting ratio and hydrocarbon reaction.Accurately measure lasting 0.2 minute of air flow rate and supposition operator suction process, calculate the volume of draw samples.Because know the accurate concentration in any moment in the detector, therefore just know the quality that sucks per unit volume, also therefore know concentration of material.In order to determine whether the lower bound that a kind of material has is lower than 10ppb, and solution is transported to the snuffing hole of calculating concentration thereafter.The expert identifies retention time with the effluent liquid of nasil gas-chromatography when noticing scent of.The mean value of all expert determinations is exactly the significance lower bound.

The necessary amount of assay is injected in the pillar to obtain the concentration of 10ppb in detector.For the typical gas-chromatography Argument List of measuring smell calibrating lower bound below.

Gas-chromatography: the 5890 serial II that have fid detector

7673 automatic samplers

Post: J ﹠amp; W Scientific DB-1

1 micron of 30 meters ID 0.25mm of length thickness

Method:

Shunting injection: 17/1 splitting ratio

Automatic sampler: per injection 1.13 microlitres

Post flow: 1.10mL/ minute

Air flow quantity: 345mL/ minute

245 ℃ of temperature ins

285 ℃ of detector temperatures

Temperature information

Initial temperature: 50 ℃

Speed: 5C/ minute

Terminal temperature: 280 ℃

Terminal time: 6 minutes

Main supposition: the time with nasil is 0.02 minute at every turn

The air of gas-chromatography is passed in the sample diluting liquid

The spices fixative

Spices can randomly combine with a kind of spices fixative.Being used for spices fixative material of the present invention is characterised in that and makes them be particularly suited for several criterion of the invention process.Used dispersible, toxicology is acceptable, not skin irritation, to spices inert, degradable and/or from that can utilize renewable resource and scentless relatively additive.Believe that the spices fixative can slow down the evaporation of more volatile composition in the spices.

The example of suitable fixative comprises the member who is selected from following material: diethyl phthalate, Moschus and their mixture.If used the spices fixative, this spices fixative weight percent of accounting for spices is from about 10% to about 50% so, preferably from about 20% to about 40%.

The fragrance carrier material

" fragrance carrier material " used herein means and can support (for example, by be absorbed in the surface or be absorbed in the hole) a kind of spices reagent and mix any material of glass particles.Such material comprises the porous solid that is selected from following material: amorphous silicate, crystalline non-layered silicate, layered silicate, lime carbonate, lime carbonate/sodium double salt, yellow soda ash, clay, zeolite, sodalite, alkali metal phosphate, large pore zeolite, chitin microballon, carboxyl alkyl cellulose, carboxyalkyl starch, cyclodextrin, porous-starch and their mixture.

Preferred fragrance carrier material is X type zeolite, y-type zeolite and their mixture.What term used herein " zeolite " related to is crystalline alumino-silicate materials.A kind of structural formula of zeolite is based on the crystal unit cell, and the minimum unit of structure is represented with following formula:

M _m/n〔(AlO ₂) _m(SiO ₂) _y〕xH ₂O

Wherein, n is the valence of positively charged ion M, and x is the water molecule number of every unit cell, and m and y are the tetrahedral sums of every unit cell, and y/m is 1 to 100.Most preferred, y/m is 1 to 5.Positively charged ion M can be the element of IA family and IIA family, for example, and sodium, potassium, magnesium and calcium.

Can be used for the zeolite that zeolite of the present invention is a kind of octahedra type, comprise X type zeolite or y-type zeolite, the have an appointment nominal pore size of 8 dusts of both, typically scope is to about 10 dusts from about 7.4.

The aluminosilicate zeolite material that can be used for the present invention's practice can have been bought.The method for preparing X type and y-type zeolite is known and obtain in normative document.Can be used for the preferred synthetic commercially available trade mark of crystalline alumino-silicate materials of the present invention is X type or Y type.

In order to illustrate rather than limit the present invention, in preferred embodiments, this crystalline alumino-silicate materials is the X type, and is selected from following material:

(I) Na ₈₆[AlO ₂] ₈₆·(SiO ₂) ₁₀₆]·xH ₂O，

(II)?K ₈₆[AlO ₂] ₈₆·(SiO ₂) ₁₀₆]·xH ₂O，

(III)Ca ₄₀Na ₆[AlO ₂] ₈₆·(SiO ₂) ₁₀₆]·xH ₂O，

(IV) Sr ₂₁Ba ₂₂[AlO ₂] ₈₆(SiO ₂) ₁₀₆] xH ₂O and their mixture, wherein, x from about 0 to about 276.Formula (I) and zeolite (II) have the hole of nominal size or the hole of 8.4 dusts.Formula (III) and zeolite (IV) have the hole of nominal size or the hole of 8.0 dusts.

In a further preferred embodiment, crystalline alumino-silicate materials is the Y type and is selected from following material:

(V)?Na ₅₆[AlO ₂] ₅₆·(SiO ₂) ₁₃₆]·xH ₂O，

(VI) K ₅₆[AlO ₂] ₅₆(SiO ₂) ₁₃₆] xH ₂O and their mixture, wherein, x from about 0 to about 276.Formula V and zeolite (VI) have the hole of nominal size or the hole of 8.0 dusts.

Being used for zeolite of the present invention is particle form, and the average particle size particle size that has is measured from about 0.5 to about 120 microns, preferably from about 0.5 micron to about 30 microns by standard particle size analytical technology.

This big or small zeolite granular allows to be carried in the fabric that they contact.In case be placed in the surface (coating matrix is washed off in laundry processes) of fabric, Zeolite support begins to discharge the reagent of the laundry usefulness of mixing in them, especially work as them under hot or moist condition.

In zeolite spices mix attachedBut-be used for X type of the present invention or y-type zeolite to preferably include the water that is less than about 10% desorb, but but more preferably less than the water of about 8% desorb with most preferably be less than the water of about 5% desorb.Such material can under reduced pressure (hold in the palm from about 0.001 to about 20) by optional, is heated to about 150-350 ℃, continues at least 12 hours, obtains through activation/dehydration for the first time.After the activation, spices is mixed with the zeolite that activated lentamente and up hill and dale, randomly be heated to about 60 ℃ and also continue to be about most 2 hours, to quicken the adsorption equilibrium in zeolite granular.With this spices/zeolite mixture cool to room temperature, become a kind of free-pouring powder type then.

Consider the restriction of zeolite pore volume, the laundry of mixing in the attached Zeolite support is calculated by the particle weight of load with the quantity of reagent, is less than approximately 20%, typically is less than about 18.5%.But, can know that particle of the present invention can surpass this level that reagent is used in the laundry of calculating by particle weight, even but known only the use can deliver reagent, and laundry still can not mixed in the zeolite with the excessive levels of reagent.Therefore, particle of the present invention can comprise the laundry reagent of calculating by weight more than 20%.Be attached in the zeolite pore because any excessive laundry can not mix with reagent (with any reagent that can not deliver is the same at present), therefore, these materials might be discharged in the washing soln when contacting with the aqueous cleaning medium immediately.

Glass particles comprises/protects the function of spices except it in zeolite granular, also can make the multiple zeolite granular that is loaded with spices agglomerate into the total particle magnitude range easily is 200 to 1000 microns, preferred 400 to 600 microns agglomerate.The many situations of dust have been reduced like this.In addition, so also alleviated trend less, that zeolite that be loaded with spices individually falls into the container bottom of filled with granular washing composition, wherein typically to have the scope of granular size be 200 to 1000 microns to granulated detergent itself.

Detergent surfactant-being included in detergent surfactant in the cleaning composition of fully allocating that the present invention provides according to granule surface activity agent of using and required effect, the weight percent in cleaning composition is at least 1%, and preferably from about 1% to about 99.8%.In a highly preferred embodiment, the weight percent of detergent surfactant in composition is from about 5% to about 80%.

Detergent surfactant can be non-ionic, anionic, amphoteric, zwitterionic or cationic.Also can use these surfactant mixtures.Preferred cleaning composition comprises the especially mixture of nonionogenic tenside of anionic detergent tensio-active agent or anion surfactant and other tensio-active agent.

Can be used for tensio-active agent limiting examples of the present invention and comprise conventional C ₁₁-C ₁₈Alkylbenzene sulfonate and primary, secondary and alkyl-sulphate, C arbitrarily ₁₀-C ₁₈Alkyl alkoxy sulfate, C ₁₀-C ₁₈Alkyl poly glucoside and their corresponding Sulfated glycan glycosides, C ₁₂-C ₁₈α-sulfonated fatty acid ester, C ₁₂-C ₁₈Alkyl and alkylphenol alcoxylates (especially ethoxylate and blended oxyethyl group/propoxylated glycerine), C ₁₂-C ₁₈Trimethyl-glycine and thetine (" sultains "), C ₁₀-C ₁₈Amine oxide and similar material.The spendable tensio-active agent of other routine is listed in the normative document.

The nonionogenic tenside that is particularly useful for cleaning composition of the present invention is the condenses of an oxyethane and a hydrophobic part, so that a kind of scope from 5 to 17 with average hydrophile-lyophile balance (HLB) to be provided, preferably from 6 to 14, more preferably from 7 to 12 tensio-active agent.Hydrophobic (oleophylic) part can be in nature aliphatic series or aromatics.Can be adjusted at an easy rate with the length of the polyoxy ethylidene group of any special hydrophobic grouping condensation and to obtain a kind of water miscible compound, this compound has the quality of balance between required hydrophilic and hydrophobic units.

Such nonionogenic tenside is especially preferred to be the C that every mol of alcohol comprises the 3-8 moles of ethylene oxide ₉-C ₁₅Primary alcohol ethoxylate, especially every mol of alcohol comprises the C of 6-8 moles of ethylene oxide ₁₄-C ₁₅Primary alconol, every mol of alcohol comprise the C of 3-5 moles of ethylene oxide ₁₂-C ₁₅Primary alconol and their mixture.

The another kind of suitable type of nonionogenic tenside comprises the polyhydroxy fatty acid amide of following formula:

(I)R ²C(O)N(R ¹)Z

Wherein, R ¹Be H, C ₁-C ₈Alkyl, 2-hydroxyethyl, 2-hydroxypropyl or their mixture are preferably C ₁-C ₄Alkyl, more preferably C ₁Or C ₂Alkyl most preferably is C ₁Alkyl (that is methyl); R ²Be C ₅-C ₃₂Hydrocarbyl portion is preferably the C of straight chain ₇-C ₁₉Alkyl or alkenyl, the more preferably C of straight chain ₉-C ₁₇Alkyl or alkenyl most preferably are the C of straight chain ₁₁-C ₁₉Alkyl or alkenyl or their mixture; Z is the polyhydroxy alkyl part, this part has a linear hydrocarbyl chain, at least 2 (with regard to Glycerose) or at least 3 (with regard to other reducing sugar) hydroxyls directly are connected on this chain or the derivative of their alkoxylate (be preferably ethoxylation or propenoxylated) on.Z preferably derives out from a kind of reducing sugar in reductive amination process.Preferred Z is a glycosyl part.Suitable reducing sugar comprises sucrose, fructose, maltose, lactose, semi-lactosi, seminose and wood sugar, also comprises Glycerose.The high dextrose maize treacle of roughage, high-fructose corn syrup and high malt sugar maize treacle also can use as the above-mentioned independent sugar of listing.These maize treacle can produce the sugared mixture of ingredients that is fit to Z.Be to be understood that and do not plan to get rid of other suitable roughage.Z preferably is selected from following groups :-CH ₂-(CHOH) _n-CH ₂OH ,-CH (CH ₂OH)-(CHOH) _N-1-CH ₂OH ,-CH ₂-(CHOH) ₂(CHOR ') (CHOH)-CH ₂OH, wherein n is from 1 to 5 integer (comprising 1 and 5), R ' is H or cyclic list-or many-carbohydrate and their alkoxy derivative.Glycosyl most preferably, wherein n is 4, especially-CH ₂-(CHOH)-CH ₂OH.

In formula (I), R can be, for example, and N-methyl, N-ethyl, N-propyl group, N-sec.-propyl, N-butyl, N-isobutyl-, N-2-hydroxyethyl or N-2-hydroxypropyl.For the highest bubble, R ¹Preferably methyl or hydroxyalkyl.Low if desired bubble, R ¹C preferably ₂-C ₈Alkyl, especially just-propyl group, different-propyl group, just-butyl, different-butyl, amyl group, hexyl and 2-ethylhexyl.

R ²-CO-N＜can be, for example, cocoamide (cocamide), stearylamide, amine hydroxybenzene, laurylamide, myristic amide, decyl amide, palmitic amide, acyl amine etc.

Soap (being soap) also can be used as the part of required detergent surfactant of the present invention and uses.

Low foaming nonionogenic tenside can be used in the automatic bowl, to help cleaning, help to remove dirty food foam, especially from protein, and can help control to form stain/film forming, and the level that is included in ideally in the cleaning composition of the present invention accounts for from about 0.1% to about 20% of composition.Usually, the tensio-active agent of bleach stable is preferred.ADD of the present invention (automatic bowl washing composition) composition preferably includes low foaming nonionogenic tenside (LFNI).LFNI can exist to calculate by weight from 0 to about 10% quantity, and preferably from about 0.25% to about 4%.Because LFNI joins and has improved setting-out effect (especially from glassy mass) in the ADD product, so LFNI the most typically uses in ADD.They are also included within the non-silicone that this paper further specifies later, the polymeric material of nonphosphate, and known this material can be removed the foam that the food dirt produces in automatic bowl.

Preferred LFNI comprises the oxyalkylated tensio-active agent of nonionic, especially the ethoxylate of deriving and from primary alconol, and with the mixture of complex surfaces promoting agent more, for example, the polyoxy propylidene/polyoxy ethylidene/anti-block polymer of polyoxy propylidene (PO/EO/PO).But the tensio-active agent of this PO/EO/PO polymer type is known to have bubble or froth breaking effect, when referring more particularly to common food dirt composition, as egg.

The present invention includes embodiment preferred, LFNI is wherein arranged, and wherein this composition being solid under about 95 °F (35 ℃), is solid under about 77 °F (25 ℃) more preferably.Preparation for convenience, the fusing point that preferred LFNI has is between about 77 °F (25 ℃) and about 140 °F (60 ℃), more preferably between about 80 °F (26.6 ℃) and 110 °F (43.3 ℃).

In a preferred embodiment, LFNI is a kind of tensio-active agent of ethoxylation, and this tensio-active agent contains from about 6 to the alcohol of about 15 moles of ethylene oxide or the reaction of alkylphenol on average basis to the single hydroxyl alcohol of about 20 carbon atoms or alkylphenol and every mole of molecule and to derive and get from containing about 8.

A kind of particularly preferred LFNI is by straight-chain fatty alcohol, and this alcohol contains from about 16 to about 20 carbon atom (C ₁₆-C ₂₀Alcohol), be preferably a kind of C ₁₈Alcohol on average contains from about 6 to about 15 moles with every mol of alcohol, preferably from about 7 to about 12 moles, most preferably from about 7 to the pure condensation of about 9 moles oxyethane and obtain.The nonionogenic tenside of the preferred ethoxylation that obtains like this has the distribution of the ethoxylate narrower with respect to mean value.

LFNI can randomly comprise calculating by weight and is up to about 15% propylene oxide.Other preferred LFNI tensio-active agent can be by being described in the method preparation in the United States Patent (USP) 4,223,163 Builloty, that be disclosed on September 16th, 1980, and this patent is included this paper in as a reference.

The present invention ADD that wherein contains LFNI very preferably utilizes the single hydroxyl alcohol or the alkylphenol of ethoxylation, and additional a kind of polyoxy ethylidene, the polyoxy propylidene block polymerization compound of comprising; The single hydroxyl alcohol of the ethoxylation of LFNI or alkylphenol part accounts in total amount LFNI from about 20% to about 100%, and preferably from about 30% to about 70%.

The suitable block polyoxy ethylidene-polyoxy propylidene polymerizable compound that satisfies the needs be described in this paper front comprises based on those of following active dydrogen compounds as initiator: ethylene glycol, propylene glycol, glycerol, TriMethylolPropane(TMP) and 1.From the initiator compounds that has single active hydrogen atom C for example _12-18Fatty alcohol can not provide satisfied foam control usually by the polymerizable compound of order ethoxylation and propoxylation preparation in ADD of the present invention.BASF-Wyandotte company limited, Wyandotte, Michigan, the trade mark are PLURONIC ^And TETRONIC ^Some block polymer surfactant compounds be applicable to very much ADD composition of the present invention.

Particularly preferred LFNI comprises the mixture of polyoxy propylidene/polyoxy ethylidene/polyoxy propylidene block polymer of from about 40% to about 70%, this mixture comprises by this mixture weight calculating, about 75%, contain the polyoxy ethylidene of 17 moles of ethylene oxide and 44 moles of propylene oxide and the anti-segmented copolymer of polyoxy propylidene, with calculate about 25% by this mixture weight, contained the polyoxy ethylidene that the TriMethylolPropane(TMP) of 99 moles of propylene oxide and 24 moles of ethylene oxide causes and the segmented copolymer of polyoxy propylidene by TriMethylolPropane(TMP) and every mole.

That be suitable for use as LFNI in the ADD composition is those LFNI with low relatively cloud point and relative high hydrophile-lyophile balance (HLB).For control foaming best in the global extent of water temperature, the cloud point of 1% solution typically is lower than about 32 ℃ in water, and is preferably lower, for example 0 ℃.

Also operable LFNI comprises that degree of ethoxylation is about 8 C ₁₈The alcohol polyethoxylated, this C ₁₈The alcohol polyethoxylated can have been bought from Olin company limited, and the trade mark is SLF18, and any biodegradable LFNI with fusing point character discusses at preamble.

Enzyme-for all purposes, comprise from the surface removal of for example fabric or plate being base with protein, being base with the carbohydrate or being the dirt of base, for preventing dye transfer, for example in laundry with the Witepsol W-S 55, and for fabric is restored, enzyme can be included in the cleaning composition of the present invention.Suitable enzyme comprises the mixture in proteolytic enzyme, amylase, lipase, cellulase, peroxidase and their any suitable sources, and this is for example originated, vegetables, animal, bacterium, mould and yeast.The preferred selection influenced by following factors: the active and/or stability of for example best pH, thermostability, to character such as the washing assistant of activated detergent, stability.In this respect, bacterial enzyme or fungous enzyme are preferred, for example bacterial amylase and proteolytic enzyme and mould cellulase.

" washing enzyme " used herein meaning is any enzyme that has cleaning, decontamination or other useful effect in laundry, hard-surface cleaning or personal care cleaning composition.Preferably washing with enzyme is lytic enzyme, for example proteolytic enzyme, amylase and lipase.For the purpose of doing washing, preferred enzyme comprises, is not restrictedly still, proteolytic enzyme, cellulase, lipase and peroxidase.Automatic bowl is amylase and/or proteolytic enzyme with enzyme very preferably, comprise the at present commercially available type and the type of improvement, though these two types increasing SYNTHETIC OPTICAL WHITNER can be compatible,, still has to a certain degree the bleaching susceptibility of deactivating though successfully improve.

Enzyme is usually to be enough to providing " amount of cleaning effect " to be impregnated in washing composition or the laundry additive composition.Term " amount of cleaning effect " relates to be anyly can on the matrix of for example fabric, container and analogue, produce cleaning, de-sludging, decontamination, make bleach, the amount of effect that deodorizing, improvement are fresh.In the convention term of present commercial formulation, typical amount is calculated by weight to and contains organized enzyme in every gram cleaning composition and be up to about 5mg, more typically arrives 3mg for 0.01mg.Unless otherwise indicated, otherwise the present composition typically comprises and calculates by weight from 0.001% to 5%, the commercially available zymin of preferred 0.01%-1%.The level that proteolytic enzyme is present in such commercial preparation usually provides every gram composition to contain from 0.005 activity to 0.1Anson unit (AU) for being enough to.To some washing composition, for example be used for the washing composition of automatic bowl, for the total amount of the active material that makes the on-catalytic effect minimizes and therefore improves into spot/film forming or other result, the content that increases organized enzyme in the commercial preparation may be ideal very.In the high density detergent compositions, more highly active level may also be an ideal very.

The suitable example of proteolytic enzyme is the subtilysin that obtains from the bacterial strain of B. withered grass (subtilis) and B. licheniformin (licheniformis).It is from being to have the bacterial strain of the Bacillaceae (Bacillus) of maximum activity to obtain between the 8-12 in the pH scope that a kind of suitable proteolytic enzyme is arranged, and this enzyme is by the A/s of Novo enterprise (this paper back is called " Novo ") of Denmark exploitation and with ESPERASE ^The trade mark is commercially available.The preparation of this kind of enzyme and similar enzyme is described in the GB 1,243,784 of Novo.Other suitable proteolytic enzyme comprises the ALCALASE of Novo ^And SAVINASE ^And Holland is international biological-synthetic company limited (Internationa Bio-Synthetics, MAXATASE Inc.) ^Protease A is open in EP 130,756 A that are disclosed on January 9th, 1985, and proteolytic enzyme B is at EP 303,761 A that are disclosed on April 28th, 1987 and be disclosed among EP 130,756 A on January 9th, 1985 open.Also can be referring to the high pH proteolytic enzyme of the Bacillus sp.NCIMB 40338 among WO 9318140 A that are described in Novo.Comprise that proteolytic enzyme, one or more other enzyme and a kind of enzymatic washing composition of reversible protease inhibitors are described among WO 9203529 A of Novo.Other preferred proteolytic enzyme comprises Procter ﹠amp; Those proteolytic enzyme among WO 9510591 A of Gamble.If desired, a kind of Procter ﹠amp that is described in; The proteolytic enzyme of the absorption with minimizing among the WO 9507791 of Gamble and the hydrolysis of increase also is suitable.The recombinant chou that is suitable for a kind of trypsin-like of the suitable washing composition of the present invention is described among the WO 9425583 of Novo.

In more detail, a kind of especially preferred proteolytic enzyme, be called " proteolytic enzyme D ", it is a kind of carbonylic hydrolase variant, the amino-acid sequence that this variant has is not found at nature, this variant derives out from predecessor's carbonylic hydrolase by being substituted in being equal to position+a plurality of amino-acid residues in 76 places of above-mentioned carbonylic hydrolase with a kind of different amino acid, preferred also can be equal to the one or more amino-acid residues that are selected from down column position and make up :+99, + 101, + 103, + 104, + 107, + 123, + 27, + 105, + 109, + 126, + 128, + 135, + 156, + 166, + 195, + 197, + 204, + 206, + 210, + 216, + 217, + 218, + 222, + 260, + 265 and/or+274, these positions all propose according to Bacillaceae alpha Amylase preparation (Bacillus amyloli-quefaciens), the numbering of this subtilysin is described in and all is filed on October 13rd, 1994, people's such as A.Baeck, title is " cleaning compositions that contains proteolytic enzyme " (" Protease-ContainingCleaning Compositions "), has U.S. serial No.08/322,676 patent application, with people's such as C.Ghosh, title is " bleaching composition that comprises proteolytic enzyme " (" Bleaching Compositions Comprising Protease Enzymes's "), has U.S. serial No.08/322, in 677 the patent application.

The amylase that the present invention is suitable, especially for, but be not restrictedly for the purpose of automatic bowl, comprise, for example be described in the α-Dian Fenmei among the GB 1,296,839 of Novo; The RAPIDASE of international biology-synthetic company limited ^TERMAMYL with Novo ^The FUNGAMYL of Novo ^Be particularly useful.Be used to improve the enzyme engineering of stability, for example oxidative stability is known.Referring to, for example, J.Biological Chem., Vol.260, No.11, in June, 1985, pp 6518-6521.Some embodiment preferred of the present composition can be utilized the amylase of the stability that has improvement in washing composition, automatic bowl type for example, and especially contrast is used for commercially available TERMAMYL in 1993 ^The amylase of oxidative stability of the reference point improvement of measuring.These preferred starch enzymes of the present invention are shared the characteristic of " enhanced stability " enzyme, the feature of this enzyme is the improvement in following one or more properties measurements on minimum degree: oxidative stability, for example, to pH be hydrogen peroxide/tetra-acetylated 1 buffered soln of 9-10; Thermostability, for example, in common wash temperature as 60 ℃; Or alkaline stability, for example, from about 8 to about 11 times, these character contrasts are measured with above-mentioned same diastatic reference point at pH.Stability is with any measurement the in the disclosed technical testing in this area.Referring to, for example, be disclosed in the document among the WO 9402597.Stability enhanced amylase can obtain from Novo or from Genencor International.The present invention's kind of starch enzyme very preferably has through site-directed mutagenesis from one or more Baccillus amylase, and especially the Baccillus α-Dian Fenmei is by the deutero-general character, and whether no matter a kind of, two or more amylase strains are parents of intermediate.With above-mentioned same comparing with reference to amylase, preferably use the stable enhanced amylase of oxidation, especially at bleaching cleaning composition of the present invention, more preferably in being different from the oxygen bleaching cleaning composition of chlorine bleaching, use.So preferred amylase comprises: (a) include the amylase among preamble, Novo, as to be disclosed on February 3rd, 1994 world patent WO 9402597 in, this enzyme further illustrates by mutant strain, use the L-Ala or the Threonine of methionine(Met) in this mutant strain, preferably Threonine replaces, this methionine(Met) is positioned at 197 of B.licheniformis α-Dian Fenmei, and known brands is TERMAMYL ^, or for example the diastatic similar position of similar parent of B.amyloliquefaciens, B.subtilis or B.stearothermophilus changes; (b) stable enhanced amylase, this amylase is described in the paper that a piece of C.Mitchinson is entitled as " oxidation resistant α-Dian Fenmei " (OxidativelyResistant alpha-Amylase) by Genencor International, and this paper is published on the 207th the whole America chemistry society conference (207th American ChemicalSociety National Meeting) of holding 13-17 day in March, 1994.Point out in the literary composition with the SYNTHETIC OPTICAL WHITNER in the washing composition α-Dian Fenmei to be lost activity, but Genencor has prepared the amylase that has improved oxidative stability from B.licheniformis NCIB8061 at automatic bowl.Methionine(Met) (Met) is consistent with the most probable resistates that will be modified.On the throne being changed on 8,15,197,256,304,366 and 438 of Met is substituted, and once replaces a position, and these replacements cause forming specific mutant strain, the particularly important is M197L and M197T, and the M197T variant is the variant that the most stable quilt is expressed.Stability is at CASCADE ^And SUNLIGHT ^Last measurement; (c) the especially preferred amylase of the present invention comprises the amylase variant of additional modification on intermediate parent body that is described among world patent WO 9510603 A, and can buy from commission merchant Novo, and its trade mark is DURAMYL ^Other particularly preferred oxidative stability enhanced amylase comprises those amylase among the world patent WO9402597 of the world patent WO 9418314 that is described in Genencor and Novo.The amylase that can use any other oxidative stability to strengthen, for example those derive from diastatic chimeric, the hydridization of known available or simple mutant strain parent form through site-directed mutagenesis.Other preferred enzyme-modified also is feasible.World patent WO 9509909 A referring to Novo.

The present invention's cellulase of great use comprises bacterium and mould type, and the pH value that preferably has is best between 5 and 9.5.United States Patent (USP) 4 people such as Barbesgoard, that be disclosed on March 6th, 1984,435,307 disclose the suitable mould cellulase from Humicola insolens or Humicola strain DSM 1800, or belong to the mould cellulase of a kind of 212 generations that Aeromonas belongs to, with the cellulase from the extraction of the hepatopancreas of sea mollusk, the truncation sea hare belongs to auricula spire (Dolabella Auricula Solander).Suitable cellulase also is disclosed in GB-A-2.075.028; Among GB-A-2.095.275 and the DE-OS-2.247.832.CAREZYME ^(Novo) be particularly useful.Also referring to the world patent WO 9117243 of Novo.

The suitable lipase that is used for washing composition comprises that this microorganism for example is disclosed in GB 1,372 by those lipase of Psedomonas group's microorganism preparation, the Pseudomonas stutzeri ATCC19.154 in 034.Also referring to the lipase in the Japanese patent application 53,20487 that is disclosed on February 24th, 1978.This lipase can (Amano Pharmaceutical Co.Ltd., Nagoya Japan) have bought, trade mark lipase P " Amano " by name or " Amano-P " from Japan Nagoya Ai Manuo Pharm Pur GmbH.Other suitable commercially available lipase comprises Amano-CES, derives from the lipase of Chromobacter viscosum, for example, make (the Toyo Jozo Co. of company limited available from Japanese peach precious jade friendship, Tagata, Chromobacter viscosum var.Lipolyticum NRRLB3673 Japan); Available from U.S. biological chemistry Products Co., Ltd (U.S.Biochemical Corp., U.S.A.) and Dutch enlightening hem with invisible stitches the Chromobacter viscosum lipase of this company (Disoynth Co.) and derive from the lipase of Pseudomonas gladioli.From Humicolalanuginosa deutero-and the LIPOLASE that buys from Novo ^Enzyme is also referring to European patent EO341, and 947, this enzyme is the lipase that the present invention preferably uses.Among world patent WO 9414951 A that the stable lipase of peroxidase and amylase variant are described in Novo.Also referring to WO 9205249 and RD 94359044.

The Cutinase enzyme that is suitable for the present invention's use is described among the WO 8809367 of Genencor.

Peroxidase can be used in combination with oxygen source, and for example, percarbonate, perborate, hydrogen peroxide etc. are used for " solution bleaching " or prevent transferring to other matrix the washing soln at washing process from the dyestuff of all removals of matrix or pigment.Known peroxidase comprises horseradish peroxidase, lignoenzyme (ligninase) and halo peroxidase, for example chloro-or bromo-peroxidase.The cleaning composition that contains peroxidase be disclosed in Novo, on October 19th, 1989 disclosed world patent WO 89099813 A and world patent WO 8909813 A of Novo in.

The scope of enzyme material and their methods in the synthesis of detergent composition of mixing also are disclosed in United States Patent (USP)s 3 people, that be disclosed on January 5th, 1971 such as the world patent WO 8908694 of world patent WO 9307263 A of Genencor International and world patent WO9307260 A, Novo and McCarty, in 553,139.Enzyme also is disclosed in United States Patent (USP)s 4,101,457 people, that be disclosed on July 18th, 1978 such as Place and the United States Patent (USP) 4,507,219 Hughes, that be disclosed on March 26th, 1985.Can be used for the enzyme material of liquid washing agent and they mixed such preparation being disclosed in the United States Patent (USP)s 4,261,868 people, that be disclosed on April 14th, 1981 such as Hora.The enzyme that is used for washing composition can make it stable through various technology.The enzyme stabilization technique discloses among European patent EO 199,405 Venegas, that be disclosed on October 29th, 1986 and the European patent EO 200,586 and illustrates at United States Patent (USP) 3,600,319 people such as Gedge, that be disclosed on August 17th, 1971.Enzyme stabilization system also is described in, and for example, United States Patent (USP) 3,519 is in 570.A kind of useful Bacillaceae, the specific proteases of AC13 class, zytase and cellulase are described among world patent WO 9401532 A of Novo.

The enzyme stabilization system-the present invention contains enzyme, comprises but does not limit, and liquid composition can comprise by the enzyme stabilization system weight and calculating, from about 0.001% to about 10%, and preferably from about 0.005% to about 8%, from about 0.01% to about 6% enzyme most preferably.The enzyme stabilization system can be any and the washing compatible stabilization system of enzyme.Such system can be provided by other preparation actives or inherently by for example, and formulator or the producer who prepares detergent enzyme add respectively.Such stabilization system can for example comprise calcium ion, boric acid, glycerol, short chain carboxy acid and their mixture, and is designed to handle the different types that depends on cleaning composition and the stabilization difficult problem of physical form.

A kind of stabilization method is a water-soluble sources of using calcium ion and/or magnesium ion in the ionic final composition providing to enzyme.Calcium ion more effectively and in the present invention is preferred than magnesium ion usually, if only use one type cationic words.Typical cleaning composition, especially liquid comprise from about 1 to about 30 in every liter of final composition, preferably from about 2 to about 20, more preferably from about 8 calcium ions to about 12 mmoles, still according to the factor that comprises diversity, type and the level of the enzyme that is impregnated in, various variations are feasible.Preferred water-soluble calcium and the magnesium salts of using comprises for example calcium chloride, calcium hydroxide, calcium formiate, calcium malate, calcium maleate, calcium hydroxide and lime acetate; More generally can use calcium sulfate or magnesium salts corresponding to the calcium salt of illustration.The level of the further increase of calcium and/or magnesium certainly is useful, for example, and in order to improve the degrease effect of tensio-active agent particular type.

Another stabilization method is the use of borate family compound.United States Patent (USP) 4,537,706 referring to Severson.The borate stablizer in use, the level in composition can be up to about 10% or higher, but for example sodium tetraborate or ortho-borate are calculated by weight level and are up to 3% and more typically are suitable for liquid washing agent and use for boric acid or other borate compound.The boric acid that replaces for example, the alternative boric acid of phenyl-boron dihydroxide, butane boric acid, right-bromophenyl boric acid or analogue uses, though used such replacement boron derivative, the level of the minimizing of total amount boron also is possible in the cleaning composition.

The stabilization system of specific cleaning compositions, automatic bowl composition for example, may further include the chlorine bleaching scavenging agent and calculate by weight from 0 to about 10%, preferably from about 0.01% to about 6%, add this bleaching scavenging agent to prevent that the chlorine bleach kind is damaged enzyme or made enzyme deactivation in many water supply things, especially under alkaline condition.The level of chlorine can be very little in the water, and typical scope, contacts with enzyme in the cumulative volume of water to about 1.75ppm from about 0.5ppm, is for example washing the dishes or is washing in the process of fabric, and useful chlorine can be relatively large; Therefore, enzyme is very difficult to the stability of the chlorine in using sometimes.Because having the perborate or the percarbonate of the ability of reacting with chlorine bleach may reside in the some compositions of the present invention, the amount that exists is illustrated respectively from stabilization system, so can use extra anti-chlorine stablizer usually, but optional, though use them can obtain the improvement of anti-chlorine stability.Suitable chlorine scavenger negatively charged ion is known widely and can buy, and if use, can be the sulphite that contains ammonium cation, hydrosulphite, thiosulfite, thiosulphate, iodide etc.The antioxidant of carbamate, ascorbate salt etc. for example, for example the organic amine and their mixture of ethylenediamine tetraacetic acid (EDTA) (EDTA) or its basic metal, monoethanolamine (MEA) can similarly be used.And specific enzyme suppresses system and can be impregnated in, and therefore different enzymes has maximum consistency.If desired, also can use other conventional scavenging agent, for example hydrosulfate, nitrate, muriate, peroxide source, for example the monohydrate of the tetrahydrate of Sodium peroxoborate, Sodium peroxoborate and SPC-D also can be used phosphoric acid salt, condensed phosphate, acetate, benzoate, Citrate trianion, formate, lactic acid salt, malate, tartrate, salicylate etc. and their mixture.In general, because the chlorine scavenger effect can (for example act on the known composition of listing respectively by it, hydrogen peroxide cource) finishes, therefore not absolute demand adds independent chlorine scavenger, does not finish this compound that affacts required degree unless do not exist in the present invention contains the embodiment of enzyme; Even the adding of scavenging agent only is in order to reach best effect.In addition, formulator can be exercised the chemist at the ordinary skill of avoiding using aspect any enzyme scavenging agent or the stablizer, and great majority are inconsistent when this kind of enzyme scavenging agent or stablizer and the allotment of other activeconstituents, if you are using.About the use of ammonium salt, such salt can mix with cleaning composition simply, but tends to planar water and/or discharge ammonia in storage process.Therefore, such material if any, for protecting ideally in particle, for example is described in the such material in people's such as Baginski the United States Patent (USP) 4,652,392.

Bleaching compounds- Bleaching agent and bleaching accelerator-cleaning composition of the present invention can be chosen wantonly and comprise bleaching agent or contain bleaching agent and the bleaching composition of one or more bleaching accelerators.When containing bleaching agent, the level of bleaching agent in cleaning composition typically can be from about 1% to about 30%, more typically from about 5% to about 20%, especially for laundering of textile fabrics.If contain the bleaching accelerator, the content of bleaching accelerator in the bleaching composition that comprises bleaching agent and bleaching accelerator is typically from about 0.1% to about 60%, more typically from about 0.5% to about 40%.

Be used for bleaching agent of the present invention and can be can be used for clean textile, cleaning of hard surfaces or other cleaning purpose any bleaching agent of cleaning composition, these cleaning purpose now known maybe can become known.These bleaching agents comprise oxygen bleaching or other bleaching agent.Perborate bleach, for example Sodium peroxoborate (for example, single-or tetrahydrate) can use in the present invention.

The another kind of bleaching agent that can not limit use comprises percarboxylic acids bleaching agent and its salt.The suitable example of this class reagent comprises the magnesium salts of monoperphthalic acid magnesium hexahydrate and metachloroperbenzoic acid, 4-nonyl amino-4-oxo Perbutyric Acid and diperoxy dodecanedicarboxylic acid.Such bleaching agent is disclosed in United States Patent (USP) 4 Hartman, that be disclosed on November 20th, 1984,483,781, U.S. Patent application 740,446 people such as Burns, that be filed on June 3rd, 1985, european patent application 0 people such as Banks, that be disclosed on February 20th, 1985,133,354 and United States Patent (USP) 4,412,934 people, that be disclosed in November 1 nineteen eighty-three such as Chung in.Bleaching agent very preferably comprises that also 6-nonyl amino-6-oxo crosses oxy hexanoic acid, and this compound is described in the United States Patent (USP)s 4,634,551 people, that be disclosed on January 6th, 1987 such as Burns.

Also can use peroxide bleaching reagent.Suitable peroxy bleaching compound comprises the peroxyhydrate of yellow soda ash and " percarbonate " SYNTHETIC OPTICAL WHITNER of equivalent, the peroxyhydrate of trisodium phosphate, the peroxyhydrate and the sodium peroxide of urea.Also can use persulphate SYNTHETIC OPTICAL WHITNER (for example, OXONE, Dupont makes sale).

The scope that preferred percarbonate bleach comprises mean particle size from about 500 microns to about 1,000 micron dried particles, calculate by weight no more than approximately 10% than about 200 microns little described particle, calculate by weight no more than about 10% than about 1,250 micron big described particle.Randomly, percarbonate can be coated with silicate, borate or water miscible tensio-active agent.Percarbonate can have been bought from various commercially available sources, for example FMC, Solvay and Tokai Denka.

Also can use the mixture of bleaching agent.

Peroxide bleaching reagent, perborate, percarbonate etc., preferably with the combination of bleaching accelerator, these bleaching accelerators cause producing on the spot corresponding to the aqueous solution (that is, in washing process) of the peroxy acid of bleaching accelerator.The various unrestricted example of accelerator is disclosed in United States Patent (USP)s 4,915,854 people, that be disclosed in April 10 nineteen ninety such as Mao and the United States Patent (USP) 4,412,934.Nonanoly acyloxy benzene sulfonate (NOBS) and tetraacetyl ethylene diamine (TAED) accelerator are typical, also can use their mixture.Other be can be used for typical SYNTHETIC OPTICAL WHITNER of the present invention and accelerator also referring to United States Patent (USP) 4,634,551.

Very preferably be those accelerators of following formula from amido deutero-bleaching accelerator:

R ¹N (R ⁵) C (O) R ²C (O) L or R ¹C (O) N (R ⁵) R ²C (O) L

Wherein, R ¹Be to contain from about 6 alkyl groups, R to about 12 carbon atoms ²Be to contain from 1 alkylidene group, R to about 6 carbon atoms ⁵Be H or contain that L is any suitable leavings group from about 1 alkyl, aryl or alkaryl to about 10 carbon atoms.Leavings group is any group of substituted bleach accelerator, and the result is bleaching on the accelerator by all-hydrolytic negatively charged ion nucleophilic attack.Preferred leavings group is the Phenylsulfonic acid root.

The preferred embodiment of following formula bleaching accelerator comprises (6-decoyl amino-caproyl) oxygen base benzene sulfonate, (the amino caproyl of 6-nonanoyl) oxygen base benzene sulfonate, (6-certain herbaceous plants with big flowers amido-caproyl) oxygen base benzene sulfonate and their mixture; as be described in United States Patent (USP) 4; 634; in 551, this patent is included this paper in as a reference.

Another kind of bleaching accelerator comprises the accelerator of benzo oxazinyl, is disclosed in the United States Patent (USP)s 4,966,723 people, that be disclosed in October 30 nineteen ninety such as Hodge, and this patent is included this paper in as a reference.Benzo oxazinyl accelerator very preferably is:

Also have another kind of preferred bleaching accelerator to comprise the acyl lactam accelerator, especially the acyl caprolactam of following formula and acyl group Valerolactim:

Wherein, R ⁶Be H or contain from about 1 alkyl, aryl, alkoxy aryl or alkylaryl group to about 12 carbon atoms.Lactan accelerator very preferably comprises benzoyl caprolactam, decoyl hexanolactam, 3,5,5-trimethyl acetyl hexanolactam, nonanoyl hexanolactam, caprinoyl hexanolactam, undecanoyl hexanolactam, benzoyl Valerolactim, decoyl Valerolactim, caprinoyl Valerolactim, undecanoyl Valerolactim, nonanoyl Valerolactim, 3,5,5-trimethyl acetyl Valerolactim and their mixture.Also referring to United States Patent (USP) 4,545,784 Sanderson, that be disclosed on October 8th, 1985, this patent is included this paper in as a reference, wherein discloses acyl caprolactam, comprises benzoyl caprolactam, is attracted in the Sodium peroxoborate.

The bleaching agent of non-oxygen bleaching reagent also is known in this area and can be used for the present invention.One type of bleaching agent that comprises photoactivation of the non-oxygen bleaching reagent of particularly important, for example sulfonated zinc and/or aluminium phthalocyanine.Referring to United States Patent (USP) 4,033,718 people such as Holcombe, that be disclosed on July 5th, 1977.If use, cleaning composition typically comprises calculates by weight such SYNTHETIC OPTICAL WHITNER of from about 0.025% to about 1.25%, especially sulfonic acid zinc phthalocyanine.

If desired, bleaching compounds can be through a kind of manganic compound catalysis.Such compound for example, is disclosed in United States Patent (USP) 5 known in this field and comprise, 246,621, United States Patent (USP) 5,244,594, United States Patent (USP) 5,194, and 416, United States Patent (USP) 5,114,606 and the open No.549 of european patent application, 271A1,549,272A1,544,440A2 and 544, the catalyzer among the 490A1 based on manganese; The preferred embodiment 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, Mn ^IV(1,4,7-trimethylammonium-1,4,7-7-triazacyclononane)-(OCH ₃) ₃(PF ₆) and their mixture.Other bleaching catalyst based on metal comprises and is disclosed in United States Patent (USP) 4,430,243 and United States Patent (USP) 5,114,611 in those bleaching catalysts.For strengthening bleaching, the use of manganese and various complex coordination bodies is also reported in following United States Patent (USP): 4,728,455; 5,284,944; 5,246,612; 5,256,779; 5,280,117; 5,274,147; 5,153,161; With 5,227,084.

As practice, rather than restriction, the present composition and method can be conditioned so that the active bleaching catalyst class of 1/10000000th order of magnitude to be provided in aqueous cleaning solution at least, and preferably provide from about 0.1ppm to about 700ppm more preferably catalyzer class in liquid in laundry from about 1ppm to about 500ppm.

The present composition and the method that are used for automatic bowl can be utilized cobalt (III) bleaching catalyst with following formula:

〔Co(NH ₃) _n(M) _m(B) _b〕T _y

Wherein, cobalt is+oxidation state of 3 valencys; N is 4 or 5 (preferably 5); M is by a site and one or more ligands of cobalt coordinate; M is 0,1 or 2 (preferably 1); B is by two sites and a kind of ligand of cobalt coordinate; B is 0 or 1 (preferably 0), when b=0, and m+n=6, when b=1, m=0, n=4; T is one or more counter anion of suitably selecting that exist with number y, and wherein y is an integer, and (y preferably 1 to 3 with the salt that obtains a kind of charge balance; Most preferably be 2, when T is negatively charged ion with an electric charge); The basic hydrolysis rate constant that wherein further described catalyzer has is less than 0.23M ^-1s ^-1(25 ℃).

Preferred T is selected from following groups: chlorine, iodine, I3-, formate, nitrate radical, nitrite anions, sulfate radical, inferior sulfate radical, citrate, acetate moiety, carbonate, bromine, PF ₆ ^-, BF ₄ ^-, B (Ph) ₄ ^-, phosphate radical, orthophosphite, silicate, tosylate, methanesulfonate and their composition.Randomly, if having in T more than a kind of anionic group, T can be by protonated so, for example, and HPO ₄ ^2-, HCO ₃ ^-, H ₂PO ^4-Deng.Say further, T can be selected from following material: unconventional inorganic anion, for example anion surfactant (for example, linear alkyl benzene sulfonate (LAS), alkyl-sulphate (AS), alkyl ethoxy sulfonate (AES) etc.) and/or anionic polymer (for example, polyacrylate, polyisobutene hydrochlorate etc.).

M partly comprises, but is not restrictedly, for example, and F ^-, SO ₄ ^-2, NCS ^-, SCN ^-, S ₂O ₃ ^-2, NH ₃, PO ₄ ^3-And carboxylate radical (monocarboxylic acid root preferably, but can have more than a kind of carboxylate radical in this part, as long as every part only has a kind of carboxylate radical to be connected on the cobalt, in this case, other carboxylate radical in the M part can be the form of the band protonated form of hydrogen or other salt).Randomly, if at M (for example, HPO ₄ ^2-, HCO ₃ ^-, H ₂PO ₄ ^-, HOC (O) CH ₂C (O) O ^-Deng) in have more than a kind of anionic group, M can be by protonated so.Preferred L partly is replacement or the unsubstituted C with following formula ₁-C ₃₀Carboxylic acid:

RC(O)O ^-

Wherein, R is preferably selected from following groups: hydrogen and C ₁-C ₃₀(preferred C ₁-C ₁₈) alkyl, the C that do not replace and replace ₆-C ₃₀(preferred C ₆-C ₁₈) aryl that do not replace and replace, and C ₃-C ₃₀(preferred C ₅-C ₁₈) heteroaryl that do not replace and replace, wherein substituting group is selected from following groups :-NR ' ₃,-NR ' ₄ ⁺,-C (O) OR ' ,-OR ' ,-C (O) NR ' ₂, wherein R ' is selected from hydrogen and C ₁-C ₆Part.Therefore substituted R like this comprises-(CH ₂) _nOH and-(CH ₂) _nNR ' ₄ ⁺Part, wherein n is from 1 to about 6 integer, preferably from about 2 to about 10, most preferably from about 2 to about 5.

Most preferred M is the carboxylic acid with following formula, and wherein R is selected from following groups: the C of hydrogen, methyl, ethyl, propyl group, straight or branched ₄-C ₁₂Alkyl and benzyl.Most preferred R is a methyl.Preferred carboxylic acid M partly comprises formic acid, phenylformic acid, sad, n-nonanoic acid, capric acid, laurostearic acid, propanedioic acid, toxilic acid, succsinic acid, hexanodioic acid, phthalic acid, 2 ethyl hexanoic acid, naphthenic acid, oleic acid, palmitinic acid, fluoroform carbonic acid, tartrate, stearic acid, butyric acid, citric acid, vinylformic acid, aspartic acid, fumaric acid, lauric acid, linolic acid, lactic acid, oxysuccinic acid, especially acetate.

B partly comprises carbonic ether, two-or higher carboxylicesters (for example, barkite, malonic ester, malate, succinate, maleic acid ester), pyridine carboxylic acid and α and beta amino acids (for example, glycine, L-Ala, Beta-alanine, phenylalanine).

The present invention's cobalt bleaching catalyst of great use is known, be described among " basic hydrolysis of transition metal complex " (" BaseHydrolysis of Transition-Metal Complexes ") of M.L.Tobe for example with their basic hydrolysis speed Adv.Inorg. Bioinorg.Meth., (1983), 2, pp 1-94.For example, provide the basic hydrolysis speed of cobalt five amine catalysts (in its literary composition, to be defined as k at 17 pages table 1 _OH), these cobalt five amine catalysts are by oxalate (k _OH=2.5 * 10 ^-4M ^-1s ^-1(25 ℃)), NCS ^-(k _OH=5.0 * 10 ^-4M ^-1s ^-1(25 ℃)), formate (k _OH=5.8 * 10 ^-4M ^-1s ^-1(25 ℃)) and acetate moiety (k _OH=9.6 * 10 ^-4M ^-1s ^-1(25 ℃)) complexing.Of great use preferred cobalt catalyst has formula (Co (NH among the present invention ₃) ₅OAc) T _y, wherein OAc represents the acetate part, cobalt five amine chloracetates especially, (Co (NH ₃) ₅OAc) Cl ₂(Wen Zhongwei " PAC "); Also can be (Co (NH ₃) ₅OAc) (OAc) ₂(Co (NH ₃) ₅OAc) (PF ₆) ₂(Co (NH ₃) ₅OAc) (SO ₄); (Co (NH ₃) ₅OAc) (BF ₄) ₂

These cobalt catalyst are easy to prepare by known method, for example, in the paper of for example above-mentioned Tobe and the method described in its reference of quoting, at United States Patent (USP) 4,810,410 people such as Diakun, that be disclosed on March 7th, 1989, J.Chem.Ed.(1989), 66(12), the method among the 1043-45; Synthetic and the characteristic (TheSynthesis and Characterization of Inorganic Compounds) of mineral compound, W.L.Jolly (Prentice-Hall; 1970), pp.461-3; Inorg.Chem., 18, 1497-1502 (1979); Inorg.Chem., 21, 2881-2885 (1982); Inorg. Chem., 18, 2023-2025 (1979); Inorg.Synthesis, 173-176 (1960); With Journal of Physical Chemistry, 56, 22-25 (1952).

These cobalt catalyst can be processed with adding material, and to reduce the color influence, if require the product aesthetic property, perhaps said composition can be manufactured to obtain catalyzer " color spot ".

As practice, rather than restriction, automatic bowl of the present invention can be conditioned so that the active cobalt catalyzer class of 1/10000000th order of magnitude to be provided in the aqueous cleaning medium with composition and method at least, and in washing liq, preferably provide to about 50ppm from about 0.1ppm, more preferably from about 1ppm to about 25ppm, cobalt catalyst class most preferably from about 2ppm to about 10ppm.In order to obtain such level in washing liq, the typical composition of the present invention comprises by composition weight and calculating from about 0.04% to about 1%, more preferably from about 0.08% to about 0.36% cobalt catalyst.

Washing assistant-detergent builder compound can randomly be included in the present composition, to help to control mineral substance hardness.Can use inorganic and organic washing-assisting detergent.Washing assistant typically uses in the fabric laundry composition, to assist in removing particulate fouling.

The level of washing assistant can change in wide range according to end-use and its required physical form of composition.When using washing assistant, composition typically comprises the washing assistant at least about 1%.Liquid preparation typically comprises to be calculated by weight from about 5% to about 50%, more preferably from about 5% to about 30% detergent builder compound.Granular preparation typically comprises calculates by weight from about 10% to about 80% more typical from about 15% to about 50% detergent builder compound.But, and do not mean that the lower or higher level that does not comprise washing assistant.

Detergent builder compound inorganic or that contain P comprises, but not restrictedly, the salt of the basic metal of polyphosphoric acid, ammonium and hydroxyalkyl ammonium (illustration is tri-polyphosphate, pyrophosphate salt and glassy polymeric metaphosphate), phosphonate, phytinic acid, silicate, carbonate (comprising supercarbonate and sesquicarbonate), vitriol and silico-aluminate.Yet some place needs the washing assistant of nonphosphate.Importantly, the present composition in addition " weak " washing assistant of so-called for example Citrate trianion (with phosphate ratio) in the presence of, or use zeolite or the issuable what is called of layered silicate washing assistant " to owe to help and wash " under the situation, astonishing effect is also arranged.

The example of silicate-like builder is an alkalimetal silicate, especially those SiO ₂: Na ₂The ratio ranges of O is 1.6: 1 to 3.2: 1 a alkalimetal silicate, and layered silicate, for example is described in the multilayer water glass in the United States Patent (USP) 4,664,839 H.P.Rieck, that be disclosed on May 12nd, 1987.The trade mark (being abbreviated as " SKS-6 " herein usually) of the crystalline layered silicate that NaSKS-6 is introduced to the market by Hoechst.Different with zeolite builders, Na SKS-6 silicate-like builder does not comprise aluminium.NaSKS-6 has the δ-Na of layered silicate ₂SiO ₅Morphology form.It can be by for example being described in German DE-A-3, and those methods in 417,649 and DE-A-3,742,043 prepare.SKS-6 is used for layered silicate very preferably of the present invention, but the present invention also can use other this layered silicate, for example has general formula NaMSi _xO _2x+1YH ₂Those layered silicates of O, wherein M is sodium or hydrogen, and x is from 1.9 to 4 numeral, is preferably 2, and y is from 0 to 20 numeral, is preferably 0.Various other layered silicates that derive from Hoechst comprise NaSKS-5, NaSKS-7 and the NaSKS-11 that exists with α, β and γ form.Point out as above-mentioned, be used for most preferably δ-Na of the present invention ₂SiO ₅(NaSKS-6 form).Also can use other silicate, for example Magnesium Silicate q-agent can play crisp reagent in granular preparation, and oxygen bleaching is played function of stabilizer, and is a composition of foam control system.

The example of carbonate builders is alkaline-earth metal and alkali-metal carbonate, openly is disclosed German patent application No.2 on November 15th, 1973, in 321,001.

The silico-aluminate washing assistant can be used for the present invention.The silico-aluminate washing assistant is extremely important in the heavy duty type particle cleaning composition that great majority have been introduced to the market at present, and also is a very important washing assistant composition in liquid washing agent.The silico-aluminate washing assistant comprises those washing assistants with following empirical formula:

Mz(zAlO ₂) _y〕·xH ₂O

Wherein, z and y are at least 6 integer, and from 1.0 to about 0.5, x is from about 15 to about 264 integer to z to the molar ratio range of y.

Aluminosilicate ion exchange material of great use can have been bought.These silico-aluminates structurally can be crystal formation or unbodied, can be naturally occurring or synthetic deutero-.The method for preparing aluminosilicate ion exchange material is disclosed in the United States Patent (USP)s 3,985,669 people, that be disclosed on October 12nd, 1976 such as Krummel.Can be used for the preferred synthetic commercially available trade mark of crystalline aluminosilicate ion exchange material of the present invention is A type zeolite, P (B) type zeolite, MAP type zeolite and X type zeolite.In particularly preferred embodiments, crystalline aluminosilicate ion exchange material has formula:

Na ₁₂〔(AlO ₂) ₁₂(SiO ₂) ₁₂〕·xH ₂O

Wherein, x is from about 20 to about 30, and especially 27.Known this material is an A type zeolite.The present invention also can use the zeolite (x=0-10) of dehydration.Preferably, the particle size diameter scope that has of silico-aluminate is about the 0.1-10 micron.

The organic detergent builder compound that is suitable for the object of the invention comprises, but is not restrictedly, various multi-carboxylate's compounds that scope is very wide.What " multi-carboxylate " used herein related to is to have a plurality of carboxylic acid groups, preferred at least 3 carboxylic acid groups' compound.The multi-carboxy acid salt washing agent joins in the composition with the form of acid usually, but also can add with the form of the salt that neutralized.When using the form of salt, basic metal, for example sodium, potassium and lithium or alkanol ammonium salts are preferred.

Be included among the multi-carboxy acid salt washing agent is various types of useful materials.A kind of very important type of multi-carboxylate comprises the ether multi-carboxylate, and this salt comprises oxygen base disuccinate, is disclosed in United States Patent (USP) 3 Berg, that be disclosed on April 7th, 1964,128,287 and United States Patent (USP) 3,635,830 people, that be disclosed on January 18th, 1972 such as Lamberti in.Also can be referring to " TMS/TDS " washing assistant in the United States Patent (USP) 4,663,071 people such as Bush, that be disclosed on May 5th, 1987.Suitable ether multi-carboxylate also comprises ring compound, and especially alicyclic compound for example is described in United States Patent (USP) 3,923,679; 3,835,163; 4,158,635; Those alicyclic compounds in 4,120,874 and 4,102,903.

Other useful detergent builder compound comprises ether hydroxypolycarboxylic acid salt, maleic anhydride and ethene or vinyl methyl ether, 1,3,5-trihydroxybenzene-2,4, the multipolymer of 6-trisulfonic acid and carboxymethyl oxygen base succsinic acid, poly-acetate is ethylenediamine tetraacetic acid (EDTA) and nitrilotriacetic acid(NTA) for example, also comprise multi-carboxylate for example mellitic acid, succsinic acid, oxygen base disuccinic acid, polymaleic acid, benzene 1,3,5-tricarboxylic acid, various basic metal, ammonium salt and the substituted ammonium salt of carboxyl methyl oxygen base succsinic acid and their soluble salt.

The Citrate trianion washing assistant, the soluble salt (particularly sodium salt) of citric acid and it for example, because they make them become the multi-carboxy acid salt washing agent of particularly important in the heavy duty type liquid washing agent from the feasibility of renewable resource acquisition and their biodegradable.Citrate trianion also can use in particulate composition, especially in the composition that is used with zeolite and/or layered silicate washing assistant.Oxygen base disuccinic acid in such composition and title complex also of great use.

The washing assistant that also is applicable to cleaning composition of the present invention is 3,3-dicarboxyl-4-oxa--1,6-adipate and disclosed allied compound in United States Patent (USP) 4,566,984 Bush, that be disclosed on January 28th, 1986.Succsinic acid washing assistant of great use comprises C ₅-C ₂₀Alkyl and alkenyl succinic and their salt.Particularly preferred compound is the dodecenyl succinic succsinic acid in this class washing assistant.The particular instance of succsinic acid washing assistant comprises: lauryl succinate, myristyl succinate, palmityl succinate, 2-dodecenyl succinic succinate (preferably), 2-ten pentaene base succinate and analogues.The lauryl succinate is preferred washing assistant in this group, is described in the european patent application 86200690.5/0,200,263 that is disclosed on November 5th, 1986.

Other suitable multi-carboxylate is disclosed in United States Patent (USP)s 4,144,226 people, that be disclosed on March 13rd, 1979 such as Crutchfield and the United States Patent (USP) 3,308,067 Diehl, that be disclosed on March 7th, 1967.Also referring to the United States Patent (USP) 3,723,322 of Diehl.

Lipid acid, for example C ₁₂-C ₁₈Monocarboxylic acid also can be incorporated in the composition separately or with above-mentioned washing assistant, especially Citrate trianion and/or succinate washing assistant, together so that additional washing assistant activity to be provided.This purposes of lipid acid causes foam to reduce usually, and this point should cause the attention of formulator.

When the washing assistant that uses based on phosphorus, especially use when being used for hand-washing the block preparation of operation, can use various alkali metal phosphates, for example known tripoly phosphate sodium STPP, trisodium phosphate and sodium orthophosphate.Also can use the phosphonate washing assistant, ethane-1-hydroxyl-1 for example, 1-diphosphonate and other known phosphonate (referring to, for example United States Patent (USP) 3,159, and 581; 3,213,030; 3,422,021; 3,400,148 and 3,422,137).

The polymerization washing agent-known polymerization washing agent, " SRA " that this paper back is used can choose wantonly and use in cleaning composition of the present invention.If use, the content of SRA in composition press composition weight calculating usually from 0.01% to 10.0%, typically from 0.1% to 5%, preferably from 0.2% to 3.0%.

Preferred SRA typically has hydrophilic segment so that hydrophobic fabric, the surface hydrophilic of polyester and nylon for example, and hydrophobic part, so that be deposited on the hydrophobic fabric, and above sticking in washing and rinse cycle complete process, this hydrophobic part plays the effect of the binding agent of hydrophilic segment so always.After handling with SRA, can make spot easier being cleaned in washing process subsequently of existence.

SRA can comprise various charged, for example negatively charged ion or even cationic, referring to United States Patent (USP) 4 people such as Gosselink, that be disclosed in September 11 nineteen ninety, 956,447, also comprise uncharged monomer, their structure can be line style, side chain or even star-like.They can comprise the end-blocking part, and it is especially effective aspect control molecular weight or change physics or surface-active property.Can project organization with charge distribution to be applicable to different fibers or fabric type and to be applicable to different washing composition or the detergent additive product.

Preferred SRA comprises oligomeric terephthalate, and typical preparation method relates at least a common catalytic transesterification/Oligomerisation of alkoxide with metal catalyst such as titanium (IV).Such ester can with extra can with 1,2,3,4 or the monomer that is incorporated in the ester structure of more position prepare, do not form the big crosslinked overall structure of density certainly.

Suitable SRA comprises it being the sulfonated products of linear ester oligopolymer basically, this oligopolymer comprise the oligomer ester main chain of terephthaloyl and oxygen base ethyleneoxy group repeating unit and covalent bonding on main chain from allyl group deutero-sulfonated end group, for example be described in United States Patent (USP) 4 J.J.Scheibel and E.P.Gosselink, that be disclosed in November 6 nineteen ninety, such oligopolymer in 968,451.Such ester oligomer can prepare through the following steps: (a) make the allyl alcohol alkoxylate; (b) make product and dimethyl terephthalate (DMT) (" DMT ") and 1 of (a) with two-stage transesterify/Oligomerisation method, 2-propylene glycol (" PG ") reaction; The product and the pyrosulphite hydrogen sodium of (b) are reacted in water.Other SRA comprises United States Patent (USP)s 4 people, that be disclosed on December 8th, 1987 such as Gosselink, 711, nonionic in 730 end capped 1,2-propylidene/polyoxy ethylidene terephthalic polyester, for example those polyester that prepare by the transesterify/Oligomerisation that gathers (ethylene glycol) methyl ether, DMT, PG and poly-(ethylene glycol) (" PEG ").Other example of SRA comprises: United States Patent (USP) 4 Gosselink, that be disclosed on January 26th, 1988,721, part in 580 and whole end capped oligomer ester of negatively charged ion, for example from ethylene glycol (" EG "), PG, DMT and 3, the oligopolymer that the 6-oxa--8-hydroxyl perfluorooctane sulfonate obtains; United States Patent (USP) 4 Gosselink, that be disclosed on October 27th, 1987,702, the end capped block polyester oligomeric compound of nonionic in 857, for example from PEG and the EG and/or the PG of DMT, methyl blocking, or those oligomeric compounds of the preparation of compositions of the PEG of DMT, EG and/or PG, methyl blocking and dimethyl-5-sulfo-m-phthalic acid sodium; With United States Patent (USP) 4 people such as Maldonado, Gosselink, that be disclosed on October 31st, 1989; 877; negatively charged ion in 896 is end capped; especially the end capped terephthalate of sulfo-aroyl; the latter be can be used for doing washing with and the fabric-conditioning product in typical SRA; example be from-ester composition of thiobenzoic acid list sodium salt, PG and DMT preparation, but randomly preferably further comprise the PEG of interpolation, PEG3400 for example.

SRA also comprises: the simple copolymerization block thing of ethylidene terephthalate or propylidene terephthalate and polyethylene oxide or poly(propylene oxide) terephthalate, referring to United States Patent (USP) 3 Hays, that be disclosed on May 25th, 1976,959,230 and United States Patent (USP) 3 Basadur, that be disclosed on July 8th, 1975,893,929; Derivatived cellulose, for example the trade mark that can buy from Dow company is the hydroxy ethers cellulose polymer compound of METHOCEL; C ₁-C ₄Alkylcellulose and C ₄Hydroxy alkyl cellulose is referring to United States Patent (USP) 4,000,093 people such as Nicol, that be disclosed on December 28th, 1976; And methyl cellulose ether, the average substitution degree (methyl) that each anhydrous grape sugar unit of this material has is from about 1.6 to about 2.3, the viscosity of solution 20 ℃ down with 2% aqueous solutions measurement from about 80 to about 120 centipoises.The commercially available trade mark of such material is METOLOSE SM100 and METOLOSE SM200, and this is the trade(brand)name of the methyl cellulose ether of Shin-etsu Kagaku Kogyo KK manufacturing.

The suitable SRA that it is characterized by poly-(vinyl ester) hydrophobic part comprises the graft copolymer of poly-(vinyl ester), for example, the C1-C6 vinyl ester, be preferably be grafted on polyalkylene oxide main chain on poly-(vinyl-acetic ester).Referring to people's such as Kud.Be disclosed in the european patent application 0 219 048 on April 22nd, 1987.Have commercially available example to comprise SOKALAN SRA, for example SOKALAN HP-22 can buy from German BASF AG.Other SRA polyester, its repeating unit contain the ethylidene terephthalate of calculating by weight 10-15% and what calculate by weight 80-90% is 300-5 from molecular-weight average, the polyoxy ethylidene terephthalate that 000 polyoxy ethylene glycol is derived and.Commercially available example comprises the ZELCON 5126 of Dupont company and the MILEASE T of ICI company.

Another preferred SRA is the oligopolymer with following empirical formula: (CAP) ₂(EG/PG) ₅(T) ₅(SIP) ₁This oligopolymer comprises terephthaloyl (T), sulfo-isophthaloyl (SIP), oxygen base ethyleneoxy group and Oxy-1; 2-propylidene (EG/PG) unit; preferred end-blocking (CAP) stops; be preferably the isethionic acid ester of modification; in oligopolymer, comprise a sulfo-isophthaloyl unit, 5 terephthaloyl unit, limit ratio; preferably be about 0.5: 1 to about 10: 1 oxygen base ethyleneoxy group and Oxy-1,2-propylidene oxygen base unit and two are from 2-(2-hydroxyl-oxethyl)-ethane sulfonic acid sodium deutero-end-blocking unit.Above-mentioned SRA preferably further comprises by oligopolymer weight and calculating, the stablizer that from 0.5% to 20% degree of crystallinity reduces, anion surfactant for example, as linear Sodium dodecylbenzene sulfonate or be selected from dimethylbenzene-, isopropyl benzene-and toluene-sulfonate in a kind of or their mixture, these stablizers or properties-correcting agent are added in the synthesising container, all these is at United States Patent (USP) 5 Gosselink, Pan, Kellett and Hall, that be disclosed in May 16 nineteen ninety-five, open in 415,807.The suitable monomers of above-mentioned SRA comprises 2-(2-hydroxyl-oxethyl)-ethane sulfonic acid sodium, DMT, dimethyl-5-sulfo-m-phthalic acid sodium, EG and PG.

Another group of preferred SRA also is oligomeric ester, comprise: (1) main chain, it comprises that (a) is selected from least one unit of dihydroxyl sulfonate, poly-hydroxy sulfonate, a unit of trifunctional at least, thereby generation ester bond, cause branched oligomeric main chain to generate, and their composition; (b) at least one unitary paraphenylene terephthalamide's base section; (c) unit of at least one unsulfonated, it is 1,2-oxygen base alkoxyl group oxygen base section; (2) one or morely be selected from following end-blocking unit: nonionic end-blocking unit, negatively charged ion end-blocking unit; for example oxyalkylated, isethionate, oxyalkylated propane sulfonate, oxyalkylated propane stilbene-4,4'-bis-(1-azo-3, 4-dihydroxy-benzene)-2,2'-disulfonate, oxyalkylated phenolsulfonate, sulfo-aromatic acyl derivative and their mixture of preferred ethoxylation.The ester of following empirical formula preferably:

{(CAP) _x(EG/PG) _y’(DEG) _y”(PEG) _y(T) _z(SIP) _z’(SEG) _q(B) _m}

Wherein, the above-mentioned definition of CAP, EG/PG, PEG, T and SIP such as this paper, (DEG) represent two (oxygen base ethylidene) oxygen base unit, (SEG) representative is from the unit of glycerine thio-ethyl ether deutero-unit and relevant portion, (B) chain unit of at least three functional groups of representative, thereby generation ester bond, cause branched oligomeric main chain, x is from about 1 to about 12, and y ' is from about 0.5 to about 25, y " from 0 to about 12; y from 0 to about 10; y '+y "+summation of y is from about 0.5 to about 25, and z is from 1.5 to about 25, and z ' from 0 to about 12; This of z+z ' is from about 1.5 to about 25, and q from about 0.05 to about 12; M is from about 0.01 to about 10, and x, y ', y ", y , z, z ', q and every mole of above-mentioned ester of m representative the mole mean number of corresponding units, and the molecular weight ranges of above-mentioned ester from about 500 to about 5,000.

The preferred SEG of above-mentioned ester and CAP monomer comprise 2-(2-, 3-dihydroxyl propoxy-) ethane sulfonic acid sodium (" SEG "), 2-{2-(2-hydroxyl-oxethyl) oxyethyl group } ethane sulfonic acid sodium (" SE3 ") and its homologue and their mixture and allyl alcohol ethoxylation and sulfonated products.Preferred SRA in this type of comprises the oxyethyl group with the 2-{2-of suitable Ti (IV) catalyst (2-hydroxyl-oxethyl) } ethane sulfonic acid sodium and/or 2-(2-{2-(2-hydroxyl-oxethyl) oxyethyl group }-oxyethyl group) ethane sulfonic acid sodium, DMT, 2-(2,3-dihydroxyl propoxy-) transesterify and the oligomerization product of ethane sulfonic acid sodium, EG and PG, its formula can be (CAP) ₂(T) ₅(EG/PG) _1.4(SEG) _2.5(B) _0.13, wherein CAP is (Na+O ₃S (CH ₂CH ₂O) _3.5)-, B is the glycerine unit, and the mol ratio of EG/PG is about 1.7: 1 with conventional vapor-phase chromatography measurement after complete hydrolysis.

The addition type of SRA comprises: (I) with the vulcabond coupler nonionic terephthalate is connected on the polymeric ester structure, referring to people's such as people's such as Violland United States Patent (USP) 4,201,824 and Lagasse United States Patent (USP) 4,240,918; (II) SRA of band carboxylate salt end group is by being added to trimellitic anhydride among the known SRA so that the end group oh group is converted into the trimellitic acid ester.Select appropriate catalyst, trimellitic anhydride is bonded on the end group of polymkeric substance by the ester of its isolated carboxylic acid rather than by the acid anhydride key is opened.Nonionic or anionic SRA may be used to parent material, as long as have can esterified hydroxyl end groups group for they.United States Patent (USP) 4,525,524 referring to people such as Tung.Other type comprises: (III) be various negatively charged ion SRA base, that be connected with urethanum with the terephthalate, referring to people's such as Violland United States Patent (USP) 4,201,824; (IV) poly-(caprolactam) and with the related copolymers of monomer such as vinyl pyrrolidone and/or dimethyl aminoethyl methylacrylic acid, comprise nonionic and cationic polymers, referring to people's such as Ruppert United States Patent (USP) 4,579,681; (V) graft copolymer also has the SOKALAN type of BASF AG in addition, prepares by Acrylic Acid Monomer is grafted on the sulfonated polyester.These SRA have de-sludging similar to known ether of cellulose and antiredeposition activity certainly: referring to Rhone-Poulenc Chemie, be disclosed in European patent EP 279,134 A in 1988.Other type also comprises: (VI) vinyl monomer such as vinylformic acid and vinyl-acetic ester are grafted to as the grafts on the caseic protein, referring to European patent EP 457,205 A of BASF AG (1991); (VII) polyester-polyamide SRA, by with hexanodioic acid, hexanolactam and polyoxyethylene glycol condensation prepared, be particularly useful for handling tynex, referring to people such as Bevan, Unilever N.V. company, be disclosed in German patent DE 2 in 1974,335,044.Other SRA of great use is described in United States Patent (USP) 4,240, in 918,4,787,989 and 4,525,524.

Sequestrant-cleaning composition of the present invention also can randomly comprise one or more iron and/or magnesium chelating substances.Such sequestrant can be selected from following material: aromaticity sequestrant that aminocarboxylate, amino phosphonates do, polyfunctional group replace and their mixture, all these defines in this paper back.Do not want to be bound by theory, can believe, the strong point of these materials is partly because they remove the special ability of iron ion and mn ion from washing soln by soluble chelating preparation.

The aminocarboxylate that can be used for optional sequestrant comprises edetate, N-Oxyethylethylenediaminetriacetic acid salt, nitrilo-triacetate, ethylenediamine tetraacetic proprionate, triethylenetetraaminehexaacetic acid salt, diethylentriamine pentacetate and ethanol diamino-acetic acid, their salt of basic metal, ammonium and replacement ammonium and their mixture.

When allowing low-level at least total amount phosphorus in cleaning composition, amino phosphonates do also can be used as sequestrant in the present composition, and comprises that the trade mark is the ethylenediamine tetraacetic (methylene phosphonic acid salt) of DEQUEST.Preferably, these amino phosphonates do do not comprise alkyl or the kiki alkenyl group more than about 6 carbon atoms.

The fragrant chelating agent that polyfunctional group replaces also can be used in the present composition.Referring to United States Patent (USP) 3,812,044 people such as Connor, that be disclosed on May 21st, 1974.This compounds of preferred sour form is a dihydroxyl dithio benzene, for example 1, and 2-dihydroxyl-3,5-dithio benzene.

Can be used for a kind of preferred biodegradable cheating agent of the present invention is ethylenediamine disuccinate (" EDDS "), especially be described in United States Patent (USP) 4 Hartman and Perkins, that be disclosed on November 3rd, 1987, (S, S) isomer in 704,233.

If use these sequestrants, the content of these sequestrants in cleaning composition of the present invention calculates by said composition weight so, usually from about 0.1% to about 10%.More preferably, if use these sequestrants, their content in this composition calculates by said composition weight, and from about 0.1% to about 3.0%.

Clay de-sludging/antiredeposition reagent-the present composition also can randomly comprise water miscible ethoxylated amine, and it has clay de-sludging and antiredeposition performance.The particle cleaning composition that comprises these compounds typically comprises from the about 0.01% water-soluble ethoxylated amine to about 10.0% (weight); Liquid detergent compositions typically comprises about 0.01% to about 5%.

Most preferred de-sludging and antiredeposition reagent are the tetrens of ethoxylation.Ethoxylated amine for example further is described in the United States Patent (USP) 4,597,898 VanderMeer, that be disclosed on July 1st, 1986.Another organizes preferred clay de-sludging-antiredeposition reagent is the cation compound that is disclosed in the european patent application 111,965 Oh and Gosselink, that be disclosed on June 27th, 1984.Other clay de-sludging/antiredeposition reagent that can use comprises the ethoxylated amine polymer that is disclosed in the european patent application 111,984 Gosselink, that be disclosed on June 27th, 1984; Be disclosed in the amphoteric ion polymer in the european patent application 112,592 Gosselink, that be disclosed on July 4th, 1984; With the amine oxide that is disclosed in the United States Patent (USP) 4,548,744 Connor, that be disclosed on October 22nd, 1985.Other clay de-sludging and/or the antiredeposition reagent that are known in the art also can be used in the present composition.The preferred antiredeposition reagent of another type comprises carboxymethyl cellulose (CMC) material.These materials are being known in the art.

Polymeric dispersant-polymeric dispersant can be to use the present composition from about 0.1% to the level of about 7% (weight), especially under the situation of zeolite and/or the existence of layered silicate washing assistant easily.Suitable polymeric dispersant comprises polymeric multi-carboxylate and polyoxyethylene glycol, though also can use other dispersion agent well known in the art.Can believe, do not want to be bound by theory, when polymeric dispersant and other washing assistant (comprising low-molecular-weight multi-carboxylate) when being used in combination, whole detergent builder compound performances have been strengthened by crystal growing restraining effect, particle de-sludging peptization and anti-redeposition.

Polymeric multi-carboxylate material can be by making the incompatible preparation of suitable polymerization of unsaturated monomers or copolymerization, preferably with their sour form.The acid that can be aggregated the unsaturated monomer that generates suitable polymeric multi-carboxylate comprises vinylformic acid, toxilic acid (or maleic anhydride), fumaric acid, methylene-succinic acid, equisetic acid, methylfumaric acid, citraconic acid and methylene radical propanedioic acid.In not comprising the polymeric multi-carboxylate of the present invention of carboxylate radical or in the monomer segment, for example vinyl methyl ether, vinylbenzene, ethene etc., the existence of dispersion agent is very suitable, condition is that such segment is formed no more than about 40% (weight).

Specially suitable polymeric multi-carboxylate can derive from vinylformic acid.Can be used for of the present invention such be that the polymkeric substance of base is the acrylic acid water-soluble salt of polymeric with vinylformic acid.The average molecular weight range of such polymkeric substance of acid form is preferably from about 2,000 to 10,000, more preferably from about 4,000 to about 7,000, most preferably from about 4,000 to about 5,000.The water-soluble salt of such acrylate copolymer can comprise that for example this class polymer soluble of the salt of basic metal, ammonium and replacement ammonium is a material known.This class polyacrylate use in cleaning composition is disclosed in, for example, and in the United States Patent (USP) 3,308,067 Diehl, that be disclosed on March 7th, 1967.

With vinylformic acid/toxilic acid is that the preferred component that the multipolymer of base also can be used as dispersion/antiredeposition reagent uses.Such material comprises the water-soluble salt of the multipolymer of vinylformic acid and toxilic acid.The average molecular weight range of such multipolymer of acid form is preferably from about 2,000 to 100,000, more preferably from about 5,000 to 75,000.Most preferably from about 7,000 to 65,000.In such multipolymer, acrylate to the segmental proportional range of maleate usually from about 30: 1 to about 1: 1, more preferably from about 10: 1 to 2: 1.The water-soluble salt of such vinylformic acid/maleic acid can comprise, for example, and the salt of basic metal, ammonium and replacement ammonium.Soluble acrylate/the maleate copolymer of this class is a material known, be described in european patent application No.66915 that is disclosed in December 15 nineteen eighty-two and the European patent EP 193 that is disclosed on September 3rd, 1986, in 360, EP 193,360 has also described the such polymkeric substance that comprises the hydroxypropyl acrylate.Other dispersion agent of great use also comprises the ter-polymers of toxilic acid/vinylformic acid/vinyl alcohol.Such material also is disclosed in the European patent EP 193,360, comprises, for example the ter-polymers of vinylformic acid/toxilic acid/vinyl alcohol 45/45/10.

The another kind of polymeric material that can be included in wherein is polyoxyethylene glycol (PEG).PEG can show the performance of dispersion agent, also can play the effect of clay de-sludging-antiredeposition reagent.For reaching these purposes, typical molecular weight ranges is from about 500 to about 100,000, preferably from about 1,000 to about 50,000, more preferably from about 1,500 to about 10,000.

Polyaspartic acid salts and polyglutamic acid dipersant also can use, and especially use simultaneously with zeolite builders.Preferably having as the dispersion reagent of poly aspartic acid is 10,000 molecular weight (on average).

Whitening agent-any optical whitening agent well known in the art or other brighten or the reagent that bleaches can be typically to be incorporated into the cleaning composition of the present invention from about 0.01% level to about 1.2% (weight).Can be used for commercially available optical whitening agent of the present invention and can be divided into the subgroup, it comprises, but not restrictedly, the derivative of following material: stilbene, pyrazoline, tonka bean camphor, carboxylic acid, methyne quinoline blue, thionaphthene-5,5-dioxide, azole, 5-and 6-unit's heterocycle and other all ingredients.Such whitening agent example is disclosed among " preparation of white dyes and application " (" The Production and Application of FluorescentBrightening Agent "), M.Zahradnik, New York John Wiley ﹠amp; Sons publishes.

The particular example that can be used for the optical whitening agent of the present composition is described in the United States Patent (USP) 4,790,856 Wixon, that be disclosed on December 13rd, 1988.These whitening agent comprise the PHORWHITE whitening agent series of Verona company.Disclosed other whitening agent comprises in this piece document: Tinopal UNPA, Tinopal CBS and Tinopal 5BM; Ciba-Geigy company; Artic White CC and Artic White CWD, 2-(4-styryl-phenyl)-2H-naphtho-(1,2-d) triazole; 4,4 '-two-(1,2,3-triazoles-2-yl)-stilbene; 4,4 '-two (styryl) phenylbenzene; And aminocoumarin.The particular example of these whitening agent comprises 4-methyl-7-diethyl amino coumarin; 1, the 2-two (ethylidene of benzimidazolyl-2 radicals-yl); 1,3-phenylbenzene-Pyrrolidine; 2,5-two (benzoxazole-2-yl) thio phenyl; 2-styryl-naphtho-(1,2-d 〕 oxazole; And 2-(stilbene-4-yl)-2H-naphtho-(1,2-d) triazole.Also referring to United States Patent (USP) 3,646,051 Hamilton, that be disclosed on February 29th, 1972.

Froth suppressorThe compound that-minimizing or inhibition foam generate can mix in the present composition.At United States Patent (USP) 4,489, in the what is called of describing in 455 and 4,489,574 " high density cleaning method " and in preceding year washing machine of European type, the foam inhibition effect of playing particularly important.

The various materials of wide range can be used as froth suppressor, and froth suppressor is known to those skilled in the art.Referring to, for example, Kirk Othmer chemical technology encyclopaedia (Encyclopedia of Chemical Technology), the third edition, the 7th volume, 430-447 page or leaf (John Wiley ﹠amp; Sons company limited, 1979).A useful especially class A foam A inhibitor comprises monobasic aliphatic carboxylic acid and its soluble salt.Referring to United States Patent (USP) 2,954,347 Wayne St.John., that be disclosed in September 27 nineteen sixty.Monobasic aliphatic carboxylic acid and its salt as froth suppressor typically have 10 to about 24 carbon atoms, the hydrocarbyl chain of limited 12 to 18 carbon atoms.Suitable salt comprises an alkali metal salt, for example the salt of sodium, potassium and lithium salts and ammonium and alkanol ammonium.

Cleaning composition of the present invention also can comprise the froth suppressor of nonsurfactant.These comprise.For example: the high-molecular weight hydrocarbon, as paraffin, fatty acid ester (for example, fatty acid glyceryl ester), the fatty acid ester of MHA, aliphatic C ₁₈-C ₄₀Ketone (for example, stearone) etc.Other froth suppressor comprises the alkylating aminotriazine of N-, for example three-or six-alkyl melamine or two-to four-alkyl diamine chloro triazine, be the product of cyanuryl chloride with two or three moles primary amine that contains 1 to 24 carbon atom or secondary amine formation, propylene oxide and a stearyl phosphoric acid salt, for example two-basic metal (for example, K, Na and Li) salt and the phosphoric acid ester of stearyl alcohol phosphoric acid ester and a stearyl phosphoric acid.Hydro carbons such as paraffin and halo paraffin can use with liquid form.Liquid hydrocarbon is a liquid under room temperature and barometric point, and the pour point scope that has is-40 ℃ and about 50 ℃ approximately, and minimum boiling point is not less than about 110 ℃ (environmental stresss).Also known, utilize preferably to have the wax shape hydrocarbon that is lower than about 100 ℃ of fusing points.Hydro carbons has constituted the preferred type of the froth suppressor of cleaning composition.The hydro carbons froth suppressor is described in, for example, and in the United States Patent (USP) 4,265,779 people such as Gandolfo, that be disclosed on May 5th, 1981.Therefore, hydro carbons comprises the saturated or undersaturated hydrocarbon compound of aliphatic series, alicyclic ring, aromatics and heterocyclic, has from about 12 to about 70 carbon atoms.Be used in this term " paraffin " that froth suppressor part is discussed and comprise the real paraffin and the mixture of cyclic hydrocarbon.

The another kind of preferred type of the froth suppressor of nonsurfactant comprises the siloxane foams inhibitor.This type comprises the use of organopolysiloxane oil, for example polydimethylsiloxane.The dispersion of organopolysiloxane oil or resin or emulsification and organopolysiloxane combine with silica dioxide granule, wherein the organopolysiloxane chemisorption or be melted on the silicon-dioxide.The siloxane foams inhibitor is known in this field, and for example, be disclosed among United States Patent (USP)s 4,265,779 people, that be disclosed on May 5th, 1981 such as Gandolfo and european patent application No.89307851.9 Starch, M.S., that be disclosed in February 7 nineteen ninety.

Other siloxane foams inhibitor is disclosed in United States Patent (USP) 3,455, and in 839, what this patent related to is the composition and the method for steeping aqueous solution, and this method is for mixing a small amount of polydimethylsiloxane liquid in said composition.

The mixture of siloxanes and silanization silica is described in, and for example, German patent application DOS2 is in 124,526.Silicone antifoam agent in the particle cleaning composition and foam control reagent are disclosed in the United States Patent (USP)s 4,652,392 people, that be disclosed on March 24th, 1987 such as people's such as Bartolotta United States Patent (USP) 3,933,672 and Baginski.

Being used for of the present invention is that basic froth suppressor illustration is the foam inhibition quantity that must contain the foam control reagent of following material with the siloxanes:

(i) polydimethylsiloxane liquid, the viscosity that under 25 ℃, has from about 20cs. to about 1,500cs..

(ii) calculate, contain from about 5 to about 50 parts silicone resin the (CH that this resin comprises in per 100 parts by the weight of (i) ₃) ₃SiO _1/2SiO in the unit ₂The unit is with (CH ₃) ₃SiO _1/2The unit is to SiO ₂Unitary ratio exists from about 0.6: 1 to about 1.2: 1 form; With

(iii) calculate, contain from about 1 to about 20 parts solid silicone in per 100 parts by the weight of (i).

In the preferred siloxane foams inhibitor of the present invention, the solvent that is used as external phase is made up of polyoxyethylene glycol or polyethylene glycol-propylene glycol copolymers or their mixture (preferably) or polypropylene glycol.Main siloxane foams inhibitor is a side chain/crosslinked, is not linear preferably.

In order to illustrate further this point, the typical liquid laundry of control foam randomly comprises from about 0.001 to about 1 with cleaning composition, preferably from about 0.01 to about 0.7, most preferably from about 0.05 to about 0.5 weight % above-mentioned siloxane foams inhibitor, this froth suppressor comprises the non-aqueous emulsion of the anti-foam reagent that (1) is main, wherein anti-foam reagent is the mixture of following material: (a) organopolysiloxane, (b) silicone compounds of resin type siloxanes or silicone resin preparation, (c) Xi Fen filler material, (d) catalyzer, to promote mix ingredients (a), (b) and reaction (c), thus generate the silane alkoxide; (2) at least a nonionic siloxane tensio-active agent; (3) polyoxyethylene glycol or polyethylene glycol-propylene glycol copolymers, this multipolymer at room temperature the solubleness in water greater than about 2 weight %; And do not contain polypropylene glycol.In particulate composition, jelly etc., can use similar quantity.Also referring to United States Patent (USP) 4,978,471 Starch, that be disclosed in December 18 nineteen ninety and United States Patent (USP) 4 Starch, that be disclosed on January 8th, 1991,983,316, United States Patent (USP) 5,288 people such as Huber, that be disclosed on February 22nd, 1994,431 and people's such as Aizawa United States Patent (USP) 4,639,489 and 4,749,740, the 1 hurdles, 46 row are to the 4th hurdle 35 row.

Siloxane foams inhibitor of the present invention preferably includes the multipolymer of polyoxyethylene glycol and polyethylene/polypropylene glycol, and the molecular-weight average of all polymkeric substance is less than about 1,000, preferably between about 100 and 800.The multipolymer of polyoxyethylene glycol of the present invention and the polyethylene/polypropylene glycol at room temperature solubleness in water is preferably greater than about 5 weight % greater than about 2 weight %.

The preferred solvent of the present invention is a polyoxyethylene glycol, and its molecular-weight average is less than about 1,000, more preferably between about 100 and 800, most preferably between 200 and 400 and the multipolymer of polyethylene/polypropylene glycol, is preferably PPG 200/PEG 300.The weight ratio of preferred polyoxyethylene glycol and polyethylene glycol-propylene glycol copolymers is between about 1: 1 and 1: 10, most preferably between 1: 3 and 1: 6.

Be used for preferred siloxane foams inhibitor of the present invention and do not contain polypropylene glycol, especially molecular weight is 4000 polypropylene glycol.They preferably do not contain the segmented copolymer of oxyethane and propylene oxide yet, as PLURONIC L101.

Can be used for the mixture that other froth suppressor of the present invention comprises secondary alcohol (for example, the 2-alkyl chain triacontanol) and has such alcohol of silicone oil, for example, be disclosed in United States Patent (USP) 4,798,679,4,075,118 and European patent EP 150,872 in siloxanes.Secondary alcohol comprises having C ₁-C ₁₆The C of chain ₅-C ₁₆Alkyl alcohol.Preferred alcohol is 2-butyl octanol, and its commercially available trade mark in Condea company is ISOFOL 12.The mixture of secondary alcohol is ISALCHEM 123 at the commercially available trade mark of Enichem company.The blended froth suppressor typically comprises the mixture of alcohol+siloxanes, and its weight ratio is 1: 5 to 5: 1.

For any cleaning composition that uses in automatic washing machine, foam should not be generated to the degree of overflowing washing machine.When using froth suppressor, froth suppressor preferably exists with " foam inhibition amount "." foam inhibition amount " meaning is the quantity that the formulator of composition can be selected this foam control reagent, thus this quantity effectively control foam cause being applicable to the low foam laundry washing composition of automatic washing machine.

The present composition generally includes from 0% to about 5% froth suppressor.When using froth suppressor, monobasic aliphatic carboxylic acid and its salt typically are not higher than about 5% quantity and exist to account for the cleaning composition weight ratio.Preferred from about 0.5% to about 3% the fatty monocarboxylic acid froth suppressor that uses.It is about 2.0% that siloxane foams inhibitor detergency usage quantity is that the weight ratio that accounts for cleaning composition is not higher than, though can use the more froth suppressor of a large amount.This upper limit is the result of practice, mainly is in order to keep the validity of minimum charge and low quantity when the effective control foam.Preferred from about 0.01% to about 1% the siloxane foams inhibitor that uses, more preferably from about 0.25% to about 5%.The value of these weight percents that the present invention uses comprises and can use any silica and operable any interpolation material in composition with organopolysiloxane.The normally used quantitative range of single stearyl phosphate froth suppressor accounts for the weight ratio from about 0.1% to about 2% of composition.The quantitative range that the hydro carbons froth suppressor typically uses from about 0.01% to about 5.0%, though can use higher levels of froth suppressor.The weight ratio that the scope that the alcohol froth suppressor typically uses accounts for final composition is 0.2%-3%.

Fabric softener-various fabric softeners in washing process, especially United States Patent (USP) 4 Storm and Nirschl, that be disclosed on December 13rd, 1977,062, the smectic clays of not really understanding in 647, and other tenderizer clay known in the art can be chosen use wantonly, levels typical in the present composition is from about 0.5% to about 10% (weight), so that provide the advantage of fabric-softening with clean fabric.The clay softening agent can be used in combination with amine and cationic softening agent, is disclosed in, for example, United States Patent (USP)s 4 people, that be disclosed on September 22nd, 1981 such as United States Patent (USP) 4,375,416 people such as Crisp, that be disclosed in March 1 nineteen eighty-three and Harris, in 291,071.

Dye transfer inhibitor-the present composition can comprise that also suppressing dyestuff transfers to one or more effective materials on the another kind of fabric from a kind of fabric in cleaning course.Usually, such dye transfer inhibitor comprises polyvinylpyrrolidonepolymers polymers, multipolymer, manganese phthalocyanine pigment, superoxide and their mixture of polyamine N-oxide pllymers, N-V-Pyrol RC and N-ethene imidazoles.If you are using, these reagent typically comprise by composition weight and calculating, from about 0.01% to about 10%, and preferably from about 0.01% to about 5%, more preferably from about 0.05% to about 2%.

More particularly, preferably be used in the unit that the polymkeric substance of N-oxide compound polyamine of the present invention comprises and have following structural: R-Ax-P; Wherein P is that a N-O group can connect the polymerizable unit on it, or the N-O group can form the polymerisable unit of part, or the N-O group can be connected on both; A be down one of array structure :-NC (O)-,-C (O) O-,-S-,-O-,-N=; X is 0 or 1; R is aliphatic series, aromatics, heterocycle or the alicyclic group of aliphatic series, ethoxylation, or the nitrogen among the N-O can connect on it or the N-O group is any composition in they of a part of these groups.R in the preferred N-oxide compound polyamine is that a heterocycle has, for example pyridine, pyrroles, imidazoles, Pyrrolidine, piperidines and their derivative.

The N-O group can be represented with following general formula:

Wherein, R ₁, R ₂, R ₃Be aliphatic series, aromatics, heterocycle or alicyclic group or their composition; X, y and z are 0 or 1; The nitrogen of N-O group can be connected or become the part in above-mentioned any one group.The unitary pKa of amine oxide＜10 in the N-oxide compound polyamine, preferred pKa＜7, preferred pKa＜6.

Can use any main polymer chain, as long as the amine oxide polymers that generates is water miscible and has the performance that suppresses dye transfer.The example of suitable polymers main chain is polyethylene, polyolefine, polyester, polyethers, polymeric amide, polyimide, polyacrylic ester and their mixture.These polymkeric substance comprise random or segmented copolymer, and wherein a kind of monomer type is a N-oxide compound amine, and other monomer type is the N-oxide compound.It is 10: 1 to 1: 1 to the ratio of N-oxide compound amine that N-oxide compound amine polymer typically has amine, 000,000.But the number of the amine oxide group in the polyamine oxide polymer can change according to suitable copolymerization or suitable N-degree of oxidation.The polyamine oxide compound can obtain in almost any polymerization degree.Typically, molecular-weight average is in 5,00 to 1000,000 scope; Preferred scope is 1,000 to 500,000; Most preferably be 5,000 to 100,000.The preferred type of this material can be with reference to " PVNO ".

The most preferably polyamine N-oxide that can be used for cleaning composition of the present invention is poly-(4-vinylpridine-N-oxide compound), and its molecular-weight average is about 50,000, and amine is about 1: 4 to the ratio of N-oxide compound amine.

The multipolymer of N-vinyl pyrrolidone and N-vinyl imidazole polymkeric substance (reftype is " PVPVI ") is also preferred to be used in the present invention.The average molecular weight range that PVPVI preferably has from 5,000 to 1,000,000, more preferably from 5,000 to 200,000, most preferably from 10,000 to 20,000.(average molecular weight range is measured with scattering of light, is described in people's such as Barth Chemical analysisIn (Chemical Analysis), Vol 113.Fit into this paper as a reference in " modernism of polymer property " (" Modern Methods of PolymerCharacterization ") is disclosed.) the PVPVI multipolymer typically have the N-vinyl imidazole to the ratio of N-vinyl pyrrolidone from 1: 1 to 0.2: 1, more preferably from 0.8: 1 to 0.3: 1, most preferably from 0.6: 1 to 0.4: 1.These multipolymers can be linear or side chain.

The present composition also can comprise Polyvinylpyrolidone (PVP) (" PVP "), and its molecular-weight average is from about 5,000 to about 400,000, preferably from about 5,000 to about 200,000, most preferably from about 5,000 to about 50,000.Concerning the technician of detergent applications, PVP is known; Referring to, for example, EP-A-262,897 and EP-A-256,696, it includes this paper in as a reference.The composition that comprises PVP also can comprise polyoxyethylene glycol (" PEG "), its molecular-weight average from about 500 to about 100,000, preferably from about 1,000 to about 10,000.Preferably, in washing soln, delivered with ppm be the PEG of unit to the ratio of PVP from about 2: 1 to about 50: 1, more preferably from about 3: 1 to about 10: 1.

Cleaning composition of the present invention can randomly contain from the particular type of the hydrophilic optical whitening agent of about 0.005% to 5% (weight), and this optical whitening agent also provides the effect that suppresses dye transfer.If you are using, the present composition preferably includes from such optical whitening agent of about 0.01% to 1% (weight).

Can be used for hydrophilic optical whitening agent of the present invention and have structural formula:

Wherein, R ₁Be selected from anilino, N-2-two-hydroxyethyl and NH-2-hydroxyethyl; R ₂Be selected from N-2-pair-hydroxyethyl, N-2-hydroxyethyl-N-methylamino, morpholinyl, chlorine and amino; M gives birth to salifiable positively charged ion, for example sodium or potassium.

In following formula, work as R ₁Be anilino, R ₂Be N-2-two-when hydroxyethyl and M were the positively charged ion of for example sodium, whitening agent was 4,4 '-two ((4-anilino-6-(N-2-two-hydroxyethyl)-s-triazine-2-yl) amino)-2,2 '-stilbene sulfonic acid and disodium salt.The commercially available trade mark of this special whitening agent type is Tinopal-UNPA-GX, is the product of Ciba-Geigy company.Tinopal-UNPA-GX is the hydrophilic optical whitening agent that preferably can be used for cleaning composition of the present invention.

In following formula, work as R ₁Be anilino, R ₂Be N-2-hydroxyethyl-N-2-methylamino and M when being the positively charged ion of for example sodium, whitening agent is 4,4 '-two ((4-anilino-6-(N-2-hydroxyethyl-N-methylamino)-s-triazine-2-yl) amino) 2,2 '-stilbene disulfonic acid and disodium salt.The commercially available trade mark of this special whitening agent type is Tinopal5BM-GX, is the product of Ciba-Geigy company.

In following formula, work as R ₁Be anilino, R ₂Be morpholinyl and M when being the positively charged ion of for example sodium, whitening agent is 4,4 '-two ((4-anilino-6-morpholinyl-s-triazine-2-yl) amino) 2,2 '-stilbene sulfonic acid and disodium salt.The commercially available trade mark of this special whitening agent type is Tinopal AMS-GX, is the product of Ciba-Geigy company.

Be selected to this special optical whitening agent type of the present invention when the selecteed polymeric dye transfer inhibitor with the preamble description is used in combination, effective dye transfer rejection especially can be provided.Selecteed like this polymeric material (for example, PVNO and/or PVPVI) and the composition of selecteed like this optical whitening agent (for example, Tinopal UNPA-GX, Tinopal 5BM-GX and/or Tinopal AMS-GX) remarkable good dye transfer restraining effect in aqueous cleaning solution, can provide than their independent uses the time.Do not want to be bound by theory, can believe, such whitening agent has this effect to be because they have high-affinity to fabric in washing soln, therefore is deposited on relatively quickly on these fabrics.In washing soln, the degree that whitening agent is deposited on the fabric can limit by the parameter that is called " on dye constant ".On dye the normally such ratio of constant: a) be deposited on whitening agent material on the fabric to b) ratio of initial whitening agent concentration in washing liq.Having the whitening agent that dyes constant on high relatively is the optimal dye transfer inhibitor of the present invention.

Certainly, the compound of known other conventional optical whitening agent type can be chosen wantonly and use in the present composition, " brighten " effect so that conventional fabric to be provided, rather than real dye transfer suppresses effect.Such purposes is routine and known to detergent compositions.

PH and buffering variation

Many automatic bowl cleaning composition of the present invention are buffer-types, and for example, they can resist the pH drops in the presence of acid dirt.But other composition of the present invention can have lower surge capability exceptionally, or can be buffered not basically.Control or the technology that changes pH comprise and not only use buffer reagent under the usage level of recommending, and comprise additional alkali, acid, pH transition system, double container etc., and this technology is known to those skilled in the art.

The preferred ADD composition of the present invention comprises the pH regulator composition that is selected from water-soluble alkaline inorganic salt and water-soluble organic or inorganic washing assistant.Select the pH regulator composition, make when ADD with 1,000-5, when the concentration of 000ppm was dissolved in the water, the scope that pH keeps was greater than about 8, preferably from about 9.5 to about 11.The preferred non-phosphorus pH regulator composition of the present invention is selected from following material:

(i) yellow soda ash or concentrated crystal soda;

(ii) water glass is preferably moisture water glass, the SiO that it has ₂: Na ₂The O ratio is from about 1: 1 to about 2: 1 with their mixture of restriction Starso quantity;

(iii) Trisodium Citrate;

(iv) citric acid

(v) sodium bicarbonate

(vi) Sodium Tetraborate is preferably borax;

(vii) sodium hydroxide; With

(viii) (i)-(mixture vii).

Embodiment preferred comprises low-level silicate (that is from about 3% to about 10% SiO, ₂).

It is the binary mixture of granular Trisodium Citrate and anhydrous sodium carbonate and the tertiary mixture of granular Trisodium Citrate trihydrate, citric acid monohydrate compound and anhydrous sodium carbonate that pH regulator very preferably becomes the illustration of sub-system.

The amount of pH regulator composition is pressed composition weight and is calculated in ADD composition of the present invention, and preferably from about 1% to about 50%.In preferred embodiments, the amount that the pH regulator composition exists in the ADD composition is from about 5% to about 40%, preferably from about 10% to about 30% (weight).

Concerning the present composition of pH value between about 9.5 and about 11 of the initial wash solution that has, particularly preferred ADD embodiment comprises by ADD weight to be calculated, from about 5% to about 40%, preferably from about 10% to about 30%, from about 15% to about 20% Trisodium Citrate and from about 5% to about 30% most preferably, preferably from about 7% to about 25%, from about 8% to about 20% yellow soda ash most preferably.

Necessary pH regulator system can replenish (promptly by other optional detergent builder compound salt, the sequestering action of improvement in hard water), wherein detergent builder compound salt is selected from nonphosphate detergent builder compound well known in the art, and this washing assistant comprises basic metal, the ammonium of various water miscible boric acid or replaces salt, hydroxy sulfonate, polyacetic acid salt and the multi-carboxylate of ammonium.The such salt of basic metal, the especially sodium of material preferably.The water miscible non-phosphorus organic washing-assisting detergent of alternate is owing to their chelating character can be used.Polyacetic acid salt and multi-carboxy acid salt washing agent's example is the salt of sodium, potassium, lithium, ammonium and the replacement ammonium of ethylenediamine tetraacetic acid (EDTA); Nitrilotriacetic acid(NTA), monosuccinic acid tartrate, disuccinic acid tartrate, oxygen base disuccinic acid, carboxyl methoxyl group succsinic acid, mellitic acid and benzene polycarboxylic acid's sodium salt.

(a) water-soluble silicate

Automatic bowl of the present invention may further include water miscible silicate with cleaning composition.Water-soluble silicate of the present invention is have water-soluble to not playing any silicate that spot/film forming characteristics cause negative impact to the ADD composition.

The example of silicate is a Starso, more generally be alkali-metal silicate, particularly SiO ₂: Na ₂The ratio ranges of O is 1.6: 1 to 3.2: 1 those alkalimetal silicates and a layered silicate, for example, and the lamina sodium silicate in United States Patent (USP) 4,664,839 H.P.Rieck, that be disclosed on May 12nd, 1987.NaSKS-6 ^It is the layered silicate (this paper is abbreviated as " SKS-6 " usually) of introducing to the market by Hoechst.Different with zeolite builders, can be used for Na SKS-6 of the present invention and other water miscible silicate and do not contain aluminium.NaSKS-6 is the δ-Na of layered silicate ₂SiO ₅Form, and can be by for example being described in German patent DE-A-3, the method preparation in 417,649 and DE-A-3,742,043.SKS-6 is used for preferred layered silicate of the present invention, but also can use other such layered silicate, for example, has general formula NaMSi _xO _2x+1YH ₂Those layered silicates of O, wherein M is sodium or hydrogen.X is from 1.9 to 4 number, preferably 2, and y is from 0 to 20 number, preferably 0.Various other the layered silicates of Hoechst company comprise NaSKS-6, NaSKS-7 and NaSKS-11, for α-, β-and γ-form.Also can use other silicate, Magnesium Silicate q-agent for example, it is crisp reagent in granular preparation, is stablizer for oxygen bleaching agent, and as a composition in the foam control system.

The silicate that is used in particular for automatic bowl (ADD) application comprises that granular aqueous ratio is 2 silicate, for example, and the BRITESIL of Pq Corp. ^H ₂O and common BRITESIL as the source ^H24, but when the ADD composition is liquid form, can use the various silicate of liquid fraction.In safe limit, Starso or sodium hydroxide can be separately or are combined and used among the ADD with other silicate and reach required level with the pH that impels washings.

The material nursing agent-ADD composition of the present invention can comprise one or more material nursing agents, is effective as corrosion inhibitor and/or antirust washing assistant.Such material is wash the dishes a preferred component with composition of machine, especially in some European countries, table ware use electroplate nickeline and fine silver still quite general, or be still under the low situation of the silicate content of a problem and composition in the aluminium protection.Usually, such material nursing agent comprises metasilicate, silicate, bismuth salt, manganese salt, paraffin, triazole, pyrazoles, thio-alcohol, mercaptan, fatty acid aluminium salt and their mixture.

When using such protecting materials, they preferably mix with low-level, for example in the ADD composition from about 0.01% to about 5%.Suitable corrosion inhibitor comprises paraffin oil, is typically the aliphatic hydrocarbon of main side chain of the scope from about 20 to about 50 of the carbonatoms that has; Preferred paraffin oil is selected from cyclic hydrocarbon is about 32: 68 main side chain to the ratio of non-cyclic hydrocarbon C ₂₅-C ₄₅Type.The paraffin oil that satisfies those characteristics is sold by German Salzbergen Wintershall company, and trade mark is called WINOG 70.In addition, add low-level Bismuth trinitrate (that is Bi (NO, ₃) ₃) also be preferred.

Other corrosion inhibition immunomodulator compounds comprises benzotriazole and reference compound; The mercaptan or the thio-alcohol that comprise thionaphthol and sulfo-anthrol; Homodisperse fatty acid aluminium salt, for example Aluminium Tristearate Micronized sterile.Formulator knows that such material reasonably and uses usually with limiting to a number or amount, to avoid any meeting to generate spot or film forming on glasswork or to have influence on the trend of composition bleaching action.For this reason, the mercaptan funcitonal rust-proof agent of very strong bleaching activity and particularly generate sedimentary common fats carboxylic acid with calcium and preferably avoid using is arranged.

Other composition-other composition of can be used for the wide range of cleaning composition can be included in the composition of the present invention, comprise other activeconstituents, carrier, hydrotropic agent, processing washing assistant, dyestuff or pigment, be used for liquid preparation solvent, be used for the solid weighting agent of bar composition etc.High if desired bubble, for example the foam growth substance of C10-C16 alkanolamide can be incorporated in the composition, and typical level is 1%-10%.The C10-C14 monoethanolamine-and diglycollic amide be a typical class A foam A growth substance.It also is effectively that such foam growth substance uses with for example above-mentioned oxidation amine, betaines and the thetine class of height bubble attaching surface promoting agent.If desired, soluble magnesium salts, for example MgCl ₂, MgSO ₄Can be added into analogue, typical level is 0.1%-2%, removes greasy performance additional foam to be provided and to strengthen.

The various cleaning ingredients of use in the present composition can randomly further be stabilized by mentioned component is adsorbed on the porous hydrophobic matrix, then hydrophobic coating are coated on the described matrix.Preferably, cleaning ingredients mixed before being attracted on the porous matrix with tensio-active agent.In use, cleaning ingredients is discharged into from matrix in the aqueous cleaning liquid, thereby plays cleaning function.

In order to illustrate in greater detail this technology, (trade mark is SIPERNATD10 to the porous hydrophobic silica, DeGussa) with the C that contains 3%-5% _13-15The decomposition of protein enzyme solution of the alcohol of ethoxylation (EO 7) nonionogenic tenside mixes.Typically, enzyme/surfactant soln is 2.5 times of silica weight.The powder that obtains is dispersed in the silicone oil that is stirring and (can uses range of viscosities to be 500-12,500 various silicone oil).The silicone oil dispersion liquid that obtains is emulsified or be added in the final washing matrix.By this method; compositions such as for example above-mentioned enzyme, SYNTHETIC OPTICAL WHITNER, bleaching accelerator, bleaching catalyst, photoaccelerators, dyestuff, fluorescent agent, fabric conditioner and hydrolyzable tensio-active agent can use at washing composition with being " protected ", comprise that liquid laundry is with in the cleaning composition.

Liquid detergent compositions can be moisture and other solvent as carrier.Low-molecular-weight primary alconol or secondary alcohol are proper, and example is methyl alcohol, ethanol, propyl alcohol and Virahol.MHA is preferred for making surface active agent solubilization, also can use but for example contain from 2 to about 6 carbon atoms with from 2 those polyvalent alcohols to about 6 oh groups (for example, 1, ammediol, ethylene glycol, glycerine and 1,2-propylene glycol).Composition can comprise from 5% to 90%, is typically such carrier of 10% to 50%.

Cleaning composition of the present invention is being used for the preferred preparation like this of aqueous cleaning operating process, and the pH of washing water is between about 6.5 and about 11, preferably between about 7.5 and 10.5.Liquid washes the dishes pH with product formulation between about 6.8 and about 9.0.The pH of laundry product is typically 9-11.The technology of control pH comprises the use of buffer reagent, alkali, acid etc. under recommended levels, and this technology is known to those skilled in the art.

High-density granulated cleaning composition

Glass particles delivery system of the present invention can be used in low density (being lower than 550 grams per liters) and the high-density granulated cleaning composition, and wherein particulate density is at least 550 grams per liters.Highdensity like this cleaning composition typically comprises from about 30% to about 90% detergent surfactant.

Low-density compositions can be by the preparation of standard spray drying process.The whole bag of tricks and equipment can be used for preparing high-density granulated cleaning composition.The commercial production in this field at present uses spray-drying tower to prepare density usually less than the granular laundry washing composition of about 500g/l.Therefore, if spraying drying is the part in the entire method, the method and apparatus that so resulting spray-dired washing granule must be described later with this paper is by further multiviscosisty.Another kind of alternative method, formulator can be got rid of spraying drying by using commercially available mixing, multiviscosisty and granulating equipment.Be exactly below being applicable to the non restrictive description of such equipment of the present invention.

Super mixer/thickener can be used for the inventive method.For example, the market ATTACH LABEL comprises an immobilized cylinder mixing drum for the recirculator of " L dige CB30 ", in the middle of it turning axle is arranged, and mixing/bite is housed on the turning axle.Other such equipment comprises the equipment of market ATTACH LABEL for " Shugi Granulator " and " Drais K-TTP 80 ".The market ATTACH LABEL can be used for further multiviscosisty for the equipment of " Lodige KM600 Mixer ".

A kind of operating method is arranged, and composition is by two mixing tanks of placing continuously and thickener prepares and multiviscosisty.Therefore, the composition of required composition can be mixed, and by a L dige mixing tank, the residence time is 0.1 to 1.0 minute then, and then by second L dige mixing tank, the residence time is 1 minute to 5 minutes.

Another kind of operating method comprises that the aqueous slurry of required preparation composition is injected in the granule surface activity agent fluidized-bed.The particle that obtains can be by Lodige equipment further by multiviscosisty.Glass particles is mixed in Lodige equipment with cleaning composition.

Particulate final densities of the present invention can be measured by various simple technology, and this technological model ground comprises a certain amount of granulated detergent is distributed in the container of known volume that the weight and the unit of calculating of measuring washing composition are the density of grams per liter.

In case having prepared with low or high-density granulated detergent is the composition of base, glass particles delivery system then of the present invention just joins in the said composition by any suitable drying-married operation.

Laundering of textile fabrics and thereon the method for depositing perfume comprise with above-described and comprising at least about the aqueous cleaning liquid of the conventional cleaning ingredients of 100ppm with at least about the above-mentioned disclosed spices delivery system contact fabric of 1ppm.Preferably, above-mentionedly liquid, aqueously comprise from about 500ppm to about 20 the conventional cleaning ingredients of 000ppm and spices delivery system from about 10ppm to about 200ppm.

The glass particles delivery system can be worked under all environment, still, is particularly useful for providing fragrance scent in storage, drying or iron process on fabric.This method comprises with comprising at least about the conventional cleaning ingredients of 100ppm with at least about the spices delivery composition contact fabric of 1ppm, store the fabric of hang airing by be at least 20% environment in humidity under regulating, in conventional automatic dryer dry fabric or provide heat to the fabric of hang airing or machine dry with the method (preferred Steam Press or wetting in advance) of low temperature flatiron, the zeolite granular with spices is loaded on the fabric.

Following unrestricted embodiment illustrates parameter and the composition that the present invention uses.Unless stated otherwise, otherwise all per-cent, part and ratio all calculate by weight.

Embodiment 1

1. be loaded with the prepare zeolite of spices

The Na-X type zeolite (＜5% residual moisture) that 10gr was activated is put into the mixing equipment of simple mixer or coffee grinding machine type.The spices of 1.5gr is added wherein in the mode that drips.This mixture stir about 10 minutes obtains being loaded with the PLZ (being loaded with the zeolite of spices) of 15%w/w.

2. the preparation of low moisture sucrose slurries (Tg=57 ℃)

75gr sucrose is mixed with the distilled water of 25gr.This system continuing heating under the stirring, until removing enough water, is obtained containing the slurries of 2-5%.Under atmospheric pressure, to cause the boiling spread of heavy-gravity slurries be 150-160 ℃ to low-level like this water.

3.PLZ and the combination of low moisture sucrose slurries

Low moisture sucrose slurries under agitation are cooled to about 90 ℃, at this moment PLZ are added this slurries.Typically, add the PLZ of 20-30% (weight), high-caliber PLZ needs high-octane input (for example, using the mixing tank or the extrusion machine of big moment), to overcome the increase of viscosity.

4. glass particles formation/size variation

The dispersion liquid of PLZ in the sucrose slurries is cooled to envrionment temperature.When this system temperature drops to the glass transition temp that is lower than sucrose, just obtained vitrification system, this system can be ground makes various granular sizes.Another kind of selectable mode, this system can be become particle or spherolite to generate the particle of required size and shape at its elastic state or plastic stage.

5. the glassy particles of step (4) and the combination of washing composition

2.22% glassy particles be introduced in the detergent compositions, the PLZ of said preparation delivery 0.67% and 0.1% spices.

Embodiment 2

Similarly implement with embodiment 1, but the be to use sucrose/Star Dri 5 mixture of 80: 20 (D.E.=10).Such system also can comprise the oligose of sucrose or other low MW and the mixture of glycan or starch, and its D.E. is less than 15, and preferred＜10 are at least 10%w/w.Typical sucrose/Star Dri 5 melt comprises 80% sucrose and contains the 20%LoDex 5 (available from U.S. Maize) of 2% water.Then this melt is joined in ZSK 30 Werner and the Pfleiderer double-screw extrusion machine, PLZ adds with the 7th zone of 20%w/w/ level at extrusion machine.Extrudate is cooled to 90 ℃ and cut and make size and be the particle of 500-1000 μ m.

Claims (3)

1. a laundry is used or cleaning composition, and said composition comprises:

(A) calculate by said composition weight, from 0.1% to 10% glass particles and

(B) calculate by said composition weight, non-the soaping of one or more of from 0.1% to 90% washed active material;

From 1 to 500 micron of the mean particle size that wherein said glass particles has, and comprise the spices that is adsorbed on the zeolite and is encased by the glassy mass of sugar, the scope of the Tg that described glassy mass has is from 50 ℃ to 200 ℃;

The composition of wherein said glass particles, the listed as parts by weight of pressing composition recently is expressed as follows with the percentage that accounts for the glass particles total amount:

(a) calculate by weight from 2% to 40% described spices;

(b) from 2% to 95% described zeolite, the surface-area that described zeolite has is 50m ²/ g or higher;

(c) from 12% to 96% sugar that is selected from sucrose, Star Dri 5, lactose and their mixture; With

(d) from 0.05% to 35% water or softening agent;

Its condition be each component concentration per-cent and must be 100%.

2. the composition in the claim 1, wherein said spices comprises calculates by weight from 50% to 100% delivered reagent.

3. the composition in the claim 1, said composition have cloth-washing detergent, the laundry form with detergent additive or fabric softener, and the sugar that wherein forms described glassy mass can be processed as extrudable liquid when 60 ℃ to 160 ℃ of temperature ranges; 40% spices of no more than described spices total amount dissociates out from described fragrance carrier material; The moisture no more than 7% that the described glass particles that is prepared into is contained.