CN1258312A - Detergent composition - Google Patents

Abstract

The invention relates to the use of a hydrotrope in a detergent composition, which comprises an anionic sulphate surfactant and which upon contact with water can form a viscous mixture of water and the particle, to reduce the viscosity of this mixture. The invention also relates to a granular detergent composition, comprising an anionic sulphate surfactant, present at a level of from 0.01 % to 95 % by weight of the composition, and a hydrotrope, present at a level of from 0.01 % to 60.0 % by weight of the composition. The invention also relates to a detergent particle comprising an anionic sulphate surfactant and a hydrotrope.

Description

Detergent composition

Technical field

The present invention relates to a kind of granular detergent composition that comprises sulphate anion surface active agent and solubilizing agent.The present invention also relates to comprise the detergent particles thing of sulphate anion surface active agent and solubilizing agent.The present invention also relates to solubilizing agent in the purposes that comprises sulphate anion surface active agent and contact this mixture viscosity of reduction in the detergent composition that just forms a kind of viscous mixt with water.

Background of invention

The washing composition human consumer always wishes to have the better cleaning performance and the washing composition of the improvement that can use economically.Therefore detergent manufacturer faces can not cause the challenge of rising owing to the productive expense of using more expensive composition or production method to cause when improving its washing composition.

The subject matter that the human consumer ran into that has now found that Betengent product human consumer, particularly clothing and dish washing detergent is in decollator, diverting device or even formation, the particularly formation of gel residue of residue or insoluble caking thing in laundry (tableware) machine.This does not wish to occur, because these residues or gel are difficult to remove from described machine and make machine present unclean outward appearance.In addition, the formation of residue, insoluble agglomerate or gel has caused the uneconomical use of Betengent product: Betengent product not exclusively is discharged in the washing water can cause relatively poor washing effect, and removing non-consumer additionally increases the washing composition consumption.This has caused the product poor efficiency or has used wastefully and do not liked by the human consumer.

Therefore, improve the release of detergent composition by necessity.A kind of method that addresses this problem that has proposed is to improve the solubleness of washing composition.This causes the variation of washing composition composition and compound method.But, form the tendency of gel or insoluble agglomerate even rapidly-soluble washing composition also has with promptly being bonded together after water contacts.Although dissolving can cause the minimizing of insoluble product and water duration of contact faster, this is not sufficient to address this problem.The washing composition releasing effect is still poor.Washing composition also can solve by the dispersiveness of improving washing composition to the problem for the treatment of washing releasing effect difference.

The applicant has been found that this problem is more obvious when using sulphate anion surface active agent (it can part or most of water-soluble) in granular detergent composition.When sulphate anion surface active agent exists with the dried particles thing, this problem even more serious.Believing that gel formation may have when contacting with water helps gel formation rather than water-soluble fully sulphate anion surface active agent causes.Its other component that may prevent washing composition then is discharged in the washing water.Also have, believe when sulphate anion surface active agent exists with the dried particles thing, gel formation increases, because described dried particles thing is hygroscopic.Described subsequently gel is difficult to disperse, and causes at machine, particularly residue and insoluble agglomerate occur in decollator or device.

The applicant has been found that the problem of gel formation and poor dispersion can solve in the described detergent composition or improves by a kind of solubilizing agent is blended into.

In general, be compound at solubilizing agent known in the art with the solubility properties that increases slightly soluble compound.Previous existing solubilizing agent is in the particularly description of various uses in liquid detergent of washing composition.WO 95/30730 has described as the solubilizing agent as phase stabilization aid in the liquid detergent.US 3926827 has described as the solubilizing agent that can keep the component of oxygen bubble, gives washing composition bigger volume.GB 1591516 has described the processing aid of solubilizing agent as the mobile detergent mixture that gains freedom.But, solubilizing agent in comprising the granular detergent composition of sulphate anion surface active agent with the purposes of the detergent composition dispersiveness that is improved not yet by known to the those skilled in the art.

In the present invention, believe that described solubilizing agent has reduced the viscosity of the gel that forms when being present in sulfate surfactant in described detergent composition or the detergent particles thing and contacting with water.By reducing the formation of in machine insoluble agglomerate or gel or residue, this has improved the dispersiveness of detergent composition in washing water.In laundry (tableware) machine particularly in decollator or diverting device the minimizing of washing composition agglomerate, residue or gel cause washing machine to have cleaner appearance and detergent composition has the performance of more efficient and low consumption.

All documents of being quoted in this manual, its relevant portion are all incorporated this paper by reference into.

The present invention's summary

The invention provides a kind of detergent composition, it comprises the sulphate anion surface active agent of the 0.01-95% that accounts for described composition weight and accounts for the solubilizing agent of the 0.01-60% of described composition weight, and the solubilizing agent of 0.0-1.8% (weight) (based on the gross weight of described composition) can be present in a kind of containing in the solubilizing agent agglomerate according to this.In a kind of embodiment preferred of the present invention, sulphate anion surface active agent all is present in the identical detergent particles with solubilizing agent.The present invention also provides a kind of detergent particles, and it comprises sulphate anion surface active agent that accounts for described composition weight 0.01-60% and the solubilizing agent that accounts for described particle weight 0.01-45%.

The present invention is also by using the solubilizing agent that reduces described mixture viscosity that the dispersiveness of the detergent composition of improvement is provided in the detergent composition that comprises the surface active agent composition (described surface active agent composition forms a kind of viscous mixt once contacting with water) that contains sulphate anion surface active agent.

Detailed description of the present invention

Sulphate anion surface active agent

Sulphate anion surface active agent of the present invention in described detergent composition, account for the 0.01-95% of its weight, preferably account for 0.5-45%, more preferably account for 1-30%, most preferably account for 3-20%.

When in the particle that is present in the detergent particles that comprises solubilizing agent, preferably spray drying, described sulphate anion surface active agent preferably account for the 0.01-60% of described particle weight, more preferably account for 0.3-30%, most preferably account for 1-20%.

Used sulphate anion surface active agent is meant linear and ramose primary and secondary alkyl-sulphate, sulfated alkyl ether, fatty oleoyl glycerine vitriol, alkyl phenol epoxy ethane ether salt, C in this ₅-C ₁₇Acyl group-N-(C ₁-C ₄Alkyl) and-N-(C ₁-C ₂Hydroxyalkyl) vitriol of the vitriol of glucosamine sulfate and alkyl polysaccharide such as alkyl polyglucoside (being described to the compound of nonionic non-sulfuric acidization in this).

Alkyl sulfate surfactant most preferably is selected from linear and ramose uncle C ₁₀-C ₁₈Alkyl-sulphate, more preferably C ₁₁-C ₁₅Branched-chain alkyl vitriol and C ₁₂-C ₁₄Straight-chain alkyl sulfate.

A kind of highly preferred sulfate surfactant is by coming from the C of tallow or Oleum Cocois ₈-C ₁₈The sodium that the alcohol sulfation produces or the vitriol of potassium.Also it is highly preferred that and to come from the sodium of palmitinic acid or stearic C16-C18 alcohol sulfation generation or the vitriol of potassium.

The positively charged ion of sulphate anion surface active agent can be hydrogen, ammonium or hydramine, but preferred sodium or potassium.

The ratio of sulphate anion surface active agent and solubilizing agent is preferably 100: 1 to 1: 2, more preferably 50: 1 to 1: 1, most preferably be 20: 1 to 2: 1.

Solubilizing agent

According to the present invention, a kind of solubilizing agent is present in the described detergent composition or particulate matter that comprises described sulphate anion surface active agent, or is used for comprising the detergent composition of the surface active agent composition of the tensio-active agent described in sulfur acid salt anionic surfactant and optional other this.

As mentioned above, be contained in the sulphate anion surface active agent (being contained in the surface active agent composition) in described detergent composition or the particulate matter in case contact with water and just to form a kind of viscous mixt.Described solubilizing agent is used to reduce the viscosity of described mixture.What therefore, used term solubilizing agent was meant the viscosity that can reduce the mixture that comprises water and sulphate anion surface active agent in this is the known any solubilizing agent of those skilled in the art.

The level of solubilizing agent is 0.01-60%, more preferably 0.1-30%, more preferably 0.3-10%, 0.5-5% most preferably again in described detergent composition, thereby the composition of 0.0-1.8% (weight) is the agglomerate that contains solubilizing agent.

The level of described solubilizing agent in particulate matter (particulate matter of preferably spray drying) be described particulate matter weight 0.01-60%, be preferably 0.1-25%, 0.4-15% more preferably, most preferably be 0.5-5%.

Preferred only high to 1.8% solubilizing agent, be more preferably up to 1.0%, most preferably 0% solubilizing agent and be contained in the agglomerate more be applicable to the present invention because have been found that the agglomeration solubilizing agent of this level.

Anyly all can be used for the present invention at solubilizing agent known in the art.That can mention in this solubilizing agent has a short chain (C ₁-C ₄) alkane-arylsulphonate.

The present invention is understood to include sulfonic acid in this.But, because the pH of detergent composition of the present invention or particulate matter is generally in alkaline range, when water (even a spot of water) existed in particulate matter or when comprising the preparation of compositions of particulate matter, described solubilizer component mainly existed with the form of ionizable salts.In other words, although described solubilizing agent can join with the form of acid in the composition, it may occur with the form of the derivative of salt.

Can be used for basic metal, alkaline-earth metal, alkylamine and ammonium salt that water-soluble salt of the present invention comprises sulfonic acid.Preferred salt is sodium sulfonate, potassium sulfonate and sulfonic acid Monoethanolamine MEA BASF and its mixture.

Specifically, tosylate, cumene sulfonate, xylenesulfonate can be used for the present invention.Most preferably toluenesulfonic acid sodium salt is preferably the toluene sodium monosulfate.

The use of solubilizing agent

Solubilizing agent of the present invention is used to comprise in the detergent composition of the surface active agent composition that contains a kind of sulphate anion surface active agent, so that the viscosity when reducing surface active agent composition and contacting with water.Preferably when solubilizing agent is used for the surface active agent composition of the first viscosity A (measuring by tensio-active agent viscosity test method as mentioned below) that 25% (weight) aqueous solution under 20 ℃ has at least 15000 centipoises (cP), has second viscosity B than the first viscosity A low 25%.

Described surface active agent composition comprises sulphate anion surface active agent and chooses any one kind of them or multiplely be selected from tensio-active agent as described herein.

The tensio-active agent viscosity test

In described tensio-active agent viscosity test, (mensuration) comprises the viscosity that all are present in the tensio-active agent in the described detergent composition and comprise a kind of surface active agent composition of sulphate anion surface active agent with the weight ratio in each comfortable described detergent composition.

At first, following mensuration comprises the viscosity A of surface active agent composition in water of sulphate anion surface active agent:

10 grams are comprised that the surface active agent composition of sulphate anion surface active agent and 30 grams comprise 0.5 gram NaSO ₄With 0.5 gram NaCO ₃Deionized water mix down at 20 ℃.The slurry that obtains was placed for 30 seconds.By the viscosity of Brookfield Digital Viscometer (DVII type) mensuration slurry, described viscometer is furnished with the measuring shaft (spindle) of a cover different diameter and has the speed governing button.Selection speed 12, measuring shaft 3.Drop in the slurry measuring shaft up to the axle scale of regulation and allow 10 seconds of its balance.Read then with centipoise (cP, 1cP=0.01 pool=10 ^-3Nsm ²) be the viscosity A of unit.

The preferred described surface active agent composition of sulphate anion surface active agent that comprises of the present invention has the viscosity A of at least 15000 centipoises.

Then, following measurement comprises the viscosity B of above surface active agent composition in water of sulphate anion surface active agent and solubilizing agent:

10 grams are comprised that the surface active agent composition of sulphate anion surface active agent and x gram solubilizing agent and 30 grams comprise 0.5 gram NaSO ₄With 0.5 gram NaCO ₃Deionized water mix down at 20 ℃.The slurry that obtains was placed for 30 seconds.Measure the viscosity of slurry by the Brookfield Digital Viscometer (DVII type) of selection speed 12, measuring shaft 3.Drop in the slurry measuring shaft up to the axle scale of regulation and allow 10 seconds of its balance.Reading with centipoise (cP) then is the viscosity B of unit.

Compare viscosity A and B, use the viscometric rate of descent of following formula then:

For the present invention, solubilizing agent and its amount are preferably and make the rate of descent of viscosity be at least 10%, and most preferably at least 25%.

Sulfonate anionic surfactant

The height preferred component of a kind of detergent composition of the present invention or particulate matter is a sulfonate anionic surfactant.

In described detergent composition the level of sulfonate anionic surfactant be described composition weight 0.01-30%, be preferably 0.5-20%, more preferably 1-16%, most preferably be 5-12%.

In described particulate matter the level of sulfonate anionic surfactant be described particulate matter weight 0.01-25%, be preferably 0.5-20%, more preferably 3-16%, most preferably be 5-15%.

Be applicable to that the sulfonate anionic surfactant in this comprises C ₅-C ₂₀Linearity or branch branched alkylbenzene sulfonate, alkyl sulfonate esters salt, C ₆-C ₂₂Uncle or secondary alkyl sulfonate, C ₆-C ₂₄The salt of alkene sulfonate, sulfonation polycarboxylic acid, alkyl glycerol sulfonate (or optional acid) is preferably from the alcohol that comes from tallow or Oleum Cocois, fatty acyl glycerol sulfonate, fatty oleoyl glycerol sulfonate and its any mixture.

The positively charged ion of described sulfonate anionic surfactant can be hydrogen, ammonium or hydramine, but preferred sodium or potassium.

A kind of highly preferred sulfonate anionic surfactant is C ₁₀-C ₁₈, preferred C ₁₀-C ₁₆, more preferably C ₁₁-C ₁₃Branch or the more preferably sodium salt or the sylvite of LINER ALKYL BENZENE SULPHONIC ACID SOFT 96.

Detergent particles

In a kind of preferred embodiment of the invention, described sulphate anion surface active agent and solubilizing agent all are contained in the detergent composition particle.Described detergent composition can be basically by this granulometric composition or can comprise particulate matter of the present invention and mixture with other particulate matter that different chemical forms.Preferred particulate matter of the present invention account for the 5-85% of described detergent composition weight, more preferably account for 10-70%, most preferably account for 30-60%.

Particulate matter of the present invention comprises above-mentioned sulphate anion surface active agent and solubilizing agent and preferred sulfonate anionic surfactant.

Particulate matter of the present invention is made by a kind of method of drying step that comprises.Described drying step has been produced final dried particles thing, its generally have be lower than 6% (weight), preferably be lower than 1% (weight), more preferably less than 0.55% (weight) even more preferably less than the free water content of 0.25% (weight).

Free water content used in this is by placing Petri dish with the basic detergent particles matter sample of 5 grams and measuring after 50 ℃ of (122) convection furnaces are placed 2 hours because the weight loss of moisture evaporation is measured.

In general, particulate matter of the present invention is according to a kind of slurry that will comprise sulphate anion surface active agent and solubilizing agent or slurry or crutcher mixture forming particle thing and according to making in the known technology exsiccant of the those skilled in the art method.A kind of preferable methods is a spraying drying.

A kind of preferred method for preparing described particulate matter comprises that preparation is commonly referred to the aqueous dispersion of each component that comprises final particulate matter of slurry or slurry or crutcher mixture.Be the flux of save energy and raising drying plant, described crutcher mixture comprises for example 40-80% of high as far as possible solid contents usually, and all the other then are water as 20-60%.Can use more water, the product that still will increase energy consumption at that rate, reduce the tower flux, obtains may glue and its flowability is relatively poor and often need the low density base-material, and can not get final detergent composition particle.

Although can use other drying means such as drum-type drying, plate-like drying, fluidised bed drying, film drying etc., most preferred method is a spraying drying, and wherein the crutcher mixture is at rising pressure (common 3-50kg/cm ², preferred 20-40kg/cm ²) under enter in the drying tower by the spraying of one or more fog nozzles, by the thin drip-dry dry glomeration particle of such dry air with the crutcher mixture that obtains.Also can use the similar spraying gun of other design to replace fog nozzle.Preferred spray tower design is the adverse current form, and the height of tower is generally 5 to 25 meters, and the hot gas of input is generally oil or the natural gas burning gaseous product under 200-400 ℃, and the temperature of working off one's feeling vent one's spleen is generally 50-90 ℃.Also can use and reach the following current tower design that is equivalent to import and Outlet Gas Temperature.

Thereby selecting to produce the thin jet size that drips of crutcher mixture makes its formation be preferably the particulate matter of 0.1-3.0 millimeter particle diameter.Best, when particulate matter shifts out from spray tower, basically the particle diameter of whole particulate matter is all in this scope, but, also can screen out non-regulation particle diameter particle, also non-regulation particle diameter particle grain size can be reduced to required particle size range or it can be circulated in spray tower or be recycled in the crutcher subsequently by sieving.

When having sulfonate anionic surfactant in final particulate matter, described sulfonate anionic surfactant can be contained in the crutcher mixture with solubilizing agent and sulphate anion surface active agent.

For drying process, particularly for spray-drying process, it may be useful that the crutcher mixture does not have nonionogenic tenside and/or cationic softening agent or cats product on substantially.Therefore, particulate matter of the present invention does not preferably have nonionogenic tenside and/or cationic softening agent or cats product basically.

Having sulphate anion surface active agent and described solubilizing agent in essentially no phosphate particle thing may be useful especially for purposes of the invention.

After finishing drying and obtaining the particulate matter of desired size scope, can choose wantonly other detergent component is joined in the described particulate matter, preferably by (it can be the dense aqueous solution with molten component, but preferably anhydrous) in a drum that tilts, be sprayed on the base-material particle surface of rotation, so particulate matter advances to discharge end from top feed end.

Described particulate matter also can import in the detergent composition by the known method of those skilled in the art.Preferred described particulate matter is dried and joins in other detergent ingredients.

Other composition

Detergent composition of the present invention or particulate matter also can comprise other composition or component.The definite character of these other compositions and the level of sneaking into will depend on the physical form of final composition and the definite character of its used washing operation.

Detergent composition of the present invention preferably comprises other detergent component of one or more tensio-active agents that are selected from other, SYNTHETIC OPTICAL WHITNER, bleach activator, acid source, auxiliary agent, organic polymer, enzyme, suds suppressor, lime soap dispersing agent, dirt suspensoid and anti redeposition agent and corrosion inhibitor.

Described particulate matter preferably includes one or more auxiliary agents as other composition, preferred aluminosilicate and/or organic polycarboxylic acid polymkeric substance, alkali source or its mixture.Best described particulate matter does not contain nonionic and/or cats product substantially.

Laughlin that authorized on December 30th, 1975 and the United States Patent (USP) 3929678 of Heuring provide typical inventory in the kind of the tensio-active agent of other negatively charged ion, nonionic, both sexes and zwitter-ion type and these tensio-active agents." tensio-active agent and washing composition " (the I volume that Schwartz, Perry and Berch compile and II volume) provides other example.The United States Patent (USP) 4259217 of the Murphy that on March 31st, 1981 authorized provides the inventory of the cats product that is suitable for.

Other anion surfactant

Can comprise one or more other anion surfactant according to detergent composition of the present invention or particulate matter.Basically any anion surfactant that is used for washing purposes all can be contained in described detergent composition or choose wantonly in described particulate matter.They can comprise alkyl ethoxy sulfate, carboxylate salt and sarcosinate surfactant salt (for example comprise sodium, potassium, ammonium and substituted ammonium salt such as one, two and tri ethanol ammonium salt).

Other anion surfactant comprises fatty acid amide, alkyl succinate and the sulfosuccinate of isethionate such as acyl isethinate, N-acyl taurine salt, methylamino esilate, the monoesters of sulfosuccinate (particularly saturated and unsaturated C ₁₂-C ₁₈Monoesters) and the diester of sulfosuccinate (particularly saturated and unsaturated C ₆-C ₁₄Diester), N-acyl sarcosinate.Resinous acid and hydrogenated resin acid also are suitable for, such as rosin, staybelite be present in or derive from the resinous acid and the hydrogenated resin acid of tallow oil.

The level of anion surfactant is preferably 4-60%, more preferably 6-30%, 10-20% (weight) most preferably in described detergent composition.

Alkyl ethoxy sulfate surfactant

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

The anionic carboxylic acid salt surfactant

The anionic carboxylate tensio-active agent that is suitable for comprises alkyl ethoxy carboxylate, many oxyethyl groups of alkyl polycarboxylic acid salt surfactant and soap (' alkyl carboxyl thing '), particularly described in this secondary soap (secondary soap).

The alkyl ethoxy carboxylate that is suitable for comprises having formula RO (CH ₂CH ₂O) _xCH ₂COO ^-M ⁺Alkyl ethoxy carboxylate, R is C in the formula ₆-C ₁₈Alkyl, x are 0 to 10, and the result that its ethoxylate distributes is that x is that 0 amount of substance (by weight) is less than 20%, and M is a positively charged ion.Many oxyethyl groups of the alkyl polycarboxylate tensio-active agent that is suitable for comprises having formula RO-(CHR ¹-CHR ²-O)-R ³Many oxyethyl groups of alkyl polycarboxylic acid salt surfactant, wherein R is C ₆-C ₁₈Alkyl, x are 1 to 25, R ¹And R ²Be selected from hydrogen, formyloxy, amber acidic group, hydroxy succinic acid base and its mixture, R ³Be selected from hydrogen, replacement or unsubstituted hydrocarbon and its mixture with 1 to 8 carbon atom.

The soap surfactants that is suitable for comprises the secondary soap surfactant that contains a carboxyl unit that links to each other with secondary carbon.The secondary soap surfactant that preferably is used for this be selected from 2-methyl isophthalic acid-undeeanoic acid, 2-ethyl-1-capric acid, 2-propyl group-1-n-nonanoic acid, 2-butyl-1-is sad and the water-soluble member of the water-soluble salt of 2-amyl group-1-enanthic acid.Some soap also can be used as suds suppressor and comprises wherein.

The basic metal sarcosinate surfactant

Other anion surfactant that is suitable for is formula R-CON (R ¹) CH ₂The basic metal sarcosinate of COOM, wherein R is C ₅-C ₁₇Linearity or ramose alkyl or alkenyl, R ¹Be C ₁-C ₄Alkyl, M are an alkalimetal ion.Preferred example has the myristyl and the oleoyl methyl sarcosinate of its sodium-salt form.

Cats product

The another kind of preferred surfactants that can be used in the detergent composition of the present invention is one or more cats products.The cats product that is suitable for comprises quaternary ammonium surfactant, and it is selected from single C ₆-C ₁₆, preferred C ₆-C ₁₀N-alkyl or alkenyl ammonium surfactant, wherein the N position of Bao Liuing is replaced by methyl, hydroxyethyl or hydroxypropyl.Another kind of preferred cationic surfactants is the C of quaternary ammonium alcohol ₆-C ₁₈Alkyl or alkenyl ester are such as the season cholinesterase.

In comprising the detergent composition of described particulate matter, the level of cats product be preferably the 0.2-20% of described composition weight, more preferably 0.5-15% in addition more preferably 1-10%, most preferably be 1-5%.

Nonionogenic tenside

Detergent composition of the present invention can comprise nonionogenic tenside.Preferred described particulate matter does not comprise nonionogenic tenside.Described nonionogenic tenside can be sprayed on the described particulate matter.Basically can use any nonionogenic tenside in this.

In comprising the detergent composition of described particulate matter, the level of nonionogenic tenside be preferably the 1-30% of described composition weight, more preferably 2-25% in addition more preferably 3-15%, most preferably be 4-12%.

Alkoxy-based non-ionic surface active agent

Basically any alkoxy-based non-ionic surface active agent all is suitable in this.Preferred ethoxylation and propoxylation nonionogenic tenside.

The preferred alkoxylated tensio-active agent can be selected from the condenses of nonionic condenses, nonionic ethoxylated alcohol, nonionic ethoxylated/propoxylated fatty alcohol, nonionic ethoxylate/propoxylated glycerine and propylene glycol of alkylphenol and the condensation product of nonionic ethoxylate and propylene oxide/ethylenediamine adduct.

Nonionic alcohol alcoxylates tensio-active agent

The condensation product of fatty alcohol and 1 to 25 mole of alkylene oxide, particularly oxyethane and/or propylene oxide is applicable in this.The alkyl chain of fatty alcohol can be straight or branched, uncle or the second month in a season and generally comprise 6 to 22 carbon atoms.Particularly preferably be the alcohol with the alkyl that contains 8 to 20 carbon atoms and the condensation product of every mol of alcohol 2 to 10 moles of ethylene oxide.

The nonionic polyhydroxy fatty acid amide surfactant

Be applicable to that the polyhydroxy fatty acid amide in this is that those have formula R ²CONR ¹The polyhydroxy fatty acid amide of Z, wherein R ¹Be H, C ₁-C ₄Alkyl, 2-hydroxyethyl, 2-hydroxypropyl, oxyethyl group, propoxy-or its mixture, preferred C ₁-C ₄Alkyl, more preferably C ₁-C ₂Alkyl, most preferably C ₁Alkyl (being methyl); R ²Be C ₅-C ₃₁Alkyl, preferred straight chain C ₅-C ₁₉Alkyl or alkenyl, more preferably straight chain C ₉-C ₁₇Alkyl or alkenyl, most preferably straight chain C ₁₁-C ₁₇Alkyl or alkenyl or its mixture; Z is polyhydroxy alkyl (at least 3 hydroxyls directly link to each other with described hydrocarbyl chain) or a kind of its alkoxylate (preferred ethoxylation or the propoxylation) derivative with a linear hydrocarbyl chain.Z preferably a kind of reducing sugar in the comfortable reductive amination process; More preferably Z is glycidyl (glycityl).

The nonionic fatty acid amide surfactant

The fatty acid amide surfactant that is suitable for comprises having formula R ⁶CON (R ⁷) ₂Tensio-active agent, R wherein ⁶For containing the alkyl of 7-21, preferred 9-17 carbon atom, each R ⁷Be selected from hydrogen, C ₁-C ₄Alkyl, C ₁-C ₄Hydroxyalkyl and-(C ₂H ₂O) _xH, wherein the scope of x is 1 to 3.

The nonionic alkyl polysaccharide surfactant

Be applicable to that the alkyl polysaccharide in this is disclosed in the United States Patent (USP) 4565647 of the Llenado that authorized on January 21st, 1986, have hydrophobic grouping and an a kind of polysaccharide such as a glycan glycosides that contains 6 to 30 carbon atoms, hydrophilic radical contains 1.3 to 10 sugared units.

Preferred alkyl poly glucoside has formula:

R ²O (C _nH _2nO) _t(glycosyl) _x

R wherein ²Be selected from alkyl, alkyl phenyl, hydroxyalkyl, hydroxyalkyl phenyl and its mixture, wherein said alkyl comprises 10 to 18 carbon atoms; N is 2 or 3; T is 0 to 10, and x is 1.3 to 8.Described glycosyl preferably comes from glucose.

Amphoterics

The optional amphoterics that uses in described detergent composition or described particulate matter comprises amine oxide tensio-active agent and alkyl both sexes carboxylic acid.

The amine oxide that is suitable for comprises having formula R ³(OR ⁴) _xN ⁰(R ⁵) ₂Compound, R wherein ³Be selected from alkyl, hydroxyalkyl, amidopropyl and alkyl phenyl or it contains the mixture of 8 to 26 carbon atoms; R ⁴Be alkylidene group or hydroxy alkylidene or its mixture that contains 2 to 3 carbon atoms; X is 0-5, preferred 0-3; Each R ⁵Be alkyl or hydroxyalkyl that contains 1 to 3 carbon atom or the polyethylene oxide base that contains 1 to 3 Oxyranyle.C preferably ₁₀-C ₁₈Alkyl dimethyl amine oxide and C ₁₀-C ₁₈The amido alkyl dimethyl amine oxide.

A kind of example of suitable alkyl both sexes dicarboxylic acid is the Miranol of the Dayton of New Jersey, the Miranol that Inc. produces ^TMC2M Conc..

Zwitterionics

Zwitterionics can be chosen wantonly and join in the described detergent composition.These tensio-active agents can be loosely referred to as the derivative of derivative, heterocyclic secondary and tertiary amine of secondary amine and tertiary amine or derivative, quaternary phosphine or uncle's sulfonium compound of quaternary ammonium.Trimethyl-glycine and sultaine are the examples of zwitterionics used in this.

The trimethyl-glycine that is suitable for is to have formula R (R ') ₂N ⁺R ²COO ^-Compound, wherein R is C ₆-C ₁₈Alkyl, each R ¹Be generally C ₁-C ₃Alkyl, R ²Be C ₁-C ₅Alkyl.Preferred trimethyl-glycine is C _12-18Dimethylamino hexanoate and C _10-18Amide group propane (or ethane) dimethyl (or diethyl) trimethyl-glycine.The coordination beet alkali surface activator also is suitable for the purposes in this.

The water-soluble additive compound

Detergent composition of the present invention can comprise the water-soluble additive compound, generally its level in described detergent composition 1-80% that is described composition weight, be preferably 10-70%, most preferably be 20-60%.

The water-soluble additive compound that is suitable for comprises water-soluble monomer polycarboxylate or its sour form, homopolymerization or copolymerization polycarboxylic acid or its salt (wherein said polycarboxylic acid comprises at least two mutual carboxylic acid groups by no more than two carbon atoms separate), borate, phosphoric acid salt and its mixture.

Although because the former thereby general preferred monomers polycarboxylate of Time, Cost And Performance aspect, described carboxylate salt or polycarboxylic acid salt assitant can be monomeric form or oligomeric form.

The carboxylate salt that contains a carboxyl that is suitable for comprises the water-soluble salt of lactic acid, oxyacetic acid and its ether derivant.The polycarboxylate that contains two carboxyls comprises water-soluble salt and the ether carboxylate and the sulfinyl carboxylate salt of succsinic acid, propanedioic acid, (second dioxy) oxalic acid, toxilic acid, diglycollic acid, tartrate, tartronic acid and fumaric acid.The polycarboxylate that contains three carboxyls specifically comprises aminosuccinic acid salt described in the carboxy methoxy-succinic acid salt described in water-soluble citrate, aconitate (aconitrate) and citraconate and succinate derivative such as the English Patent 1379241, the lactoxy succinate described in the English Patent 1389732 and the Netherlands patent applications 7205873 and the 2-oxa--1 of oxypolymerization carboxylate salt material described in English Patent 1387447,1,3-tricarballylic acid salt.

The polycarboxylic acid that contains four carboxyls comprises disclosed oxo disuccinate, 1,1,2 in the English Patent 1261829,2-ethane tetracarboxylic acid hydrochlorate, 1,1,3,3-propane tetracarboxylic acid salt and 1,1,2,3-propane tetracarboxylic acid salt.Contain the substituent polycarboxylate of sulfo group comprise English Patent 1398421 and 1398422 and United States Patent (USP) 3936448 in the sulfonation pyrolytic Citrate trianion described in disclosed sulfo-succinic acid salt derivative and the English Patent 1439000.Preferred polycarboxylate is hydroxycarboxylate's Citrate trianion particularly that per molecule contains three carboxyls at the most.

Borate auxiliary agent and under washing composition storage or wash conditions, can produce the boratory auxiliary agent that forms borate substance that contains and can be used as water-soluble additive in this.

The example of the water-soluble phosphoric acid salt assitant that is suitable for has the salt of alkali-metal tri-polyphosphate, trisodium phosphate, potassium pyrophosphate and ammonium pyrophosphate, sodium orthophosphate and potassium orthophosphate, partially poly-/sodium phosphate (wherein the polymerization degree is about 6 to 21) and phytic acid.

Part solubilized or insoluble auxiliary compound

Detergent composition of the present invention and/or particulate matter can comprise the solvable or insoluble auxiliary compound of part, its exist level be generally described detergent composition weight 1-80%, be preferably 10-70%, most preferably be 20-60%.

In described particulate matter, the solvable or insoluble auxiliary compound of part exist level be preferably described particulate matter weight 5-85%, be preferably 15-60%, most preferably be 20-50%.

Basically the example of water-insoluble auxiliary agent comprises sodium silicoaluminate.

The aluminosilicate zeolite that is suitable for has structure cell formula Na _z[(AlO ₂) _z(SiO ₂) _y] .xH ₂O, wherein z and y are at least 6; The molar ratio of z and y is 1.0 to 0.5, and x is at least 5 and be preferably 7.5 to 276, more preferably 10 to 264.Described silico-aluminate material is that hydrated form and being preferably contains 10-28%, more preferably contains the crystallization of 18-22% combination water.

Described aluminosilicate zeolite can be a natural materials, but is preferably synthetic materials.The synthetic crystallization aluminosilicate ion exchange material can be purchased with the title of zeolite A, zeolite B, zeolite P, X zeolite, zeolite HS and its mixture.Zeolite A has formula

Na ₁₂[(AlO ₂) ₁₂(SiO ₂) ₁₂] .xH ₂O wherein x is 20 to 30, particularly 27.X zeolite has formula

Na ₈₆[(AlO ₂) ₈₆(SiO ₂) ₁₀₆].276H ₂O。

Preferred particulate matter of the present invention does not comprise crystalline layered silicate.But the crystalline layered silicate that is preferred in the detergent composition has general formula:

NaMSi _xO _2x+1.yH ₂O wherein M is sodium or hydrogen, and x is a number of 1.9 to 4, and y is a number of 0 to 20.Such crystalline layered sodium silicate is disclosed among the EP-A-0164514, and its preparation method is disclosed among DE-A-3417649 and the DE-A-3742043.Here, the x in the superincumbent general formula has 2,3 or 4 value and is preferably 2.Most preferred material is can be with the name of an article of the NaSKS-6 6-Na available from Hoechst AG ₂Si ₂O ₅

The perhydrate SYNTHETIC OPTICAL WHITNER

A kind of preferred component in addition of described detergent composition and/or detergent particles thing is the perhydrate SYNTHETIC OPTICAL WHITNER, such as metal perborate, metal percarbonate, particularly sodium salt.Perborate can be a hydration or four hydrations.SPC-D has formula 2Na ₂CO ₃.3H ₂O ₂, and can be used as crystalline solid and purchase.

Crossing a Potassium Persulphate, crossing a Sodium Persulfate (sodium per) is the another kind of optional inorganic perhydrate salts that is used for detergent composition of the present invention.

The organic peracid bleach system

A kind of preferred feature of detergent composition and/or particulate matter is the organic peracid bleach system.In a kind of embodiment preferred, described bleach system comprises hydrogen peroxide cource and organic peracid bleach precursor compound.The preparation of organic peracid is undertaken by described precursor and hydrogen peroxide cource situ reaction.Preferred hydrogen peroxide cource comprises that inorganic hydrogen peroxide compound SYNTHETIC OPTICAL WHITNER is such as perborate bleach disclosed by the invention.In another kind of embodiment preferred, the ready-formed organic peracid directly is blended in the described composition.The composition of mixture that contains the hydrogen peroxide cource that is combined with prefabricated organic peracid and organic peracid precursor is also among plan.

The peracid bleach precursor

The peracid bleach precursor is to separate in the reaction compound with hydroperoxidation at the full water (perhydrolysis) that forms peracid.General peracid bleach precursor can be expressed from the next:

L is a leavings group in the formula, and X can be that any structure of the peracid that produces in the all-hydrolytic reaction that makes is substantially Functionality.The level that is blended into the peracid bleach precursor compound in the described detergent composition be preferably the 0.5-20% of described detergent composition weight, more preferably 1-15%, most preferably be 1.5-10%.

The peracid bleach precursor compound that is suitable for generally comprises one or more N-or O-carboxyl groups, the optional type from wide region of described precursor.The type that is fit to comprises the acylated derivatives of acid anhydrides, ester, imide, lactan and imidazoles and oxime.The example of the useful matter in these types is disclosed among the GB-A-1586789.The ester that is suitable for be disclosed in GB-A-836988,864798,1147871,2143231 and EP-A-0170386 in.

Leavings group

Described leavings group (hereinafter being called the L group) must have enough activity for the all-hydrolytic reaction that takes place in window of opportunity (being wash(ing)cycle).But if L is too active, this activator will be difficult to stably be used for bleaching composition.

Preferred L group is selected from:

With its mixture, wherein R ¹For alkyl, aryl or contain the alkaryl of 1 to 14 carbon atom, R ³Be the alkyl chain that contains 1 to 8 carbon atom, R ⁴Be H or R ³, Y is H or solubilizing group.R ¹, R ³And R ⁴Any all can be replaced by any functional group basically, described functional group comprises for example alkyl, hydroxyl, alkoxyl group, halogen, amine, nitrosyl radical, acid amides and ammonium or alkyl ammonium group.

Preferred solubilization group has :-SO ₃ ^-M ⁺,-CO ₂ ^-M ⁺,-SO ₄ ^-M ⁺,-N ⁺(R ³) ₄X ^-And O＜--N (R ³) ₃And most preferably-SO ₃ ^-M ⁺With-CO ₂ ^-M ⁺, R wherein ³Be the alkyl chain that contains 1 to 4 carbon atom, M provides the deliquescent positively charged ion of bleach activator, and X is for providing bleach activator deliquescent negatively charged ion.Preferred M is basic metal, ammonium or replaces ammonium cation, most preferably sodium and potassium, and X is halogen root, hydroxide radical, methylsulfate or acetic acid anion.

Alkyl percarboxylic acids bleach precursor

Alkyl percarboxylic acids bleach precursor forms percarboxylic acids in the all-hydrolytic reaction.Preferred such precursor provides peracetic acid in the all-hydrolytic reaction.

The alkyl peroxycarboxylic acid precursors compound of preferred imide type comprises N, N, N ¹, N ¹-tetrem acidylate alkylene diamines (wherein said alkylidene group comprises 1 to 6 carbon atom), particularly those described alkylidene groups comprise those compounds of 1,2 and 6 carbon atom.Preferred especially tetra acetyl ethylene diamine (TAED).Described TAED preferably is not present in of the present invention gathering in the particulate matter, but preferably is present in the detergent composition that comprises described particulate matter.

Other preferred alkyl peroxycarboxylic acid precursors comprises 3,5,5-trimethyl acetyl oxygen base benzene sulfonic acid sodium salt (different NOBS), acyloxy benzene sulfonic acid sodium salt in the ninth of the ten Heavenly Stems (NOBS), acetoxyl group benzene sulfonic acid sodium salt (ABS) and penta-acetyl glucose.

The alkyl peracid precursors that acid amides replaces

The alkyl peracid precursors compound that acid amides replaces in this is stable, and it comprises the compound with following general formula:

R wherein ¹Be the alkyl of 1 to 14 carbon atom, R ²Be the alkylidene group that contains 1 to 14 carbon atom, R ⁵Be H or the alkyl that contains 1 to 10 carbon atom, L can be any leavings group basically.The bleaching activity immunomodulator compounds that such acid amides replaces is described among the EP-A-0170386.

Peroxybenzoic acid precursors

The peroxybenzoic acid precursors compound provides peroxybenzoic acid in the all-hydrolytic reaction.The O-acidylate peroxybenzoic acid precursors compound that is fit to comprises and replacing and unsubstituting phenenyl methanoyl benzene sulfonate and sorbyl alcohol, glucose and all carbohydrates benzoylated product of benzozlating agent and the compound of those imide types, comprises the urea that N-benzoyl succinimide, four benzoyl quadrols and N-benzoyl replace.The imidazoles type peroxybenzoic acid precursors that is suitable for comprises N-benzoyl imidazoles and N-benzoyl benzo imidazoles.The N-carboxyl groups peroxybenzoic acid precursors that contains that other is useful comprises N-benzoyl pyrrolidone, dibenzoyl taurine and benzoyl Pyrrolidonecarboxylic acid.

The positively charged ion peracid precursors

Positively charged ion peracid precursors compound produces the positively charged ion peracid in the all-hydrolytic reaction.

In general, the positively charged ion peracid precursors forms by the acid moieties of crossing that replaces the peracid precursors compound that is fit to positive charge functional group such as ammonium or alkyl ammonium group (preferred second ammonium or first ammonium).The positively charged ion peracid precursors is general to be present in the solid-state detergent composition as the form with a kind of salt of suitable negatively charged ion such as halide ion.

The peracid precursors compound that is replaced by such positively charged ion can be peroxybenzoic acid or its substitutive derivative, precursor compound as indicated above.Perhaps, described peracid precursors compound can be the alkyl peroxycarboxylic acid precursors compound as indicated above or the alkyl peracid precursors of acid amides replacement.

The positively charged ion peracid precursors is described in United States Patent (USP) 4904406; 4751015; 4988451; 4397757; 5269962; 5127852; 5093022; 5106528; English Patent 1382594; EP 475512; 458396 and 284292; And among the JP 87-318332.

The example of preferred cation peracid precursors is described in UK Patent Application 9407944.9 and U.S. Patent application 08/298903,08/298650,08/298904 and 08/298906.

The positively charged ion peracid precursors that is suitable for comprises alkyl or the tetra-acetylated glucose benzoyl peroxide of benzoyloxy benzene sulfonate, N-acidylate hexanolactam and single benzoyl that any ammonium or alkylammonium replace.The positively charged ion peracid precursors of preferred N-acidylate hexanolactam class comprises trialkyl ammonium methylene radical benzoyl caprolactam and trialkyl ammonium methylene radical alkyl hexanolactam.

Benzoxazine organic peracid precursor

The same precursor compound that is disclosed in the benzoxazine type among for example EP-A-332294 and EP-A-482807 in addition that is suitable for particularly has those compounds of following formula: R wherein ₁Be H, alkyl, alkaryl, aryl or aralkyl.

The ready-formed organic peracid

Except organic peracid bleach precursor compound, perhaps as the surrogate of organic peracid bleach precursor compound, described organic peracid bleach system can comprise a kind of ready-formed organic peracid, and its level is generally the 1-15% of described composition weight, more preferably 1-10%.

A kind of organic peracid compound of preferred type is the compound that the acid amides of following general formula replaces:

R wherein ¹Be alkyl, aryl or the alkaryl of 1 to 14 carbon atom, R ²For containing alkylidene group, arylidene and the alkarylene of 1 to 14 carbon atom, R ⁵Alkyl, aryl or alkaryl for H or 1 to 10 carbon atom.The organic peracid compound that such acid amides replaces is described among the EP-A-0170386.

Other organic peracid comprises diacyl and four acyl peroxides, particularly diperoxy dodecandioic acid, diperoxy dodecane dicarboxylic acid and diperoxy n-Hexadecane bisgallic acid.Brassylic acids crossed by one and two mistake nonane diacids, one and two and N-O-phthalic amido peroxide caproic acid also is applicable in this.

Acid source

Acid source or acid source can be present in described detergent composition or the particulate matter.In the time of in being contained in detergent composition or particulate matter, preferred existence can with the alkali source of described acid source generated reactive gas.

In described detergent composition the level of acid source be preferably 0.5-10%, more preferably 1-7%, most preferably be 2-5% (weight).

Described acid source is preferably the non-hygroscopic material that can improve storage stability.But a hydration acid also can be used hereinto.Preferred organic acid and its derivative.Described acid is preferably water soluble acid.The acid that is suitable for comprises citric acid, pentanedioic acid, succsinic acid or hexanodioic acid, monosodium phosphate, sodium pyrosulfate, boric acid or its salt or ester.Particularly preferably be citric acid.

Bleaching catalyst

The optional bleaching catalyst that contains transition metal that comprises of described composition.A kind of bleaching catalyst of application type is a kind of catalyst system, it comprises a kind of the have active heavy metal cation of definite bleach catalyst such as copper, iron or manganese positively charged ion, have little or no the active assistant metal positively charged ion of bleach catalyst such as zinc or aluminium cations, with a kind of sequestering agent, particularly ethylenediamine tetraacetic acid (EDTA), ethylenediamine tetraacetic (methylene phosphonic acid) and its water-soluble salt that has clear and definite stability constant for catalysis and assistant metal positively charged ion.This catalyzer is disclosed in the United States Patent (USP) 4430243.

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

The example of the bleaching catalyst that is suitable for is referring to United States Patent (USP) 4246612 and 5227084.Also can be referring to having described monokaryon manganese (IV) title complex such as Mn (1,4,7-trimethylammonium-1,4,7-7-triazacyclononane) (OCH ₃) ₃-(PF ₆) United States Patent (USP) 5194416.What also have another type is manganese (III) and/or (IV) and have a water-soluble complexes of ligand of the non-carboxylate salt polyol of at least three adjacent C-OH base as disclosed bleaching catalyst in United States Patent (USP) 5114606.The double-core Mn that other example comprises with four-N-dentate and two-N-dentate ligand cooperates comprises N ₄Mn ^III(μ-O) ₂(Mn ^IVN ₄) ⁺[Bipy ₂Mn ^III(μ-O) ₂Mn ^IVBipy ₂]-(ClO ₄) ₃

Other bleaching catalyst that is suitable for is disclosed in for example European Patent Application No. 408131 (cobalt complex catalyzer), European patent application published number 384503 and 306089 (catalysis of metalloporphyrin agent), US4728455 (manganese/multidentate ligand catalyzer), US4711748 and European patent application published number 224952 (being adsorbed on the Mn catalyst on the silico-aluminate), US4601845 (aluminosilicate carrier) with manganese and zinc or magnesium salts, US4626373 (manganese/ligand catalyzer), US4119557 (ferric iron composition catalyst), German patent specification 2054019 (cobalt sequestrant catalyzer), Canadian Patent 866191 (containing the transition metal salt), among US4430243 (sequestrant of tool manganese positively charged ion and on-catalytic metallic cation) and the US4728455 (managanese gluconate catalyzer).

The heavy metal ion sequestering agent

Detergent composition of the present invention and/or particulate matter preferably comprise the heavy metal ion sequestering agent as optional components.The heavy metal ion sequestering agent here is meant the component that is used for the chelating heavy metal ion.These components also can have the ability of chelating calcium and magnesium, but preferably they demonstrate selectivity in conjunction with heavy metal ion such as iron, manganese and copper.

The heavy metal ion sequestering agent exist level be generally described composition weight 0.005-20%, be preferably 0.1-10%, more preferably 0.25-7.5%, most preferably be 0.5-5%.

The heavy metal ion sequestering agent that is suitable in this includes organic phosphonates such as amino alkylidenyl poly-(alkylene phosphonic acids salt), basic metal ethane 1-hydroxyl diphosphonate and nitrilo trimethylene phosphonic salt.

Preferably diethylenetriamine five (methylene phosphonic acid salt), quadrol three (methylene phosphonic acid salt), hexamethylene-diamine four (methylene phosphonic acid salt) and hydroxy ethylene 1 in above-mentioned substance, the 1-diphosphonate.

Other heavy metal ion sequestering agent that is suitable for hereinto comprises nitrilotriacetic acid(NTA) and polyamino carboxylic acid such as ethylenediamine tetraacetic acid (EDTA), ethylidene pentaacetic acid, ethylenediamine disuccinic acid, quadrol two pentanedioic acids, 2-hydroxyl propylene diamine disuccinic acid or its salt.Particularly preferably be quadrol-N, N '-disuccinic acid (EDDS) or its basic metal, alkaline-earth metal, ammonium or substituted ammonium salt, or its mixture.

Other is applicable to that the heavy metal ion sequestering agent in this is an iminodiacetic acid derivatives, such as at 2-hydroxyethyl oxalic acid described in EP-A-317542 and the EP-A-399133 or glyceryl iminodiethanoic acid.Also be applicable in this at the iminodiethanoic acid described in the EP-A-516102-N-2-hydroxypropyl sulfonic acid and aspartic acid N-carboxymethyl-N-2-hydroxypropyl-3-sulfonic acid sequestering agent.At the Beta-alanine-N described in the EP-A-509382, N '-oxalic acid, aspartic acid-N, single acetate of N '-oxalic acid, aspartic acid-N-and imino-diacetic succsinic acid sequestering agent also are suitable for.

EP-A-476257 has described the sequestering agent of the amino based that is fit to.EP-A-510331 has described and has come from collagen protein, Keratin sulfate or caseic suitable sequestering agent.EP-A-528859 has described a kind of suitable alkyl imino oxalic acid sequestering agent.Pyridine dicarboxylic acid and 2-phosphinylidyne butane-1,2, the 4-tricarboxylic acid also is suitable for.G-NH2-N, N '-disuccinic acid (GADS), quadrol-N, N '-two pentanedioic acid (EDDG) and 2-hydroxyl propylene diamine-N, N '-disuccinic acid (HPDDS) also is suitable for.

Enzyme

The another kind of component that preferably can be used in described detergent composition or the optional particulate matter is one or more additional enzymes.Optional described enzyme or its part can be present in the particulate matter of agglomeration of the present invention or extruding.

Preferred additional enzymes material comprises the lipase of purchasing, at, amylase, neutrality and Sumizyme MP, esterase, cellulase, polygalacturonase, Sumylact L and the peroxidase that is routinely added in the detergent composition.The enzyme that is suitable for can be referring to the discussion in United States Patent (USP) 3519570 and 3533139.

Preferred commercialization proteolytic enzyme comprises the proteolytic enzyme that Novo Industries A/S (Denmark) sells with trade(brand)name Alcalase, Savinase, Primase, Durazym and Esperase, the proteolytic enzyme that Gist-Brodades sells with the trade(brand)name of Maxatase, Maxacal and Maxapem, the proteolytic enzyme that proteolytic enzyme that Genencor Intemational sells and Solvay Enzymes sell with trade(brand)name Opticlean and Optimase.Can add according to the amount of the proteolytic enzyme in the composition of the present invention is the 0.0001-4% organized enzyme of described composition weight.

Preferred amylase for example comprises the α-Dian Fenmei that obtains from the specific bacterial strain of a kind of B.licheniformis, and it is described in greater detail among the GB-1269839 (Novo).Preferred commercial amylase comprises the amylase that amylase that Gist-Brocades for example sells with trade(brand)name Rapidase and Novo Industries A/S sell with trade(brand)name Termamyl and BAN.Can add according to the diastatic amount in the composition of the present invention is the 0.0001-2% organized enzyme of described composition weight.

In described composition, can exist and account for composition weight 0.0001-2%, preferred 0.001-1%, the active lipolytic enzyme of 0.001-0.5% most preferably.

Lipase can obtain from fungi or bacterial origin, for example from producing the lipase that lipase bacterial strain Humicola sp., Thermomyces sp. or Pseudomonas sp (comprising Pseudomonaspseudoalcaligenes or pseudomas fluorescens) produce.Lipase from the mutant strain of these bacterial strains of chemistry or genetics variation also can be used in this.A kind of preferred lipase derives from Pseudomonas pseudoalcaligenes, and it is described among special permission European patent EP-B-0218272.

Another kind of in this preferred lipase as described in European patent application EP-A-0258068 by the clone from the gene of Humicola lanuginosa and in as host's Aspergillusoryza expressing said gene obtain, it can be available from the NovoIndustri A/S of Denmark Bagsvaerd, and commodity are called Lipolase.This lipase also is described in the people's such as Huge-Jensen that authorized on March 7th, 1989 the United States Patent (USP) 4810414.

Organic polyhydroxyl compound

Organic polyhydroxyl compound is according to the preferable additives of detergent composition of the present invention and/or particulate matter and preferably as the component existence of any granular component, wherein they can be used for granular component is bonded together.The organic polyhydroxyl compound here is meant any polymerizable organic compound that is used as dispersion agent and anti redeposition agent and soil-suspending agent basically usually in detergent composition, comprises the high molecular organic polyhydroxyl compound that is called the clay flocculating agent in this.

Organic polyhydroxyl compound generally with account for described composition weight 0.1-30%, preferred 0.5-15%, most preferably the level of 1-10% is blended in the detergent composition of the present invention.

The example of organic polyhydroxyl compound comprises water-soluble organic homopolymerization or copolymerization polycarboxylic acid or its salt, and wherein said polycarboxylic acid comprises at least two by the mutual isolated carboxyl of no more than two carbon atoms.The polymkeric substance of back one type is disclosed among the GB-A-1596756.It is the multipolymer of multipolymer such as the molecular weight with 20000-100000, particularly 40000-80000 of the polyacrylate of 2000-5000 and itself and maleic anhydride that the example of this salt has molecular weight.

Be suitable at this polyamino compound, comprise the polyamino compound that comes from aspartic acid, such as those disclosed compound in EP-A-305282, EP-A-305283 and EP-A-351629.

The terpolymer that comprise the terpolymer of the monomeric unit that is selected from toxilic acid, vinylformic acid, poly aspartic acid and vinyl alcohol, particularly has a 5000-10000 molecular-weight average also is applicable to this.

Other is applicable to that the organic polyhydroxyl compound in the detergent composition that adds in this comprises derivatived cellulose such as methylcellulose gum, carboxymethyl cellulose, Vltra tears and Natvosol.

The another kind of organic polyhydroxyl compound that is suitable for is a polyoxyethylene glycol, particularly those molecular weight 1000-10000, more preferably 2000-8000,4000 polyoxyethylene glycol most preferably from about.

This another kind of organic compound that is used for this as a kind of preferred clay suspending agent/anti redeposition agent can be the cationic monoamine of ethoxylation and the diamines of following formula:

Wherein X is for being selected from H, C ₁-C ₄The non-ionic group of alkyl or hydroxy alkyl ester or ether group and composition thereof, a are 0 to 20, preferred 0 to 4 (for example ethylidene, propylidene, hexa-methylene), and b is 1 or 0; For positively charged ion monoamine (b=0), n is at least 16, and general range is 20 to 35; For cationic diamine (b=1), it is about 12 that n is at least, and general range is about 12 to about 42.

Other dispersion agent/anti redeposition agent that is used for this is described among EP-B-011965 and US4659802 and the US 4664848.

Press down foam system

When being mixed with machine washing during composition, described detergent composition preferably comprise account for described composition weight 0.01-15%, preferred 0.05-10%, most preferably 0.1-5%'s presses down foam system.

Be applicable to that the foam that presses down in this is to consist essentially of any known defoaming compounds, for example siloxanes defoaming compounds and 2-alkyl alcanol defoaming compounds.

The defoaming compounds here is meant the foam that is used to suppress detergent composition solution and produces, particularly is suppressed at any compound of foamy that produces when stirring described solution or the mixture of compound.

The particularly preferred defoaming compounds that is used for this is siloxanes defoaming compounds (being defined as the defoaming compounds that comprises silicone components in this).This siloxanes defoaming compounds generally also comprises silica component.Here and general in whole the sector used term " siloxanes " comprise the various polymkeric substance that contain the higher molecular weight of siloxane unit and various types of alkyl.Preferred siloxanes defoaming compounds is a polysiloxane, particularly has the unitary polydimethylsiloxane of trimethyl silyl end-blocking.

Other defoaming compounds that is suitable for comprises mono carboxylic lipid acid and its soluble salt.These materials are disclosed in the United States Patent (USP) 2954347 of the Wayne St.John that authorizes September 27 nineteen sixty.As the mono carboxylic lipid acid of suds suppressor and its salt generally have 10 to 24, the hydrocarbyl chain of preferred 12 to 18 carbon atoms.The salt that is suitable for comprises an alkali metal salt such as sodium, potassium and lithium salts and ammonium and alkanol ammonium salts.

Other defoaming compounds that is suitable for comprises for example high molecular weight fatty acid ester (for example fatty acid triglycercide), the fatty acid ester of monohydroxy-alcohol, aliphatic C ₁₈-C ₄₀Ketone (for example stearone) N-alkylation aminotriazine such as three to six alkyl melamines or as cyanuric chloride and two or three moles contain that the primary amine of 1 to 24 carbon atom or secondary amine forms two to tetraalkyl diammonium chloride triazine, propylene oxide, two stearic amide and single stearyl two basic metal (for example sodium, potassium, lithium) phosphoric acid salt and phosphoric acid ester.

The preferred foam system that presses down comprises:

(a) defoaming compounds, preferred siloxanes defoaming compounds most preferably comprises the siloxanes defoaming compounds of following material simultaneously:

(i) account for described siloxanes defoaming compounds weight 50-99%, preferably account for the polydimethylsiloxane of 75-95%; With

(ii) account for the silicon-dioxide of described siloxanes/silicon-dioxide defoaming compounds weight 1-50%, preferred 5-25%; Wherein said silica/silicon oxygen alkane defoaming compounds mixes with the level of 5-50%, preferred 10-40% (weight);

(b) a kind of compound dispersing agent most preferably comprises a kind of 72-78% of the having polyoxyalkylene content and 1: 0.9 to 1: 1.1 the oxyethane and siloxane glycol (silicone glycol) the rake multipolymer of propylene oxide ratio that account for its weight 0.5-10%, preferred 1-10%; A kind of particularly preferred such siloxane glycol rake multipolymer is can be available from the DCO544 (trade(brand)name) of DOW Corning;

(c) a kind of inert support fluid compound most preferably comprises the C of the degree of ethoxylation of a kind of 5-50 of having that accounts for its weight 5-80%, preferred 10-70%, preferred 8-15 ₁₆-C ₁₈Ethoxylated alcohol.

A kind of highly preferred granular foam system that presses down is described among the EP-A-0210731 and comprises a kind of siloxanes defoaming compounds and the organic support material of a kind of 50-85 of having ℃ fusing point, and wherein said organic support material comprises the lipid acid of the carbochain of a kind of monoesters of glycerine and a kind of 12-20 of having carbon atom.EP-A-0210721 discloses other preferred granular foam system that presses down, and wherein said organic support material is a kind of lipid acid or alcohol or its mixture with fusing point of 12 to 20 carbon atoms and 45-80 ℃.

The clay softening system

Described detergent composition can comprise a kind of clay softening system that comprises the clay mineral compound and the clay flocculating agent of choosing any one kind of them.

Described clay mineral compound is preferably the smectic clays compound.Smectic clays is disclosed in United States Patent (USP) 3862058,3948790,3954632 and 4062647.European patent EP-the A-299575 of Procter and GambleCompany and EP-A-313146 have described the organic polymer clay flocculating agent that is suitable for.

The polymeric dye transfer inhibitor

Described detergent composition also can comprise the polymeric dye transfer inhibitor of 0.01-10%, preferred 0.05-0.5% (weight).

Described polymeric dye transfer inhibitor is preferably from multipolymer, polyvinylpyrrolidonepolymers polymers or its mixture of polyamine N-oxide polymkeric substance, N-vinyl pyrrolidone and N-vinyl imidazole.

A) polyamine N-oxide pllymers

Be applicable to that the polyamine N-oxide pllymers in this comprises the unit with following structural:

Wherein P is that polymerizable unit and A are

-O-,-S-,-N-; X is 0 or 1; R is aliphatic series, aliphatic, the aromatics of ethoxylation, heterocycle or alicyclic group or its combination, the part that the nitrogen of N-O group can join with it or wherein the nitrogen of N-O group is these groups.

Described N-O group can be represented by following universal architecture:

R wherein ₁, R ₂And R ₃Be aliphatic group, aromatics, heterocycle or alicyclic group or its combination, x or/and y or/and z is 0 or 1 and the part that nitrogen can join with it or wherein the nitrogen of N-O group constitutes these groups of N-O group wherein.Described N-O group can be the part of polymerizable unit (P) or can be incorporated on the polymeric skeleton or both molectrons.

The polyamine N-oxide that the wherein said N-O group that is suitable for constitutes the part of polymerizable unit comprises that R is selected from the polyamine N-oxide of aliphatic series, aromatics, alicyclic or heterocyclic group.One class of described polyamine N-oxide comprises wherein one group of polyamine N-oxide of the part of the nitrogen formation R group of N-O group.Preferred polyamine N-oxide compound is that those R are the polyamine N-oxide of heterocyclic group such as pyridine, pyrroles, imidazoles, tetramethyleneimine, piperidines, quinoline, acridine and its derivative.

Other polyamine N-oxide that is suitable for is attached to polyamine oxide compound on the polymerizable unit for N-O group wherein.A kind of this polyamine N-oxide of preferred type comprises the have general formula polyamine N-oxide of (I), and R is aromatics, heterocycle or alicyclic group in the formula, and wherein N-O functional group's nitrogen is the part of described R group.It is the polyamine oxide compound of heterogeneous ring compound such as pyridine, pyrroles, imidazoles and its derivative that such example has R.

Described polyamine N-oxide can almost obtain with any polymerization degree.As long as described material has required water-soluble and dye suspension ability, the polymerization degree is unimportant.In general, its average molecular weight range is 500 to 1000000.

B) multipolymer of N-vinyl pyrrolidone and N-vinyl imidazole

What be suitable in this is that average molecular weight range is N-vinyl imidazole and the N-vinylpyrrolidone copolymers of 5000-50000.Preferred multipolymer has 1 to 0.2 the N-vinyl imidazole and the molar ratio of N-vinyl pyrrolidone.

C) Polyvinylpyrolidone (PVP)

Detergent composition of the present invention also can utilize has the Polyvinylpyrolidone (PVP) (" PVP ") of molecular-weight average for 2500-400000.The Polyvinylpyrolidone (PVP) that is suitable for can be available from the ISP Corporation of New York NY and Montreal, CAN, and commodity are called PVP K-15 (viscosity molecular weight is 10000), PVP K-30 (molecular-weight average is 40000), PVP K-60 (molecular-weight average is 160000) and PVP K-90 (molecular-weight average is 360000).PVP K-15 also can be available from ISP Corporation.Other Polyvinylpyrolidone (PVP) that is suitable for can comprise Sokalan HP 165 and Sokalan HP 12 available from BASFCooperation.

D) Ju Yi Xi oxazolidinone

Detergent composition of the present invention also can use Ju Yi Xi oxazolidinone as the polymeric dye transfer inhibitor.Described Ju Yi Xi oxazolidinone has 2500 to 400000 molecular-weight average.

E) polyvinyl imidazol

Detergent composition of the present invention also can utilize polyvinyl imidazol as the polymeric dye transfer inhibitor.Described polyvinyl imidazol preferably has 2500 to 400000 molecular-weight average.

White dyes

Detergent composition of the present invention also can be chosen the hydrophilic white dyes of some type that comprises about 0.005-5% (weight) wantonly.

The hydrophilic white dyes that can be used among the present invention comprises those white dyess with following structural:

R wherein 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, morpholino, chlorine and amino; M is salt-forming cation such as sodium or potassium.

R in following formula ₁Be anilino, R ₂For N-2-two-when hydroxyethyl and M were positively charged ion such as sodium, described white dyes was 4,4 '-two [(4-anilino-6-(N-2-two-hydroxyethyl)-s-triazine-2-yl) amino]-2,2 '-stilbene disulfonic acid and disodium salt.By Ciba-Geigy Corporation commercialization, commodity are called Tinopal-UNPA-GX to the white dyes of this particular type.Tinopal-UNPA-GX is the preferred wetting ability white dyes that can be used in the detergent composition of the present invention.

R in following formula ₁Be anilino, R ₂When being positively charged ion such as sodium for N-2-dihydroxy ethyl-N-2-methylamino and M, described white dyes is 4,4 '-two [(4-anilino-6-(N-2-hydroxyethyl-N-methylamino)-s-triazine-2-yl) amino]-2,2 '-stilbene disulfonic acid disodium salt.The white dyes of this particular type is by Ciba-Geigy Corporation commercialization, and commodity are called Tinopal 5BM-GX.

R in following formula ₁Be anilino, R ₂When being positively charged ion such as sodium for morpholino and M, described white dyes is 4,4 '-two [(4-anilino-6-morpholino-s-triazine-2-yl) amino]-2,2 '-stilbene disulfonic acid, sodium salt.The white dyes of this particular type is by Ciba-Geigy Corporation commercialization, and commodity are called Tinopal AMS-GX.

Other optional member

Other optional member that is fit to be included in described detergent composition and/or the particulate matter comprises spices, pigment and weighting agent salt, and sodium sulfate is preferred weighting agent salt.

The pH of described composition

Described detergent composition preferably has at least 10.0, more preferably have 10.0-12.5, most preferably have the pH (measuring with 1% distilled water solution) of 10.5-12.0.

The form of described composition

Described composition can be made into various physical form, but preferably granular.Described composition can be that the what is called that low density grainy detergent composition form or be applicable to joins in the washing machine concentrates granular detergent composition, and the latter can join washing machine or can join washes or can freely join washing machine but preferably be added in the bottom of washing machine by means of decollator by means of the diverting device that places the washing machine drum and dirty fabric to be washed.

Median size according to granular composition base-material of the present invention can be the 0.1-5.0 millimeter, but the diameter of particulate matter that preferably should no more than 5% greater than the diameter of 1.7 millimeters and no more than 5% particulate matter less than 0.15 millimeter.

Defined term median size is calculated by on serial Tyler sieve described composition sample being sieved into a plurality of parts (general 5 parts) in this.The weight part that obtains is like this mapped to screen-aperture.Median size is got the screen-aperture by 50% (weight) sample.

The tap density of granular detergent composition be generally at least 500 grams per liters, more preferably 650-1200 fill/liter.Tap density is measured by simple funnel and cup device, described device comprise one be fixedly mounted on one on the support conical hopper and a plate valve is housed bottom and can allows the content of funnel be vented to place axially-aligned cylindrical cup below the funnel at it.Funnel is 130 millimeters high and has the internal diameter of 130 millimeters and 40 millimeters at its highest and lowest end respectively.It is mounted to the above 140 millimeters places of seating face of disembarking, its bottom.The total height of described cup is 90 millimeters, and internal height is 87 millimeters, and internal diameter is 84 millimeters.Nominal volume is 500 milliliters.

When measuring, funnel is filled powder with hand, open plate valve and allow in the powder overfill cup.To be full of the cup from frame shift out and by the straight flange utensil for example cutter strike off excess powder along its upper limb.The cup that will be full of is then weighed and the powder weight value that obtains is doubled and obtains with the grams per liter is the tap density of unit.Replicate measurement when needing.

Clothes washing method

Machine washing method in this generally comprises dirty clothing with dissolving or having disperseed the water washing solution according to machine washing detergent composition of the present invention of significant quantity to handle in washing machine.The detergent composition of significant quantity is meant as the situation of conventional products dosage that usually is suitable in routine machine washing method and washing soln volume and the products of 40 to 300 grams is dissolved or dispersed in 5 to 65 liters the washing soln.

The packing of described composition

The commodity of described bleaching composition can be packaged in any suitable container, comprise in the container that constitutes with paper, cardboard, plastics and any suitable lamination film-making.European Patent Application No. 94921505.7 has been described a kind of preferred Packaging Method.

Used abbreviation in the following example

In described detergent composition, used abbreviation has following meaning:

LAS: linear C ₁₂Sodium alkyl benzene sulfonate

TAS: tallow alkyl sodium sulfate

C45AS:C ₁₄-C ₁₅Linear alkyl sodium sulfate

CxyEzS: with the C of z moles of ethylene oxide condensation _1x-C _1yBranched-chain alkyl sodium sulfate

C45E7: with the C that is mainly of average 7 moles of ethylene oxide condensations _14-15Straight chain primary alcohol

C25E3: with the C of average 3 moles of ethylene oxide condensations _12-15Branched-chain primary alcohol

C25E5: with the C of average 5 moles of ethylene oxide condensations _12-15Branched-chain primary alcohol

CEQ:R ₁COOCH ₂CH ₂N ⁺(CH ₃) ₃, R wherein ₁=C ₁₁-C ₁₃

QAS:R ₂N ⁺(CH ₃) ₂(C ₂H ₄OH), R wherein ₂=C ₆-C ₁₄

Soap: come from 80/20 the tallow and the linear alkyl carboxylic acid sodium of coconut oil blend

STS: toluenesulfonic acid sodium salt

SXS: sodium xylene sulfonate

SBS: benzene sulfonic acid sodium salt

TFAA:C ₁₆-C ₁₈Alkyl N-methyl glucose amide

TPKFA:C ₁₂-C ₁₄The full cut lipid acid of topping

STPP: anhydrous sodium tripolyphosphate

Zeolite A: main particle size range is 0.1 to 10 micron formula Na ₁₂(AlO ₂SiO ₂) ₁₂.27H ₂The hydrated sodium aluminosilicate of O

NaSKS-6: formula δ-Na ₂Si ₂O ₅Crystalline layered silicate

Citric acid: Citric Acid, usp, Anhydrous Powder

Carbonate: the anhydrous sodium carbonate of particle diameter between 200 to 900 microns

Supercarbonate: the anhydrous sodium bicarbonate of size distribution between 400 microns to 1200 microns

Silicate: amorphous sodium silicate (SiO ₂: Na ₂O; 2.0 ratio)

Sodium sulfate: anhydrous sodium sulphate

Citrate trianion: size distribution between 425 to 850 microns, acidity is 86.4% two hydration trisodium citrates

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

CMC: Xylo-Mucine

QEAI: two ((C ₂H ₅O) (C ₂H ₄O) _n) (CH ₃)-N ⁺-C ₆H ₁₂-N ⁺-(CH ₃) two ((C ₂H ₅O)-(C ₂H ₄O) _n), wherein n is 20 to 30

Proteolytic enzyme: is the proteolytic ferment of 4KNPU/g by NOVO Industries A/S with the activity that trade(brand)name Savinase sells

Alcalase: the activity of being sold by NOVO Industries A/S is the proteolytic ferment of 3AU/g

Cellulase: is the cellulolytic enzyme of 1000CEVU/g by NOVOIndustriesA/S with the activity that trade(brand)name Carezyme sells

Amylase: is the amylolytic enzyme of 60KNU/g by NOVO Industries A/S with the activity that trade(brand)name Termamyl 60T sells

Lipase: is the lipolytic enzyme of 100kLU/g by NOVO Industries A/S with the activity that trade(brand)name Lipolase sells

Endoenzyme: the activity of being sold by NOVO Industries A/S is the endo-dextranase of 3000 CEVU/g

PB4: rational formula NaBO ₂.3H ₂O.H ₂O ₂Sodium perborate tetrahydrate

PB1: rational formula NaBO ₂.H ₂O ₂Anhydrous sodium perborate monohydrate SYNTHETIC OPTICAL WHITNER

Percarbonate: rational formula 2Na ₂CO ₃.3H ₂O ₂SPC-D

NOBS: the nonanoly acyloxy benzene sulfonate of sodium-salt form

NAC-OBS: (nonanoyl amido hexanoyl) oxygen base benzene sulfonate of sodium-salt form

TAED: tetra acetyl ethylene diamine

DTPMP: by the diethylenetriamine five (methylene phosphonic acid salt) of Monsanto with trade(brand)name Dequest 2060 sales

EDDS: the sodium salt of ethylenediamine disuccinic acid

Photosensitizer: the sulfonation phthalocyanine phthalocyanine zinc of in bleaching dextrin dissolved polymers, sealing

Whitening agent 1:4,4 '-two (2-sulfo group styryl) biphenyl disodium

Whitening agent 2:4,4 '-two (4-anilino-6-morpholino-1,3,5-triazines-2-yl) amino) stilbene-2,2 '-disulfonic acid disodium

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

PVNO: polyvinylpyridine N-oxide compound

PVPVI: the multipolymer of Polyvinylpyrolidone (PVP) and vinyl imidazole

SRP1: the end capped ester of sulfo group benzoyl of tool oxyethylene group oxygen and terephthaloyl skeleton

SRP2: the short block polymer of diethoxyization poly-(1, the inferior propyl ester of 2-terephthalic acid)

Silicone antifoam agent: with the polydimethylsiloxane Foam Control of siloxanes-olefin oxide multipolymer as dispersion agent, the ratio of described Foam Control and described dispersion agent is 10: 1 to 100: 1

Basicity: % (weight) a great deal of that uses the NaOH of the alkaline release test method acquisition described in this

In the following example, all levels all refer to the % (weight) of described composition.

Embodiment 1

Following high-density granulated laundry detergent composition A prepares according to the present invention to F:

	?????A	?????B	?????C	?????D	?????E	?????F
							?LAS	????6.0	????8.0	????8.0	????12.0	????14.0	????8.0
?C25E3	????3.4	?????-	????3.4	????3.4	?????-	????3.4
							?C46AS	?????-	????2.0	?????-	?????-	????3.0	????4.0
?TAS	????3.0	????7.0	????5.0	????2.0	????1.0	????0.5
							?STS	????5.0	????1.5	????3.5	????1.2	????0.8	????1.8
?QAS	?????-	?????-	????0.8	?????-	?????-	????0.8
							Zeolite A	????18.1	????18.1	????18.1	????18.1	????18.1	????18.1
Carbonate	????13.0	????13.0	????13.0	????27.0	????27.0	????27.0
							Silicate	????1.4	????1.4	????1.4	????3.0	????3.0	????3.0
Vitriol	????26.1	????26.1	????26.1	????26.1	????26.1	????26.1
							?MA/AA	????0.3	????0.3	????0.3	????0.3	????0.3	????0.3
?CMC	????0.2	????0.2	????0.2	????0.2	????0.2	????0.2
							?PB4	????9.0	????9.0	????9.0	????9.0	????9.0	????9.0
?TAED	????1.5	????1.5	????1.0	????1.5	?????-	????1.5
							?NAC-OBS	?????-	?????-	????0.5	????1.0	????2.0	?????-
DTPMP	????0.25	????0.25	????0.25	????0.25	????0.25	????0.25
							?EDDS	?????-	?????-	????0.25	????0.4	?????-	?????-
?HEDP	????0.3	????0.3	????0.3	????0.3	????0.3	????0.3
							Proteolytic enzyme	????0.26	????0.26	????0.26	????0.26	????0.26	????0.26
Amylase	????0.1	????0.1	????0.1	????0.1	????0.1	????0.1
							The photosensitization SYNTHETIC OPTICAL WHITNER	???15ppm	???15ppm	???15ppm	???15ppm	???15ppm	???15ppm
Whitening agent 1	????0.09	????0.09	????0.09	????0.09	????0.09	????0.09

Spices	????0.3	????0.3	????0.3	????0.3	????0.3	????0.3
							Silicone antifoam agent	????0.5	????0.5	????0.5	????0.5	????0.5	????0.5
Miscellaneous/low amount thing	Mend 100%
							Density (g/l)	????850	????850	????850	????850	????850	????850

Embodiment 2

Following granular laundry detergent compositions G prepares according to the present invention to I:

	?????G	?????H	?????I
				?LAS	????5.25	????5.61	????8.0
?TAS	????1.25	????1.86	????1.57
				?C45AS	?????-	????2.24	????3.89
?C25E3S	?????-	????0.76	????1.18
				?C45E7	????3.25	?????-	????5.0
?C25E3	?????-	????5.5	?????-
				?QAS	????0.8	?????-	????2.0
?STS	????1.8	????1.5	?????-
				?SBS	?????-	?????-	????2.0
?STPP	????19.7	?????-	?????-
				Zeolite A	?????-	????19.5	????19.5
NaSKS-6/ citric acid (79: 21)	?????-	????10.6	????10.6
				Carbonate	????6.1	????21.4	????21.4
Supercarbonate	?????-	????2.0	????2.0
				Silicate	????6.8	?????-	?????-
Vitriol	????39.8	?????-	????14.3
				?MA/AA	????0.8	????1.6	????1.6
?CMC	????0.2	????0.4	????0.4
				?PB4	????5.0	????12.7	?????-
?TAED	????0.5	????3.1	?????-
				?DTPMP	????0.25	????0.2	????0.2

?HEDP	?????-	????0.3	????0.3
				Proteolytic enzyme	????0.26	????0.85	????0.85
Lipase	????0.15	????0.15	????0.15
				Cellulase	????0.28	????0.28	????0.28
Amylase	????0.1	????0.1	????0.1
				?PVP	????0.9	????1.3	????0.8
Photosensitization SYNTHETIC OPTICAL WHITNER (ppm)	????15	????27	????27
				Whitening agent 1	????0.08	????0.19	????0.19
Whitening agent 2	?????-	????0.04	????0.04
				Spices	????0.3	????0.3	????0.3
Silicone antifoam agent	????0.5	????2.4	????2.4
				Miscellaneous/low amount thing	Mend 100%
Density (g/l)	????750	????750	????750

Embodiment 3

Following granular detergent agent formulation prepares according to the present invention.

	?????J	?????K	?????L	?????M
					The spray-dried granules thing
LAS	?????-	????5.0	?????-	????6.0
					TAS	????7.0	????3.0	????8.0	????5.0
Zeolite A	?????-	????27.0	?????-	????20.0
					STPP	????24.0	?????-	????24.0	?????-
Vitriol	????9.0	????6.0	????13.0	?????-
					?MA/AA	????2.0	????4.0	????6.0	????4.0
Silicate	????7.0	?????-	????3.0	????3.0
					?CMC	????1.0	????1.0	????0.5	????0.6
Whitening agent 1	????0.2	????0.2	????0.2	????0.2
					Silicone antifoam agent	????1.0	????0.1	????0.1	????0.3
?DTPMP	????0.4	????0.4	????0.2	????0.4

STS	????12.0	????1.8	????1.0	????2.5
					Spraying
C45E7	?????-	?????-	?????-	?????-
					C45E2	????2.5	????2.5	?????-	?????-
C45E3	????2.6	????2.5	?????-	?????-
					Spices	????0.3	????0.3	????0.3	????0.2
Silicone antifoam agent	????0.3	????0.3	????0.3	?????-
					Dry additive
Vitriol	????3.0	????3.0	????5.0	????10.0
					Carbonate	????6.0	????13.0	????15.0	????14.0
?PB1	?????-	?????-	?????-	????1.5
					?PB4	????18.0	????18.0	????10.0	????18.5
?TAED	????3.0	????2.0	?????-	????2.0
					?NAC-OBS	?????-	????2.0	????4.0	?????-
Proteolytic enzyme	????1.0	????1.0	????1.0	????1.0
					Lipase	????0.4	????0.4	????0.4	????0.2
Amylase	????0.2	????0.2	????0.2	????0.4
					The photosensitization SYNTHETIC OPTICAL WHITNER	?????-	?????-	?????-	??15ppm
Miscellaneous/low amount thing	To 100%

Embodiment 4

Following granular detergent agent formulation prepares according to the present invention.

	????N	????O	????P	????Q	????R	????S
							The spray-dried granules thing
?LAS	????22.0	????5.0	????4.0	????9.0	????8.0	????6.0
							?C45AS	?????-	????7.0	????6.0	?????-	?????-	?????-
?TAS	????7.0	????4.0	????3.0	????1.8	????2.0	????3.0
							?STS	????0.9	????1.5	????1.7	????11.8	????3.0	????1.5
Zeolite A	????6.0	????16.0	????14.0	????19.0	????16.0	????14.0

MA/AA	????6.0	????3.0	????3.0	????3.0	????2.0	????3.0
							?AA	?????-	????3.0	????3.0	?????-	?????-	?????-
Vitriol	????7.0	????18.3	????11.3	????14.0	????15.3	????10.0
							Silicate	????5.0	????1.0	????1.0	?????-	????1.0	?????-
Carbonate	????28.3	????9.0	????7.0	????15.7	????14.0	????10.0
							?PEG4000	????0.5	????1.5	????1.5	?????-	?????-	?????-
?EDDS	????2.0	?????-	?????-	????0.1	????0.2	????0.3
							?HEDP	????0.4	?????-	????0.5	????0.2	????0.5	????0.5
?QEA	?????-	?????-	????0.8	?????-	????0.8	????0.5
							?QAS	?????-	?????-	?????-	????1.0	????0.5	?????-
Whitening agent 2	????0.2	????0.3	????0.3	????0.3	????0.3	????0.3
							Spraying
C25E9	????1.0	?????-	?????-	?????-	?????-	?????-
							?C45E7	?????-	????2.0	????2.0	????3.5	????2.0	????2.0
Spices	????1.0	????0.3	????0.3	????1.0	????0.3	????0.3
							Agglomerate
TAS	????0.5	?????-	?????-	?????-	????1.0	????0.9
							?C45AS	?????-	????5.0	????5.0	?????-	????5.0	????5.0
?LAS	?????-	????2.0	????2.0	?????-	????2.0	????2.0
							Zeolite A	?????-	????7.5	????7.5	?????-	????7.5	????7.5
Carbonate	?????-	????4.0	????4.0	?????-	????4.0	????4.0
							?PEG?4000	?????-	????0.5	????0.5	?????-	?????-	?????-
Miscellaneous (water etc.)	?????-	????2.0	????2.0	?????-	?????-	????2.0
							Dry additive
PB4	?????-	????1.0	????4.0	?????-	????5.0	????0.5
							?TAED	????6.0	????2.0	?????-	????2.0	????1.6	????2.5
Percarbonate	?????-	????5.0	????12.5	?????-	?????-	?????-
							Carbonate	?????-	????5.3	????1.8	????14.0	????4.0	????8.0
?NOBS	????4.5	?????-	????6.0	?????-	?????-	????0.6

Lipase	????0.4	????0.4	????0.4	????0.2	????0.4	????0.4
							Cellulase	????0.1	????0.2	????0.2	????0.2	????0.2	????0.2
Amylase	????0.1	????0.3	????0.3	????0.6	????0.6	????1.1
							Proteolytic enzyme	????1.0	????0.5	????0.5	????1.5	????1.0	????1.2
?PVPVI	?????-	????0.5	????0.5	?????-	?????-	?????-
							?PVP	????0.5	????0.5	????0.5	?????-	?????-	?????-
?PVNO	?????-	????0.5	????0.5	?????-	?????-	?????-
							?SRP1	?????-	????0.5	????0.5	?????-	?????-	?????-
?SKS-6	?????-	?????-	????0.5	????4.5	????2.0	????3.5
							Citric acid	?????-	????1.0	?????-	????1.0	????1.5	????2.0
?QAS	?????-	?????-	????1.0	????1.0	????1.0	????1.5
							?QEA	????1.0	?????-	?????-	????1.0	?????-	?????-
Silicone antifoam agent	?????-	????0.2	????0.2	????0.3	????0.2	????0.2
							Miscellaneous/low amount thing	To 100%

Embodiment 5

Preparing down according to the present invention, mask body is used for containing of colored clothes washing of zero SYNTHETIC OPTICAL WHITNER detergent formulations:

	?????T	????U
			The spray-dried granules thing
TAS	????9.0	????7.0
			Zeolite A	????15.0	????15.0
Vitriol	?????-	????5.0
			?LAS	?????-	????6.0
?DTPMP	????0.4	????0.5
			?CMC	????0.4	????0.4
?MA/AA	????4.0	????4.0
			?STS	????2.5	????1.4
Agglomerate

C45AS	?????-	?????-
			?LAS	????6.0	????5.0
?TAS	????3.0	????2.0
			Silicate	????4.0	????4.0
Zeolite A	????10.0	????15.0
			?CMC	?????-	?????-
?MA/AA	?????-	?????-
			Carbonate	????9.0	????7.0
Spraying
			Spices	????0.3	????0.3
?C45E7	????4.0	????4.0
			?C25E3	????2.0	????2.0
Dry additive
			MA/AA	?????-	?????-
?NaSKS-6	?????-	?????-
			Citrate trianion	????10.0	?????-
Supercarbonate	????7.0	????3.0
			Carbonate	????8.0	????5.0
?PVPVI/PVNO	????0.5	????0.5
			?Alcalase	????0.5	????0.3
Lipase	????0.4	????0.4
			Amylase	????0.6	????0.6
Cellulase	????0.6	????0.6
			Silicone antifoam agent	????5.0	????5.0
Dry additive
			Vitriol	????0.0	????9.0
Miscellaneous/low amount thing	To 100%
			Density (g/l)	????700	????700

Embodiment 6 following granular detergent agent formulations prepare according to the present invention.

	????V	????W	????X
				The spray-dried granules thing
TAS	????3.0	????10.0	????7.0
				Zeolite A	????30.0	????22.0	????6.0
Vitriol	????19.0	????5.0	????7.0
				?MA/AA	????3.0	????3.0	????6.0
?LAS	????14.0	?????-	????8.0
				?C45AS	????5.0	????7.0	?????-
Silicate	?????-	????1.0	????5.0
				Soap	?????-	?????-	????2.0
Whitening agent 1	????0.2	????0.2	????0.2
				Carbonate	????8.0	????16.0	????20.0
?DTPMP	?????-	????0.4	????0.4
				?STS	????1.8	????8.5	????1.2
Spraying	?????-	????1.0	????5.0
				?C45E7	????1.0	????1.0	????1.0
Dry additive
				PVPVI/PVNO	????0.5	????0.5	????0.5
Proteolytic enzyme	????1.0	????1.0	????1.0
				Lipase	????0.4	????0.4	????0.4
Amylase	????0.1	????0.1	????0.1
				Cellulase	????0.1	????0.1	????0.1
?NOBS	?????-	????6.1	????4.5
				?PB1	????1.0	????5.0	????6.0
Vitriol	?????-	????6.0	?????-
				Miscellaneous/low amount thing	To 100%

Embodiment 7 following granular detergent compositions prepare according to the present invention.

	????Y	????Z
			The spray-dried granules thing
TAS	????6.0	?????-
			Zeolite A	????20.0	?????-
?STPP	?????-	????20.0
			?LAS	????6.0	????6.0
?C68AS	?????-	????2.0
			Silicate	????3.0	????8.0
?MA/AA	????4.0	????2.0
			?CMC	????0.6	????0.6
Whitening agent 1	????0.2	????0.2
			?DTPMP	????0.4	????0.4
?STS	????0.8	????7.5
			Spraying
C45E7	????5.0	????5.0
			Silicone antifoam agent	????0.3	????0.3
Spices	????0.2	????0.2
			Dry additive
STS	????0.5	????0.4
			Carbonate	????14.0	????9.0
?PB1	????1.5	????2.0
			?PB4	????18.5	????13.0
?TAED	????2.0	????2.0
			The photosensitization SYNTHETIC OPTICAL WHITNER	???15ppm	???15ppm
Proteolytic enzyme	????1.0	????1.0
			Lipase	????0.2	????0.2
Amylase	????0.4	????0.4

Cellulase	????0.1	????0.1
			Vitriol	????10.0	????20.0
Miscellaneous/low amount thing	To 100%
			Density (g/l)	????700	????700

Claims (19)

1. granular detergent composition, it comprises:

A) account for the sulphate anion surface active agent of the 0.01-95% of described composition weight;

B) account for the solubilizing agent of described composition weight 0.01-60%, wherein the solubilizing agent of 0.0-1.8% (weight) (based on the gross weight of described composition) can be present in a kind of agglomerate that contains solubilizing agent.

2. according to the granular detergent composition of claim 1, the level that exists of wherein said sulphate anion surface active agent is the 3-20% of described composition weight.

3. according to each granular detergent composition of aforementioned claim, the level that exists of wherein said solubilizing agent is the 0.3-10% of described composition weight.

4. according to each granular detergent composition of aforementioned claim, wherein said sulphate anion surface active agent comes from the alcohol of tallow oil or from palmitinic acid or stearic alcohol from a kind of.

5. according to each granular detergent composition of aforementioned claim, wherein said solubilizing agent is the salt of a kind of benzene sulfonate, tosylate, xylenesulfonate or cumene sulfonate.

6. according to the granular detergent composition of claim 5, wherein said solubilizing agent is toluenesulfonic acid sodium salt.

7. according to each granular detergent composition of aforementioned claim, wherein the ratio of sulphate anion surface active agent and solubilizing agent is 50: 1 to 1: 1.

8. according to each granular detergent composition of aforementioned claim, wherein the ratio of sulphate anion surface active agent and solubilizing agent is 20: 1 to 2: 1.

9. according to each granular detergent composition of aforementioned claim, wherein sulfonate anionic surfactant exists with the level of the 0.01-30% that accounts for described composition weight.

10. according to the granular detergent composition of claim 9, wherein said sulfonate anionic surfactant is a kind of linear alkyl benzene sulfonate.

11. according to each granular detergent composition of aforementioned claim, it does not contain the agglomerate of solubilizing agent basically.

12. a detergent particles thing that is used for detergent composition, it comprises:

A) a kind of sulphate anion surface active agent that accounts for described composition weight 0.01-50%;

B) a kind of solubilizing agent that accounts for described composition weight 0.01-25%.

13. a method for preparing according to the particulate matter of claim 12, it comprises the following steps:

A) described sulphate anion surface active agent and described solubilizing agent are mixed with water and forms contain the moisture particulate matter;

B) with the particulate matter drying of step a).

14., wherein undertaken by spraying drying in the drying of particulate matter described in the step b) according to the method for claim 13.

15., wherein be dried to the particulate matter that free water content is lower than 6% (weight) in particulate matter described in the step b) according to the method for claim 13 or 14.

16. according to the detergent particles thing of claim 12, wherein said particulate matter is spray-dired particulate matter.

17. according to claim 12,14 or 15 each detergent particles thing, its level that exists in described detergent composition is the 5-85% of described composition weight.

Use solubilizing agent reduces the viscosity of this mixture in the detergent composition that just can form viscous mixt 18. contact at a kind of surface active agent composition that comprises the sulfur acid salt anionic surfactant and this tensio-active agent in case with water, thereby improves the dispersiveness of described detergent composition.

19. the purposes of solubilizing agent in the detergent composition of the surface active agent composition that comprises the sulfur acid salt anionic surfactant, described surface active agent composition is the viscosity that has at least 15000 centipoises under 20 ℃ in 25% (weight) aqueous solution (measuring by tensio-active agent viscosity test method), after wherein solubilizing agent being joined in the described surface active agent composition, the viscosity drop of this surface active agent composition low at least 25%.