CN1181175C

CN1181175C - Detergent particles and processes for making them

Info

Publication number: CN1181175C
Application number: CNB008118728A
Authority: CN
Inventors: C・A・莫里森; C·A·莫里森; 多诺霍; S·J·多诺霍; 丈; G·辛普森
Original assignee: Procter and Gamble Ltd
Current assignee: Procter and Gamble Ltd; Procter and Gamble Co
Priority date: 1999-06-21
Filing date: 2000-06-20
Publication date: 2004-12-22
Anticipated expiration: 2020-06-20
Also published as: CN1375001A; CA2375408A1; EP1187900A1; BR0011836B1; WO2000078908A1; AR024429A1; BR0011836A; AU5625700A; JP2003503545A; MXPA02000060A

Abstract

Methods for making articulate detergents are disclosed. The detergent particulates are formed from a combination of pre-formed detergent particulates and other detergent ingredients may also be preformed such as blown powders, extrudates or agglomerates or particulate raw materials. Selection of the feed streams into a low or moderate shear mixing process enable of the finished detergent particle to be controlled without requiring careful control of the conditions.

Description

Detergent particles and preparation method thereof

Invention field

The present invention relates to improving one's methods of granular detergent composition and this composition of preparation.Detergent composition of the present invention is fit to any purging method, such as laundry and dishwashing detergent composition.This particulate composition can directly use with their particle form or can at first adopt any standard preparation technology to make detergent tablet such as the die mould method.

Background of invention

In order to satisfy human consumer's needs, except good cleaning performance was provided, detergent composition also must satisfy multiple other requirements, comprised good attractive in appearance, good flowing property, satisfactory stability and good dispersing property in washing water.In order to satisfy all these requirements, the complexity of detergent composition rises with the product category that is provided is existing.Therefore, it is quite important to prepare the used formulation flexibility of this complex combination thing, many methods of known preparing washing agent composition.

In view of human consumer's this high performance requirements, evenly metering is important all the more in composition to realize all detergent active, particularly under the situation that the senior detergent component that exists with low amount in washing composition has a significant effect to one of above-mentioned performance characteristic.This problem is owing to the appearance of " concentrating " or low metering granulated detergent product increases the weight of.At present these low metering washing composition are had high demand, because it is saved the energy and can sell by small packages, this is more convenient for the human consumer before use.Yet in low metering washing composition, actives is to exist with low-down content, and in the per unit metering, considerable change can take place the concentration of this actives.For some concentrated cleaning products, confirmed to have performance issue, the inventor finds that now this is because the variation of prescription promptly has considerable change to the low levels detergent component that one or more above-mentioned performance factors have a significant effect in each time metering.

Summary of the invention

The present invention has reduced these problems thus by a kind of method is provided, in the method, this low metering/efficient fruit component can be in whole detergent formulations homodisperse.Centrifugation is reduced to minimum, does not need to add high levels of filler this low metering/efficient fruit component is mixed in the larger particles.

According to the present invention, a kind of preparing washing agent particulate method now is provided, comprise the washing composition basal granule of selecting to have geometric mean diameter 500-2000 micron, in to low shear mixer, the washing composition active particle is adhered on the washing composition basal granule, wherein the geometric mean diameter of washing composition active particle be not more than the washing composition basal granule geometric mean diameter 40%, the detergent active that is comprised is selected from spices, enzyme, optical white, catalyzer, the dirt release agent polymkeric substance, suds suppressor, bleaching compounds, whitening agent and layered silicate, and the geometric mean diameter of washing composition active particle is higher than 10 μ m and is lower than 200 μ m.

The present invention also provides by the detergent particles of this method preparation and has mixed these particulate detergent composition.

As described herein, its meaning is that the detergent active particle is attached on the washing composition basal granule, two kinds of components appear in the detergent composition in proper order as single detergent particles.

Detailed Description Of The Invention

Physical properties

This washing composition active particle preferably has geometric mean diameter and is lower than 200 μ m, preferably is lower than 150 μ m and even is lower than 100 μ m.The geometric mean diameter of washing composition active particle of the present invention is preferably greater than 20 μ m generally greater than 10 μ m, even can be greater than 40 μ m or greater than 60 μ m.

As described herein, term " geometric mean diameter " meaning is to adopt based on any standard quality granulometry technology, preferably how much mass mean diameter of one group of discontinuous particulate of measuring by dry sieving.The method for sieving that is fit to is according to ISO3118 (1976).The device that is fit to is a Type B RO-Tap testing sieve vibrator, uses the 8 inches sieves that can select granularity.As described herein, it is that the geometric widths of best-fit is the log-normal function of above-mentioned granularity data that " geometric standard deviation " of term size-grade distribution or " span " (Span) are looked like, and this can remove the ratio (D8 of the diameter at 84.13% place by the diameter with 50% place of cumulative distribution _4.13/ D ₅₀) realize; Referring to Gotoh etc., Powder Technology Handbook, the 6-11 page or leaf, MarcelDekker 1997.

The geometric mean diameter of this washing composition basal granule is 500-2000 μ m.The geometric mean diameter of this washing composition basal granule is generally greater than 550 μ m, or even greater than 600 μ m or 650 μ m.Preferably, the geometric mean diameter of this washing composition basal granule is lower than 1500 μ m.

It is that 1-is about 2 that prepared detergent particles preferably has geometric standard deviation, preferred 1.0-1.7, more preferably from about 1.0-1.4.The washing composition that preferably comprises the complete formula of this detergent particles also has such geometric standard deviation.

The geometric mean diameter of preferred washing composition active particle be not more than the washing composition basal granule geometric mean diameter 20%, more preferably no more than 10%, in addition can be lower than the washing composition basal granule geometric mean diameter 5%.In detergent particles, the particle that generally is not more than 25% weight is to be obtained from the washing composition active particle, preferably is not more than 10% weight.Even be not more than 5% or not even under the situation greater than 2% weight, the present invention also is suitable in the ratio of the detergent particles that is obtained from the washing composition active particle.

As described herein, pile of grounds density uncompacted, that do not pat that term " tap density " is meant, measure as follows, excessive particulate samples is poured in the smooth metal container (for example 500ml volume cylinder) by funnel, wipe excessive stores off from the edge of this container, measure the remaining powder quality, and with volume of a container divided by this quality.

The bulk density of prepared detergent particles and washing composition basal granule generally is higher than 200g/l, may be up to 1500g/l.The tap density of finished product detergent composition that especially preferably comprises detergent particles prepared in accordance with the present invention is preferably greater than 600g/l greater than 550g/l, or even greater than 650g/l.Thus, the tap density of prepared detergent particles is generally 400g/l-1100g/l, generally greater than 500g/l, or even greater than 550 or 650g/l, generally be lower than 1000g/l or be lower than 900g/l.The present invention is particularly useful for making has low density such as being lower than 550 or even be lower than 500 or the detergent particles of 450g/l.

The washing composition basal granule that uses in the inventive method can comprise single detergent component of particle form, maybe can be the premixture of detergent component.Comprise at the washing composition basal granule under the situation of premixture, each detergent component can mix simply, maybe can comprise the ready-formed particle, this ready-formed particle comprises two or more detergent components or its mixture, randomly with the arbitrary combination of sole cleaning agent component.The prefabricated particle that is fit to that is used for basal granule can prepare by spraying drying, agglomeration, agglomerating (marumerisation), extruding or die mould method, and all these methods that are used for the cleaning composition component are that prior art is known.Particularly preferred prefabricated particle is the powder that is obtained by spray drying process, agglomeration and extruding.Spray-dried powders is a particularly suitable.For example in fluidized-bed, the prefabricated particle by the fluidized bed agglomeration preparation is particularly preferred according at least a low shear-mixed step.Particularly preferred particle is the unexamined application of submitting to today as at us, describes among the document number CM2158F.

Be used for preparing the suitable spray-drying process of this prefabricated particulate and for example be described in EP-A-763594 or EP-A-437888.Prepare prefabricated particulate appropriate methodology and be the agglomerate that is described among for example WO93/25378, EP-A-367339, EP-A-420317 or the EP-A-506184, form prefabricated particulate appropriate methodology by extruding and for example be described among the WO91/02047.

This prefabricated particle can its wet or dry state add in the mixing tank.Preferred they be to add in the mixing tank with dry state, in addition, their hygrometric state mobile in may the subtend mixing tank has disadvantageous effect.In addition, preferred ready-formed particle is to form in the fs of middling speed-low velocity shear mixing tank, and the washing composition active particle adds in subordinate phase, so the ready-formed particle can be a hygrometric state when contacting with the washing composition active particle.Thus, the ready-formed particle can for example be the powder or the extrudate of agglomerate, blowing, and it does not also experience final drying stage.

Generally, this means that in this technology content as the solvent of tackiness agent is than the desired quantity height that exists in the finished particle washing composition.Generally, solvent is a water, and wet granular has the free water yield and for example is prefabricated particulate 15-30% weight.Yet the ready-formed particle had experienced drying step before adding mixing tank usually, so water-content is lower than 15% weight, preferably was lower than 10% weight.The general free water content that adds the washing composition basal granule in the mixing tank is lower than 15% weight, preferably is lower than 10% weight.

Preferably, the washing composition basal granule comprises tensio-active agent or surfactant mixtures.The tensio-active agent that is fit to is described in hereinafter.Washing composition basal granule or the surfactant content that constitutes the prefabricated grain fraction of total washing composition basal granule or its part are preferably the 5-80% of this grain fraction weight.The amount of preferred surfactant is higher than 10% or even be higher than 30%.The amount of preferred surfactant is lower than 70% or even be lower than 50%.Comprise under the situation of tensio-active agent that in washing composition ready-formed basal granule component general, in addition it also comprises washing assistant or alkaline reagents such as yellow soda ash, zeolite or phosphoric acid salt.For example, in these components every kind exists separately or with form of mixtures, and its amount is higher than 5% of prefabricated groups of grains component, preferably is higher than 10% or even be higher than 20% weight.Particularly preferred builder component is yellow soda ash and/or zeolite.Zeolite A and zeolite MAP all are fit to for two kinds.

This washing composition basal granule preferably also comprises organic washing-assisting detergent such as poly carboxylic acid or its salt such as citric acid, tartrate, oxysuccinic acid, succsinic acid and their salt or polymeric multi-carboxylate such as polymkeric substance or its multipolymer based on vinylformic acid or toxilic acid.This component generally content in this particle is lower than 15% weight of this grain fraction, preferably is lower than 10% weight of this grain fraction.

Other preferred ingredients in prefabricated grain fraction are sequestrant such as phosphine acid salt chelator NTA, DTPA and succinic acid derivative sequestrant, and are as described below.The content of these components in the washing composition basal granule preferably is lower than 5% weight, or even is lower than 2% weight.Suds suppressor and/or dirt release agent polymkeric substance and/or bleach activator also are preferred ingredients in this prefabricated particle.

In grain fraction is under the situation of detergent raw material, and any granular detergent component all is fit to.They can be solid-state tensio-active agent or soaps, and water-soluble or dispersible polymeric material, enzyme, bleaching component such as bleach-activating agent or SYNTHETIC OPTICAL WHITNER salt are such as peroxy salt.The optimal one-component of particle form comprises inorganic component, particularly water-soluble inorganic component such as washing assistant and SYNTHETIC OPTICAL WHITNER salt such as alkali metal percarbonate and/or perborate.These components are more detailed description hereinafter.

Mix in the detergent particles itself or suitable detergent component that the back adds the detergent composition of preparation complete formula is discussed hereinafter.

The washing composition active particle is selected from spices, enzyme, optical white, catalyzer, dirt release agent polymkeric substance, suds suppressor, bleaching compounds, whitening agent and layered silicate.

Spices

Preferred washing composition active particle comprises spices.Can use any spices or flavor compositions.Yet it must be solid or combine with other components, so that they have solid form.For example, it can be downloaded to particulate vector such as zeolite, or on any other known solid carrier, for example describes in WO94/16046, ES93000006, EP-A-535942 and EP-A-294206.More preferably, it exists with capsule form.The capsule that is fit to is described in for example WO94/12613, EP-A-539025, EP-A-478326, EP-A-383406, EP-A-382464, EP-A-346034, EP-A-70719.Particularly preferred capsule comprises starch.

Preferred spices contains at least a lower molecular weight volatile components, and for example molecular weight is 150-450, or preferred 350.Preferably, the spices component comprises oxygen containing functional group.Preferred functional group is aldehyde, ketone, alcohol or ether functional group or its mixture.

Enzyme

This washing composition active particle can comprise one or more enzymes.The enzyme that is fit to comprises commercially available lipase, at, amylase, neutrality and Sumizyme MP, cellulase, restriction endonuclease (endolase), esterase, polygalacturonase, Sumylact L and the peroxidase that is routinely added in the detergent composition.Suitable enzyme is discussed in United States Patent (USP) 3519570 and 3533139 to some extent.

Those proteolytic enzyme that preferred commercially available proteolytic enzyme comprises those proteolytic enzyme of being sold with trade(brand)name Alcalase, Savinase, Primase, Durazym and Esperase by Novo Industries A/S (Denmark), sold with trade(brand)name Maxatase, Maxacal and Maxapem by Gist-Brocades, those proteolytic enzyme of selling by Genencor International and those proteolytic enzyme of selling with trade(brand)name Opticlean and Optimase by Solvay Enzymes.Proteolytic enzyme is pressed the content that composition weight meter can the 0.0001%-4% organized enzyme and is added in the present composition.

Preferred amylase comprises, for example α-Dian Fenmei in greater detail among the GB-1269839 (Novo).Preferred commercially available amylase comprises those amylase of for example being sold those amylase and sold with trade(brand)name Termamyl, Duramyl and BAN by Novo IndustriesA/S with trade(brand)name Rapidase by Gist-Brocades.Preferred amylase can be those that describe in PCT/US9703635 and WO95/26397 and WO96/23873.Amylase adds in the present composition with the content of 0.0001%-2% weight organized enzyme.

Based on the content in the finished product detergent composition, lipolytic enzyme can 0.0001%-2% weight, preferably 0.001%-1% weight, the most preferably active lipolytic enzyme content existence of 0.001%-0.5% weight.Lipase can be obtained by fungi or bacterial origin, for example by the detritus enzyme belong to, the bacterial strain of the generation lipase of Thermomicrobium (Thermomyces) or Rhodopseudomonas obtains, described bacterial strain comprises pseudomonas pseudoalcaligenes or Pseudomonas fluorescens.Lipase chemical or that genetically altered mutation obtains by these bacterial strains also can be used among the present invention.Preferred lipase is obtained by pseudomonas pseudoalcaligenes, and it is described in the European patent EP-B-0218272 that authorizes.In addition-kind of preferred lipase, as described in European patent application EP-A-0258068, be the gene that obtains by fetal hair detritus bacterium by the clone and express the lipase that this gene obtains in as the host at aspergillus oryzae, it is from NovoIndustri A/S Bagsvaerd, Denmark, Lipolase is purchased with trade(brand)name.This lipase also is described among the US4810414 of the Huge-Jensen of on March 7th, 1989 promulgation etc.

Optical white

Preferred washing composition active particle comprises the optical white particle.The preferred optical white of the present invention comprises the compound with porphines or porphyrin structure.In the literature, porphines and porphyrin are to use as different name, but routinely, porphines is represented the simplest without any substituent porphyrin; Its mesoporphyrin is the subclass of porphines.In this application, the porphines of indication comprises porphyrin.The porphines structure optimization comprises metallic element or positively charged ion, preferred Ca, Mg, P, Ti, Cr, Zr, In, Sn or Hf, more preferably Ge, Si or Ga, or more preferably Al, most preferably Zn.Preferred light SYNTHETIC OPTICAL WHITNER compound or composition are selected from following substituting group and are replaced: alkyl such as methyl, ethyl, propyl group, the tertiary butyl and aromatic ring system such as pyridine, pyridine-N-oxide, phenyl, naphthyl and anthryl.

Optical white compound or component can have as substituent solubilizing group.In addition, or in addition, optical white can comprise can solubilising photobleaching compound the polymerization component, for example PVP, PVNP, PVI or its co-polymer or its mixture.

Highly preferred photobleaching compound has phthalocyanine structure, and it preferably has above-mentioned metallic element or positively charged ion.Phthalocyanine can be substituted, and the example that is fit to is included in 1-4, and 6,8-11,13,15-18,20,22-25,27 the substituted phthalocyanine structure in one or more atom sites place.

Preferred one group of optical white comprises polymeric component and bonded photobleaching component with it, and wherein the weight ratio of polymeric component and photobleaching component is 1: 1-1000: 1, preferred 20: 1-100: 1.Particularly preferred polymerizable compound is to form by being selected from following monomeric unit: N-vinyl pyrrolidone, N-vinyl acetamide, N-vinyl imidazole, N-Yi Xi oxazolidinone, N-vinyl triazole, 4-vinylpridine and 4-vinylpridine-N-oxide compound.Preferred photobleaching compound is a metal, preferred zinc phthalocyanine or aluminium phthalocyanine.This optical white is described among the GB-232939A.

The dirt release agent polymkeric substance

Preferred dirt release agent polymkeric substance (SRP ' s) generally has the hydrophilic segment that makes hydrophobic fiber such as polyester and nylon surface hydrophilic, with the hydrophobic part that is deposited on the hydrophobic fiber and keeps being attached thereto in whole washing and rinse cycle, so it is as the fixture of hydrophilic segment.This can be so that spot easier being cleaned in washing process afterwards that produces subsequently of handling with SRP.Preferred SRPs comprises oligomeric terephthalate, and it generally by comprising the method preparation of at least a transesterify/oligomerization, carries out under metal catalyst such as titanium alkoxide (IV) usually.This ester can use can by one, two, three, four or more position add other monomers preparations of ester structure, certainly, do not form fine and close full crosslinking structure.

The SRPs that is fit to comprises the sulfonated products of the ester oligomer that is straight chain basically; it contains oligomer ester skeleton and the oxyalkylene oxygen repeating unit and the allyl group deutero-sulfonation terminal portions covalently bound with skeleton of terephthaloyl, for example described in the U.S. Pat 4968451 of J.J.Scheibel that authorizes in November 6 nineteen ninety and E.P.Gosselink.This ester oligomer can prepare through the following steps: (a) ethoxylation allyl alcohol; (b) product and terephthalic acid dimethyl ester (" DMT ") and 1 that will (a) in two step transesterify/oligomerization process, 2-propylene glycol (" PG ") reacts; (C) in water with the product of (b) and sodium metabisulfite reaction.Other SRPs comprises the nonionic end capped 1 in the people's such as Gosselink that authorized on December 8th, 1987 the U.S. Pat 4711730,2-propylidene/polyoxyethylene terephthalic acid polyester, for example by poly-(ethylene glycol) methyl ether, DMT, the product of the transesterify of PG and poly-(ethylene glycol) (" PEG ")/oligomerization preparation.Other SRA ' s example comprises part and the whole end capped oligomer esters of negatively charged ion in the U.S. Pat 4721580 of the Gosselink that authorized on January 26th, 1988, as derive from ethylene glycol (" EG "), PG, DMT and 3, the oligopolymer of 6-two oxa-s-8-hydroxyl perfluorooctane sulfonate; Nonionic end-blocking block polyester oligomeric compound in the U.S. Pat 4702857 of the Gosselink that on October 27th, 1987 authorized, for example by DMT, methyl (Me)-end capped PEG and EG and/or PG preparation, perhaps by DMT, EG and/or PG, the product of the mixture preparation of end capped PEG of Me-and dimethyl-5-sulfoisophthalic acid sodium; With the Maldonado that authorized on October 31st, 1989; negatively charged ion in people's such as Gosselink the U.S. Pat 4877896; especially the end capped terephthalate of sulfo group aroyl; the latter is typical useful SRPs in laundry and fabric-conditioning product, an example be by-sulfosalicylic acid list sodium salt, the ester composition that PG and DMT prepare; randomly; but the PEG that preferably also contains adding, for example, PEG3400.SRPs also comprises: the simple copolymerization block thing of ethylene terephthalate or terephthalic acid propylene glycol ester and polyoxyethylene or polyoxypropylene terephthalate, referring to the U.S. Pat 3959230 of the Hays on May 25th, 1976 and the U.S. Pat 3893929 of the Basadur on July 8th, 1975; Derivatived cellulose such as the hydroxy ethers cellulose polymer compound bought from Dow by METHOCEL; C ₁-C ₄Alkylcellulose and C ₄Hydroxy alkyl cellulose is referring to the people's such as Nicol on December 28th, 1976 U.S. Pat 4000093; And methyl cellulose ether, it is about 1.6-2.3 that its each anhydroglucose unit has average substitution degree (methyl), and the soltion viscosities of measuring under 20 ℃ by 2% the aqueous solution are about 80-120 centipoise.This material can be by METOLOSE SM100 ^TMWith METOLOSE SM200 ^TMBuy, they are methyl cellulose ethers of being produced by Shin-etsu Kagaku Kogyo KK.

Another kind of SRPs is included in those that describe in people's such as people's such as Violland U.S. Pat 4201824 and Lagasse the U.S. Pat 4240918; With the SRAs that has the carboxylicesters end group, the conversion terminal hydroxy group becomes the trimellitate preparation among known SRP ' s by trimellitic acid 1,2-anhydride is added for it.By suitable selecting catalyst, trimellitic acid 1,2-anhydride forms the end group banded key with polymkeric substance, and this is to carry out by the isolated carboxylicesters of trimellitic acid 1,2-anhydride rather than by opening the acid anhydride key.Nonionic or negatively charged ion SRPs can be used as starting raw material, as long as have can esterified hydroxyl end groups for they, referring to people's such as people's such as Tung U.S. Pat 4525524 and Violland U.S. Pat 4201824.

It is that 1.5-2.7 and number-average molecular weight are alkyl and the hydroxyalkyl ether Mierocrystalline cellulose of 2000-100000 that the dirt release agent polymkeric substance that is fit to can be selected from that (a) contain 1-4 carbon atom and have molar substitution at moieties; (b) comprising with mol ratio is 1: 10 the ethylene glycol terephthalate and the polymkeric substance of polyethylene oxide terephthalate; (c) comprising with mol ratio is 1: 10-10: the polymkeric substance of 1 propylene glycol ester terephthalate and polyethylene oxide terephthalate, described polyethylene oxide terephthalate contains polyethylene oxide unit that number-average molecular weight is 500-10000 and described dirt release agent, and to have number-average molecular weight be 1000-100000; (d) comprise with the ethylene glycol terephthalate of any ratio and/or propylene glycol ester terephthalate with the polyethylene oxide of any ratio and/or the polymkeric substance of poly(propylene oxide), make ethylene glycol terephthalate add that propylene glycol ester terephthalate and polyethylene oxide add that the mol ratio of poly(propylene oxide) is 1: 10-10: 1, it is 250-10000 that described polyethylene oxide unit and described poly(propylene oxide) unit respectively have number-average molecular weight, and it is 1000-100000 that described dirt release agent has number-average molecular weight; With its mixture; As in EP-A-271312 in greater detail.

Suds suppressor

This washing composition active particle can comprise suds suppressor.The suitable foam that presses down is to comprise any basically known defoamer compound, comprises for example polysiloxane defoamers compound and 2-alkyl alkanol defoamer compound or soap.

It is to detergent composition solution that defoamer compound is here looked like, and for example inhibiting any compound or its mixture are played in foaming that produces when particularly stirring this solution or foaming.

Being used for the particularly preferred defoaming compounds of the present invention is the polysiloxane defoaming compounds, and it is defined as any defoaming compounds that comprises the polysiloxane component at this paper.This polysiloxane defoaming compounds generally also contains silica component.Used herein and also be that the term " polysiloxane " of industrial common employing comprises the various relative high molecular weight polymers that contain siloxane unit and all kinds alkyl.Preferred polysiloxane defoaming compounds is a siloxanes, particularly has the unitary polydimethylsiloxane of trimethyl silyl end-blocking.

Other suitable defoaming compounds comprise monobasic aliphatic carboxylic acid and its soluble salt, as are described among the US2954347 of the Wayne St.John that authorizes September 27 nineteen sixty.Monobasic aliphatic carboxylic acid and salt thereof as suds suppressor generally have the 10-24 of containing carbon atom, the hydrocarbyl chain of preferred 12-18 carbon atom.The salt that is fit to comprises an alkali metal salt, sodium salt for example, sylvite, and lithium salts and ammonium salt and alkanol ammonium salts.

Other suitable defoaming compounds comprise for example high-molecular weight fatty acid ester (as glycerine fatty acid three esters), monohydroxy-alcohol fatty acid ester, aliphatic C ₁₈-C ₄₀Ketone (as stearone), N-alkylation aminotriazine, as three to six alkyl melamines or two to the tetraalkyl diammonium chloride for triazine, it is that cyanuryl chloride and 2 or 3 moles contain the uncle of 1-24 carbon atom or the reaction product of secondary amine, propylene oxide, distearyl acid amides and single stearyl di(2-ethylhexyl)phosphate basic metal (as sodium, potassium, lithium) salt and phosphoric acid ester.The preferred foam system that presses down comprises:

(a) defoamer compound, preferred polysiloxane defoamers compound, the polysiloxane defoamers compound that most preferably comprises following combination of components: polydimethylsiloxane, its content accounts for the 50%-99% of polysiloxane defoamers compound, preferred 75%-95% weight; And silicon-dioxide, its content accounts for the 1%-50% of polysiloxane/silicon-dioxide defoamer compound, preferred 5%-25% weight; The incorporation of wherein said silicon-dioxide/polysiloxane defoamers compound is 5%-50%, preferred 10%-40% weight;

(b) a kind of compound dispersing agent, most preferably comprise silicone glycol comb copolymer (rakecopolymer), its polyoxyalkylene content is 72%-78%, the ratio of oxygen ethene and oxypropylene is 1: 0.9-1: 1.1, its content is 0.5%-10%, such as the DCO544 that is purchased from DOW Corning company;

(c) a kind of inertia carrying object compound, most preferably it comprises C ₁₆-C ₁₈Ethoxylated alcohol, its ethoxylation degree are 5-50, preferred 8-15, and its content is 5%-80%, preferred 10%-70% weight.

Particularly preferred granular suds suppressing system is disclosed among the EP-A-0210731, should pressing down foam system, to comprise a kind of polysiloxane defoaming compounds and a kind of fusing point be 50-85 ℃ organic support material, wherein organic support material comprises the monoesters of glycerine and a kind of lipid acid, and described lipid acid has the carbochain that contains 12-20 carbon atom.EP-A-0210721 discloses other preferred granular suds suppressing systems, and wherein organic support material is lipid acid or the alcohol with the carbochain that contains 12-20 carbon atom, or its mixture, and its fusing point is 45-80 ℃.

Other highly preferred foam systems that press down comprise polydimethylsiloxane or polysiloxane mixture for example polydimethylsiloxane, silico-aluminate and multi-carboxy acid copolymer, for example lactic acid (laic) and acrylic acid multipolymer.

Bleaching compounds

This washing composition active particle can comprise one or more bleaching compounds.The bleaching compounds that is fit to comprises bleach-activating agent, ready-formed peracid and persalt such as alkali metal percarbonate and/or perborate.The chemical property of these components in more detail hereinafter exercise question for discussing in the paragraph of " detergent component ".Preferred bleaching compounds is that bleach-activating agent is such as the TAED, the NOBS that hereinafter discuss, ISONOBS etc. and persalt such as alkali metal percarbonate and/or perborate.Sodium salt is particularly preferred.

Whitening agent

The whitening agent that is fit to comprises that hydrophilic white dyes is such as having those of following formula structure:

R wherein ₁Be selected from anilino, N-2-pair-hydroxyethyl and NH-2-hydroxyethyl; R ₂Be selected from N-2-pair-hydroxyethyl, N-2-hydroxyethyl-N-methylamino-, morpholino, chlorine and amino; With M be salt-forming cation such as sodium or potassium.

In following formula, R ₁Be anilino, R ₂Be N-2-two-when hydroxyethyl and M were positively charged ion such as sodium, whitening agent was 4,4 '-two [(4-anilino-6-(N-2-two-hydroxyethyl)-guanamine-yl) amino]-2,2 '-stilbene disulfonic acid and disodium salt.Such special whitening agent can be bought from Ciba-Geigy company according to trade(brand)name Tinopal-UNPA-GX commercial.Tinopal-CBS-X and Tinopal-UNPA-GX are the preferred hydrophilic white dyess that can be used in the detergent composition of the present invention.

In following formula, R ₁Be anilino, R ₂Be N-2-hydroxyethyl-N-2-methylamino-and M when being positively charged ion such as sodium, whitening agent is 4,4 '-two [(4-anilino-6-(N-2-hydroxyethyl-N-methylamino-)-guanamine-yl) amino]-2,2 '-stilbene disulfonic acid disodium salt.Such special whitening agent by Ciba-Geigy company with Tinopal 5BM-GX ^TMSell.

In following formula, R ₁Be anilino, R ₂Be morpholino and M when being positively charged ion such as sodium, whitening agent is 4,4 '-two [(4-anilino-6-morpholino-guanamine-yl) amino]-2,2 '-stilbene disulfonic acid, sodium salt.Such special whitening agent is pressed Tinopal-DMS-X by Ciba-Geigy company ^TMWith Tinopal AMS-GX ^TMSell.

Layered silicate

The crystalline layered silicate that is fit to for example is described among the US4663839.The crystalline layered silicate of rich δ-phase is preferred, such as in WO97/19156, describe those.

Catalyzer

This washing composition active particle also can comprise granules of catalyst.The catalyzer that is fit to comprises the bleaching catalyst that contains transition metal.A kind of bleaching catalyst of suitable type is to comprise the active heavy metal cation of the bleach catalyst with definition such as copper, iron or manganese positively charged ion, have very little or do not have the active assistant metal positively charged ion of bleach catalyst such as zinc or aluminium cations, with the catalyst system of the sequestrant (sequestrant/chelant) with catalysis and the defined stability constant of assistant metal positively charged ion, described sequestrant is ethylenediamine tetraacetic acid (EDTA), ethylenediamine tetraacetic (methylene phosphonic acid) and its water-soluble salt particularly.This catalyzer is disclosed in US 4,430, in 243.

The bleaching catalyst of other types comprises and is disclosed in US 5,246,621 and US 5,244,594 in manganese basigamy compound.The preferred embodiment of these catalyzer comprises: Mn ^IV ₂(u-O) ₃(1,4,7-trimethylammonium-1,4,7-7-triazacyclononane) ₂(PF ₆) ₂, Mn ^III ₂(u-O) ₁(u-OAc) ₂(1,4,7-trimethylammonium-1,4,7-7-triazacyclononane) ₂(ClO ₄) ₂, Mn ^IV ₄(u-O) ₆(1,4, the 7-7-triazacyclononane) ₄(ClO ₄) ₂, Mn ^IIIMn ^IV ₄(u-O) ₁(u-OAc) ₂(1,4,7-trimethylammonium-1,4,7-7-triazacyclononane) ₂(ClO ₄) ₃And their mixture.Other are described among the EP-A-549272.Other ligands that are fit to comprise 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 fit to is referring to US 4,246, and 612 and 5,227,084.Also referring to US 5,194,416, it has lectured for example Mn (1,4,7-trimethylammonium-1,4,7-7-triazacyclononane)-(OCH of monokaryon manganese (IV) title complex ₃) ₃(PF ₆).As the another kind of bleaching catalyst that is disclosed among the US5114606 is the water-soluble complexes of the polyol ligand of manganese (III) and/or the non-carboxylate salt that (IV) and at least has three continuous C-OH groups.Other examples comprise the double-core Mn title complex that cooperates with four-N-dentate and two-N-dentate ligand, comprise N ₄Mn ^III(u-O) ₂Mn ^IVN ₄ ⁺[Bipy ₂Mn ^III(u-O) ₂Mn ^IVBipy ₂]-(ClO ₄) ₃

Other bleaching catalysts that are fit to are disclosed in the following document, EP408 for example, 131 (cobalt complex catalyzer), EP384,503 and 306,089 (metal-porphyrin catalysts), US4,728,455 (manganese/polygamy position polymerization of olefin using catalyst body catalyst), US 4,711, and 748 and EP224,952 (being adsorbed in the Mn catalyst on the silico-aluminate), US 4,601,845 (being carried on manganese and zinc or magnesium salts on the silico-aluminate), US 4,626,373 (manganese/ligand catalyzer), US 4,119,557 (iron complex catalyzer), DE 2,054,019 (cobalt chelates catalyzer), CA 866,191 (salt that contain transition metal), US 4,430,243 (sequestrant with manganese positively charged ion and on-catalytic metallic cation) and US 4,728,455 (gluconic acid Mn catalysts).

Preferred washing composition active particle comprises spices, optical white and/or catalyzer.Spices and/or optical white are particularly preferred.The present invention particularly preferred aspect, the washing composition active particle comprises the spices of sealing.The present invention other particularly preferred aspect, the washing composition active particle comprises optical white.

The washing composition active particle will change according to the relative granularity of these two kinds of components with the preferred proportion of washing composition original washing powder.Preferably, in final detergent composition, the weight percentage of any washing composition active particle is not more than 10% weight of washing composition basal granule, preferably is lower than 5% weight, or even is lower than 2% or 1% weight.Especially, the ratio of washing composition active particle can be low to moderate 5% or 2% or 1% weight of washing composition original washing powder, the geometric mean particle size of preferred washing composition active particle is not more than 20% of washing composition basal granule geometric mean particle size, preferably is not more than 10% or even be lower than 5% or even 2% or 1%.

Detergent particles itself can contain all components in the complete formula washing composition, or can mix with each detergent component of other detergent components such as the particle form that constitutes a washing composition basal granule part or as above-mentioned ready-formed detergent particles.Each detergent component of particle form can be any detergent component of following particle form.Preferably, detergent composition of the present invention comprises greater than 30% weight, more preferably greater than 50% weight, or even high to 80-90% weight, or even 95% weight according to detergent particles of the present invention.The content of detergent particles of the present invention is high more, just promotes washing composition from evenly metering or in the preparation unit dosage in blocks evenly with regard to the metering, effect of the present invention is big more the granulated detergent packing.

Method of the present invention can comprise the step that adds tackiness agent in mixing tank, to promote the preparation of required detergent particles.Generally, this tackiness agent is the liquid of solution or melt form, can be sprayed on the grain fraction by spraying in the direct adding mixing tank or along with they enter mixing tank.Preferably, tackiness agent adds in the mixing tank by for example spraying directly.Add the tackiness agent purpose and be by provide bonding to detergent component or tackiness agent to strengthen nodulizing.Tackiness agent can be any conventional washing composition tackiness agent, be preferably selected from water, anion surfactant, nonionogenic tenside, polyoxyethylene glycol, polyvinylpyrrolidone, polyacrylate, organic acid or its salt such as citric acid or Citrate trianion, and composition thereof.The adhesive material that other are suitable comprises those that list herein, is described in people's such as Beerse United States Patent (USP) 5,108,646 (Procter ﹠amp; Gamble company) in, its disclosure is hereby incorporated by.Tackiness agent must be compatible with the washing composition active particle, and this is that those skilled in the art recognize.Therefore, when water had otherwise impact to the stability of washing composition active particle, tackiness agent should be substantially free of water.

Therefore, an aspect of of the present present invention adds first kind of charging of washing composition original washing powder in the mixing tank, and second kind of charging that will comprise the washing composition active particle in addition adds in the mixing tank and tackiness agent also is present in the mixing tank.Tackiness agent can directly add in the mixing tank or before one or both these chargings enter mixing tank by the third charging; contact with washing composition basal granule or washing composition active particle, for example washing composition active particle (or a certain proportion of basal granule) can be entrained in the tackiness agent.Be divided at mixing tank under the situation of same district not, these three kinds of components can add in the same district or randomly can add not in the same district.In the preferred embodiment of the invention, before adding tackiness agent, washing composition basal granule and washing composition active particle are by pre-mixing.

The present invention in addition preferred aspect, after washing composition basal granule and washing composition active particle mixed, it is bonding that two kinds of components take place, and other liquid ingredient is applied to prepared particle outside.This further coating can have coating material or the detergent component described below that the chemical constitution identical with tackiness agent maybe can be any other.

The middling speed of Shi Yonging to low velocity shear mixing tank can be LodigeKM (trade mark) (plough formula) moderate-speed mixers or by the mixing tank of Fukae, Draes, Schugi preparation or only at the mixing tank of middling speed blended resembling trade mark to the low velocity shear for example in the present invention.Lodige KM (plough formula) moderate-speed mixers, it is to be used for the preferred mixing tank of the present invention, comprises the resting barrel that level is hollow, centre of the drum is equipped with turning axle, connects several plow-shape blades around axle.Preferred blade is with about 15rpm-140rpm, and more preferably from about 80rpm-120rpm speed is rotated.Grinding or pulverizing is to be finished by cutting knife, and generally its size is less than the size of rotation axis, and preferably it is operated with about 3600rpm.Kin other mixing tanks that are applicable to this method comprise LodigePloughshare ^TMMixing tank and Drais  K-T 160 mixing tanks.Generally, in the methods of the invention, shear and not to be greater than the shearing that is produced by Lodige KM mixing tank, the plough sheet end speed of this mixing tank is lower than 10m/s or even is lower than 8m/s or even lower.

Preferably, the mean residence time of various detergent raw material components in low or moderate-speed mixers is preferably at about 0.1 minute-30 minutes, and most preferably the residence time is about 5 minutes of about 0.5-.The density of the detergent agglomerate that in this way, makes is desirable level.

Be used for other mixing tanks that are fit to of the present invention and be low or very low velocity shear mixing tank such as rotating cylinder cyclone agglomerator, cylinder (rotary drum) cyclone agglomerator, disc type cyclone agglomerator and fluidized bed agglomeration device.

The fluidized bed agglomeration device is particularly preferred.Typical fluidized bed agglomeration device is to depress at plus or minus, operates under surperficial air velocity 0.1-4m/s.The intake air temperature is generally from-10 or 5 ℃ high to 250 ℃.Yet the intake air temperature generally is lower than 200 ℃, or even is lower than 150 ℃.Preferred fluidized bed pelletizer is such operation, and the flux numerical value FN of fluidized-bed is at least about 2.5-about 4.5.Flux numerical value (FN _m) be the tripping speed (U of fluidizing agent _e) and pellet density (p _p) with respect to gauged distance (D at spraying plant _o) under be sprayed onto liquid mass flux (q in the fluidized-bed _Liquid) the ratio.This flux numerical value provides the estimation to the fluidized bed process parameter of granulation in the control fluidized-bed.This flux numerical value can be expressed as the mass flux of determining by following formula:

FN _m=log ₁₀[{ P _pU _e}/q _Liquid]

Or press the volume flux that following formula is determined:

FN _v=log ₁₀[{ U _e}/q _{V liquid}]

Q wherein _{V liquid}It is the volume that is sprayed onto in the fluidized-bed.The calculating of this flux numerical value and the description detailed of its purposes are in WO98/58046, and its disclosure is quoted for referencial use at this paper.

In addition, fluidized-bed generally be lower than at stokes (Stokes) numerical value about 1, more preferably from about 0.1-0.5 operation down.Stokes numerical value is that a kind of of particles coalesce measures, and it has been described in equipment particle generation blended degree in the fluidized-bed for example.Stokes numerical value is determined by following formula:

Stokes numerical value=4pvd/9u

Wherein p is an apparent particle density, and v is a tripping speed, and d is that median size and u are the viscosity of tackiness agent.The description detailed of stokes numerical value and its purposes is in WO99/03964, and its disclosure is quoted for referencial use at this paper.

Therefore, be under the fluidized bed for solid mixing situation at mixing tank, washing composition basal granule of the present invention is admitted in the fluidized-bed that randomly has a plurality of interior " sections " or " district ".Section or district are any discontinuous zones in the fluidized-bed, and these terms can be used alternatingly at this paper.Processing condition in the section can be different or be similar to the processing condition of other sections in fluidized-bed/moisture eliminator.The fluidized-bed that should be understood that two vicinities is equal to and has the single fluidised bed of multistage.Each charging of washing composition basal granule and washing composition active particle can be in different section or same section adding, and this depends on for example water content of granularity and charging.Carry different material to reduce to different sections the heat of fluidized-bed is carried, and optimized the granularity and the homogeneity that has increased its shape of prepared detergent particles.

This bed generally is to use the warm air fluidisation, so that the dry moisture content of drying or part is such as the binder liq from the component in the fluidized-bed.Under tackiness agent is sprayed to situation in the fluidized-bed, sprays generally and realize that by nozzle this nozzle can provide the thin spraying or the atomisation of tackiness agent, reaches with particle and closely mixes.Generally, the drop size that is obtained by atomizer is lower than about 2 times of particle size.This atomize effect can be finished by making air-atomized conventional two-fluid spray nozzle, or finishes by conventional pressure nozzle in addition.In order to realize such atomizing, solution or slip rheological charactristics are when atomizing, have viscosity and are lower than about 500 centipoises, preferably are lower than about 200 centipoises.Although the position of nozzle in fluidized-bed can be almost any position, preferred positions is to make any liquid ingredient such as tackiness agent become vertically downward spraying.This structure that can for example use the top to spray realizes.In order to obtain best result, the position of nozzle be placed in the fluidized-bed particulate fluid height place or on.Fluid height generally is to be determined by the height of overflow or spillway.Can follow optionally coating area of conduct after the agglomeration/granulation zone of fluidized-bed, then be drying zone and cooling zone.Certainly, one skilled in the art will realize that it also is possible that another kind is arranged, to obtain particle of the present invention.

General condition in the fluidized bed plant of the present invention comprises about 20 minutes mean residence times of (i) about 1-, (ii) about 100-600mm un-fluidized-bed degree of depth, (iii) The droplet sizes is lower than 2 times of mean particle size in this, preferably be not more than about 100 microns, more preferably no more than 50 microns, (iv) jetting height is generally apart from fluidized-bed column plate 150-1600nm or preferably apart from fluidized-bed top 0-600mm, (the about 4.0m/s of v) about 0.1-, preferred 1.0-3.0m/s fluidizing velocity, (iv) Chuan temperature is about 200 ℃ of about 12-, preferred 15-100 ℃.Moreover, one skilled in the art will realize that the condition in the fluidized-bed can be according to many factors vary.

The detergent particles for preparing in this mixing tank also can be further processed by adding the coating agent; to improve the particulate color; increase the particulate whiteness or improve the particulate flowability; this detergent particles is discharged mixing tank or moisture eliminator afterwards; if then optional drying step is added in the back segment of mixing tank or mixing tank, can obtain high-density granulated detergent composition by the inventive method preparation.Those skilled in the art will recognize that do not breaking away under the scope of the invention, can make in all sorts of ways washing composition dry and that cooling is discharged.Because mixing tank is relatively to operate under the low temperature, the requirement of apparatus cools is not generally needed in the methods of the invention, further reduced the preparation cost of finished product thus.

Another kind of optional procedure of processing comprises that apply agent such as zeolite and/or pyrolytic silicon-dioxide continuous the adding in mixing tank, to impel the detergent particles that makes easily to flow and to suppress undue agglomeration.This coating agent generally has mean particle size and is lower than 100 microns, preferably is lower than 60 microns, even more preferably less than 50 microns.

After forming detergent particles of the present invention, before or after drying step and randomly, after detergent particles and other detergent components are mixed and made into the detergent composition of complete formula, can carry out any coating processing immediately.Preferably, some such coating agent also have the active character of washing composition.Particularly preferred coating agent is the aqueous solution of tensio-active agent or tensio-active agent.

Be suitable as the original washing powder component and/or describe hereinafter as washing composition active particle component and/or as the detergent component that adds in the detergent particles of the present invention with some other components of making complete formula detergent composition of the present invention.

Detergent component

Tensio-active agent

Being used for the tensio-active agent that the present invention is fit to is to be issued to negatively charged ion, nonionic, both sexes and the zwitterionic classes tensio-active agent that provides among the US 3,929,678 of Laughlin and Heuring on December 30th, 1975.Other example provides in following document: " tensio-active agent and washing composition " (Surface Active Agents) (I volume and II volume, Schwartz, Perry and Berch).The catalogue of suitable cats product is issued on March 31st, 1981 among the US 4,259,217 of Murphy and provides.

Preferably, comprise this particulate detergent particles of the present invention and composition and comprise additional anion surfactant.Any basically anion surfactant that is used for the decontamination purpose all can be included in this detergent composition.These can comprise anion sulfate, sulfonate, carboxylate salt and sarcosinate surfactant (for example, comprise sodium, potassium, ammonium and substituted ammonium salt, as one, two and triethanolamine salt).Preferred anionic vitriol and sulfosalt surfactant.

The content of anion surfactant in this detergent particles is lower than 25% weight, or even be lower than 20% weight, but in comprising described particulate finished product detergent composition, preferably its content is 0.1%-60%, more preferably 1%-40%, most preferably 5%-30% weight.

Other anion surfactants comprise that the anionic carboxylic acid salt surfactant is such as alkyl ethoxy carboxylate, alkyl polyethoxye multi-carboxylate and soap (" alkyl carboxylate ") are such as being selected from following water-soluble substances: the water-soluble salt that the water-soluble salt of the water-soluble salt of 2-methyl isophthalic acid-undecanoic acid, 2-ethyl-1-capric acid, the water-soluble salt of 2-propyl group-1-n-nonanoic acid, 2-butyl-1-are sad and the water-soluble salt of 2-amyl group-1-enanthic acid.Some soap class also can be used as suds suppressor and adds.Other suitable anion surfactants are formula R-CON (R ¹) CH ₂The basic metal sarcosinate of COOM, wherein R is C ₅-C ₁₇-straight or branched alkyl or alkenyl, R ¹Be C ₁-C ₄Alkyl, M are alkalimetal ion.Other anion surfactants comprise isethionate, as fatty acid amide, alkyl succinate and the alkyl sulfo succinate of acyl isethinate, N-ethanoyl taurate, methylamino esilate, monoesters (the particularly saturated and unsaturated C of sulfosuccinate ₁₂-C ₁₈Monoesters), the diester of sulfosuccinate (particularly saturated and unsaturated C ₆-C ₁₄Diester), N-acyl sarcosinate.Resinous acid and hydrogenated resin acid also suit, as rosin, staybelite, and the resinous acid and the hydrogenated resin acid that are present in butter or obtain by butter.

Be applicable to that anion sulfate tensio-active agent of the present invention comprises straight chain and side chain primary and secondary alkyl-sulphate, alkyl ethoxy sulfate, fatty oil acylglycerol vitriol, alkylphenol oxygen Vinyl Ether vitriol, C ₅-C ₁₇Acyl group-N-(C ₁-C ₄Alkyl) and-N-(C ₁-C ₂Hydroxyalkyl) vitriol of glucosamine sulfate and alkyl polysaccharide is as the vitriol (compound of nonionic non-sulfuric acid salinization is described hereinafter) of alkyl polyglucoside.Alkyl sulfate surfactant is preferably selected from straight chain and side chain uncle C ₁₀-C ₁₈Alkyl-sulphate, more preferably C ₁₁-C ₁₅Branched-chain alkyl vitriol and C ₁₂-C ₁₄Straight-chain alkyl sulfate.Alkyl ethoxy sulfate surfactant is preferably selected from every mole by the C of 0.5-20 moles of ethylene oxide ethoxylation ₁₀-C ₁₈Alkyl-sulphate.More preferably, alkyl ethoxy sulfate surfactant be every mole by 0.5-7, the C of the oxyethane ethoxylation of preferred 1-5 mole ₁₁-C ₁₈, C most preferably ₁₁-C ₁₅Alkyl-sulphate.

Preferred surfactants combination is preferred alkyl-sulphate and/or sulfonate and alkyl ethoxy sulfate surfactant, randomly with the mixture of cats product.This mixture is disclosed among the PCT number of patent application WO93/18124.

Be applicable to that anionic sulphonate tensio-active agent of the present invention comprises C ₅-C ₂₀Linear alkylbenzene sulfonate, alkyl ester sulfonate, C ₆-C ₂₂Uncle or secondary paraffin sulfonate, C ₆-C ₂₄Alkene sulfonate, sulfonation poly carboxylic acid, alkyl glycerol sulfonate, fatty acyl group glycerol sulfonate, fatty oil base glycerol sulfonate and its any mixture.

Basically any alkoxy-based non-ionic surface active agent or mixture all are applicable to the present invention.Preferred ethoxylation and propoxylation nonionogenic tenside.

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

The condensation product of Fatty Alcohol(C12-C14 and C12-C18) and 1-25 mole alkylene oxide, particularly oxyethane and/or propylene oxide is specially adapted to the present invention.Particularly preferably be every mole of straight or branched, uncle or the secondary alcohol of alkyl and the condensation product of 2-10 moles of ethylene oxide with 6-22 carbon atom.

Be applicable to that polyhydroxy fatty acid amide of the present invention is to have those of following structural formula: R ²CONR ¹Z, wherein R ¹Be H, C ₁-C ₄Alkyl, 2-hydroxyethyl, 2-hydroxypropyl, oxyethyl group, propoxy-or its mixture, preferred C ₁-C ₄Alkyl; R ²Be C ₅-C ₃₁Alkyl; Z is the polyhydroxy alkyl with the straight-chain alkyl that is connected directly to few 3 hydroxyls, or its alkoxy derivative (preferred ethoxylation or propoxylation).Z is preferably obtained in reductive amination process by reducing sugar.More preferably Z is a glycosyl.

Be applicable to that alkyl polysaccharide of the present invention is described among the US4565647 of the Llenado that authorized on January 21st, 1986, they have the hydrophobic grouping that contains 6-30 carbon atom, and the hydrophilic polysaccharide group that comprises 1.3-10 sugar unit, for example many glycosides.Preferred alkyl polyglycoside has following formula:

R ²O (C _nH _2nO) _t(glycosyl) _X

R wherein ²Be selected from alkyl, alkyl phenyl, hydroxyalkyl, hydroxyalkyl phenyl and its mixture, wherein alkyl contains 10-18 carbon atom; N is 2 or 3; T is 0-10; X is 1.3-8.This glycosyl is preferably obtained by glucose.

Be used for the amphoterics that the present invention is fit to and comprise amine oxide surfactant and alkyl both sexes carboxylic acid.Suitable amine oxide comprises formula R ³(OR ⁴) _xN ⁰(R ⁵) ₂Those compounds, R wherein ³Be selected from the alkyl, hydroxyalkyl, acyl group amido propyl group and the alkyl phenyl that contain 8-26 carbon atom, or its mixture; R ⁴Be alkylidene group or the hydroxy alkylidene that contains 2-3 carbon atom, or its mixture; X is 0-5, preferred 0-3; Each R ⁵Be alkyl or the hydroxyalkyl that contains 1-3 carbon atom, perhaps contain the polyoxyethylene group of 1-3 oxyethylene group group.Preferred C ₁₀-C ₁₈Alkyl dimethyl amine oxide and C ₁₀-C ₁₈Acyl group amidoalkyl dimethyl oxidation amine.

Zwitterionics also can add in the detergent composition of the present invention.These tensio-active agents can be described as the derivative of derivative, heterocyclic secondary and the tertiary amine of secondary amine and tertiary amine widely, or the derivative of quaternary ammonium, quaternary phosphine or uncle's sulfonium compound.Trimethyl-glycine is such as C ₁₂-C ₁₈Dimethyl Ammonium hexanoate and C ₁₀-C ₁₈Acyl group amido propane (or ethane) dimethyl (or diethyl) trimethyl-glycine and sultaine tensio-active agent are the examples that is used for zwitterionics of the present invention.

Be used for the cats product that the present invention is fit to and comprise quaternary ammonium surfactant.The preferably single C of quaternary ammonium surfactant ₆-C ₁₆, preferred C ₆-C ₁₀N-alkyl or alkenyl ammonium surfactant, wherein all the other positions of N are replaced by methyl, hydroxyethyl or hydroxypropyl.Preferred monoalkoxyization and bis-alkoxy amine tensio-active agent in addition.

The cationic ester tensio-active agent for example is disclosed among the US4228042,4239660 and 4260529 such as the cholinesterase tensio-active agent, and they also are fit to, and it preferably has the cation mono alkoxylated amines tensio-active agent of following general formula I:

R wherein ¹Be C ₁₀-C ₁₈Alkyl and their mixture, particularly C ₁₀-C ₁₄Alkyl, preferred C ₁₀And C ₁₂Alkyl, X provide any suitable negatively charged ion of charge balance, preferred chlorine or bromine.The content of the cation mono alkoxylated amines tensio-active agent in the detergent composition of the present invention is generally 0.1%-20%, preferred 0.2%-7%, most preferably 0.3%-3.0% weight.

Positively charged ion bis-alkoxy amine tensio-active agent such as:

Also be fit to, wherein R ¹Be C ₁₀-C ₁₈Alkyl and its mixture, preferred C ₁₀, C ₁₂, C ₁₄Alkyl and its mixture, X provides any suitable negatively charged ion of charge balance, preferred chlorine.

Bleach-activating agent

Detergent particles preferably comprises bleach-activating agent with the detergent composition that contains them, and preferred package contains organic peroxyacid bleach precursor.Preferred said composition comprises at least two kinds of peroxyacid bleach precursors as defined herein, preferred at least a hydrophobic peroxyacid bleach precursor and at least a hydrophilic peroxyacid bleach precursor.This precursor and hydrogen peroxide cource situ reaction produce organic peroxide acid then.Bleach-activating agent can be in addition, or comprise the ready-formed peroxyacid bleach in addition.

Preferred bleach-activating agent is present in this detergent particles.Preferred bleach-activating agent exists as independent, composite grain.Hydrophobic peroxyacid bleach precursor preferably includes has oxygen-compound of Phenylsulfonic acid base, preferred NOBS, DOBS, LOBS and/or NACA-OBS.Hydrophilic peroxyacid bleach precursor preferably includes TAED.

Peroxyacid bleach precursor

Peroxyacid bleach precursor is the compound that produces peroxy acid in crossing hydrolysis reaction with hydroperoxidation.Usually, peroxyacid bleach precursor is expressed from the next:

Wherein, L is a leavings group, and X is any functional group substantially, makes the peroxy acid structure that produces when crossing hydrolysis be:

For the object of the invention, hydrophobic peroxyacid bleach precursor produces the following formula peroxy acid, and wherein X comprises the group of at least 6 carbon atoms and the peroxyacid bleach that hydrophilic peroxyacid bleach precursor produces following formula, and wherein X is the group that comprises 1-5 carbon atom.

Leavings group hereinafter referred to as the L group must have enough reactivities to hydrolysis (perhydrolysis) reaction of crossing that occurs in the Best Times section (for example cycles of washing).But if L is too active, this activator will be difficult to stably be used for bleaching composition.Preferred L group is selected from following radicals or its mixture:

With

With

Wherein, R ¹Be alkyl, aryl or the alkaryl that comprises 1-14 carbon atom, R ³For comprising the alkyl chain of 1-8 carbon atom, R ⁴Be H or R ³, Y is H or solubilization radical.R ¹, R ³And R ⁴In any can be replaced by any functional group basically, comprise for example alkyl, hydroxyl, alkoxyl group, halogen, amino, nitrosyl radical, amido and ammonium or alkyl ammonium group.

Preferred solubilization radical is-SO ₃ ^-M ⁺,-CO ₂ ^-M ⁺,-SO ₄ ^-M ⁺,-N ⁺(R ³) ₄X ^-And O＜--N (R ³) ₃, most preferably-SO ₃ ^-M ⁺With-CO ₂ ^-M ⁺, wherein, R ³For comprising the alkyl of 1-4 carbon atom, M is for providing deliquescent positively charged ion to bleach-activating agent, and X is for providing deliquescent negatively charged ion to bleach-activating agent.Preferred M is the ammonium cation of basic metal, ammonium or replacement, most preferably sodium and potassium, and X is halogen, hydroxide radical, methylsulfate or acetic acid anion.

The content of peroxyacid bleach precursor compound in the finished product detergent composition is preferably 0.5%-30%, more preferably 1%-15%, most preferably 1.5%-10% weight.Hydrophilic and hydrophobic bleach agent precursor are when existing, and its ratio is preferably 10: 1-1: 10, more preferably 5: 1-1: 5, or even 3: 1-1: 3.Suitable peroxyacid bleach precursor compound comprises one or more N-or O-carboxyl groups usually, and this precursor can be selected from type widely.Suitable type comprises the acylated derivatives of acid anhydrides, ester, imide, lactan and imidazoles and oxime.The example of the useful matter in these classes is disclosed in GB-A-1586789.Suitable ester is disclosed in GB-A-836988,864798,1147871,2143231 and EP-A-0170386.

Alkyl percarboxylic acids bleach precursor forms percarboxylic acids when crossing hydrolysis.Preferred such precursor provides peracetic acid when crossing hydrolysis.Preferred imide-type alkyl peroxycarboxylic acid precursors compound comprises N, N, N ¹, N ¹-tetra-acetylatedization Alkylenediamine, wherein, alkylidene group comprises 1-6 carbon atom, and particularly wherein alkylidene group comprises those compounds of 1,2 and 6 carbon atom.Preferred especially tetraacetyl ethylene diamine (TAED) is as hydrophilic peroxyacid bleach precursor.Other preferred alkyl peroxycarboxylic acid precursors comprise 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 peroxy acids precursor compound that acid amides replaces is applicable to the present invention, comprises those of following general formula:

Or

R wherein ¹Be aryl or alkaryl with about 1-14 carbon atom, R ²Be alkylidene group, arylidene and the alkyl arylene that contains 1-14 the carbon atom of having an appointment, R ⁵Be H or alkyl, aryl or the alkaryl that contains 1-10 carbon atom, L can be any leavings group basically.R ¹Preferably contain 6-12 the carbon atom of having an appointment, R ²Preferably contain 4-8 the carbon atom of having an appointment.R ¹Can be the straight or branched alkyl, contain the aryl of side chain, substituting group or the two replacement or alkaryl and can obtain that described natural source comprises for example butter fat by synthetic source or natural source.R ²The similar structures variant also allow.R ²Can comprise alkyl, aryl, wherein said R ²Also can contain halogen, nitrogen, sulphur and other typical substituting group or organic compound.R ⁵Preferably H or methyl.R ¹And R ⁵Should not contain altogether and surpass 18 carbon atoms.The bleach activating immunomodulator compounds that such acid amides replaces is described among the EP-A-0170386.Preferred R ¹And R ⁵Form ring structure with nitrogen and carbon atom.

The preferred embodiment of this class bleach precursor comprises the peroxyacid precursor compound that acid amides replaces; be selected from (6-decoyl amino-caproyl) the oxygen base benzene sulfonate that is described among the EP-A-0170386; (6-caprinoyl amino-caproyl) oxygen base benzene sulfonate; with highly preferred (the amino caproyl of 6-nonanoyl) oxygen base benzene sulfonate and their mixture.

What also be fit to is the peroxybenzoic acid precursors compound, and it provides peroxybenzoic acid when crossing hydrolysis; The benzoxazine organic peroxy acid precursor described in EP-A-332294 and the EP-A-482807 and when crossing hydrolysis, produce the positively charged ion peroxyacid precursor compound of positively charged ion peroxy acid for example.The positively charged ion peroxyacid precursor is stated in following document: US 4,904, and 406; 4,751,015; 4,988,451; 4,397,757; 5,269,962; 5,127,852; 5,093,022; 5,106,528; U.K.1,382,594; EP 475,512; 458,396 and 284,292; JP87-318,332.

The example of preferred cation peroxyacid precursor is stated in UK number of patent application 9407944.9 and Application No. 08/298903,08/298650,08/298904 and 08/298906.

Suitable positively charged ion peroxyacid precursor comprises alkyl that ammonium or alkylammonium replace or in the tetra-acetylated glucose benzoyl peroxide of benzoyloxy benzene sulfonate, N-acidylate hexanolactam and single benzoyl any.Preferred N-acylations hexanolactam cationoid peroxyacid precursor comprises trialkyl ammonium methylene radical benzoyl caprolactam and trialkyl ammonium methylene radical alkyl hexanolactam.

Particle of the present invention or composition except that comprising organic peroxyacid bleach precursor compound or as an alternative also can comprise the ready-formed organic peroxide acid, and its content is 0.1-15% usually, more preferably 1-10% weight.The compound that a preferred class organic peroxy acid compound replaces for the acid amides of describing in EP-A-0170386.Other organic peroxide acids comprise diacyl and four acyl peroxides, particularly diperoxy dodecanedioic acid, diperoxy tetradecane diacid and diperoxy Thapsic acid.Single-as and two to cross nonane diacid, single-or two cross undecane dicarboxylic acid and the amino oxy hexanoic acid of crossing of N-naphthoyl also is suitable for the present invention.

Peroxide source

Inorganic perhydrate salt is the preferred source of superoxide.By the weight of particle of the present invention or composition, preferably the content of these salt is 0.01%-50% weight, more preferably 0.5%-30% weight.The example of inorganic perhydrate salt comprises: perborate, percarbonate, superphosphate, persulphate and persilicate.Inorganic perhydrate salt is an alkali metal salt normally.Inorganic perhydrate salt is not mixed by the crystalline solid forms of supplementary protection can.But for some perhydrate salt, the preferred version of this particulate composition is the coated form that adopts this material, thereby good storage stability is provided for perhydrate salt in particulate product.The suitable coating material comprises inorganic salt such as alkalimetal silicate, carbonate or borate, or its mixture, perhaps organic substance such as wax, oil or fatty soap.

Sodium peroxoborate is preferred perhydrate salt, and it can be standard type NaBO ₂H ₂O ₂Monohydrate or tetrahydrate NaBO ₂H ₂O ₂-3H ₂The O form.

Alkali metal percarbonate, particularly SPC-D are the preferred perhydrate of the present invention.SPC-D is to have corresponding to 2Na ₂CO ₃-3H ₂O ₂The addition compound of formula, it can crystalline solid be purchased.The peroxide Potassium peroxysulfate is that another kind is applicable to inorganic perhydrate salt of the present invention.

Sequestrant

As described herein, sequestrant has been meant the detergent component of chelating heavy metal ion effect.These components also can have calcium and magnesium sequestering power, but preferably their selective binding heavy metal ion such as iron, manganese and copper.

In detergent particles or finished product detergent composition, the content of sequestrant is generally the 0.005%-10% of said composition or composition weight, preferred 0.1%-5%, more preferably 0.25%-7.5%, most preferably 0.3%-2%.

The sequestrant that is fit to includes organic phosphonates, as amino alkylidenyl many (alkylene phosphonic acids salt), basic metal ethane 1-hydroxyl diphosphonate and nitrilo trimethylene phosphonic salt, preferred diethylenetriamine five (methylene phosphonic acid salt), quadrol three (methylene phosphonic acid salt), hexamethylene-diamine four (methylene phosphonic acid salt) and hydroxyl-ethylidene 1,1-diphosphonate, 1,1-hydroxyl ethane di 2 ethylhexyl phosphonic acid and 1,1-hydroxyl ethane dimethylene phosphonic acids.

Other are applicable to that sequestrant of the present invention comprises nitrilotriacetic acid(NTA) and polyamino carboxylic acid, as ethylenediamine tetraacetic acid (EDTA), ethylenediamine disuccinic acid, quadrol two pentanedioic acids, 2-hydroxyl propylene diamine disuccinic acid or its any salt, and iminodiacetic acid derivatives, as 2-hydroxyethyl oxalic acid or glyceryl iminodiethanoic acid, as EP-A-317,542 and EP-A-399, described in 133.The present invention also can adopt as EP-A-5126,102 described iminodiethanoic acid-N-2-hydroxypropyl sulfonic acid and aspartic acid N-carboxymethyl N-2-hydroxypropyl-3-sulfonic acid sequestrant.The present invention also can adopt EP-A-509,382 described Beta-alanine-N, N '-oxalic acid, aspartic acid-N, single acetate of N '-oxalic acid, aspartic acid-N-and imino-diacetic succsinic acid sequestrant.EP-A-476,257 have described the suitable sequestrant based on amino.EP-A-510,311 have described the suitable sequestrant that is obtained by collagen, Keratin sulfate or casein.EP-A-528,859 have described a kind of suitable alkyl imino oxalic acid sequestrant.Pyridine dicarboxylic acid and 2-phosphinylidyne butane-1,2, the 4-tricarboxylic acid also is fit to.Glycine acid amides-N, N '-disuccinic acid (GADS), quadrol-N, N '-two pentanedioic acid (EDDG) and 2-hydroxyl propylene diamine-N, N '-disuccinic acid (HPDDS) also is fit to.Particularly preferably be diethylene triaminepentaacetic acid(DTPA), quadrol-N, N '-disuccinic acid (EDDS) and 1, the ammonium salt of 1-hydroxyl ethane di 2 ethylhexyl phosphonic acid or its basic metal, alkaline-earth metal, ammonium or replacement, or its mixture.The sequestrant that particularly comprises amino or amido may be the SYNTHETIC OPTICAL WHITNER sensitivity and be suitable in the present composition.

The water soluble detergency promoter compound

Component of the present invention or composition preferred package contain water-soluble washing-aid compound, and general content in detergent composition is 1%-80% weight, preferred 10%-60% weight, more preferably 15%-40% weight.

Detergent composition of the present invention can comprise phosphatic washing assistant material.Preferred its content is 0.5%-60%, more preferably 5%-50%, more preferably 8%-40%.Phosphatic washing assistant material preferably includes tetrasodium pyrophosphate or even more preferably anhydrous sodium tripolyphosphate.

Suitable water soluble detergency promoter compound comprises water-soluble monomer multi-carboxylate or its sour form, homopolymerization or copolymerization poly carboxylic acid or its salt, wherein poly carboxylic acid comprises each other the mixture that is no more than at least two carboxyls, borate and aforementioned any compound that two carbon atoms separate open.

Carboxylate salt or multi-carboxy acid salt washing agent can be monomer type or oligomer types, but because Cost And Performance, the multi-carboxylate of preferred monomers type usually.The suitable carboxylate salt that contains a carboxyl comprises the water-soluble salt and the ether derivant thereof of lactic acid, oxyacetic acid.The multi-carboxylate of containing two carboxyls comprises the water-soluble salt of succsinic acid, propanedioic acid, (ethylidene dioxy base) oxalic acid, toxilic acid, Glyoxylic acid hydrate, tartrate, tartronic acid and fumaric acid and ether carboxylate and sulfinyl carboxylate salt.The multi-carboxylate or its acid that contain three carboxyls comprise particularly water-soluble citrate, aconitate and citraconate, and the succinate derivative, as English Patent 1,379,241 described carboxy methoxy-succinic acid salt, the newborn acyloxy succinate described in the English Patent 1389732, HOII P 7205873 described aminosuccinic acid salt, and English Patent 1,387,447 described oxygen multi-carboxylate material, for example 2-oxa-s-1,1,3-tricarballylic acid salt.The most preferred poly carboxylic acid that contains three carboxyls is a citric acid, and preferably its content is 0.1%-15%, more preferably 0.5%-8% weight.

The multi-carboxylate of containing four carboxyls comprises English Patent 1,261,829 described oxygen disuccinate, 1,1,2,2-ethane tetracarboxylic acid hydrochlorate, 1,1,3,3-propane tetracarboxylic acid salt and 1,1,2,3-propane tetracarboxylic acid salt.Comprise the substituent multi-carboxylate of sulfo group and comprise English Patent 1,398,421 and 1,398,422 and U.S. Pat 3,936,448 described sulfo-succinic acid salt derivatives, and English Patent 1,439,000 described sulfonation pyrolytic Citrate trianion.Preferred multi-carboxylate is contained the hydroxycarboxylate of 3 carboxyls of as many as, Citrate trianion more specifically for per molecule.

The parent acid of monomer or oligomeric multi-carboxylate's sequestrant or can replenish as useful builder component with the mixture of its salt, for example, citric acid or Citrate trianion/citric acid mixture.

The borate washing assistant and can washing composition store or wash conditions under to produce the boratory washing assistant that forms borate substance that contains be the useful water soluble detergency promoter of the present invention.

The suitable example of water-soluble phosphate washing assistant is an alkali metal tripolyphosphates, trisodium phosphate, potassium and ammonium, and sodium orthophosphate and potassium, partially poly-/sodium phosphate, wherein the polymerization degree is about 6-21, and phytate.

The example of organic polyhydroxyl compound comprises water-soluble organic homopolymerization or copolymerization poly carboxylic acid or its salt, and wherein poly carboxylic acid comprises at least two and is no more than the carboxyl that two carbon atoms separate are opened each other.The polymkeric substance of latter's type is disclosed in GB-A-1, in 596,756.The example of this salt be molecular weight 1000-5000 polyacrylate and with the multipolymer of maleic anhydride, this multipolymer has molecular weight 2000-100,000, particularly 40,000-80,000.

Polyamino compound can be used for the present invention, comprises those materials that obtained by aspartate-derived, for example EP-A-305282, EP-A-305283 and EP-A-351629 described those.

Part solubility or insoluble washing-aid compound

Particle of the present invention or detergent composition can contain part solubility or insoluble washing-aid compound, and generally its content in detergent composition is 0.5-60% weight, preferred 5-50% weight, most preferably 8-40% weight.Basically the example of water-insoluble washing assistant comprises sodium silicoaluminate.As above-mentioned, in one embodiment of this invention, preferably only there is a spot of silico-aluminate washing assistant.

The aluminosilicate zeolite that is suitable for has unit structure cell formula Na _z[(AlO ₂) _z(SiO ₂) _y] .xH ₂O, wherein z and y are at least 6, and the mol ratio of z and y is 1.0-0.5, and x is at least 5, preferred 7.5-276, more preferably 10-264.Alumino-silicate materials can be hydrated form, and preferably xln contains 10-28%, preferred 18-22% combination water.Aluminosilicate zeolite can be natural product, but preferably synthetic obtaining.Synthetic crystallization type aluminosilicate ion exchange material can be by zeolite A, zeolite B, zeolite P, the X zeolite of registration, and zeolite HS and composition thereof buys.Zeolite A has following formula:

Na ₁₂[(AlO ₂) ₁₂(SiO ₂) ₁₂].xH ₂O

Wherein x is 20-30, particularly 27.X zeolite has formula:

Na ₈₆[(AlO ₂) ₈₆(SiO ₂) ₁₀₆].276H ₂O。

Zeolite MAP builder is another kind of preferred aluminosilicate zeolite.The content of zeolite MAP can be 1-80%, more preferably 15-40% weight.Zeolite MAP is stated in EP 384070A (Unilever).It is defined as the ratio with silicon and aluminium and is not more than 1.33, is preferably 0.9-1.33, more preferably the zeolite P type alkali metal aluminosilicate of 0.9-1.2.Making us interested especially is silicon and the ratio of aluminium is not more than 1.15, is not more than 1.07 zeolite MAP more specifically.

In preferred situation, the granularity of zeolite MAP detergent builders is represented as mean particle size d ₅₀, its value is 1.0-10.0 μ m, more preferably 2.0-7.0 μ m, most preferably 2.5-5.0 μ m.d ₅₀Value is that expression 50 weight % particulate diameters are worth less than this.This granularity specifically can be by the routine analysis technical measurement, and the microscope that employing scanning electron microscope as described herein is carried out is measured or measured with laser particle size analyzer.Other determine d ₅₀The method of value is stated in EP 384070A.

Other detergent components

The preferred component of the present composition is dyestuff and painted particle or spot decorations, and it may be the SYNTHETIC OPTICAL WHITNER sensitivity.Dyestuff used herein can be the aqueous solution or the non-aqueous solution of tinting material or tinting material.Preferred coloring agent is the aqueous solution that comprises tinting material, and it can be any amount to reach the suitably dyeing of detergent particles or spot decorations, as mentioned above, preferably makes the content of dye solution reach 2% weight of dyed particles, more preferably reaches 0.5% weight.Dyestuff also can with the nonaqueous carrier material mixing, for example comprise the on-aqueous liquid material of nonionogenic tenside.Randomly, dyestuff also comprises for example organic binder bond material of other components, and it can be non-water liquid.

Tinting material can be any suitable tinting material.The specific examples of the tinting material that is fit to comprises E104-food Huang 13 (quinoline yellow), E110-food Huang 3 (sunset yellow FCF), E131-food indigo plant 5 (patent blue V), ultramarine blue (trade(brand)name), E133-food indigo plant 2 (brilliant blue FCF), E140-natural green 3 (chlorophyll and CHLOROPHYLLINE), E141 and pigment Green 7 (chlorating CuPc).Preferred tinting material can be monastral blue BV lotion (trade(brand)name) and/or Pigmasol Green (trade(brand)name).

The another kind of preferred component of particle of the present invention or composition is spices or flavor compositions.The present invention can use any flavor compositions.Spices also can be encapsulated.Preferred spices contains at least a lower molecular weight volatile components, and for example molecular weight is 150-450, or preferred 350.Preferably, the spices component comprises oxygen containing functional group.Preferred functional group is aldehyde, ketone, alcohol or ether functional group or its mixture.

The another kind of highly preferred component that is used for particle of the present invention or composition is one or more additional enzymes.Preferred additional enzymes material comprises commercially available lipase, at, amylase, neutrality and Sumizyme MP, cellulase, restriction endonuclease (endolase), esterase, polygalacturonase, Sumylact L and the peroxidase that is routinely added in the detergent composition.Suitable enzyme is discussed in United States Patent (USP) 3519570 and 3533139 to some extent.

About the washing composition active particle, preferred enzyme has been discussed more than.This enzyme is also preferably as the component of washing composition original washing powder or as adding the additional detergent component that forms the washing composition of complete preparation in the detergent particles of the present invention.

Detergent particles of the present invention or composition also preferably contain the hydrophilic white dyes of some type of 0.005%-5% weight of having an appointment, preferably as above-mentioned washing composition active particle component.The Tinopal-UNPA-GA of example for selling by the Ciba Geigy merchant of company ^TMAnd Tinopal-CBS-X ^TMOther comprise the Tinopal 5BM-GX that is sold by the Ciba Geigy merchant of company ^TM, Tinopal-DMS-X ^TMWith Tinopal AMS-GX ^TM

Optical white

As above-mentioned, optical white is the preferred component of said composition, and as discussed above, and preferably it exists with washing composition active particle form.Yet they can randomly be present in the washing composition basal granule or conduct adds the additional detergent component that forms the detergent composition of the present invention of complete preparation in the detergent particles of the present invention.

Organic polyhydroxyl compound

Organic polyhydroxyl compound is that the present invention is preferred in addition, and preferably its composition as any grain fraction exists, and they play the effect that for example grain fraction is bonded together.So-called organic polyhydroxyl compound looks like here and is meant any basically organic polyhydroxyl compound that is used as dispersion agent, anti redeposition agent or soil-suspending agent in detergent composition usually, be included in any high molecular organic polyhydroxyl compound that is stated as the clay flocculating agent herein, comprise that ethoxylation (gathering) amine of quaternary saltization of the present invention removes great soil group dirt agent/anti redeposition agent.

By the weight of composition or component, the incorporation of organic polyhydroxyl compound in finished product detergent composition of the present invention is generally 0.01%-30%, preferred 0.1%-15%, more preferably 0.5%-10%.

Comprising the ter-polymers, particularly molecular-weight average that are selected from toxilic acid, vinylformic acid, poly aspartic acid and vinyl alcohol monomeric unit is 5, and 000-10, those of 000 also are applicable to the present invention.

Other organic polyhydroxyl compounds that are fit to add in the detergent composition of the present invention comprise derivatived cellulose, as methylcellulose gum, carboxymethyl cellulose, Vltra tears and Natvosol.Other useful organic polyhydroxyl compounds are that polyoxyethylene glycol, particularly molecular weight are 1000-10000, more preferably 2000-8000, most preferably from about those polyoxyethylene glycol of 4000.The highly preferred polymeric component of the present invention is the U.S. Pat 5415807 according to the U.S. Pat 4968451 of Scheibel etc. and Gosselink etc., particularly according to the cotton and the non-cotton dirt release agent polymkeric substance of U.S. Patent application 60/051517.

Be used for another kind of organic compound of the present invention, it is the dirty dispersion agent/anti redeposition agent of a kind of preferred soil, and it can be cationic ethoxy monoamine and the diamines with following formula:

Wherein X is a non-ionic group, is selected from H, C ₁-C ₄Alkyl or hydroxyalkyl acrylate or ether group and its mixture, a are 0-20, preferred 0-4 (as 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 20-35; For cationic diamine (b=1), n is at least about 12, and general range is about 12-about 42.

Be used for other dispersion agent/anti redeposition agents of the present invention and be described in EP-B-011965, US4659802 and US 4664848.

The suds suppressor system

The suds suppressor system preference also exists with washing composition active particle form as described herein.Yet this component can be present in the washing composition basal granule or conduct adds the additional detergent component that forms the detergent composition of complete preparation in the detergent particles of the present invention.

The polymeric dye transfer inhibitor also can be present in detergent particles of the present invention or the composition.When existing, by the finished product detergent composition, general its content is 0.01%-10%, preferred 0.05%-0.5%, and preferably it is selected from multipolymer, polyvinylpyrrolidonepolymers polymers or its mixture of polyamine N-oxide pllymers, N-vinyl pyrrolidone and N-vinyl imidazole, and wherein these polymkeric substance can be cross-linked polymers.

Above-mentioned polymerization dirt release agent also preferably exists as the washing composition active particle.Yet they can be in addition or in addition are present in the washing composition basal granule or as the additional detergent component that adds preparation finished product detergent composition in the detergent particles of the present invention.

Other optional ingredients that are fit to be included in the present composition comprise colorant and filling salt, and sodium sulfate is preferred filling salt.

Highly preferred composition contains the about 10% weight organic acid of the 2%-that has an appointment, optimization citric acid.Preferred combination carbonate also, can there be a small amount of (for example being lower than about 20% weight) neutralizing agent, buffer reagent, phase modifier, hydrotropic agent, enzyme stabilizers, polyacid, foaming regulator, opalizer, antioxidant, sterilant and dyestuff, for example those (they quote for referencial use at this paper) of describing in the U.S. Pat 4285841 of the Barrat that authorizes on August 25th, 1981 etc.

Detergent composition of the present invention can comprise the SYNTHETIC OPTICAL WHITNER based on chlorine as annexing ingredient.Yet because detergent composition of the present invention is a solid, great majority are not suitable in these detergent composition based on the liquid bleach of chlorine, have only particle or powdery to be fit to based on the SYNTHETIC OPTICAL WHITNER of chlorine.In addition, the user can add the SYNTHETIC OPTICAL WHITNER based on chlorine in the detergent composition in the beginning of washing stage or process.Should in the aqueous solution, can form hypochlorite based on the SYNTHETIC OPTICAL WHITNER of chlorine.Hypochlorite ion is chemically being represented by formula OCl.

Those SYNTHETIC OPTICAL WHITNER that produce hypochlorite in the aqueous solution comprise basic metal and alkaline-earth metal hypochlorite, hypochlorite affixture, chloramines, chlorimide, chloro-acid amide and chlorine imide.Specific examples comprises clorox, potassium hypochlorite, monobasic Losantin, binary magnesium hypochlorite, Efficacious Disinfeitant dodecahydrate, potassium dichloroisocyanurate, Surchlor GR 60, Surchlor GR 60 dihydrate, trichlorocyanuric acid, 1,3-two chloro-5,5-T10, N-chloro sulphamide, chloramine-T, dichloramine-T, chloramine B and dichloramine B.Being used for the preferred SYNTHETIC OPTICAL WHITNER of the present composition is clorox, potassium hypochlorite or its mixture.Preferably the SYNTHETIC OPTICAL WHITNER based on chlorine can be pure as jade pure (Triclosan, trade(brand)name).

Most of SYNTHETIC OPTICAL WHITNER of above-mentioned generation hypochlorite can solid or spissated form be purchased, and in preparation present composition process, be dissolved in water.Some above-mentioned materialss can be buied by the aqueous solution.

Clothes washing method

Machine washing method of the present invention generally comprises the machine-wash wash water solution of detergent composition of the present invention who is used in the washing machine dissolving or disperses significant quantity and handles soiled clothes.The detergent composition of the significant quantity meaning is meant at 5-65 and rises dissolving or dispersion 10g-300g product in the washing soln of volume that this is typical products consumption and the washing soln volume that is generally used in the conventional machine washing method.Preferred washing machine can be so-called low-load washing machine.

Aspect preferred use, said composition is formulated into and makes it be applicable to hard surface cleaning or hand washing.Another preferred aspect, detergent composition is to be used for pre-treatment or to soak dirty and pollute the pre-treatment of fabric or soak composition.

Embodiment

That uses in an embodiment writes a Chinese character in simplified form.

In detergent composition, the component symbol of writing a Chinese character in simplified form has the following meaning:

LAS: straight chain C ₁₁- ₁₃Sodium alkyl benzene sulfonate

TAS: tallow alkyl sodium sulfate

Side chain AS: as the branched-chain alkyl sodium sulfate of describing among the WO99/19454

C _XyAS: C _1X-C _1YSodium alkyl sulfate

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

C _XyE _zS: with the C of Z moles of ethylene oxide condensation _1X-C _1YSodium alkyl sulfate

C _XyE _Z: with the condensation of average Z moles of ethylene oxide mainly be straight chain

C _1X-C _1yPrimary alconol

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

QAS1 ：R ₂N ⁺(CH ₃) ₂(C ₂H ₄OH)，R ₂＝C ₈-C ₁₁

APA: C ₈-C ₁₀The amido propyl-dimethyl amine

Soap: straight-chain alkyl carboxylic acid's sodium, by butter and coco-nut oil fatty acid

80/20 mixture obtains

STS: toluenesulfonic acid sodium salt

CFAA: C ₁₂-C ₁₄(cocounut oil) alkyl N-methyl glucose amide

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

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

STPP: anhydrous sodium tripolyphosphate

TSPP: tetrasodium pyrophosphate

Zeolite A: formula Na ₁₂(AlO ₂SiO ₂) ₁₂.27H ₂The hydrated sodium aluminosilicate of O,

Its primary particle size is that the 0.1-10 micron (is pressed anhydrous expression

The weight meter).

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

Citric acid: Citric Acid, usp, Anhydrous Powder

Borate: Sodium Tetraborate

Carbonate: anhydrous sodium carbonate, its granularity is at 200-900 μ m

Supercarbonate: anhydrous sodium bicarbonate, its size-grade distribution is at 400-1200 μ m

Between

Silicate: amorphous sodium silicate (SiO ₂: Na ₂O ratio=2.0: 1)

Vitriol: anhydrous sodium sulphate

Sal epsom: anhydrous magnesium sulfate

Citrate trianion: citrate trisodium dihydrate, activity 86.4%, granularity branch

Cloth is at the 425-850 micron

MA/AA: 1: 4 toxilic acid/acrylic copolymer, molecular-weight average are approximately

70000

MA/AA (1): 4: 6 toxilic acid/acrylic copolymer, molecular-weight average are approximately

10000

AA: the polyacrylic acid sodium polymer of molecular-weight average 4500

CMC: Xylo-Mucine

Ether of cellulose: the polymerization degree is 650 methyl cellulose ether, by Shin Etsu

Chemicals buys

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

The proteolytic ferment of selling has 3.3% weight organized enzyme

Proteolytic enzyme I: the proteolytic ferment of describing in WO95/10591 has

4% weight organized enzyme is gone out by Genencor Int.Inc.

Sell

Alcalase: by the proteolytic ferment of Novo Industries A/S sale,

Has 5.3% weight organized enzyme

Cellulase: by Novo Industries A/S with trade(brand)name Carezyme

The cellulase of selling has 0.23% weight organized enzyme

Amylase: by Novo Industries A/S with trade(brand)name Termamyl

The amylase that 120T sells has 1.6% weight organized enzyme

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

The lipolytic enzyme of selling has 2.0% weight organized enzyme

Lipase (1): by Novo Industries A/S with trade(brand)name Lipolase

The lipolytic enzyme that Ultra sells has 2.0% weight activity

Enzyme

Endoenzyme (Endolase): endoglucanase, sell by Novo Industries A/S

Sell, have 1.5% weight organized enzyme

PB4: standard type NaBO ₂.3H ₂O.H ₂O ₂Sodium peroxoborate four hydrations

Thing

PB1: standard type NaBO ₂.H ₂O ₂The anhydrous sodium perborate SYNTHETIC OPTICAL WHITNER

Percarbonate: standard type 2Na ₂CO ₃3H ₂O ₂SPC-D

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

NAC-OBS: (6-nonanoyl caproyl) oxygen benzene sulfonate

TAED: tetraacetyl ethylene diamine

DTPA: diethylene triaminepentaacetic acid(DTPA)

DTPMP: diethylenetriamine five (methylene phosphonic acid), by Meng Shan all with

Trade(brand)name Dequest 2060 sells

EDDS: quadrol-N, N '-disuccinic acid, sodium-salt form (S, S)

Isomer

Photoactivated SYNTHETIC OPTICAL WHITNER: the sulfonation phthalocyanine phthalocyanine zinc of sealing with the dextrin soluble polymer (1)

Photoactivated SYNTHETIC OPTICAL WHITNER: the aluminum phthalocyanine of sealing with the dextrin soluble polymer (2)

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

Whitening agent 2: 4,4 '-two (4-phenylaminos-6-morpholino-1,3,5-triazines-2-

Base) stilbene-2:2 '-disulfonic acid disodium amino)

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

PEGx: polyoxyethylene glycol, molecular weight are x (general 4000)

PEO: polyoxyethylene, molecular-weight average 50000

TEPAE: ethoxylation tetren

PVI: polyvinyl imidazol, molecular-weight average 20000

PVP: polyvinylpyrrolidonepolymers polymers, molecular-weight average 60000

PVNO: polyvinylpyridine N-oxide polymer, molecular-weight average

50000

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

Molecular-weight average 20000

QEA: 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, n=20-30 wherein

SRP1: the end capped polyester of negatively charged ion

SRP2: the short embedding of diethoxyization poly-(phthalic acid 1,2 inferior propyl ester)

The section polymkeric substance

PEI: polyethylene imine based, molecular-weight average 1800, each nitrogen is former

Sub-average degree of ethoxylation is 7 oxygen ethene residues

Polysiloxane defoamers: the polydimethylsiloxane foam control agent with as the silica of dispersion agent

Alkane-oxyalkylene copolymers, described foam control agent and described dispersion

The ratio of agent is 10: 1-100: 1

Opalizer: water base single styrene latex mixture, by BASF

Aktiengesellschaft is with trade(brand)name Lytron 621

Sell

Wax: paraffin

HMEO: hexamethylene-diamine four (oxyalkylene) 24

Below be embodiments of the invention.

Example I

This embodiment has illustrated good dispersion and the deliquescent detergent particles that evenly easily flows, has even color and particle shape prepared according to the methods of the invention.With multiple detergent raw material component dried mixing in the annular vertical mixing screw, every batch is 200kg, prepares several.The laboratory scale example that the pre-compound of this heap is added-every crowd 40kg in the cylinder type that has Internal baffle (Barrate type) mixing tank that horizontally rotates.Extraction part premixture also adds in the mixing tank.To have possible the doing than small-particle of segregation mixes in mixing tank.

Use air atomization nozzle that adhesive C 45AE7 is sprayed onto in the mixing tank.Product was mixed 2 minutes, in this mixing tank, added caking inhibiter (zeolite A) and remix 1 minute.Product is delivered in the bin.With the mixing step of other fluid additives such as spices in, the back adds other detergent additives such as enzyme, percarbonate and painted carbonic acid salting stain decorations, makes the finished product washing composition.

Component accounts for the % weight of combined feed total feed

Add the dry substance in the premixture to

The washing composition premixture ^*98.48%

Optical white 0.02%

The spices encapsulation object 0.5% of Class1

The spices encapsulation object 0.2% of type 2

Tackiness agent

C45AE7 alcohol ethoxylate 0.7%

Caking inhibiter

Zeolite A 0.1%

*=comprise linear alkylbenzene sulphonic acid (13.4% weight), zeolite A (40%), sodium sulfate (23.5%), yellow soda ash (8.4%), sal epsom (0.7% weight), EDDS (0.4% weight), MA/AA (2.5% weight), soap (1.5% weight), QAS1 (2.0% weight), HEDP (0.3% weight), white dyes (0.5% weight), water (5.3% weight), hexa-methylene four (oxygen ethene) diamines 24 (1.5% weight).

Example II

This embodiment has also illustrated the inventive method and 1 parameter in conjunction with the embodiments.Press the premixture of embodiment 1 preparation dry detergent material, it has following listed composition.Extraction part premixture also adds in the mixing tank.To use air atomization nozzle to be sprayed onto in the mixing tank with PEG4000 blended C45AE7 tackiness agent.This premixture that viscosity is increased mixed 1 minute.To have possible the doing than small-particle of segregation mixes in mixing tank.Product mixed 2 minutes and in mixing tank, add caking inhibiter (zeolite A) and remix 1 minute.Product is delivered in the bin.With the mixing step of other fluid additives such as spices in, the back adds other detergent additives such as enzyme, percarbonate and painted carbonic acid salting stain decorations, makes the finished product washing composition.

Component accounts for the % weight of combined feed total feed

Add the dry substance in the premixture to

The washing composition premixture ^*98.48%

Optical white 0.02%

The spices encapsulation object 0.5% of Class1

The spices encapsulation object 0.2% of type 2

Tackiness agent

C45AE7 alcohol ethoxylate 1.0%

PEG4000 0.5％

Caking inhibiter

Zeolite A 0.2%

EXAMPLE III

This embodiment has also illustrated the inventive method and 1 parameter in conjunction with the embodiments.Press the premixture of embodiment 1 preparation dry detergent material, it has following listed composition.Extraction part premixture also adds in the mixing tank.Use air atomization nozzle to be sprayed onto in the mixing tank in the C45AE5 tackiness agent.This premixture that viscosity is increased mixed 1 minute.To have possible the doing than small-particle of segregation mixes in mixing tank.Product mixed 2 minutes and in mixing tank, add caking inhibiter (zeolite A) and 15 seconds of remix.Product is delivered in the bin.With the mixing step of other fluid additives such as spices in, the back adds other detergent additives such as enzyme, percarbonate and painted carbonic acid salting stain decorations, makes the finished product washing composition.

Component accounts for the % weight of combined feed total feed

Add the dry substance in the premixture to

The washing composition premixture ^*97.78%

Optical white 0.02%

The spices encapsulation object 0.4% of Class1

The spices encapsulation object 0.1% of type 2

Tackiness agent

C45AE5 alcohol ethoxylate 1.5%

Caking inhibiter

Zeolite A 0.2%

EXAMPLE IV

This embodiment has also illustrated the inventive method and 1 parameter in conjunction with the embodiments.Press the premixture of embodiment 1 preparation dry detergent material, it has following listed composition.Extraction part premixture also adds in the mixing tank.Use air atomization nozzle to be sprayed onto in the mixing tank in the C45AE7 tackiness agent.This premixture that viscosity is increased mixed 1 minute.To have possible the doing than small-particle of segregation mixes in mixing tank.Further spray tackiness agent, small-particle is fixed on the big main body particulate surface.Product mixed 2 minutes and in mixing tank, add caking inhibiter (zeolite A) and remix 1 minute.Product is delivered in the bin.With the mixing step of other fluid additives such as spices in, the back adds other detergent additives such as enzyme, percarbonate and painted carbonic acid salting stain decorations, makes the finished product washing composition.

Component accounts for the % weight of combined feed total feed

Add the dry substance in the premixture to

The washing composition premixture ^*98.2%

Optical white 0.02%

The spices encapsulation object 0.5% of Class1

The spices encapsulation object 0.2% of type 2

Adhesive fluid

C45AE7 alcohol ethoxylate 1.0%

Caking inhibiter

Zeolite A 0.08%

EXAMPLE V

This embodiment has also illustrated the inventive method and 1 parameter in conjunction with the embodiments.Press the premixture of embodiment 1 preparation dry detergent material, it has following listed composition.Extraction part premixture also adds in the mixing tank.

In still, with thin can isolating particles dispersed to carrying object such as among the C45AE7, use low shear agitation, mixed 10 minutes.The suspension pump of this fine particle in fluid delivered to nozzle and be atomised on the pre-mixing particle in mixing tank.

Product mixed 2 minutes and in mixing tank, add caking inhibiter (zeolite A) and remix 1 minute.Product is delivered in the bin.With the mixing step of other fluid additives such as spices in, the back adds other detergent additives such as enzyme, percarbonate and painted carbonic acid salting stain decorations, makes the finished product washing composition.

Component accounts for the % weight of combined feed total feed

Add the dry substance in the premixture to

The washing composition premixture ^*96.48%

Optical white 0.02%

Adhesive fluid

C45AE7 alcohol ethoxylate 3.0%

Caking inhibiter

Zeolite A 0.5%

Other example composition

In following examples, all content are to represent by the % weight that accounts for total finished product detergent composition:

Table

Following composition is according to composition of the present invention:

	A	B	C	D	E	F	Granularity (average μ m)	Span	Δ E raw material is with respect to the heterochromia of final product composition having	Sphericity (on average)
	A	B	C	D	E	F	Granularity (average μ m)	Span		Sphericity (on average)	1. spraying Dry Particle							450μm	1.8	2.4	1.9
LAS	4.0	5.0	11.0	7.0	4.0	5.0					1. spraying Dry Particle							450μm	1.8	2.4	1.9
LAS	4.0	5.0	11.0	7.0	4.0	5.0					TAS	-	-	-	-	-	1.0
C ₄₅AS	1.0	-	-	-	1.0	-					TAS	-	-	-	-	-	1.0
C ₄₅AS	1.0	-	-	-	1.0	-					C16-C17 side chain AS	2.0	3.0	-	-	2.0	-
DTPA, HEDP and/or EDDS	0.5	0.6	0.5	0.7	1.0	0.5					C16-C17 side chain AS	2.0	3.0	-	-	2.0	-
DTPA, HEDP and/or EDDS	0.5	0.6	0.5	0.7	1.0	0.5					MgSO4	0.5	0.4	0.5	0.4	0.5	0.5
Yellow soda ash	10.0	7.0	8.0	8.0	3.0	10.0					MgSO4	0.5	0.4	0.5	0.4	0.5	0.5
Yellow soda ash	10.0	7.0	8.0	8.0	3.0	10.0					Sodium sulfate	5.0	2.0	2.0	5.0	3.0	3.0
Zeolite A	18.0	20.0	18.0	10.0	20.0	17.0					Sodium sulfate	5.0	2.0	2.0	5.0	3.0	3.0

SKS-6	-	-	-	-	-	-
SKS-6	-	-	-	-	-	-					MA/AA or AA	1.0	1.5	1.0	0.6	1.0	0.6
QAS1	1.0	0.5	1.0	-	0.8	1.0					MA/AA or AA	1.0	1.5	1.0	0.6	1.0	0.6
QAS1	1.0	0.5	1.0	-	0.8	1.0					Whitening agent	0.1	0.05	0.05	0.06	0.05	0.05
HMEO	0.5	0.5	1.0	0.5	1.0	1.0					Whitening agent	0.1	0.05	0.05	0.06	0.05	0.05
HMEO	0.5	0.5	1.0	0.5	1.0	1.0					Soap	-	1.5	1.0	1.5	-	1.5
											Soap	-	1.5	1.0	1.5	-	1.5
											2. At premixture In Component
Spray-dired particle (1)	50.0	50.0	48.0	40.0	40.0	50.0					2. At premixture In Component
Spray-dired particle (1)	50.0	50.0	48.0	40.0	40.0	50.0					Nonionic AE7/AE5	-	-	5.0	-	-	-
Yellow soda ash	2.0	8.0	-	4.0	6.0	5.0	200μm	1.5	4.0	1.5	Nonionic AE7/AE5	-	-	5.0	-	-	-
Yellow soda ash	2.0	8.0	-	4.0	6.0	5.0	200μm	1.5	4.0	1.5	Sodium sulfate	-	-	-	-	2.0	1.0	350μm	1.6	3.5	1.5
The QAS1 agglomerate	-	-	-	2.0	-	1.0	500μm	2.7	5.0	2.1	Sodium sulfate	-	-	-	-	2.0	1.0	350μm	1.6	3.5	1.5
The QAS1 agglomerate	-	-	-	2.0	-	1.0	500μm	2.7	5.0	2.1	The nonionic agglomerate				10.0	-	-	500μm	1.9	8.3	1.8
The SKS-6/LAS agglomerate	-	-	-	12.0	-	-	350μm	1.8	14.6	1.9	The nonionic agglomerate				10.0	-	-	500μm	1.9	8.3	1.8
The SKS-6/LAS agglomerate	-	-	-	12.0	-	-	350μm	1.8	14.6	1.9	The polysiloxane defoamers agglomerate	2.5	2.5	2.0	0.5	-	2.5	500μm	2.0	14.3	1.5
SRP1	0.5	-	-	-	0.5	0.3	500μm	2.0	10.4	2.0	The polysiloxane defoamers agglomerate	2.5	2.5	2.0	0.5	-	2.5	500μm	2.0	14.3	1.5
SRP1	0.5	-	-	-	0.5	0.3	500μm	2.0	10.4	2.0	The TAED agglomerate	2.5	2.5	3.0	-	-	-	550μm	1.5	11.4	1.6

The SKS-6 powder	3.5	3.5	9.0	-	3.5	5.0	60μm	1.9	6.0	1.7
The SKS-6 powder	3.5	3.5	9.0	-	3.5	5.0	60μm	1.9	6.0	1.7	The TAED powder	-	-	-	-	1.5	2.0	80μm	1.7	9.5	1.6
											The TAED powder	-	-	-	-	1.5	2.0	80μm	1.7	9.5	1.6
											3. be applied to pre-Mix On the compoundPre-mixing tackiness agent (2)
PEG4000	5.0
PEG4000	5.0										PEG1500				6.0
AS，LAS， MBAS					5.0	6.0					PEG1500				6.0
AS，LAS， MBAS					5.0	6.0					The water of (when drying, removing) tackiness agent		10.0	15.0
											The water of (when drying, removing) tackiness agent		10.0	15.0
											Other additives of preparation finished product detergent formulations are added in the back
4. spray Material
4. spray Material											Spices	0.4	0.2	0.4	0.4	0.5	0.3
											Spices	0.4	0.2	0.4	0.4	0.5	0.3

5. do Add Material
5. do Add Material							Premixture (2)	70.0	65.0	55.0	65.0	70.0	60.0
Enzyme (proteolytic enzyme, lipase, amylase, cellulase)	2.0	1.5	1.0	1.3	1.2	1.5	Premixture (2)	70.0	65.0	55.0	65.0	70.0	60.0
Enzyme (proteolytic enzyme, lipase, amylase, cellulase)	2.0	1.5	1.0	1.3	1.2	1.5	NACAOBS	3.0	2.5	3.0	3.5	3.5	2.5
SPC-D	13.0	10.0	10.0	12.0	12.0	10.0	NACAOBS	3.0	2.5	3.0	3.5	3.5	2.5
SPC-D	13.0	10.0	10.0	12.0	12.0	10.0	Optical white	0.02	0.02	0.02	0.02	0.02	0.02
The spices encapsulation object	0.7	0.5	0.6	0.8	0.9	0.4	Optical white	0.02	0.02	0.02	0.02	0.02	0.02
The spices encapsulation object	0.7	0.5	0.6	0.8	0.9	0.4	Citric acid	6.0	4.0	2.0	4.0	6.5	5.0
Yellow soda ash spot decorations	1.0	1.0	1.0	0.5	1.5	1.5	Citric acid	6.0	4.0	2.0	4.0	6.5	5.0
Yellow soda ash spot decorations	1.0	1.0	1.0	0.5	1.5	1.5	Zeolite A	0.1	-	-	0.3	-	-
The TAED agglomerate	-	-	-	3.0	-	-	Zeolite A	0.1	-	-	0.3	-	-
The TAED agglomerate	-	-	-	3.0	-	-	The polysiloxane defoamers agglomerate	-	-	-	-	3.0	-
							The polysiloxane defoamers agglomerate	-	-	-	-	3.0	-
							6. be applied toCoating in the premixture (2)

Burkeite (using) with 30% weightaqueous solution	4.0	5.0	8.0	-	5.0	-
Burkeite (using) with 30% weightaqueous solution	4.0	5.0	8.0	-	5.0	-	Whitening agent 15	0.1	0.1	-	-	-	-
							Whitening agent 15	0.1	0.1	-	-	-	-
							Add to 100% filler
							Add to 100% filler
							Finished product
Mean particle size	600μm	600μm	600μm	800μm	800μm	600μm	Finished product
Mean particle size	600μm	600μm	600μm	800μm	800μm	600μm	Span (geometric standard deviation)	1.4	1.2	1.4	1.2	1.4	1.6
Circularity (on average)	1.30	1.20	1.35	1.40	1.45	1.40	Span (geometric standard deviation)	1.4	1.2	1.4	1.2	1.4	1.6
Circularity (on average)	1.30	1.20	1.35	1.40	1.45	1.40	Whiteness W=L-3b	98.0	96.5	98.5	92.0	97.0	101.5

Described the present invention thus in detail, without departing from the present invention, can do various variations, this is that those skilled in the art are conspicuous, should not think that the present invention is limited in the content described in the specification sheets.

Claims

1. preparing washing agent particulate method, comprise the washing composition basal granule of selecting to have geometric mean diameter 500-2000 micron, in to low shear-mixed step, the washing composition active particle is adhered on the washing composition basal granule, the geometric mean diameter of this washing composition active particle be not more than the washing composition basal granule geometric mean diameter 40%, the detergent active that is comprised is selected from spices, enzyme, optical white, catalyzer, the dirt release agent polymkeric substance, suds suppressor, bleaching compounds, whitening agent and layered silicate, and the geometric mean diameter of washing composition active particle is higher than 10 μ m and is lower than 200 μ m.

2. according to the method for claim 1, wherein first kind of charging of washing composition basal granule added in the mixing tank, second kind of charging that will comprise the washing composition active particle adds in the mixing tank and also have tackiness agent in mixing tank, and it plays the washing composition active particle is adhered to effect on the washing composition basal granule.

3. according to the method for claim 2, wherein tackiness agent directly adds in the mixing tank by the third charging.

4. according to each method among the claim 1-3, wherein before washing composition basal granule or washing composition active particle add mixing tank, tackiness agent is added wherein.

5. according to each method among the claim 1-3, wherein the geometric mean diameter of washing composition active particle be not more than the washing composition basal granule geometric mean diameter 20%.

6. according to each method among the claim 1-3, wherein the geometric mean diameter of washing composition active particle be not more than the washing composition basal granule geometric mean diameter 10%.

7. according to each method among the claim 1-3, wherein the geometric mean diameter of washing composition active particle be not more than the washing composition basal granule geometric mean diameter 5%.

8. according to each method among the claim 1-3, wherein the washing composition active particle comprises optical white.

9. according to each method among the claim 1-3, wherein the washing composition active particle comprises solid particulate, and this solid particulate comprises spices.

10. according to each method among the claim 1-3, wherein the geometric mean diameter of washing composition active particle is not more than 150 microns.

11. according to each method among the claim 1-3, wherein low shear mixer comprises the cylinder type mixing tank.

12. according to each method among the claim 1-3, wherein the washing composition basal granule comprises agglomerate, granulated detergent raw material, spray-dired powder or its mixture.

13. the detergent particles for preparing according to the method for above-mentioned each claim.

14. detergent composition that comprises according to the detergent particles of claim 13.