CN1358225A - Cleaning compositions and tablets - Google Patents

Abstract

The present invention relates to tablets and detergent compositions comprising a compressed clay component, which is compressed prior to introduction into the tablets or compositions. The compressed clay component provides an improved disintegration, dispersion or dissolution of the tablets or compositions. In laundry detergents or tablets, the selected compressed clay materials have shown to provide good softening as well.

Description

Cleaning compositions and sheet

Invention field

The present invention relates to the various uses of downtrodden clay material, particularly relate to the sheet or the cleaning compositions of the clay that comprises compacting.

Background of invention

Clay has been used for washing composition for many years, provides soft to give the fabric with this cleaning compositions.They be described to can be dried add in other detergent particles or with other component blended materials.EP-A-313146 has described the agglomerate that contains 60%-99% clay, paraffin and wetting Agent for Printing Inks, and they are added in the detergent composition.

Also mentioned the fragmentation that clay helps sheet, for example it is described among EP-A-328880 and the EP-A-799886.

The inventor now finds to be pressed before clay material mixes sheet or cleaning compositions, can improvedly decompose, distribution and/or solvency action.The sheet of downtrodden clay before they find for example to comprise and mix in the sheet decomposes faster than the sheet that comprises not downtrodden same clay material before mixing in the sheet.They also find, particularly suppress the employed amount of pressure of clay for obtain helping to decompose, distribution or dissolved clay particle be important.

The inventor finds that also in cleaning compositions, downtrodden clay component has improved the distribution and/or the dissolving of detergent component.Be sure of that this is because the result that the product agglomerate that caking or gelled product are formed that the clay of compacting causes decomposes, particularly when contacting, for example in the feeder compartment of washing machine with water or moisture content.

The inventor also finds when mild clay is pressed and mixes then in cleaning compositions or the sheet, the decomposition that not only is improved, distribution or solvency action, but also obtained good fabric sofetening effect.They find to compare with the clay agglomerate that comprises adhesive material such as paraffin, even can improved soft effect.

Summary of the invention

The invention provides the cleaning compositions or its component that comprise downtrodden clay component.

The invention still further relates to the sheet that comprises active ingredient and downtrodden clay component, preferred cleaning foil, tablet, plant nutrition sheet, vegetable fertilizer tablet.

Sheet, composition and component also are provided, have wherein obtained clay component with the compacting of 10MPa pressure at least clay material.

For example form the clay component of compacting by the compacting clay material, the clay component that will suppress mixes and can obtain this, composition or component in sheet, cleaning or detergent composition or the component then.

This sheet or composition be solid cleaning composition or sheet preferably, preferred laundry composition or sheet.

The invention still further relates to closely knit clay component in particulate composition or sheet, particularly at cleaning compositions or plant nutrition tablet composition or sheet, vegetable fertilizer composition or sheet, or be used to improve the purposes of the dissolving or the disintegration of this composition or sheet in pharmaceutical composition or the sheet.The downtrodden clay component of detailed Description Of The Invention

The downtrodden clay component of the present invention can comprise any clay material well known in the prior art, yet preferably it comprises not downtrodden clay material, and this clay material can help decomposition or dissolving or be dispensed to a certain degree.When being used for cleaning compositions of the present invention or sheet, the clay material in the downtrodden clay component preferably provides the softish clay material to fabric.

For the object of the invention, should be understood that before downtrodden clay component is in mixing the present composition, component or sheet to be pressed.Yet the clay material in the downtrodden clay component can mix with other components before compacting, as hereinafter in greater detail.

Downtrodden clay component can obtain by any method, and this method comprises the step that makes the clay material withstanding pressure, and this clay material randomly mixes with other components.For the object of the invention, no any clay agglomerate of applying pressure intentionally, for example known as prior art by EP-A-313146, be not understood that it is a kind of method that pressure is provided to clay material.

Preferable methods comprises makes clay material stand 10MPa at least, or 20MPa or even the step of 40MPa pressure at least at least.For example this can randomly combine with one or more other components by making the clay material tablet forming or rolling clay material and realize, forms clay gall, preferably reduces size then, for example grinds downtrodden clay gall, forms downtrodden clay particle.This particle can be impregnated in sheet or the cleaning compositions then.

Tabletting method and rolling method are that prior art is known.For example, can or use the Chilsonator rolling apparatus of buying from Fitzpatrick company to carry out the compacting of clay in Lloyd 50K tabletting machine.

Various method or the Ginding process that reduce size also are that prior art is known.The step that reduces size can comprise that two or more each size reduce or the grinding stage, for example at first sheet is broken into little agglomerate, grinds this agglomerate then and forms particle.

Therefore this clay component particulate state preferably.Preferably, the particulate composition of at least 90% weight has 150 microns-2000 microns of granularities, and more preferably 200 microns-1500 microns, or even 250 microns-1200 microns.More preferably 90% particle has 400 microns-1100 microns of granularities, or even 500 microns-1000 microns.Preferred do not have granularity to be lower than 100 microns or even be lower than 150 microns fine particle and exist basically.

For example, use the sieve of available granularity and collect be retained on the sieve corresponding to the part of minimum particle size and the part by sieve corresponding to maximum particle size, screening can obtain the particle of desired particle size by the particle that size reduces or grinding steps obtains.

This clay component can comprise other components, for example adhesive material.Spendable adhesive material is as in the sheet those of being generally used for described in hereinafter.For clay component of the present invention, the preferred adhesive material comprises liquid such as water, and also has fusible viscosity or solid material under the impregnable temperature of clay.Preferred adhesive is oils, paraffin, glycerine, polyalkylene glycol, (nonionic) tensio-active agent and/or water.

Also can there be granulation aid, dehumidizier and/or wetting Agent for Printing Inks.

This clay component preferably comprises at least 40%, or even at least 60% weight clay material, comprise the water of hydration that is included in the clay material.Preferably, this clay component comprises at least 70% or even at least 80% or even at least 90% or even the clay material of at least 95% weight.Preferred this clay component is grouped into by clay and water and the natural small number of groups that exists in clay.

It is highly preferred that smectic clays, for example be disclosed in United States Patent (USP) 3862058,3948790,3954632 and 4062647 and European patent EP-A-299575 and EP-A-313146, the full name of applicant of all these all is a Procter and Gamble company.

Term smectic clays of the present invention comprises that aluminum oxide wherein is present in clay in the lattice silicate and magnesium oxide and is present in clay in the lattice silicate.Typical smectic clays compound comprises having general formula Al ₂(Si ₂O ₅) ₂(OH) ₂.nH ₂The compound of O and have a formula M g ₃(Si ₂O ₅) ₂(OH) ₂.nH ₂The compound of O.The smectic clays tendency is taked expandable three-decker.

The specific examples of the smectic clays that is fit to comprises those that are selected from following type: montmorillonite, hectorite, volchonskoite, nontronite, saponite and sauconite particularly have those of alkali or alkaline-earth metal ions in the crystal lattices structure.

Preferably can be three layers of expandable aluminium-silicate, it is characterized in that the dioctahedron crystal lattices, and expandable three layers of Magnesium Silicate q-agent have the trioctahedron crystal lattices.

Above-mentioned as this paper, the clay that uses in the present composition contains cation balance ion such as proton, sodium ion, potassium ion, calcium ion, magnesium ion etc.Get used to according to main or unique a kind of positively charged ion difference clay that is adsorbed.For example, the sodium clay is that the positively charged ion that wherein is adsorbed mainly is a kind of clay of sodium.This positively charged ion that is adsorbed can be included in the aqueous solution in the cationic permutoid reaction that exists.The general permutoid reaction that contains smectite-type clay is represented by following equation:

Clay (Na)+NH ₄OH-terre verte (NH ₄)+NaOH

Because in above-mentioned balanced reaction, the ammonium ion of 1 equivalent weight replaces the sodium of 1 equivalent weight, people get used to measuring cation exchange capacity (CEC) (being sometimes referred to as " basic exchange capacity ") by milligramequivalent/100g clay (meq/100g).The cation exchange capacity (CEC) of clay is to measure with several method, comprises electrodialysis, with ammonium ion exchange, and titration then, or by the Yamamoto Methylene Blue ZF method, it is listed in Grimshaw " chemistry of clay and physics ", 264-265 page or leaf, interdisciplinary science (1971) fully.The cation exchange capacity (CEC) of clay mineral relates to the swelling properties of this factor such as clay, the electric charge of clay, and it is determined by crystalline network etc. to small part again.

Terre verte has the about 70meq/100g of ion-exchange capacity such as nontronite, and montmorillonite, and it has ion-exchange capacity greater than 70meq/100g, finds that it can be used among the present invention, and this is that they can effectively deposit on the fabric, provide required soft effect.Therefore, the useful preferably clay material characteristics of the present invention is to have ion-exchange capacity three layers of smectite-type clay of expansible at least about 50meq/100g.

The preferred clay of the present invention can be buied by the extensive stock name, for example from Georgia Kaolin company, and Elizabeth, Thixogel#1 that the New Jersey is buied and Gelwhite GP; From American Colloid company, Skokie, Volclay BC that the Illinois is buied and Volclay #325; Black Hills Bentonite BH450 that buys from International Minerals and Chemicals and the VeegumPro and Veegum F that buys from R.T.Vanderbilt.People recognize that this smectite type mineral substance that obtains by above-mentioned trade(brand)name can comprise the mixture of various discrete mineral plastids.The mixture of this smectite minerals matter is applicable to the present invention.

Montmorillonitic clay is that the present invention is preferred, and sodium or Ca-montmorillonite are particularly preferred for providing soft effect.The smectic clays, particularly montmorillonite that are fit to are sold by various suppliers, comprise English China Clays, Laviosa, Georgia Kaolin and Colin StewartMinchem.Gelwhite GP is the terre verte of extremely white form, and therefore when preparation white composition of the present invention or sheet, it is preferred.Volclay BC contains at least 3% iron (to be expressed as Fe in lattice ₂O ₃) the smectite-type clay mineral, it has very high ion-exchange capacity, is to be used for one of most economical and effective clay of the present invention, considers that from the angle of product performance it is preferred.

Organophilic clay also can be used for the present invention.They are clays of hydrophobically modified, and it has the organic ion that replaces inorganic metal ion by the known ion-exchange techniques of prior art.The clay of these kinds mixes with organic solvent easily, and has the ability of organic solvent in the absorption interlayer.Being used for example or hydrophobic clay that the present invention suits is from Rheox ofHighstown, Bentone SD-1, SD-2 and SD-3 that N.J. buys.

The granularity of clay material that is used to form the clay component of the present invention compacting depends on the final size of clay component.Preferably, before compacting, clay material has granularity 0.01 μ m-800 μ m, more preferably 1 μ m-400 μ m, most preferably 5 μ m-200 μ m or even to 150 μ m.

The highly preferred downtrodden clay component of the present invention, sheet, component or composition also comprise one or more other disintegrating agents or partitioning agent or wicking action agent except comprising downtrodden clay component.

The preferred disintegrating agent of the present invention is that those are worked as water when contact swelling and will comprise the sheet of disintegrating agent or the disintegrating agent that grain breakage becomes small pieces.This will improve dispersion or the distribution of product in solution.Possible disintegrating agent is described in the pharmaceutical excipient handbook (PharmaceuticalExcipients) (1986).The examples of disintegrants that is fit to comprises starch; The starch of natural, modification or pre-gelledization; Sodium starch gluconic acid; Natural gum; Agar gum; Guar gum; Viscogum BE; Kuteera gum; Pectin; Yellow kind glue; Croscarmylose sodium, polyvinylpolypyrrolidone, Mierocrystalline cellulose, carboxymethyl cellulose, alginic acid and its salt comprise sodiun alginate, silicon-dioxide, Polyvinylpyrolidone (PVP), soybean polysaccharide, ion exchange resin and its mixture.

Be used for granular detergent composition of the present invention, preferred other disintegrating agents of sheet camber particularly of the present invention are water expansible fibre element such as Solka-floc and Arbocel preferably, with avicel cellulose such as the Lattice that buys by FMC and water-soluble salt such as sodium acetate.

Other components that not downtrodden clay also can be used as sheet of the present invention or cleaning compositions exist, particularly when this sheet or composition are used for soft fabric.

The foaming of the gas system that can provide when contacting with water also preferably is provided in the downtrodden clay component of the present invention, sheet or composition.Preferred this system is included in water and exists down can one to react and form the acid source and the carbonate source of carbon dioxide.

The suitable acid that the present invention uses comprises SOLID ORGANIC, mineral or mineral acid, its salt or derivatives thereof or its mixture.Preferred this acid is one, two or three protonic acids.This acid comprises list or poly carboxylic acid, optimization citric acid, adipic acid, pentanedioic acid, 3 chetoglutaric acid, citromalic acid, tartrate, toxilic acid, fumaric acid, oxysuccinic acid, succsinic acid, propanedioic acid.Their sour form is preferably used in this acid, can preferably use their anhydrous form, or its mixture.Derivative also comprises the ester that this is sour.Surprisingly, by using tartrate, toxilic acid, particularly oxysuccinic acid, described particle provides physics and/or the chemical stability improved through standing storage in the exsiccant effervescent granules in existing discovery.

The carbonate source that is fit to comprises carbonate, supercarbonate and percarbonate, especially supercarbonate and/or carbonate.The carbonate that is fit to that the present invention uses comprises salt of wormwood, lithium, sodium and saleratus, lithium, sodium etc., wherein preferred yellow soda ash and potassium.The supercarbonate that is fit to that the present invention uses comprises any alkali metal hydrocarbonate, and as lithium, sodium, potassium etc., wherein sodium bicarbonate and potassium are preferred.Supercarbonate can be preferable over carbonate, and is more effective because they are weight, and promptly the supercarbonate of similar weight has bigger CO than carbonate ₂" deposit ".Yet the selection of carbonate in dry effervescent granules or supercarbonate or its mixture can be depending on the desired pH of water-bearing media of the dry effervescent granules of dissolving.For example in water-bearing media, require high relatively pH (for example being higher than pH9.5), the preferred mixture that uses carbonate separately or use carbonate and supercarbonate, wherein the content of carbonate is higher than the content of supercarbonate, the weight ratio of general carbonate and supercarbonate is 0.1-10, more preferably 1-5, most preferably 1-2.

This cleaning compositions, component or sheet can preferably contain the clay flocculating agent, and by the weight of composition, preferably its content is 0.005%-10%, more preferably 0.05%-5%, most preferably 0.1%-2%.

Therefore the effect of this clay flocculating agent is all to combine the clay compound particle in the washing soln in this way, helps them to deposit on the fabric face in the washing.Therefore this effect requires to be different from the clay dispersion immunomodulator compounds, and the clay dispersion immunomodulator compounds normally adds and helps in the laundry detergent composition to remove clay soil from fabric, and they are dispersed in the washing soln.

Preferably as clay flocculating agent of the present invention be to have a weight-average molecular weight 100000-10000000, preferred 150000-5000000, the more preferably organic polymer materials of 200000-2000000.

The organic polymer materials that is fit to comprises containing and is selected from oxyalkylene, particularly oxyethane, acrylamide, vinylformic acid, vinyl alcohol, vinyl pyrrolidone and monomeric homopolymer of inferior quadrol or multipolymer.The homopolymer of oxyethane particularly, it is preferred also having acrylamide and vinylformic acid.

Described with the european patent number EP-A-299575 of Procter and Gamble company name and EP-A-313146 and to be used for the agent of the preferred organic polymer clay flocculating of the present invention.

The inorganic clay flocculation agent also is suitable for the present invention, and its typical example comprises lime and alum.

This flocculation agent preferably is present in the basic particle of the washing composition that generally comprises one or more tensio-active agents and washing assistant such as in detergent agglomerate, extrudate or the spray-dried granules.

The clay material that is preferred for preparing the downtrodden clay component of the present invention has the free water yield and is lower than 30%, preferably be lower than 23% or even be lower than 18% or even be lower than 12%, this means that its free water yield is such, when 10 the gram clay materials under the ventilation situation, drying is 1 hour in 105 ℃ baking oven, the former weight loss of this clay material is less than 30%, preferably is less than 23% or even less than 18% or even less than 12%.Sheet

Sheet of the present invention can be to be used for providing any of active ingredient to the medium that comprises solvent.Preferred sheet form is the tablet that active ingredient such as medicament is provided to water-bearing media, comprises the sheet of nutrient for plants or fertilizer or comprises the sheet of sterilant.

It is highly preferred that the detergent tablet that detergent active is provided to cleaning solution such as preferred laundry or wash up solution or hard surface cleaning solution.The preferred ingredient of cleaning sheet of the present invention is described in hereinafter.

Preferred this sheet is to provide softish laundry sheet to the fabric in the washing.

When this sheet is to clean or during detergent tablet, they preferably comprise, by the weight of this sheet, the downtrodden clay component of 0.05%-30%, more preferably 1%-20%, or even 2%-15% or even 3%-12% weight.

This sheet can comprise coating.This sheet can be coated, so that sheet does not absorb moisture content or only absorbs moisture content with very slow speed.This coating is also preferably firm, so that sheet stands the damaged or wearing and tearing that the moderate mechanical impact causes no more than very low amount in use, packing and transportation.At last, coating is preferably frangible, so that the fragmentation when standing stronger mechanical impact of this sheet.In addition, if coated material disperses under alkaline condition or easily by tensio-active agent emulsification, this is favourable.This helps avoid at washing stage visible residue attached to the problem on the window of front-loading washing machine with also avoided particle or coated material group is deposited in the loading of washing.

Preferred this coating comprises one or more decomposition agents as herein described, or even the downtrodden clay component of the present invention.

The coated material that is fit to is a carboxylic acid, preferred dicarboxylic.Particularly suitable dicarboxylic acid is selected from oxalic acid, propanedioic acid, succsinic acid, pentanedioic acid, hexanodioic acid, pimelic acid, suberic acid, nonane diacid, sebacic acid, undecane diacid, dodecanedioic acid, undecane dicarboxylic acid and its mixture.This coated material preferably has 40 ℃-200 ℃ of fusing points.

This coating can be used with several different methods.Two kinds of preferred coating methods are a) to apply and b with melting material) with the solution coating of this material.

In a), coated material is to use and be solidificated on the sheet being higher than under the temperature of its fusing point.At b) in, coated material is to use as solution, solvent is dried, and stays adherent coating.Basically insoluble material can be administered on the sheet by for example spraying or flooding.Usually, when melting material was sprayed onto on the sheet, its meeting fast setting formed adherent coating.When sheet is dipped in the melting material, take out then, can cause the coated material fast setting when cooling off fast again.Obviously, have fusing point and be lower than 40 ℃ insoluble basically material and at room temperature be not enough to solidify, find to have fusing point and be higher than the use that do not gear to actual circumstances of about 200 ℃ material.Preferably, the fusing point of material is at 60 ℃-160 ℃, more preferably 70 ℃-120 ℃.

" fusing point " meaning is when material slowly heats in kapillary for example, the temperature when becoming transparent liquid.

Can use the coating of any desired thickness according to the present invention.For most of purposes, coating accounts for the 1%-10% of sheet weight, preferred 1.5%-5%.

Preferred sheet of the present invention comprises one or more tackiness agents.For example, disperse in order further to promote, non-agglomerative tackiness agent can be attached in the particle, forms sheet.

If use non-agglomerative tackiness agent, suitable non-cementitious adhesive comprises synthetic organic polymer for example polyoxyethylene glycol, Polyvinylpyrolidone (PVP), polyacrylate and water-soluble polyacrylate multipolymer.Pharmaceutical excipient handbook second edition has been listed the tackiness agent of following type: Sudan Gum-arabic, alginic acid, Carbomer, Xylo-Mucine, dextrin, ethyl cellulose, gel, guar gum, hydrogenated vegetable oil Class1, Natvosol, Vltra tears, Liquid Glucose, neusilin, Star Dri 5, methylcellulose gum, polyisobutene hydrochlorate, polyvinyl pyrrolidone, sodium alginate, starch and zein.Most preferred tackiness agent also has active cleanup action in laundry, cationic polymers for example, i.e. for example five amine, the poly-ethyleneamines of ethoxylation, toxilic acid acrylate copolymer of ethoxylation hexamethylene-diamine quaternary ammonium compound, two or six ethylidene triamines or other materials.

Preferably spray non-agglomerative adhesive material, it has and is lower than 90 ℃ thus, preferably is lower than 70 ℃, even more preferably less than 50 ℃ suitable fusing point, so as not destroy or the matrix of degrading in other active constituents.Most preferred is the liquid adhesive (promptly not in the aqueous solution) of non-water, and it can the fusion form spray.But they can also be to add the solid binder that mixes in the matrix by doing, but it has bond property in sheet.

The preferred usage quantity of non-agglomerative adhesive material is the 0.1%-15% of composition, more preferably less than 5%, particularly if it is non-laundry active substance, then is lower than 2% of sheet weight.

Preferably avoid using the cementitious adhesive of liquid or fusion form, for example nonionogenic tenside.Nonionogenic tenside and other cementitious adhesives are not precluded within outside the composition, but preferably they are components as particulate material, rather than are worked in the detergent tablet as liquid.The preparation of sheet

Can comprise the clay of compacting simply with solid constituent, mix and suppress this mixture and prepare washing composition of the present invention or cleaning sheet with the conventional tabletting machine that uses in the medicine industry for example.Preferably, main component is to use with particle form.Any liquid components, for example tensio-active agent or suds suppressor can mix in the solid particulate component according to a conventional method.

Can use the ordinary method spraying drying such as washing assistant and tensio-active agent component, then with suitable pressure compacting.Preferably, sheet of the present invention is with being lower than 100000N, more preferably less than 50000N, even more preferably less than 20000N, most preferably is lower than the system of defeating of 10000N.Yet, when applying agent when being used to apply label, even can use lower power to prepare label, for example be lower than 5000N or even be lower than 3000N.

The particulate material of clay component that is used to prepare the non-compacting of sheet of the present invention can prepare by any granulating or prilling process.An example of this method is spraying drying (in following current or a Countercurrent Spray Dryer), and generally it obtains low bulk density 600g/l or lower.In high-shear batch mixer/tablets press by granulation and closely knit or (for example use Lodige by continuous granulation and densification process ^(R)CB and/or Lodige ^(R)The KM mixing machine) can prepare the particulate material of higher density.Other methods that are fit to comprise fluidized bed process, die mould method (die mould for example rolls), push and prepare any particulate matter with some chemical processes such as flocculence, crystallization etc.Each particle can also be any other particulate, particle, bead or particulate.The component of particulate material can mix with any conventional equipment, and interrupter method is suitable for for example concrete mixer, Nauta mixing machine, ribbon blender or any other equipment.In addition, this blending means can be carried out continuously, by the weight of metering each component on moving belt, and mixes them in one or more cylinders or mixing machine.Can on the mixture of some or all particulate material components, spray non-agglomerative tackiness agent.Other liquid components also can be sprayed onto on the mixture of independent or premixed component.For example, can spray spices and white dyes slip.Preferably near the ending of technology the time, spray adhesive makes mixture that low viscosity be arranged, and afterwards the flow promotor of pulverizing (separant is zeolite, carbonate, silicon-dioxide for example) is added in the particulate material.

As mentioned above, for the clay component of compacting, available any die mould rule such as compressing tablet, briquetting or extruding, preferred compressing tablet preparation contains the sheet of the clay component of compacting, such as detergent tablet.The equipment that is fit to that also can be used for preparing the clay component of the present invention's compacting comprises the single cycle of standard or rolling forming press (Courtoy for example ^(R), Korch ^(R), Manesty ^(R), or Bonals ^(R)).Prepared in accordance with the present invention preferably has diameter 20mm-60mm, and preferably at least 35 is also high to 55mm, and weight is between 25-100g.The ratio of the height of sheet and diameter (or width) was preferably greater than 1: 3, more preferably greater than 1: 2.The pressure for preparing these sheets uses surpasses 100000kN/m ², preferably be no more than 30000kN/m ², more preferably no more than 5000kN/m ², even more preferably no more than 3000kN/m ², be most preferably not exceeding 1000kN/m ²In the preferred embodiment of the invention, sheet has density and is at least 0.9g/cc, and more preferably 1.0g/cc at least preferably is lower than 2.0g/cc, more preferably less than 1.5g/cc, even more preferably less than 1.25g/cc, most preferably is lower than 1.1g/cc.

Available known technology prepares multilayer tablet.Cleaning compositions and component

Downtrodden clay component can be used in any composition or its component, to improve its dissolving or decomposition, in cleaning compositions, pharmaceutical composition, plant nutrition promotor composition or vegetalization fertilizer composition, as long as these compositions allow to mix the particulate composition.Therefore, general said composition is a solids composition, particularly particulate composition.

Highly preferred composition is cleaning compositions or its component.

Said composition can take various physical form to comprise particle, sheet, lozenge and bar, even liquid form.Liquid can be moisture or non-water base, and can be gel form.Said composition can be that pretreatment compositions maybe can be conventional washing composition.Said composition is granular detergent composition particularly, preferred so-called concentrate composition, and it is suitable for adding in the washing machine by the feeding device that is put in the washing machine drum with the dirty fabric that loads.

This granular detergent composition or its component can be passed through prepared in various methods, comprise spraying drying, do to mix, extruding, agglomeration and granulation.

Cleaning compositions of the present invention or component also have above-mentioned cleaning foil preferably to comprise, by the weight of this sheet, and 0.05%-30%, more preferably 1%-20% or even 2%-15% or even the clay of 3%-12%.

The clay composition of this compacting can be included in the detergent particles.Yet the clay of preferred this compacting is the independent grain fraction existence as composition, to help dissolving, dispersion or the distribution of composition, is particularly taking place under bonding or the agglomerative situation when contacting with water.This situation particularly takes place when composition comprises bonding component such as nonionogenic tenside.When the clay component of compacting when having preferably than volume particle size, promptly 90% weight have the 400-1100 micron or even the 500-1000 micron, it is particularly preferred that the clay component of this compacting mixes as particle separately.

When downtrodden clay component mixed in the detergent particles, obviously detergent particles had the bigger granularity of specific viscosity local soil type branch.This clay composition is specially adapted to comprise mean particle size greater than 350 microns, be preferably greater than 400 or even 500 microns or even greater than 600 or even the composition of 700 microns detergent particles in.

Herein Ding Yi term mean particle size be by with composition sample at one group of sieve, preferred Taylor (Tyler) sieve top sieve is divided into that mass part (common 5 parts) calculates.With the aperture mapping of the relative sieve of each several part weight that obtains thus, mean particle size is the aperture size that the sample of 50% weight passes through.

In preferred embodiments, said composition preferably includes (when existing as independent grain fraction, do not comprise downtrodden clay particle) its weight at least 60%, more preferably at least 80% has mean particle size 450-1400 micron, and preferred 500 or even 600 microns-1100 microns or even 700-1000 micron.Even preferred said composition comprise be lower than 20% or even be lower than 10% or even the grain fraction that is lower than 5% weight (when when grain fraction exists separately, do not comprise downtrodden clay particle) have granularity and be lower than 200 microns, or even be lower than 350 microns or even be lower than 425 microns; Also preferred said composition comprises, weight by composition, be lower than 20% or even be lower than 10% or even be lower than 5% weight particles component (when when separately grain fraction exists, do not comprise downtrodden clay particle) have granularity greater than 1700 microns, or even greater than 1400 microns or even greater than 1180 microns.

This detergent composition or its component also can comprise other decomposition agents and/or foaming source.Other components of cleaning combination and sheet

The present composition and detergent tablet contain other detergent components.The physical form that the definite character of these annexing ingredients and incorporation thereof will depend on composition or component with and the definite character of the washing operation that is used for.

The present composition preferably also has one or more other detergent components, is selected from tensio-active agent, SYNTHETIC OPTICAL WHITNER, bleaching catalyst, alkaline system, washing assistant, phosphatic washing assistant, organic polyhydroxyl compound, enzyme, suds suppressor, lime soap dispersing agent, dirt suspension and anti redeposition agent, dirt release agent, spices, whitening agent, optical white and other corrosion inhibitors.Tensio-active agent

Preferably contain one or more tensio-active agents according to composition of the present invention, these tensio-active agents are selected from anion surfactant, nonionogenic tenside, cats product, amphoterics and zwitterionics and its mixture.

Be issued to the US3 of Laughlin and Heuring on December 30th, 1975, provided the general catalogue of negatively charged ion, nonionic, both sexes and zwitterionics class and the kind of these tensio-active agents in 929,678.Other example is given in following document: " tensio-active agent and washing composition " (Surface Active Agents and Detergents) (I volume and II volume, Schwartz, Perry and Berch).The catalogue of suitable cats product was issued among the US 4,259,217 of Murphy on March 31st, 1981.

Both sexes and zwitterionics generally are to be used in combination with one or more negatively charged ion and/or nonionogenic tenside when existing.Cats product

Preferably comprise additional anion surfactant according to composition of the present invention.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.

Highly preferred surfactant system comprises sulfonate as described herein and sulfate surfactant, preferred straight or branched alkylbenzene sulfonate and alkyl ethoxy sulfate, the described cats product of preferred combination such as text.

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.The anion sulfate acid salt surfactant

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.

The particularly preferred aspect of the present invention is to adopt the mixture of preferred alkyl-sulphate and/or sulfonate and alkyl ethoxy sulfate surfactant.This mixture is disclosed among the PCT number of patent application WO 93/18124.The anion sulfoacid salt surfactant

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.The anionic carboxylic acid salt surfactant

Suitable anionic carboxylate tensio-active agent comprises alkyl ethoxy carboxylate, alkyl polyethoxye multi-carboxylate's tensio-active agent and soap (" alkyl carboxylate "), the secondary soap class of particularly as described herein some.

Suitable alkyl ethoxy carboxylate comprises having formula RO (CH ₂CH ₂O) _xCH ₂COO ^-M ⁺Those, wherein, R is C ₆-C ₁₈Alkyl, x are 0-10, and the distribution of its ethoxylate is such, by weight, x be 0 amount of substance less than 20%, M is a positively charged ion.Suitable alkyl polyethoxye multi-carboxylate tensio-active agent comprises having formula RO-(CHR ₁-CHR ₂-O)-R ₃Those, wherein R is C ₆-C ₁₈Alkyl, x is 1-25, R ₁And R ₂Be selected from hydrogen, formyloxy, amber acidic group, hydroxy succinic acid base and its mixture, R ₃Be selected from hydrogen, have replacement or unsubstituted alkyl and its mixture of 1-8 carbon atom.

Suitable soap surfactant comprises secondary soap surfactant, and it comprises the carboxyl unit that links to each other with secondary carbon(atom).Being used for the preferred secondary soap surfactant of the present invention is to be 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-ten-alkanoic 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.The basic metal sarcosinate surfactant

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.Preferred examples is the myristyl and the oleoyl methyl sarcosinate of sodium-salt form.Alkoxy-based non-ionic surface active agent

Basically any alkoxy-based non-ionic surface active agent all is 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.Nonionic alcohol alcoxylates tensio-active agent

The condensation product of Fatty Alcohol(C12-C14 and C12-C18) and 1-25 mole alkylene oxide, particularly oxyethane and/or propylene oxide is applicable to the present invention.The alkyl chain of Fatty Alcohol(C12-C14 and C12-C18) can be straight or branched, and it is uncle or secondary alcohol, comprises 6-22 carbon atom usually.Particularly preferably be the every mol of alcohol of alkyl and the condensation product of 2-10 moles of ethylene oxide with 8-20 carbon atom.The nonionic polyhydroxy fatty acid amide surfactant

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, more preferably C ₁Or C ₂Alkyl, most preferably C ₁Alkyl (being methyl); R ²Be C ₅-C ₃₁Alkyl, preferred straight chain C ₅-C ₁₉Alkyl or alkenyl, more preferably straight chain C ₉-C ₁₇Alkyl or alkenyl, most preferably straight chain C ₁₁-C ₁₇Alkyl or alkenyl, or its mixture; Z is 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.The nonionic fatty acid amide surfactant

Suitable fatty acid amide surfactant comprises those with following formula: R ⁶CON (R ⁷) ₂, R wherein ⁶For comprising 7-21, the alkyl of preferred 9-17 carbon atom, each R ⁷Be selected from hydrogen, C ₁-C ₄Alkyl, C ₁-C ₄Hydroxyalkyl and-(C ₂H ₄O) _xH, wherein x is 1-3.The nonionic alkyl polysaccharide surfactant

Be applicable to that alkyl polysaccharide of the present invention is described among the US 4565647 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) _XR 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.Amphoterics

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.

The example of suitable alkyl both sexes dicarboxylic acid is Miranol (TM) C2M Conc., by Miranol, and Inc., Dayton, NJ produces.Zwitterionics

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 and sultaine tensio-active agent are the examples that is used for zwitterionics of the present invention.

Suitable trimethyl-glycine is those compounds with following formula: R (R ') ₂N ⁺R ²COO ^-, wherein R is C ₆-C ₁₈Alkyl, each R ¹Be generally C ₁-C ₃Alkyl, R ²Be C ₁-C ₅Alkyl.Preferred trimethyl-glycine is C ₁₂-C ₁₈Dimethyl Ammonium hexanoate and C ₁₀-C ₁₈Acyl group amido propane (or ethane) dimethyl (or diethyl) trimethyl-glycine.The compound betaine tensio-active agent also is applicable to the present invention.Positive in the plane surface promoting agent

Be used for the suitable cats product of washing composition of the present invention and comprise quaternary ammonium surfactant.The preferably single C of quaternary ammonium surfactant ₆-C ₁₆Preferred 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 suitable cats product of another group that can be used for detergent composition of the present invention or its component is the cationic ester tensio-active agent.This cationic ester tensio-active agent is water dispersible preferably, is to comprise at least one ester bond (promptly-COO-) and the compound with surfactant properties of at least one positively charged ion charged group.

Suitable cationic ester tensio-active agent comprises the cholinesterase tensio-active agent, for example is disclosed in US 4228042,4239660 and 4260529.

In a kind of preferred situation, ester bond and positively charged ion charged group are spaced apart base and are separated from each other in surfactant molecule, described spacer is made up of a kind of chain, this chain comprises at least three atoms (i.e. three atom chain lengths), preferred 3-8 atom, more preferably 3-5 atom, most preferably 3 atoms.The atom that forms the spacer chain is selected from carbon, nitrogen and Sauerstoffatom and its any mixture, and condition is that any nitrogen-atoms in described chain or Sauerstoffatom only link to each other with carbon atom in the chain.Therefore, got rid of for example have-O-O-(being superoxide) ,-N-N-and-spacer of N-O-key, and comprise for example having-CH ₂-O-CH ₂-and-CH ₂-NH-CH ₂The spacer of-key.In preferred situation, the spacer chain only comprises carbon atom, and most preferably described chain is a hydrocarbyl chain.Cation mono alkoxylated amines tensio-active agent

This paper it is highly preferred that the cation mono alkoxylated amines tensio-active agent with general formula I:

R wherein ¹Be to contain about 18 carbon atoms of the 6-that has an appointment, preferred about 16 carbon atoms of 6-, the most preferably from about alkyl or the alkenyl of about 14 carbon atoms of 6-; R ²And R ³Each is the alkyl that contains about 3 carbon atoms of 1-independently, preferable methyl, most preferably R ²And R ³It all is methyl; R ⁴Be selected from hydrogen (preferably), methyl and ethyl, X ^-Provide electroneutral negatively charged ion, for example chlorine, bromine, methylsulfate, sulfate radical etc.A is an alkoxyl group, particularly oxyethyl group, propoxy-or butoxy; P is that 0-is about 30, and preferred 2-is about 15, and most preferably 2-about 8.

ApR among the preferred formula I ⁴P=1 and be hydroxyalkyl with no more than 6 carbon atoms, thus-the OH group separated with quaternary nitrogen atoms by no more than 3 carbon atoms.Particularly preferred ApR ⁴Group is-CH ₂CH ₂OH ,-CH ₂CH ₂CH ₂OH ,-CH ₂CH (CH ₃) OH and-CH (CH ₃) CH ₂OH, and-CH ₂CH ₂OH is particularly preferred.Preferred R ¹Group is a straight chained alkyl.Straight chain R with 8-14 carbon atom ¹Group is preferred.

Be used for the highly preferred cation mono alkoxylated amines of another kind of the present invention tensio-active agent and have following formula:

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.

As described, the compound of the above-mentioned type comprises wherein oxyethyl group (CH ₂CH ₂O) unit (EO) is by butoxy, isopropoxy [CH (CH ₃) CH ₂O] and [CH ₂CH (CH ₃O] unit (i-Pr) or positive propoxy unit (Pr) or EO and/or Pr and/or the unitary mixture of i-Pr displaced those.

Be used for the content of the cation mono alkoxylated amines tensio-active agent of detergent composition of the present invention, the weight by composition is preferably 0.1%-20%, more preferably 0.2%-7%, most preferably 0.3%-3.0%.Positively charged ion dialkoxy amine tensio-active agent

Positively charged ion dialkoxy amine tensio-active agent preferably has general formula I I:

R wherein ¹Be to contain about 18 carbon atoms of the 8-that has an appointment, preferred about 16 carbon atoms of 10-, the most preferably from about alkyl of about 14 carbon atoms of 10-or alkenyl part; R ²Be the alkyl that contains 1-3 carbon atom, preferable methyl; R ³And R ⁴Can change independently, they are selected from hydrogen (preferably), methyl and ethyl; X ^-Be to be enough to provide electroneutral negatively charged ion, for example chlorine, bromine, methylsulfate, sulfate radical etc.A and A ' can change independently, respectively are selected from C ₁-C ₄Alkoxyl group, particularly oxyethyl group (promptly-CH ₂CH ₂O), propoxy-, butoxy and their mixture; P is that 1-is about 30, and preferred 1-is about 4, and q is that 1-is about 30, and preferred 1-is about 4, and most preferably p and q are 1.

Be used for the highly preferred positively charged ion dialkoxy of the present invention amine tensio-active agent and have following formula: R wherein 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.About above-mentioned positively charged ion dialkoxy amine formula, in preferred compound, R ¹Be by (cocounut oil) C ₁₂-C ₁₄Moieties lipid acid obtains, R ²Be methyl, ApR ³And A ' pR ⁴All are monosubstituted ethoxies.

Be applicable to that other positively charged ion dialkoxy amine tensio-active agents of the present invention comprise the compound of following formula:

R wherein ¹Be C ₁₀-C ₁₈Alkyl, preferred C ₁₀-C ₁₄Alkyl, p are that 1-is about 3 independently, and q is that 1-is about 3, R ²Be C ₁-C ₃Alkyl, preferable methyl, X is a negatively charged ion, particularly chlorine or bromine.

Other compounds of the above-mentioned type comprise wherein oxyethyl group (CH ₂CH ₂O) unit (EO) is by butoxy (Bu), isopropoxy [CH (CH ₃) CH ₂O] and [CH ₂CH (CH ₃O] unit (i-Pr) or positive propoxy unit (Pr) or EO and/or Pr and/or the unitary mixture of i-Pr displaced those.The perhydrate SYNTHETIC OPTICAL WHITNER

Preferred other components of said composition are perhydrate SYNTHETIC OPTICAL WHITNER, peroxyboric acid metal-salt for example, percarbonic acid metal-salt, particularly sodium salt.Perborate can be monohydrate or tetrahydrate.SPC-D has corresponding to 2Na ₂CO ₃3H ₂O ₂Chemical formula, it can be purchased by crystalline solid forms.

Peroxide Potassium peroxysulfate, its sodium salt are the optional inorganic perhydrate salts of another kind that is used for detergent composition of the present invention.The organic peroxide acid bleach systems

Present composition preferable feature is the organic peroxide acid bleach systems.In a kind of embodiment preferred, bleach systems contains hydrogen peroxide cource and organic peroxide acid bleach precursor compound.Situ reaction by precursor and hydrogen peroxide cource can produce organic peroxide acid.Preferred hydrogen peroxide cource comprises inorganic hydrogen peroxide compound SYNTHETIC OPTICAL WHITNER, perborate bleach for example of the present invention.In another preferred embodiment, the ready-formed organic peroxide acid is introduced directly in the composition.Also can imagine the composition that contains with the mixture of ready-formed organic peroxide acid blended hydrogen peroxide cource and organic peroxy acid precursor.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:

In detergent composition weight, the content of peroxyacid bleach precursor compound is preferably 0.5-20%, more preferably 1-15%, most preferably 1.5-10%.

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.Leavings group

Leavings group hereinafter referred to as the L group must have enough reactivities to the hydrolysis reaction of crossing that occurs in the Best Times section (for example wash(ing)cycle).But if L is too active, this activator will be difficult to stably be used for bleaching composition.

Preferred L group is selected from following radicals or its mixture: 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.Alkyl percarboxylic acids bleach precursor

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).TAED preferably is not present in the agglomerated particle of the present invention, comprises in this particulate detergent composition but preferably be present in.

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 that acid amides replaces

The alkyl peroxy acids precursor compound that acid amides replaces is applicable to the present invention, comprises the compound of following general formula:

Wherein, R ¹For having the alkyl of 1-14 carbon atom, R ²For having the alkylidene group of 1-14 carbon atom, R ⁵For H or comprise the alkyl of 1-10 carbon atom, L can be any leavings group basically.The bleach activating immunomodulator compounds that the acid amides of the type replaces is stated in EP-A-0170386.Peroxybenzoic acid precursors

The peroxybenzoic acid precursors compound provides peroxybenzoic acid when crossing hydrolysis.Suitable O-acylations peroxybenzoic acid precursors compound comprises and replacing and unsubstituted benzoyloxy benzene sulfonate; and Sorbitol Powder, glucose and all sugar are carried out benzoylated product with benzoylation reagent; those compounds of inferior acid amide type comprise the urea that N-benzoyl succinimide, four benzoyl quadrols and N-benzoyl replace.Suitable imidazole type peroxybenzoic acid precursors comprises N-benzoyl imidazoles and N-benzoyl benzo imidazoles.The peroxybenzoic acid precursors that contains the N-acyl group that other are useful comprises N-benzoyl pyrrolidone, dibenzoyl taurine and benzoyl Pyrrolidonecarboxylic acid.The positively charged ion peroxyacid precursor

Positively charged ion peroxyacid precursor compound produces the positively charged ion peroxy acid when crossing hydrolysis.

Usually, the positively charged ion peroxyacid precursor is by with positively charged functional group such as ammonium or alkyl ammonium group, and preferred ethyl or ammonium methyl group replace the peroxy acid part of suitable peroxyacid precursor compound and form.The positively charged ion peroxyacid precursor has suitable negatively charged ion such as halogen ionic salt is present in the solid detergent composition as a kind of usually.

The peroxyacid precursor compound that this positively charged ion replaces can be the derivative of peroxybenzoic acid or its replacement, precursor compound as the aforementioned.Perhaps, the peroxyacid precursor compound can be the alkyl peroxy acids precursor of alkyl peroxycarboxylic acid precursors compound as described below or acid amides replacement.

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 US number of patent application 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.Benzoxazine organic peroxy acid precursor

What also be suitable for is benzoxazine type precursor compound, EP-A-332 for example, and 294 and EP-A-482, those described in 807 particularly have the compound of following formula: Wherein, R ₁Be H, alkyl, alkaryl, aryl or aralkyl.Prefabricated organic peroxide acid

Detergent composition of the present invention except that comprising organic peroxyacid bleach precursor compound or as an alternative also can comprise the ready-formed organic peroxide acid, and by the weight of composition, its content is 1-15% usually, more preferably 1-10% weight.

A preferred class organic peroxy acid compound is the compound with acid amides replacement of following general formula:

Wherein, R ¹Be alkyl, aryl or the alkaryl with 1-14 carbon atom, R ²Be alkylidene group, arylidene and the alkyl arylene with 1-14 carbon atom, R ⁵For H or have alkyl, aryl or the alkaryl of 1-10 carbon atom.The organic peroxy acid compound that such acid amides replaces is described among the 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.Bleaching catalyst

Said composition can contain a kind of bleaching catalyst that contains transition metal.

A kind of bleaching catalyst of suitable type is to comprise the active transition-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 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 US4, and 430,243.

The bleaching catalyst of other types comprises and is disclosed in US 5,246, the manganese basigamy compound in 621 and US5,244,594.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 in the European patent application publication No. 549272.Other are applicable to that ligand of the present invention comprises 1,5,9-trimethylammonium-1,5,9-triazododecane, 2-methyl isophthalic acid, 4,7-7-triazacyclononane, 2-methyl isophthalic acid, 4,7-7-triazacyclononane, 1,2,4,7-tetramethyl--1,4,7-7-triazacyclononane and its mixture.

Also can select to be used for bleaching catalyst of the present invention as suitable component of the present invention.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 US5,194,416, 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 US 5114606 is the water-soluble complexes of the ligand of manganese (III) and/or the non-carboxylate salt polyol that (IV) and at least has three continuous C-OH groups.Preferred ligand comprises Sorbitol Powder, iditol, galactitol, mannitol, Xylitol, arabitol, adonitol, meso-tetrahydroxybutane, meso-inositol, lactose and its mixture.

U.S. Pat 5114611 has been lectured bleaching catalyst, comprises the title complex of transition metal and non-(greatly) ring ligand, and described transition metal comprises Mn, Co, Fe or Cu.Described ligand has formula: R wherein ¹, R ², R ³And R ⁴Each can be selected from the alkyl and the aryl of H, replacement, makes each R ¹-N=C-R ²And R ³-C=N-R ⁴Formation five or six-ring.Described ring also can be substituted.B is an abutment, is selected from O, S, CR ⁵R ⁶, NR ⁷And C=O, wherein R ⁵, R ⁶And R ⁷Each can be H, alkyl or aryl, comprises replacing or unsubstituted group.Preferred ligand comprises pyridine, pyridazine, pyrimidine, pyrazine, imidazoles, pyrazoles and triazole ring.Randomly, described ring can be substituted base for example alkyl, aryl, alkoxyl group, halogen and nitro replacement.Particularly preferably be ligand 2,2 '-two pyridine amine.Preferred bleaching catalyst comprises Co, Cu, the two pyridine methane of Mn, Fe-and two pyridine amine complex.Highly preferred catalyzer comprises Co (2,2 '-two pyridine amine) Cl ₂, two (different sulfo-cyanato-) two pyridine amine cobalts (II), three pairs of pyridine amine cobalts (II) perchlorate, Co (2,2 '-two pyridine amine) ₂O ₂ClO ₄, two (2,2 '-two pyridine amine) copper (II) perchlorate, three (two-2-pyridine amine) iron (II) perchlorate and its mixture.

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 are disclosed in the following document, for example European patent application publication No. 408,131 (cobalt complex catalyzer), European patent application publication No. 384,503 and 306,089 (metal-porphyrin catalyst), US 4,728,455 (manganese/polygamy position polymerization of olefin using catalyst body catalyst), US 4,711, and 748 and European patent application publication No. 224,952 (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).

Bleaching catalyst generally is to be used for the present composition and method with catalytically effective amount." catalytically effective amount " meaning be this amount no matter under which type of contrast experiment's condition of use, all be enough to strengthen the spot on bleaching and the removal target substrates or some spots of being concerned about.This experiment condition will change according to washing plant type of using and user's custom.Some users select to use very hot water; Other users use temperature or even cold water in washing operation.Certainly, the catalytic performance of bleaching catalyst will be subjected to the influence of these Considerations, can suitably be adjusted in the amount of the bleaching catalyst that uses in the washing composition of complete formula and the bleaching composition.In actual applications, do not limited to, the present composition and method can be conditioned so that provide in wash water solution at least about per active bleaching catalyst of 1/10000000th, preferably provide about 1ppm to about 200ppm catalyzer in washing soln.In order to further specify this point, using under perborate and bleach precursor 40 ℃, the European wash conditions of pH 10, about 3 micromole's Mn catalysts are effective.Under U.S.'s condition,, may need concentration to increase 3-5 doubly in order to obtain equifinality.The water soluble detergency promoter compound

Present composition preferred package contains water-soluble washing-aid compound, and by the weight of composition, generally its content is 1-80%, preferred 10-60%, more preferably 15-40%.

Detergent composition of the present invention preferably comprises 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 and is no more than at least two carboxyls that two carbon atoms separate are opened each other, and described washing-aid compound also comprises the mixture of borate and aforementioned any compound.

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 by the weight of composition, preferably its content is 0.1%-15%, more preferably 0.5%-8%.

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.Be partly dissolved or insoluble washing-aid compound

The present composition can comprise part solubility or insoluble washing-aid compound, presses composition weight meter, and generally its content in detergent composition is 0.5-60%, preferred 5-50%, most preferably 8-40%.

The example of most of insoluble washing assistant comprises sodium silicoaluminate.

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 in addition preferred aluminosilicate zeolite.

With composition weight meter, the content of zeolite MAP is 1-80%, more preferably 15-40%.

Zeolite MAP is stated in EP 384070A (Unilever).It is defined as the ratio that the zeolite P type alkali metal aluminosilicate has silicon and aluminium and is not more than 1.33, is preferably 0.9-1.33, more preferably 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 particle diameter of zeolite MAP detergent builders is represented as 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 meant that 50 weight % particulate diameters are worth less than this.Particle diameter specifically can be measured or be measured with laser particle size analyzer as the microscope that adopts scanning electron microscope to carry out by the routine analysis technical measurement.Other determine d ₅₀The method of value is stated in EP 384070A.Heavy metal ion chelating agent

The present composition preferably comprises the heavy metal ion chelating agent as optional ingredient.So-called heavy metal ion chelating agent has been meant the component of chelating heavy metal ion effect at this paper.These components also can have calcium and magnesium sequestering power, but preferably they demonstrate the selectivity in conjunction with heavy metal ion such as iron, manganese and copper.

The content of heavy metal ion chelating agent is generally the 0.005-10% of the present composition or composition weight, preferred 0.1%-5%, more preferably 0.25-7.5%, most preferably 0.3-2%.

Be suitable for heavy metal ion chelating agent of the present invention and include organic phosphonates, as amino alkylidenyl many (alkylene phosphonic acids salt), basic metal ethane 1-hydroxyl diphosphonate and WSI 3310 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 in the above-mentioned substance, 1-diphosphonate, 1,1-hydroxyl ethane di 2 ethylhexyl phosphonic acid and 1,1-hydroxyl ethane dimethylene phosphonic acids.

Other are applicable to that heavy metal ion chelating agent 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-hydroxy propylidene diamines disuccinic acid or its any salt.

Other are applicable to that heavy metal ion chelating agent of the present invention is an iminodiacetic acid derivatives, as 2-hydroxyethyl oxalic acid or glyceryl iminodiethanoic acid, and 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 disclose the suitable sequestrant based on amino.EP-A-510,311 disclose the suitable sequestrant that is obtained by collagen, Keratin sulfate or casein.EP-A-528,859 disclose 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 (EDDC) 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.Enzyme

Another preferred ingredient that is used for the present composition is one or more additional enzymes.

Preferred additional enzymes material comprises the commercial lipase of purchasing, 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 US3519570 and 3533139 to some extent.

Those proteolytic enzyme that the preferred commercial proteolytic enzyme of purchasing 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.Press composition weight meter, the content that proteolytic enzyme can the 0.0001%-4% organized enzyme adds in the present composition.

Preferably amylase comprises, for example the α-Dian Fenmei that the special bacterial strain by bacillus licheniformis of detailed description obtains among the GB-1269839 (Novo).The preferred commercial amylase of purchasing 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.Highly preferred amylase is to be described among PCT/US 9703635 and WO 95/26397 and the WO 96/23873 those.

By the weight of composition, amylase adds in the present composition with the content of 0.0001%-2% organized enzyme.

By the weight of composition, lipolytic enzyme can 0.0001%-2%, preferably 0.001%-1%, the most preferably active lipolytic enzyme content existence of 0.001%-0.5%.

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.The lipase that is obtained by the mutation of the chemistry of these bacterial strains or genetic modification also can be used among the present invention.Preferred lipase is obtained by pseudomonas pseudoalcaligenes, and it is stated in the European patent EP-B-0218272 that authorizes.

Another preferred lipase of the present invention is 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 Novo Industri 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.Organic polyhydroxyl compound

Organic polyhydroxyl compound is the preferred annexing ingredient of the present composition, and it preferably exists as the component of any grain fraction, 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.

Press composition weight meter, the incorporation of organic polyhydroxyl compound in detergent composition of the present invention is generally 0.01-30%, preferred 0.1-15%, more preferably 0.5-10%.

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.

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.Press down foam system

When detergent composition of the present invention is mixed with the composition that is used to machine-wash, can comprise a kind of foam system that presses down, by the weight of composition, its content is 0.01-15%, preferred 0.02-10%, more preferably 0.05-3%.

Be used for the suitable foam system that presses down of the present invention and can comprise any basically known defoamer compound, comprise for example polysiloxane defoamers compound and 2-alkyl alkanol defoamer compound.

Defoamer compound is meant detergent composition solution, any compound or its mixture that for example suppress foaming or forming process that produce when particularly stirring this solution.

Being used for the particularly preferred defoamer compound of the present invention is the polysiloxane defoamers compound, and it is defined as any defoamer compound that comprises the polysiloxane component at this paper.This polysiloxane defoamers compound 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 defoamers compound is a siloxanes, particularly has the unitary polydimethylsiloxane of trimethyl silyl end-blocking.

Other suitable defoamer compound comprise monobasic aliphatic carboxylic acid and its soluble salt.These substance descriptions are in the US 2954347 of the Wayne St.John of mandate on 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 defoamer compound 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, and preferred polysiloxane defoamers compound most preferably comprises the polysiloxane defoamers compound of following combination:

(i) polydimethylsiloxane, its content accounts for the 50-99% of polysiloxane defoamers compound, preferred 75-95%; With

(ii) silicon-dioxide, its content accounts for the 1-50% of polysiloxane/silicon-dioxide defoamer compound, preferred 5-25%; 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 rake formula multipolymer (rakecopolymer), its polyoxyalkylene content is 72-78%, and the ratio of oxygen ethene and oxypropylene is 1: 0.9-1: 1.1, its content is 0.5-10%, preferred 1-10% weight; Particularly preferred the type silicone glycol rake formula multipolymer is DCO544, is purchased with trade(brand)name DCO544 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 carrier material, wherein the organic carrier 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 the organic carrier material is to have lipid acid or the alcohol that contains 12-20 carbon atom carbochain, 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.The polymeric dye transfer inhibitor

The present composition also can comprise 0.01-10%, the polymeric dye transfer inhibitor of preferred 0.05-0.5% weight.

The polymeric dye transfer inhibitor is preferably selected from multipolymer, polyvinylpyrrolidonepolymers polymers or its mixture of polyamine N-oxide pllymers, N-vinyl pyrrolidone and N-vinyl imidazole, so these polymkeric substance can be cross-linked polymers.White dyes

The present composition also can randomly contain the hydrophilic white dyes of some type of have an appointment 0.005% to 5% (weight).

Can be used for hydrophilic white dyes of the present invention and have the 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 can be bought from Ciba-Geigy company according to trade(brand)name Tinopal 5BM-GX in commerce.

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 can be bought from Ciba-Geigy company is commercial according to trade(brand)name Tinopal-DMS-X and Tinopal AMS-GX.The polymerization dirt release agent

Can randomly use the polymerization dirt release agent in the present composition, hereinafter referred is " SRA ".If you are using, SRA ' s generally accounts for 0.01% to 10.0% of composition weight, is typically 0.1% to 5%, and preferred 0.2% to 3.0%.

The hydrophobic part that preferred SRA ' s generally has the hydrophilic segment that makes hydrophobic fiber such as polyester and nylon surface hydrophilic and 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 SRA.

Preferred SRA ' s comprises the terephthalate of oligomerisation, and it generally by comprising the method preparation of at least a transesterify/oligomerisation reaction, 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.

SRA ' the s 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/oligomerizations, 2-propylene glycol (" PG ") reacts; (C) in water with the product of (b) and sodium metabisulfite reaction.Other SRA ' s 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 transesterify/oligomerisation preparation of PG and poly-(ethylene glycol) (" PEG ").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 oligomerisation 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 SRA ' s in laundry and fabric-conditioning product; one example be by-sulfosalicylic acid list sodium salt, the ester composition of PG and DMT preparation, but randomly preferably also contain the PEG of adding; for example, PEG3400.

SRA ' s 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 2.3 for about 1.6-that its each anhydroglucose unit has average substitution degree (methyl), the aqueous solution by 2% 20 ℃ down the soltion viscosities of mensuration be about 120 centipoises of about 80-.This material can be buied by METOLOSESM100 and METOLOSE SM200, and they are the trade(brand)names by the methyl cellulose ether of Shin-etsu Kagaku Kogyo KK production.

Another kind of SRA ' s comprises: (I) use vulcabond coupler and polyester construction banded nonionic terephthalate, referring to people's such as people's such as Violland U.S. Pat 4201824 and Lagasse U.S. Pat 4240918; (II) have the SRA ' s of carboxylicesters end group, it becomes the trimellitate preparation by trimellitic acid 1,2-anhydride being added among the known SRA ' s to transform terminal hydroxy group.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 SRA ' s can be used as starting raw material, as long as have can esterified hydroxyl end groups for they, referring to people's such as Tung U.S. Pat 4525524.Other types comprise: (III) link the SRA ' s based on the negatively charged ion terephthalate of urethanes, referring to people's such as Violland U.S. Pat 4201824.Other optional ingredients

Be fit to be included in other optional ingredients in the present composition and comprise and spraying and spices, pigment and the filling salt of capsule form that sodium sulfate is preferred filling salt.

That uses among the embodiment writes a Chinese character in simplified form

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

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

TAS: tallow alkyl sodium sulfate

CxyAS: C _1x-C _1ySodium alkyl sulfate C46SAS: C ₁₄-C ₁₆Secondary (2,3) sodium alkyl sulfate CxyEzS: with the C of Z moles of ethylene oxide condensation _1x-C _1ySodium alkyl sulfate CxyEz: with the 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 ₁₄QAS1: R ₂N ⁺(CH ₃) ₂(C ₂H ₄OH), R ₂=C ₈-C ₁₁SADS: formula 2-(R) C ₄H ₇-1,4-(SO ₄-) ₂C ₁₄-C ₂₂Alkyl two sulphur

Acid sodium, wherein R=C ₁₀-C ₁₈MBAS: the average degree of branching is the C of 1.5 methyl or ethyl branch ₁₂-C ₁₈

The alkyl sulfate surfactant MES of medium branching: C ₁₈The x-sulfo methyl ester APA of lipid acid: C ₈-C ₁₀Amido propyl-dimethyl amine soap: straight-chain alkyl carboxylic acid's sodium, by 80/20 of butter and coconut fatty acid

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 ₁₆-C ₁₈Top full cut lipid acid STPP: anhydrous sodium tripolyphosphate TSPP: tetrasodium pyrophosphate zeolite A: formula Na ₁₂(AlO ₂SiO ₂) ₁₂27H ₂The hydrated sodium aluminosilicate of O, just

The level granularity is 0.1-10 micron (weight of representing by moisture-free basis) NaSKS-6: formula δ-NaSi ₂O ₅The crystalline layered silicate citric acid: Citric Acid, usp, Anhydrous Powder borate: Sodium Tetraborate carbonate: granularity is a 200-900 micron anhydrous sodium carbonate supercarbonate: size-grade distribution is at the anhydrous sodium bicarbonate silicate of 400-1200 micron: 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%, size-grade distribution

At 425-850 micron MA/AA: 1: 4 toxilic acid/acrylic copolymer, the about 70000MA/AA of molecular-weight average (1): 4: 6 toxilic acid/acrylic copolymer, the about 10000AA of molecular-weight average: the polyacrylic acid sodium polymer CMC of molecular-weight average 4500: the plain ether of sodium carboxyme-thylcellulose fibre: the polymerization degree is 650 methyl cellulose ether, by Shin Etsu

Chemicals buys enzyme: 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 WO 95/10591 has 4%

The weight organized enzyme, sell Alcalase by Genencor Int.Inc.: by the proteolytic ferment of NOVO Industries A/S sale,

Have 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 amylase II: disclosed amylase lipase in PCT/US9703635: by NOVO Industries A/S with trade(brand)name Lipolase

The lipolytic enzyme of selling has 2.0% weight organized enzyme restriction endonuclease: endoglucanase (Endoglucanase), sell by Novo (Endolase) Industries A/S, and have 1.5% weight organized enzyme PB4: standard type NaBO ₂.3H ₂O.H ₂O ₂Sodium perborate tetrahydrate PB1: standard type NaBO ₂.H ₂O ₂Anhydrous sodium perborate SYNTHETIC OPTICAL WHITNER SPC-D: standard type 2NaCO ₃3H ₂O ₂SPC-D DOBS: the last of the ten Heavenly stems acyloxy benzene sulfonate, sodium-salt form DPDA: diperoxy dodecanedioic acid NOBS: nonanoly acyloxy benzene sulfonate, sodium-salt form randomly comprises branch

Separate agent NACA-OBS: (6-nonanoyl caproyl) oxygen benzene sulfonate randomly comprises branch

Separate agent LOBS: 12 carbon acyloxy benzene sulfonate DOBS of sodium-salt form: the acyloxy benzene sulfonate DOBA in the last of the ten Heavenly stems of sodium-salt form: caprinoyl aminobenzoic acid TAED: tetraacetyl ethylene diamine DTPA: diethylene triaminepentaacetic acid(DTPA) DTPMP: diethylenetriamine five (methylene phosphonic acid), by Meng Shan all with merchant

Name of an article Dequest 2060 sells EDDS: quadrol-N, N '-disuccinic acid, (S, S) isomer, sodium

Salt form 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 HEDP amino): hydroxyl ethane 1,1-di 2 ethylhexyl phosphonic acid PEGx: polyoxyethylene glycol, molecular weight is x (general 4000) PEO: polyoxyethylene, molecular-weight average 50000TEPAE: ethoxylation tetren PVI: polyvinyl imidazol, molecular-weight average 20000PVP: polyvinylpyrrolidonepolymers polymers, molecular-weight average 60000PVNO: polyvinylpyridine N-oxide compound, molecular-weight average 50000PVPVI: the multipolymer of Polyvinylpyrolidone (PVP) and vinyl imidazole is flat

Average molecular weight 20000QEA: two ((C ₂H ₅O)-(C ₂H ₄O) _n) (CH ₃)-N ⁺-C ₆H ₁₂-N ⁺-(CH ₃)

Two ((C ₂H ₅O)-(C ₂H ₄O)) _n, wherein the n=20-30 clay 1: with the polynite of 20MPa pressure compacting, 90% has granularity 400

-100 microns clays 2 of micron: with the wilkinite of 20MPa pressure compacting, 90% has granularity 400

-100 microns clays 3 of micron: according to any clay SRP1 of embodiment 1: the end capped polyester SRP2 of negatively charged ion: the short block of diethoxyization poly-(phthalic acid 1,2 inferior propyl ester)

Copolymer fibre element: Mierocrystalline cellulose such as Solka-floc or Arbocel or micro-crystallization

Mierocrystalline cellulose such as LatticePEI available from FMC: polyethylene imine based, molecular-weight average 1800, each nitrogen-atoms

Average degree of ethoxylation is that 7 oxygen ethene residue polysiloxane disappear: the polydimethylsiloxane foam control agent with as the poly-silica infusion alkane-oxyalkylene copolymers of dispersion agent, described foam control agent and described dispersion agent

Weight ratio is 10: 1-100: 1 opalizer: water base single styrene latex mixture, and by BASF

Aktiengesellschaft sells wax with trade(brand)name Lytron 621: the paraffin optical white: comprising weight ratio is 1: 80-1: 120 Phthalocyanine Zinc or aluminium peace

The Polyvinylpyrolidone (PVP) of average molecular weight 30000-50000

Reagent, it is sealed with starch and sugar derivatives

Embodiment 1

With 20 gram clays, for example wilkinite or polynite, its particle of 90% has granularity and is lower than 110 microns, puts into the mould with diameter 5.4cm and apply 45kN power with Lloyd 50K tabletting machine this clay compacting is prepared the clay component of compacting into about the sheet of 10cm thickness.Divide several partial crushings with the sheet that obtains, each several part is added in Combimax 700 food-processor, grind the clay component that forms granular compacting thus.Sieving the utmost point that these particles obtain divides its 95% weight to have the granularity of 500-1000 micron.

Repeat same method, but apply 25kN power then.

Repeat same method, two kinds of situations when using 25kN and 45kN power, but suppress agglomeration wilkinite or the polynite that also comprises 10% weight paraffin agglomerate and 5% weight wetting Agent for Printing Inks agglomerate then.Embodiment 2 detergent tablets:

	Embodiment A	Embodiment B	Embodiment C	Embodiment D	Embodiment E	Embodiment F
							??％	??％	??％	??％	??％	??％
	Clay 3	??8.0	??10.0	??14.5	??11.0	??15.0							??4.0
Flocculation agent agglomerate (PEO, zeolite, MA/AA, water)							??2.0	??1.5	??5.8	??3.0	?? ??-	??-
	The negatively charged ion agglomerate	??38	??24	??38	??24	??38							??24
The positively charged ion agglomerate							??5.0	??5.0	??5.0	??5.0	??5.0	??5.0
	SPC-D	??8	??8	??8	??8	??8							??8
The bleach-activating agent agglomerate							??2.31	??2.31	??2.31	??2.31	??2.31	??2.31
	Yellow soda ash	??2.67	??45.33	??17.00	??31.00	??10.86							??37.14
The EDDS/ sulphate particle							??0.19	??0.19	??0.19	??0.19	??0.19	??0.19
	Hydroxyl ethane di 2 ethylhexyl phosphonic acid tetra-na salt	??0.34	??0.34	??0.34	??0.34	??0.34							??0.34
Fluorescent agent							??0.15	??0.15	??0.15	??0.15	??0.15	??0.15
	Phthalocyanine sulfonic acid zinc encapsulation object	??0.027	??0.027	??0.027	??0.027	??0.027							??0.027

Soap powder	??1.40	??1.40	??1.40	??1.40	??1.40	??1.40
							Suds suppressor	??2.6	??2.6	??2.6	??2.6	??2.6	??2.6
Mierocrystalline cellulose	??3.0	??2.0	??1.5	??-	??-	??3.0
							Citric acid	??4.0	??4.0	??4.0	??4.0	??4.0	??4.0
Proteolytic enzyme	??0.45	??0.45	??0.45	??0.45	??0.45	??0.45
							Sodium acetate	??0.3	??0.5	??2.0	??-	??3.0	??-
Cellulase	??1.0	??0.20	??0.30	??0.50	??0.50	??1.20
							Amylase	??0.20	??0.20	??0.20	??0.20	??0.20	??0.20
Tackiness agent
							Cationic polymers	??0.75	??0.75	??0.75	??0.75	??0.75	??0.75
PEG?4000	??1.25	??1.25	??1.25	??1.25	??1.25	??1.25

Negatively charged ion agglomerate 1 comprises 40% anion surfactant, 27% zeolite and 33% carbonate.

Negatively charged ion agglomerate 2 comprises 40% anion surfactant, 28% zeolite and 32% carbonate.

The positively charged ion agglomerate comprises 20% cats product, 56% zeolite and 24% vitriol.

The bleach-activating agent agglomerate comprises 81%TAED, 17% vinylformic acid/maleic acid (sour form) and 2% water.

Quadrol N, N-disuccinic acid sodium salt/sulphate particle comprises 58% quadrol N, N-disuccinic acid sodium salt, 23% vitriol and 19% water.

Phthalocyanine sulfonic acid zinc encapsulation object is 10% active.

Suds suppressor comprises 11.5% polysiloxane oil, 59% zeolite and 29.5% water.Embodiment 3 is according to granular detergent composition of the present invention:

	???G	????H	????I	????J	????K	????L
							Agglomerate
????LAS	???7.0	????5.0	????10.0	????14.0	????2.0	????-
							????C245AS	???3.0	????2.0	????2.0	????2.0	????2.5	????2.5
Clay 3	???10.0	????5.0	????-	????-	????-	????-
							????C45AE3S	???1.0	????1.0	????1.0	????-	????-	????0.5
????C28AS	???2.0	????1.0	????2.0	????1.0	????0.5	????3.5
							Silicate	???0.2	????-	????1.0	????-	????0.3	????0.8
Yellow soda ash	???6.0	????3.0	????8.0	????-	????3.0	????3.0
							????MBAS	???-	????2.0	????-	????-	????5.0	????8.0
????SKS-6	???0.7	????4.0	????-	????0.5	????1.0	????2.0
							????HEDP/EDDS	???0.1	????0.7	????0.3	????-	????-	????0.5
Zeolite A	???10.0	????6.0	????6.0	????12.0	????9.0	????10.0
							????CMC	???0.5	????-	????0.3	????0.8	????-	????0.5
Agglomerate
							????TAED	???5.0	????3.0	????-	????2.0	????4.0	????3.0
CMC or MA/AA	???1.0	????0.5	????-	????0.5	????1.0	????1.0
							Clay 3	???-		????-	????-	????-	????2.0
Agglomerate
							Zeolite A	???2.0	????1.0	????-	????1.0	????-	????2.0
Suds suppressor	???0.5	????0.5	????0.3	????0.2	????0.1	????0.2
							????MA/AA	???0.5	????-	????-	????0.2	????-	????0.2
Agglomerate
							????QAS	???1.0	????0.5	????1.0	????-	????1.0	????-

Zeolite	????2.0	????1.0	????-	????-	????2.0	????-
							Carbonate	????0.5	????1.0	????-	????-	????-	????-
????MA/AA	????-	????0.1	????-	????-	????-	????-
							????PEO	????5.0	????-		????1.5	????3.0	????2.0
Clay 3	????-	????-	????-	????10.0	????4.0	????5.0
							Dried additive
????QEA	????1.0	????0.5	????-	????-	????1.0	????-
							Clay 3	????5.0	????2.0	????12.0	????10.0	????8.0	????2.0
????HEDP/DTPA/EDDS	????0.3	????0.5	????-	????0.5	????0.5	????0.5
							????MA/AA	????1.0	????2.0	????3.0	????-	????2.0	????2.0
Sal epsom	????0.1	????0.2	????-	????-	????-	????0.3
							Whitening agent	????0.1	????-	????0.2	????0.2	????-	????0.2
Zeolite	????1.0	????2.0	????3.0	????4.0	????5.0	????2.0
							SKS-6/ silicate	????10.0	????6.0	????5.0	????10.0	????10.0	????12.0
Enzyme	????0.5	????0.8	????0.3	????1.2	????1.2	????1.0
							????CMC	????0.2	????-	????0.3	????-	????0.5	????0.5
Soap	????0.5	????-	????-	????0.5	????1.0	????-
							????NACAOBS	????-	????3.0	????-	????-	????-	????3.0
Optical white	????0.1	????0.1	????0.5	????-	????0.2	????-
							Spot jewelry	????0.5	????0.2	????0.7	????-	????0.3	????-
Carbonate	????6.0	????5.0	????2.0	????-	????8.0	????7.0
							Sodium-chlor	????0.2	????-	????0.5	????-	????0.5	????-
Sodium sulfate	????2.0	????3.0	????-	????8.0	????-	????3.0
							Percarbonate	????18.0	????10.0	????-	????22.0	????20.0	????10.0
Citric acid	????1.0	????0.5	????2.0	????3.0	????2.0	????-
							Spray
????AE5	????-	????0.5	????-	????-	????2.0	?????-
							Spices	????0.2	????0.1	????0.5	????0.2	????0.2	????0.2
Whitening agent	????0.1	????0.2	????0.1	????0.1	????0.1	????0.1
							Optical white	????-	????-	????-	????-	????-	????0.01

Embodiment 4 is according to granular detergent composition of the present invention:

	????M	????N	????O	????P	????Q	????R
							Spray-dired powder
Base-material: LAS	????7.0	????6.0	????3.0	????-	????4.0	????-
							???MBAS	????-	????-	????-	????5.0	????-	????-
???SADS	????-	????-	????-	????-	????3.0	????-
							Tallow alkyl vitriol	????1.0	????-	????1.0	????1.0	????-	????1.0
???C245AS	????-	????-	????0.5	????-	????-	????1.0
							Sodium sulfate	????3.0	????5.0	????3.0	????2.0	????-	????3.0
???C24AE35	????-	????0.5	????-	????0.5	????-	????0.7
							Clay 1 or 2	????10.0	????-	????-	????-	????-	????-
???PEO	????0.5	????1.5	????3.0	????4.0	????5.0	????2.0
							Yellow soda ash	????3.0	????6.0	????1.0	????3.0	????5.0	????3.0
Sodium sulfate	????-	????1.0	????2.0	????2.0	????-	????5.0
							Zeolite A	????16.0	????10.0	????5.0	????10.0	????6.0	????-
???MA/AA	????1.0	????-	????1.0	????0.5	????1.0	????-
							Sal epsom	????0.1	????0.1	????-	????0.1	????-	????0.1
Whitening agent	????0.2	????0.1	????-	????-	????0.3	????0.5
							Sequestrant	????0.5	????0.5	????-	????0.3	????0.2	????0.4
Water	????0.2	????0.1	????0.1	????0.05	????0.05	????0.3
							Agglomerate
???LAS	????-	????3.0	????5.0	????2.0	????-	????5.0
							???C45AS	????-	????2.0	????3.0	????2.0	????-	????-
Carbonate	????-	????5.0	????7.0	????5.0	????-	????-
							Vitriol	????-	????3.0	????-	????2.0	????-	????3.0
Zeolite A	????-	????4.0	????8.0	????3.0	????-	????9.0
							Optical white	????-	????0.05	????0.05		????-	????-
Dried additive

????QEA	????1.0	????1.0	????1.0	????-	????1.0	????-
							Suds suppressor	????0.5	????0.5	????0.5	????1.0	????0.2	????0.3
Percarbonate/perborate	????20.0	????14.0	????-	????22.0	????18.0	????10.0
							????TAED	????4.0	????3.0	????-	????-	????2.0	????3.5
????NACA?OBS	????-	????3.0	????-	????4.2	????2.5	????-
							Zeolite A	????6.0	????3.0	????5.0	????-	????7.0	????12.0
SKS-6/ silicate	????8.0	????12.0	????5.0	????9.0	????-	????8.0
							Citric acid/citrate	????2.0	????1.0	????3.0	????-	????-	????2.0
Spot jewelry (carbonate)	????0.3	????0.5	????0.4	????-	????-	????0.5
							Yellow soda ash	????5.0	????-	????8.0	????10.0	????-	????6.0
Sodium sulfate	????10.0	????5.0	????-	????3.0	????-	????14.0
							Clay 2 or 3	????-	????15.0	????12.0	????4.0	????6.0	????10.0
Soap	????0.5	????0.5	????-	????-	????0.5	????-
							Enzyme	????1.0	????1.5	????1.0	????1.0	????1.0	????1.0
????SRP	????0.1	????0.2	????0.3	????-	????0.3	????-
							????HEDP/EDDS/DTPA	????0.5	????0.5	????-	????0.2	????0.8	????0.3
Spray
							????AE5	????-	????3.0	????1.5	????-	????-	????-
Spices	????0.3	????0.3	????0.2	????0.5	????0.2	????0.3

Embodiment 5

	????S	????T	????U	????V	????W	????X
							The powder of blowing
??LAS	????23.0	????8.0	????7.0	????9.0	????7.0	????7.0
							??TAS	????-	????-	????-	????-	????1.0	????-
??C45AS	????6.0	????6.0	????5.0	????8.0	????-	????-
							??C45AE35	????-	????1.0	????1.0	????1.0	????-	????-
??C45E35	????-	????-	????-	????-	????2.0	????4.0
							??SADS	????0.5	????-	????-	????-	????-	????-
Zeolite A	????10.0	????18.0	????14.0	????12.0	????10.0	????14.0
							??MA/AA	????-	????0.5	????-	????-	????-	????2.0
??MA/AA(1)	????7.0	????-	????-	????-	????-	????-
							Clay 1 or 3	????-	????-	????6.0	????10.0	????-	????-
Vitriol	????5.06.3	????6.3	????14.3	????11.0	????15.0	????19.3
							Silicate	????10.0	????1.0	????1.0	????1.0	????1.0	????1.0
Carbonate	????15.0	????20.0	????10.0	????20.7	????8.0	????6.0
							??PEG4000	????0.4	????1.5	????1.5	????1.0	????1.0	????1.0
??DTPA	????-	????0.9	????0.5	????-	????-	????0.5
							Optical white 2	????-	????0.05	????0.005	????-	????0.3	????0.5
Whitening agent 2	????0.3	????0.2	????0.3	????-	????0.1	????0.3
							Spray
??C45E7	????-	????2.0	????-	????-	????2.0	????2.0
							??C25E9	????3.0	????-	????-	????-	????-	????-
??C23E9	????-	????-	????1.5	????2.0	????-	????2.0
							Spices	????0.3	????0.3	????0.3	????2.0	????0.3	????0.3
Agglomerate
							??C45AS	????-	????5.0	????5.0	????2.0	????-	????5.0
??LAS	????-	????2.0	????2.0	????-	????-	????2.0
							??PEO	????-	????3.0	????3.0	????2.0	????-	????1.0

Clay 3		????3.0	????-	????7.0	????-	????5.0
							Zeolite A	????-	????7.5	????7.5	????8.0	????-	????7.5
Carbonate	????-	????4.0	????4.0	????5.0	????-	????4.0
							????PEG4000	????-	????0.5	????0.5	????-	????-	????0.5
Other (water etc.)	????-	????2.0	????2.0	????2.0	????-	????2.0
							Dried additive
????QAS(1)	????-	????-	????-	????-	????1.0	????-
							Clay 2 or 3	????3.0	????-	????6.0	????-	????11.0	????6.0
Citric acid/oxysuccinic acid	????-	????-	????5.0	????3.0	????2.0	????5.0
							????PB4	????-	????-	????-	????-	????12.0	????1.0
????PB1	????-	????4.0	????3.0	????-	????-	????-
							Percarbonate	????4.0	????-	????-	????2.0	????-	????10.0
Carbonate	????-	????5.3	????1.8	????-	????4.0	????4.0
							????NOBS	????4.0	????-	????6.0	????-	????-	????0.6
Methylcellulose gum	????0.2	????-	????-	????-	????-	????-
							????SKS-6	????8.0	????-	????-	????-	????-	????-
????STS	????-	????-	????2.0	????-	????1.0	????-
							Isopropyl benzene sulfonic acid	????-	????1.0	????-	????-	????-	????2.0
Optical white	????0.01	????-	????-	????0.1	????0.1	????-
							Lipase	????0.2	????-	????0.2	????-	????0.2	????0.4
Cellulase	????0.2	????0.2	????0.2	????0.3	????0.2	????0.2
							Amylase	????0.2	????-	????0.1	????-	????0.2	????-
Proteolytic enzyme	????0.5	????0.5	????0.5	????0.3	????0.5	????0.5
							????PVPI	????-	????-	????-	????-	????0.5	????0.1
????PVP	????-	????-	????-	????-	????0.5	????-
							????PVNO	????-	????-	????0.5	????0.3	????-	????-
????QEA	????-	????-	????-	????-	????1.0	????-
							????SRP1	????0.2	????0.5	????0.3	????-	????0.2	????-
Polysiloxane defoamers	????0.2	????0.4	????0.2	????0.4	????0.1	????-
							Sal epsom	????-	????-	????0..2	????-	????0.2	????-

Silicon-dioxide	????0.2	????0.2	????0.2	?-	????0.2	?-
							Other/subsidiary to 100%

Embodiment 6

Preparation is following according to the detergent formulations that does not contain SYNTHETIC OPTICAL WHITNER that is used in particular for washing colored clothes of the present invention:

	????Y	????Z	????AA
				The powder of blowing
Zeolite A	????15.0	????15.0	????-
				Vitriol	????0.0	????5.0	????-
??LAS	????3.0	????3.0	????-
				??DTPMP	????0.4	????0.5	????-
??CMC	????0.4	????0.4	????-
				??MA/AA	????4.0	????4.0	????-
Agglomerate
				??C45AS	????-	????-	????11.0
??LAS	????6.0	????5.0	????-
				??TAS	????3.0	????2.0	????-
Silicate	????4.0	????4.0	????-
				??PEO	????2.0	????1.0	????1.5
Zeolite A	????10.0	????15.0	????13.0
				??CMC	????-	????-	????0.5
??MA/AA	????-	????-	????2.0
				Carbonate	????9.0	????7.0	????7.0
Optical white 2	????-	????0.005	????-
				Spray
??EFAA	????-	????2.0	????-
				Spices	????0.3	????0.3	????0.5
??C25E3	????2.0	????2.0	????2.0
				Dried additive
??MA/AA	????-	????-	????3.0

??NaSKS-6	????-	????-	????12.0
				Citrate trianion	????10.0	????-	????8.0
Supercarbonate	????7.0	????3.0	????5.0
				Carbonate	????8.0	????5.0	????7.0
??PVPVI/PVNO	????0.5	????0.5	????0.5
				??Alcalase	????0.5	????0.3	????0.9
Lipase	????0.4	????0.4	????0.4
				Clay 3	????11.0	????7.0	????10.0
Amylase	????0.6	????0.6	????0.6
				Cellulase	????0.6	????0.6	????0.6
Polysiloxane defoamers	????5.0	????5.0	????5.0
				Vitriol	????0.0	????9.0	????0.0
Other/subsidiary to 100%	????100.0	????100.0	????100.0
				Density (g/ liter)	????700	????700	????700

Embodiment is the composition according to of the present invention or granular preparation form below 7.

	??BB	??CC	??DD	??EE	??FF	??GG	??HH	??II	???JJ	??KK	??LL
												??C 11-C 13Sodium alkyl benzene sulfonate	??12.0	??16.0	??23.0	??19.0	??18.0	??20.0	??16.0	??8.5	???5	??20.0	??6.0
??C 14-C 15Alcohol sodium sulfate		??4.5	??-		??-	???-	??4.0		???-	???-	???-
												??C 14-C 15Alcohol ethoxylate (0.5) vitriol			??-	??-	??-	???-	???-	??-	???-	???-	???-
??C 14-C 15Alcohol ethoxylate (3) vitriol	??-	??-	??2.0	??-	??1.0	??1.0	???1.0	??-	???-	???-	???-
												??C 14-C 15Alcohol ethoxy sodium (or mixture of different ethoxylation degrees)	??2.0	??2.0	???-	??1.3	??-	??-	???5.0	??5.5	???4.0	???-	???-

?C 9-C 14The alkyl dimethyl ethoxyl quaternary ammonium salt			????-	???-	???1.0	???0.5	??2.0	???-	???-	???-	???-
												Tallow fatty acid			????-	???-	???-	???-	??1.0	???-	??-	???-	???-
Tallow alcohol ethoxylate (50)	???-	??-	????-	???-	???-	???-	??-	???-	??-	???-	???-
												Tripoly phosphate sodium STPP/zeolite	???23.0	??25.0	????14.0	???22.0	???20.0	??10.0	??20.0	???30.0	???20.0	???25.0	???25.0
Yellow soda ash	???25.0	??22.0	????35.0	???20.0	???28.0	??41.0	??30.0	???30.0	???25.0	???45.0	???24.0
												Sodium polyacrylate (45%)	???0.5	??0.5	????0.5	???0.5	???-	??-	??-	???-	???-	???-	???-
Polyacrylic acid/sodium maleate polymkeric substance	???-	??-	???1.0	???1.0	???1.0	??2.0	??0.5	???0.5	???1.0	???-	???-
												Water glass (1: 6 ratio NaO/SiO 2)(4 ?6％)	???3.0	??6.0	???9.0	???8.0	???9.0	??6.0	??8.0	??5.0	???6.0	???8.0	???5.0

Sodium sulfate	???-	???-	???-	???-	???-	???2.0	??3.0	???-	???-	???-	??8.0
												Sodium peroxoborate/SPC-D	???5.0	???5.0	???10.0	???-	???3.0	???1.0	??-	???20.0	???14.0	???-	??-
Poly-(ethylene glycol), MW～4000 (50%)	???1.5	???1.5	???1.0	???1.0	???-	????-	??0.5	???-	???-	???-	??0.5
												Xylo-Mucine	???1.0	???1.0	???1.0	???-	???0.5	????0.5	??0.5	???0.5	???0.5	???-	??0.5
Citric acid	???-	???-	???-	???-	???-	????-	??-	???-	???-	???-	??-
												??NOBS/ ??DOBS	???-	???1.0	???-	???-	???1.0	????0.7	??-	???-	???-	???-	??-
??TAED/PAP	???1.5	???1.0	???2.5	???-	???3.0	????0.7	??-	???4.5	???5.0	???-	??-
												Sequestrant	???0.5	???0.5	???0.5	???-	???1.0	????-	??-	???0.5	???0.5	???-	??-
??SRP	???1.5	???1.5	???1.0	???1.0	???-	????1.0	??-	???1.0	???1.0	???-	??-
												Clay 3	???5.0	???6.0	???12.0	???7.0	???10.0	????4.0	??3.0	???7.0	???10.0	???6.0	??8.0
Flocculation agent PEO	???0.2	???0.2	???3.0	???2.0	???0.1	????1.0	??0.5	???2.0	???0.5	???1.0	??0.5
												Wetting Agent for Printing Inks	???-	???-	????-	???-	???0.5	????0.5	??-	???-	???0.5	???-	??-
Wax	???0.5	???-	????-	???-	???-	????0.5	??-	???-	???0.5	???-	??-
												Mierocrystalline cellulose	???0.5	???2.0	????-	???-	???3.0	????2.0	??-	???-	???1.5	???-	??1.0
Sodium acetate	???2.0	???1.0	???3.0	???-	???-	????-	??-	???1.0	???0.5	???4.0	??1.0
												Moisture content	???7.5	???7.5	???6.0	???7.0	???5.0	???3.0	??5.0	???5.0	???5.0	???8.0	??10.0
Sal epsom	???-	???-	???-	???-	???-	???0.5	??1.5	???-	???-	???-	??-

Soap/suds suppressor	???-	???-	?????0.5	???0.5	???0.8	???0.6	???1.0	??1.0	???0.8	???0.5/ ???0.0	???1.0/ ???0.0
												Enzyme, comprise amylase, cellulase, proteolytic enzyme and lipase	???-	???-	?????-	???-	???2.0	???1.5	???2.0	??0.5	???1.0	???1.0	???1.0
Spot jewelry	???2.5	???1.1	???0.5	???1.4	???-	???-	???2.2	???1.0	???1.6	???1.0
												Subsidiary, spices for example, PVP, PVPVI/PVN O, whitening agent, optical white	???2.0	???1.0	???1.0	???1.0	???2.5	???1.5	???1.0	???1.0	???0.5	???0.5	???0.5

Claims (15)

1. a cleaning compositions or its component, it comprises a kind of downtrodden clay component.

2. sheet, it comprises a kind of active ingredient and a kind of downtrodden clay component.

3. according to sheet, composition or the component of claim 1 or 2, it is obtained by following method: the compacting clay material forms the clay component of compacting, and the clay component that will suppress mixes in sheet, cleaning compositions or the component then.

4. require each described, composition or component according to aforesaid right, wherein defeat the system clay material and obtain clay component with 10MPa at least.

5. require each described, composition or component according to aforesaid right, wherein downtrodden clay component is a particulate state, and its at least 90% weight has granularity 200-1500 micron.

6. require each described, composition or component according to aforesaid right, wherein clay component comprises adhesive material.

7. according to each described of claim 1-5, composition or component, wherein clay component does not contain the non-aqueous adhesive material of any interpolation.

8. require each described, composition or component according to aforesaid right, its medium clay soil comprises terre verte.

9. require each described, composition or component according to aforesaid right, it comprises one or more other disintegrating agents, preferred water-soluble salt such as sodium acetate and/or avicel cellulose.

10. require each described or composition according to aforesaid right, it is solid laundry or wash up sheet or composition, and by the weight of said composition or sheet, it comprises the downtrodden clay component of 0.5%-30% weight.

11. according to each described of claim 1-9, it is a kind of tablet.

12. a downtrodden clay particle, it comprises clay material and foaming system, and this foaming system comprises acid source and carbonate source, and/or disintegrating agent, is preferably selected from material, avicel cellulose and/or the water-soluble salt of water-swellable.

13. a pharmaceutical composition, plant nutrition composition or vegetalization fertilizer composition, it comprises a kind of downtrodden clay component.

14. a closely knit clay component is used to improve the purposes of the dissolving or the disintegration of said composition or sheet in granular composition or sheet, particularly cleaning compositions or sheet plant nutrition composition or sheet, vegetalization fertilizer composition or sheet or pharmaceutical composition or sheet.

15. cleaning compositions according to Claim 8 or sheet are used for providing the softish purposes to the fabric of handling with said composition or sheet.