CN1157470C - Foaming system and its detergent composition - Google Patents

Abstract

The present invention relates to a foam controlling system which is especially suitable for being used in a detergent composition. The present invention contains a foaming component capable of providing foam without agitation and a foam suppressing component of delayed release. The preferable foam suppressing component of delayed release is incorporated in a carrier in a releasable way, and thereby, the release of the foam suppressing agent is delayed. The present invention also discloses a detergent composition containing the foam controlling system.

Description

Foaming system and detergent composition thereof

Invention field

The present invention relates to be used for the new foaming system of detergent composition.More particularly, the present invention relates to be used for the granular detergent composition of new foaming component of containing of cleaning fabric.

Background of invention

Various application for example all wish to produce foam in processes such as washing.In the detergent composition, known more distinctive tensio-active agents provide foaming effect in washing water.Not only to form required foam, but also wish to be easy to generate foam, and make foam keep required duration.For example, wish detergent composition in case contact with water and to produce foam immediately.Although there are the various foamy reasons of why wishing to produce, a known reason is to use the human consumer of detergent composition that the cleansing power of foamy formation with detergent composition directly interrelated.

Although wish to produce foam, also there are some problems in foam in washing process.For example, the foam that produces in the discharging washing process may be difficult.Particularly for the machine-washing method, before the stage, foam can hinder washing soln from the outside discharging of washing machine at rinse.Therefore, wish progressively to suppress foamy and to form after after a while.

Therefore, need produce foam in early days, for example when detergent composition contacts water at the beginning, come control foam but after foam forms, need to press down the bubble component at washing process.

Prior art does not all provide all advantages of the present invention and effect.

Summary of the invention

The present invention has satisfied above-mentioned needs, the present invention relates to a kind of control foam system that is specially adapted to detergent composition, and but it contains need not stir just can provide that foamy foaming component and delay discharge the bubble component.The invention still further relates to the detergent composition that contains this control foam system.

By reading disclosure of the present invention and appending claims, above-mentioned feature of the present invention and other features, others and its advantage are clearly for those skilled in the art.

Detailed Description Of The Invention

Although this specification sheets combines with claims, point out that directly content of the present invention is thought in protection with special requirement, believe by reading over below the present invention and describe in detail, can understand the present invention better.In this manual, unless otherwise indicated, all percentage ratios, ratio and ratio are by weight, and all temperature are with a degree centigrade expression, and molecular weight is a weight-average molecular weight, and radix point is with point (.) expression.All documents of quoting at this paper as a reference.Quoting of any document is not to admit in this prior art required for protection, and relevant retrievable any content is determined.

" comprising " as herein described, the meaning is other steps and other component that can add, do not influence net result.This term also comprise term " by ... form " and " substantially by ... composition ".

The term of this paper " alkyl " meaning is straight or branched, saturated or undersaturated hydrocarbyl portion.Unless otherwise indicated, moieties is preferably saturated or have the unsaturated alkyl of two keys, preferably has one or two pair key.The moieties that comprises acyl group in the term " alkyl ".

The present invention relates to a kind of control foam system that is specially adapted in the detergent composition, but it contains need not stir just can provide that foamy foaming component and delay discharge the bubble component.That preferably should delays discharge but steeping component is the polysiloxane suds suppressor, but mix in the carrier with delivery mode, postpone the release of polysiloxane suds suppressor thus.

When control foam system at first enters in the water when contact with water, need not stir the component that foams with regard to quick and stable generation foam.When this paper uses, term " foam " meaning is any type of bubble that forms, and comprises foaming and effervesce.Stirring dispensablely, produce but can strengthen foamy, is preferred thus.Preferred foaming component is in case contact with water and just to produce bubble, and its average bubble granularity is about 400 microns or lower, and preferably about 200 microns or lower, more preferably from about 100 microns or lower.

After foam formed, through after a while, the bubble component that presses down that postpones to discharge was released, and foam is suppressed, and in other words is to be controlled by reducing foam volume.According to when should suppressing foam, but by selecting the time of pressing down the control lag of bubble component of suitable type.For example,, when stirring, press down the bubble component and can immediately reduce bubble in the water, so preferably after about 120 seconds, bubble is reduced about at least 30% for some machine-washing conditions.For example under other conditions of machine-washing, after second, bubble is reduced to about 40%-70% at about 360-600, or in other words is suppressed basically before the stage at rinse in addition.

For the hand washing condition, the preferred bubble component that presses down does not reduce bubble in the water in the starting stage of washing, is preferred because keep the foam volume of long period.

In a kind of preferred embodiment, it is the dried particles of respectively opening that the pressing down of component and delay release of foaming steeped component.Term " drying " is understood that feed particles is anhydrous basically, promptly except the moisture content of raw material itself, does not add entry.Generally, the content of water is lower than the about 5% of total particle weight, preferably be lower than about 3%, more preferably less than about 1.5%.

For example, in detergent composition, granular detergent composition for example, this final product composition having also contains two types of particulate mixtures except containing other conventional decontamination components.In another kind of embodiment preferred, a kind of particle is the part as other conventional decontamination components.Separately particle is a particularly suitable, because the different amount of people's may command is controlled thus and foamed component and press down the conveying of bubble component in washing process, for example can reach more effective and the interior conveying of certain hour, so that optimum performance to be provided.

Although do not wish bound by theory, particularly interim in the morning of washing stage, it is believed that the detergent composition that contains control foam system is of value to cleanup action.For example, believe that foam helps tensio-active agent in the detergent composition to moving on the dirt that need are removed and/or on the fabric.In addition, believe that foam also helps the wetting of detergent composition and dissolving.In addition, believe that foam provides early stage deposit place and helped dirt to be suspended in the washing soln for the tensio-active agent that does not deposit on the wet fabric.

This control foam system still is a stability in storage.For example, this component is not degraded in the storage process in being exposed to the moisture of air.In addition, because the foam component contains effervescent granules, in detergent composition, mix the dissolution characteristics that control foam system has improved the active constituent that exists in the detergent composition.

Additional benefit of the present invention is to have improved the relevant distribution character of detergent composition of the present invention, and for example expection is used for the detergent composition of tumbling-box washing machine.In fact, the difficulty that conventional high-density granulated detergent composition exists is that they are not easy to flow out from the load hopper of washing machine, promptly when granular composition is passed through the water-wet of load hopper mobile, detergent components can bond together, and causes staying at the rear portion of load hopper considerable wetting and adherent powder residue.When using this granular detergent composition in the measuring apparatus in the cleaning-drum, also run into similar problem.When having effervescent granules in the granular detergent composition, general when being used for washing machine, improved feed and, provide good preservation stability about potential feed problem.

The detergent composition that contains control foam system is solid laundry or dishwashing compositions, preferably particle, extrudate or sheet preferably.The density of preferred granular detergent composition is at least about 500g/l, more preferably at least about 700g/l.The detergent composition and the pressing down of component and delay release of foaming steep component and also can comprise other components as described herein.The definite character of these other components and its incorporation depend on the application of component or composition and the physical form of component and composition.

A. component foams

The foaming component preferably contains effervescent granules.In case the known any effervescent granules that can produce gas that contacts with water of prior art all can use.Preferred effervescent granules be included in water exist down can with the acid source of alkali source generated reactive gas.

Acid source can be any organic, mineral or mineral acid, or derivatives thereof or its mixture.Preferred acid source includes machine acid.Acid source preferably is anhydrous or non-hygroscopic basically, and should acid preferably water miscible.Preferred acid source is over-drying.The acid source component that is fit to comprises acid or monocarboxylic acid or polycarboxylic salt form.This preferred acid comprises and is selected from citric acid, oxysuccinic acid, toxilic acid, fumaric acid, aspartic acid, pentanedioic acid, tartrate, propanedioic acid, succsinic acid or hexanodioic acid, monosodium phosphate, boric acid, 3chetoglutaric acid, citromalic acid and its mixture.Citric acid, toxilic acid or oxysuccinic acid are particularly preferred.

Calculate by this acid source sample of screening on serial Tyler sieve, preferably this acid source provides about 75 microns-1180 microns of mean particle size, more preferably from about 150 microns-710 microns acidic cpd.

Effervescent granules preferably comprises alkali source.Can all can be present in this particle with any alkali source of acid source generated reactive gas, comprise the source that can produce nitrogen, oxygen and carbon dioxide gas.Preferred perhydrate SYNTHETIC OPTICAL WHITNER and silicate material.Alkali source preferably is anhydrous or non-hygroscopic basically.Preferred alkali source is over-drying.

The preferred gas that produces is carbonic acid gas, so alkali source preferably carbonate source, particularly carbonate.Preferred carbonate example is alkaline-earth metal and alkaline carbonate, comprise yellow soda ash or potassium, sodium bicarbonate or potassium, mixture with concentrated crystal soda or potassium and itself and calcium carbonate superfine powder for example is disclosed in the disclosed German patent application 2321001 on November 15th, 1973.Alkali metal percarbonate also is the carbonate source that is fit to, and it can combine existence with one or more other carbonate source.

Carbonate and supercarbonate are preferably amorphous structure.Carbonate and/or supercarbonate can apply with coating.About 75 microns or bigger of carbonate and bicarbonate particles mean particle size, preferred about 150 μ m or bigger, 250 μ m or bigger more preferably from about, preferred about 500 μ m or bigger.Preferred carbonate is such particle: carbonate or supercarbonate sample are sieved on serial Tyler sieve calculate, granularity is less than about 20% (weight) less than the particle of about 500 μ m.In addition, or except above-mentioned carbonate, carbonate or supercarbonate sample sieved on serial Tyler sieve calculate, preferred size less than the particle of 150 μ m be less than 60% or even 25%, and granularity is less than 5% greater than the particle of 1.18mm, and more preferably granularity is less than 20% greater than the particle of 212 μ m.

The acid source that exists in grain nuclear and the mol ratio of alkali source are preferably about 60: about 1: 60 of 1-, more preferably from about 20: about 1: 20 of 1-, more preferably from about 10: about 1: 10 of 1-, more preferably from about 5: about 1: 3 of 1-, more preferably from about 3: about 1: 2 of 1-, more preferably from about 2: about 1: 2 of 1-.

In preferred embodiments, effervescent granules optionally contains acid source and alkali source bonded tackiness agent.Preferably, effervescent granules is included as tackiness agent or its mixture of total particle weight about at the most 50%, and is preferably about at the most 35%, and more preferably about at the most 20%.The tackiness agent that is fit to that the present invention uses be well known by persons skilled in the art those, comprise anion surfactant such as C6-C20 alkyl or alkylaryl sulphonate or vitriol, preferred C8-C20 alkylbenzene sulfonate, derivatived cellulose, the for example poly carboxylic acid of carboxymethyl cellulose and homopolymerization or copolymerization or its salt, nonionogenic tenside, the corresponding C10-C20 alcohol ethoxylate that contains the 5-100 moles of ethylene oxide of preferred every mol of alcohol, the corresponding C15-C20 primary alcohol ethoxylate that contains the 20-100 moles of ethylene oxide of more preferably every mol of alcohol.Wherein, corresponding tallow alcohol ethoxylate (TAE25) or the corresponding tallow alcohol ethoxylate (TAE50) that contains 50 moles of ethylene oxide of every mol of alcohol that contains 25 moles of ethylene oxide of every mol of alcohol is preferred.Other preferred adhesive comprise polymeric material, are the Polyvinylpyrolidone (PVP) of 12000-700000 and the polyoxyethylene glycol of molecular-weight average 600-10000 as molecular-weight average.Other examples that maleic anhydride and ethene, methylvinylether, methylacrylic acid or acrylic acid multipolymer are polymeric binders.Other tackiness agents also comprise C10-C20 one and two glyceryl ethers, and C10-C20 lipid acid.In needing the embodiment of the present invention of tackiness agent, the C8-C20 alkylbenzene sulfonate is particularly preferred.

In another kind of embodiment preferred, the foaming component also can contain minimizing water-air surface tensile surfactivity component.Preferred surfactivity component has and is higher than 45 ℃ fusing point, is preferably selected from nonionic alkoxylate acid amides, fatty acid alkyl ester or alcohol alcoxylates.Particularly preferred surfactivity component is selected from the condensation product of polyhydroxy fatty acid amide and Fatty Alcohol(C12-C14 and C12-C18) and about 1-15 mole alkylene oxide.If use the surfactivity component, the weight ratio of surfactivity component and effervescent granules is preferably about 20: about 1: 10 of 1-.

In another preferred embodiment, the foaming component also can comprise the short infusion of interpolation.Short infusion combines with effervescent granules and can strengthen foamy formation.Short infusion can be the part of identical particle or the composition of conduct foaming component, or short infusion can be independent individual particles or independent chuck.

Preferred short infusion comprises amine oxide, polyoxyethylene glycol, Monoethanolamine MEA BASF, diethanolamine, Fatty Alcohol(C12-C14 and C12-C18), sugar, protein, trimethyl-glycine and its mixture.

The amine oxide that is fit to comprises having formula R ³(OR ⁴) _xN ⁰(R ⁵) ₂Those compounds, R wherein ³Be selected from alkyl, hydroxyalkyl, acyl group amido propionyl and the alkyl phenyl or its mixture that contain 8-26 carbon atom; 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, or contain the polyoxyethylene group of 1-3 ethylene oxide group.C preferably ₁₀-C ₁₈Alkyl dimethyl amine oxide, and C _10-18Acyl group amidoalkyl dimethyl oxidation amine.

The trimethyl-glycine that is fit to is formula R (R ') ₂N ⁺R ²COO ^-Those compounds, wherein R is C ₆-C ₁₈Alkyl, each R ¹Generally be C ₁-C ₃Alkyl, R ²Be C ₁-C ₅Alkyl.Preferred trimethyl-glycine is C _12-18Dimethyl Ammonium hexanoate and C _10-18Acyl group amido propane (or ethane) dimethyl (or diethyl) trimethyl-glycine.The compound betaine tensio-active agent also is applicable to the present invention.

The foaming component can prepare by ordinary method, comprises the part as film-making technology, extrusion process and/or agglomeration process.No matter the foaming component is particle or be included in form in the particle, preferably such: the grain graininess of about 80% weight is greater than 75 microns (greater than particles of 80% weight on 200 order Tyler sieve) and be less than about 10% weight particles granularity greater than 2cm; The grain graininess of preferred 80% weight is greater than about 150 microns (80% weight is on 100 order Tyler sieves) and be less than about 10% weight particles granularity greater than about 1cm; Or more preferably 80% weight particles granularity greater than about 300 microns (80% weight 48 purpose Tyler sieve above) be less than about 10% weight particles granularity greater than about 0.5cm; Or even more preferably about 500 microns of this average particle size (on 32 order Tyler sieve) to about 3000 microns, more preferably from about 710 microns (on 24 order Tyler sieve) extremely about 1180 microns (sieving) by 14 purpose Tyler.

B. component is steeped in pressing down of postponing to discharge

Use the pressing down of delay release of pressing down the bubble amount to steep component among the present invention.Term " component is steeped in pressing down of the postponing to discharge " meaning is to press down the bubble component and just to begin to suppress foam through after a while.According to when requiring to suppress foam, but by selecting the time of pressing down the control lag of bubble component of suitable type.Term " presses down the bubble amount ", and the meaning is the amount of selected this component control foam of prescription teacher of detergent composition to required degree.The amount that presses down the bubble component changes along with the detergent components of selecting.

The preferred bubble component that presses down that postpones to discharge is that polysiloxane presses down the bubble component.A kind of preferred polysiloxane presses down the bubble component and contains the polysiloxane foam control agent that average droplet size is the 1-50 micron, but it mixes water-soluble with delivery mode or water-dispersible, basically on-surface-active, washing composition is impermeable and non-hygroscopic carrier in, polysiloxane presses down the bubble component and is substantially free of water-soluble hygroscopic relatively inorganic salt, and be erose particle, its minimum size is not less than about 0.05cm, and overall dimension is at least greater than about 20% of minimum size.

The preferred component that suppresses contains the polysiloxane foam control agent, and it is isolated with other decontamination components of detergent composition basically.This " completely cutting off " realizes by mix this control agent in water-soluble or water-dispersible organic carrier matrix.This matrix optimization is non-surface active basically, non-hygroscopic material, and it does not interact with control agent.In addition, carrier must not permeated by the decontamination component basically, to suppress undesirable interaction of polysiloxane/washing composition and/or polysiloxane/alkali.In addition, carrier matrix of the present invention preferably except polysiloxane, does not contain the tensio-active agent of adding.The selection of carrier should guarantee that when it mixed with water, carrier matrix dissolving or dispersion can discharge the effect that the polysiloxane foam control agent is finished its control foam.

As the silicone materials of the preferred polysiloxane foam control agent of the present invention can be the alkylating silicone materials of several classes, they separately or with various solid materials, for example aerosil and xerogel and various types of water drain silica combination.In industrial practice, term " polysiloxane " has become general term, and it comprises that various relative high-molecular weight contain the polymkeric substance of siloxane unit and all kinds alkyl.Say that briefly the polysiloxane Foam Control can be described as the siloxanes with following general structure main chain:

Wherein x is 20-2000, R and R ' each alkyl or aryl, particularly methyl, ethyl, propyl group, butyl or phenyl naturally.Molecular weight is that the polydimethylsiloxane (R and R ' are methyl) of 200-200000 and Geng Gao all can be used as Foam Control.Silicone materials can be from Dow Corning company with trade(brand)name Silicone200Fluids ^Be purchased.The polydimethylsiloxane that is fit to has viscosity 2 * 10 at 25 ℃ when together using with silicon-dioxide and/or silicone resin ^-5-1.5 * 10 ^-3m ²s ^-1(20-1500cs).

In addition, other silicone materials, wherein side chain R and R ' base are alkyl, aryl or mixed alkyl and aryl, also show useful control bubble character.These materials prepare with method hydrolysis well known in the art by suitable alkyl, aryl or mixed alkyl aryl or aralkyl polysiloxane dichloride and water easily.The specific examples of this polysiloxane foam control agent that is suitable for as the present invention, that can mention for example has diethyl polysiloxane, dipropyl polysiloxane, dibutyl polysiloxane, methylethyl polysiloxane, a phenyl methyl polysiloxane etc.Dimethyl polysiloxane is because it is low-cost and obtain easily, is particularly suitable of the present invention.

Polysiloxane in the carrier matrix " drop " is the about 50 μ m of the about 1-of its mean diameter preferably, the about 40 μ m of preferably about 5-, and about 30 μ m of 5-more preferably from about are to obtain maximum validity.It is very ineffective that diameter is lower than the drop of about 5 μ m, and diameter increases little greater than the drop validity of about 30 μ m.Hereinafter disclosed other polysiloxane Foam Controls require similar size.

The second kind of highly preferred type that is used for polysiloxane Foam Control of the present invention comprises the alkylation siloxanes type of above disclosure and the mixture of solid silica.This mixture of polysiloxane and silicon-dioxide can be by being fixed on polysiloxane silicon-dioxide (SiO ₂) on the surface, for example prepare by the catalytic reaction method that discloses in the United States Patent (USP) 3235509.Zhi Bei the mixture foam control agent that comprises polysiloxane and silicon-dioxide by this way, the ratio of preferred polysiloxane and silicon-dioxide is 19: 1-1: 2, preferred 10: 1-1: 1.Silicon-dioxide can chemistry and/or physical bond to polysiloxane, by the weight of polysiloxane, its amount is preferably 5%-20%, preferred 10%-15%.It is about 1000 that the granularity of the silicon-dioxide that uses in this silicon-dioxide/polysiloxane Foam Control should preferably be no more than, and preferably is no more than 100nm, the preferred about 50nm of 5nm-, and more preferably 10-20nm, the specific surface area of silicon-dioxide should surpass about 5m ²/ g is preferably greater than about 50m ²/ g.

In addition, the Foam Control that contains polysiloxane and silicon-dioxide can mix with the water drain silica with above-mentioned scope granularity and surface-area by the polysiloxane type fluid that will above disclose and prepares.Can use any preparation water drain silica in several known methods, it can be used in combination with the polysiloxane as foam control agent in the present invention.For example, the silicon-dioxide of forging system can react (i.e. " silanization ") with the trialkyl chlorosilane, and hydrophobic trialkylsilanyl is fixed on the silica sphere.In preferred and known method, the silicon-dioxide of the system of forging is contacted with the trimethylammonium chlorosilane, and preparation is used for the silicon-dioxide of the preferred hydrophobic silaneization of the present composition.

In other method,, obtain being used for the hydrophobic silica of the present composition: the ammonium salt of the metal of longer chain fatty acid, ammonium and replacement, for example sodium stearate, aluminum stearate etc. by silicon-dioxide is contacted with any following compound; Silyl halides, for example ethyl trichlorosilane, butyl trichlorosilane, thricyclohexyl chlorosilane etc.; And chain alkyl amine or ammonium salt, for example hexadecyl Trimethylamine, hexadecyl trimethyl ammonium chloride etc.

Preferred foam control agent of the present invention comprises hydrophobic silanization (most preferably trimethyl silicone hydride) silicon-dioxide, and its granularity is about 10nm-20nm, and specific surface area is greater than about 50m ²/ g, its dimethylpolysiloxanefluids fluids with molecular weight 500-200000 is closely mixed, and the weight ratio of polysiloxane and silanized silica is 10: 1-1: 2.This foam control agent preferably includes polysiloxane: the weight ratio of silanized silica is 10: 1-1: 1 polysiloxane and siloxanes silicon-dioxide.Blended hydrophobic silaneization (particularly trimethyl silicone hydride) silicon dioxide-poly-siloxanes foam control agent is providing in wide temperature range very foamy control, infers that this is because polysiloxane controlled release from the silanized silica surface.

The Foam Control of another kind of type of the present invention comprises the silicone materials in being adsorbed onto on the solid of type mentioned above and the solid.This Foam Control comprises polysiloxane and solids, wherein polysiloxane: the ratio of solids is 20: 1-1: 20, preferred 5: 1-1: 1.The example of the solid adsorbent that polysiloxane of the present invention is fit to comprises clay, starch, diatomite, Fuller's earth etc.The alkalescence of this solid adsorbent is unimportant for the present composition, is stable because found polysiloxane when mixing with it.Disclosed as this paper, sorbent material+polysiloxane Foam Control must be coated with or be impregnated in hereinafter described in the solid support material by bag, and is isolated with the detergent components that makes the polysiloxane and the present composition effectively.

The polysiloxane foam control agent of the another kind of preferred type of the present invention comprises polysiloxane fluid, polyorganosiloxane resin and silicon-dioxide.The polysiloxane fluid that is used for this control bubble mixt is any kind that above discloses, but preferred dimethyl polysiloxane.The polysiloxane " resin " that is used for this composition can be any alkylation polyorganosiloxane resin, but normally by those of methyl-monosilane preparation.Polyorganosiloxane resin is described as " three-dimensional " polymkeric substance by the generation of alkyl three chloro silane hydrolyzates usually, and polysiloxane fluid is by dichloro-silane hydrolyzate preparation " two dimension " polymkeric substance.Silicon-dioxide component in this composition is a poromerics, for example has the granularity of above disclosure and the pyrogenic silica aerogel and the xerogel of surface-area.

Mixing polysiloxane fluid/polyorganosiloxane resin/the earth silicon material that is used for the present composition can prepare by the mode that discloses in the United States Patent (USP) 3455839.These blended materials can be purchased from Dow Corning company.According to United States Patent (USP) 3455839, this material can be described as the mixture of mainly being made up of following material: for 25 ℃ of following viscosity 2 * 10 ^-5-1.5 * 10 ^-3m ²s ^-1Per 100 parts of weight polydimethylsiloxane fluids (20cs-1500cs), (a) 5-50, preferred 5-20 weight part is by (CH ₃) ₃SiO _1/2Unit and SiO ₂The silicone resin that the unit constitutes, wherein (CH ₃) ₃SiO _1/2Unit and SiO ₂Unitary ratio is about 0.6/1-about 1.2/1; (b) 1-10, preferred 1-5 weight part solid silica gel, preferred aerogel.

In addition, this blended polysiloxane/polyorganosiloxane resin/silicon-dioxide foam control agent must combine with the impermeable solid support material of the washing composition that is used for the present composition.

The polysiloxane foam control agent of the above-mentioned type preferably mixes (promptly apply, capsule seals, be capped, internalization, basically with which in other words) water-soluble basically or water dispersible, in non-hygroscopic solid support material, this solid support material must have impenetrability to washing composition and alkali, itself must be non-surface active basically.Basically the on-surface-active meaning is that solid support material itself does not interact with silicone materials by this way: before silicone materials is discharged in the washing water, not emulsified, or in other words disperseed excessively, the granularity that is the polysiloxane drop should keep greater than 1, more preferably greater than 5mm.

Certainly, when preparation dry powder or granular detergent composition, also preferred its polysiloxane control bubble component at room temperature is exsiccant and cohesionless basically.Therefore, solid support material that the present invention preferably uses or vehicle, mouldable organic compound are suitable for and are melted, mix with the polysiloxane foam control agent, and cooling afterwards forms solid thin-sheet.The multiple examples of such carriers material of the present invention that is applicable to is arranged.Because but the polysiloxane foam control agent is to mix in the carrier with delivery mode, when composition mixed with water, polysiloxane was released in the water-bath like this, so preferred carrier materials is water miscible.Yet water-dispersible material is also available, because in adding water-bath the time, they also discharge polysiloxane.

Known variety carrier material has desired solubility/dispersibility and on-surface-active, non-hygroscopic and essential feature such as washing composition is impermeable is basically basically arranged basically.Yet having basically, the polyoxyethylene glycol of on-surface-active feature (PEG) is that the present invention is highly preferred.Can use molecular weight 1500-100000, preferred 3000-20000, the more preferably PEG of 5000-10000.

Find surprisingly, the Fatty Alcohol(C12-C14 and C12-C18) of height ethoxylation, for example condensation also is that the present invention is useful at least about the tallow alcohol of 25 molar ratio oxyethane.Other pure condensess that contain high ethoxylate ratio (25 and greater than 25) also are that the present invention is useful.This highly ethoxylatedization thing does not obviously have need control the surfactivity feature that bubble character applies effect or influence to polysiloxane of the present invention reagent place.The various other materials that can be used as carrier of the present invention also can be used, for example gelatin, agar, Sudan Gum-arabic and various algae deutero-gel.

Solid support material very preferably is 0.2%-15%, preferred 0.25%-5%, and more preferably 0.25%-2% contains 12-30, preferred 14-20, the more preferably mixture of the PEG of the lipid acid of 14-16 carbon atom and equal amount.This solid support material has provided better foaming character curve in washing process, compare with independent PEG, and more foam is provided when beginning, provides still less foam at terminal hour.Lipid acid has postponed to press down bubble particulate solvability, has postponed the release of polysiloxane thus.Soap and/or wax also can be used for replacing lipid acid.

Preferred erose particle polysiloxane control bubble component can suit to be prepared into highly preferred sheet form, this preparation is that the polysiloxane foam control agent is mixed the polysiloxane drop that forms appropriate size with the fusion solid support material, and film-making, for example by grinding or extruding and laminate, this solid support material of cooling curing is broken into this sheet the particle of appropriate size.In another kind of preferable methods, suds suppressor is dispersed in the fusion solid support material, for example cooling off on the roller or cooling off the fusion solid support material on the belt cooler and make film, then described film is broken into the thin slice of appropriate size.The thickness of this thin slice should be 0.05-0.15cm, preferred 0.05-0.1cm.When this method of use, the polysiloxane foam control agent is contained in the solid support material effectively, so that when this material mixed with detergent composition fully or mixes in the detergent composition, polysiloxane was not gone up substantially and contacted with the detergent surfactant component.

In order to be provided for the granular NAG control bubble component in the dry granular shape detergent composition, the thin slice of polysiloxane foam control agent and solid support material should be cured basically.This can realize by using belt cooler, can cool off flap or thin slice apace, and melting carrier is hardened.Also can use extruding technology.

Will be appreciated that it is not crucial being used for the isolated carrier amount of the detergent components of the polysiloxane foam control agent of the present invention and the present composition, only need to use enough carrier bulks basically institute's polysiloxane all to be mixed wherein and get final product.Equally, preferred enough solid support materials prevent broken too early sufficient intensity so that the particle that obtains has.Generally, the part by weight that uses carrier and polysiloxane foam control agent is greater than 2: 1, and preferred 5: 1-100: 1, more preferably 20: 1-40: 1.

The selected granularity of using in the present composition of foam control particles component is compatible with the rest part of detergent composition.Control bubble component of the present invention can not separated in detergent composition significantly.Generally, overall dimension 600-2000, particle and the spray-dried detergent particle of preferred 800-1600 μ m are compatible.Therefore, most of particle should have these overall dimensions.Most of particle maximum diameter should be 1.5 with the ratio of minimum diameter: 1-5: 1, preferred 1.5: 1-4: 1.

Except polysiloxane, but other control bubble components that mix in the solid support material with delivery mode comprise monoester fat carboxylic acid and its soluble salt.They generally have 10-24 carbon atom, the hydrocarbyl chain of preferred 12-18 carbon atom.The salt that is fit to comprises an alkali metal salt, for example sodium, potassium and lithium salts and ammonium and alkanol ammonium salt.Other control that is fit to bubble components comprise high molecular weight fatty acid ester (for example fatty acid triglycercide), the fatty acid ester of monohydroxy-alcohol, 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 reaction product, propylene oxide, distearyl acid amides and single stearyl di(2-ethylhexyl)phosphate basic metal (as sodium, potassium, lithium) salt and the phosphoric acid ester of secondary amine.

Except above-mentioned polysiloxane presses down the bubble component, can use that other postpone to discharge but the bubble component.For example, can use and contain foam control agent and (i) alkylalkoxy silane and the (ii) defoaming composition through sealing of the reaction product of polysiloxane condensation cure catalyst, wherein foam control agent is sealed by described reaction product.Prepare among the GB2318355 that this method of preferably sealing defoaming composition is described in disclosed General Electric company on April 22nd, 1998.In another example, by the even rosin/polysiloxane mixture of the mixture of liquid polydimethylsiloxane and the caustic soda aqueous solution and molten rosin preparation also can be used as postpone to discharge press down the bubble component.Because rosin/polysiloxane mixture is solvable under comparatively high temps, thisly presses down the bubble effect and be specially adapted to washing water and discharge through the delay under the heated wash conditions after a while.Also referring to the GB1340043 of disclosed Griffiths on the 5th etc. December in 1978.

Press down in the example of bubble component based on polysiloxane at another, the carrier of foam control agent can be the solid particulate structure of modified-cellulose, and it is dissolved in water, but because the cellulose surface swelling, thereby with low relatively speed dissolving.Prepare the United States Patent (USP) 4894177 of authorizing Dow Corning company January 16 nineteen ninety that this example that presses down the preferred method of bubble component sees also Starch etc.In another example, foam control agent can be enclosed in the micro-capsule that is made of core and polymer shell, so that destroy polymer shell, sustained release core material (foam control agent) by the effect of alkali.

In another example, microcapsule can be used for postponing to discharge presses down the bubble component.A kind of preferred microcapsule are by in the oil phase of stable O/w emulsion, in the presence of the polymerization starter that forms radical, polymerization (i), (ii), (iii) and (iv) prepare, in polymerization process, the temperature of polymerization reaction mixture can improve continuously or periodically, (i) be greater than 40% weight maleic anhydride, (ii) be that at least a monoene of 0-99% weight belongs to unsaturated monomer, it is oil-soluble and is different from maleic anhydride monomer, it (iii) is 0-80% weight cross-linking monomer, it is oil-soluble and is different from maleic anhydride, its molecule has at least two unsaturated unconjugated double bonds of olefinic, (iv) be the water miscible monoene of 0-20% weight belongs to unsaturated monomer, described percentage ratio is the total of pressing monomer (i)-(iv).Relevant detailed technology is described the United States Patent (USP) 5596051 of authorizing BASF on January in 1997 21 referring to Jahns etc.

C. decontamination component

Detergent composition of the present invention can comprise known other decontamination components of prior art.In addition, the foaming component and/or postpone to discharge press down the bubble component and also can contain the decontamination component.The definite character of these other components and its incorporation will depend on that the physical form of composition is used for the definite classification of washing operation with it.

Detergent composition preferably contains one or more other decontamination components, is selected from tensio-active agent, SYNTHETIC OPTICAL WHITNER, alkalimetal silicate, washing assistant, sequestrant, enzyme, filler, soil-suspending agent, white dyes, dispersion agent, dirt release agent, photoactivated SYNTHETIC OPTICAL WHITNER, dyestuff, dye transfer inhibitor, pigment, spices, clay softening system, cationic fabric softener and its mixture.

Particularly, preferably this particle comprises at least a or multiple anion surfactant as herein described and preferred one or more cats products.Also preferably this particle also contains or replaces above-mentioned component to contain washing assistant material as herein described and albic material.

This detergent composition can contain one or more tensio-active agents, these tensio-active agents are selected from as above-mentioned anion surfactant, cats product, amphoterics, zwitterionics or nonionogenic tenside and its mixture.Be issued to the US3 of Laughlin and Heuring on December 30th, 1975,929,678 have provided the general catalogue of these tensio-active agents.Other example is given in " tensio-active agent and washing composition " (I volume and II volume, Schwartz, Perry and Berch).The catalogue of suitable cats product is given the US4 that is issued to Murphy on March 31st, 1981, in 259,217.

Anion surfactant

Any anion surfactant that is used for the decontamination purpose all is fit to.Example comprise anion sulfate, sulfonate, carboxylate salt and sarcosinate surfactant (comprise for example sodium, potassium, ammonium and substituted ammonium salt, such as one, two and triethanolamine salt etc.).The preferred anionic sulfate surfactant.

Other anion surfactants comprise isethionate, for example monoesters (the particularly saturated and unsaturated C of fatty acid amide, alkyl succinate and the alkyl sulfo succinate of acyl isethinate, N-ethanoyl taurate, methylamino esilate, 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, for example rosin, staybelite, and the resinous acid and the hydrogenated resin acid that are present in the butter or are obtained by butter.

By said composition or particulate weight, the content of anion surfactant can be 0.5%-80%, preferred 3%-60%, more preferably 5%-35%.The ratio of stablizer and anion surfactant is preferably 1: 20-20: 1, more preferably 1: 6-6: 1.

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 ₉-C ₂₂Alkyl-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 0.5-50 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 preferred 1-5 moles of ethylene oxide ethoxylation ₁₁-C ₁₈, preferred C ₁₁-C ₁₅Alkyl-sulphate.

The particularly preferred aspect of the present invention is to adopt the mixture of preferred alkyl-sulphate and alkyl ethoxy sulfate surfactant.This mixture is disclosed among the PCT number of patent application WO93/18124.

The anion sulfoacid salt surfactant

Be applicable to that anionic sulphonate tensio-active agent of the present invention comprises C ₅-C ₂₀Straight or branched alkylbenzene sulfonate, alkyl ester sulfonate, particularly methyl ester sulfonate, C ₆-C ₂₂Uncle or secondary paraffin sulfonate, C ₆-C ₂₄Alkene sulfonate, sulfonated poly carboxylic acid, alkyl glycerol sulfonate, fatty acyl group glycerol sulfonate, fatty oil acylglycerol 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 ethoxylate should make 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 the replacement or the unsubstituted alkyl of 1-8 carbon atom, or its mixture.

Suitable soap class tensio-active agent comprises secondary soap surfactant, and it comprises the carboxyl unit that links to each other with secondary carbon(atom).Being preferred for 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-undecanoic acid, 2-ethyl-1-capric acid, the water-soluble salt of 2-propyl group-1-n-nonanoic acid, 2-butyl-1-are sad and the water-soluble salt of 2-amyl group-1-enanthic acid.Some soap class also can be used as suds suppressor and adds.

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.

Cats product

Another kind of preferred surfactants is a cats product, and by said composition or particulate weight, preferably its content is 0.1%-60%, more preferably 0.4%-20%, most preferably 0.5%-5%.When existing, the ratio of anion surfactant and cats product is preferably 25: 1-1: 3, more preferably 15: 1-1: 1, most preferably 10: 1-1: 1.The ratio of cats product and stablizer is preferably 1: 30-20: 1, more preferably 1: 20-10: 1.

The preferred cationic tensio-active agent is selected from cationic ester tensio-active agent, cation mono alkoxylated amines tensio-active agent, positively charged ion dialkoxy amine tensio-active agent and its mixture.

Cation mono alkoxylated amines tensio-active agent

Be used for the cation mono alkoxylated amines tensio-active agent that the present invention chooses wantonly and have general formula:

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 11 carbon atoms of 6-; R ²And R ³Be the alkyl that contains about 3 carbon atoms of 1-independently of one another, preferable 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 selected from C ₁-C ₄Alkoxyl group, particularly oxyethyl group (promptly-CH ₂CH ₂O-), propoxy-, butoxy and its mixture; P is that 1-is about 30, and preferred 1-is about 15, and most preferably 1-about 8.

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

R wherein ¹Be C ₆-C ₁₈Alkyl and their mixture, preferred C ₆-C ₁₄, C particularly ₆-C ₁₁Alkyl, preferred C ₈And C ₁₀Alkyl, 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.

Positively charged ion dialkoxy amine tensio-active agent

Be used for positively charged ion dialkoxy amine tensio-active agent of the present invention and have general formula:

R wherein ¹Be to contain about 18 carbon atoms of the 6-that has an appointment, preferred about 16 carbon atoms of 6-, more preferably 6-is about 11, most preferably from about the alkyl of about 10 carbon atoms of 8-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-is 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 as shown in the formula:

R wherein ¹Be C ₆-C ₁₈Alkyl and its mixture, preferred C ₆, C ₈, 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 ¹By not at the same level part of (cocounut oil) C ₁₂-C ₁₄The alkyl fatty acid deutero-, R ²Be methyl, ApR ³And A ' pR ⁴Each is monosubstituted ethoxy naturally.

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

R wherein ¹Be C ₆-C ₁₈Alkyl, preferred C ₆-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.

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) ₂Compound, 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 particle of the present invention or contain in the grains of composition of the present invention.These tensio-active agents broadly are described as secondary amine and tertiary amines derived thing, heterocyclic secondary and tertiary amines derived thing, 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 the compound 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.

The water soluble detergency promoter compound

Said composition preferably contains the water soluble detergency promoter compound, and by said composition or particulate weight, generally its content is 1%-80%, preferred 10%-70%, most preferably 20%-60%.

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, the mixture of borate, phosphoric acid salt and aforementioned any compound each other.

Carboxylate salt or multi-carboxy acid salt washing agent can be monomer type or oligomer types, but because Cost And Performance, preferred monomers multi-carboxylate 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, diglycollic acid, tartrate, tartronic acid and fumaric acid and ether carboxylate and sulfinyl carboxylate salt.The multi-carboxylate of containing three carboxyls specifically comprises 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 multi-carboxylate of containing four carboxyls comprises English Patent 1,261,829 described oxygen connection succinates, 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.Contain 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, Citrate trianion more specifically at the most for per molecule.

The borate washing assistant and can washing composition store or wash conditions under produce boratory, to contain the washing assistant that forms borate substance 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.

Part solubility or insoluble washing-aid compound

Said composition can contain part solubility or insoluble washing-aid compound, and by said composition or particulate weight, generally its content is 1%-80%, preferred 10%-70%, most preferably 20%-60%.

Basically the example of water-insoluble washing assistant comprises sodium silicoaluminate.The aluminosilicate zeolite unit structure cell that is fit to is suc as 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 as shown in the formula:

Na ₁₂[(AlO ₂) ₁₂(SiO ₂) ₁₂]-xH ₂O

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

It is as follows to be used for the preferred crystalline layered silicate general formula of the present invention:

NaMSi _xO _2x+1·yH ₂O

Wherein M is sodium or hydrogen, and x is the numerical value of 1.9-4, and y is the numerical value of 0-20.This class crystalline layered sodium silicate is disclosed among the EP-A-0164514, and their preparation method is disclosed among DE-A-3417649 and the DE-A-3742043.Here, the x in the above general formula is preferably 2,3 or 4, is preferably 2.Most preferred material is δ-Na ₂Si ₂O ₅, it is buied by the NaSKS-6 trade(brand)name from Hoechst.

The perhydrate SYNTHETIC OPTICAL WHITNER

Preferred other components of said composition are perhydrate SYNTHETIC OPTICAL WHITNER, for example peroxyboric acid metal-salt, percarbonic acid metal-salt, particularly sodium salt.Perborate can be monohydrate or tetrahydrate.SPC-D has corresponding to 2Na ₂CO ₃-3H ₂O ₂Chemical formula, it can be purchased by crystalline solid forms.Peroxide Potassium peroxysulfate, sodium salt are the optional inorganic perhydrate salt of another kind that is used for detergent composition of the present invention.

The organic peroxide acid bleach systems

The preferred feature of composition 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 perhydrate 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 prefabricated organic peroxide acid blended hydrogen peroxide cource and organic peroxide acid precursor mixture.

Peroxyacid bleach precursor

Peroxyacid bleach precursor was the compound that produces peroxy acid in the 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:

By particulate weight, the content of peroxyacid bleach precursor compound is preferably 0.5-80%, by the weight of composition, and more preferably 5-45%, most preferably 3-15%.

Suitable peroxyacid bleach precursor compound comprises one or more N-or O-carboxyl groups usually, and this precursor has very wide range of choice.Suitable type comprises the acylated derivatives of acid anhydrides, ester, imide, lactan and imidazoles and oxime.The example of suitable species is disclosed in GB-A-1586789 in these types.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:

With

With

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

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

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, and N ', N '-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:

Or

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, and as ammonium or alkyl ammonium group, the peroxy acid of the peroxyacid precursor compound that preferred ethyl or the replacement of ammonium methyl group are suitable partly forms.The positively charged ion peroxyacid precursor has a suitable negatively charged ion as a kind of usually, is present in the solid detergent composition as halogen ionic salt.

The peroxyacid precursor compound that this positively charged ion replaces can be the derivative of peroxybenzoic acid or its replacement, as above-mentioned precursor compound.Perhaps, the peroxyacid precursor compound can be alkyl peroxycarboxylic acid precursors compound, or the alkyl peroxy acids precursor of acid amides as described below replacement.The positively charged ion peroxyacid precursor is stated in following document: US4,904,406; 4,751,015; 4,988,451; 4,397,757; 5,269,962; 5,127,852; 5,093,022; 5,106,528; U.K.1,3 82,594; EP475,512; 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-acetylize 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

Benzoxazine type precursor compound also is suitable for, EP-A-332 for example, and 294 and EP-A-482, those described in 807, particularly as shown in the formula those:

Wherein, R ₁Be H, alkyl, alkaryl, aryl or aralkyl.

Prefabricated organic peroxide acid

The organic peroxide acid bleach system can also substitute by the ready-formed organic peroxide acid except that comprising organic peroxyacid bleach precursor compound, and in the weight of composition, its content is generally 1-15%, more preferably 1-10%.The compound that the acid amides that a preferred class organic peroxy acid compound is following general formula replaces:

Or

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 disclosed among the EP-A-0179386.Other organic peroxide acid comprises diacyl and four acyl peroxides, particularly diperoxy dodecane three 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 randomly contains a kind of bleaching catalyst that contains transition metal.A kind of bleaching catalyst of suitable type is to comprise the active heavy metal cation of the bleach catalyst with definition, 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 with defined stability constant catalysis and the cationic sequestrant of assistant metal, 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 type comprises and is disclosed in US5, the manganese basigamy compound in 246,621 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 is 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.

For example, the bleaching catalyst that is fit to is referring to US4, and 246,612 and 5,227,084.Also referring to US5,194,416, it has introduced for example Mn (1,4,7-trimethylammonium-1,4,7-7-triazacyclononane)-(OCH of monokaryon manganese (IV) title complex ₃) ₃(PF ₆).As the another kind of bleaching catalyst that is disclosed among the US5114606 is the water-soluble complexes of manganese (III) and/or the non-carboxylic acid polyol ligand that (IV) and at least has three continuous C-OH groups.Other example comprises the double-core Mn title complex that cooperates with four-N-dentate and two-N-dentate ligand, comprises N ₄Mn ^III(u-O) ₂Mn ^IVN ₄ ⁺[Bipy ₂Mn ^III(u-O) ₂Mn ^IVBipy ₂]-(ClO ₄) ₃

Other bleaching catalysts that are fit to are disclosed in the following document, 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), US4,728,455 (manganese/polygamy position polymerization of olefin using catalyst body catalyst), US4,711,748 and European patent application publication No. 224,952 (being adsorbed in the Mn catalyst on the silico-aluminate), US4,601,845 (being carried on manganese and zinc or magnesium salts on the silico-aluminate), US4,626,373 (manganese/ligand catalyzer), US4,119,557 (iron complex catalyzer), DE2,054,019 (cobalt chelates catalyzer), CA866,191 (salt that contain transition metal), US4,430,243 (sequestrant) and US4 with manganese positively charged ion and on-catalytic metallic cation, 728,45 5 (gluconic acid Mn catalysts).

Heavy metal ion chelating agent

Said composition preferably contains the heavy metal ion chelating agent as optional components.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 in conjunction with heavy metal ion, as the selectivity of iron, manganese and copper.The content of heavy metal ion chelating agent is generally the 0.005%-20% of the present composition or particle weight, preferred 0.1%-10%, more preferably 0.25-7.5%, most preferably 0.5%-5%.Be used for the heavy metal ion chelating agent that the present invention is fit to and include organic phosphonates, as amino alkylidenyl many (alkylene phosphonic acids salt), basic metal ethane 1-hydroxyl diphosphonate and nitrilo trimethylene phosphonic salt.

Preferred Diethylenetriamine five (methylene phosphonic acid salt), quadrol three (methylene phosphonic acid salt), six methylene diamines four (methylene phosphonic acid salt) and hydroxyl-ethylidene 1 in the above-mentioned substance, the 1-diphosphonate.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), inferior second pentaacetic acid, ethylenediamine disuccinic acid, quadrol two pentanedioic acids, 2-hydroxy propylidene diamines disuccinic acid or its any salt.Preferred especially quadrol-N, N '-disuccinic acid (EDDS) or its an alkali metal salt, alkaline earth salt, ammonium salt or substituted ammonium salt, or its mixture.

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.At EP-A-516, the iminodiethanoic acid described in 102-N-2-hydroxypropyl sulfonic acid and aspartic acid N-carboxymethyl N-2-hydroxypropyl-3-sulfonic acid sequestrant also are applicable to the present invention.At EP-A-509, the Beta-alanine-N described in 382, N '-oxalic acid, aspartic acid-N, single acetate of N '-oxalic acid, aspartic acid-N-and imino-diacetic succsinic acid sequestrant also are fit to.

EP-A-476,257 have described the suitable sequestrant based on amino.EP-A-510,311 have described the suitable sequestrant that is obtained by collagen, Keratin sulfate or casein.EP-A-528,859 have described a kind of suitable alkyl imino oxalic acid sequestrant.Pyridine dicarboxylic acid and 2-phosphinylidyne butane-1,2, the 4-tricarboxylic acid also is fit to.Glycine acid amides-N, N '-disuccinic acid (GADS), quadrol-N, N '-two pentanedioic acid (EDDC) and 2-hydroxyl propylene diamine-N, N '-disuccinic acid (HPDDS) also is fit to.

Enzyme

The another kind of preferred ingredient that is used for said composition is one or more additional enzymes.Preferred additional enzymes material comprises commercially available lipase, at, amylase, neutrality and Sumizyme MP, esterase, cellulase, polygalacturonase, Sumylact L and the peroxidase that is routinely added in the detergent composition.Suitable enzyme was discussed in US3519570 and 3533139.The proteolytic enzyme that preferred commercially available proteolytic enzyme comprises the proteolytic enzyme 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, the proteolytic enzyme of selling by Genencor International and the proteolytic enzyme of selling with trade(brand)name Opticlean and Optimase by Solvay Enzymes.Proteolytic enzyme can add in the present composition by the content of composition weight meter with the 0.0001%-4% organized enzyme.

Preferably amylase comprises, for example the α-Dian Fenmei that the special bacterial strain by bacillus licheniformis of detailed description obtains among the 6B-1269839 (Novo).Preferred commercially available amylase for example comprises amylase of being sold with trade(brand)name Rapidase by Gist-Brocades and the amylase of being sold with trade(brand)name Termamyl and BAN by Novo IndustriesA/S.By the weight of composition, amylase adds in the present composition with the content of 0.0001%-2% organized enzyme.

By particulate weight, the content of lipolytic enzyme can be the active lipolytic enzyme of 0.0001%-10%, by the weight of composition, and preferred 0.001%-3%, most preferably 0.001%-0.5%.

Lipase can be obtained by fungi or bacterial origin, and for example the bacterial strain by the generation lipase of Humicola, thermophilic Pseudomonas (Thermomyces sp.) or Rhodopseudomonas obtains, and described bacterial strain comprises pseudomonas pseudoalcaligenes or Pseudomonas fluorescens.Lipase chemical or that genetically altered mutant obtains by these bacterial strains also can be used for the present invention.Preferred lipase is obtained by pseudomonas pseudoalcaligenes, and it is described in the European patent EP-B-0218272 that authorizes to some extent.

Described in the another kind of preferred lipase of the present invention such as the European patent application EP-A-0258068, it is the gene that obtains by fetal hair detritus bacterium by the clone, and this gene of expression obtains in as host's aspergillus oryzae, it is from Novo Industri A/S Bagsvaerd (Denmark), and Lipolase is purchased with trade(brand)name.This lipase also is described among the US4810414 of the Huge-Jensen that authorized on March 7th, 1989 etc.

Organic polyhydroxyl compound

Organic polyhydroxyl compound is preferred in the said composition.So-called organic polyhydroxyl compound means any basically organic polyhydroxyl compound that is used as dispersion agent, anti redeposition agent and soil-suspending agent in detergent composition usually, is included in any high molecular organic polyhydroxyl compound of introducing as the clay flocculating agent herein.

The incorporation of organic polyhydroxyl compound in detergent composition by particulate weight, is generally 0.1%-50%, and preferred 0.5%-25% is by the weight of composition, most preferably 1%-15%.

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 the latter's one type is disclosed in GB-A-1, in 596,756.The example of this salt be molecular weight MWt 2000-5000 polyacrylate and with the multipolymer of maleic anhydride, the molecular weight of this multipolymer is 20000-100,000, particularly 40,000-80,000.Polyamino compounds can be used for the present invention, comprises the material that is obtained by aspartate-derived, for example those described in EP-A-305282, EP-A-305283 and the EP-A-351629.

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.

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

Wherein X is a non-ionic group, is selected from H, C ₁-C ₄Alkyl or hydroxy alkyl ester 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-111965, US4659802 and US4664848.

The clay softening system

Said composition can contain the clay softening system, the clay flocculating agent that it comprises the clay mineral compound and optionally adds.The clay mineral compound is the terre verte compound preferably.Terre verte disclosed in US3682058,3948790,3954632 and 4062647.The EP-A-299575 of Procter andGamble company and EP-A-313146 have described suitable organic polymer clay flocculating agent.

The polymeric dye transfer inhibitor

Particle of the present invention or 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.

A) polyamine N-oxide pllymers

Be applicable to that polyamine N-oxide pllymers of the present invention contains the unit of following structural:

Wherein P is polymerisable unit, and

A is:

-O-,-S-,-N-; X is 0 or 1;

R is aliphatic group, ethoxylation aliphatic group, aromatic group, heterocyclic radical or alicyclic radical or its arbitrary combination, and wherein the nitrogen-atoms of N-O group can be connected with above-mentioned group, or the nitrogen of N-O group is the part of these groups.

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

Or

R wherein ₁, R ₂And R ₃Be aliphatic group, aromatic group, heterocyclic radical or alicyclic radical or its combination; X or/and y or/and z is 0 or 1; And the part that wherein nitrogen of N-O group can be connected with these groups or wherein the nitrogen of N-O group constitutes these groups.The N-O group can be the part of this polymerizable unit (P), or can link to each other with polymer main chain, or can be the combination of above two kinds of situations.

Wherein the N-O group suitable polyamine N-oxide that constitutes this polymerizable unit part comprises polyamine N-oxide, and wherein R is selected from: aliphatic group, aromatic group, alicyclic group or heterocyclic group group.The described polyamine N-oxide of one class comprises wherein one group of polyamine N-oxide of the nitrogen formation R-group part of N-O group.The R of preferred polyamine N-oxide compound is a heterocyclic group group, as pyridine, pyrroles, imidazoles, tetramethyleneimine, piperidines, quinoline, acridine and its derivative.

Other suitable polyamine N-oxide is the polyamine oxide compound that links to each other with polymerizable unit of N-O group wherein.The preferred type of this class polyamine N-oxide comprises the polyamine N-oxide of general formula (I), and wherein R is aromatic group, heterocyclic group or alicyclic group, and wherein the nitrogen of N-O functional group is the part of described R group.The example of these compounds is that wherein R is the polyamine oxide compound of heterogeneous ring compound such as pyridine, pyrroles, imidazoles and its derivative.

Polyamine N-oxide can almost obtain with any polymerization degree.The polymerization degree is not crucial, as long as described material has the ability of required water-soluble and suspension dyestuff.Usually, average molecular weight range is 500-1000,000.

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

The molecular-weight average that is suitable for N-vinyl imidazole of the present invention and N-vinylpyrrolidone copolymer is 5,000-50,000.The mol ratio of preferred its N-vinyl imidazole of multipolymer and N-vinyl pyrrolidone is 1-0.2.

C) Polyvinylpyrolidone (PVP)

The present composition also can adopt Polyvinylpyrolidone (PVP) (" PVP "), and its molecular-weight average is 2,500-400,000.Suitable Polyvinylpyrolidone (PVP) can be from ISP company (New York, NY) and Montreal (Canada) (viscosity-average molecular weight is 10 with ProductName PVP K-15,000), (molecular-weight average is 40 to PVP K-30,000), (molecular-weight average is 160 to PVP K-60,000) and PVP K-90 (molecular-weight average is 360,000) be purchased.PVP K-15 also can be purchased from ISP company.Other is suitable is the Polyvinylpyrolidone (PVP) that can be purchased from BASF AG, comprises Sokalan HP 165 and Sokalan HP 12.

D) Ju Yi Xi oxazolidinone

The present composition also can adopt Ju Yi Xi oxazolidinone as the polymeric dye transfer inhibitor.The molecular-weight average of described Ju Yi Xi oxazolidinone is 2,500-400,000.

E) polyvinyl imidazol

The present composition also can adopt polyvinyl imidazol as the polymeric dye transfer inhibitor.The molecular-weight average of described polyvinyl imidazol is preferably 2,500-400,000.

White dyes

The also optional hydrophilic white dyes that contains some type of have an appointment 0.005% to 5% (weight) of the present composition.Can be used for hydrophilic white dyes of the present invention and comprise those with 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; And M is a salt-forming cation, as sodium or potassium.

In following formula, R ₁Be anilino, R ₂Be N-2-two-hydroxyethyl and M are positively charged ions, during as sodium, this whitening agent is 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 is sold with trade(brand)name Tinopal-UNPA-GX by Ciba-Geigy company commercial.Tinopal-UNPA-GX is the preferred hydrophilic white dyes that can be used in the detergent composition of the present invention.In following formula, R ₁Be anilino, R ₂Be that N-2-hydroxyethyl-N-2-methylamino-and M are positively charged ions, during as sodium, this 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 is sold with trade(brand)name Tinopal 5BM-GX by Ciba-Geigy company commercial.In following formula, R ₁Be anilino, R ₂Be that morpholino and M are positively charged ions, during as sodium, this whitening agent is 4,4 '-two [(4-anilino-6-morpholino-guanamine-yl) amino]-2,2 '-Stilbene disulfonic acid sodium salt.Such special whitening agent is sold with trade(brand)name TinopalAMS-GX by Ciba-Geigy company commercial.

Cationic fabric softener

Cationic fabric softener also can add in the present composition, and the cationic fabric softener that is fit to comprises water-insoluble tertiary amine or two long-chain acid amides material, and they are disclosed among GB-A-1514276 and the EP-B-0011340.Cationic fabric softener generally amounts to and adds 0.5%-15% weight, usually 1%-5% weight.

The pH of composition

This detergent composition preferably has acid or alkaline pH according to Application Areas or its additional component.Preferred this particle or composition are pressed 1% measured in solution in the distilled water, and its pH is at least 3.0, preferred 4.0-12.5.

D. clothes washing method

In the hand washing method, this method generally comprises in groove or container, contacts and/or handle dirty fabric with wash water solution that contains detergent composition or solid soap bar.The human consumer makes the solid soap bar contact with dirty fabric by friction.After all fabrics are rubbed, in container, add fresh water and rinse fabric.Can repeat this rinse process.In general hand washing method, also can use and clean or friction tool.

In the machine washing method, this method generally comprises uses the wash water solution that contains detergent composition to handle soiled clothes, wherein dissolve or disperseed the detergent composition of significant quantity, preferred significant quantity is that about 5-65 rises in the washing soln of volume and dissolves or the about 10g-300g product of dispersion.

In a kind of method of soaking fabric, dirty fabric is immersed in the immersion aqueous solution that contains detergent composition, through one period working lipe.Then, from soaking solution, take out fabric.

Embodiment

Following examples further describe and illustrate the embodiment in the scope of the invention.Providing these embodiment only is for illustrative purposes, does not think limitation of the present invention, because do not breaking away under essence of the present invention and the scope, its many variations all are possible.

In following examples, all content are represented by the weight % of composition.Following examples are to explanation of the present invention, do not mean that restriction or define the scope of the invention in addition.Unless otherwise indicated, all umbers used herein, percentage ratio and ratio by weight percentage ratio represent.

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

In illustrational foaming system and cleaning combination, the component symbol of writing a Chinese character in simplified form has following implication:

LAS: straight chain C ₁₂Sodium alkyl benzene sulfonate

TAS: tallow alkyl sodium sulfate

C45AS: C ₁₄-C ₁₅Straight-chain alkyl sulfate

MES: C ₁₈The alpha-sulfo methyl esters of lipid acid

C _XyE _zS: with the C of Z moles of ethylene oxide condensation _1X-C _1yBranched-alkyl sulfuric acid

Sodium

MBASx, y: the sodium alkyl sulfate of the mid-chain branched of average x carbon atom, its

Comprise an average y carbon atom in the middle branching unit

C ₄₈SAS: C ₁₄-C ₁₈Secondary alcohol sodium sulfate

SADExS: formula 2-(R) C ₄H ₇-1,4-(SO ₄-) ₂C ₁₄-C ₂₂Alkyl two sulfuric acid

Sodium, wherein R=C ₁₀-

C ₁₈, condensation z moles of ethylene oxide

C _XYE _Z: with the C of average Z moles of ethylene oxide condensation _1X-C _1yBranched-chain primary alcohol

QASI ：R ₂N ⁺(CH ₃) ₂(C ₂H ₄OH)，R ₂＝50％-60％C ₉；40％-

50％C ₁₁

QAS1I ：R ₁N ⁺(CH ₃)(C ₂H ₄OH) ₂，R ₁＝C ₁₂-C ₁₄

Soap straight-chain alkyl carboxylic acid sodium is mixed by 80/20 of butter and Oleum Cocois

Thing obtains

TFAAI: C ₁₂-C ₁₄Alkyl N-methyl glucose amide

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

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

STPP: anhydrous sodium tripolyphosphate

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

Granularity is the 0.1-10 micron

Zeolite AII: over-drying zeolite AI

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

Citric acid I: Citric Acid, usp, Anhydrous Powder

Citric acid II: citric acid monohydrate compound

Oxysuccinic acid: anhydrous oxysuccinic acid

Toxilic acid: Maleic Acid, Anhydrous

Aspartic acid: anhydrous aspartic acid

Carbonate I mean particle size is a 200-900 micron anhydrous sodium carbonate

Carbonate II: mean particle size is a 100-200 micron anhydrous sodium carbonate

Supercarbonate: size-grade distribution is at the anhydrous sodium bicarbonate of 400-1200 micron

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

Sodium sulfate: anhydrous sodium sulphate

The Citrate trianion citrate trisodium dihydrate, activity 86.4%, size-grade distribution exists

Between the 425-850 micron

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

CMC: Xylo-Mucine

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

The proteolytic ferment of selling, activity

4KNPU/g

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

Active 3AU/g

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

The cellulolytic enzyme of selling is lived

Property 1000CEVU/g

Amylase: by Novo Industries A/S with trade(brand)name Termamyl 60T

The amylolytic enzyme of selling,

Active 60KNU/g

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

The lipolytic enzyme of selling, activity

100KLU/g

Endolase: the glucose restriction endonuclease, sell by Novo Industries A/S,

Active 3000CEVU/g

PB4: standard type NaBO ₂.3H ₂O.H ₂O ₂Sodium perborate tetrahydrate

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

Percarbonate: standard type 2NaCO ₃3H ₂O ₂SPC-D

NAC-OBS: (nonanoyl caproyl) oxygen benzene sulfonate, sodium-salt form

NOBS: nonanoly acyloxy benzene sulfonate, sodium-salt form

DPDA: diperoxy dodecanedioic acid

PAP: N-phthalyl amido is crossed oxy hexanoic acid

NAPAA: nonanoyl amido peroxide hexanodioic acid

NACA: 6-nonyl amino-6-oxo-caproic acid

TAED: tetraacetyl ethylene diamine

DTPMP Diethylenetriamine five (methylene phosphonic acid), by the broad-mouthed receptacle for holding liquid mountain all with trade(brand)name

Dequest 2060 sells

Light activating agent: sulfonation phthalocyanine phthalocyanine zinc of sealing or aluminium

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

Whitening agent 24,4 '-two (4-phenylaminos-6-morpholino-1,3,5-triazines-2-yl)

Amino) Stilbene-2:2 '-disulfonic acid disodium

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

PVNO: polyvinylpyridine N-oxide compound

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

QEA two ((C ₂H ₅O)-(C ₂H ₄O) _n) (CH ₃)-N ⁺-C ₆H ₁₂-N ⁺-(CH ₃)

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

SRP1: sulfo group with oxygen ethyleneoxy group and phthaloyl main chain

The end capped ester of benzoyl

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

Multipolymer

Postpone to discharge: contain the 10% weight polysiloxane/silicon-dioxide fluid and 90% of having an appointment

The sheeting of the polyoxyethylene glycol that presses down bubble weight molecular weight about 8000.Should be thin

The granularity of composition 1 sheet material be 2000 microns-Yue 500 microns (

The 10/+35Tyler sieve mesh)

Postpone to discharge: contain the 10% weight polysiloxane/silicon-dioxide fluid, about 0 of having an appointment

Press down bubble-7% weight palmitinic acid or Hyfac ^Lipid acid and surplus are molecular weight

The sheeting of the polyoxyethylene glycol of composition 2 about 8000.The grain of this sheeting

Degree is 2000-500 micron (10/+35Tyler sieve mesh)

Short infusion polyoxyethylene glycol, amine oxide, monoethanolamine, diethanolamine, fat

A kind of or its mixture in alcohol, sugar, protein and the trimethyl-glycine.

In following examples, all content are represented by the parts by weight of composition.

Controlled foaming system example

Following examples have illustrated foaming system of the present invention, and wherein each system or its mixture all can be used in the detergent composition.

As mentioned above, controlled foaming system of the present invention can prepare with any known method of preparation particulate in the prior art.

In foaming system, there are many different modes that the bubble component combines that press down that how will foam component and postpone release.For example, the foaming component and press down the bubble component can be by agglomeration, or mix with other optional components, form a kind of solid particulate.In addition, the foaming component can be two kinds of independent particles with pressing down the bubble component.In detergent composition, can use a kind of solid particulate or two kinds of foaming systems that independent particle constitutes.

Embodiment 1

Foaming system A-J

	A	B	C	D	E	F	G	H	I	J
											TFAAI/TFAAII	31.0	28.0	11.0	27.5	13.0	15.0	22.0	15.0	-	10.0
C24E3/C24E5	-	-	28.0	-	25.0	22.0	-	5.0	10.0	10.0
											PEG4000	5.0	5.3	-	5.0	-	-	7.0	5.0	-	5.0
Citric acid I	13.5	14.0	20.0	15.5	16.0	15.0	15.0	10.0	-	10.0
											Toxilic acid	-	-	-	-	-	-	-	-	10.5	10.0
Yellow soda ash I	13.5	-	20.0	-	-	-	-	-	15.0	10.0
											Yellow soda ash II	-	14.0	-	6.0	14.0	10.0	10.0	10.0	5.0	-
Sodium bicarbonate	-	-	-	6.0	-	-	10.0	-	5.5	5.0
											Zeolite AII	18.0	35.7	20.0	18.0	-	9.0	10.0	5.0	14.0	17.0
LAS	9.0	-	-	-	12.0	-	-	10.0	-	13.0
											QASI/QASII	9.0	-	-	-	-	-	6.0	3.0	-	-
TAED/NOBS/ NACA-OBS	-	-	-	19.0	10.0	-	-	7.0	20.0	-
											Perborate/percarbonate	-	-	-	-	-	19.0	-	10.0	-	-
Press down bubble component 1	1.0	3.0	-	-	10.0	-	10.0	-	-	5.0
											Press down bubble component 2	-	-	1.0	3.0		10.0	-	10.0	10.0	5.0
Short infusion	-	-	-	-	-	-	10.0	10.0	10.0	-

Foaming system A-J produces the average bubble granularity when contacting with water be about 400 microns or littler bubble, and when mixture is stirred, but the bubble component will reduce the bubble in the water.After mixture was stirred for the first time, in the time of about 6-10 minute, bubble was reduced about at least 40%-70%.

Following examples have illustrated and have comprised the foam cleaning combination of component of the present invention.

Embodiment 2

Below be high-density of the present invention and the detergent formulations (can be granular or sheet) that contains SYNTHETIC OPTICAL WHITNER:

	a	b	c
				The blowing powder
Zeolite A	5.0	5.0	15.0
				Sodium sulfate	0.0	5.0	0.0
LAS	20.0	30.0	20.0
				C45AS	3.0	5.0	20.0
QAS	-	-	1.5
				DTPMP	0.4	0.4	0.4
CMC	0.4	0.4	0.4
				MA/AA	4.0	2.0	2.0
Foaming system A	20.0
				Foaming system B	-	15.0	-
Foaming system G	-	-	10.0
				Spray (on particle)
The spices of sealing	0.3	0.3	0.3
				C25E3	-	-	2.0
Dried additive
				QEA	-	-	0.5
Citrate trianion	5.0	-	2.0
				Supercarbonate	-	3.0	-

Carbonate	8.0	10.0	5.0
				NAC OBS	6.0	-	-
Mn catalyst	-	-	0.3
				NOBS	-	2.0	-
PB1	14.0	7.0	-
				MW 5,000,000 polyethylene oxide	-	-	0.2
Wilkinite	-	-	10.0
				Citric acid	-	-	0.5
Proteolytic enzyme	1.0	1.0	1.0
				Lipase	0.4	0.4	0.4
Amylase	0.6	0.6	0.6
				Cellulase	0.6	0.6	0.6
Short infusion	5.0	1.0	5.0
				Dried additive
Sodium sulfate	0.0	3.0	0.0
				Surplus (water and other)	100.0	100.0	100.0
Density (g/ liter)	750	800	700

Embodiment 3

Below be high density detergent agent formulation of the present invention:

	d	e
			Foaming system A	45.0
Foaming system H		60.0
			Spray
C25E3	-	1.0
			Spices	0.5	0.5
Dried additive
			HEDP	0.5	0.3
SKS6	13.0	10.0
			Citrate trianion	-	1.0
NAC OBS	4.1	-
			TAED	0.8	-
Percarbonate	20.0	5.0
			SRP1	0.3	0.3
Proteolytic enzyme	1.4	1.4
			Lipase	0.4	0.4
Cellulase	0.6	0.6
			Amylase	0.6	0.6
QEA	1.0	-
			Short infusion	5.0	-
Whitening agent 1	0.2	0.2
			Whitening agent 2	0.2	-
Density (g/ liter)	700	850

Should clear and definite embodiment described herein and embodiment only be the purpose of explanation, do not breaking away under essence of the present invention and the scope, those skilled in the art can propose various modifications or variation.

Claims (11)

1. a control foam that is specially adapted to detergent composition is to comprise:

(a) need not stir just can provide foam or blistered foaming component and

(b) component is steeped in pressing down that delay discharges,

The component that wherein foams comprises effervescent granules, and effervescent granules comprises acid source and carbonate and/or supercarbonate; Wherein postpone to discharge to press down the bubble component be the polysiloxane suds suppressor, but mix in the carrier with delivery mode, make this polysiloxane suds suppressor postpone to discharge thus; Wherein the average droplet size of polysiloxane suds suppressor is the 1-50 micron, but with delivery mode mix water-soluble or water dispersible, basically non-surface active, washing composition is impermeable and non-hygroscopic carrier in, polysiloxane presses down the bubble component and is substantially free of water-soluble, hygroscopic relatively inorganic salt, this system is erose particle, its minimum size is not less than 0.05cm, and overall dimension is greater than minimum size at least 20%.

2. the control foam of claim 1 is, the bubble average bubble granularity that produces when the component that wherein foams contacts with water is 400 microns or littler.

3. the control foam of claim 2 is, the bubble average bubble granularity that produces when the component that wherein foams contacts with water is 200 microns or littler.

4. the control foam of claim 3 is, the bubble average bubble granularity that produces when the component that wherein foams contacts with water is 100 microns or littler.

5. the control foam of claim 1 is, wherein acid source is selected from the salt hydrate or the anhydrous salt of acid and acid, be monoprotic acid or poly carboxylic acid, be selected from citric acid, oxysuccinic acid, toxilic acid, fumaric acid, aspartic acid, pentanedioic acid, tartrate, propanedioic acid, succsinic acid or hexanodioic acid, monosodium phosphate, boric acid, 3chetoglutaric acid, citromalic acid and its mixture.

6. the control foam of claim 1 is; wherein effervescent granules also comprises tackiness agent; it is selected from derivatived cellulose; the poly carboxylic acid of carboxymethyl cellulose and homopolymerization or copolymerization or its salt; C6-C20 alkyl or alkylaryl sulphonate or vitriol; every mol of alcohol contains the C10-C20 alcohol ethoxylate of 5-100 moles of ethylene oxide; molecular-weight average is the Polyvinylpyrolidone (PVP) of 12000-700000; molecular-weight average is the polyoxyethylene glycol of 600-10000; maleic anhydride and ethene; methylvinylether; methylacrylic acid or acrylic acid multipolymer; C10-C20 one and two glyceryl ethers, C10-C20 lipid acid and its mixture.

7. the control foam of claim 1 is, wherein non-hygroscopic carrier is a polyethylene glycol carrier, and this carrier also comprises 0.2%-15% lipid acid or has the soap of 10-30 carbon atom, and/or wax.

8. the control foam of claim 1 is, the foaming component that wherein postpones to discharge also comprises short infusion, and it is selected from amine oxide, polyoxyethylene glycol, Monoethanolamine MEA BASF, diethanolamine, Fatty Alcohol(C12-C14 and C12-C18), sugar, protein, trimethyl-glycine and its mixture.

9. the control foam of claim 1 system wherein foams component and the bubble component that presses down that postpones to discharge is a dried particles independently separately, and the mean particle size of the component that wherein foams is 75 microns-1180 microns.

10. the granular detergent composition of a control foam system that comprises claim 1, wherein also comprise the decontamination component, be selected from SYNTHETIC OPTICAL WHITNER, dyestuff, dye transfer inhibitor, pigment, spices, clay softening system, cationic fabric softener and its mixture of tensio-active agent, SYNTHETIC OPTICAL WHITNER, alkalimetal silicate, washing assistant, sequestrant, enzyme, filler, soil-suspending agent, white dyes, dispersion agent, dirt release agent, photoactivation.

11. the method for cleaning and soaking fabric comprises fabric is contacted one period working lipe with containing the solution of water with claim 10 granular detergent composition, makes it to be enough to clean described fabric.