CN1198916C - Structural liquid detergent composition - Google Patents

Abstract

An aqueous detergent composition having a physical form selected from the group consisting of liquids, pourable gels and non-pourable gels, said composition comprising surfactant and water, which composition is structured with a lamellar phase formed of at least some of the surfactant and at least some of the water, the composition being substantially clear at 25 DEG C.

Description

Structural liquid detergent composition

Invention field

The present invention relates to aqueous liquid detergent compositions, it contain enough detergent active materials and, optionally, enough dissolved ionogen are to produce laminate structure.

Background of invention

Aqueous liquid detergent compositions one of usually can two kinds of diverse ways structurizing to give the fine-particle solid of the preferred flow characteristics of human consumer and/or cloudy appearance and/or suspension, for example detergent builder compound or abrasive particle.

First method adopts " external structure agent ", for example glue or polymer viscosifier.Second method is to form to form lamellar phase " internal structure " by tensio-active agent and water, and the latter is contained the dissolved ionogen usually.

Lamellar phase is a kind of surfactant structure of particular types, and it is especially known by various reference, H.A.Barnes for example, ' washing composition ', Ch.2, K.Walters (Ed), rheometry: industrial application, J.Wiley ﹠amp; Sons, Letchworth 1980.

But lamellar phase itself is considered to subspeciation class, plane lamellar phase and stratiform drop.Product can only contain the plane lamellar phase or only contain the stratiform drop or two kinds of forms are present in the like products jointly.

Existence in detergent product laminate phase can detect by method known to those skilled in the art, for example optical technology, various rheological measurement method, X ray or neutron diffraction and electron microscope method.

The stratiform drop is made up of the onion-like structure of concentric bilayer surfactant molecule, therein water entrainment or electrolyte solution (water).Wherein the system of this drop of airtight package provides physical stability and the very desirable combination that has the solid suspension character of useful flowing property.

The example that contains the disperse phase of stratiform drop but do not contain the internal structured liquid of suspended solids provides in US4244840, and wherein the example of suspended solid fine particles is open in specification sheets EP-A-160342, EP-A-38101, EP-A-104452 and above-mentioned US4244840.Other is open in European patent specification EP-A-151884, and its laminate drop is called ' spherocrystal '.

The known embodiment that also has the product that contains the plane lamellar phase, layered phase can be dispersed in the whole liquid or as being dispersed in the dispersion layer that contains in the water continuous phase and distribute.The stratiform Chang Butai that communicates in plane is suitable for have preferred flowing property than stratiform drop, but they being very suitable for the thickening product or giving its other human consumer preferred character in conjunction with the solid material that suspends.

The liquid product that lamellar phase causes producing is muddy (promptly muddy).Be in liquid, aqueous product, to produce the effect of certain vision happiness, need to produce the laminate structure detergent liquid of clarification basically (being substantial transparent).Have mainly compare with the product of microstructure by the product of the microstructure of plane stratiform phase composite with stratiform drop normally not too muddy.Yet these products have uneven outward appearance usually, be not clarifying basically, thereby they do not have charming outward appearance.In addition, in these plane sandwich-like products, be difficult to add enough function ionogen usually, for example washing assistant or buffering ionogen and keep transparency simultaneously.So far people only can produce commercial available liquid washing agent, and it is transparent by using the external structure agent in the isotropic liquid in itself basically, as open among the GB-A-1303810.

Summary of the invention

A first aspect of the present invention provides the aqueous detergent compositions with the physical form that is selected from liquid, dumpable gel and non-gel of toppling over, described composition contains tensio-active agent and water, said composition the part surface promoting agent and the lamellar phase structureization of portion water formation at least at least, composition is a substantial transparent at 25 ℃.

It is when lamellar phase is stratiform drop form that a kind of method of the transparency that a first aspect of the present invention gives is provided, and adds deflocculated polymkeric substance in composition, even there is not deflocculated polymkeric substance, composition has been colloid-stabilised.Therefore, a second aspect of the present invention provides the aqueous detergent compositions with the physical form that is selected from liquid, dumpable gel and non-gel of toppling over, described composition contains the disperse phase of the stratiform drop in containing water continuous phase, composition also contains deflocculated polymkeric substance, when not having deflocculated polymkeric substance for 25 ℃, composition does not have obviously higher viscosity, is colloid-stabilised.

It is equally when lamellar phase is stratiform drop form that the another kind of method of the transparency that a first aspect of the present invention gives is provided, the principal dimension mark subcritical value of drop.Therefore, a third aspect of the present invention provides the aqueous detergent compositions with the physical form that is selected from liquid, dumpable gel and non-gel of toppling over, and described composition contains the disperse phase of the stratiform drop in containing water continuous phase, the D of its laminate drop _{V, 90}Less than 2 microns, D _{V, 90}90% diameter that has less than described value of the volume of=all drops.

The transparency that a first aspect of the present invention provides also can provide by the specific refractory power of coordinating lamellar phase and water in essence.Therefore, a fourth aspect of the present invention provides the aqueous detergent compositions with the physical form that is selected from liquid, dumpable gel and non-gel of toppling over, described composition contains the aqeous external phase of stratiform, and wherein the specific refractory power of lamellar phase and the difference that contains between the specific refractory power of water continuous phase make composition have at least 5% the optical transmittance as giving a definition.

In a fourth aspect of the present invention, stratiform can be regulated by following specifically described method respectively with the specific refractory power that contains water.Yet a kind of favorable method of regulating the specific refractory power of water is by the specific refractory power of dissolving sugar increase therein.Though the known a small amount of non-sugar polyol (for example glycerine or Sorbitol Powder) that adds in aqueous liquid detergent of people is stable to be used for enzyme, uses sugar, for example has the material of six-membered ring structure, it is new being specifically used for obtaining transparency.Therefore, a fifth aspect of the present invention provides the aqueous detergent compositions with the physical form that is selected from liquid, dumpable gel and non-gel of toppling over, and described composition contains lamellar phase and water, and this water contains the sugar that is dissolved in wherein.

The also claimed any composition that shows the feature of any two or more aspects of the present invention simultaneously of applicant.

The detailed description of invention

The product form

Composition according to any aspect of the present invention has physical form, and it can be liquid, dumpable gel or non-gel of toppling over.These forms are characterized by product viscosity easily.In these definition, unless clearly explanation is on the contrary arranged, in whole specification sheets, all viscosity is being measured under the shearing rate of 21s-1 and under 25 ℃ temperature.

According to the composition of any aspect of the present invention, they are liquid, preferably have the 1500mPa.s of being no more than, and more preferably no more than 1000mPa.s, are most preferably not exceeding the viscosity of 500mPa.s.

According to the composition of any aspect of the present invention, they are dumpable gels, preferably have 1500mPa.s at least, but are no more than 6000mPa.s, more preferably no more than 4000mPa.s, are most preferably not exceeding 3000mPa.s, especially are no more than the viscosity of 2000mPa.s.

According to the composition of any aspect of the present invention, they are non-gels of toppling over, and preferably have 6000mPa.s at least, but be no more than 12000mPa.s, more preferably no more than 10000mPa.s, be most preferably not exceeding 8000mPa.s, especially be no more than the viscosity of 7000mPa.s.

Transparency

It is substantial transparent that a first aspect of the present invention needs composition, preferably this be meant composition optical transmittance at least 5%, most preferably 10%, more preferably 25%, the optical length by 1cm under 25 ℃ especially＞50%.

These measuring results can use Perkin Elmer UV/VIS spectrometer Λ 12 or Brinkman PC801 colorimeter at the 520nm wavelength water to be obtained as 100% standard.

According to of the present invention first (or any other) aspect, the transparency of composition is not got rid of composition and is colored, and for example adds the composition of dyestuff, and its condition is its not obvious reduction transparency.In addition, if according to human consumer's needs, can comprise that opalizer is to reduce transparency.In this case, the definition of transparency that is used for the composition of any aspect of the present invention will be applied to not have basis (on an equal basis) composition of opalizer.

Other visible solid

As mentioned above, structure can be used for the suspended particulates solid, for example detergent builder compound or abrasive particle.Thereby they are the too little outward appearance that gives the composition muddiness simply usually.Yet in the composition aspect any of the present invention, but suspending phase does not influence the transparency of most liquid to obtain charming visual effect to a spot of big particulate functional mass.

Yet, purely for visual effect, can also be in the composition aspect any of the present invention suspended particulates or spot, these particulates can be colored.This particulate or spot can for example be selected from material any in the detergent product of previously known, though be not in the transparent in itself internal structured liquid.

Externally the example of this spot is described in GB-A-1303810 in the structuring liquid, and it discloses a kind of dumpable washing or rinsing aqueous detergent compositions, wherein adds the clearly visible component of the particulate form of 500mm diameter at least.These particulates contain to be in the suds and have the reagent of useful effect, and its encapsulate capsule is at inert support, for example in wax or the gelatin.For keeping particle suspension, composition contains suspension aids, for example natural gum or clay.

The example that contains (nontransparent) internal structured liquid of visible granular or spot discloses in GB-A-2194793.Visible granular contains carrier substance, for example tripoly phosphate sodium STPP and/or wilkinite and pigment.Preferred these spots have 1-1000mm (being most preferably not exceeding 100mm) mean particle size, constitute and press composition weight meter 0.5%-15%, most preferably 1%-5%.

GB-A-2247028 has described a kind of laminate structure aqueous detergent liquid, also is opaque basically, but wherein disperses micro dissolution in water or be not dissolved in the particulate or the drop of the dyestuff of water basically.

People can also use the coloured speckle or the particulate that are used for being dispersed in nonaqueous detergent liquid of previous suggestion.They are described in EP-0635569, in view of the above, contain carrier substance as the spot of particulate, for example SYNTHETIC OPTICAL WHITNER, washing assistant, clay, abrasive material, enzyme or biological polymer and relative dyestuff or pigment.These particulates must have D (3, the 2) mean particle size of 50mm-less than 500mm.

The application of nearlyer (unexposed) in internal structured liquid field is an aqueous liquid detergent compositions; it is opaque basically; but contain the surfactant structure lamellar phase; lamellar phase can the suspended particulates solid and is dispersed in the external phase; coloured particulate is suspended mutually by layered; wherein coloured particulate contains polymer shell, wherein comprises core substance, and coloured particulate also contains tinting material.

According to this undocumented application, the tinting material of coloured particulate can be included in shell and/or the core, tinting material can contain dyestuff and/or pigment material and (as required) and mix with core substance and/or polymer shell material, disperses therein and/or dissolving therein.When tinting material is included in the core (no matter whether also being included in the shell), according to the gross weight meter of toner and core substance, the quantity of tinting material is preferred 0.01%-2%, more preferably 0.1%-1%.When tinting material was adding of shell or other part, then according to the gross weight meter of toner and shell, it was preferably with 0.01%-4%, and more preferably 0.1%-1% is included by weight.

Core substance preferably occupies the 10%-99% of look particulate weight, more preferably 30%-98%.

Polymer shell can contain any polymkeric substance that is not dissolved in the composition rest part basically, the preferred embodiment of suitable polymers is polyoxymethylene melamine urea (PMMU), polymeric amide, cellulose polymer compound, polyvinyl alcohol (PVA), urethane and a carrageen (promptly 3,6-dehydration-d-Polygalactan, it is a polysaccharide) etc.

Suitable core substance comprises diethyl phthalate, alginate and paraffin oil.

The D of coloured particulate (3,2) mean diameter is the 250-2500 micron, more preferably 300-2200 particulate, most preferably 350-2000 micron.

For the optimum dispersion in liquid detergent composition, the mean density of preferred coloured particulate for do not contain coloured particulate composition density ± 35%, more preferably ± 30% or ± 25% and preferred ± 20% also, also more preferably ± 18%, most preferably ± 15% between.

The another kind of method of visual appearance that improves the composition of any aspect of the present invention is to add functional mass, and the encapsulate capsule material (encapsulate) of enzyme for example, this encapsulate capsule material are can yes or no colored.Yet, they usually will be sufficiently greatly with obviously as seen, thereby the liquid volume between the particulate still shows transparency basically.

Enzyme encapsulate capsule material

The enzyme encapsulate capsule material of above-mentioned suitable species is used for effective protective enzyme and avoids the disadvantageous effect of UV irradiation.Therefore, importantly enzyme sufficiently is included in the encapsulate capsule material to prevent any obvious leakage of enzyme in liquid detergent composition in storage process, promptly when storing for 4 weeks down for 37 ℃, preferably be less than 50%, more preferably less than 40%, most preferably be less than 30% the capsular enzyme of bag and leak in the liquid detergent composition.

Enzyme encapsulate capsule material can contain polymkeric substance, but this is not a restricted condition.If polymkeric substance is present in the capsule, partial polymer should be not dissolved in the liquid washing agent at least, and they disperse or dissolve when dilution.

The example of synthetic polymer is:

The polyvinyl alcohol of-different molecular weight and hydrolysis degree (PVA), it is defined as homopolymer or multipolymer, the therein ethylene yl acetate is the monomer unit that begins most, wherein great majority or all the acetic ester part be hydrolyzed into alcohol moiety (for example from the Airvol series of Air Products, from the Mowiol series of Hoechst) subsequently

-polymeric amide (obtaining) by diamines and dicarboxylic acid reaction

-polyester (obtaining) by two pure and mild dicarboxylic acid reactions

-polyureas

-urethane

-Resins, epoxy

Other example of natural polymer comprises:

-methylcellulose gum (for example Methocal A15LV, from Dow Chemical)

-hydroxy propyl cellulose (for example Klucel L or Klucel G, from Aqualon)

-HYDROXY PROPYL METHYLCELLULOSE

-carrageenin (K or I form) (dissimilar) from FMC

-alginate (for example Manucol DM or DH, from Kelco)

-gellan gum (for example Kelcogel, from Kelco)

-gelatin

Other reference: be used for the polymkeric substance of makeup and the encyclopedia of thickening material, 108 volumes, in May, 1993,95-135.

If there is polymkeric substance in capsule, they can be used as little solid particulate and exist, and perhaps are dispersed in the whole particulate or preferentially are arranged in capsular part, for example in capsular skin.Polymkeric substance also can be used as hydrated particulate and exists, and it can be scattered in whole particulate or be arranged in capsular part.Polymkeric substance can also be in capsule the form of onion ring be present in capsular core or as the shell around the core.

The enzyme capsule also can contain hydrophobic or fatty substance, and their example is:

-paraffin (preferred vaseline)

-tri-glyceride

-lipid acid

-Fatty Alcohol(C12-C14 and C12-C18)

The mixture of-lipid acid and fatty acid soaps

-ester (for example ceto stearic acid stearyl)

If capsule contains hydrophobic substance, they are damp proof with protective enzyme.Hydrophobic substance should be encapsulated in enzyme solia particle or the drop that exists in the capsule.

Capsule also can contain other component:

-density properties-correcting agent, for example sucrose

-structural agent, for example silica or zeolite

-filler, for example talcum, wilkinite

-scavenging agent, for example ammonium sulfate

-softening agent

-anti-agglomeration or layering agent

-releasing agent

Therefore, in preferred embodiments, enzyme encapsulate capsule material can contain polymkeric substance, and preferred enzyme encapsulate capsule material contains the polymkeric substance that is selected from polyvinyl alcohol, polymeric amide, polyester, polyureas, urethane, Resins, epoxy, methylcellulose gum, hydroxy propyl cellulose, HYDROXY PROPYL METHYLCELLULOSE, carrageen acid, alginate, gellan gum, gelatin and their mixture.

The example of enzyme encapsulate capsule material can find in WO93/07263, EP-A-585295, EP-A-356239, US-A-5281356, US-A-5281355 and GB-A-2186884.

Enzyme encapsulate capsule material has the 30-5000 micron, preferred 200-3000 micron, the most preferably D between the 500-2500 micron (3,2) mean diameter.Particulate form can be from the random sphere that becomes, and in a preferred form, they should be subglobulars, but should not be limited to this.

Enzyme encapsulate capsule material has 700-2500kg/m ³, more preferably 800-2000kg/m ³And 900-1500kg/m most preferably ³Enzyme encapsulate capsule material density (in detergent solution, measuring).

Enzyme can be uniformly distributed in whole particulate (matrix capsule), be arranged in capsule (core-shell capsule) core or be present in the zone of any other restriction of capsule, onion shape area for example.

Enzyme can be present in the capsule as small particle by solid form, and it can contain true protein or the mixture of protein and other material (optionally with the matrix of other component in) optionally.Enzyme can also enzyme solution the small droplets form or be present in the capsule as solid and mixtures of liquids (soup compound).

Enzyme encapsulate capsule material can contain any detergent enzyme, comprises proteolytic enzyme, lipase, amylase, peroxidase, cellulase or their mixture.

The example of proteolytic enzyme is that commerce can obtain type, for example Alcalase ^TM, Durazym ^TM, Relase ^TM, Sayinase ^TM, from Novo Nordisk and Optimase ^TM, Purafect ^TM, Properase ^TM, from GenencorInternational.

The example of lipase is Lipolase ^TM, from Novo Nordisk and Lipomax ^TM, from Genencor International.

The example of cellulase is Celluzyme ^TMAnd Carezyme ^TM, from NovoNordisk and Clazinase ^TM, from Genencor International.

Diastatic example is Termamyl ^TM, from Novo Nordisk and Maxamyl ^TM, from Genencor International.

Enzyme is proteolytic enzyme preferably.

When enzyme was proteolytic enzyme, protein content was preferably 0.1%-20%, more preferably 0.5%-10%, most preferably 1%-5%.

When enzyme was proteolytic enzyme, enzymic activity was 100GU/mg-20000GU/mg, more preferably 500-10000GU/mg, most preferably 1000-5000GU/mg.

Deflocculated polymkeric substance

According to a second aspect of the invention, transparency can add deflocculated polymkeric substance realization by (when lamellar phase contains the stratiform drop).

According to the specification sheets of EP-A-346995, the dependency of stability and/or viscosity and volume fraction advantageously influences by add the deflocculated polymkeric substance that contains hydrophilic skeleton and one or more hydrophobic side chains in lamellar dispersions.

The theory of these deflocculated polymkeric substance effects is skins that hydrophobic chain adheres to the bilayer of stratiform drop, and hydrophilic segment is outwards expanded.These hydrophilic " brushes " cause the spatial stability effect of drop, and its condition is that " brush " surpasses certain-length.For surfactant mixture commonly used, for adhering to bilayer, the optimum length of polymer hydrophobic chain is C ₁₂-C ₁₅, the length of tensio-active agent in about drop.

Therefore, people are known adds deflocculated polymkeric substance in the structurized aqueous liquid detergent of usefulness stratiform dispersion of droplets.Yet in these conventional compositions, it is in the stable and dumpable base composition (same combination that does not promptly have polymkeric substance) that polymkeric substance adds known.Aspect practical, EP-A-346995 is defined as the effect of the polymkeric substance in stable and dumpable composition with conventional deflocculation, thereby the same combination that does not contain deflocculated polymkeric substance has obviously higher viscosity and/or becomes unstable.

In contrast, the composition of a second aspect of the present invention is that the same combination that do not contain deflocculated polymkeric substance under 25 ℃ does not have obviously higher viscosity and is stable.

Preferred term " does not have obviously higher viscosity " and is meant at 21s ^-1Under the shearing rate, the difference of viscosity is no more than 500mPa.s, preferably is no more than 250mPa.s.

Term " stable " is meant preferably that when playing 21 days by preparation time under 25 ℃ composition produces and is no more than 2% as seen be separated by volume, when more preferably playing 90 days by preparation time under 25 ℃, is less than 0.1% as seen be separated by volume.The composition of the present invention of where face in office is according to these definition preferably " stable ".

Therefore, when any composition of the present invention contains deflocculated polymkeric substance, it can contain one or more EP-A-346995 and/or deflocculated polymkeric substance as described below.

Usually the quantity of the deflocculated polymkeric substance in the composition aspect any of the present invention is by composition weight meter 0.01%-5.0%, most preferably 0.1%-2.0%.

For example EP-A-438215 discloses with for example can being C ₆-C ₁₂The secondary alcohol chain transfer agents preparation of simple function group secondary alcohol has the method for the vinylformic acid telogen of functional group dead-end group.These substance descriptions are as detergent additives, especially sequestrant or anti-sludging agent.This material prepares as polymerization starter with for example ditertiary butyl peroxide, in various possible initiators are described, has mentioned lauryl peroxide.

The deflocculated polymkeric substance that only contains a hydrophobic part and some particular variety that is connected in the hydrophilic chain terminal position is open in EP-A-623670.

The different subtype of deflocculated polymkeric substance is described in EP-A-623670, yet, the material that many reality are given an example is the mercaptan polyacrylic ester, promptly this material is by in the presence of the hydrophobic chain transfer agent that contains 5-25 carbon atom and end-SH group, and polymeric acrylic acid forms in the radical polymerization process.It is open in US-A-5489395, US-A-5489397 and EP-A-691399 to have sulphur heterodesmic similar substance between the hydrophilic and hydrophobic part of molecule.

The suitable deflocculated polymkeric substance of another kind contains the oligopolymer or the polymkeric substance of disclosed formula (I) in our undocumented International Patent Application WO 98/55576:

Q ¹-X ¹-Y ¹-Z-W (I) is Q wherein ¹-expression hydrophobic part ,-X ¹-and-Y ¹-be respectively not exist or represent suitable linking group ,-Z-represents hydrophilic chain; Represent H or formula-Y with-W ²-X ²-Q ²Group, each-X ²,-Y ²With-Q ²Be selected from X as defined above respectively ¹, Y ¹And Q ¹Definition.

Q ¹The C that preferred expression optionally replaces ₅-C ₃₀Alkyl, C ₅-C ₃₀Thiazolinyl or C ₅-C ₃₀Aralkyl or hydrophobic monomer residue are for example from TEMPO (2,2,6, the 6-tetramethyl-piperidyl-1-oxygen base) part of methacrylic acid Lauryl Ester or hydrophobically modified.Alkyl, thiazolinyl or aralkyl most preferably contain 8-18 carbon atom, preferred straight chain or only limit to side chain.Preferred X ¹Be not exist or expression (CH ₂-) _nGroup, wherein n is 1 or 2 or X ¹Be phenyl, preferred Y ¹Be not have or represent carbonyl, ester bond, hydroxyl C _1-5Alkyl or formula (SiR ¹R ²) silyl, R wherein ¹And R ²Expression-CH respectively ₃Or-C ₂H ₅Or Y ¹Be thia-, azepine-, carboxyl-(being ester), carboxyl-azepine-, phosphoryl, phosphono or phosphine oxide base key, be not H but its condition is W.

Group-Z-is straight or branched or crosslinked slightly molecular composition preferably, and it contains the more hydrophilic monomeric unit of one or more types.Preferred hydrophilic monomer itself is enough water miscible, to form at least 1% solution by weight when being dissolved in the water.To the only restricted of structure-Z-is that formula (I) polymkeric substance that generates must be appropriate to add in the aqueous liquid detergent compositions of active structureization, with corresponding to independent hydrophilic segment, the polymkeric substance that is H-Z-H is dissolved in relatively, promptly the solvability in water preferably surpasses 1g/l under room temperature and 3.0-12.5pH value, more preferably surpass 5g/l, most preferably surpass 10g/l.

Group-Z-preferably mainly is a straight chain, and more preferably the main chain of skeleton accounts at least 50% of skeleton weight, preferably surpasses 75%, most preferably surpasses 90%.

Group-Z-is made up of monomeric unit usually, and it can be selected from the different units that can be obtained by the polymer manufacture process.

The example of this class monomeric unit that comprises alone or in combination in-Z-is:

(i) unsaturated C ₁-C ₆Acid, ether, alcohol, aldehyde, ketone or ester, preferably these monomeric units are monounsaturated.Vinyl alcohol, propenal, alkenyl alcohol and vinylacetic acid that the example of proper monomer is vinylformic acid, methacrylic acid, toxilic acid, Ba Dousuan, methylene-succinic acid, equisetic acid, citraconic acid, vinyl methyl ether, vinyl sulfonic acid ester, obtain by the hydrolysed ethylene yl acetate.Also comprise corresponding salt, an alkali metal salt for example is as sodium salt.

(ii) ring element, undersaturated or contain can form in other groups of monomer key.In connecting these monomers, monomeric ring structure can be to be kept perfectly or ring structure can be by fracture to form skeleton structure.The example of ring monomeric unit is a sugar unit, for example carbohydrate and glucosides; Oxyalkyl units, for example oxyethane and hydroxyl propylene oxide; And maleic anhydride.

(iii) other unit, for example glycerine, polyoxyalkylene or unsaturated polyol.

Be included in-each above-mentioned monomeric unit among the Z-can be by group, and for example amino, ammonium, acid amides, sulfonate, vitriol, phosphonate, phosphoric acid salt, hydroxyl, carboxyl and oxide groups replace.

Group-Z-preferably is made up of one or both monomer types, but also can use three kinds or multiple different monomers type in hydrophilic skeleton.The example of preferred hydrophilic skeleton is: the multipolymer of the multipolymer of acrylic acid homopolymer, vinylformic acid and toxilic acid, poly-(2-hydroxyethylmethacry,ate), glycan, ether of cellulose, Polyglycerine, polyacrylamide, polyvinyl alcohol/polyvinyl ether copolymer, polyvinylsulfonic acid sodium, poly-2-sulfato ethyl-methyl acrylate, polyacrylamide amino methyl propane sulfonate and vinylformic acid and three methanol-based propane triacrylate.

Group-Z-also optionally contains a small amount of hydrophobic units relatively, and for example by have the material that the deliquescent polymkeric substance that is lower than 1g/l obtains in water, its condition is that the overall solvability of hydrophilic polymer skeleton still satisfies above-mentioned solvability needs.The example of insoluble polymer is polyvinyl acetate, poly-methyl methacrylate base ester, polyacrylic acid ethyl ester, polyethylene, polypropylene, polystyrene, polybutene oxide compound, poly(propylene oxide) and poly-hydroxypropyl acetic ester relatively.

The preferred subclass of formula (I) oligopolymer or polymkeric substance (hereinafter referred to as " material of the present invention ") comprise respectively wherein W be the material of H and wherein W be-Y ²-X ²-Q ², part or all of X ², Y ²And Q ²Be different from X respectively ¹, Y ¹And Q ¹And wherein W is-Y ²-X ²-Q ², each X ², Y ²And Q ²With X ¹, Y ¹And Q ¹Identical material.

If W is H, only there is the single hydrophobic part that is connected in hydrophilic segment one end.This material is ideally as deflocculated material.If W is group-Y ²-X ²-Q ², then a hydrophobic grouping being arranged respectively at the two ends of hydrophobic part, this material can be used for the intentional bridge joint of stratiform drop, in order to for example to increase viscosity.

Certainly, as mentioned above, deflocculation is used for suppressing viscosity when high-volume fractional usually increases, and therefore, bridge joint is undesirable in essence.Yet the bridge joint material that contains a pair of hydrophobic grouping (W is not a hydrogen) within the scope of the invention.For example can use the predetermined mixture of material of the present invention, it contains deflocculated material increases viscosity with control stiffness and a bridge joint material with controllable method.

Bridge joint material per molecule on average has the hydrophobic (Q above ¹/ Q ²) group, preferred two or more such hydrophobic groupings.The molecular weight of bridge joint material (Mw) is greater than (x.Mi+Mo) as a result, be preferably greater than (x.Mi+2Mo), more preferably greater than 2 (x.Mi+Mo), x is the molecular ratio of hydrophilic monomer and hydrophobic monomer, Mi is the molecular-weight average of hydrophilic radical, and Mo is the molecular-weight average of hydrophobic grouping.

The bridge joint polymkeric substance preferably uses conventional aqueous polymerization method preparation, but adopt polymerization process wherein to have the method for carrying out in suitable co-solvents, the ratio of wherein carefully monitoring water and cosolvent is with the polymkeric substance that forms under the condition that remains on enough mutabilities with the precipitation of the polymkeric substance avoiding unwanted homopolymerization process and formed by hydrophobic monomer.Method of the present invention provides a kind of product, and it is stable and transparent, and it does not show that when static gel or product separate.Suitable cosolvent is selected from Virahol, n-propyl alcohol, acetone, rudimentary (C ₁-C ₄) alcohol, ester and ketone and wherein the ratio of water and cosolvent be less than 1.5, be more preferably less than 1.0, be more preferably less than 0.75, especially less than 0.5.

Use the deflocculated material of preferable definition and the mixture of bridge joint material can control rheol degree, thereby can not contain " cocktail " of the polymkeric substance that the method by EP-A-346995 forms.

Yet, should understand deflocculated (W=H) or the bridge joint (W=-Y of the formula of formation (I) ²-X ²-Q ²) any method of oligopolymer or polymkeric substance will not form 100% pure substance.Yet sample oligopolymer of the present invention or polymkeric substance will contain the oligopolymer or the polymer material with formula (I) structure of high weight percentage, though do not need all percentage ratio will have the same structure of formula (I).Therefore, the preferred sample of oligopolymer of the present invention and/or polymer material or can contain in batches oligopolymer and/or the polymkeric substance of having as the general formula in the claim 1 (I) by gross weight at least 50%, or optionally as formula (I) polymkeric substance that defines in specification sheets or any other claim or the preferred subclass of oligopolymer.In rising order preferred, this weight percentage is more preferably by total lot amount or example weight at least 65%, 70%, 75%, 80%, 85% or 90%.

The stratiform drop

Of the present invention second and the third aspect be applied to the subgroup of composition, wherein lamellar phase contains the stratiform drop.

A third aspect of the present invention is dependent on such discovery, i.e. the size of the major portion by restriction stratiform drop promptly makes their D _{V, 90}Less than 2 microns, be more preferably less than 1.0 microns, for example less than 0.5 micron, be more preferably less than 0.2 micron, also preferably less than 0.1 micron with especially can produce transparency less than 0.05 micron.The D of drop _{V, 90}Be defined as 90% of all droplet sizes have less than shown in diameter.Actual D for given sample _{V, 90}Value can be measured by the following method: prepare the electron microscope picture of liquid detergent composition with the ratio of enlargement of 15000-60000 (preferred about 30000), measure each diameter drop relative populations and calculate the cumulative volume distribution of sizes by the accumulation diameter size distribution that obtains; Or use laser scanning particle size analyzer, for example Malvern Mastersizer.

The D of drop _{V, 90}But the subcritical value is for example by adding deflocculated polymkeric substance according to a second aspect of the invention or passing through to use as disclosed so-called surface of stability promoting agent among the EP-A-328177 as the part of surfactant mixture.Generation comprises working method less than other method of the stratiform drop of definition size, wherein uses shear conditions to apply high liquid stress, and this will explain in detail in the part of following relevant processing.

Specific refractory power

A fourth aspect of the present invention needs the specific refractory power of lamellar phase and water to match in so basically mode to make composition have at least 5% optical transmittance.

Specific refractory power (the n of lamellar phase _Lam) can be by using the specific refractory power (n of each component in lamellar phase _k) and the volume fraction (v of this component of in lamellar phase, existing _k/ v _Lam) use following formula to calculate:

$\frac{n_{\mathrm{lam}}^2-1}{n_{\mathrm{lam}}^2+2}*V_{\mathrm{lam}}=\underset{k=1}{\overset{n}{\mathrm{\Σ}}}\frac{n_k^2-1}{n_k^2+2}*V_k$

As a whole, the specific refractory power of liquid detergent composition can for example be measured as follows.Make the thin layer (preferably about 1mm) of the light of wavelength 589nm, measure input angle and reflection angle, calculate specific refractory power with the Snellius equation subsequently by liquid detergent composition.Another preferred method of measuring specific refractory power is to use the internal reflection measuring method, for example by using Atago numeral refractometer RX-1000 or Bellingham and Stanley refractometer RFM91.In order to measure the specific refractory power of opaque system, it is especially favourable adopting the internal reflection measuring method.

The specific refractory power of corresponding water can be by by detergent composition water phase separated (for example centrifugal by (super)) or prepare composition individually, thereby insoluble component only joins its solubility limit, omits dispersive and measures mutually.

Difference between the specific refractory power of preferred lamellar phase and the specific refractory power of water more preferably no more than 0.01, also preferably is not more than 0.005 for being not more than 0.02, especially is not more than 0.002.

Cooperate for obtaining basic specific refractory power, can increase the specific refractory power of water and/or can reduce the specific refractory power of lamellar phase.

The specific refractory power of water can be passed through dissolved substance increase therein, yet the material that causes the specific refractory power increase that adds usually influences the physical stability of system, as ionogen and solubilizing agent.Other low-molecular-weight relatively material can obviously not influence the stability or the viscosity of composition, though because some influence of the annexing ingredient of water, it will influence the volume fraction of lamellar phase and/or the viscosity of water inevitably.Usually these materials are low-molecular-weight relatively neutral nonelectrolyte materials, be particularly useful for increasing the specific refractory power of water and what total system character was not had disadvantageous effect is sugar (as a fifth aspect of the present invention is needed), because this material is effective and relatively low cost.

Yet it is optional from containing one or more sugar and derivatived celluloses that make the hydrophilic substituent that they are dissolved in water to be usually used for increasing the water-soluble nonelectrolyte material of water specific refractory power.

Suitable steamed bun stuffed with sugar is drawn together monose, for example glucose and fructose, disaccharides, for example sucrose, sucrose, lactose, maltose and cellobiose.Can also use glucose syrup, they contain list, two and the mixture of polysaccharide, and the list and two sugar moieties of preferred carbohydrate mixture should be at least 50%.As mentioned above, people are known to use non-sugar polyol on a small quantity in aqueous liquid detergent, and for example glycerine or Sorbitol Powder are used for the stability of enzyme.This material also can be used for being used in the composition of the present invention specific refractory power and cooperates, but following stationery body is described, and quantity will be higher than the quantity that is used for enzyme stability.

What be used for equally that specific refractory power cooperates is polysaccharide, water-soluble glue for example, and for example guar gum, xanthan gum, gum arabic and tragacanth gum, though not too preferred, because these components are being used for the quantity that specific refractory power cooperates and are adding the fashionable viscosity that increases total system with suitable.

The material that is used to increase other kind of water specific refractory power is a polyvalent alcohol, as glycerine and polyoxyethylene glycol.

The needed quantity of water-soluble nonelectrolyte material that is chosen in the composition is cooperated to influence basic specific refractory power.Yet, press general composition weight meter, minimum quantity is generally 2.5%, and is preferred 5%, and especially 10%.Press general composition weight meter, the maximum quantity of water-soluble nonelectrolyte material is generally 50%, and is preferred 40%, and especially 30%.Specify the special range of these quantity if desired, use any specific minimum value to match with any specific maximum value.

Detergent active material

The specific refractory power of lamellar phase can reduce by selecting suitable tensio-active agent or surfactant mixtures.A kind of suitable method is to get rid of the aralkyl tensio-active agent basically, for example alkylbenzene sulfonate, the i.e. sum of aralkyl tensio-active agent, by total surfactant (comprising any soap) weight, should be lower than 30%, preferably be lower than 10%, more preferably less than 5%, especially be lower than 1%.Most preferably there is not this aralkyl tensio-active agent fully.

Form the surfactant mixture that lamellar phase does not use the aralkyl material for preparation is applicable to, people can for example use uncle and/mixture of secondary alkane vitriol or sulfonate material and one or more nonionogenic tensides.

The example of suitable alkane sulphur (sulphur) hydrochlorate is sodium alkyl sulfate and potassium, especially senior (the C that is produced by for example butter or Oleum Cocois by sulfonation ₈-C ₁₈) uncle or the material that obtains of secondary alcohol.

Suitable nonionogenic tenside especially comprises the compound that contains hydrophobic grouping and active hydrogen atom, for example fatty alcohol, acid, acid amides and oxyalkylene, especially independent oxyethane or with the reaction product of propylene oxide.Concrete nonionic detergent compounds is the alkyl (C that has oxyethane ₆-C ₁₈) product for preparing of uncle or uncrimping chain or branched-chain alcoho and the reaction product by condensed epoxy ethane and propylene oxide and quadrol.Other so-called nonionic detergent compounds comprises long chain tertiary amine oxide compound, long chain tertiary phosphine oxide and dialkyl sulphoxide.

Total alkane sulphur (sulphur) hydrochlorate is preferably 90 with the weight ratio of total nonionic: 10-10: 90, more preferably 80: 20-50: 50.

Another the suitable surfactant mixture that is used for this purposes contains one or more soaps and one or more nonionogenic tensides.

Suitable soap comprises the long-chain list that for example contains 12-18 carbon atom-or the alkali metal soap of dicarboxylic acid, and the acid of this quasi-representative is oleic acid, ricinoleate acid and the lipid acid that obtained by Viscotrol C, rape seed oil, peanut oil, Oleum Cocois, palm-kernel oil or their mixture.Can use these sour sodium or potash soaps.

With the suitable nonionogenic tenside of soap blended be aforesaid.Total soap is preferably 60 with the weight ratio of total nonionic: 40-90: 10, more preferably 70: 30-80: 20.

In other preferred composition, partly or entirely detergent active material is a stabilized surfactant, and it has greater than the mean alkyl chain of 6 carbon atoms long, and it has more than or equal to 6.4 salt tolerant analyses ability.These stabilized surfactant are open in EP-A-328177.The example of these materials is the polyalkoxylated phosphoric acid salt of alkyl, the polyalkoxylated sulfosuccinate of alkyl, dialkyl group phenylbenzene oxidation thing stilbene-4,4'-bis-(1-azo-3, 4-dihydroxy-benzene)-2,2'-disulfonate, alkyl polysaccharide and their mixture.The advantage of these tensio-active agents is that they are the tensio-active agents with relative low-refraction, and these tensio-active agents trend towards reducing the drop size of stratiform drop.Two kinds of effects have positive interaction to the transparency of system.

Yet, need to prepare the content of tensio-active agent with the specific refractory power that reduces lamellar phase except any, in a broad sense, detergent active material in the composition can contain one or more tensio-active agents usually, and it can be selected from negatively charged ion, positively charged ion, nonionic, zwitter-ion and amphiprotic substance and their mixture (condition is compatible mutually).For example their optional leisures " tensio-active agent ", volume 1, Schwartz ﹠amp; Perry, Interscience 1949 and " tensio-active agent ", volume II, Schwartz, Perry ﹠amp; Berch (Interscience 1958), at " McCutcheon ' s emulsifying agent and washing composition " of present version, by McCutcheondivision of Manufacturing Confectioners Company publication or at " Tensid-Taschenbuch ", H. Stache, 2nd, Edn,., Carl HanserVerlag, Muenchen; Wien, any kind of of describing in 1981, subspecies class and concrete material.

Under many (but not being whole) situation, total detergent active material can be by general composition weight meter 2%-60%, for example 5%-40% and 10%-30% existence by weight usually.Yet a kind of composition of preferred kind contains at least 15% by general composition weight meter, more preferably at least 25%, and at least 30% detergent active material especially.Under the surfactant mixture situation,, will cause the definite ratio of each component of this stability and viscosity will depend on electrolytical type and quantity as the situation of conventional structure liquid.

Anion surfactant commonly used normally has the organic sulfate that contains about 8-22 carbon atom alkyl and the water-soluble alkali metal salts of sulfonate, and used term alkyl comprises the moieties of senior acyl residue.

Except that the above-mentioned anion surfactant of having mentioned about specific refractory power control, if desired, people also can adopt conventional alkyl (C ₉-C ₂₀) benzene sulfonic acid sodium salt and potassium, especially linear secondary alkyl (C ₁₀-C ₁₅) ether of benzene sulfonic acid sodium salt, alkyl glycerol ether sodium sulfate, the especially higher alcohols that obtains by butter or Oleum Cocois and the synthol that obtains by oil.Other suitable anion surfactant comprises Oleum Cocois fat direactive glyceride sodium sulfate and sodium sulfonate, senior (C ₆-C ₁₈) the Fatty Alcohol(C12-C14 and C12-C18) oxyalkylene; especially the sodium of the sulfuric ester of oxyethane and sylvite, lipid acid; for example coconut fatty acid is with the isethionic acid esterification with the sodium of the fatty acid amide of sodium hydroxide neutral reaction product, N-methyltaurine and sylvite, alkane monosulfonate, for example, and by making alpha-olefin (C _8-20) react the material that obtains and make paraffinic hydrocarbons and SO with sodium bisulfite ₂And Cl ₂Reaction, material and the alkene sulfonate that obtains to produce random sulfonate with basic hydrolysis subsequently, this term are used for description by making alkene, especially C ₁₀-C ₂₀Alhpa olefin and SO ₃Reaction is with the material of post neutralization and the preparation of hydrolysis reaction product.

Water

The quantity of water is preferably 5-95% in composition, more preferably 25-75%, and 30-50% most preferably especially preferably is lower than by weight 45%.

Ionogen

Though can in independent water, form the stratiform disperse phase of tensio-active agent, in many cases, contain water continuous phase and preferably contain the dissolved ionogen.The term ionogen that is used for this paper is meant any water insoluble nonionic material.Yet, in the stratiform dispersion liquid, not that whole ionogen are essential dissolved, suspend but can be used as solia particle, because total electrolyte concentration of liquid is higher than electrolytical solubility limit.Also can use electrolyte mixture, wherein one or more electrolyte dissolutions are in aqueous phase, and one or more only are the solid phase that suspends basically.Two or more ionogen also can distribute with proper ratio in this two-phase.This part ground depends on method, for example adds the order of component.On the other hand, term " salt " comprises all organic and inorganic substance except that tensio-active agent and water, and no matter whether they are ionic, and this term comprises electrolytical subgroup (water-soluble ionogen).

Yet, there is restriction to (promptly suspending) electrolytical size of the non-dissolving in these prescriptions and quantity, this purpose with transparency is consistent.Quantity as the independent sightless small particle of entity should be so low so that the definition according to a first aspect of the invention of the volume of liquid keeps substantial transparent.The quantity of big relatively particulate (being visible as independent entity promptly) should make them have charming visual effect, as above-mentioned " visible solid ".

The only restricted of total amount to detergent active material and ionogen (if existence) is in composition of the present invention, and they must form moisture stratiform dispersion liquid together.Therefore, within the scope of the invention, the surfactant types of non-constant width and the variation of content can be arranged.Surfactant types and for the ratio of the stabilising liq that obtains having desired structure select will be fully in those skilled in the art's ability.

Preferred composition contains 1%-60%, the salting-out electrolyte of 10-45% especially, and salting-out electrolyte has the implication of describing in the EP-A-79646 specification sheets.Optionally also can comprise the molten ionogen of some salt (defining in the following description book), its condition is kind and quantity and other component compatibility, and composition is still consistent with the claimed definition of the present invention.Part or all of ionogen (no matter salt molten or saltout), or any water-insoluble salt basically that exists can have detergent builder compound character.Under any circumstance, preferred composition of the present invention comprises detergent builder compound, and it partly or entirely is an ionogen.Builder material is any any material that can reduce the content of the free calcium ions in the washings, will preferably provide other beneficial property to composition, for example produces alkaline pH, the dirt and the dispersion fabric mild clay material that suspend and removed by fabric.

Detergent builder compound

As mentioned above, water-soluble inorganic detergent builder compound (if being dissolved in aqueous phase) is an ionogen, but any solid matter that surpasses solubility limit will be suspended by lamellar phase usually.

If exist, the example of inorganic phosphor-contained detergent builder compound comprises the water-soluble salt of pyrophosphate salt, orthophosphoric acid salt, polyphosphate and phosphonate, especially an alkali metal salt.The specific examples of inorganic phosphate builders comprises phosphatic sodium of tri-polyphosphate, phosphoric acid salt and hexamethyl and potassium, also can use the phosphine acid salt chelator washing assistant.

If exist, the example of the inorganic detergent builder compound of phosphorated does not comprise the water-soluble alkali metal salts of carbonate, supercarbonate, silicate and crystallization and amorphous aluminosilicate.Specific examples comprises yellow soda ash (containing or do not contain calcite seed crystal), salt of wormwood, sodium bicarbonate and potassium, silicate and zeolite, though keep simultaneously adding having restriction aspect the quantity of solia particle of substantially transparent degree and the volume fraction.

Aspect inorganic builders, we preferably include the ionogen that promotes other electrolyte dissolution, for example use sylvite to promote the solvability of sodium salt.Therefore, the electrolytical quantity of dissolved can obviously increase (crystallization solvency action) described in UK patent specification GB1302543.

If exist; the example of organic detergent builder compound comprises polyacetic acid salt, carboxylate salt, multi-carboxylate, many ethanoyl carboxylate salt, carboxymethyl oxygen base succinate, carboxymethyl oxygen propylmalonic acid salt, quadrol-N, the ammonium salt of basic metal, ammonium and the replacement of N-disuccinate, polyepoxysuccinic acid salt, oxydiethanoic acid salt, Sanya second tetramine six acetates, N-alkyl imino diacetin or dipropionate, alpha-sulfo-soap, dipicolinates, oxidation of polysaccharides, poly-hydroxy sulfonic acid and their mixture.

Specific examples comprises the ammonium salt of sodium, potassium, lithium, ammonium and the replacement of ethylenediamine tetraacetic acid (EDTA), nitrilotriacetic acid(NTA), oxygen di-succsinic acid, mellic acid, benzene polycarboxylic acid and citric acid, tartrate monosuccinic acid salt and tartrate disuccinate.

Aspect organic washing-assisting detergent, also need to add and only be partially dissolved in the polymkeric substance that contains in the water continuous phase, it makes viscosity reduce (owing to dissolved polymers adds sufficiently high quantity to obtain second effect, especially help and wash, because undissolved part is not created in basically when all dissolved the unstable that takes place).Equally for inorganic builders, keep simultaneously adding having identical restriction aspect quantity and the volume fraction of non-dissolve polymer phase of substantially transparent degree.

Other polymkeric substance

The example of partly soluble polymkeric substance comprises known many polymkeric substance and copolymer salt as detergent builder compound.For example, can use (comprise helping to wash and wash polymkeric substance) polyethylene glycols, polyacrylate(s), polymaleic acid ester, glycan, glycan sulfonate and any their multipolymer with non-helping.Preferred partly soluble polymkeric substance contains multipolymer, and it comprises an alkali metal salt of many vinylformic acid, polymethyl acrylic acid or Malaysia acid or anhydride.The composition that preferably contains these multipolymers has and surpasses 8.0 pH.Usually the quantity of viscosity drop low-grade polymer can extensively change according to the prescription of all the other compositions, yet typical amounts is 0.5-4.5% by weight.

In addition, or except partly soluble polymkeric substance, can comprise also in composition of the present invention being dissolved in other polymkeric substance that contains water and have the electrolyte-resistant ability that surpasses 5 gram sodium nitrilo triacetates by weight in 5% aqueous solutions of polymers basically fully that described second polymkeric substance has also that vapour pressure in 20% aqueous solution is equal to or less than by weight the vapour pressure of 2% reference substance or greater than the vapour pressure of the aqueous solution of the polyoxyethylene glycol of molecular-weight average 6000 at 100ml; Described second polymkeric substance has at least 1000 molecular weight.

The adding of water-soluble polymers makes prescription have the stability (with respect to the composition that does not contain water-soluble polymers) of improvement or have low viscosity under identical viscosity under same stable.Even making that under the situation that viscosity reduces, water-soluble polymers also can reduce the viscosity drift.At this, the stability and the lower viscosity of improvement are meant any this effect that surpasses by deflocculated polymkeric substance brought.

Especially have the very much not water-soluble polymers with partly soluble polymkeric substance of dissolved constituent preferred the adding.Though this is because the ability of washing that helps of partly soluble polymkeric substance is good (because can stably add quite high quantity), it will not be best (because than major general's dissolving) that viscosity reduces.Therefore, water-soluble polymers can be used for reducing viscosity to desired level.

Water-soluble polymers can be for example with 0.05-20% adding by weight, though be enough by general composition weight meter 0.1-10% usually, 0.2 to 3.5-4.5% especially by weight.We find to exist the suffertibility of deflocculated polymkeric substance increase to the high levels of water-soluble polymkeric substance, and do not have stability problem.Many different polymkeric substance can be used as this water-soluble polymers, and its condition is to satisfy electrolyte-resistant ability and vapour pressure requirement.The former reaches the quantitative measurement of the required sodium nitrilo triacetate (NaNTA) of the cloud point of the 100ml5%w/w polymers soln under 25 ℃ in water as needs, and system is adjusted to neutral pH, and is promptly about 7, and this preferably carries out with sodium hydroxide.Most preferably the electrolyte-resistant ability is 10gNaNTA, especially 15g.The latter represents that vapour pressure is sufficiently low to have sufficient water binding ability, and that is explained as among applicant's the specification sheets GB-A-2053249 is such.Preferred measuring process 10% aqueous concentration by weight, especially 18% reference solution carries out.

Can be used as water-soluble polymers, if the polymkeric substance type species that they satisfy above-mentioned requirements comprises polyethylene glycols, Dextran, Dextran sulfonate, polyacrylic ester and polyacrylic ester/maleic acid.

Water-soluble polymers must have at least 1000 molecular-weight average, but preferred 2000 minimum average B configuration molecular weight.

In detergent composition, use aforesaid portion water dissolubility and use water miscible polymkeric substance we European patent specification EP-A-301882 and EP-A-301883 in describe.

Solubilizing agent

Though can add a spot of solubilizing agent, for example lower alcohol (for example ethanol) or alkanolamine (for example trolamine) are to guarantee the globality of stratiform disperse phase, and we do not have solubilizing agent by preferred composition of the present invention basically.Solubilizing agent is meant any water-soluble reagent, and it trends towards improving the solvability of tensio-active agent in the aqueous solution.

Other optional ingredient

Except that said components, can also there be many optional ingredients, enzyme optionally adds with enzyme stabilizers.With the enzyme of encapsulate scrotiform formula, above describing as obvious visible suspending components.

Other optional ingredient comprises suds booster, for example alkanolamide, the especially single ethanol amide that is obtained by palm kernel fatty acid and coconut fatty acid, fabric softener, for example clay, amine and amine oxide; Suds suppressor, oxygen discharge SYNTHETIC OPTICAL WHITNER, for example Sodium peroxoborate and SPC-D; The peracid bleach precursor, chlorine discharges SYNTHETIC OPTICAL WHITNER, for example trichloroisocyanuric acid, inorganic salt, sodium sulfate for example, and exist with considerably less quantity usually, fluorescent agent, spices, sterilant and tinting material, greasy dirt release polymers, for example Poly Ethylene Terephthalate-Poly OxyEthylene Terephtalates or its (part) sulfonate modification (comprise Permalose and Aquaperle (trade mark), from ICI, Gerol and Repe-O-Tex (trade mark), from Rhone-Poulenc and Sokalan HP22 (trade mark), from BASF); Anti redeposition agent, for example Xylo-Mucine; Anti-dye-transfer, for example PVP, PVI and their multipolymer.

In above-mentioned these optional ingredients, for the present invention, there is not the lamellar dispersions of deflocculated polymkeric substance can be higher to the reagent of its very stable sensitivity, more useful quantity adds.These reagent can have problems when not having deflocculated polymkeric substance, because they trend towards promoting the flocculation of stratiform drop.The example of this reagent is water-soluble polymers, suitable washing assistant, for example succsinic acid washing assistant, fluorescent reagent, as Blankophor RKH, Tinopal LMS and Tinopal DMS-X and Blankophor BBH and metal chelator, especially phosphonate type, for example Dequest that sells by Mansanto.

Method

Composition of the present invention can be by being used to prepare any ordinary method preparation of liquid detergent composition.Preferable methods is included in disperses electrolyte components (if existence) and a small amount of component except that temperature sensitive component (if existence) in the pyritous water, under agitation add builder material (if existence), detergent active material subsequently, cooling mixture subsequently, add any temperature sensitive a small amount of component, enzyme for example, spices etc.Deflocculated polymkeric substance (if use) for example electrolyte components adds afterwards or as last component.

Preparation and method for processing after can influence the optical transmittance and the transparency of the composition of being produced substantially.For of the present invention second and the third aspect, especially preferably use shear conditions (preferred 10000s at least ^-1) to apply high liquid stress and to help producing substratum shape drop.In preparation process, for example can adopt shear conditions (wherein " shearing " be meant and comprise shearing or extensional or both deformation rates) in the stage forming the stratiform drop.

Therefore, a sixth aspect of the present invention provides the method for compositions of preparation any one or many aspects of the present invention (but especially second and/or the third aspect), and this method is included in 10000s at least ^-1Under the shearing rate blend compositions to the small part component, subsequently the composition that obtains is mixed with any all the other components.

In preparation process, can improve by adopting the viscosity higher mixture by high fluid stress and the less stratiform drop subsequently that applies the high-shear generation.For this reason, before tensio-active agent, preferably add sugar component (if existence) to form a some thickened mixt at the stratiform drop.Yet, it should be noted sugared chemosensitivity.The sugar of pH sensitivity for example, for example fructose should not be exposed to extreme pH in preparation process.

The viscosity higher mixture also can apply high-shear with the enriched material to final product and adopts dilution step subsequently by removing the part process water, for example prepares as the part of the method described in the specification sheets of patent application WO96/20270.In addition, shear conditions can put on final composition after preparation process.High-shear can be passed through static device, and for example shear valve applies as the Saunders diaphragm valve.Preferably it uses dynamic device, and for example dynamically grinding machine applies.The example of this device comprises by Silverson, Fryma or Janke ﹠amp; The equipment that Kunkel makes and please the specification sheets of WO96/20270 in patent in the equipment described.Preferred shear should online installation so that the inflation of composition is reduced to minimumly, inflation will reduce optical transmittance and transparency.The obviously inflation if composition becomes can add degassing step, as centrifugal in preparation process.

Following embodiment is used to further specify the present invention, is not to limit the present invention by any way.

All percentage ratios are weight percentage, except as otherwise noted.

All numerical ranges in specification sheets and claims can change around scope.

At last, the term that is used for specification sheets or claims " comprises " and does not plan to get rid of any term, step or the feature of specifically not mentioning.

Embodiment

The present invention will illustrate with following embodiment, and in all embodiments, except as otherwise noted, all percentage ratios are by weight.

Component	Wt% (except as otherwise noted)
						Comparative example	Embodiment 1	Embodiment 2	Embodiment 3
Non-ionic, Synperonic A7	3.0	3.0	3.0	3.0
					Oleic acid, Priolene 6907	7.0	7.0	7.0	7.0
NaOH is to pH～9.0	0.99	0.99	0.99	0.99
					STP	12.5	12.5	12.5	12.5
Deflocculated polymkeric substance (1)				1.0
					Water	To 100%	To 100%	To 100%	To 100%
The sucrose % of Jia Ruing in addition		20	40	20
					Stability	OK	OK	OK	OK
Viscosity (mPas is at 21 s-1)	150	320	340	690
					Optical transmittance (%) is at 520nm	0.2	12	46	66

These embodiment show:

-not have the sample of deflocculated polymkeric substance be stable

-add sugar to increase transparency

-add deflocculated polymkeric substance to obtain higher transparency

Component	Wt% (unless explanation is arranged in addition)
								Comparative example	Embodiment 4	Embodiment 5	Comparative example	Embodiment 6	Embodiment 7
LAS-acid	7.0	7.0	7.0	7.0	7.0	7.0
							Non-ionic, Synperonic A7	3.0	3.0	3.0	3.0	3.0	3.0
NaOH is to pH～8.0	0.86	0.86	0.86	0.86	0.86	0.86
							STP	11.0	11.0	11.0
Lemon clavulanic acid sodium 2aq				12.5	12.5	12.5
							Deflocculated polymkeric substance (1)		1.0	1.0		1.0	1.0
Water	To 100%	To 100%	To 100%	To 100%	To 100%	To 100%
							The sucrose % of Jia Ruing in addition		20	40		10
The fructose % of Jia Ruing in addition						40
							Stability	Unstable	OK	OK	OK	OK	OK
Viscosity (mPas is at 21 s-1)	40	550	630	180	600	380
							Optical transmittance (%) is at 520nm	0.04	61	67	0.2	9.2	19
Dv, 90 (microns)	＞10		0.8

These embodiment show:

-not have the sample of deflocculated polymkeric substance be stable

-add sugar to increase transparency

-add deflocculated polymkeric substance to obtain higher transparency

-effect is not restricted to sucrose

Component	Wt% (unless explanation is arranged in addition)
								Comparative example	Embodiment 8	Embodiment 9	Embodiment 10	Embodiment 11	Embodiment 12
LAS-acid	5.0	5.0	5.0	5.0	5.0	5.0
							Non-ionic, Synperonic A7	3.0	3.0	3.0	3.0	3.0	3.0
APG， Glucopon 600CS	2.0	2.0	2.0	2.0	2.0	2.0
							NaOH is to pH～8.5	0.61	0.61	0.61	0.61	0.61	0.61
STP	11.0	11.0	11.0	11.0	11.0	11.0
							Deflocculated polymkeric substance (1)				1.0	1.0	1.0
Water	To 100%	To 100%	To 100%	To 100%	To 100%	To 100%
							The sucrose % of Jia Ruing in addition		20	40		20	40
Stability	OK	OK	OK	OK	OK	OK
							Viscosity (mPas is at 21 s-1)	140	210	270	410	480	470
Optical transmittance (%) is at 520nm	0.2	5.2	38	8.8	51	53

Component	Wt% (unless explanation is arranged in addition)
				Comparative example	Embodiment 13
LAS-acid	5.0	5.0
			Non-ionic, Synperonic A7	3.0	3.0
APG，Glucopon 600CS	2.0	2.0
			NaOH is to pH～10	0.61	0.61
Trisodium Citrate 2aq	12.5	12.5
			Deflocculated polymkeric substance (1)		1.0
Water	To 100%	To 100%
			The sucrose % of Jia Ruing in addition		40
Stability	OK	OK
			Viscosity (mPas is at 21 s-1)	200	590
Optical transmittance (%) is at 520nm	0.13	16

Component	Parts by weight (except as otherwise noted)
				Embodiment 14	Embodiment 15
LAS-acid	9.4	14.1
			LES	15	10
NaOH	1.15	1.72
			Trisodium Citrate 2aq	17.1	17.1
Deflocculated polymkeric substance (2)	0.25	0.25
			Water	To 100%	To 100%
Stability	OK	OK
			Viscosity (mPas is at 21 s-1)	6170	6980
Optical transmittance (%) is at 520nm	35	10

Raw material

The about Cl2 alkyl benzene sulphonate (ABS) of LAS-acid is from Huls

LES lauryl ether (about 3 oxyethane) sodium sulfate, Manro Bes

70, from Hickson Manro

Synperonic A7 is with the C13-15 alcohol of 7EO group ethoxylation, from ICI

Oleate Priolene 6907 is from Unichema

The APG alkyl polyglucoside, Glucopon 600CS is from Henkel

STP three (gathering) sodium phosphate, Thermphos NW is from Knapsack

Or three (gathering) sodium phosphate, Rodiaphos HPA-3.5 comes

From Rhone Poulenc

Trisodium Citrate .2aq Trisodium Citrate is from Merck

The polymer A ll of deflocculated polymkeric substance (1) EP346995 is from National Starch

Deflocculated polymkeric substance (2) Marchon XB 16 is from Albright ﹠amp; Wilson

Sucrose is from Cooperatieve Suiker Maatschappij, lotus

Blue

Fructose is from Merck

Following embodiment all illustrates to apply to shear and produces transparent useful influence.In embodiment A and B, apply shearing with the dynamic grinding machine of Silverson LN4 to the finished product, with the highest setting, 10 minutes.Sample is centrifugal subsequently to remove air.

Glucose+the Silverson of embodiment 16-19-different concns, the about 50000s of shearing rate ^-1

Component	Wt% (unless explanation is arranged in addition)
												Comparative example	Embodiment 16	Relatively fall	Embodiment 17	Comparative example	Embodiment 18	Comparative example	Embodiment 19	Comparative example	Embodiment A 5
LAS-acid	7.7	7.7	7.7	7.7	7.7	7.7	7.7	7.7	7.7	7.7
											Non-ionic, Dobanol 25-7	3.3	3.3	3.3	3.3	3.3	3.3	3.3	3.3	3.3	3.3
NaOH is to pH～7	0.86	0.86	0.86	0.86	0.86	0.86	0.86	0.86	0.86	0.86
											Trisodium Citrate	10.0	10.0	10.0	10.0	10.0	10.0	10.0	10.0	10.0	10.0
Deflocculated polymkeric substance (Narl, ex DC1)	1.0	1.0	1.0	1.0	1.0	1.0	1.0	1.0	1.0	1.0
											Water	To 100%	To 100%	To 100%	To 100%	To 100%	To 100%	To 100%	To 100%	To 100%	To 100%
The glucose % of Jia Ruing in addition	10	10	20	20	30	30	40	40	50	50
											Shear	Not	Be	Not	Be	Not	Be	Not	Be	Not	Be
Stability	OK	OK	OK	OK	OK	OK	OK	OK	OK	OK
											Viscosity (mPas is at 21 s-1)	Do not survey	Do not survey	Do not survey	Do not survey	Do not survey	Do not survey	Do not survey	Do not survey	Do not survey	Do not survey
Optical transmittance (%)	1.4	14.8	2.2	27.8	1.6	30.8	1.9	40.6	1.7	47.8
											Dv，90	5.5	1.19	4.8	1.14	Do not survey	0.91	Do not survey	1.35	Do not survey	1.01

Sugar+Silverson that embodiment 20-22 is different (about 50000s of shearing rate ^-1), this further specifies the benefit of shearing, and the benefit of higher list and disaccharides content in commercial ' glucose ' syrup also is described.It illustrates that also shearing is inadequate under the situation of not adding sugar (cooperation of part specific refractory power).

Component	Wt% (unless explanation is arranged in addition)
									Comparative example	Comparative example	Embodiment 20	Comparative example	Embodiment 21	Comparative example (#)	Embodiment 20 (##)
LAS-acid	7.7	7.7	7.7	7.7	7.7	7.7	7.7
								Non-ionic, Dobanol 25-7	3.3	3.3	3.3	3.3	3.3	3.3	3.3
NaOH is to pH～7	0.86	0.86	0.86	0.86	0.86	0.86	0.86
								Trisodium Citrate	10.0	10.0	10.0	10.0	10.0	10.0	10.0
Deflocculated polymkeric substance (Narlex DC1)	1.0	1.0	1.0	1.0	1.0	1.0	1.0
								Water	To 100%	To 100%	To 100%	To 100%	To 100%	To 100%	To 100%
The glucose % of Jia Ruing in addition	Do not have	50	50
								The fructose % of Jia Ruing in addition	Do not have			50	50
" glucose " syrup % solid of Jia Ruing in addition	Do not have					50	50
								Shear	Be	Not	Be	Not	Be	Be	Be
Stability	OK	OK	OK	OK	OK	Sepa ration	OK
								Viscosity (mPas is at 21 s-1)	720	670	670	660	650	Do not survey	Do not survey
Optical transmittance (%)	1.0	1.7	43.0	2.0	10.5	Do not survey	22.2
								Dv，90	Do not survey	4.8	1.01	9.9	1.25	Do not survey	Do not survey

#Cerestar 01411-solids content, the 3%th, monose (glucose), 12% disaccharides (maltose) and 85% 3 and polysaccharide ##Cerestar 01632-solids content, the 38%th, monose (glucose), 37% disaccharides (maltose) and 25% 3 and polysaccharide

Other shearing device of embodiment 23-26.The benefit that this explanation is sheared is not restricted to Silverson.

Component	Wt% (unless explanation is arranged in addition)
								Comparative example	Comparative example	Embodiment 23	Embodiment 24	Embodiment 25	Embodiment 26
LAS-acid	7.7	7.7	7.7	7.7	7.7	7.7
							Non-ionic, Dobanol 25-7	3.3	3.3	3.3	3.3	3.3	3.3
NaOH is to pH～7	0.86	0.86	0.86	0.86	0.86	0.86
							Trisodium Citrate	10.0	10.0	10.0	10.0	10.0	10.0
Deflocculated polymkeric substance (Narlex DC1)	1.0	1.0	1.0	1.0	1.0	1.0
							Water	To 100%	To 100%	To 100%	To 100%	To 100%	To 100%
The glucose % of Jia Ruing in addition	20	20	20	4.35	9.1	20
							Shear	Not	Be	Be	Be	Be	Be
About shearing rate		5,000 seconds -1	40,000 to 80,000 seconds -1	About 10 6Second -1	About 10 6Second -1	About 10 6Second -1
							Stability	Be	Be	Be	Be	Be	Be
Viscosity (mPas is at 21 s-1)	Do not survey	Do not survey	Do not survey	Do not survey	Do not survey	Do not survey
							Optical transmittance (%)	1.2	2.7	8.3	6.0	9.7	28.0
Dv，90	4.37	Do not survey	1.32	Do not survey	Do not survey	Do not survey

Device among the embodiment 23 is the example of the dynamic mixer described among the patent application WO96/20270.This is that mixing tank is shifted in chamber, uses the improvement that moves axially with respect to the rotor of stator.It makes the sectional area that is used for liquid-flow increase successively and reduce with at least 5 the factor along device by arranging cavity, has in conjunction with effectively shearing and extension field of flow function.The result of C1 represents the mean value of different machines operational condition.

Embodiment 24-26 is the embodiment that produces through static shear equipment.It is model " A " Sonolator, is made by Sonic Corporation.Composition is depressed by diameter 0.032cm at about 150 crust back ofs the body ²Annular nozzle (aperture) 30 ℃ of following pumpings.

Second comparing embodiment shows that low-level shearing can provide insufficient increase of transmissivity.

Embodiment 27: dumpable gel

Component	Wt% (unless otherwise indicated)
				Comparative example	Embodiment 27
LAS-acid	14.8	14.8
			Neodol 1-5	22.23	22.23
NaOH	6.6	6.6
			KOH	3.4	3.4
To pH	～8.4	～8.4
			Citric acid 1aq	13.1	13.1
Deflocculated polymkeric substance (Narlex DC1)	4.0	4.0
			Water	To 100%	To 100%
The fructose % of Jia Ruing in addition	0	60
			Stability	Be	Be
Viscosity (mPas is at 21 s-1)	450	4730
			Optical transmittance (%)	0.06	5.5

Foregoing description and embodiment illustrate embodiment selected of the present invention.In view of the above, those skilled in the art can advise various improvement, and all these within the spirit and scope of the present invention.

Claims (10)

1. aqueous liquid detergent compositions with the physical form that is selected from liquid, dumpable gel and non-gel of toppling over, described composition contains the tensio-active agent and the water of 2%-60% weight, said composition the part surface promoting agent and the lamellar phase structureization of portion water formation at least at least, this laminate structure contains the stratiform drop, layered drop is dispersed in and contains in the water continuous phase, it is characterized in that the D of stratiform drop _{V, 90}Less than 2 microns, said composition is transparent at 25 ℃, and has at least 5% optical transmittance by the 1cm optical length under 25 ℃, and it is characterized in that the difference between the specific refractory power of lamellar phase and the specific refractory power of water is for being not more than 0.005.

2. the composition of claim 1 is characterized in that the D of stratiform drop _{V, 90}Less than 1 micron.

3. the composition of claim 1, the specific refractory power that it is characterized in that water increases by dissolving sugar therein.

4. the composition of claim 1 is characterized in that the specific refractory power of lamellar phase reduces by the tensio-active agent that does not have the aralkyl tensio-active agent.

5. the composition of claim 1 is characterized in that also containing deflocculated polymkeric substance.

6. the composition of claim 1 is characterized in that it is colloid-stabilised not having the composition of deflocculated polymkeric substance.

7. the composition of claim 6, it has the physical form of the disperse phase of the stratiform drop that contains in containing water continuous phase, composition also contains deflocculated polymkeric substance, when not having deflocculated polymkeric substance for 25 ℃, said composition is colloid-stabilised, and there is not obviously higher viscosity,, this means at 21s ^-1Under the shearing rate, the difference of viscosity is no more than 500mPa.S.

8. the composition of claim 1 is characterized in that electrolyte dissolution is in water.

9. the composition of claim 1 is characterized in that it has at least 10% optical transmittance by the 1cm optical length under 25 ℃.

10. the composition of claim 9, it has at least 50% optical transmittance by the 1cm optical length under 25 ℃.