CN1100339A - Concentrated aqueous based surfactant compositions - Google Patents

Abstract

The use of a stabiliser comprising a hydrophilic polymeric chain of more than four hydrophilic monomer groups and/or having a mass greater than 300 amu, linked at one end to a hydrocarbon-soluble hydrophobic group to reduce or prevent the flocculation of systems comprising a flocculable surfactant and a liquid medium which is capable of flocculating said surfactant and in which said stabiliser is capable of existing as a micellar solution at a concentration of at least 1% by weight.

Description

Concentrated aqueous based surfactant compositions

The present invention relates to dense aqueous based surfactant compositions, it contains high-load tensio-active agent and/or ionogen, it is undesirable full-bodied that these materials make product have usually, perhaps is divided into two-phase or multiphase when leaving standstill, and the tensio-active agent phenomenon of flocculating in a large number perhaps occurs.

Liquid laundry detergent is compared with the washing powder that accounts for whole cloth-washing detergents market significant proportion has many advantages.For dissolubility washing assistant a little less than runny moisture surface activating agent inner suspension, as tripoly phosphate sodium STPP, or the needs of insoluble washing assistant such as zeolite impel development structure type tensio-active agent (structured surfactants).These are pseudo-plasticity compositions, and works wherein (structurant) is a kind of tensio-active agent or a kind of tensio-active agent/water lyophily intermediate phase (lyotropic mesophase).

The introducing that contains the concentrated detergent powder of higher concentration active ingredient than traditional washing powder has had the trend of competing with the liquid laundry agent.Need denseer liquid laundry agent to satisfy this competition on the market, particularly need to contain the dense aqueous surfactant compositions of the builder salt of dissolved or suspension.The electrolytical adding of a large amount of tensio-active agents and/or dissolved may impel the flocculation that produces high viscosity and/or unsettled structure-type tensio-active agent.

Unacceptable solvent on the environment for use need solve the problem of the water-insoluble or weak dissolubility agricultural chemicals that suspends with new method in liquid medium.The structure-type surfactant system has been represented a kind of like this method.Yet the throwing out of this system connection has seriously limited the exploitation of proper product with the crystal growth of suspended solids.

When the preparation dye bath, perhaps during printing ink, those dyestuff or pigment water-insoluble or weak dissolubility also need to be suspended in runny the thicking liquid to avoid re-using fine powder.

In the presence of polyelectrolyte, the trend that surfactant structure produces flocculation or generation decomposition has hindered the trial in the structure-type tensio-active agent with dyestuff and pigment suspension, described polyelectrolyte usually just is added into pigment before grinding, perhaps play the grinding aid effect.

Softener, toiletry and pharmaceutical preparation also often need prepare the stable suspension of in runny water-bearing media dispersed solid or liquid.This water-bearing media can require the ionogen of high density, and tensio-active agent or both perhaps mix polyelectrolyte.

Oil drilling slurry is to be used for lubricated drill bit and the breaking up rock that bores is transported to the face of land from drill bit.Find that the structure-type tensio-active agent can be used for preparing required rheology and solid suspension powder.This mud needs to tolerate very high electrolyte concentration, for example when salt deposit is passed in boring.This mud contains weighting agent (weighting agent) usually, and as barite, calcite or rhombohedral iron ore are beneficial to get into darker place.Yet getting into final stage, these mud contained usually the solubility weighting agent for example the single fluid of calcium chloride or Calcium Bromide replace.The ionogen of these dissolved alkaline-earth metal is to the high flocculation of most of surfactant structure deposits yields.

Pressing the weight of water and tensio-active agent and calculate, is 30% or more when (weight) at surfactant concentration, and the trend of most of tensio-active agents formation thickness intermediate phase had once limited the ability of enriching liquid detergent or other surfactant systems.Intermediate phase, or mesomorphic phase, be expression than solid low but than typical liquid high ordinal number arranged, such as one dimension or two dimension, partial 3-D.

Many tensio-active agents up to about 30% form micellar solution (L ₁-phase), wherein tensio-active agent is dispersed in the water with micella, and they are aggregates of surfactant molecule, to such an extent as to can't see them with opticmicroscope very for a short time.

Micellar solution looks the same many purposes that have with real solution.Many detergent surfactants of about 30% form a kind of M-phase, and it is a kind of liquid crystal with hexagonal symmetry, and usually are a kind of fixed ceroidlike material.This product is difficult for flowing, and can not be used as liquid detergent significantly.At higher concentration, as surpassing 50%(weight), some concentration range is as mutually more runny with formation one below 80% 60% or more usually, the G-phase.

G-is the normal runny phase of non newtonian (shear-thinning) mutually, but typically has viscosity, flow characteristics and muddiness, and the oyster white phenomenon does not attract the human consumer like this, is not suitable for directly using as for example cloth-washing detergent.Attempt in early days solid suspension is failed to succeed at typical G-mutually, the product of producing is difficult for flowing.The flowed G-that existing report has a dilution in the wide relatively d-gap suspended solids of being on good terms is made runny suspension.

Under the situation of higher concentration, as be higher than about 70% or 80%, most tensio-active agents form a hydration solid.Particularly some formation of nonionogenic tenside contains the water droplet (L of dispersive micellar size ₂-phase) liquid phase.L ₂-find mutually to be not suitable for being used as liquid detergent, because it is difficult for disperseing in water, and tangible gelatigenous tendency.They are suspended solids not.Other can observedly comprise viscosity isotropic (V) phase mutually, and it is a fixed, has glassy.

At polarizing microscope, electron microscope and x-ray diffraction or scattering of neutrons are by its outward appearance, and the bound energy of rheology and structure (texture) is discerned different phases.

The relevant different mutually related following term of discussing in specification sheets need make an explanation or define: " optical isotropy " tensio-active agent usually and be not inclined to the polarization plane of Plane of rotation polarized light.If a sample places between two optical flat polarization things, the plane of polarization of this two material is orthogonal, irradiate light is on a plain film, and when observing by the another one plain film, the sample of optical isotropy tensio-active agent manifests basically unlike brighter around them.It is brighter basically that optically anisotropic substance manifests.Adopt microscope to observe by the polarizer that crosses one another, the optical anisotropy intermediate phase typically shows characteristic structure (characteristic textures).And that optical isotropy shows mutually usually is dark, is essentially the continuous spectrum of atypism.

" Newtonian liquid " has the viscosity that keeps stable under the different shear rate shape.The purpose of this specification sheets is, if in shearing rate during up to 1000/ second, the essentially no variation person of its viscosity is regarded as Newtonian liquid.

L ₁Be mobile mutually, optical isotropy, the typical Newtonian liquid of display structure not under polarizing microscope.Only under very high very big multiple, could arrive the structure of this phase, under x-ray diffraction under the very little angle or scattering of neutrons normal circumstances, still see the broad peak of a single typical liquid structure, L with electron microscopic observation ₁The viscosity of phase is low usually, but also can significantly rise in limited time when concentration reaches going up of this phase.

L ₁-be single mutually, thermodynamically stable phase, it can be considered to the aqueous solution, and wherein solute molecule is combined into spheric, bar-shaped or disc-shaped micelle, their diameter generally is about 4-10 millimicron (nanometers).

" stratiform " is to comprise a large amount of be arranged in parallel or by the phase of the separated double-layer surface-active agent of liquid medium mutually.They comprise that promptly solid-state phase also comprises typical liquid crystalline G-phase.G-is typical runny non newtonian, anisotropic product mutually.They are typical thickness outward appearance, have the oyster white material of distinctive " greasy shape " outward appearance when mobile.They form distinctive structure under polarizing microscope, and (freeze fractured) sample of observing its freezing crushing under the Electronic Speculum has a layer sample outward appearance.X-ray diffraction or scattering of neutrons illustrate a stratiform structure equally, its main peak typically 4 and 10nm between, be generally 5-6nm.When at the twice of main peak Q value or higher integral multiple, higher order peak (order peaks) appears.Q is momentum transfer vector (momentum transfer vector), and when lamellar phase, it relates to the repetition interval d that draws through following formula.

Q＝ (2nπ)/(d)

Wherein, n is peak order (order of peak)

G-can comprise the state and the spherocrystal that becomes with a large amount of homocentric sphere hull shapes of the parallel lamella of the main body that constitutes above-mentioned typical G-phase with several multi-form existence mutually, and each spherocrystal all is double-deck tensio-active agent.It is the composition of former structure attitude at least in part that term in this specification sheets " stratiform " will apply to.Back one type of prevailing at least this transparent composition is referred to as " spherocrystal shape " thing, and the external phase in wherein back one type is a kind of isotropic basically solution that contains the dispersive spherocrystal.The diameter of spherocrystal typically between 0.1 to 50 micron, therefore is different from micella basically.Different with micellar solution, spherocrystal shape composition is the heterogeneous system that comprises at least two phases basically.They are anisotropic, non newtonian.When closely knit and stable, spherocrystal has good solid suspension performance.The composition that contains the external phase of non-spherocrystal shape circular layer contains some spherocrystal usually, but does not have dispersible solid or other phase times, and it is typical transparence.And be referred to as " the combined thing of G-".G-is write as L α-phase mutually in the literature sometimes.

M-is typical fixed mutually, the product of anisotropic class ceraceous sample.Under polarizing microscope, has distinctive structure, have the sexangle diffraction pattern with x-ray diffraction, scattering of neutrons contains a main peak, and the value corresponding to recurrence interval (repeat spacing) is between the 4-10nm usually, higher order peak is arranged sometimes, and its first peak Q value is 3 of main peak Q value ^0.5Doubly.Bimodal Q value subsequently with main peak.M-is write as the H-phase mutually in the literature sometimes.

L ₂-phase and L ₁Mutually opposite, be included in the micellar solution of the water in the successive liquid surfactant medium.With L ₁The same mutually, they are isotropic and newton.

Viscosity isotropy or " VI " they are typical fixed mutually, non newtonian, optically isotropic, and be that the typical case is transparent at least in pure.VI is the diffraction pattern of cubic symmetry mutually when x-ray diffraction, and scattering of neutrons is 2 of main peak Q value ^0.5With 3 ^0.5Doubly locate to occur a main peak and higher order peak.

Reported increase, after micellar phase, occurred a kind of cubes mesomorphic phase immediately along with the concentration of room temperature lower surface promoting agent.Someone proposes this VI phase, is called I sometimes ₁Phase may be from the heap of the micella in the cubic(al)grating (may be sphere).Further increase surfactant concentrations under the room temperature and usually cause producing hexagon phase (M ₂), it produces after lamellar phase (G).When I occurring ₁Phase time mostly just can be observed in a narrow concentration range, is typically just at L ₂Mutually on the concentration range of Xing Chenging.This is to be made of the little surfactant aggregates closely in the continuum of water mutually for the position indicating of this VI in phasor.

According to the report I ₂The anti-phase of phase (is I ₂Phase) also may be between opposite sexangle (M ₂) and L ₂Mutually.It is made up of the tensio-active agent continuum that contains water micellar cube array.Be called V ₁A kind of form of selecting of the VI phase of phase is observed mutually and between the concentration of G phase at M, and it comprises a pair of continuous system.This situation shows I ₂Higher viscosity is arranged mutually.Also supposed a kind of at G and M ₂What exist mutually is anti-phase, V ₂Phase.

Observe or proposed several other intermediate phase, comprised the nematic phase that contains wired spline structure.

Term " structure-type tensio-active agent " is used for representing runny, the non newtonian composition of flow-like, and it relies on the existence of tensio-active agent intermediate phase or solid phase, has the ability of physical property ground suspended solids, and these solid particulates are dispersed in the solvent phase.The latter is ionogen water (aqueous eletrolyte phase) normally.Tensio-active agent exists with the closely knit spherocrystal form that is dispersed in aqueous phase mutually usually.Alternative, continuous net-shaped moisture distribution of the lamellar phase of the flowability of skim or a pair of and lamellar phase also can exist.Sexangle usually is not enough to flow form the basis of body structure surface active agent mutually, but can exist exceptionally.Fail to observe and cube can sufficiently flow mutually.L ₁Or L ₂Mutually itself can not structurizing, they lack suspension property, but can exist with for example external phase form, and in its laminate or spherocrystal were dispersed in mutually, it also can exist by disperse phase, for example is dispersed in a continuous stratiform or the isotropic phase.

Body structure surface active agent is different from the microemulsion of thermodynamic stable system.Microemulsion is a kind of micellar solution (L basically ₁Phase), wherein hydroaropic substance is wrapped among the micella.

The body structure surface active agent also colloidal system with dynamic stabilization is different.The particle of disperse phase very little (as＜1 micron) is enough to be subjected to the influence of pedesis in colloidal system.Therefore to keep through the frequent stirring of interior phase disperseing.On the contrary, it mechanically is stable that body structure surface active agent shows, and its particle does not move in surfactant structure.When this system remains static, can monitor not motion of particles suspended, but be enough to break this structure to relevant shearing stress with inclining, this product is flowed.

Just when the opposite reference of describing herein viscosity viscosity apparatus, 100 rev/mins and 20 ℃ of viscosity that determine with the Brookfield4 axle.About 21/ second of this corresponding shearing rate.This is the sign of quasi-viscous liquid easy mobility.

Often need be under surpassing its deliquescent situation with solid or liquid dispersion in water-based.This dispersion system should easily flow ideally and after leaving standstill for a long time, also keep disperseing uniformly.

Have been found that structure attitude tensio-active agent as suspension matrix than traditional method dispersion system, colloid for example, the use of the use of microemulsion or thickening material or mineral substance works etc. has many advantages.

The example of application structure surfactant system comprises the scouring agent that contains solid detergent, contains the hard surface cleaner of abrasive grains, toiletry, dyestuff and pigment suspension, agricultural-chemical suspension liquid, drilling mud and lubricant.Water sample body structure surface active agent composition, for example liquid laundry agent, makeup, and agricultural chemicals, dyestuff and other solid suspension matrix usually require to contain a large amount of tensio-active agents and/or ionogen.

Tensio-active agent exists with the spherocrystal form usually.Spherocrystal has tangible tendency of flocculation, particularly when polyelectrolyte concentration.This tendency can cause unstable and/or very high viscosity.

Also observed same effect with other body structure surface systems.The objective of the invention is to reduce flocculation and/or viscosity, and/or increase this heavy-gravity, stability easily flocculation and/or the unstable structure tensio-active agent.

The tensio-active agent that often produces the specific type of instability or flocculation problems is the one group of tensio-active agent that comprises fabric regulator.They typically have two groups of C ₁₅-C ₂₅Alkyl or kiki alkenyl group (being generally the Tallow, beef group), and generally be cationic or amphoteric.

One special problem is at the high-load washing assistant of composition acquisition that contains effective combinations-of surfactants that is used for washing synthetic textiles.Have been found that high-load solid detergent, for example tripoly phosphate sodium STPP or zeolite can cause the high viscosity that can not make us accepting.

The stability of tensio-active agent or flocculation problems are not always contained the electrolytical composition restriction of excess.When attempting to comprise soluble polymer in the body structure surface active agent system, they also produce this class problem.For example these polymkeric substance can be desirable as the soil suspension agent, grinds auxiliary, and film shaped dose of paint or enamelled are perhaps to prevent the growth of xln in agricultural-chemical suspension liquid.

Use the washing composition of zeolite builders to also have other problem, promptly they to the effect of removing dust than the washing composition of poly-phosphate washing assistant come poor.Noticed among the EP-A-0419264 that the effect as the zeolite of washing assistant can increase in the presence of some coassist agent widely, this coassist agent is some amino phosphonates do that obtains with the oligopolymer form usually (aminophosphinates).Unfortunately, fail to find the quantity of the amino phosphonates do with meaning (aminophosphinates) that can in not causing the zeolite builders liquid detergent that is separated, use.

Body structure surface active agent record to some extent in a large amount of open source literatures, they comprise GB2123846, GB215380, EP-A-0452106 and EP-A-0530708

Following patent documentation also relates to the structure washing composition:

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Though in the overwhelming majority's example, will be present in this structure in the following described prescription, and be not enough to and stably solid to be remained in the suspension.

EP-A-0388239 discloses a kind of body structure surface active agent in formulation of pesticide.

EP-A-0430602 described in drilling mud or the liquid of other functions in the body structure surface active agent that uses.

EP-A-0472089 has described the body structure surface active agent that uses in dyestuff and pigment suspension.

EP-0301883 has described certain polymkeric substance and has lowered the application of agent in liquid cleaner as viscosity.Yet the polymkeric substance of describing in above-mentioned open source literature is ineffective so especially.As a result, disclose a large amount of patents relevant with the more specifically polymkeric substance of the reduction viscosity effect of attempting to provide higher (referring to EP-A-0346933, EP-A-0346994, EP-A-0346995, EP-A-0415698, EP-1-0458599, GB-2237813, WO91/05844, WO91/05845, WO91/06622, WO91/06623, WO91/08280, WO91/08281, WO91/09102, WO91/09107, WO91/09108.WO91/09109 and WO91/09932).It is said that these polymkeric substance of certain class are that deflocculation agent causes the preparation that the infiltration of spherocrystal is shunk with other.These polymkeric substance are relatively costly products, and the washing effect Relative Contribution to this prescription is very little like this.They typically have pectination, and the skeleton of a hydrophilic polymer is arranged, and have a large amount of hydrophilic side chains on the skeleton, and are perhaps opposite.

We find that some tensio-active agent has good effect in the flocculation spherocrystal of deflocculate or other surfactant systems now, these tensio-active agents form micella, and in the ionogen aqueous phase solubilized of body structure surface active agent 10%(weight at least), they can reduce the viscosity of heavy-gravity system too and/or stablize unsettled body structure surface active agent prescription.They have surfactivity in addition, also prescription are had the auxiliary agent effect sometimes.Stablizer and/or deflocculation agent that the present invention adopts are to have C ₄-C ₂₅Hydrophobic grouping, for example tensio-active agent of alkyl or alkenyl group, particularly C ₆-C ₂₀Alkyl, with a hydrophilic radical, this hydrophilic radical is the polymkeric substance of hydrophilic monomer typically, perhaps particularly a kind of substituting group polymer of monomers with hydrophile function, or a kind of polymer of monomers with chain that connects hydrophilic substituent, this monomer is to be connected in described hydrophobic group one end.The average quality of described hydrophilic radical is greater than 300amu, is generally greater than 500, and preferably greater than 900amu, the best is greater than 1000amu.Hydrophilic radical normally contains more than 4, the polymkeric substance of general about 6 to 8 monomer unit, and this depends on the recurrence interval of monomeric size and surfactant structure.The tensio-active agent that shows these features is referred to as " described stablizer " in this article.The character and the concentration that depend on the ionogen phase as the selection of the tensio-active agent of described stablizer.

The ionogen of common type is that polyvalent is cationic in scouring agent, for example tripoly phosphate sodium STPP or Potassium tripolyphosphate, perhaps Tripotassium Citrate or Trisodium Citrate, according to it dissolving and help the ability of washing, usually being used to needs in the prescription of polyelectrolyte concentration.

At Trisodium Citrate, or in other polyvalent cation electrolyte solutions, described stablizer preferred example is an alkanol, or the polyelectrolyte of alkylthio terminal, polyacrylic ester for example, polymethacrylate, or poly-crotonate (polycrotonate).

Known water-soluble polyacrylate with alkanol or mercaptan chain terminator is used for coating, pasted paper and non-woven fabrics textile industry field are (for example, JP04081405, JP01038405 and JP62085089) and be used for (for example JP62280203 and JP1947384) in the middle of the manufacturing of latex.The calcium salt of same polymer is also put down in writing as carbon black and ferric oxide the dispersion agent in water in JP01310730.

We have found that polycarboxylate with 4 above hydrophilic monomer units or other polyelectrolyte at deflocculate, reduce viscosity, stablely contain the electrolytical liquid detergent of multivalent anions aspect and have better effect than aforesaid polymkeric substance.The chain quilt of described monomer unit, for example C ₆-C ₂₅Fatty alcohol, mercaptan or amine cover, perhaps by C ₆-C ₂₅Alkyl carboxylate's (ester), phosphoric acid salt, hypophosphite, or phosphorous acid ester group (hereinafter claim " described polyelectrolyte stablizer) covers.Described polyelectrolyte stablizer also strengthens the use properties of liquid detergent.

The another kind of polyelectrolyte that uses as described stablizer in the multivalent anions ionogen is an alkyl oxide polycarboxylate product, and it is by to having C ₈-C ₂₅Alkyl and polyoxyethylene chain as polyethoxylated alcohols (polyethoxylated alcohol), add in the compound as methylene-succinic acid, toxilic acid, or unsaturation carboxylic acid or their salt such as fumaric acid, and the employing free-radical initiator is made.This product typically has one, and preferably a plurality of ethoxy groups and one are preferably a plurality of 1,2-two propyloics (1,2-dicarboxy ethyl groups).

In EP0129328 and its English Patent GB9314277.6 that awaits the reply, this alkyl oxide polycarboxylate has been described.

The example of another described stablizer is the poly-sulfo-maleate (polysulphomaleate) that alkyl covers.

Another kind effective described stablizer in the multivalent anions ionogen is the alkylpolyglycosides (alkyl polyglycoside) with high relatively polymerization degree.We have found that alkylpolyglycosides is reducing viscosity, the stable aspect of improving dense water sample body structure surface active agent system is extremely effective, and subsidiary strengthening the property.

The described stablizer that another kind is used in the multivalent anions ionogen is sugar ester or glycolipid.(sucrose ester) is invalid for sucrose ester, but all effective as the contour oligomeric sugar ester of palmitinic acid maltose pentose ester (maltopentaose palmitate).The ester that preferably has 4 above glucosides groups.Sugar ester for the effect of assembling liposome referring to J.Colloid and Interface Sci.Vol152 No.2 Sept.1992.

We also find when the alkyl ethoxy compound generally plays the stablizer function of this system in multivalent anions type ionogen enough stable.

Second type ionogen is the polyvalent cation type, as calcium chloride.It can be as the solubility weight agent (weighting agent) in the drilling mud if desired.Polycarboxylate generally is not enough to dissolving and uses as stablizer in the presence of the high density polyvalent cation.Polysulfonate, as alkyl polyvinylsulfonic acid salt or alkyl poly-(2-acrylamide-2-methyl propane sulfonic acid salt) is preferred, contain more than 6, the alkyl polyethoxylated of 20 vinyloxy group units (ethylene oxy units) is also effective.

The ionogen of the third type is included in the monovalent cation and the negatively charged ion of high density, as Repone K.The polyelectrolyte solvability is bad in this system, but good as described stabilizer function as the senior poly-b-oxide of the poly-b-oxide of 7-80 mole alkyl.

Even also can cause the ionogen of the another kind of type of serious flocculation problems under low relatively concentration is conventional polyelectrolyte, as bitter edible plant sulfonic acid and formaldehyde multipolymer, (uncapped) polyacrylate of carboxymethyl cellulose or non-covering or polymaleic acid salt.In the body structure surface active agent system, usually require the typical non-micellar polymkeric substance that forms.Require to grind to form very thin powder as pigment suspension, usually a small amount of polyelectrolyte is added as grinding auxiliary, this body structure surface active agent produces serious flocculation as a result.

We have found that common effect is rather good aspect the deflocculate of pure ethoxyquin compound in this system, and since the existence of the soluble polymer of other types to present in unstable or the full-bodied system effect also good.

We also further find in the presence of described stablizer, will high-load relatively amino phosphonates do (aminophosphinates) adding liquid detergent compositions in and do not produce any unsettled situation.

Our also further discovery deflocculation agent such as stablizer as described constantly adds unsettledly, or in the heavy-gravity prescription time, its viscosity begins to descend, until obtain a kind of stable liquid product.If add the deflocculation agent of volume, its viscosity rises to maximum before descending once more, along with further adding produces the combined thing of G-of a transparent high workability, and has good suspension characteristic.Further adding can produce-transparent L ₁-phase is unstructuredness significantly.The potential value of this product is to be applied to limpid washing composition or the shampoo that those do not need the solid suspension characteristic.

We have found by mixing high-load relatively nonionic surfactant and water soluble detergency promoter, potassium metaphosphate for example, combinations such as Potassium tripolyphosphate particularly can obtain high-load washing assistant and to the high-efficient washing effect of synthetic textiles with being used in combination as tripoly phosphate sodium STPP suspension washing assistant.

In this system, it requires the ionogen and a high proportion of nonionogenic tenside, the particularly nonionogenic tenside of polyethoxylated type of high density.We find that also this forms under normal circumstances the very novel uneven body structure surface active agent system of heavy-gravity.This new system comprises an isotropy (isotropic) phase, and we think that it is a kind of as L ₂The rich tensio-active agent phase of-phase, it is dispersed in and may is or may comprises that we think L ₁In the external phase of the isotropic phase of-phase,, be a kind of anisotropy phase perhaps as lamellar phase in some cases.In some cases, disperse phase wherein can comprise a L in a continuous lamellar phase ₂-phase.In addition, we do not illustrate L ₂L mutually ₁The phase dispersive forms.

We find that such new texture surfactant system can be stable and be formed with the solid suspension system of usefulness with described stablizer.

According to first embodiment of the present invention, the invention provides a kind of application of stablizer, should stable comprise and a kind ofly have the hydrophilic polymeric chain of 4 above hydrophilic monomer groups and/or have quality greater than 300amu's, the hydrophobic grouping of hydrocarbon dissolubility that is connected in the one end is to reduce or to prevent to contain the flocculation of this system of the tensio-active agent that can flocculate and fluid matrix, the liquid-based mass-energy described tensio-active agent that flocculates wherein, wherein said stablizer is in 1%(weight at least) form with micellar solution during concentration exists.

According to second embodiment of the invention, the invention provides a kind of formation micella application of compound, this compound is in 18%(weight) have weight in the Tripotassium Citrate aqueous solution greater than 1%() solubleness to reduce the viscosity of viscosity body structure surface active agent system, and/or make unsettled surfactant system be transformed into stable structure or micellar surface promoting agent system, described system contains 10%(weight at least by the system gross weight) the solubility of multivalent anions remove to dissolve tensio-active agent ionogen (dissolved surfactant-desolubilising electrolyte).

The 3rd embodiment of the present invention provides a kind of C ₅-C ₂₅Alkyl oxide gathers hydroxy acid salt, and the application of alkylpolyglycosides or described polyelectrolyte stablizer comprises the moisture viscosity that contains the composition of tensio-active agent of the solubility ionogen with polyvalent cation with stable or reduction.

According to the 4th embodiment of the present invention, the invention provides a kind of moisture surface-active compositions, said composition consists essentially of: but at least a energy self forms flocculation system, and/or in the presence of flocculation agent, can form the tensio-active agent of flocculation system; Contain enough flocculation agents,, form a kind of continuous water of system of flocculating with described tensio-active agent as needs; With the stablizer that can form the micellar compound at described aqueous phase, this stablizer has the hydrophilic polymeric group of the monomer unit more than 4 and/or is connected in the plastid greater than 300amu (mass) of hydrophobic grouping one end with at least 4 carbon atoms, and its content is enough to suppress the flocculation of this system.

The 5th embodiment according to the present invention the invention provides a kind of water-bearing structure surfactant composition (aqueous structured surfactant composition), and said composition consists essentially of: water; The tensio-active agent of at least a formation structure; By a certain proportion of soluble surfactant flocculation agent of water weight, it is enough to form (ⅰ) flocculation, (ⅱ) unsettled and/or (ⅲ) viscosity body structure surface active agent composition with the tensio-active agent of described formation structure and water; With at least a stablizer, this stablizer is a kind of formation micellar compound, and it comprises the C that is connected in hydrophilic radical one end ₆-C ₂₀Alkyl group, described hydrophilic radical has quality greater than 300amu's and/or comprise a kind of polymkeric substance with 4 above hydrophilic monomer units, this described stablizer dissolution degree in containing the described aqueous electrolyte liquid of described ratio is a 50%(weight), the quantity of described stablizer is enough to provide respectively (ⅰ) a kind of less flocculation, (ⅱ) body structure surface active agent composition more stable and/or that (ⅲ) viscosity is lower.

The 6th embodiment according to the present invention the invention provides a kind of water-bearing structure surfactant composition, and it contains: water; The tensio-active agent of at least a formation structure; A certain proportion of soluble, remove dissolving (desolubilising) tensio-active agent ionogen, described composition is enough to form (ⅰ) flocculation, (ⅱ) instability and/or (ⅲ) viscosity body structure surface active agent composition with water and tensio-active agent by weight; With a kind of stablizer that forms the micellization compound that contains, it comprises C ₆-C ₂₅The groups that is connected hydrophilic radical one end, described hydrophilic radical has quality greater than 300amu's and/or comprise the polymkeric substance of at least 4 hydrophilic monomer units, and therefore described stablizer dissolution degree in containing with the described electrolytical aqueous solution of described ratio is 5%(weight at least).The quantity of described stablizer is enough to provide respectively (ⅰ) less flocculation, (ⅱ) body structure surface active agent composition more stable and/or that (ⅲ) viscosity is lower.

The 7th embodiment according to the present invention, the invention provides a kind of water base, spherulite composition (aqueous-based, spherulitic composition), said composition comprises by composition weight meter 10%(weight at least) tensio-active agent and by described composition weight meter 10%(weight at least) the solubility ionogen, do not have described stablizer in the presence of, can form the composition that is divided into two or more parts after (ⅰ) leaves standstill, or (ⅱ) having a stable composition greater than 0.8Pas viscosity defined herein, described stablizer is enough to respectively (ⅰ) to be reduced or prevents this separation and/or (ⅱ) reduce described viscosity.

The 8th embodiment according to the present invention, the invention provides a kind of stable, runny, the spherulitic crystal structure surfactant composition, said composition comprises: water; Enough tensio-active agents are to form a kind of structure in the presence of ionogen; At least solubility 10%(weight) with multivalent anions go to dissolve surfactant salt, salt concn is for to be enough to form (ⅰ) unsettled with water and described tensio-active agent in the described composition, and/or (ⅱ) can flocculate, spherulitic crystal structure surfactant composition (spherulitic structured surfactant composition); With a kind of stablizer, this stablizer has the C that is connected with an end of a hydrophilic radical ₆-C ₂₀Alkyl, the quality of this hydrophilic radical is greater than 300amu and have many hydroxyls, carboxylate salt, sulfonate, phosphoric acid salt, vitriol or phosphate group, therefore, described stablizer is dissolved in the aqueous solution of described salt under described concentration, it is more stable that the quantity of described stablizer is enough to form respectively (ⅰ), and/or (ⅱ) the lower spherulite composition of viscosity.

The 9th embodiment according to the present invention the invention provides a kind of water-bearing structure surfactant composition, and said composition comprises: water; Enough tensio-active agents are to form a kind of structure in the presence of ionogen; Remove to dissolve the solubility polyvalent metal salt of described tensio-active agent, salt concn is enough to that to form (ⅰ) a kind of unsettled with surfactivity in the composition, and/or (ⅱ) its viscosity greater than the spherocrystal system of flocculating of 0.8Pas; With comprise a kind of a kind of stablizer that forms the micellization compound, it comprises C ₆-C ₂₀Alkyl and have quality greater than the hydrophilic radical of 300amu and be with many ethoxylates, sulfonate, phosphoric acid salt, sulfuric acid or phosphate group, described stablizer, be at least 5%(weight with the dissolution degree in the aqueous solution of the polyvalent metal salt of described concentration), it is stable that the quantity of described stablizer is enough to form respectively (ⅰ), and/or (ⅱ) the lower spherulite composition of viscosity.

The tenth embodiment according to the present invention the invention provides a kind of water-bearing structure surfactant composition, and said composition comprises: water; Enough tensio-active agents are to form a kind of structure in the presence of ionogen; At least 10%(weight) basic metal or univalent anion ammonium salt, this salt removes to dissolve described tensio-active agent, salt concn is enough to form (ⅰ) a kind of unsettled spherocrystal system with tensio-active agent, and/or (ⅱ) has the flocculation system of viscosity greater than 0.8Pas; Have at least 8 with each molecule and be preferably 25-75 ethyleneoxy group group, and optionally contain the C that reaches ten propylidene oxygen base groups ₆-C ₂₀Alkyl alkoxylates, it is stable that its quantity is enough to form respectively (ⅰ), spherulite composition and/or (ⅱ) the lower spherulite composition of viscosity.

The 11 embodiment according to the present invention the invention provides a kind of fabric-conditioning compositions, and said composition comprises: water; Have two C ₁₅-C ₂₅Alkyl or the positively charged ion or the amphoteric fabric regulator of alkenyl; The flocculation agent of q.s to be forming a heavy-gravity with described fabric conditioner and water, flocculation and/or Unstable Systems; With the described stablizer of q.s, with reduction viscosity and/or degree of flocculation, and/or stable said composition.

The 12 embodiment according to the present invention the invention provides the suspension of a kind of solid such as pigment, and this suspension comprises: water; The formation body structure surface active agent of q.s is to form a kind of structure with water; The non-micella polyelectrolyte of the formation of q.s (for example, grinding auxiliary) is with the described structure of flocculating; The solid suspended particle; With the stablizer that contains formation micellization compound, it has C ₄-C ₂₀An alkyl and a hydrophilic radical, the quality of described hydrophilic radical is greater than 300amu and/or be a kind of 4 above unit polymer of monomers, and its quantity is enough to form the body structure surface active agent composition of less flocculation.

The 13 embodiment according to the present invention the invention provides a kind of surfactant composition, and it comprises: water; Form body structure surface active agent; If need, the solubility ionogen of q.s is to form the body structure surface active agent system; Enough is soluble, and non-formation micellar copolymerization thing is with the viscosity of described body structure surface active agent system of flocculating, and/or removes to dissolve this system and enough described stablizer reducing the degree of flocculation and/or the viscosity of said composition, and/or stablizes described composition.

The 14 embodiment according to the present invention the invention provides a kind of liquid detergent compositions, and it comprises: water; Form body structure surface active agent; The body structure surface active agent system of enough solubility ionogen to form with described tensio-active agent and water; The zeolite builders that suspends; The amino phosphonates do that following molecular formula is represented (aminophosphinate):

RR ' NCR ' ₂PO(OH) CR ' ₂NRR ' is (I) or polymkeric substance or oligopolymer with repeating unit of following molecular formula:

Wherein each R group can be identical or different, it is optional from the alkyl that replaces, cycloalkyl, alkenyl, aromatic base, aralkyl, alkaryl, or the alkoxyalkyl group of 1-20 carbon atom, wherein each group can optionally be replaced one or many, and each R ' base can be identical or different, can be the R group of hydrogen or above-mentioned definition, R ' ' is a divalent alkyl, the ring alkylidene group, alkarylene (alkarylene) is by the alkylene group of Sauerstoffatom or the fracture of arylidene group, n is 0 or 1 to 10 integer, with and polymkeric substance or oligopolymer; The amount of described amino phosphonates do is enough to increase described system viscosity, flocculates or goes molten (destablilise) described system; Enough stablizers are to reduce viscosity and/or flocculating degree and/or stable said composition.

The 15 embodiment according to the present invention, the invention provides the combined thing of a kind of G-, it contains water, tensio-active agent and optionally use solubility ionogen and/or suspended solids, and be suitable under the situation of no deflocculation agent, to form a kind of composition that contains intermediate phase, after leaving standstill, this composition is divided into two or more parts, and/or show its viscosity greater than 0.8 pool defined herein second, with enough deflocculation agent stablizer as described to form the low G-of a stable combined thing of G-and/or viscosity mutually.

The 16 embodiment according to the present invention, the invention provides a kind of limpid liquid micellar solution, it contains water, tensio-active agent, optionally use the solubility ionogen to form a kind of composition that contains intermediate phase under the situation that is adapted at not having deflocculation agent, with the deflocculation agent of enough stablizer as described, to form one clearly, L ₁Micellar solution.

The 17 embodiment according to the present invention the invention provides a kind of body structure surface active agent composition, and it comprises: water; Form the tensio-active agent of structure, by the tensio-active agent gross weight, it contains the nonionogenic tenside of at least 30% weight; With enough water-soluble ionogen form with continuous aqueous phase in an anisotropy (as stratiform) one isotropic, liquid state, the structure disperse phase of tensio-active agent or tensio-active agent/water.

Preferred isotropy tensio-active agent/water is a kind of L ₂Phase, described tensio-active agent/water can comprise L ₂Phase.

The 18 embodiment according to the present invention the invention provides a kind of body structure surface active agent composition, and it comprises: water; Form structure tensio-active agent it contain 30%(weight at least) nonionogenic tenside; With enough water-soluble ionogen with at isotropic water (as L ₂-phase) form in a kind of isotropic, liquid state, tensio-active agent or tensio-active agent/water are (as L ₂-phase) structure is disperseed.

Preferably, according to the described the 12 and the 13 embodiment, described stablizer exists can stablize these cenotypes.

Water medium

Some tensio-active agent particularly can be in water as oil soluble surfactants such as Isopropylamine alkylbenzene sulfonates, even form flocculation under no electrolytical state, structural system.In these examples, water medium can be made up of water basically.Yet most tensio-active agent particularly only produces flocculation in the electrolyte solution of high density in the presence of the solubility ionogen.

The present invention's composition typically contains high-load solubility and removes to dissolve the tensio-active agent ionogen.Be typically, by height to the electrolytical concentration of weight solubility of saturated prescription greater than 10%, as greater than 14%, 15%(weight particularly).For example, the enough electrolytical concentration of dissolved can be between 16% to 40%.Can over-saturation there be excessive formation suspended solids part in the ionogen solid.

Ionogen can typically be a kind of of following four kinds of main types:

(ⅰ) multivalent anions salt: potassium metaphosphate preferably wherein, Potassium tripolyphosphate and Trisodium Citrate or potassium.

This ionogen generally is preferred for washing composition, and the prescription that is used for agricultural chemicals and pigment and dye bath.

(ⅱ) polyvalent cation salt: preferred salt is calcium chloride and Calcium Bromide.Other salt comprises fontanel zinc, bariumchloride and nitrocalcite.Preferably agent is used for drilling fluid to these ionogen as solubility weight.This salt particularly suitable complete with closely knit solution (completion and packing fluid).

(ⅲ) have the monovalent cation salt of univalent anion: these salt comprise fontanel choline metal or fontanel amine, Repone K for example, sodium-chlor, potassiumiodide, Sodium Bromide, or brometo de amonio, perhaps citric acid alkali metal or ammonium salt.Sodium-chlor is specially adapted to drilling fluid, and this liquid is used to bore the stratum through tolerance salt.

(ⅳ) polyelectrolyte: it comprises the non-micellar polyelectrolyte of formation, for example unlapped polyacrylate, polymaleic acid salt or other polycarboxylates, sulfonic acid lignin or bitter edible plant sulfonic acid and formaldehyde multipolymer.This polyelectrolyte has extra high throwing out to body structure surface active agent, even also is like this when lower concentration.With described polyelectrolyte stablizer or alkyl polyethoxylated, or alkylpolyglycosides can this class ionogen of deflocculate.

In order to form the structure that can support solid matter and/or the flocculation that causes body structure surface active agent, the amount of general relevant with its solubility tensio-active agent is bigger, and required ionogen is then fewer.Usually the preferred ionogen of selecting to help the composition function, and because economic reasons is usually used cheap ionogen.The electrolytical amount that adds is by the quantity decision of the performance that requires to provide suitable (for example scourability of sanitising agent).Obtain ideal viscosity and stability with described stablizer then.

Yet electrolyte concentration depends on desired structure type in other respects, viscosity and consider Time, Cost And Performance.Usually we select to form the spherocrystal system, as us at GB-A-2,153,380 and EP-A-0530708 described in, purpose is the balance that obtains the satisfaction of suspended solids between flowability and high efficiency.This structure can not be obtained usually, can unless exist at a certain amount of ionogen.

Except cost issues, select ionogen also may depend on the purposes that suspension is desired to think.Laundry product often contains the solubility builder salt.Composition can contain auxiliary or synergistic matter as ionogen or the part as ionogen.The ionogen of selecting should chemically be complementary with the desire suspended matter.The typical ionogen of the present invention's use comprises basic metal, alkaline-earth metal, and ammonium or amide, they comprise muriate, bromide, iodide, fluorochemical, orthophosphoric acid salt, condensed phosphate, potassium metaphosphate for example, tripoly phosphate sodium STPP, phosphonate (phosphonates), as the acetyl diphosphonate, or amino three (methylene phosphonic acid salt), ethene diamino four (methylene phosphonic acid salt) and divinyl triammonium five (methylene phosphonic acid salt), vitriol, supercarbonate, carbonate, borate, nitrate, oxymuriate, chromic salt, formate, acetate, oxalate, Citrate trianion, lactic acid salt, tartrate, silicate, hypochlorite if desired, is regulated the stability that pH value improves suspended solids or dispersion liquid, reduce toxicity, bronsted lowry acids and bases bronsted lowry, for example hydrochloric acid, sulfuric acid, phosphoric acid or acetate, or sodium hydroxide, potassium, ammonium or calcium or alkaline silicate.

Form the ionogen of infusible precipitate with tensio-active agent, perhaps may form big crystallization, as preferably do not adopt greater than 1mm crystalline ionogen when leaving standstill.The concentration of above-mentioned sodium sulfate for example, the saturation concentration that approaches 20 ℃ of compositions is unfavorable.The vitriol of saturation concentration when therefore our composition selected does not contain above its 20 ℃ particularly contains the composition of the vitriol of saturation concentration when being lower than its 15 ℃.

Because expense, we like adopting sodium salt as ionogen, although also usually need exist sylvite to obtain low viscosity and polyelectrolyte concentration sometimes in electrolytic solution.Lithium and cesium salt were also successfully attempted, but they can not use in commercial formulation.Calcium salt such as calcium chloride and Calcium Bromide etc. have been used to drilling fluid system, and their relative high-density help providing the weight of mud.Other also can use as bases such as organic basess, and for example low-alkylamine and alkanolamine comprise monoethanolamine, trolamine and Isopropylamine.

Except that substituting the solubility ionogen with water medium, also may contain the flocculation of solvable amount or remove to stablize the nonelectrolyte polymkeric substance, its quantity can be flocculated and/or be removed to stablize described tensio-active agent.Comprise polyvinyl alcohol or polyoxyethylene glycol among the embodiment.

Stablizer

We believe that described stablizer plays the flocculation inhibitor at least basically.We observe especially, and the adding stablizer has fairly obvious benefit in the surfactant system of height flocculation.

Do not have this stablizer, usually be difficult to obtain a composition that the keying action of rheological properties and wash characteristics is arranged.Composition is not that too sticking to be difficult for toppling over and to hang cup be exactly unstable, is divided into two-layer or multilayer.Along with tensio-active agent and/or help the increase of washing composition total concn, difficulty also strengthens.Commercial pressure for denseer liquid detergent demand brings a specific question for manufacturers, adopts described stablizer to solve.

Preferably reconciliation statement surface-active agent and/or electrolytical concentration obtain a kind of composition, and when adding described stablizer, said composition is in room temperature, leave standstill when 0 ℃ or 40 ℃ or most preferably above-mentioned two kinds of temperature and do not produce precipitation in three months.Also can regulate the composition that concentration obtains a kind of shear stable, it is desirable to, be subjected under the normal shearing force, not increase the composition of viscosity basically.To such an extent as to might the option table surface-active agent and electrolytical concentration when not having described stablizer but under high viscosity, can obtain above-mentioned feature.Add stablizer then to reduce its viscosity.

According to the present invention, its composition should comprise the weight by total composition 0.005-20%() stablizer, be preferably 0.01-5%, preferably 0.05-2%.

When in the ionogen multivalent anions being arranged, as Trisodium Citrate, the hydrophilic segment of our preferred stabilizer has many carboxyls and/or hydroxyl, as alkyl oxide polycarboxylate particularly, alkylpolyglycosides, poly-dihydroxy acid amides (polyglycamide) and/or described polyelectrolyte stablizer.

When ionogen comprises polyvalent cation, the stablizer that we preferably use has many sulfonate, phosphoric acid salt, vitriol or phosphonate groups, polyvinyl sulfonate for example, alkyl gathers (2,2-acrylamido methyl propane sulfonic acid salt), sulfonated alkyl polyvinyl alcohol, poly-sulfonated alkyl polystyrene, alkyl polyethylene phosphoric acid salt, alkyl polyvinylphosphonic acid salt, or poly-(vinyl sulfonate) alkyl poly-alkoxylation thing.

When ionogen is the basic metal fontanelle compound, or identical monovalence system, alkylethoxylate preferably used, it preferably has more than 7 above oxyethyl groups, particularly surpasses 10, is typically to surpass 20, as 25-75, particularly 30-60, the best is a 40-55 oxyethyl group.

The present composition can contain one or more described stablizers.

The stablizer that the present invention uses is characterized in that it being the tensio-active agent with a hydrophilic segment and a hydrophobic part.Hydrophobic part mainly comprises at least a C ₆-C ₂₅Alkyl, or alkenyl, preferably single C ₈-C ₂₀Alkyl or alkenyl are as straight chained alkyl.Hydrophobic part optionally comprises aryl, alkaryl, cycloalkyl, branched-chain alkyl, polytrimethylene oxygen base (polypropylenoxy), or polybutylene oxygen base group.In some example, may or preferably use butyl group as hydrophobic part.Hydrophilic segment requires relatively large, preferably contains many hydrophilic functional groups, as hydroxyl, and carboxyl or sulfonate.

Have the not effect of alkylglycoside of one or two glycosides residue, and the alkylglycoside with the glycosides residue more than 7 or 7 has very strong effect, this fact shows the size of required hydrophilic segment.Extent of polymerization preferably greater than 1.3, and has the poly-glycosides that wide distribution contains a large amount of senior glycosides to be very useful greater than about 1.2 poly-glycosides (polyglycosides), and its effect increases along with the increase of the polymerization degree.Yet find basically by two glycosides the alkylpolyglycosides part relative nullity that three glycosides or four glycosides are formed.And the part of mainly being made up of seven glycosides is very effective, and this is just to compare with the most preferred embodiment of described polyelectrolyte stablizer in dense citrate solution.Equally, per molecule has the alkyl oxide polycarboxylate of 1 to 3 ethylene oxide residue and 2 to 3 carboxyls of average out to, is relative nullity, and have more than 3,8 above residues and more than 4 particularly, particularly the carboxylate salt of 8 above carboxyls is generally more effective.For example, it is very effective in citric acid solution to have 11 moles of b-oxides of 10 or 10 above carboxyls.

Glucose ester is generally invalid, but oligomeric sugar ester, as Fructus Hordei Germinatus pentose (malto pentaose), or senior oligose, as the ester of partially hydrolysed starch of great use.

In system, very effective as the senior b-oxide of 25% Repone K of 7-80 mole such as 20-50 mole b-oxide, but rudimentary b-oxide, such as 3 moles of oxide compound relative nullities.

Generally, the effect of polymeric tensio-active agent as if with depend on that tensio-active agent hydrophilic segment mean polymerisation degree is compared and depend on senior composition (for example have MMW, or greater than the polymkeric substance of tetramer) more greater than 100 hydrophilic group.

Have a kind of method can judge whether a kind of particular compound shows its necessary solvability, promptly measure its solvability in concentrating aqueous electrolyte liquid, preferred ionogen is the ionogen in the composition, or other ionogen identical with its chemical feature.

For example, as the liquid detergent of auxiliary agent or similar system, wherein ionogen at least mainly is made up of the multivalent anions compound with citric acid, and a kind of ionogen easily is a Tripotassium Citrate, as contains 15% weight and close to citric acid is full, as the solution of 16%-18%.The solvability of stablizer should be at least 10%, is preferably at least 2%, is preferably at least 3% again, is preferably in 5%(weight at least).For example, can do a test, in the 18% Tripotassium Citrate aqueous solution, add enough concentration, as greater than 30% the stablizer aqueous solution, to obtain 5%(weight in the whole solution) stablizer.

Be not subjected to the restriction of any theory, we believe stablizer hydrophobic part can with outer double-deck combination of spherocrystal, hydrophilic segment can the very big surface that is enough to by spherocrystal, prevents flocculation, as long as its enough dissolving in the water-based of circumference.

The feature of the key of stablizer of the present invention is that they are linear structure substantially, the normally essential such class tensio-active agent with the linear hydrophilic polymeric base that is covered by a hydrophobic group on the one end group.This is just in time opposite with the pectination of emphasizing about deflocculation in the prior art, and wherein hydrophilic bond has many hydrophobic side chains or opposite.The surfactant stabilisers that we believe the present invention is deflocculate more effectively, simultaneously composition all surfaces activity is had contribution.

This stablizer preferably has the weight of strict 25 ℃ of water of micellar concentration (as %(weight)) less than 0.5, more preferably be less than 0.4, particularly be less than 0.35, more particularly be less than 0.3.We are preferably greater than 1 * 10 ^-5Stablizer with strict micella component.

Preferred this stablizer can provide 20-50mNl ^-1, as 28-38mNl ^-1Surface tension.

Described stablizer is the compound represented of general formula R XA typically, and wherein R is C ₆-C ₂₅Alkyl, alkaryl or alkenyl.X represents O, CO ₂, S, NR ^-1, PO ₄R ², or PO ₃R ¹, and R ¹Be hydrogen or alkyl, as C ₁-C ₄Alkyl, perhaps A group, and A is a hydrophilic radical for example comprises greater than 4 monomer unit and at one end is connected in X, and X is hydrophilic, by total solution weight, be enough to make stablizer in desiring the deflocculate system solvability in the aqueous electrolyte liquid greater than 5%(weight).A can be the polyelectrolyte group, or poly-glycosides group, the polyvinyl alcohol gene, or polyvinylpyrrolidone--based, or poly-b-oxide, have at least six monomeric genes.

The polyelectrolyte stablizer

Described polyelectrolyte stablizer is preferably represented by (I):

（I）R-X-【CZ ₂-CZ ₂】nH

Wherein R and X are the meanings that has as hereinbefore, and at least one Z represents carboxy CO OM and M is H or metal or alkali, and this polymkeric substance is water-soluble like this, and other Z is H or C ₁～C ₄Alkyl, n=1 to 100 is preferably 5～50, and preferably 10～30.

Alkyl or alkenyl R preferably have 8～24, and more preferably 10～20,12～18 carbon atoms particularly.R can be straight or side chain is mainly alkyl or alkenyl, as cocoyl, and lauryl, spermaceti base, stearyl, patmityl, hexadecyl, fatty acyl (tollowyl), oleoyl, decyl, linoleyl, dodecyl or linolenyl gene.R can optionally be C ₆～C ₁₈The alkyl phenyl group.

The ratio of hydrophobic part and hydrophilic segment should be preferably in the stablizer (I) is enough to guarantee that polymkeric substance dissolves in the full sodium carbonate solution that closes.

Stablizer is in water, and the solvability in the time of 20 ℃ is greater than 5%(weight), more preferably greater than 10%.

Described polyelectrolyte stablizer is preferably linearity, and is water-soluble, and end is a polyacrylate, polymaleic acid salt, and poly-first acrylate perhaps contains hydrophobic part (R) and at least one hydrophilic segment (CZ ₂-CZ ₂) poly-cronate (polycrotonates).Also can use as multipolymers such as acrylate/maleate copolymers.

Vinylformic acid or maleic acid monomer unit also can neutral salt exist, and perhaps the form with acid exists, or salt, sour blended form exist.Acrylic Acid Monomer unit preferably neutralizes with sodium.They also can optionally neutralize with potassium, lithium, ammonium, calcium or organic bases in addition.

Hydrophilic and the hydrophobic part of described polyelectrolyte stablizer preferably links to each other with sulphur atom,, preferably uses sulphur carboxylic overlie polymer that is.

For the tensio-active agent by (I) expression, preferably, the molecular-weight average of this tensio-active agent is preferably 500 greater than 250, preferably greater than 1000.

Described polyelectrolyte stablizer is present in the aqueous based surfactant compositions provided by the invention, and its content is by total composition, between 0.01 and 5%(weight) between, 0.05～30%(weight preferably), as 0.1 and 2%(weight) between.

Prepare described polyelectrolyte stablizer (I) in the following manner:

Hydrophilic monomer, as vinylformic acid, with the hydrophobic chain terminator, as the preferred in the proper ratio 90:10 to 50:50 of n-Hexadecane thiol, as 70: 30 to 80: 20, in solvent He in the presence of the free radical starting agent, react, its solvent is an acetone, free radical starting agent is as Diisopropyl azodicarboxylate, until finished polyreaction in about 2 hours through refluxing.In case reaction is finished, through removing solvent, add alkali as rotary evaporation, the polymer product that neutralization obtains as NaOH solution makes (I).

The alkyl oxide polycarboxylate

Described stablizer optionally is the poly-alkoxylation thing of the poly carboxylic acidization of general formula (I) expression:

Wherein R is the straight or branched alkyl, alkaryl or alkenyl, and perhaps straight or branched alkyl, perhaps alkenyl carboxylic group, R has 6～25 carbon atoms, each R in all cases ¹Be OCH ₂CH ₂Or OCH(CH ₃) CH ₂Group, each R ²Be OC ₂H ₃Group or OC ₃H ₅Group, each R ³Be C(R ⁵) ₂C(R ⁵) ₂Group, its quantity is 1～4, is preferably 2, each R ³R in the group ⁵Be CO ₂The A group, other R ⁵Base is C ₁-C ₂Alkyl, hydroxyalkyl or carboxyalkyl group, or H preferably, R ⁴Be OH, SO ₄B, SO ₃B, OR, sulfo-succinyl, OCH ₂CO ₂B, or R ⁶ ₂NR ⁷, R ⁶Be C ₁-C ₄Alkyl or hydroxyalkyl, R ⁷Be C ₁-C ₂₀Alkyl, phenyl, CH ₂CO ₂B, or-＞the O base, or PO ₄B ₂, B makes described carboxylic acid can form the positively charged ion of water-soluble salt, and as basic metal, or alkaline earth salt, each Z is 1-5 preferably 1, and y is at least 1 and (x+y) have the mean value of 1-50, wherein a R ¹And R ²Gene can randomize or along poly-alkoxide base thing chain ordered arrangement.

For example we preferably use the alkyl oxide polycarboxylate, for example pass through at least one, be preferably more than two, as 3 to 30 moles unsaturated carboxylic acids or its salt, as methylene-succinic acid, high horse acid, perhaps be preferably toxilic acid and add the alkyl polyethoxylated, as polyethoxylated alcohols, or lipid acid, for example adopt free radical starting agent and those alkyl oxide polycarboxylates of obtaining.

For example,, exist down, can heat the aqueous solution of polyethoxye compound, as poly-ethoxylated alcohol with as the sodium salt of unsaturated acid such as sodium maleate as dibenzoyl peroxide at peralcohol.Operable other carbonyl acid comprise vinylformic acid, methylene-succinic acid, aconic acid, angelicic acid, methylacrylic acid, fumaric acid and tiglic acid.

Preferably, this polycarboxylate has one " skeleton ", and it comprises 2-50 ethyleneoxy group group, 3-40 more preferably, as 5-30, particularly 8-20 ethyleneoxy group group and many side chains, each side chain comprises one 1,2-dicarboxyl ethyl, 1,2,3, the senior teleomeric derivative of 4-tetracarboxylic butyl or carboxylic acid.Described alkyl oxide polycarboxylate has more than 4 at least, and preferably at least six, as 8-50 carboxyl.

Alkylpolyglycosides

Described stablizer can be alkylpolyglycosides in addition.Alkylpolyglycosides is by the alkylation reducing sugar, as fructose or the product that obtains of glucose preferably, is typically the product that makes in the existence of sulfonic acid catalyst and Fatty Alcohol(C12-C14 and C12-C18) reaction, or by low alkylpolyglycosides, as being with C ₆-C ₂₅The methyl of alcohol, ethyl, the product that the commentaries on classics ether effect (transetherification) of the poly-glycosides of propyl group or butyl makes, the polymkeric substance of glycosides residue depends on the ratio and the reaction conditions of alcohol, but its polymerization degree generally is 1.2-10.The present invention preferably alkylpolyglycosides of usefulness has greater than 1.3, more preferably greater than 1.5, and particularly greater than 1.2, the polymerization degree of 2-20 for example.

The poly-alkoxylation thing

Alkyl poly-alkoxylation thing is as C ₈-C ₂₀The alkyl polyethoxylated, poly-propoxylated glycerine, or blended ethoxylate/propoxylated glycerine can be used as described stablizer is particularly at the polyelectrolyte or the univalent anion of dilution, as the dense alkali of fontanelle compound or nitrate, or use in the alkaline earth salt.Except alcohol alcoxylates, other have C ₆-C ₂₀The poly-alkoxylation thing of alkyl, as the ethoxylation carboxylic acid, ethoxylated fatty amine, alkyl glycerol base oxethyl thing, alkyl anhydro sorbitol ethoxylate or ethoxylated alkyl phosphoric acid salt also can use.

Other stablizers

In addition, described stablizer can optionally be alkyl or alkyl thiol polyvinyl alcohol, or the alkyl polyvinylpyrrolidone.In addition, ethanol or carboxylic salt can be with 1, and 2-propylene oxide reaction generates the poly-1,2 epoxy prapane of alkyl and with the product of hot aqueous bases hydrolysis.Sugar ester and especially two or oligomeric sugar ester, as sucrose stearate, or Malaysia pentose cetylate also can be used as described stablizer, for example the poly-sulfo-maleic acid ester (alkyl polysulphomaleates) of alkyl.

The interpolation of described stablizer

Better in the deflocculate effect that prevents the prescription that the general comparison of described stablizer has been flocculated aspect the flocculation.Yet, before adding the electrolysis degree, stablizer being added in the tensio-active agent, we see sometimes, and viscosity takes place to change continuously significantly when storing.Therefore we preferably add most at least described stablizers after ionogen.In order to keep enough flowability, need when beginning, add a fraction of at least stablizer usually, but the add-on when beginning remains on preferably and need obtain the minimum amount that can mix system to mix each component.

Viscosity

As long as the present invention do not having under the situation of described stablizer, water base dense structure, or the surfactant composition that contains intermediate phase generally is unstable, high thickness does not flow and is not suitable for being used as, for example the matrix of detergent composition or suspended solids.With 5 of Brookfield RVT viscosity apparatuss, the viscosity of measuring during 20 ℃ of 100rpm greater than 4Pas is not common for such some compositions.Other compound is divided into a relative heavy-gravity layer of the water layer of a relative thin and the tensio-active agent that contains vast scale after leaving standstill, and also has other layer sometimes, and this depends on for which type of added ingredients.

Water base body structure surface active agent composition of the present invention its preferably at 21s- ¹Shearing rate; Or have the 2Pas of being not more than under the above-mentioned viscosity measurement condition, preferably be not more than 1.6Pas, if preferred especially greater than the surfactant composition of 1.4Pas viscosity.Generally our purpose provides a kind of its viscosity less than 1.2Pas, particularly less than 1Pas, as the composition less than 0.8Pas.

In the practice, surfactant composition of the present invention usually under the above-mentioned condition of this paper its viscosity more than 0.3Pas, more than 0.5Pas.

It is desirable to, to using the Betengent product human consumer, the viscosity of the present composition is by as above being determined as 0.7-1.2Pas to show desired flowing property.

Tensio-active agent

The present composition contains enough at least tensio-active agents usually to form a structural system.For some tensio-active agent, its consumption can hang down 2%(weight), but general requirement is at least 3% when most of, more generally be at least 4%, 5% weight (by the weight of tensio-active agent) typically.

Detergent composition of the present invention, by the gross weight of composition, total surfactant content is at least 10%, and preferably at least 20%, particularly greater than 25%, as greater than 30%.Surfactant concentrations does not surpass 80% of composition weight in the practice.Described stablizer is the part of all surfaces promoting agent.

In the composition amount of tensio-active agent preferably greater than q.s go dissolve tensio-active agent electrolytical in the presence of, form one stable, the minimum dose of the body structure surface active agent system of suspended solids.

Tensio-active agent can comprise negatively charged ion, positively charged ion, nonionic, amphoteric and/or zwitterionic classes, or the tensio-active agent of its mixture.

Anion surfactant can comprise C ₁₀-C ₂₀Alkylbenzene sulfonate, or the salt of alkyl oxide sulphur, it is with natural fat or has 1-20,2-10 preferably is as the synthetic C of 3-4 ethyleneoxy group group ₁₀-C ₂₅, as C ₁₂-C ₁₄Alcohol ethoxyization is optionally used the unreacted alcohol of stripping, again with the reaction of ethoxylated product and sulfating agent (sulphating agent), and with in the alkali and the product that makes of the alkyl oxide sulfuric acid of generation.This term also comprise alkyl glycerol vitriol (alkyl glyceryl sulphates) and, the alkyl ethoxy/propoxy-vitriol of random or block copolymerizationization.

Anion surfactant also can comprise C ₁₀-C ₂₀, as C ₁₂-C ₁₈Alkyl-sulphate.

Tensio-active agent can comprise C ₈-C ₂₀, as C ₁₀-C ₁₈Fatty soap.This fatty soap can be full and/or unsaturation, straight or branched.

Preferred example comprises dodecanoate, tetradecanoic acid, stearate, oleate, linoleate, palmitate and coconut and tallow soap.Wherein foaming control is an important factor, and we especially preferably use the soap class, as ethanolamine soap, and particularly monothanolamine soaps has found that its stored refrigerated is good and scourability is good.

By further embodiment, soap and/or carboxylic acid are by the tensio-active agent gross weight, and its weight ratio is at least greater than 20%, preferred 20-75%, and 25-50% preferably, as, 29-40%.

Tensio-active agent can comprise other anion surfactants, as alkene sulfonate, and paraffin sulfonate, taurides, the carboxylic esilate, ether sulfonate, ether carboxylate, aliphatic ether sulfonate, as alkyl glycerol sulfonate, sulfosuccinate, or sulphossuccinamates.The total amount of other anion surfactants is less than 45%(weight by the tensio-active agent gross weight), more preferably amount is less than 40%, preferably is less than 30%, as is less than 20%(weight).

The positively charged ion of any anion surfactant generally is a sodium, also can be potassium, lithium, and calcium, magnesium, ammonium perhaps has the alkylammonium of 6 aliphatic carbon atoms, comprises the sec.-propyl ammonium, monoethanolamine ammonium, di-alcohol ammonium, and triethanol ammonium.

Ammonium and alcohol salt are generally easily molten not as sodium salt.Also can with above-mentioned sun from mixture.

Tensio-active agent contains one or more above nonionogenic tensides.They preferably include alkoxylate C ₈-C ₂₀, preferred C ₁₂-C ₁₈Alcohol.Alcoxylates can be an ethoxylate, propoxylated glycerine, or blended ethoxylate/propoxylated glycerine alcohol.Particularly preferably have 2-20, the particularly ethoxylate of 2.5-15 ethyleneoxy group.

Described alcohol can be Fatty Alcohol(C12-C14 and C12-C18) or side chain synthol.The HLB of preferred its nonionic part is 6-16.5, particularly 7-16, as 8-15.5.We select for use two or more to have the mixture of the nonionogenic tenside of above weighted mean HLB value.

Other ethoxylation and/or propoxylation ionic surfactant pack are drawn together C ₆-C ₁₆Alkane phenyl alcoxylates, alkoxylated fatty acid, alkoxylated amines, alkoxylated alkanols acid amides and alkoxylated alkyl anhydro sorbitol and/or glyceryl ester.

Other available ionic surfactant pack are drawn together amine oxide, fatty alkylolamide, for example coconut single ethanol amide, coconut diethanolamide and alkylamine ethyl fructoside and glucoside.

The weight ratio of nonionogenic tenside is preferably at least 2% by the tensio-active agent gross weight, is generally to be less than 40%, be typically to be less than 30%, and as 3-25%, 5-20% particularly.Yet, comprise that also its nonionogenic tenside is the composition of tensio-active agent gross weight 40-100%, and can use as certain.

Tensio-active agent can be also can comprise a large amount of or a spot of both sexes and/or cats product, as trimethyl-glycine, tetrahydroglyoxaline, amido amine (amidoamines), quaternary ammonium surfactant and have two chain alkyls is as the cationic fabric conditioner of Tallow, beef group.Fabric conditioner that can deflocculate of the present invention comprises two tallow base dimethyl ammoniums, two tallow ylmethyl puratized agricultural spray salt, two tallow base tetrahydroglyoxalines, two tallow base amido amine and quaternized two tallow base tetrahydroglyoxaline and amido amine.The negatively charged ion of fabric conditioner for example, can be maybe to comprise Methylsulfate (methosulphate), oxymuriate, vitriol, acetate, lactic acid salt, Citrate trianion, or fumarate.The present invention's that we select for use composition does not contain a large amount of positively charged ions and anionic two kinds of tensio-active agents.

Amino phosphinates (Aminophosphinates)

The present invention's one specific feature is to be used for the stable zeolite that contains suspension and one and the structure liquid detergent compositions of amino phosphinates coassist agent.

This coassist agent can comprise the compound of following formula:

The polymkeric substance or the oligopolymer that perhaps have following general formula repeating unit:

Wherein, each R group can be identical or different, and it optionally is the alkyl that replaces, cycloalkyl, alkenyl, aryl, aralkyl, alkaryl, or the alkoxy-alkyl group of 1-20 carbon atom, wherein each is optionally replaced by one or many, and each R ' base can be identical or different, it is H, or as the R group of preceding definition, R " be divalent alkyl, ring alkylidene group; alkarylene; the alkylidene group that interrupts by Sauerstoffatom or alkylidene group, and n is 0 or integer and its polymkeric substance or the oligopolymer of 1-10.All are at R, R ' or R " on functional group in the presence of carbonyl compound or Hypophosporous Acid, 50 or mineral acid, should not have non-reversibility ground to decompose.

Described coassist agent can be the polymeric or the oligomeric amino hypophosphite (Phosphinate) of logical formula II repeating unit of band or logical formula I compound, and wherein R contains at least a sulphur or phosphorus atom.It also can be from Methionin, the amino sorbyl alcohol of 1-, 4-aminobutyric acid, or 6-Aminocaproic Acid.It is corresponding to 2 units that lead to formula II that the quality of polymerization or oligomeric hypophosphite can be minimum, and perhaps maximum is 1000 as 200, can be low to moderate 244amu as its quality, or high to 100,000amu or higher, and as 500,000amu.

Phosphinates can free acid, perhaps by existing with its part neutral salt form at least.Preferred cationic is an alkalimetal ion, preferably sodium or potassium or lithium, but also can be other monovalencies, divalence or Tricationic, as the ammonium of ammonium and organic replacement, (comprising quaternary ammonium), triethyl-or triethanol ammonium for example, four phosphorus , as tetra methylol phosphorus, alkaline-earth metal ions such as calcium and magnesium or other metal ions such as aluminium.Preferred salt, or part salt is water miscible is at least 10g/1 as solubleness in its water 20 ℃ the time, particularly is at least 100g/1.

R ' group preferably all is a hydrogen atom.They can be respectively alkyl also, as methyl, ethyl, aryl, as phenyl, tolyl, cycloalkyl, aralkyl, as benzyl, alkoxyalkyl (alkoxyalkyl), as the alcoxyl amyl group, perhaps at least by once or these groups of replacing of secondary, as the alkyl that replaces, as the fontanel substituted alkyl, carboxyalkyl, phosphonic acids alkyl, the aryl of replacement, as hydroxyphenyl, nitrophenyl.

The R group is represented the alkyl that replaces, as ethyl or methyl, or aryl, as phenyl, tolyl, perhaps for example thiazole or triazolyl of heterocycle, particularly at least one, be preferably whole R basis representation and cut group with the one or more functional groups that can coordinate with metal ion, as carbonyl, carboxyl, amino, imino-, amide group, phosphonic acids, hydroxyl, sulfonic acid, arsenate and inorganic and organic ester thereof are as sulfuric ester or phosphoric acid ester and and salt.Phosphinates can cut is with many different R groups.If such as more than one amine is added in the reaction mixture, and can therefrom isolated situation promptly be like this.

Using preferred phosphinates is more such materials as coassist agent, and R base band at least wherein has at least one carboxylic acid substituent, as-C ₆H ₄COOH, particularly a carboxyalkyl group that contains 2-12 carbon atom, when for example synthesizing phosphinates with glycine, for-CH ₂The COOH group, during with the synthetic phosphinates of aspartic acid, for-CH(COOH) CH ₂The COOH group, during with the synthetic phosphinates of L-glutamic acid, for-CH(COOH) CH ₂CH ₂The COOH group.

Phosphinates can be optionally active, such as at least 1 R, R ' or R " group is in the example of chirality, perhaps when two R ' groups on one or more carbon atoms of logical formula I or (II) be like this when being inequality.Substituent arrangement around each chiral center can be the ether configuration.Vacation can be divided into optical isomer with known method with racemic mixture if required.

Make Hypophosporous Acid, 50 and ammonia at carbonyl compound, can be ketone or aldehyde or its mixture and mineral acid existence down reaction generate phosphinates (phosphinates) and Hypophosporous Acid, 50 (hyporhosphorous acid) can be added reaction with its acid or as the form such as the sodium hypophosphite of its salt.Vaporize water is finished reaction.

The detailed description of coassist agent preparation is referring to EP-0419264.

The content of the coassist agent in the structure liquid surfactant is limited in usually and is lower than about 2%(weight) or lower, because it has the tendency of rock steady structure tensio-active agent.By using described stablizer, may be in conjunction with a large amount of coassist agents, as reaching 10%, be preferably 2-8%, by the gross weight of composition) as 3-6%(weight.

The solid that suspends

The major advantage of preferred compositions of the present invention is that they have the solid particulate ability that can suspend, to obtain a kind of dumpable suspension that precipitates.

The present composition can contain solid up to for example 80% suspension by composition total weight, is generally to reach 30%, as 10-25%.The character and the purposes of the combination of the use of determining measured in suspension.As in detergent composition, usually require to contain insoluble washing assistant, as the washing assistant of zeolite or a spot of solubility, as tripoly phosphate sodium STPP, it can be suspended in the body structure surface active agent matrix.

Surfactant system of the present invention also can be used for suspending: abrasive material, and as talcum, silicon, calcite, thick zeolite is as hard surface cleaner; Or agricultural chemicals, to obtain water-dispersion, contain the dumpable composition of water-insoluble agricultural chemicals, there is not the solvent of deleterious poisonous soil dust or hostile environment.They also are used to provide dyestuff, pigment, and medicine, the suspension of sterilant perhaps as drilling mud, contains suspension shale and/or weight agent such as sodium-chlor, calcite, barite, square aluminium ore or rhombohedral iron ore.

Their exfoliant that can be used to suspend comprise talcum, earth, polymeric beads, sawdust, silica, seed, Pericarppium arachidis hypogaeae or Lin Suanergai, pearlisers such as mica, the glyceroyl list-or two-hard acid ester salt, or the ethylene glycol list-or two-hard acid ester salt, natural oil is as Oleum Cocois, night paper spring (evening primrose) oil, peanut oil, meadow foam oil, Prunus amygdalus oil, Lipoval A, persic oil, perhaps jojoba oil, Synthetic Oil, as the polysiloxane grease, VITAMIN, anti-scurf agent is as, Zinc Omadine, the disulphide of selenium, albumen, tenderizer is as lanolin or sec.-propyl nutmeg acid esters, wax and sun-screening agent such as titanium dioxide and zinc oxide.

Washing assistant

Detergent composition of the present invention preferably contains the suspended particle of solubility washing assistant and/or solid detergent, to obtain a kind of synergic liquid detergent.It is a kind of by improving the compound that is used for the cosurfactant cleaning function of dissolved calcium and/or magnesium to use " washing assistant " to be meant herein.The also auxiliary alkalescence that keeps washings of general washing assistant.Typical washing assistant comprises sequestering agent and recombiner, as tripoly phosphate sodium STPP, potassium pyrophosphate, tertiary sodium phosphate, sodium ethylene diamine tetracetate, Trisodium Citrate or NTA nitrile triacetic acid sodium (Sodium nitrol-triacetate), ion-exchanger such as zeolite and throw out, as yellow soda ash and salt of wormwood, and other alkali such as water glass.Described stablizer has also had a effect to all washing assistants.Preferred washing assistant is zeolite and tripoly phosphate sodium STPP.The concentration of washing assistant can reach 50% of composition weight, as 15-30%.

PH

The composition dilute with water that uses as lotion is measured preferably alkalescence of its PH later, to obtain accounting for the solution of composition weight 1%, as 7-12, is more preferably 8-12, most preferably is 9-11.

Hydrotropic agent

The present composition can optionally contain a spot of hydrotropic agent, as sodium xylene sulfonate, and toluenesulfonic acid sodium salt or sodium isopropyl xanthate, its concentration is the as many as 5% of composition total weight, is preferably and is no more than 2%, as 0.1%-1%.Hydrotropic agent is attempted the failure surface active agent structures, so importantly do not want excessive use.Its main effect is the viscosity that reduces prescription, but may make prescription unstable too much.

Solvent

Except water, composition can contain solvent.Yet as hydrotropic agent, solvent is also attempted the structure of failure surface promoting agent.Yet also the formulation cost that they increase as molten growth substance does not but have the improvement of essence to scourability.Based on the reason of environment, do not need them, it is to be to provide solvent-free composition that the present invention has special value.Therefore what our solvent selected for use accounted for composition total weight is less than 6%, more preferably is less than 5%, most preferably less than 3%, particularly is less than 2%, more especially is less than 1%, as is less than 0.5, as mixable alcohol of this water or ethylene glycol.Though the composition that we adopt needs a spot of glycerine or propylene glycol sometimes, does not have solvent basically.Sometimes need ethanol, the about 3%(weight of its concentration as many as), as 1-20 to tart up.This concentration usually can be approved the destabilization that can't cause this system.

Polymkeric substance

The present composition can comprise various polymkeric substance.Particularly it may be combined with the polyelectrolyte of consumption, as polyethylene hydrochlorate or the polymaleic acid salt that also covers.This polymkeric substance can use, because they can reduce viscosity, and because have the effect that helps washing composition, can have protection against corrosion or antiscale activity.Unfortunately their also failure surface active agent structures can not add body structure surface active agent and don't go to stablize this system with effective dose.Found that heavy dose of relatively polyelectrolyte adding structure can be washed agent combines with described stablizer, does not produce and stablizes this structure.Can provide like this than only being the stable product that the low viscosity that reaches of stablizer requires.

Some examples of the polymkeric substance that contains in the prescription are precipitation agents, as Xylo-Mucine, and the anti-whipping agent of anti-whipping agent such as polysiloxane, enzyme stabilizers, as polyvinyl alcohol and polyvinylpyrrolidone, dispersion agent such as Sulfite lignin and sealing agent such as glue and resin.We find to grind auxiliary, are very useful as dimethyl bitter edible plant sodium sulfonate/formaldehyde condensation compound, and are the same with dyestuff or formulation of pesticide, and the solid that suspends in the composition needs to grind.

The amount that adds polymkeric substance is decided by the application target of this polymkeric substance.In some cases, can be for few to 0.01%(weight) even lower.Amount 0.1～10% commonly used is 0.2-5% particularly, as 0.5-2%(weight)

Other detergent additives

The detergent composition of suspended solids of the present invention can comprise conventional detergent additives; as anti-redeposition agent (being typically Xylo-Mucine); white dyes; sequestering agent; anti-whipping agent; enzyme; enzyme stabilizers; the storage agent; dyestuff; pigment; spices; fabric conditioner; as negatively charged ion fabric softener or wilkinite; opalizer; the SYNTHETIC OPTICAL WHITNER that bleach activator and/or chemistry mix; we find peroxygen bleach such as Sodium peroxoborate particularly the present invention used the SYNTHETIC OPTICAL WHITNER of seal protection, more stable than the prescription decomposition aspect of conventional liquid detergent.General all conventional detergent additives can be suspended in the composition of the present invention; this additive is surpassing under the situation of their solubleness in washing composition; form with solid particulate or drop is distributed in the detergent composition, and with they react withs not.

Use

Except novel laundry detergent is provided, outside fabric conditioner and the flushing breast (scouring creams), stable structure tensio-active agent of the present invention can be used for makeup, comprises shampoo, liquid soap, emulsion, vanishing cream, face cream, ointment, sterilant, tooth powder and hemostatic drug.

This tensio-active agent is for dyestuff and condensed pigment, and printing-ink, pesticide concentrates and drilling mud all provide valuable suspension matrix.In the presence of dense thick solubility ionogen, as Calcium Bromide, they are specially adapted to the closely knit liquid in oil field and (are used to fill the gap between well casing and the boring in the past, mechanical shock takes place to prevent the former), and in the oil well finish liquid (completion fluid) or as cutting liquid or lubricant.

Cenotype

The combined thing of G-of the present invention is mobile strong, but also is used as the suspended solids system.Preferably make this composition with described stablizer, also can make with other deflocculation agent, as EP0346995, the polymkeric substance described in GB2287813 and the WO9106622.

Stable and the novel L that the present invention is identical ₁System also can be made with other deflocculation agents rather than described stablizer.Their it goes without doing suspension matrix, but satisfy limpid liquid washing agent and the needs of shampoo under high level of surfactant and ionogen condition.

We find to use the very water-soluble ionogen of high density especially, when preparation contains the composition of a high proportion of relatively nonionogenic tenside as potassium pyrophosphate, obtain a kind of structure phase of not appearing in the newspapers in the past, it contains isotropy dispersive phase, comprise particle diameter and typically be the 1-50 micron, we believe that it is by a micellar phase, may be a kind of L ₂Opposite micellar phase perhaps in some cases, may be anhydrous liquid surfactant and a kind of typical isotropic phase, may be L ₁The perhaps external phase of aqueous electrolyte, perhaps a kind of mobile intermediate phase such as we think the anisotropy phase composite of the dilution that may be lamellated G-phase.

We are also noted that and add enough dissolved ionogen continuously in the compositions that contains a high proportion of relatively nonionogenic tenside, cause a kind of formation of typical spherulite composition at the beginning, and the electroconductibility of said composition is through a peak value, so reduce to minimumly, it rises to maximum value for the second time apace subsequently.Taking place near Schwellenwert place one obvious variation, this moment is corresponding is that disperse phase is closely filled from little in the external phase of formerly isotropy or weak anisotropy, and the anisotropy spherocrystal becomes bigger, the isotropy droplet that the gap is bigger.In through first electroconductibility that approaches the electroconductibility Schwellenwert, find best solid suspension system.

Novel texture system of the present invention typically contains the nonionogenic tenside that accounts for tensio-active agent gross weight 15%-100%, usually be at least 30%, as 40-90%, be in particular 50-80%, for example pure ethoxyquin compound, or alkylphenol b-oxide are with anion surfactant such as alkylbenzene sulfonate, alkyl-sulphate, or alkyl ethoxy vitriol.Composition also contains high-content solubility ionogen, as is at least 15%(weight) be in particular greater than 18%, be preferably greater than 20%, as potassium pyrophosphate and/or Tripotassium Citrate.

The novel texture composition generally tends to flocculation, and needs the existence of described stablizer so that topple over.

The present invention will further specify by following embodiment.

The preparation method's method that is used as the thiol polyacrylate (thiol polyacrylate) of described stablizer among the following embodiment is to be 24: 76 thiol n-Hexadecane (hexadecanethiol) and vinylformic acid reaction with weight ratio.There is the Diisopropyl azodicarboxylate of 0.005 weight part to exist during reaction, is dissolved in the acetone in weight concentration by total solution weight total overall reaction thing 55%.Backflow mixture 1 hour distills acetone, and resistates is dissolved in 17%(weight) generate 35%(weight in the aqueous sodium hydroxide solution) surfactant soln.Product more than 5% is dissolved in 18% potassium citrate solution.Also be soluble in 25% the potassium citrate solution, at least 1% is dissolved in 35% Klorvess Liquid.

Embodiment 1

A kind of laundry detergent composition comprises: % weight

Sodium alkyl benzene sulfonate 8

Trolamine alkyl-sulphate 2

Fatty Alcohol(C12-C14 and C12-C18) 3mole ethoxylate 11

Tripoly phosphate sodium STPP 20

Potassium pyrophosphate 20

The anti-whipping agent 0.33 of siloxanes

Alendronate sequestering agent 1

White dyes 0.05

Spices 0.8

Level is weighed

Said composition is with the preparation of the thiol polyacrylic acid salt stabilizing agent of various concentration, and its viscosity is to record at 100rpm20 ℃ with 4 of " Brookfield RVT " viscosity apparatuss.It the results are shown in Table 1.

Table 1

Wt% stablizer viscosity Pas

0????????＞4.0

0.1????????1.31

0.26????????1.17

0.52????????1.39

0.78????????1.6

1.25????????2.8

Product comprises that isotropy drips grain, the L in its seemingly isotropic external phase ₂Phase.

Embodiment 2

With a large amount of aqueous surfactant compositions of preparation shown in the following table 2.Trisodium Citrate added continuously reaches 16.3%(weight in each composition) (measuring) with monohydrate.Each composition through uniform stable but heavy-gravity zone, when it reaches maximum citric acid concentration, has experienced flocculation and has separated under certain citric acid concentration.In each composition, add 2%(weight) 27%(weight) the above-mentioned thiol polyacrylic acid salt stabilizing agent aqueous solution, and stir, generates a kind of uniformly, deflocculate, flowable liquid is the spherocrystal type through the microscopy confirmation.

Embodiment 3

The composition of listing in the table 3 all is stable, mobile, spherocrystal type liquid.They are heavy-gravity when not having described stablizer, and the paste of flocculation is divided into the clearly bottom of a kind of curdy piece thing and about 10% volume after leaving standstill.

N, B all components are represented with 100% solid.

Table 3

	A	B	C
				Water potassium hydroxide NaOH MEA fluorescent whitening agent calcium chloride sodium ethylene diamine tetracetate C12－14Alkyl benzene sulphonate (ABS) C 12－14Alkyl 3mole ethoxylate C 12－14Alkyl 8mole ethoxylate C 12－14Alkyl ethoxy sodium sulphate Trisodium citrate dihydrate natrium citricum monohydrate zeolite sodium pyroborate kodalk potash diethylenetriamine five (methylene phosphonic acid) sodium enzyme alkylpolyglycosides (dp=1.35) thiol polyacrylate PTPP C12－18Lipid acid (STPK) viscosity Brookfield Sp4,100rpm Pa S	To 100 1.64-2.87 0.15 0.2-19.0 7.0---12.5 18.0 2.0--3.0 0.4 0.7---1.05	To 100 1.9-3.06 0.15 0.2-22.0 7.0---12.5 18.5 2.0--3.0 0.4 0.7---1.575	To 100-1.7 2.6 0.15 0.2 0.55 27.6-9.0-14.5---4.0--1.4-0.25--0.6

Continuous table 3

	D	E	F	G
					Water potassium hydroxide NaOH MEA fluorescent whitening agent calcium chloride sodium ethylene diamine tetracetate C12－14Alkyl benzene sulphonate (ABS) C 12－14Alkyl 3mole ethoxylate C 12－14Alkyl 8mole ethoxylate C 12－14Alkyl ethoxy sodium sulphate Trisodium citrate dihydrate natrium citricum monohydrate zeolite sodium pyroborate kodalk potash diethylenetriamine five (methylene phosphonic acid) sodium enzyme alkylpolyglycosides (dp=1.35) thiol polyacrylate PTPP C12－18Lipid acid (STPK) viscosity Brookfield Sp4,100rpm Pa S	To 100-1.7 2.6 0.15 0.2 0.55 27.6 2.0--14.5---4.0--1.4 4.3---0.85	To 100 3.45-2.8 0.15 0.2-20.0 5.0 5.0--12.5--3.0-4.0 0.4-0.25-10.0 0.42	To 100 3.45-2.8 0.15 0.2-20.0 5.0 5.0-----3.0-4.0 0.4-0.25 12.5-0.36	To 100 1.0--0.15 0.2--8.5-9.0-12.0 24.0--1.0-0.4-0.25-4.5 1.26

Embodiment 4

Make a kind of alkaline laundry detergents of substituting use by following prescription; As in hospital, using, be suitable for automatic dispersion.

Weight %

Sodium hydroxide 6.8

Nonyl phenyl-9 mole ethoxylate 13.4

Straight chain C ₁₂-C ₁₄Sodium alkyl benzene sulfonate 14.0

Divinyl triamine five (methylene radical phosphoric acid) sodium 7.0

Anti-redeposition agent 7.0

White dyes 0.05

Sulphur carboxylic polyacrylate 0.4

Do not having under thiol polyacrylate (thiol Polyacrylate) the stablizer situation, product is highly viscous, and tends to be divided into one in the thin liquid phase in the outside of curdling piece.Dose stablizer and generate a kind of mobile, stable, spherocrystal type composition.Add excessive thiol polyacrylate continuously and can cause that viscosity rises to maximum.Yet add to amount to 30% thiol polyacrylic acid salt surfactant produce one thin, mobile, transparent G phase with good solid suspension characteristic.Further adding stablizer generates a kind of limpid, optical isotropy, newton's micellar solution.

Embodiment 5

By mix the liquid laundry detergent that following component prepares a kind of high density by the order that provides.

Component/addition sequence %w/w component component form

Water balance

Sodium hydroxide 5.92 (47% solution)

Citric acid 9.47 powder

Thiol polyacrylate 0.4

C _12-149 mole 9.0 of alcohol

Ethoxylate

Monoethanolamine 5.2

Straight chain C _12-1427.6 (96.5%)

Alkyl benzene sulphonate (ABS)

Dyestuff 0.025 (1% solution)

White dyes 0.15

Calcium chloride 0.2

Sodium ethylene diamine tetracetate 0.55

Dihydrate

Sodium metaborate 4.0

Thiol polyacrylate 0.6

Liquid of protease 0.05

Amylase liquid 1.4

Product is opaque, and is stable, the spherocrystal detergent composition that flows, 0.65Pas when its viscosity is 21/ second.

Embodiment 6

The liquid laundry prescription that preparation is following

Component % activeconstituents

A????????B

White dyes 0.5 0.5

Straight chain C _12-14Sodium alkyl benzene sulfonate 12 12

Thiol polyacrylate 0.75 0.5

Salt of wormwood 6.0 6.0

Potassium tripolyphosphate 14.0-

Tetrapotassium pyrophosphate-7.5

C _12-143 moles of oxyethyl group sodium sulfate 3.0 3.0 of alkyl

Ethoxylized fatty alcohol ¹8.0 4.5

Tripoly phosphate sodium STPP 20 23.5

Spices 0.5 0.5

Coating 0.0075 0.0075

Level is weighed equal amount

1 the C of weight such as comprises ₁₂-C ₁₄3 mole ethoxylates and C ₁₂-C ₁₄8 mole ethoxylates.

Embodiment 7

The prescription (weight) that the dense dye suspensions of preparing has:

Yellow dyes (" terasil Gelb ") 35%

Straight chain C _12-14Sodium alkyl benzene sulfonate 6.5%

Alkyl ethoxy sodium sulfate 3.25%

Repone K 2%

Dimethyl bitter edible plant sodium sulfonate formaldehyde condensation products 6%

26% moisture thiol acrylate stabiliser solution 5%

Water 42.25%

Said composition is a mobile, stable and composition water-dispersion, and when no stablizer, said composition is a heavy-gravity, high flocculation.

Embodiment 8

The dense dye suspensions of preparing has following prescription by weight:

Yellow dyes (" Terasil " Gelb) 35%

95% active Isopropylamine straight chain 5%

C _12-14Alkyl sulfate

30% moisture thiol polyacrylate stabiliser solution 5%

40% moisture dimethyl bitter edible plant sodium sulfonate/6%

Formaldehyde condensation products

Water 49%

Said composition is a mobile, and stable is also soluble in water.When no stablizer, flocculation, concurrent living dispersive dye precipitated separate surfactants appear in composition.

Embodiment 9

The metal degreasing of preparing (dirt) agent has prescription by weight:

Nonyl phenyl 9-mole ethoxylate 8.2%

C _12-143 moles of ethoxylations 10.3% of alkyl

30% thiol acrylic acid brine solution 1.5%

40% ethyl pentyl group aqueous sodium persulfate solution 6.8%

Tripoly phosphate sodium STPP 24.0%

The 15% sodium orthophosphate aqueous solution 47.90%

25% aqueous sodium hydroxide solution 1.3%

Said composition is a mobile and stable, and when no stablizer, it is a heavy-gravity, leaves standstill the back and separates.

Embodiment 10

The two kinds of drilling muds (liquid) that gone out by following formulated comprise (weight %)

A????????°????????B

C _12-143 mole 6.8 6.7 in alkyl

Oxyethyl group calcium sulfate

Calcium oxide 0.8 0.8

Water 54.5 53.6

The anti-whipping agent 0.2 0.4 of siloxanes

Calcium chloride dihydrate 34.1 34.0

C _12-14Alkyl 3.6 3.9

Phenylsulfonic acid

C ₁₂-C ₁₆Alkyl 20

Mole ethoxylate (stablizer) 0 1.2

Sample A is high flocculation, and generates a kind of viscoelastic liquid, and it stirs with 300rpm and usually forms colloid when shearing.Its initial value (yield point) is 0.1N before shearing A, 21 seconds ^-1The time viscosity be 0.5Pas, when shearing greatly viscosity degradation to be essentially constant viscosity its for 0.17Pas.

On the contrary, the sample B that contains stablizer is stable, and having initial value is 0.1N, 21 seconds ^-1Viscosity is the fluid of 0.55Pas, shears along with increasing, and viscosity number rises to steady state value 0.09Pas.

After 300rpm mixing 15 minutes, the initial value of product is 0.17N, and viscosity was at 21 seconds ^-1Be 0.38Pas, its viscosity drops to a steady state value 0.087Pas when high shear rate.Said composition is applicable to drilling mud, and liquid is dosed in the space, finishes liquid or sealing liquid.

Embodiment 11

Press with following formulated drilling mud:

Weight %

C _12-143 moles of oxyethyl group calcium sulfate 6.7 of alkyl

Calcium oxide 0.8

H ₂O 51.8

The anti-whipping agent 0.4 of siloxanes

Calcium chloride dihydrate 34.0

C _12-14Alkyl benzene sulphonate (ABS) 3.9

Poly-AMPS stablizer * 3.0

* this stablizer is the polymkeric substance of 2-acrylamide-2-methyl propane sulfonic acid, and its mean polymerisation degree is 12.

Product is stable, and its initial value is 0.17N, and 21/ second viscosity is 1.7Pas, and stable viscosity is 0.13Pas.After stirring in 300rpm15 minute, its initial value is 0.3N, 21 seconds ^-1Viscosity be 1.0Pas, and it drops to a stationary value 0.9Pas when increasing shearing rate.

Embodiment 12

The following dense surfactant system of preparation in the Repone K ionogen, and add alcohol 20 b-oxide that rubs and make it deflocculate.

Straight chain C _12-14Alkylbenzene sodium sulfate 12%

Alkyl ethoxy sodium sulfate 6%

Repone K 18%

C _16-18Alcohol (20ED) 0.5%

Ethoxylate

Water 63.5%

Said composition is mobile, and is stable, and its viscosity (21/ second shearing rate) is 0.35Pas.When not having pure b-oxide stablizer, it is a heavy-gravity, and it is isolating to leave standstill the back.

Embodiment 13

The viscosity of the deflocculation of stablizer and deflocculate system is by the concentration control of the destabilizing agent that adds.Need a spot of stablizer to be used for deflocculate, it is structure and the component that depends on deflocculate system deflocculation agent.In case obtain deflocculation, when increasing destabilizing agent concentration, the viscosity of this system increases to maximum then by minimum.

Embodiment 14

For the surfactant system of each flocculation, as if exist a kind of between the headgroup size of deflocculate tensio-active agent and the relation between the deflocculation.If a series of have headgroup magnitude range tensio-active agent to be used as deflocculation agent tested, can observe this situation.

Be the example of surfactant system below, this body can be used the alkylpolyglycosides deflocculate.

C ₁₂-C ₁₄Alkyl benzene sulphonate (ABS) 30%

C ₁₂-C ₁₄Alkyl 8 mole ethoxylates 10%

Tripotassium Citrate monohydrate 15%

Alkyl polyglucoside X%

Level is weighed

The polymerization degree of alkyl polyglucoside can be defined as the mean number of the repetition glucoside unit of each alkyl polyglucoside molecule, its available GLC or GPC technical measurement.

Therefore, can be illustrated for the effect of deflocculation through the poly-polyglycoside DP of observation alkyl about the effect of deflocculation agent headgroup size deflocculation.In above-mentioned system, X is the minimum dose that can cause the desired APG of deflocculation.

Embodiment 15

Believe surfactants, in the kind of flocculating with have between the minimum deflocculation kind,, a significantly difference is arranged all by the size of its headgroup with enough big headgroup for each flocculation.

The surfactant system of available alkyl polyglucoside deflocculate is shown below.

C ₁₂-C ₁₄Alkyl benzene sulphonate (ABS) 30%

Monoethanolamine

C ₁₂-C ₁₄8 mole 10% in alkyl

Ethoxylate

Tripotassium Citrate monohydrate 15%

Alkyl polyglucoside X

Level is weighed

Embodiment 16

As if the contact between headgroup size and the deflocculation partly come from the relation in headgroup size and spherocrystal interlayer gap.

Having observed less clearance needs the headgroup size of less deflocculate.Describe by following embodiment:

System 1 system 2

C _12-14Alkyl benzene sulphonate (ABS) 30% 30%

Monoethanolamine

C _12-14Alkyl 8 moles 10% 10%

Ethoxylate

Tripotassium Citrate monohydrate 15% 40%

Alkyl polyglucoside DP1.27 X% X%

Level is weighed equal amount

Interlayer gap (A) (x-ray diffraction instrument)

Embodiment 17

Mix following component in the indicated order.

Component %w/w solid

Water balance to 100%

C _12-14Alkyl 1.32dp Portugal 1.00

Glucosides (adding) with 70% solution

White dyes (TINOPAL CBS/X) 0.15

Lime acetate 0.20

Potassium hydroxide (adding) 1.64 with 50% solution

Monoethanolamine 2.87

Steam stripped palm hull lipid acid 4.00

Citric acid tri potassium monohydrate 11.50

C _12-14Sodium alkyl benzene sulfonate 19.00

Anti-whipping agent 0.05

Zeolite 18.00

Spices 1.30

C _12-14Alcohol 3 mole ethoxylates 7.00

Borax 2.00

Anti-whipping agent 0.05

Enzyme (SAVINASE 16.01 EX) 0.40

Fungistat (PROXL GXL) 0.05

Dyestuff 0.002

C _12-14Alkyl 1.32dp

Glucoside (with 70% solution) 1.00

" TINOPAL " " SAVINASE " and " PROXEL " are registered trademarks.

Said composition is a mobile, and is stable, opaque, spherocrystal liquid, and it has following characteristics:

PH(is dense) 9.5

The PH(1% dope) 9.0

Viscosity (Brookfield RVT sp4 1000rpm) 1.0Pas

Density 1.25gcm ^-3

In the presence of no alkyl polyglucoside, this product height flocculation when mixing end, is observed thickening slightly, and it can be able to calibration by adding alkyl polyglucoside.

Embodiment 18

Mix following combination in the indicated order.

Component %w/w solid

Water balance to 100%

White dyes (TINOPAL CBS/X) 0.1

Disodium ethylene diamine tetraacetate 0.55

Calcium chloride dihydrate 0.20

Dyestuff 0.025

Sodium hydroxide 5.92

Monoethanolamine 5.20

Citric acid 9.47

Thiol polyacrylic acid stablizer 0.0625

Linear alkyl benzene sulphonic acid 12.00

Sodium metaborate 4.00

Thiol polyacrylic acid salt stabilizing agent 0.1875

Enzyme 1.40

This product is stable, mobile, spherocrystal liquid.Under the situation of no stablizer, product seriously flocculates.

Embodiment 19-21

Mix following component by the order of the following stated.

Product is a mobile, and is opaque, no solid, stable liquid.Do not having under the situation of stablizer, this product is immobilising.

Embodiment 22 and 23

Mix following component by the order that illustrates:

This product in each example is mobile liquid.When not having stablizer, make a kind of high viscosity, curdy product with identical prescription.

Claims (20)

1, a kind of aqueous surfactant composition consists essentially of: at least a energy self and/or form the tensio-active agent of flocculation system in the presence of flocculation agent; One contains enough flocculation agents, as needs, continuous water and described tensio-active agent form a flocculation system; It is characterized in that having stablizer, this stablizer is to form the micellar compound at described aqueous phase, and the hydrophilic polymeric group that surpasses 4 monomer unit is arranged, its quality is at least 300amu, described hydrophilic radical is connected an end of the hydrophobic group of at least 4 carbon atoms, suppresses the flocculation of this system with enough dosage.

2, by described a kind of stable, the mobile spherulitic crystal structure surfactant composition of claim 1, comprising: water; Enough tensio-active agents are to form a structural system in the presence of electrolytical; The dissolved of at least 10% weight, tensio-active agent-go dissolved salt, this salt has multivalent anions, the concentration of salt described in the described composition forms (ⅰ) a kind of unsettled and/or (ⅱ) flocculation, spherocrystal type body structure surface active agent composition for being enough to described water and tensio-active agent; With a kind of have be connected its quality and be C greater than hydrophilic radical one end of 300amu _6-20Alkyl group and a large amount of hydroxyls, the carboxylic acid group, sulfonic group, phosphonate group, the stablizer of sulfuric acid or phosphate group, therefore, this stablizer is dissolved in the aqueous solution of described salt with described concentration, the amount of described stablizer is enough to provide respectively (ⅰ) more stable, and/or (ⅱ) more low viscous spherulite composition.

3, aqueous surfactant as claimed in claim 1 comprises: water; There are the enough tensio-active agents that form structural system at ionogen; The dissolved polyvalent metal salt, it removes to dissolve described tensio-active agent, the concentration of salt described in the composition is so that to form (ⅰ) a kind of unsettled with described tensio-active agent, and/or (ⅱ) its viscosity greater than the spherocrystal system of the flocculation of 0.8Pas; With a kind of stablizer, it comprises a kind of micelle formation compound, and this compound comprises C _6-20Alkyl and hydrophilic radical, its quality is greater than 300amu and a large amount of ethoxy compounds is provided, hydroxyl, sulphonate-base, phosphonic acids alkali, sulfate salt and/or phosphate group, described stablizer is with described concentration, dissolution degree is 5%(weight at least in described polyvalent metal salt brine solution), the dosage of described stablizer is enough to provide respectively (ⅰ) a kind of stable, and/or (ⅱ) more low viscous spherulite composition.

4, water-bearing structure surfactant composition as claimed in claim 1 comprises: water; In the presence of ionogen, form enough tensio-active agents of body structure surface active agent composition; The basic metal of at least 10% weight or the ammonium salt of monovalent anion, this salt removes to dissolve described tensio-active agent, the concentration of described salt is enough to that to form (ⅰ) unsettled with described tensio-active agent, spherocrystal system and/or (ⅱ) a kind of system of flocculation, and the viscosity of this body second is greater than 0.8Pas; And C _6-20Alkyl alkoxide, its each molecule have at least 8 vinyloxy group groups and 0 to 10 propenyl oxygen base group, and its quantity is enough to form respectively (ⅰ) stable spherulite composition and/or (ⅱ) more low viscous spherulite composition.

5, fabric-conditioning compositions as claimed in claim 1 comprises: water; Have two C _15-25The negatively charged ion of alkyl or kiki alkenyl group or both sexes fabric conditioner; Enough flocculation agents and described fabric conditioner and water form a kind of heavy-gravity, system flocculation and/or unsettled; And enough described stablizer reduction viscosity and/or degree of flocculation, and/or stablize described composition.

6, surfactant composition as claimed in claim 1 comprises: water; Structure forms tensio-active agent; As needs, enough dissolved ionogen are to form the body structure surface active agent system; Enough dissolved, non-micella-formation polymkeric substance improve viscosity with flocculation, and/or remove to stablize described body structure surface active agent system and enough described stablizer reducing degree of flocculation and/or viscosity, and/or stablize described composition.

7, composition as claimed in claim 1 comprises: water; Enough structures form tensio-active agent from independent with described water, or in the presence of ionogen, form a kind of structure; If need, enough ionogen are to form described structure with described water and described tensio-active agent; Enough non--micelle formation polyelectrolyte are with the described structure of flocculating; The stablizer that contains micelle formation compound, this compound have the C that is connected with an end of described hydrophilic radical _4-20Alkyl or alkenyl group, the quality of described hydrophilic radical is greater than 300amu and/or have polymkeric substance more than 4 hydrophilic monomer units, and its quantity is enough to form a kind of body structure surface active agent composition that flocculates few.

8, liquid detergent compositions as claimed in claim 1 comprises: water; Structure forms tensio-active agent; Enough dissolved ionogen are to form a kind of body structure surface active agent system with described tensio-active agent and water; The zeolite synergistic agent that suspends; Amino phosphonates do with the following formula surface:

RR’NCR’ ₂PO（OH）CR’ ₂NRR’（Ⅰ）

The polymkeric substance or the oligopolymer that perhaps have following general formula repeating unit:

[-PO（OH）CR′ ₂NR（R′′NR） _nCR′ ₂-]（Ⅱ）

Wherein each R group can be identical or different, it is the alkyl that selectivity replaces, cycloalkyl, alkenyl, aryl, aralkyl, the alkoxyalkyl of alkaryl or 1-20 carbon atom, each carbon atom can be by the replacement one or many of selectivity, each R ' group can be identical or different, is the R group of hydrogen or above-mentioned definition, and R ' ' is a divalent alkyl, the ring alkylidene group, alkyl arylene (alkarylene), by Sauerstoffatom or an arylene group terminated alkylene group, n is 0 or the integer of 1-10, with its polymkeric substance or oligopolymer, the amount of described amino phosphonates do is enough to increase viscosity, flocculation and/or go to stablize described body structure surface active agent system; Enough described tensio-active agents are to reduce its viscosity and/or degree of flocculation respectively and/or to stablize described composition.

9, the combined thing of a kind of G-, it contains water, tensio-active agent and optionally dissolved ionogen and/or suspended solids, and under the situation of no deflocculation agent, make it to form a kind of composition that contains intermediate phase, said composition is divided into two or more parts after leaving standstill, and/or demonstrates its viscosity greater than 0.8Pas, and enough deflocculation agents are to form a kind of stable combined thing of G-and/or the G-phase of viscosity reduction respectively.

10, a kind of body structure surface composition comprises: water; Structure forms tensio-active agent, by the gross weight of tensio-active agent, comprises the nonionogenic tenside of at least 3% weight; A kind of as L with enough water-soluble ionogen in moisture stratiform or anisotropy external phase, to form ₂The structure of the isotropy tensio-active agent phase of phase is disperseed.

11, composition as claimed in claim 1, wherein said stablizer comprise a hydrophilic polymer group, and this group comprises and is selected from acrylate, methylacrylate, and maleate and crotonate also are connected C _6-256-8 monomer unit of alkyl one end, for example, at C ₁₀-C ₂₀One end terminated of alkyl thiol.

12, composition as claimed in claim 1, wherein said stablizer comprise the C of 4 above glucoside residues that tool is enough ₆-C ₂₀Alkyl polyglucoside reduces its viscosity and/or degree of flocculation with being effective and/or stablizes described composition.

13, composition as claimed in claim 1, wherein said stablizer contain the poly carboxylic acid poly-alkoxylation thing (I) that following general formula is represented

Wherein R is a straight or branched alkane, and alkaryl or alkenyl group perhaps have side chain or the branched-chain alkyl or the alkenyl carboxylic group of 6-25 carbon atom, each R ¹Be OCH ₂CH ₂Or OCH(CH ₃) CH ₂Group, each R ²Be OC ₂H ₃Perhaps OC ₃H ₅Group, each R ³Be C(R ⁵) ₂C(R ⁵) ₂Group, quantity 1-4 group wherein, 2 groups preferably, each R ³R in the group ⁵Be CO ₂The A group, each other R ⁵Group is C ₁-C ₂Alkyl, hydroxyalkyl or carboxyalkyl group or, be preferably H, R ⁴Be OH, SO ₄B, SO ₃B, OR, sulfo-amber acidic group OCH ₂CO ₂B, or R ⁶ ₂NR ⁷, R ⁶Be C ₂-C ₄Alkyl or hydroxyalkyl, R ⁷Be C ₁-C ₂₀Alkyl, phenyl, CH ₂CO ₂B, or-＞0 base or PO ₄B ₂, B makes described hydroxy acid can form the positively charged ion of water-soluble salt, and as basic metal, or alkaline-earth metal, each Z is 1-5, is preferably 1, and y is at least 1 and the mean value of the 1-50 that (x+y) has, wherein R ¹And R ²Group can randomize or along poly-alkoxylation thing chain ordered arrangement; Preferably tool is more than the alkyl polyethoxylated and the reactant of last saturated carboxylic acid salt in the presence of free radical starting agent of 4 oxyethyl group groups, as have a 4-30 vinyloxy group alkyl polyethoxylated, this vinyloxy group group with 3-30 maleate radical reaction mistake.

14, as claim 4, composition described in one of 9 to 11 and 23 to 25, wherein said stablizer comprises a polyacrylate, and it comprises that the hydrophobic group with at least 4 carbon atoms contains the polyalkylene oxide base group of at least 6 vinyloxy group groups with at least one.

15, composition as claimed in claim 1, wherein said stablizer comprise the alkyl polyethoxylated with 8-16 vinyloxy group group.

16, composition as claimed in claim 1, wherein said water contains dissolved Tripotassium Citrate and/or sodium, potassium pyrophosphate and/or sodium, and/or Potassium tripolyphosphate and/or sodium.

17, composition as claimed in claim 1, wherein said polyvalent metal salt comprises the alkaline-earth metal fontanelle compound, as chlorination and/or Calcium Bromide and/or barium.

18, composition as claimed in claim 1, wherein said monovalent salt comprise a kind of alkaline-earth metal fontanelle compound, as chlorination and/or Sodium Bromide and/or potassium.

19, liquid detergent compositions as claimed in claim 1 comprises: water; By the tensio-active agent of composition total weight 20-60%, described tensio-active agent comprises by the anion surfactant of tensio-active agent gross weight 0-80% with by the nonionogenic tenside of the 20-100% of tensio-active agent gross weight; The tri-polyphosphate that is selected from by composition total weight 8-50%, dissolved sylvite in pyrophosphate salt and the citric acid, all the dissolved electrolyte concentration is enough to provide a kind of heavy-gravity with described tensio-active agent and water, spherocrystal system flocculation and/or unsettled and/or a kind of flocculation dispersion in isotropy or the continuous aqueous phase isotropic liquid of anisotropy tensio-active agent phase; Enough described stablizers are to reduce its viscosity and/or degree of flocculation and/or to stablize described composition; Solid detergent by the suspension of the 0-35% of composition total weight.

20, composition as claimed in claim 1 is made up of following component: water basically; Tensio-active agent is as C ₁₀-C ₂₀The alkyl benzene sulphonate (ABS) Isopropylamine, it can form a stable spherocrystal system in water, and its concentration is the normal concentration that forms this system; The polyelectrolyte of lf dose grinds auxiliary; Suspended solids such as dyestuff or agricultural chemicals; Described stablizer with effective content.