CN102858942B - Microcapsule Incorporation In Structured Liquid Detergents - Google Patents

Abstract

A process for the incorporation of microcapsules with anionic charge into a structured aqueous concentrated liquid detergent comprising at least 30 wt%, preferably at most 65 wt%, total surfactant of which at least 5 wt% based on the total composition is anionic surfactant, including soap, and an external structurant, the process comprising the combining of two premixes; Premix A which is the structured aqueous concentrated liquid detergent composition without microcapsules and Premix B which comprises an aqueous dispersion of the microcapsules with anionic charge, characterised in that: Premix B is a slurry of microcapsules with a maximum viscosity at 25 DEG C of 100 mPas and at least 90 wt% of the microcapsules having a particle size in the range 5 to 30 microns, and that Premix B is added to Premix A and the resulting combined mixture is passed through a static in-line mixer with an energy input of from 20 to 500 J/kg to form, immediately after the mixer, a structured liquid comprising less than 10%, based on the total number of groups of microcapsules, agglomerated groups of microcapsules, an agglomerated group of microcapsules being defined as a group having more than 5 microcapsules grouped together.

Description

In structurized liquid washing agent, introduce microcapsule

Technical field

The present invention relates to microcapsule to introduce improving one's methods in the structurized aqueous liquid detergent that comprises at least 30 % by weight total surfactants.

Background technology

Be desirably in and in liquid washing agent, use microcapsule.The microcapsule with the shell of protective core inclusion can make its inclusion delayed release and/or when its inclusion by otherwise stable preparation is provided while interacting with bulk liquid.Such microcapsule are known in described detergent applications, and have proposed to be included in aqueous liquid detergent compositions.These microcapsule are little to be seen by naked eyes hardly to using in a large number and work as to introduce when this liquid.But they can cause this liquid muddiness.Some microcapsule can be suspensible in unmodified liquid.Proportion not too may require to make this liquid modifying by thickening or structurizing system close to other microcapsule of coupling, thereby avoids creaming or sedimentation.The type of such microcapsule is perfume compound encapsulants (encapsulate) with melamino-formaldehyde shell of recording as in US-A-5 066 419.These microcapsule can alternatively contain the fabric treating additive of other liquid, as dope dye, lubricant etc.This inclusion in described microcapsule is not critical to the present invention.

When such microcapsule are added to concentrated surfactant soln, especially comprise external structure agent as in the cellulosic solution of hydrogenated castor oil or primitive fiber time, have been found that experience agglomeration becomes caking to these microcapsule in the introducing stage.These agglomerates keep not disperseing in this liquid.Strengthen like this visuality of these microcapsule.In the time that liquid is shifted out from container, also cause the inhomogeneous dosage of its inclusion in each washing.Finally, if the microcapsule of described agglomeration exist to reach the saltation point on fabric, the inclusion of stating so microcapsule in this place is uneven distribution on surface excessive distribution and at this fabric.This may cause undesired effect, as fabric damage maybe needs to use than the more microcapsule of necessary situation.Therefore, expect very much to avoid microcapsule firm agglomeration in aqueous liquid detergent.

Concentrated type refers to be 30 % by weight or larger total surfactant content (comprising soap).

WO09135765A discloses a kind of method for the production of structurized liquid detergent composition, said composition comprises disperse phase beneficial agent, this beneficial agent can be perfume compound microcapsule, the cellulosic structure agent of primitive fiber, the tensio-active agent of the anion surfactant of at least 5 % by weight and 25-55 % by weight, the method comprises the Mierocrystalline cellulose pre-mixture preparation process of the primitive fiber that utilizes high shear mixing, (ii) preparation respectively of aqueous surfactant mixture, utilize the Mierocrystalline cellulose pre-mixture of primitive fiber and the combination of this tensio-active agent of high shear mixing, perfume compound microcapsule can be dispensed in the structurized liquid of structurized concentrated surfactant of gained later.This high shear mixing step adopts on-line mixing method, as by making these two bursts of process flow contact to realize before on-line mixing machine.The granularity of microcapsule is 5-50 μ m, preferably 10-30 μ m.

The embodiment 4 of WO09135765A discloses the detailed content that adds perfume compound microcapsule.It is in the MFC structuring liquid of 40-50 % by weight that the perfume compound encapsulant of 1.5 % by weight is added to tensio-active agent level.Adopt Heidolph stirrer, this adds and carries out 30 seconds, mixes and continues 5 minutes (if necessary).Heidolph laboratory mixing machine is driving water screw or the paddle stirrer setting up.It is not static online stirrer.The disclosure that does not have the characteristic of any detergent product by making by this way and form.We have found that to add by this way fashionablely, some perfume compound microcapsule is tending towards running into the problem of agglomeration.

In US2005026800A, microcapsule are stirred in the washing liquid by the moisture pre-mixture of heavy-filth liquid (HDL) detergent composition and structurizing pre-mixture are mixed to make.By HDL component being mixed with water and make this HDL pre-mixture in suitable container, under suitable stirring, and by hydrogenated castor oil and other structurizing reagent pre-mixture compositions are mixed to make this structurizing reagent pre-mixture.Then these microcapsule are slowly added in described structuring liquid, and hold it under gentle stirring the-the 88th section.

Other prior aries do not provide the details that microcapsule add mode, or narration be stirred in.

From US2005026800A is open with other, recognize and hydrogenated castor oil (HCO) can be used as to external structure agent and rheology modifier so that such concentrated type liquid washing agent is stable.

In WO2010/034736, we have narrated perfume compound microcapsule are introduced and utilized in the structurized concentrated type liquid washing agent of hydrogenated castor oil.Described microcapsule are added as the perfume compound slurry of encapsulation, and adopt blade-paddle mixer to mix.By eyes and by microscope from visually evaluating said preparation, taking identify whether exist be separated or no this encapsulant also as monodispersed.At 5 DEG C, test 12 weeks, at 37 DEG C, test 12 weeks and test 4 weeks at 50 DEG C after, said composition does not show loss or the change that structurizing or encapsulant disperse.Although we find that described microcapsule do not have further agglomeration at present, provide unacceptable a large amount of perfume compound encapsulant of agglomeration substantially by the initial dispersion of paddle stirrer.There is not redispersion in these agglomerates.For the reason of explaining above, the existence of agglomeration shaped material is not hoped like this.

The object of this invention is to provide for the preparation of the improving one's methods of concentrated type external structure liquid washing agent, liquid washing agent wherein can make the spices that microcapsule for example encapsulate suspend, and it is sightless for naked eyes.

Summary of the invention

According to the present invention, it provides a kind of the microcapsule with anionic charge has been introduced to the method in structurized moisture concentrated type liquid washing agent, the total surfactant that this washing composition comprises at least 30 % by weight, preferred maximum 65 % by weight, with external structure agent, in this total surfactant, at least 5 % by weight based on this total composition are anion surfactant, and this anion surfactant comprises soap, and the method comprises mixes two kinds of pre-mixtures; Pre-mixture A is not containing the structured aqueous concentrated type liquid detergent composition of microcapsule, and pre-mixture B comprises the aqueous dispersion with the microcapsule of anionic charge, it is characterized in that:

Pre-mixture B is that peak viscosity is the slurry of the microcapsule of 100 mPas at 25 DEG C, and the granularity of these microcapsule of at least 90 % by weight is 5-40 μ m, preferably 5-30 μ m; And

Pre-mixture B is added to pre-mixture A, and the energy input that adopts 20-500 J/kg by the mixture of the mixing of gained by static on-line mixing machine, just to form structurized liquid after this mixing machine, this structuring liquid comprises the agglomeration group that group sum based on microcapsule is less than 10% microcapsule, and the agglomeration group of microcapsule is restricted to be had more than 5 groups of microcapsule in groups together.

Preferably, the peak viscosity of described pre-mixture B is 50 mPas, more preferably 20 mPas, even more preferably 15 mPas.

Agglomeration type refers to more than 5 microcapsule in groups together.This for example by take this liquid Photomicrograph, and the microcapsule group counting that exists for the form of the group taking 1,2,3,4 or 5 microcapsule, and measure for the group of the microcapsule to exist more than the agglomerate of 5 microcapsule counts, we are defined as agglomeration type microcapsule.If described group is such agglomeration type microencapsulation form more than 10%, the excessive agglomeration of these microcapsule and not within the scope of the present invention so.

In order to obtain low viscous pre-mixture B, may need the viscosity of the feed slurry enriched material that reduces microcapsule.If necessary, this for example can realize by dilute with water.

Can described in impouring, in container, described microcapsule slurry be added and become owner of liquid by online injection or in stirring.Then, the online static mixer by this mixture by having applied enough energy to be to break described agglomerate, and avoids making single microcapsules rupture simultaneously and retain this liquid structure.Unexpectedly, further agglomeration is very effective in time to preventing described microcapsule for the structuring liquid of gained.

Described external structure agent is preferably hydrogenated castor oil (castor wax or trihydroxy-tristearin).This external structure agent can be alternatively another fiber reagent, as the external structure agent of the Mierocrystalline cellulose of primitive fiber or any other type.

Described microcapsule comprise solid shell.We have found that described agglomeration problem seems to be restricted to the microcapsule of holding anionic charge.Can in the situation that not forming agglomerate and therefore not needing method of the present invention, the microcapsule with anionic charge be added in concentrated liquid.Certainly, if necessary, can also make the mixture that contains cationic microgel capsule disperse this microcapsule by online static mixer.

Most preferably, described microcapsule have melamino-formaldehyde shell.Other suitable shell materials can be selected from (gathering) urea, (gathering) ammonia ester, starch/polysaccharide and aminoplastics.

Described microcapsule can be perfume compound encapsulant.We have found that comprising the more microcapsule of minor diameter makes described agglomeration problem more serious.The diameter of these microcapsule is for being less than or equal to 40 microns.Even if this upper dimension bound is guaranteed the tuftlet form of maximum 5 particles, they should also keep substantially invisible.Most preferably there are the microcapsule of certain diameter.

Very narrow size-grade distribution is favourable, and for example microcapsule of 90 % by weight are 8-11 μ m.Minimize like this amount of the potential high surface area material that can be used as tackiness agent and larger particle is combined.

Due to this more short grained high surface area, the microcapsule of 2-5 μ m can not adopt the method according to this invention effectively to disperse.By contrast, the microcapsule that are greater than 40 μ m do not require other processing conventionally, because in the situation that need to not inputting from online static mixer energization, this less total surface area is enough to prevent firmly agglomeration.But if necessary, the method can be for larger particle.

The method is the most effective for the microcapsule of 5-30 μ m.Shift out microcapsule that 0.1-is less than 1 μ m and improved the dispersion of described microcapsule.Thought the minimizing due to high surface area material.

Disperse once described microcapsule sneaked in described structuring liquid and by described on-line mixing machine, this structure has prevented any agglomeration very effectively, even also like this under high levels of surfactant exists.

The method can be for the preparation of the concentrated type liquid composition of external structure, the tensio-active agent including anion surfactant (any soap all counts and is anion surfactant) that it comprises at least 30 % by weight, this anion surfactant comprises 0.1-2.0 % by weight microcapsule, and wherein the ratio of the microcapsule (in 5 or more group) of microcapsule and the agglomeration in 5 or group is still less greater than 9:1.

In the time that hydrogenated castor oil is used as to described external structure agent, the level of the applicable 0.15-0.5 % by weight with total composition exists.Preferably, it has dendritic structure, and wherein said fiber is wound and the minor axis (minor dimension) of this fiber is maximum 40 nm.

The specific embodiment of the present invention

All per-cent of mentioning is all with the weighing scale of described total composition, unless illustrated in addition herein.

pre-mixture A

Although adopt in principle the method for any prior art or any other appropriate method can form pre-mixture A, when by hydrogenated castor oil when the external structure agent, more preferably use as in WO2010/034736, recorded, also as below the method for description.

If use the Mierocrystalline cellulose of primitive fiber, preferably use the distortion of the method for recording in WO09135765A.

external structure agent

Preferred external structure agent is hydrogenated castor oil.Select as one, can use the Mierocrystalline cellulose of primitive fiber, this material and character thereof and be all recorded in disclosed document for the purposes of external structure agent, for example WO09135765A (Unilever) and US2008108541A (C P Kelco).

hydrogenated castor oil

Viscotrol C, also referred to as Semen Ricini oil, is the rape oil obtaining from castor-oil plants (Ricinus communis) bean or pea.Viscotrol C is colourless to extremely flaxen liquid, that it is flat taste or there is no smell or taste.It is triglyceride level, and wherein approximately 90% fatty acid chain is ricinolic acid (the cis-octadecenoic acid of 12-hydroxyl-9-).Oleic acid and linolic acid are other important components.The controlled hydrogenation of Viscotrol C generates complete hydrogenated castor oil, and it is used in the method according to this invention and product.At room temperature, hydrogenated castor oil is the white hard wax melting at the temperature of about 86-88 DEG C.Supplier is, for example, and Hindustan Unilever, its supply thin slice or particle, Cognis (powder), Vertellus (thin slice) or Elementis (thin slice or particle) or its any combination.Being suitable for hydrogenated castor oil of the present invention is, for example can be purchased from the Thixcin R of Elementis.

structural method

When hydrogenated castor oil is used as to external structure agent---pre-mixture A, can adopt the method comprising the steps to be prepared:

A) by under stirring, tensio-active agent and alkali being added to the water to prepare the first pre-mixture, temperature at least 55 DEG C, preferred temperature be 55-70 DEG C, more preferably 60-65 DEG C and most preferably be approximately 65 DEG C, pH is 7.5-11, preferred 8-10.

B) by under stirring, at the temperature of at least 70 DEG C, preferred 70-75 DEG C, hydrogenated castor oil is added in liquid non-aqueous organic solvent so that described hydrogenated castor oil is dissolved in described liquid non-aqueous organic solvent and prepares the second pre-mixture, and wherein said non-aqueous organic solvent preferably comprises free fatty acids or nonionogenic tenside or its mixture;

C) under mixing, the second pre-mixture of step b) is added to the first pre-mixture of step a), temperature is 55-70 DEG C, more preferably 55-65 DEG C, most preferably is 60-65 DEG C at least 55 DEG C, preferred temperature, and weight ratio b) and a) is 1:40-1:10, be preferably 1:30-1:15, the ratio of about 1:20 more preferably; Thereby this hydrogenated castor oil keeps dissolving;

D) mixture in step c) is cooled to the temperature lower than 50 DEG C, preferably lower than 40 DEG C, more preferably less than 30 DEG C, and stores subsequently this mixture until the crystallization from solution of described hydrogenated castor oil.

Preferably, in step a), the concentration of tensio-active agent is the 20-65 % by weight of total mixture in this step, more preferably 25-60 % by weight, and most preferably be 25-45 % by weight.In step a), described tensio-active agent preferably comprises synthetic anionic and/or nonionic surface active agent.More preferably, the tensio-active agent in step a) comprises synthetic aniorfic surfactant---linear alkylbenzene sulfonate (LAS).The pH of the pre-mixture in step a) is preferably 9-10.

The first pre-mixture in step a) comprises tensio-active agent and alkali in water, and preferably also comprises hydrotropic agent.Hydrotropic agent is the compound of solubilising hydrophobic compound in aqueous solution.Conventionally, hydrotropic agent is made up of hydrophilic segment and hydrophobic part, can not cause spontaneous self aggregation, and therefore they does not form the micella as tensio-active agent but this hydrophobic part is too small.Hydrotropic agent is used for to detergent formulations to obtain more concentrated surfactant formulations.Suitable hydrotropic agent is for example glycerine and propylene glycol.Preferably, the first pre-mixture in step a) is transparent liquid at the leading temperature (prevailing temperature) of step c).Alkali in pre-mixture in step a) preferably includes alkali metal hydroxide or trolamine, and more preferably, neutralizing agent comprises sodium hydroxide, trolamine or its mixture.Conventionally, the pre-mixture in step a) is the micellar solution of this tensio-active agent in water.

The preparation of the second pre-mixture is included at least 70 DEG C, preferably at the temperature of 70-75 DEG C, hydrogenated castor oil is dissolved in liquid non-aqueous organic solvent.Preferably, the mixture that this solvent comprises free fatty acids or nonionogenic tenside or these materials.More preferably, this solvent comprises free fatty acids, and most preferably, this free fatty acids comprises the C12-C18 lipid acid that straight chained alkyl is saturated.In this step b), free-water is not added in the solvent of container.Preferably, under low shearing condition, prepare this second pre-mixture; More preferably, only adopt gentle mixing.There is like this advantage, in the time mixing this second pre-mixture, only require low-yield input.Suitably, at the leading temperature of the second pre-mixture in step b) in this step b), be transparent liquid.

Preferably, the concentration of the hydrogenated castor oil in this second pre-mixture is for like this, thereby the 0.15-0.5 % by weight that to make in the concentration of the final liquid detergent composition that can obtain by the inventive method be said composition, is preferably the 0.15-0.35 % by weight of this total composition, 0.2-0.35 % by weight most preferably be 0.22-0.28 % by weight even more preferably.In step b), the concentration of hydrogenated castor oil in the second pre-mixture is preferably the 1.5-20 % by weight of this pre-mixture, more preferably the 1.5-10 % by weight of this pre-mixture, 1.7-5 % by weight most preferably be 3.4 % by weight-5 % by weight even more preferably.Preferably, described the second pre-mixture only comprises solvent and hydrogenated castor oil, and wherein, described solvent preferably comprises free fatty acids or nonionogenic tenside or its mixture, for the reason relevant to step c) of explained later, this solvent most preferably is free fatty acids.

In the method according to the invention, in step c), described the second pre-mixture is added in described the first pre-mixture under stirring, the weight ratio of the wherein said second and first pre-mixture is 1:40-1:10, be preferably 1:30-1:15, and about 1:20 more preferably.Most preferred the second pre-mixture forms 6 % by weight that are less than of described total preparation, most preferably is approximately 5 % by weight of described total preparation.Temperature in step c) is at least 55 DEG C, preferably 55-70 DEG C, and more preferably 55-65 DEG C, most preferably is 60-65 DEG C.

In the time that in step b), the solvent in described the second pre-mixture comprises free fatty acids, the alkali in described the first pre-mixture is as the neutralizing agent of described lipid acid, and by described the first and second pre-mixtures being mixed to form soap in step c).The soap of this formation causes the solvent of all or part of removal for described hydrogenated castor oil, and thinks the crystal seed that the method is dendritic structure as its subsequent crystallisation.By carefully choosing nonionic surfactant solution, available similar effect will undergo phase transition in the time being added to anionic surfactant solution, but this phase transformation is preferred not as neutralize the chemical phase transformation obtaining due to described free fatty acids solvent.In step c), under gentle mixing, described the first and second pre-mixtures are mixed.Conventionally, at the leading temperature in step c), the mixture in step c) is limpid, this temperature at least 55 DEG C, be preferably 55-70 DEG C, be shown as described the second pre-mixture and be dissolved in completely aptly in described the first pre-mixture.Conventionally at this temperature, all the components be all dissolve and described hydrogenated castor oil there is no crystallization.Mix by the gentleness in step c), before described crystallisation process starts, the hydrogenated castor oil of institute's solubilising is mixed equably.In step d), by the mixture in step c) be cooled to lower than the temperature of 50 DEG C, preferably lower than 40 DEG C, more preferably less than 35 DEG C, even more preferably less than 30 DEG C.Subsequently, store this mixture until the crystallization from solution of described hydrogenated castor oil.Those skilled in the art can determine the time of crystallization of described hydrogenated castor oil, because the crystallization of this hydrogenated castor oil can become muddy from visually observing by liquid.Otherwise, can form by the crystal of conventional observation by light microscope hydrogenated castor oil to whether.Preferably, this cooling step d), under low shearing condition, is carried out when gentle this mixture of mixing.In this case, low shearing means that this shearing is not enough to destroy the dendritic structure occurring.

In a preferred method, in step d), the mixture in step c) is cooled to the temperature lower than 50 DEG C with the rate of cooling of 1 DEG C of maximum per minute.Preferably, in step d), mixture in step c) is cooled to lower than the temperature of 40 DEG C, more preferably 30 DEG C, and rate of cooling is 1 DEG C of maximum per minute, preferably 0.7 DEG C of per minute, even more preferably 0.5 DEG C of per minute, 0.4 DEG C of per minute at most most preferably at most at most.When this preferred cooling step of application is d) time, be present in hydrogenated castor oil in described pre-mixture and suitably start crystallization under in described cooling step process, lower than the temperature of 55 DEG C.

In another preferred method, in step d), the mixture of step c) was cooled in 5 minutes to the temperature lower than 40 DEG C, then at the temperature lower than 40 DEG C, this mixture is stored at least 5 minutes.Preferably, in step d), in 5 minutes, more preferably, in 3 minutes, the mixture of step c) is cooled to the temperature lower than 35 DEG C, then at the temperature lower than 35 DEG C, this mixture is stored at least 5 minutes.More preferably, in step d), the mixture of step c), in 5 minutes, most preferably, in 3 minutes, is cooled to the temperature lower than 30 DEG C, then at the temperature lower than 30 DEG C, this mixture is stored at least 5 minutes.Even more preferably, the mixture of step c) 3 or be even cooled to the temperature lower than 40 DEG C in 2 minutes, is then stored at least 5 minutes by this mixture at the temperature lower than 40 DEG C.Most preferably, the mixture of step c) 3 or be even cooled to the temperature lower than 30 DEG C in 2 minutes, is then stored at least 5 minutes by this mixture at the temperature lower than 30 DEG C.In another preferred embodiment, at the leading temperature after there is described cooling step, described mixture is stored at least 8 minutes, or more preferably at least 10 minutes.When this quick cooling step of application is d) time, in the mixture storage process after cooling fast, the hydrogenated castor oil being present in described pre-mixture suitably starts crystallization.

The example of such method for rapid cooling is instantaneous cooling in plate-type heat exchanger, wherein described mixture is cooled to lower than 30 DEG C within the time of approximately 1 minute.In the time applying such method for rapid cooling, this mixture is by the time that keeps at least 5 minutes at the temperature lower than 40 DEG C.Within this hold-time, the temperature of described mixture is kept continuing lower than 40 DEG C, and the crystallization of described hydrogenated castor oil occurs in described pre-mixture and has occurred at the described temperature keeping after cooling fast.

In this step d), obtain opaque quasi-viscous liquid, its profile preferably with shear shinning is to provide the dumpable liquid being easily allocated in washing apparatus.The hydrogenated castor oil of described solubilising can be self-assembled into dendritic structure.Dendritic structure is the highly branched structure with the solid material of core (with the branch of extending from this core).In step d), when cooling described mixture, described dendritic structure seems to form by a series of nucleogenesiss, and then crystal is grown from these nucleation sites (causing forming described dendrimers).Described nucleation site can be described as to the core of this branch molecule.Aptly, described hydrogenated castor oil grows up to become three-dimensional branched structure from running through this core of described preparation, forms three-dimension scaffold shape.Described hydrogenated castor oil forms with branch molecular form, and wherein branch molecule is preferably dimensioned to be (approximately 100 microns at most) of micron size.The fibre network that this branch molecule height of formation is wound around.The common thickness of branch's (or fiber) of branch molecule is 20-40 nanometer, and conventionally extends at most more than 10 microns.Relatively long and the thin and length-to-diameter ratio of these branches of this branch molecule is 1000:1 rank.Compare down, as recorded in EP 1 502 944 and other documents, the length-to-diameter ratio of the prior art linear structure system being formed by emulsion crystallization mostly is 200:1 most.The minor axis of the particle being made by described solvent method is also much smaller than being obtained by described aqueous emulsions method.According to EP 1 502 944, the preferred minor axis of described linear structure agent is 5-15 micron.Under the lower limit of 1 micron of even mentioning in EP1 502 944, in prior art, the fiber of linear structure is also greater than two times of the branch molecular thickness being formed by described solvent method.Because the size of described dendritic structure has been disturbed the transmitance of light through described preparation, thus the crystallization of described hydrogenated castor oil to cause the described preparation to become translucent.Easily make the microstructure of described branch molecule and the linear structure of prior art distinguish by microscopic examination and by its rheological and suspension.

water

The present invention is particularly suitable for microcapsule to add and comprise in the composition that is less than 40 % by weight water.When in the time that the composition of high reactivity level of the present invention is combined, this low-level water makes the more difficult dispersion of described microcapsule.But the present invention also can be applicable to have the high surfactant composition of higher levels of water.

tensio-active agent

Adopt method of the present invention to make described liquid detergent composition, it comprises preferred 30-65 % by weight, more preferably 30-60 % by weight, and the more preferably tensio-active agent of 35-45%, is preferably selected from anionic, non-ionic type, cationic, amphoteric ion type activated detergent material or its mixture.In the context of the present invention, aniorfic surfactant had both comprised soap and had also comprised synthetic aniorfic surfactant.The minimum level of aniorfic surfactant is 5 % by weight.Conventionally, the tensio-active agent of described surfactant system can be selected from and be recorded in following tensio-active agent in open: ' the 1st volume (Schwartz and Perry by Interscience company delivered in 1949) of Surface Active Agents', the 2nd volume is (by the Schwartz of Interscience company, Perry and Berch delivered in 1958), delivered by Manufacturing Confectioners Company ' the current version of McCutcheon's Emulsifiers and Detergents', or ' Tenside Taschenbuch', H. Stache, the 2nd edition, Carl Hauser Verlag, 1981.

Be soap (soap) according to the preferred ingredient of liquid detergent composition of the present invention.Preferably, the organic non-aqueous solvent using in the step b) of method of the present invention comprises lipid acid.Preferably, the straight chained alkyl lipid acid that described lipid acid comprises saturated C12-C18.The example that is suitable for lipid acid of the present invention comprises the lipid acid derived from Zoomeric acid, safflower, Sunflower Receptacle, soybean, oleic acid, linolic acid, linolenic acid, ricinolic acid, rapeseed oil or its mixture pure or sclerosis.The example of preferred lipid acid is hydrogenated coconut fatty acid oil, for example Prifac 5908 (Uniqema being reached by Dutch person of outstanding talent supplies).Also can use in the present invention saturated and mixture undersaturated lipid acid.

To recognize that described lipid acid will mainly be present in (final) liquid detergent composition with soap form.Suitable positively charged ion comprises sodium, potassium, ammonium, monoethanolamine ammonium, di-alcohol ammonium, triethanol ammonium, tetra-allkylammonium, and for example tetramethyl-ammonium is until four decyl ammonium cations.

The amount of lipid acid is desirably in the concrete property in final liquid detergent composition by depending on and changes.Preferably, 0-30%, more preferably 1-20%, most preferably the lipid acid of 2-10 % by weight is present in according in liquid detergent composition of the present invention.Synthetic anionic and the mixture of nonionic surface active agent are particularly useful to the present invention.

Non-ionic detergent tensio-active agent is known in the art.They are conventionally by forming with organic hydrophobic grouping chemically combined water lyotropy polyoxyalkylene or list or di alkanolamide group, described organic hydrophobic grouping for example contains the alkylphenol of approximately 12 carbon atoms of 6-of having an appointment derived from alkyl group wherein, primary, secondary, tertiary fatty alcohol (or its alkyl is added a cover the derivative of (alkyl-capped)) wherein preferably has the dialkyl phenol of 8-20 carbon atom, alkyl wherein has approximately 24 carbon atom monocarboxylic acids of 10-, and polyoxypropylene.Conventionally be also list-and the di alkanolamide of lipid acid, wherein the alkyl group of this fatty acid group contains approximately 20 carbon atoms of 10-and silane alcohol base (alkyloyl) has 1-3 carbon atom.Any list-and di alkanolamide derivative in, optionally can there is the polyalkylene oxide groups of group group and this molecule hydrophobic part after connecting.In all tensio-active agents that contain polyoxyalkylene, this polyalkylene oxide groups is preferably made up of 2-20 ethylene oxide group or oxyethane and propylene oxide group.In type below, particularly preferably be and be recorded in those in EP 225 654 A.Other are the nonionisable substance of those ethoxylations preferably, and it is to have the fatty alcohol of 9-18 carbon atom and the condensation product of 3-11 moles of ethylene oxide condensation.These examples are the alcohol of C9-18 and the condensation product of average 3-9 moles of ethylene oxide.What be preferred for liquid detergent composition of the present invention is the straight chain primary alcohol on average with the C12-C15 of 3-9 ethylene oxide group.

The alcohol of the ethoxylation that preferred nonionic surface active agent is C12-C18, comprises 3-9 oxyethylene unit in its each molecule.The more preferably primary alconol of the ethoxylation of the straight chain of C12-C15, it on average has 5-9 ethylene oxide group, more preferably on average has 7 ethylene oxide groups.

The synthetic aniorfic surfactant that is suitable for available detergent compound is generally and has alkyl group the organo-sulfate of (containing having an appointment approximately 22 carbon atoms of 8-) and the water-soluble alkali metal salts of sulphonate, term alkyl is for comprising the moieties of senior carboxyl groups, this aniorfic surfactant comprises alkyl-sulphate, sulfated alkyl ether, alkylaryl sulfonate, alkyloyl isethionate, alkyl succinate, alkyl sulfo succinate, N-alkyloyl sarcosinate, alkyl ether carboxy acid salt, sulfonated α-olefin and acyl methyl taurine salt, especially its sodium salt, magnesium salts, ammonium salt and list-, two-and triethanolamine salt.Described alkyl and carboxyl groups contain 8-22 carbon atom conventionally, preferably 8-18 carbon atom, and also more preferably 12-15 carbon atom, and can be undersaturated.Each molecule of described sulfated alkyl ether and alkyl ether carboxy acid salt can contain one to ten oxyethane or propylene oxide units, and each molecule preferably comprises one to three ethylene oxide unit.

The example of suitable synthetic anionic comprises Sodium Lauryl Sulphate BP/USP, Zetesol NL, lauryl sulfo-succinic acid ammonium, Texapon Special, Zetesol AP, cocoyl ethylenehydrinsulfonic acid sodium, lauroyl ethylenehydrinsulfonic acid sodium and N-sodium lauryl sarcosinate.Most preferred synthetic aniorfic surfactant comprises synthetic aniorfic surfactant-linear alkylbenzene sulfonate (LAS).Being suitable for other synthetic aniorfic surfactant of the present invention is fatty alcohol oxyethyl group ether sodium sulfate (SAES), preferably comprises high-caliber C12 alcohol ethoxy ether sodium sulfate.

Preferred surfactant system is the mixture of synthetic anionic and non-ionic detergent active material and additional cationic or amphoteric surfactant.The primary alconol (ethoxylate of 3-9 EO) of the especially preferred ethoxylation that is fatty alcohol oxyethyl group ether sulfate (AES) and C12-C15 and the mixture of quaternary amines salt cationic tensio-active agent.

Preferred surfactant system is synthetic anionic and non-ionic detergent active material and soap and additional cationic or amphoteric surfactant.Synthetic anion surfactant can exist with the amount of approximately 5%-approximately 70 % by weight of total surfactant material.

In the preferred embodiment of the invention, described detergent composition also comprises cationic surfactant or amphoteric surfactant, wherein this cationic or amphoteric surfactant is with the 1-20% of total surfactant, preferably 2-15%, and more preferably the concentration of 3-12 % by weight exists.

Operable suitable cationic surfactant is the quaternary amine of straight or branched that replace or non-substituted.Preferred cationic surfactant is following formula:

R1R2R3R4N+?X-

Wherein, R1 is alkyl, C8-C22-thiazolinyl, C8-C22-alkyl alkenyl amide base propyl group or the C8-C22-alkoxyl group thiazolinyl ethyl of C8-C22-, R2 is the group of C1-C22-alkyl, C2-C22-thiazolinyl or formula-A-(OA) n-OH, R3 and R4 are the group of C1-C22-alkyl, C2-C21 – thiazolinyl or formula-A-(OA) n-OH, A is-C2H4-and/or-numeral and X that C3H6-and n are 0-20 are negatively charged ion.The compound can be commercial and that preferred example is above formula of this cationic surfactant, the alkyl group that wherein R1 is C12/14, R2 is the group of formula-A-(OA) n-OH, wherein A for-C2H4-and n be zero, and R3 and R4 be all-CH3(is C1-alkyl).This cationic surfactant is can be commercial.For example, with title Praepagen HY purchased from Clariant.The common example of suitable amphoteric and amphoteric ionic surfactant is alkyl betaine, alkylamidoalkyl trimethyl-glycine, amine oxide, aminopropionate, amino glycinate, amphoteric imidazole salt compound, alkyl dimethyl betaine or alkyl two (polyethoxye) trimethyl-glycine.

optional composition

In composition herein, can comprise a variety of optional members for detergent composition, it comprises other activeconstituentss, hydrotropic agent, processing aid, dyestuff or pigment, carrier, washing assistant, antioxidant, spices, detersive enzyme, suds suppressor, sequestrant, clay remover/anti redeposition agent, whitening agent, fabric softener, dye transfer inhibitor, SYNTHETIC OPTICAL WHITNER etc.; To wherein some be explained in more detail below.

carrier

Liquid detergent composition of the present invention can contain the various solvents as carrier.Low-molecular-weight primary alconol or secondary alcohol by methyl alcohol, ethanol, propyl alcohol and Virahol example are suitable.Other suitable solid support materials are glycol, as molecular weight to be 200-5000 single, two, three-propylene glycol, glycerine and polyoxyethylene glycol (PEG).Described composition can contain 1 % by weight-50 % by weight, common 5 % by weight-30 % by weight, preferably such carrier of 2 % by weight-10 % by weight.

washing assistant

In described liquid detergent compositions, can there are one or more washing assistants.

In the time existing; the example of suitable organic washing-assisting detergent comprises polyacetic acid, carboxylic acid, poly carboxylic acid, many ethanoyl carboxylic acid, carboxyl methoxyl group succsinic acid, carboxyl methoxy propyl diacid, quadrol-N, ammonium salt and its mixture of the polysaccharide of N-disuccinic acid, poly-epoxy succinic acid, oxygen base oxalic acid, triethylenetetraaminehexaacetic acid, N-alkyl imino oxalic acid or dipropionic acid, alpha-sulfo-fatty acid, pyridine dicarboxylic acid, oxidation, basic metal (alkaline metal) salt, ammonium salt and the replacement of poly-hydroxy sulfonic acid.

Concrete example comprises the ammonium salt of sodium salt, sylvite, lithium salts, ammonium salt and the replacement of ethylene amino-tetraacethyl, nitrilotriacetic acid(NTA), oxygen base disuccinic acid, melitic acid (melitic acid), the polycarboxylic acids of benzene and citric acid, tartrate monosuccinic acid ester and tartrate disuccinic acid ester.

antioxidant

Preferably comprise the antioxidant of 0.005-2 % by weight by the available liquid detergent compositions of the method according to this invention.Preferably, this antioxidant exists with the concentration of 0.01-0.08 % by weight.

Antioxidant is the material of recording as in Kirk-Othmer (the 3rd volume, the 424th page) and Uhlmans Encyclopedia (the 3rd volume, the 91st page).A kind of can be the alkylating phenol with following general formula for antioxidant of the present invention:

Wherein, the straight or branched alkyl that R is C1-C22, preferable methyl or C3-C6 branched-chain alkyl; C3-C6 alkoxyl group, preferably methoxyl group; R1 is the branched-chain alkyl of C3-C6, preferred tertiary butyl; X is 1 or 2.Sterically hindered phenolic compound is according to the alkylating phenol of the preferred type of this formula.Such preferred sterically hindered phenolic compound is 2,6-di-tert-butyl hydroxy toluene (BHT).

The antioxidant that can be applicable to the other types of the present invention's use is cumarone or the 1-benzopyran derivatives with following formula:

Wherein, R1 maybe can make R1 form C5-C6 cyclic hydrocarbon group group together with R2 for alkyl respectively with R2 independently; B does not exist or is CH2; R4 is C1-C6 alkyl; R5 be hydrogen or-C (O) R3, wherein R3 is the alkyl of hydrogen or C1-C19; R6 is the alkyl of C1-C6; R7 is the alkyl of hydrogen or C1-C6; X is CH2OH or CH2A, and wherein A is the phenyl of nitrogenous unit, phenyl or replacement.Preferred nitrogenous A unit comprises amino, 1-pyrrolidyl, piperidino-(1-position only), morpholino, 1-piperazinyl (piperazino) and composition thereof.

Can also use antioxidant as tocopherol sorbate, butylated hydroxy-benzoic acid and salt thereof, gallate and alkanol ester thereof, uric acid and its salt and alkanol ester, Sorbic Acid and its salt and dihydroxyl fumaric acid and its salt.

spices

Preferably comprise the perfume composition of the 0.001-3 % by weight of described total composition by the available liquid detergent composition of the method according to this invention, preferably the 0.01-2 % by weight of this total composition.Described perfume composition preferably comprises the fragrance components based on described liquid composition at least 0.01 % by weight, and this fragrance components is selected from terpene, ketone, aldehyde and composition thereof.Described perfume composition can be made up of described fragrance components completely, but this perfume composition is essentially the complex mixture of the perfume compound of various distinct fragrance agent types.On this point, described perfume composition preferably comprises at least 0.1%, and more preferably at least 1.0%, also more preferably this fragrance components of at least 5 % by weight.

detersive enzyme

' detersive enzyme ' used herein refers to any enzyme in laundry applications with clean, scale removal or other beneficial effects.Can for the suitable enzyme in the present composition comprise any suitable source proteolytic enzyme, amylase, lipase, cellulase, peroxidase, and composition thereof, this source is as vegetables, animal bacteria, fungi and yeast.Preferred selection is subject to factor as the impact of pH activity, thermostability and the stability on active bleach detergent and auxiliary agent etc.In this respect, bacterial enzyme and fungal enzyme are preferred, as bacteria protease and fungal cellulase.Enzyme is comprised in this detergent composition for various purposes, and this object comprises the removal of protein-based, glycosyl or triglyceride level base dirt, and it is for preventing the dye transfer (refugee dye transfer) of migration, and stores for fabric.

Conventionally to be enough to the providing level of " effectively clean consumption " that enzyme is introduced in detergent composition.Term " effectively clean consumption " refers to that any can realization on handled base material clean, de-sludging, remove earth, brighten or the pure and fresh amount of improving effect.Aspect the putting into practice of common commercial operation, by weight, common amount mostly is every gram of detergent composition approximately 50 mg most, is more typically the organized enzyme of 0.01 mg-30 mg.Unless otherwise indicated, otherwise composition of the present invention can comprise 0.001-3% conventionally, preferably the commercial zymin of 0.01-1 % by weight.

Proteolytic enzyme is conventionally to be enough to the providing level of 0.005-0.1 Anson unit (AU) activity/g composition to be present in such commercial formulation.In highly concentrated detergent formulations, may wish higher activity level.Suitable proteolytic enzyme example is the subtilisin specifically obtaining from subtilis and lichem bacillus strain.A kind of suitable proteolytic enzyme is that the Bacillus strain from the scope that is 8-12 at pH with maximum activity obtains, and is developed and sell with Esperase by the NovoZymes of Denmark.

Other suitable proteolytic enzyme comprise Alcalase and the Savinase Relase of NovoZymes, and Dutch International Bio-Synthetics, the Maxatase of Inc..

Described composition can additionally be included in disclosed enzyme in WO 01/00768.

The suitable lipase using in the present composition comprises by those of pseudomonas group's microorganisms, and this pseudomonas group is as at GB 1,372, disclosed Pseudomonas stutzeri ATCC 19.154 in 034.Most suitable lipase is derived from pubescence humicola lanuginosa and the lipase that can obtain with trade name Lipex from Novozymes.

Preferably, preferably in order to cooling step in forming the method for pre-mixture A d) afterwards, enzyme is added in described composition.

suds suppressor

Can by for reducing or suppress the compound of formation of foam and introduce in composition of the present invention.As US-A-4, the what is called " high density cleaning method " of recording in 489,455 and US-A-4,489,574 neutralize for European roller washing machine, suds suppressor all but be even more important.

A variety of materials can be used as to suds suppressor, and suds suppressor is well-known to those skilled in the art.For example referring to, Kirk Othmer Encyclopedia of Chemical Technology, the third edition, the 7th volume, 447 pages of 430-(John Wiley & Sons, Inc., 1979).The suds suppressor that one class is useful especially comprises mono carboxylic lipid acid and soluble salt thereof.Referring to US-A-2,954,347.Mono carboxylic lipid acid and salt thereof as suds suppressor have approximately 24 carbon atoms of 10-conventionally, preferably the hydrocarbyl chain of 12-18 carbon atom.Suitable salt comprises that an alkali metal salt is as sodium salt, sylvite and lithium salts and ammonium salt and alcohol ammonium salt.The favourable bubble effect that presses down obtains from the fatty acid mixt that comprises lauric acid, tetradecanoic acid, palmitinic acid, stearic acid, eicosanoic acid and behenic acid.Such preferred saturated fatty acid is the trade mark of Prifac 5908(Uniqema).

Detergent composition herein can also contain the suds suppressor of nonsurfactant.These suds suppressors comprise that for example high-molecular-weight hydrocarbons for example, for example, as fatty acid ester, the ketone (, stearone) of aliphatics C18-C40 etc. of paraffinic hydrocarbons, fatty acid ester (, fatty acid triglycercide), monovalent alcohol.

The nonsurfactant suds suppressor of preferred type comprises polysiloxane suds suppressor.Such suds suppressor comprises and uses poly-organopolysiloxane oil as polydimethylsiloxane, poly-organopolysiloxane oil or the dispersion of resin or the combination of emulsion and poly-organopolysiloxane and silica granule, and wherein this poly-organopolysiloxane is by chemical absorption or fuse on described silica.Polysiloxane suds suppressor be in the art known and be for example recorded in US-A-4, in 265,779.

For the washing composition of any washing machine for automatic washing, the degree that foam should not be formed into them and overflows washing machine.

In the time using, suds suppressor preferably exists with " pressing down the amount of bubble "." press down the amount of bubble " and refer to that the formulating of recipe person of said composition can select the amount of foam control reagent, this foam control reagent will be enough to control the low foam scouring agent of foam to obtain using in the washing machine of automatic washing.Composition herein generally comprises the suds suppressor of 0.1%-approximately 5%.

If wish high foam, can be conventionally with the level of 1%-10% by suds booster as the alkylolamide of C10-C16 introduce as described in composition.The single ethanol amide of C10-C14 and diglycollic amide example the typical types of this suds booster.If desired, can conventionally add soluble magnesium salts as MgCl with the level of 0.1-2% ₂, MgSO ₄deng, extra foam to be provided and to improve degrease performance.

sequestrant

Liquid detergent composition herein can also optionally contain one or more iron, copper and/or magnesium chelating substances.Such sequestrant can be selected from aromatic chelating agent of aminocarboxylate/ester, amino phosphonates do/ester, polyfunctional group replacement and composition thereof, and it is all as hereinafter limited.

If you are using, these sequestrants form approximately 0.1-approximately 10 % by weight of detergent composition herein conventionally.More specifically, if you are using, this sequestrant will form approximately 0.1-approximately 3.0 % by weight of such composition.

clay remover/anti redeposition agent

Composition of the present invention can also optionally contain the amine of the water-soluble ethoxylation with clay removal and antiredeposition performance.Liquid detergent composition is conventionally containing having an appointment the such reagent of 0.01%-approximately 5%.

The tetren that a kind of preferred decontamination and anti redeposition agent are ethoxylation.The amine of suitable ethoxylation is also recorded in US-A-4, in 597,898.

The preferred anti redeposition agent of other types comprises carboxymethyl cellulose (CMC) material.These materials are well known in the art.

whitening agent

Any optical whitening agent as known in the art or other can be brightened to reagent is introduced in liquid detergent composition herein with the level of approximately 0.05 % by weight-Yue 1.2 % by weight conventionally.Can be categorized into subgroup by being used for coml optical whitening agent of the present invention, it comprises but is unnecessarily defined as stilbene derivative, pyrazoline, tonka bean camphor (cournarin), carboxylic acid, methine cyanines class, dibenzothiophene-5, the heterocycle of 5-dioxide, azole, 5-and 6-ring and other plurality of reagents.The example of such whitening agent is disclosed in " the The Production and Application of Fluorescent Brightening Agents " that John Wiley & Sons publishes, M. Zahradnik, in New York (1982).

fabric softener

Optionally, conventionally with approximately level use various penetrating washing types (through-the-wash) fabric softener of this composition of 10 % by weight of about 0.5%-, especially for US-A-4,062, the imperceptible montmorillonitic clay of recording in 647 and other soft claies as known in the art, to provide and the benefit of clean fabric fabric sofetening simultaneously.As for example US-A-4,375,416 and US-A-4,291,071 is disclosed, and clay softening agent can be used in combination with amine and cationic softener.

dye transfer inhibitor

Composition of the present invention can also comprise one or more materials that effectively suppresses dyestuffs and be transferred to from a fabric another in cleaning course.Conventionally, such dye transfer inhibitor comprises multipolymer, manganese phthalocyanine, peroxidase of polyvinylpyrrolidonepolymers polymers, polyamines N-oxide polymer, NVP and N-vinyl imidazole and composition thereof.If you are using, such reagent forms approximately 0.01 %-approximately 10 % by weight of described composition conventionally, preferably approximately 0.01 %-approximately 5%, and 0.05%-approximately 2% more preferably from about.

sYNTHETIC OPTICAL WHITNER

Optionally, can contain SYNTHETIC OPTICAL WHITNER or bleach system according to composition of the present invention.This SYNTHETIC OPTICAL WHITNER or bleach system for example can be: (a) separately and/or the peroxide type SYNTHETIC OPTICAL WHITNER of mixing with bleach-activating agent and/or transition-metal catalyst; (b) do not basically contain the transition-metal catalyst in the composition of superoxide type.

In the last few years, developed the bleaching catalyst for decontamination, and can be in the present invention.The example of operable transition metal bleach catalyzer is for example finding in WO-01/48298, WO-00/60045, WO-02/48301, WO-00/29537 and WO-00/12667.Select as one, the free ligand that this catalyzer can be used as formation original position complex compound provides.

Bleach-activating agent is also known in the art.The definite binding mode that is used for the bleach-activating agent of peroxide bleaching agent compound is unknown, but believes peracid by described activator and inorganic peroxy compounds reaction and form, and then this peracid discharges active oxygen by decomposition.They normally contain the compound of N-acyl group or O-acyl residue in molecule, and this compound in washings with it the peralcohol of contact bring into play its activation.

The representative instance of the activator in these groups is the Alkylenediamine of many acidylates, as N, and N, N1, N1 – tetra acetyl ethylene diamine (TAED) and N, N, N1, the tetra-acetylated methanediamine of N1-(TAMD); With acidylate glycoluril, as tetra-acetylated glycoluril (TAGU); Triacetyl cyanurate and carbonic acid sulfo group phenyl chlorocarbonate sodium.

Peroxide bleaching agent is also well known in the art, for example peracid (for example, PAP), perborate, percarbonate, peroxidation hydrate and its mixture.That concrete preferred example comprises is single-and tetrahydrate form can be commercial Sodium peroxoborate, and sodium carbonate peroxidation hydrate.In WO 02/077145, find example and other transition-metal catalyst of other hydrogen peroxide (peroxyl) type and activator.

Also preferably in described composition, comprise the stablizer for SYNTHETIC OPTICAL WHITNER or bleach system, for example ethylenediamine tetramethylene phosphonic acid ester and diethylenetriamine pentamethylenophosphonic acid(DTPP) ester or other suitable Organophosphonates or its salt.These stablizers can use with acid or salt form, and it is the form of calcium salt, magnesium salts, zinc salt or aluminium salt.This stablizer can be with maximum approximately 1 % by weight, and the level of preferred about 0.1%-approximately 0.5 % by weight exists.

Due to a lot of SYNTHETIC OPTICAL WHITNER and bleach system in aqueous liquid detergent unstable and/or adversely with described composition in other components (for example; enzyme) interact; for example; they can be for example by encapsulating or protected by the structurized liquid composition of preparation, thereby they suspend with solid form.

Can also use optical white, comprise singlet oxygen optical white.

pre-mixture B

Except any viscosity altered contents, be generally water, but also can use hydrotropic agent, pre-mixture B comprises described microcapsule.

microcapsule

The key element of the composition by prepared in accordance with the method for the present invention is the microcapsule with anionic charge of at least 0.01 % by weight.Such microcapsule can be by being deposited on base material as transmitted various beneficial agents on clothing textiles.In order to obtain maximum benefit, they should be scattered in well to whole described liquid detergent composition, and must make the not significantly agglomeration of the overwhelming majority of described microcapsule.We find that any microcapsule that become agglomeration in the course of processing all keep like this in container and by therefore in the process that uses said composition by uneven distribution.

This is very undesirable.The inclusion of described microcapsule is generally liquid.For example, spices, oil, fabric-softening additive and fabric care additive are possible inclusion.The present invention is also non-specific for the content of any particular type.The shell cored type microcapsule that preferred microcapsule are particle form.As used herein, term shell cored type microcapsule refer to wherein that at 40 DEG C water-insoluble or complete water-insoluble shell substantially surrounds the encapsulant of the core that comprises beneficial agent or be made up of beneficial agent (it is for liquid or be scattered in liquid vehicle).

Suitable microcapsule are to be recorded in those in US-A-5 066 419, and it has frangible dressing, preferably aminoplastics polymkeric substance.Preferably, this dressing is the reaction product that is selected from the amine of urea and trimeric cyanamide or its mixture and is selected from the aldehyde of formaldehyde, acetaldehyde, glutaraldehyde or its mixture.Preferably, the 1-30 % by weight that this dressing is described particle.

The shell cored type microcapsule of other type are also suitable in the present invention.Prepare other such beneficial agents and comprise as being recorded in the polymkeric substance precipitation on interface and the deposition in as coacervate in GB-A-751 600, US-A-3 341 466 and EP-A-385 534 as the mode of perfume compound microcapsule, and as be recorded in other polymerization approachs in US-A-3 577 515, US-A-2003/0125222, US-A-6 020 066 and WO-A-03/101606 as interface condensation.The microcapsule with carbamide resin wall are recorded in US-A-6 797 670 and US-A-6 586 107.

Other are specifically related in the patent application of liquid, aqueous middle use carbamide shell cored type microcapsule is WO-A-98/28396, WO02/074430, EP-A-1244768, US-A-2004/0071746 and US-A-2004/0142868.

White oil be highly refine, the colourless hydrocarbon ils of low volatility and wide region viscosity; For the lubricated of food and textile manufacturing machine and as medicine oil and mineral oil.The microcapsule by trimeric cyanamide outsourcing that contain white oil are slight anionic (with negative charges).Have been found that the surface charge on described microcapsule affects its dispersiveness.Low electric charge seems to cause existing too small Coulomb repulsion/stability, and consequently they can not keep separately in low water (concentrating) preparation.This is even worse for high concentration anionic composition.It is worse for the weak anionic particle of certain size that this problem seems.

Perfume compound encapsulant is the microcapsule that are suitable for preferred type of the present invention.

The preferred perfume compound microcapsule that used are in the present invention shell cored type microcapsule.As used herein, term shell cored type microcapsule refer to wherein that at 40 DEG C water-insoluble substantially or complete water-insoluble shell surround the encapsulant of the core that comprises perfume compound or be made up of perfume compound (comprising any liquid vehicle for it).

The shell cored type perfume compound microcapsule of preferred type comprise and are disclosed in those in WO 2006/066654 A1.These microcapsule comprise and have the core that is scattered in the approximately 5%-approximately 50 % by weight perfume compound in about 95%-approximately 50 % by weight solid support materials.This solid support material is preferably the solid-state fatty alcohol of non-polymer or fatty ester carrier material, or its mixture.Preferably, the molecular weight of this ester or alcohol is about 100-approximately 500, and fusing point is approximately 37 DEG C-Yue 80 DEG C, and is essentially water-insoluble.On the outside surface of the core that comprises described perfume compound and described solid support material, be wrapped in substantially in water-insoluble dressing.Similarly microcapsule are disclosed in US 5,154, in 842 and its be also suitable.

The microcapsule that are recorded in US-A-5 066 419 have frangible dressing, and this dressing is preferably aminoplastics polymkeric substance.Preferably, this dressing is the reaction product that is selected from the amine of urea and trimeric cyanamide or its mixture and is selected from the aldehyde of formaldehyde, acetaldehyde, glutaraldehyde or its mixture.Preferably, the 1-30 % by weight that this dressing is described particle.

The shell cored type microcapsule of other type are also suitable in the present invention.The mode of preparing other such perfume compound microcapsule comprises as being recorded in the polymkeric substance precipitation on interface and the deposition in as coacervate in GB-A-751 600, US-A-3 341 466 and EP-A-385 534, and as is recorded in other polymerization approachs in US-A-3 577 515, US-A-2003/0125222, US-A-6 020 066 and WO-A-03/101606 as interface condensation.The microcapsule with carbamide resin wall are recorded in US-A-6 797 670 and US-A-6 586 107.

Other are specifically related in the patent application of liquid, aqueous middle use carbamide shell cored type microcapsule is WO-A-98/28396, WO02/074430, EP-A-1244768, US-A-2004/0071746 and US-A-2004/0142868.

These microcapsule can be connected in suitable base material, for example, so that the permanent fragrant of desired release after cleaning course completes to be provided.

liquid detergent composition

Present method provides structurized liquid detergent composition, and the agglomerated form that in the microcapsule that wherein exist, waste and size are expanded does not account for remarkable ratio.These microcapsule are concentrated and have the tensio-active agent that is more than or equal to 30 % by weight, and external structure system, are preferably hydrogenated castor oil, exist with the concentration of the 0.15-0.5 % by weight of total composition.

Preferably, the 30-65 % by weight that is described total composition according to the concentration of the tensio-active agent in liquid detergent composition of the present invention, more preferably 32-60 % by weight, and 35-50 % by weight most preferably.

Described liquid cleansing composition can be formulated as to concentrated cleaning liquor, to directly apply to base material, or after dilution, be applied to base material, as before using this liquid composition by human consumer or in washing device or dilute in process.

Although can be for clean any suitable base material according to the compositions and methods of the invention, preferred base material be clothing textiles.Clean can contact time enough by the liquid medium that makes simply this base material form with by liquid cleansing composition or to be made by it and carry out.But, preferably, cleaning medium on this base material or that wrap up this base material is stirred.

product form

Be preferably concentrated type liquid cleansing composition by the available liquid detergent composition of the method according to this invention.The physical form of this liquid composition contains from dumpable liquid, dumpable gel to not dumpable gel.Such form characterizes with the viscosity of this product easily.In these limit, except clear and definite contrary explanation, in whole application specification, all viscosity of mentioning is all at 21 s ^-1shearing rate and the temperature of 25 DEG C under measure those.This shearing rate is the shearing rate that conventionally liquid when toppling over from bottle is implemented.Liquid detergent composition prepared in accordance with the present invention is the liquid of shear shinning.

The preferred viscosity of dumpable liquid detergent composition is for not higher than 1,500 mPa.s, more preferably no higher than 1,000 mPa.s, also more preferably no higher than 500 mPa.s.At 21 s ^-1under, this viscosity is usually less than 500 mPa.s.

The preferred viscosity of liquid detergent composition as dumpable gel is at least 1,500 mPa.s, but not higher than 6,000 mPa.s, more preferably no higher than 4,000 mPa.s, also more preferably no higher than 3,000 mPa.s and especially for not higher than 2,000 mPa.s.

The preferred viscosity of not dumpable gel is at least 6,000 mPa.s but not higher than 12,000 mPa.s, more preferably not higher than 10,000 mPa.s, also more preferably not higher than 8,000 mPa.s and especially not higher than 7,000 mPa.s.

For purposes of the present invention, when composition in the case of with disperse with the perfume compound encapsulant suspending keep even within the time of about 3 months at 5-50 DEG C of temperature time, think that said composition is physically stable.

Also with reference to indefiniteness embodiment, the present invention is described below.

Embodiment 1

List in the composition (pre-mixture A) in table 1 by the method preparation as recorded in PCT/EP2009/062313, its associated viscera repeats foregoing.The conventional neutralisation of the method based on for the production of LAS/SLES/NI and the active heavy duty liquid laundry detergent of soap base.After neutralization, add enzyme and perfume compound.

Table 1-pre-mixture A

Obtain described liquid detergent composition by following method:

pre-mixture 1

The agitator that utilization is set up, under the stirring of 150 rpm, adds 200 g deionized waters in 3 L beakers and is heated to 30 DEG C.Then, 1.47 g optical whitening agents are added in this solution, and be accompanied by and add 50 g glycerine, 90 g propylene glycol and 57.5 g neutralization bases---sodium hydroxide and 31.5g trolamine.Then, in extremely rapid succession add 201 g Nonionic 7EO, 128 g linear alkyl benzene sulphonic acid and 20 g citric acids, this produces a large amount of neutralization heat and takes temperature to 65-70 DEG C.Keep the basal temperature of this 65-70 DEG C until add pre-mixture 2.

pre-mixture 2

Adopt under the stirring of 100 rpm, make 47g Prifac 5908 be dissolved in 500 ml beakers separately and be heated to 70-75 DEG C.Then, making 2 g hydrogenated castor oils---the Thixcin of Elementis is dissolved in hot lipid acid.Make this pre-mixture stir again 5-10 minute, to guarantee to dissolve completely and the mixing of external structure agent.Complete when transparent when this pre-mixture 2 solution, dissolving completes.

pre-mixture A:(pre-mixture 1+ pre-mixture 2)

Below by by pre-mixture 2(70-75 DEG C) add pre-mixture 1(65-70 DEG C) in this two kinds of pre-mixtures are mixed, improve and stir to 200 rpm and these two kinds of pre-mixtures are fully mixed 10 minutes.Then, add 16 g sequestering agents, then add 96 g Zetesol NLs (sLES), and make mixture remix 10 minutes before being cooled to 30 DEG C.Coolingly complete by the naturally cooling time of 2 hours, or alternatively adopt plate-type heat exchanger cooling so that main mixture is cooled to 30 DEG C and keep under this low temperature 10 minutes being less than in 1 minute from 60-65 DEG C by main batch.

Subsequently, add 0.08 g illuminating colour, and 10.5 g enzymes and 10 g perfume compound, and make mixture remix 10 minutes before pumping from container to form pre-mixture A.This mixture is that yielding stress is approximately 0.3 Pa and at 21 s ^-1lower viscosity is the quasi-viscous liquid of 350 mPas.

pre-mixture B

The microcapsule that use have melamino-formaldehyde shell, are that mean particle size is the anionic of 15.8 μ m.They can solids content be that 46.8 % by weight and slurry viscosity are the slurry form acquisition of 425 mPas.In the time adopting isopyknic water dilution, the viscosity of the pre-mixture B of gained at 25 DEG C is 10 mPas.

In the batch blender stirring in slurry formula, only adopt container to stir, 2 parts of pre-mixture B are added in 98 parts of pre-mixture A, and stir about 15 minutes.This causes the formation of microcapsule agglomerate, and agglomerate is scattered in mixture well.

In order to attempt to smash described agglomerate, then pump is taken out described mixture with the online static mixer of process.Be paddle stirrer by the common mixed tensor of such mixing machine supply approximately 100 times.

In the time adopting such paddle stirrer to sneak in a usual manner in liquid, these microcapsule produce the dispersion of 70:30 than (non-Fu Ju Wu ︰ agglomerate as defined above), compare down, and employing the method according to this invention is 96:4.

Microcapsule level on the final mixture disperseing is 0.46%.

The microscope visual detection of the microcapsule of described dispersion has also proved that present method does not cause breaking of microcapsule.

Claims (7)

1. one kind for introducing microcapsule with anionic charge the method for structurized moisture concentrated type liquid washing agent, the total surfactant that this washing composition comprises at least 30 % by weight, with external structure agent, in described total surfactant, at least 5 % by weight based on this total surfactant are anion surfactant, this anion surfactant comprises soap, and the method comprises mixes two kinds of pre-mixtures; Pre-mixture A is not containing the structurized moisture concentrated type liquid detergent composition of microcapsule, and pre-mixture B comprises the aqueous dispersion with the microcapsule of anionic charge, it is characterized in that:

Pre-mixture B is that peak viscosity is the slurry of the microcapsule of 100 mPas at 25 DEG C, and the granularity of these microcapsule of at least 90 % by weight is 5-30 μ m; With

Pre-mixture B is added to pre-mixture A, and the energy input that adopts 20-500 J/kg makes the mixture of mixing of gained by static on-line mixing machine, just to form structurized liquid after this mixing machine, the agglomeration group that this structuring liquid comprises the total microcapsule that are less than 10% of group based on microcapsule, the agglomeration group of microcapsule is restricted to be had more than 5 groups of microcapsule in groups together

Wherein said microcapsule comprise shell, and this shell comprises the material that is selected from (gathering) urea, (gathering) ammonia ester, polysaccharide and aminoplastics.

2. method according to claim 1, wherein reduces the viscosity of pre-mixture B by dilute with water.

3. method according to claim 1 and 2, wherein said external structure agent is hydrogenated castor oil (castor wax).

4. method according to claim 1 and 2, wherein said microcapsule comprise melamino-formaldehyde shell.

5. method according to claim 1 and 2, wherein said shell comprises starch.

6. method according to claim 1 and 2, wherein said microcapsule are perfume compound encapsulant.

7. method according to claim 1 and 2, the total surfactant that wherein said washing composition comprises maximum 65 % by weight.