CN102224233A

CN102224233A - Liquid detergents

Info

Publication number: CN102224233A
Application number: CN2009801468533A
Authority: CN
Inventors: R·M·克雷文; C·L·多伊尔; A·D·格林; I·J·赫西; A·J·莱夫里; J·菲利普; J·赖斯
Original assignee: Unilever NV
Current assignee: Unilever PLC; Unilever NV
Priority date: 2008-09-25
Filing date: 2009-09-23
Publication date: 2011-10-19
Also published as: WO2010034736A1; EP2326705A1

Abstract

The present invention relates to phosphate free liquid detergent compositions. The invention provides a method for production of liquid detergent compositions, wherein the hydrogenated castor oil crystallises on cooling from a premix of warm non-aqueous organic solvent to form a dendritic structure. In addition, the invention provides a liquid detergent composition obtainable by this method comprising hydrogenated castor oil and encapsulated perfume.

Description

Liquid washing agent

Technical field

The present invention relates to be used to prepare the method for the liquid detergent composition that is used to do washing, contain hydrogenated castor oil.The invention still further relates to can be by the liquid detergent composition of this method acquisition.

Background technology

Because liquid washing agent is easy to use, they are used to clean clothing by the human consumer more and more.Nowadays, liquid washing agent is sold as concentrated liquid detergent more and more, and it contains the tensio-active agent that total concn is 30-60wt% usually, especially more than 40% active substance, compares with the peak concentration 20wt% of non-concentrated liquid detergent.This advantage for human consumer and industry is that the amount of liquid that need to throw in is little, and therefore needs the liquid tonnage much less producing, pack, transport and store, and keeps identical detersive power simultaneously.

Known and hydrogenated castor oil (HCO) can be used as external structure agent (external structurant) and rheology modifier to stablize this spissated liquid washing agent.US 3 354 091 discloses uniform, dumpable basically, strong detersive power aqueous liquid detergent compositions, and it is made up of following material substantially: 5-30wt% basic metal negatively charged ion organic sulfonic acid washing composition, 10-30wt% potassium polyphosphate, 4-12wt% hydrotropic agent, 0.1-1wt% are easy to be enough to suppress the isolating hydrogenated castor oil of described carboxymethyl cellulose salt from the basic metal carboxymethyl cellulose of washing composition and phosphatic solution separating and 0.01-1wt% usually.Described composition can randomly further contain fatty acid alkyl amide to improve detersive power and to change foaming power.When using, preferably solid alkylolamide and castor wax (castor wax) (hydrogenated castor oil) are added as mixture with the fusion form.In embodiment 1, fusion dodecanoyl Yi Bingchunan and castor wax and under agitation add in advance as blend at 71 ℃.The fusing point of described castor wax is that the 84-87 ℃ of fusing point with described alkylolamide is about 65-66 ℃.Enough information is not provided in this document, and whether fusion or its are dissolved in the described fused isopropanol amide to learn described castor wax.With the research of nonionic as the solvent of hydrogenated castor oil, we believe described castor wax in case become liquid it will be dissolved in the described nonionic being higher than 66 ℃ from us.Details about rate of cooling is not provided.Technical problem is the stabilization of water-soluble carboxymethyl sodium cellulosate in the presence of phosphate builders.There is not solid matter to be suspended in the described uniform liquid.

GB1,034,202 disclose the available method of preparation liquid detergent composition, it is included in the aqueous concentrates that under agitation prepares castor wax and anionic detergent in the water in the temperature that is higher than 88 ℃, and slowly cool off this mixture to form described castor wax stable in described enriched material with the speed that is no more than 2.8 ℃/minute, fine dispersions, and described enriched material mixed to form uniform liquid detergent composition with extra water and identical or different washing composition, it can be toppled in room temperature, and contains total washing composition that 0.1 castor wax and 5 that arrives 1wt% arrives 50wt% in thin stabilising dispersions.

GB 1,034, and 202 have provided the method for a kind of ordinary method that becomes preparation HCO external structure system (external structuring system).In essence, prepare spissated structurized liquid with the form of aqueous emulsion, its can be used as that enriched material is cooled and then with the remainder cold mixing of the structurized preparation of needs.Then, any solid material that is suspended of waiting can be joined in the liquid of such formation.

WO 02/40627 A2 discloses the liquid detergent composition that contains the structurizing system, and wherein said structurizing system can contain hydrogenated castor wax.Described structurizing system particularly linear structure system and/or non-linear structure system (is the disk-like structure system, wherein structurising agent flocks together to form disk-like structure, and described disk-like structure can interact to cause the structurizing system with other disk-like structure).The method that is used to prepare described linear structure system at the page 5 of this document is described to comprise that mixture heating up with water and HCO to the fusing point that is higher than described HCO, then under agitation with described mixture cool to room temperature, thereby forms the linear structure system.Randomly, also add tensio-active agent and salt to this pre-composition.The existence of water and dispersive wax causes in the formation of the temperature emulsion that raises with subsequently from the crystallization of described emulsion, to form specific linear structure system.The 40th page of formation that has further confirmed emulsion, wherein the amount of agitation before the regulation cooling is enough to all fused HCO of emulsification.

EP1 396 536 A1 disclose the structurizing system of suitable stabilising liq fabric treatment composition, and it comprises:

(A) non-polymer, crystalline, contain the structurising agent (structuring agent) of hydroxyl, it is at the 0.1-80wt% of described structurizing system, most preferably can crystallization spreads all over the linear structure network of fluid matrix (for example HCO) with formation in the concentration of 2-6wt%;

(B) nonionic emulsifying agent (C that for example has the ethoxylation of 1-11 EO group ₈-C ₂₀Alcohol);

(C) concentration is the 0.1wt% of described structurizing system to the anionic emulsifier of 8.0wt% (C for example ₁₁-C ₁₃Alkylbenzene sulfonate); With

(D) liquid vehicle (water of adding or C ₁-C ₄Alcohol, or their mixture).It is believed that described anionic emulsifier by with the particle size of described structurising agent mixture control linear structure formed material (thread-like structuring material), wherein said line is long and thick relatively.This type of structurizing system preferably constitutes the 4-15wt% of described liquid handling components and fabrics.In the practice, work in described HCO pre-composition in order to make described anionic emulsifier, described system will always comprise some water (for example from described tensio-active agent).All embodiment utilize the water of such adding.

The method that is used to prepare this linear structure system is also disclosed in EP 1 396 536 A1, it is by mixing various components, be heated to above the temperature (90 ℃) of described structurising agent melt temperature, under agitation stored at least one hour, and be cooled to be lower than the temperature (70 ℃) of described structurising agent melt temperature with the speed that is preferably 1.5 to 2.5 ℃/minute in this temperature.This method also is based on the crystallization of the emulsion droplet of fused hydrogenated castor oil.Surfactant acid is neutralized in pre-composition in the presence of described water, and neutralization heat can be used for the described HCO of fusion.

Spicer P.T. and Hartel R.W.(Australia J. Chem 2005,58 655-659) have described by form the mechanism of this type of linear structure from the emulsion crystallization.

EP 1 502 944 A1 disclose a kind of similar structurizing system, wherein in pre-composition, hydrogenated castor oil is mixed with anion surfactant, then this pre-composition is mixed with other composition of aqueous liquid detergent, contain the liquid washing agent of the visibly different pearl of maximum 5wt% with preparation.Melt temperature (about 90 ℃) by moisture pre-composition being heated to above described hydrogenated castor oil also prepares the described pre-composition of emulsion preparation, then with this emulsion quick cooling to 70 ℃ with the described hydrogenated castor oil of crystallization, slow cool to room temperature then.Like this, in described hydrated matrix, form described linear structureization.As EP 1 396 536, surfactant acid is neutralized in described pre-composition in the presence of water, and neutralization heat can be used for the described HCO of fusion to form described pre-composition oil in water miscible liquid.

In EP 1 502 944, can neutral density pearl can be mixed in the described structurized liquid at last with the remainder of surfactant system and 2.5 parts of these aqueous structurized enriched materials in mixed at room temperature then.Described detergent composition most preferably contains 10 to 35wt% tensio-active agent.Use the suspend problem of visible pearl of linear structure system to be that described composition shear shinning is very serious, even the push-through packs dispensing product just is enough to make described composition shear shinning to the point of its visible pearl that possibly can't suspend reliably in the mode of abundant distribution wherein, if particularly they are designed to delivery functions composition in the dosage that each is poured out.

WO 2006/005068A1 discloses the liquid detergent composition that contains hydrogenated castor oil, and it is used as and can spreads all over structural agent (structurant) use that fluid matrix forms the linear structure system.It is 10 to the tensio-active agent of 45wt% that described liquid detergent composition preferably contains concentration, and the concentration of hydrogenated castor oil is illustrated as about 0.19-0.28wt% of described whole composition.In the method that is used for preparing this liquid detergent composition, do not provide details about temperature and rate of cooling.

WO 2007/130562 A2 has described liquid laundry detergent compositions, and it can contain organic external structure agent such as hydrogenated castor oil.It is believed that when these structural agents in the text in the liquid, aqueous matrix of composition or in pre-composition during in-situ crystallization, these structural agents work by forming the linear structure system, wherein said pre-composition is used to form this liquid, aqueous matrix.Be heated to above the temperature of the fusing point of described structural agent by aqueous mixture, then keep described liquid to be in simultaneously described mixture cool to room temperature and shears this type of crystallization of generation these materials.Described wire system can comprise wire network fibrous or that twine.Can also form rosaceous (in the form of rosettes) non-fibrous particle.Particle in the network can have about 1.5:1 to the aspect ratio of about 200:1, and can have about 1 micron and arrive about 100 microns size.

WO 99/38389 discloses the liquid personal cleansing composition that contains lipotropy actie skin moisturizer, extending oil (weighting oil), stablizer (for example trihydroxy-tristearin), tensio-active agent and water.This mixture as preparing independent pre-composition, mixes these by combining step, is maintained at about 88 ℃ temperature and slowly is cooled to about 25-40 ℃ temperature to prepare.

In a word, use HCO to follow following method as the nearest prior art of external structure agent: by preparing pre-composition from the described HCO of aqueous emulsion crystallization to form the linear structure enriched material, it then can the diluted liquid that has some suspension properties with formation.Its shortcoming is that any emulsive tensio-active agent that is used for also enters the finished product, and they may take place to interact unfriendly with the surfactant system of selecting for this product there.In addition, with described pre-composition with must be before remaining component is mixed with described pre-composition cooling, this may cause high latency in successive processes.At last, described linear structure system has serious shear shinning behavior, this means that it can not keep the suspension and the dispersed particles of solid material reliably in by the process of the described product of squeeze receptacle duplicate allocation.

An object of the present invention is to provide the alternative method that is used to prepare with the structurized liquid washing agent of HCO, described liquid washing agent can suspend and have insoluble particles less than about 100 microns typical sizes, for example encapsulated spices (encapsulated fragrances), it is sightless to eyes.

Summary of the invention

We have been found that now, can reach this purpose and other purpose by the method that is used to prepare liquid detergent composition, wherein hydrogenated castor oil is added the liquid organic solvent at least 70 ℃ temperature, wherein said organic solvent preferably contains free fatty acids, or nonionogenic tenside, or their mixture, to form pre-composition.This pre-composition is added in the batch of material of another pre-composition that contains tensio-active agent and neutralization reagent in the water at least 55 ℃ temperature then, so that the micella solubilising of described hydrogenated castor oil in the described tensio-active agent to be provided.When this mixture-controlled cooling, the dissolved hydrogenated castor oil is self-assembled into and is dendritic structure (dendritic structure), produces the resulting structure agent (structurant) with suspended solids (the encapsulated perfume compound that especially has the particle size that is less than 200 μ m) ability that is used for liquid detergent composition thus.

The dendritic structure that is formed by this dissolved molecular dispersion body method of HCO is different from the prior art linear structure agent that forms by the fusion emulsion process on outward appearance and performance.

Described dendritic structure is considered to from solution crystallization and directly enters body product (bulk product) and need not the follow-up dispersive result that any described structurizing system enters the second section of liquid preparation.We find that this method forms different structurizing forms, and the shear shinning of the liquid that forms like this and the solid suspension performance different shape that for some are used, is better than using the emulsification method route to obtain the linear structure system form those.

An advantage of the present invention is the detergent liquid that the obtains encapsulated spices that is particularly suitable for suspending, and it is sightless to human eye.Produced attractive liquid detergent composition thus, it has tempting fragrance for consumers.

Therefore, a first aspect of the present invention provides the method that is used to prepare without phosphorus (phosphate free) liquid detergent composition, and it comprises following steps:

A) by under agitation at least 55 ℃ temperature tensio-active agent and alkali being added preparation first pre-composition in the entry, it has 7.5 to 11 pH;

B) thus by under agitation hydrogenated castor oil being added at least 70 ℃ temperature in the liquid non aqueous organic solvent described hydrogenated castor oil is dissolved in preparation second pre-composition in the described liquid non aqueous organic solvent, described liquid non aqueous organic solvent is preferably selected from nonionogenic tenside and free fatty acids and their mixture;

C) under at least 55 ℃ temperature is being mixed, with the b of 1:40 to 1:10) will add from described second pre-composition of step b) in described first pre-composition from step a) a) weight ratio, described thus hydrogenated castor oil remains in the solution;

D) mixture with step c) is cooled to be lower than 50 ℃ temperature, and store subsequently this mixture up to described hydrogenated castor oil from solution crystallization.

E) so under mixing, will have in the liquid of encapsulated spices adding from the refrigerative external structureization of step d) of the highest 200 microns particle size.

Use non-aqueous organic solvent to have the advantage that is better than using in the prior art aqueous emulsion system in step b): they comprise the formation of more spissated pre-composition, this means that owing to its lower quality, its lower specific heat and its more low temperature that need be heated to described pre-composition needs the less heat input.When it is used at liquid suspended solids material (especially encapsulated spices), described solvent method also provides different and more excellent microtexture for described HCO.

A second aspect of the present invention provides the liquid detergent composition that can obtain by the method according to first aspect present invention, it contains the encapsulated spices of the suspension with the highest 200 microns particle size, wherein said hydrogenated castor oil (hydrogenated castor oil) external structure agent exists with 0.15 to 0.5wt% concentration of whole composition, and has that reduced size (minor dimension) is up to 40 nanometers and aspect ratio (aspect ratio) is the dendritic structure of about 1000:1.

Embodiment

Unless otherwise indicated, otherwise all percentage ratios of mentioning herein all are based on whole composition calculates by weight.

Initial in this article detersive power (primary detergency) is described as be in initial or the washing for the first time the clean effect to spot.Fabric is stain and is handled with laundry detergent composition of the present invention subsequently.Described laundry composition is called as initial detersive power to the clean effect (measuring as greasiness removal) of spot.This is different processes for the antifouling of so-called use polymkeric substance, use the antifouling polymer treatment fabric (by washing or other this type of processing) that is to use of polymkeric substance, stain described fabric then, described antifouling polymeric has easier effect of removing spot.

Such as used in this article, " transparent " is meant that composition or mixture or phase or composition preferably have greater than 25% at spectrographic visible part (about 410-800nm), more preferably greater than 30%, most preferably greater than 40%, best greater than 50% optical transmittance.Perhaps, absorbancy can be substantially equal to 25% transmission for being less than 0.6(after tested) or have transmissivity greater than 25%, wherein the % transmissivity equals: 1/10 absorbancy * 100%.For the present invention, as long as a wavelength in visible-range has the transmissivity greater than 25%, just think transparent/translucent.

In the context of the present invention, translucent material is defined as only allows light to pass them diffusely, thus the material that can't clearly be distinguished at the object of opposite side.

In the context of the present invention, shear shinning liquid is meant at the relative thickness of low shearing condition (for example static), at shear conditions when bottle is toppled over described liquid (for example when from) heavy-gravity liquid not too then.The shear shinning rheological characteristics can be measured with viscometer or accurate rheometer and correcting measuring spindle (correct measurement spindle).

Be used to prepare the method for liquid detergent composition

In a first aspect of the present invention, provide to be used to prepare the phosphate-free liquid detergent method for compositions, it may further comprise the steps:

A) by under agitation at least 55 ℃ temperature, preferably 55 to 70 ℃ temperature, more preferably 60 to 65 ℃, most preferably tensio-active agent and alkali added preparation first pre-composition in the entry at about 65 ℃, it has 7.5 to 11, is preferably 8 to 10 pH;

B) by at least 70 ℃ temperature, preferably 70 to 75 ℃ temperature, thereby under agitation hydrogenated castor oil is added in the liquid non aqueous organic solvent and described hydrogenated castor oil to be dissolved in preparation second pre-composition in the described liquid non aqueous organic solvent, wherein said non-aqueous organic solvent preferably contains free fatty acids, or nonionogenic tenside, or their mixture;

C) under mixing at least 55 ℃ temperature, preferably 55 to 70 ℃ temperature, more preferably 55 to 65 ℃ temperature, most preferably arrive 1:10 with 1:40 at 60 to 65 ℃, be preferably the b of 1:30 to 1:15) to a) weight ratio, more preferably will add from described second pre-composition of step b) in described first pre-composition from step a) with the ratio of about 1:20; Described thus hydrogenated castor oil remains in the solution;

D) mixture with step c) is cooled to be lower than 50 ℃, preferably is lower than 40 ℃, more preferably less than 30 ℃ temperature, and store subsequently this mixture up to described hydrogenated castor oil from solution crystallization.

Preferably, in step a) surfactant concentrations be in this step whole mixture 20 to 65wt%, more preferably 25 to 60wt% and most preferably be 25 to 45wt%.In a preferred embodiment, the detergent composition that can be obtained by the method according to this invention is spissated detergent composition.In step a), described tensio-active agent preferably contains synthetic anionic and/or nonionogenic tenside.More preferably, the described tensio-active agent in the step a) contains synthetic anion surface active agent linear alkylbenzene sulfonate (LAS).The pH of the pre-composition in the step a) is preferably 9 to 10.Produce correct structurizing when adding the agent of dissolved external structure at second pre-composition from step b), described temperature is at least 55 ℃.

First pre-composition in the step a) contains tensio-active agent and alkali in water, and preferably also contains hydrotropic agent.Hydrotropic agent is the compound of solubilizing hydrophobic compound in the aqueous solution.Typically, hydrotropic agent is made up of hydrophilic segment and hydrophobic part, thereby but described hydrophobic part is too little to cause spontaneous self aggregation, and therefore they form micella unlike tensio-active agent.Hydrotropic agent is used in the detergent formulation so that can realize denseer surfactant formula.The hydrotropic agent that is fit to is for example glycerine and propylene glycol.Preferably, described first pre-composition of step a) is transparent liquid in the advantage temperature (prevailing temperature) of step c).Alkali in the described pre-composition of step a) preferably contains alkali metal hydroxide or trolamine, and more preferably described neutralizing agent contains sodium hydroxide, trolamine or their mixture.Typically, the described pre-composition of step a) is the micellar solution of described tensio-active agent in water.

Be at least 70 ℃, the temperature that is preferably 70 to 75 ℃ prepares second pre-composition, and it contains the hydrogenated castor oil that is dissolved in the liquid non aqueous organic solvent.Preferably, described solvent contains free fatty acids, or nonionogenic tenside, or these mixture.More preferably, described solvent contains free fatty acids and most preferably described free fatty acids contains the saturated C of straight chained alkyl ₁₂-C ₁₈Lipid acid.In this step b), the described solvent in container does not add free-water.Preferably, described second pre-composition of preparation under low shearing condition; More preferably, only apply gentle mixing.This has the advantage that only needs low-yield input when mixing described second pre-composition.Suitably, the advantage temperature of second pre-composition of this in the step b) in this step b) is transparent liquid.

Preferably, the concentration of hydrogenated castor oil is to make to be 0.15 to 0.5wt% of described composition by the concentration in the final liquid detergent composition of method acquisition of the present invention in described second pre-composition, be preferably 0.15 to 0.3wt%, even more preferably 0.15 arrive 0.25wt% and most preferably be 0.17 to 0.25wt% of whole composition.Therefore, in described second pre-composition of step b) the concentration of hydrogenated castor oil be preferably described pre-composition 1.5 to 20wt%, more preferably 1.5 to 10wt%, in addition more preferably 1.7 to 5wt% and the 3.4 wt % that most preferably are described pre-composition to 5wt%.Preferably, described second pre-composition only contains solvent and hydrogenated castor oil, and wherein said solvent preferably contains free fatty acids, or nonionogenic tenside, or their mixture, for the reason of explaining below about step c), most preferably described solvent is a free fatty acids.

In the method according to the invention, in step c), described second pre-composition is under agitation added in described first pre-composition, wherein said second and the weight ratio of first pre-composition be 1:40 to 1:10, be preferably 1:30 to 1:15 and 1:20 more preferably from about.Most preferably described second pre-composition constitute whole preparation less than 6wt%, about 5wt% of whole preparation most preferably.Described temperature in the step c) is at least 55 ℃, is preferably 55 to 70 ℃, more preferably 55 to 65 ℃, most preferably is 60 to 65 ℃.

When the solvent in described second pre-composition of step b) contained free fatty acids, the alkali in described first pre-composition played the effect of the neutralizing agent of described lipid acid, and by in step c), described first and second pre-compositions mixing being formed soap.This formation of soap causes the elimination wholly or in part of the solvent of described hydrogenated castor oil, and thinks that this process plays the effect that its subsequent crystallisation becomes the seed of dendritic structure.The nonionic surfactant solution that will have phase transformation by careful selection when adding anionic surfactant solution can obtain similar effects, but such physical phase transition is preferred not as the chemical phase transformation that causes owing to the described free fatty acids solvent of neutralization.

Because described second pre-composition only forms the sub-fraction of whole liquid detergent composition, therefore the liquid of small volume need be heated to and compare relative low temperature with the method for prior art relatively.This is an advantage of method of the present invention, and it causes conserve energy.Another advantage is that the mixing of described first and second pre-compositions is preferably carried out under low the shearing, preferably only applies gentle the mixing to described mixing process.This compared with prior art also causes conserve energy aspect mixing.

In step c), the combination under gentleness is mixed of described first and second pre-compositions, and do not wish to be limited by theory, after described second pre-composition (from step b)) is added described first pre-composition (from step a)), it is believed that in described preparation because the interaction between described hydrogenated castor oil and water and the tensio-active agent, described hydrogenated castor oil is maintained in the solution by the micella solubilising.Usually, the mixture of step c) also is limpid in the advantage temperature of step c), and described advantage temperature is at least 55 ℃, is preferably 55 to 70 ℃, illustrates that described second pre-composition is dissolved in described first pre-composition suitably fully.Usually in this temperature, all the components all in solution and described hydrogenated castor oil non-crystallizable.Mix by the gentleness in the step c), described dissolved hydrogenated castor oil was mixed before crystallisation process begins equably.

In step d), will be cooled to be lower than 50 ℃ from the mixture of step c), preferably be lower than 40 ℃, more preferably be lower than 35 ℃, even more preferably be lower than 30 ℃ temperature.Then, store this mixture up to described hydrogenated castor oil from solution crystallization.When the technician can determine the crystallization of described hydrogenated castor oil, observes visually because the crystallization of described hydrogenated castor oil can become muddy by liquid.In addition, by the opticmicroscope of routine, can observe the crystallization of hydrogenated castor oil whether form.Preferably, under low shearing condition, when mixing described mixture, gentleness implements this cooling step d).In this case, low shearing means that described shearing is not enough to destroy the dendritic structure of appearance.

In a preferred embodiment of the inventive method, in step d), the mixture of step c) is cooled to be lower than 50 ℃ temperature with maximum 1 ℃/minute rate of cooling.Preferably, in step d) with the mixture of step c) with maximum 1 ℃/minute, preferred maximum 0.7 ℃/minute, even more preferably maximum 0.5 ℃/minute, most preferably maximum 0.4 ℃/minute rate of cooling is cooled to be lower than 40 ℃, more preferably 30 ℃ temperature.When using this preferred cooling step d) time, the hydrogenated castor oil that is present in the described pre-composition in the temperature that is being lower than 55 ℃ during this cooling step suitably begins crystallization.

In another preferred embodiment of method of the present invention, the mixture with step c) in step d) was cooled to be lower than 40 ℃ temperature within 5 minutes, then this mixture was stored 5 minutes in the temperature that is lower than 40 ℃ at least.Preferably, in step d) with the mixture of step c) in 5 minutes, more preferably at 3 minutes internal cooling to the temperature that is lower than 35 ℃, then this mixture was stored 5 minutes in the temperature that is lower than 35 ℃ at least.More preferably, in step d) with the mixture of step c) in 5 minutes, most preferably at 3 minutes internal cooling to the temperature that is lower than 30 ℃, then this mixture was stored 5 minutes in the temperature that is lower than 30 ℃ at least.Even more preferably, with the mixture of step c) 3 or even 2 minutes internal cooling to the temperature that is lower than 40 ℃, then stored at least 5 minutes in the temperature that is lower than 40 ℃.Most preferably, with the mixture of step c) 3 or even 2 minutes internal cooling to the temperature that is lower than 30 ℃, then stored at least 5 minutes in the temperature that is lower than 30 ℃.In another preferred embodiment, at described cooling step the back takes place and in described advantage temperature described mixture was stored 8 minutes at least, or more preferably stored at least 10 minutes.When using this quick freezing step d), suitably begin crystallization at the hydrogenated castor oil that during described mixture is stored, exists in the described pre-composition after the described quick cooling.

An example of this method for rapid cooling is the quick cooling (flash cooling) in plate-type heat exchanger, wherein with described mixture at about 1 minute time internal cooling to being lower than 30 ℃.When using this method for rapid cooling, described mixture will be maintained at least 5 minutes the time of temperature that is lower than 40 ℃.In this hold-time, keep the temperature of described mixture to be lower than 40 ℃ all the time, and the crystallization that described hydrogenated castor oil will take place in the temperature that keeps described pre-composition in the back takes place in described quick cooling.

In this step d), obtain opaque quasi-viscous liquid, it preferably has shear shinning curve (shear thinning profile) so that the dumpable liquid that is assigned to easily in the washing machine to be provided.Do not wish to be limit by theory, we have determined that the method according to this invention causes the formation of dendritic structure by the crystallization of described hydrogenated castor oil.Described dissolved hydrogenated castor oil suitably is self-assembled into this type of dendritic structure.Dendritic structure is the highly branched structure of tool nuclear solid material, and it has the branch of extending from described nuclear.The a series of nucleogenesiss of described dendritic structure during seemingly by the described mixture of cooling in step d), then crystallization causes forming dendritic crystal from these nucleation sites growths and forms.Described nucleation site can be described as the nuclear of described dendrimers (dendrimer).Suitably, described hydrogenated castor oil becomes to spread all over the three-dimensional branched structure of described preparation from this nucleus growth, forms three-dimensional rack (scaffold).The described hydrogenated castor oil of dendrimers form forms structured network, and wherein the gravel size decision of dendrimers is micron-sized (micron-sized) (the most about 100 microns).Described dendrimers forms the fibrous network that highly tangles.The thickness that the branch of dendrimers (or fiber) typically has 20 to 40 nanometers, and typically extend to greater than 10 microns.These branches of described dendrimers are long relatively and thin, and have the aspect ratio of about 1000:1.By contrast, has the aspect ratio of maximum 200:1 by the prior art linear structure system (as described in EP 1,502 944 and other places) that forms from the emulsion crystallization.Particulate reduced size (minor dimension) by solvent method according to the present invention preparation is also than those much smaller that obtains by described aqueous emulsion process.According to EP 1 502 944, it is 5 to 15 microns for the preferred reduced size of described linear structure agent.Even 1 micron the lower limit of in EP1 502 944, mentioning, the fiber of the prior art linear structure also twice greater than the dendrimers that forms by described solvent method is thick.It is translucent that the crystallization of described hydrogenated castor oil causes described preparation to become, because size stray light the seeing through from described preparation of dendritic structure.The microtexture of described dendrimers and prior art linear structure are by microscopy and by their rheological property and suspension property and easily being distinguished.Compare with the dendrimers network with extending of the entanglement of structurizing system according to the present invention, the notable feature of prior art is the discrete feature of the fiber of described line.

The dendritic support of the three-dimensional tree of hydrogenated castor oil has been supported the adding of the especially encapsulated spices of particle (perfume compound) (its can not by the human eye finding).Therefore, in the method according to the invention, afterwards encapsulated spices was added in the mixture from step d), and described encapsulated spices preferably has 0.01 to 200 micron average particle size particle size.More preferably, described encapsulated spices has 1 to 100 micron, most preferably is 1 to 50 micron average particle size particle size.The liquid detergent composition of Xing Chenging has good physical stability like this.The rheological characteristics of described dendritic structure system seems that to the manufacturing of described composition and follow-up transportation, storage and use be favourable.Described composition shear shinning is enough to be mixed into wherein and not disruptive degree to breakable capsule, and in case remove the described capsule maintenance of low shear-mixed dispersion, and during transportation and particularly work as described product quilt by pushing and/or toppling over from packing and divide timing, if applied high-shear afterwards, can sedimentation or be separated on the surface.In this, for the perfume compound capsule, the viscograph of described product is compared more superior with the linear structure system, and described linear structure system has under high-shear than low viscosity, and this can cause described capsule some take place to move along with the time.

Liquid detergent composition

A second aspect of the present invention provides the liquid detergent composition that can obtain by the method according to first aspect present invention, wherein said hydrogenated castor oil exists with 0.15 to 0.5wt% concentration of whole composition, and has the dendritic structure of above definition.Preferably, the concentration of hydrogenated castor oil is 0.15 to 0.3wt% of whole composition, even more preferably 0.15 arrives 0.25wt% and most preferably be 0.17 to 0.25wt%.

Do not wish to be limit by theory, our imagination is when the concentration of hydrogenated castor oil in can be by the liquid detergent composition of method of the present invention acquisition is too high, this liquid detergent composition will be thick and stickingly and bad to topple over assignment problem when causing using and dissolving properties.When the concentration of hydrogenated castor oil is too low, the described structurized liquid encapsulated perfume particle in the described preparation that can not stably suspend.

Preferably, according to surfactant concentrations in the liquid detergent composition of the present invention be whole composition 20 to 65wt%, more preferably be 25 to 60wt% and be most preferably 25 to 45wt%.

Described liquid cleansing composition can be mixed with spissated cleaning liq, be used to be applied directly to substrate, or be used for being applied to substrate after the dilution, for example by the human consumer or in washing plant before using described liquid composition or during dilution.

Though can be used to clean any suitable substrate according to the compositions and methods of the invention, preferred substrate is the laundry fabric.Can implement cleaning by making described substrate contact time enough with the liquid medium that constitutes by described liquid cleansing composition or prepare simply.But, preferably, be stirred in described suprabasil cleaning medium or comprise the cleaning medium of described substrate.

Described encapsulated spices is finished the lasting fragrance that discharges ideally afterwards with oneself being attached to suitable substrate to be provided at cleaning process.

Product form

Can be by the preferably spissated liquid cleansing composition of liquid detergent composition of the method according to this invention acquisition.Have preferably from dumpable liquid, dumpable gel to the physical form of dumpable gel not according to the liquid composition of second aspect present invention.These forms characterize by product viscosity easily.In these definition, unless there is clear and definite opposite explanation, all viscosity of mentioning all are at 21s in the whole specification sheets ^-1Shearing rate and 25 ℃ thermometric viscosity.This shearing rate is the shearing rate that is applied to usually when bottle is toppled on the liquid.Liquid detergent composition according to the present invention is the liquid of shear shinning.

Preferably have according to the dumpable liquid detergent composition of second aspect present invention and to be no more than 1,500mPa.s is more preferably no more than 1,000 mPa.s, also more preferably no more than the viscosity of 500mPa.s.Typically, described viscosity is at 21s ^-1Be lower than 500 mPa.s.

Can be by the liquid detergent composition of method acquisition of the present invention, it is dumpable gel, preferably have at least 1,500 mPa.s but be no more than 6,000 mPa.s are more preferably no more than 4,000 mPa.s, also more preferably no more than 3,000 mPa.s with especially be no more than the viscosity of 2,000 mPa.s.

Preferably have at least 6,000 mPa.s as the composition of either side according to the present invention of dumpable gel not but be no more than 12,000 mPa.s, more preferably no more than 10,000 mPa.s, also more preferably no more than 8,000 mPa.s and especially be no more than the viscosity of 7,000 mPa.s.

Comparing with the linear structure system of prior art, is about 1Pa.s in the described viscosity of the shear-stress of 5Pa, compares with 0.3Pa.s and is 0.7Pa.s in the higher shear of 10Pa, and on the other side is 0.2Pa.s.On the other hand, be similar for two types structurizing in the viscosity of low shear-stress (0.1Pa).This means that the trend that the capsule of suspension is separated in transit is lower for product according to the present invention.But with regard to sneaking into described capsule during manufacture easily, it is good that structurizing system of the present invention is compared with described wire system.

For the present invention, when composition 5 to 50 ℃ temperature when about 3 months time keeps even for the perfume compound capsule of dispersive and suspension, think that then composition is a physically stable.

Hydrogenated castor oil

Viscotrol C is also referred to as ricinus oil, is the vegetables oil from the beans acquisition of castor-oil plants (Ricinus communis).Viscotrol C is colourless to very shallow xanchromatic liquid, has light smell or nothing and smells tasteless.It is that wherein about fatty acid chain of 90 percent is the tri-glyceride of ricinolic acid (12-hydroxyl-9-cis-octadecenic acid).Oleic acid and linolic acid are other main ingredients.The controlled hydrogenation of Viscotrol C obtains complete hydrogenant Viscotrol C, and it is used to the method according to this invention and product.In room temperature, hydrogenated castor oil is hard Chinese wax, and it is in about 86 to 88 ℃ temperature fusion.Supplier is for example Hindustan Unilever(supply thin slice or particle), the Cognis(powder), the Vertellus(thin slice) or Elementis(thin slice or particle), or any their mixture.The hydrogenated castor oil of Shi Heing is the Thixcin R that for example obtains from Elementis in the present invention.

Water

Preferably, be 10 to 80wt% of whole composition according to the amount of water in the liquid detergent composition of the present invention, more preferably 20 to 60wt%, most preferably be 20 to 50wt%.Preferably there are at least some water in formation for the dendritic structure that promotes described hydrogenated castor oil.

Tensio-active agent

Liquid detergent composition of the present invention can contain 20 to 65wt%, and more preferably 25 to 60wt% and 25 to 45wt% tensio-active agent most preferably, be preferably selected from negatively charged ion, nonionic, positively charged ion, zwitter-ion activated detergent material or their mixture.In the context of the present invention, anion surfactant refers to the synthetic anion surfactant.

Usually, the tensio-active agent of described surfactant system can be selected from ' Surface Active Agent ' Vol.1, Schwartz ﹠amp; Perry, Interscience 1949, Vol.2, Schwartz, Perry ﹠amp; Berch, Interscience 1958, current edition or ' Tenside-Taschenbuch ' of ' McCutcheon ' s Emulsifiers and Detergents ' that Manufacturing Confectioners Company publishes, H. Stache, 2 ^NdEdn., Carl Hauser Verlag, the tensio-active agent of describing in 1981.

Except above-mentioned tensio-active agent, be soap (salt of lipid acid) according to a kind of preferred compound in the liquid detergent composition of the present invention.Preferably, the organic non-aqueous solvent that uses in the step b) of method of the present invention contains lipid acid.Preferably, described lipid acid contains the saturated C of straight chained alkyl ₁₂-C ₁₈Lipid acid.The example that is fit to the lipid acid of the present invention's use comprises derived from the pure fatty acid of Zoomeric acid, Thistle oil, sunflower seed oil, soybean oil, oleic acid, linolic acid, linolenic acid, ricinolic acid, rapeseed oil or their mixture or through hardened lipid acid.An example of preferred lipid acid is the hydrogenant coco-nut oil fatty acid, and for example Prifac 5908(is by Uniqema, Gouda, Netherlands supply).Here also can use saturated and mixture unsaturated fatty acids.

Be that described lipid acid is present in main form with soap in described (finally) liquid detergent composition with what recognize.The positively charged ion that is fit to comprise sodium, potassium, ammonium, monoethanolamine ammonium, di-alcohol ammonium, triethanol ammonium, tetra-allkylammonium for example tetramethyl-ammonium to four decyl ammonium cations.

The amount of lipid acid will change according to the special properties of needs in the final liquid detergent composition.Preferably, 0 to 30wt%, more preferably 1 arrive 20wt%, most preferably 2 to 10wt% lipid acid is present in according in the liquid detergent composition of the present invention.

The mixture of synthetic anionic and nonionogenic tenside is particularly useful in liquid detergent composition of the present invention.

In the art, the nonionic detergent tensio-active agent is known.They usually by with derived from the chemically combined water-soluble poly oxyalkylene of organic hydrophobic grouping of for example following material (polyalkoxylene) or single-or two-alkylolamide group form: wherein alkyl group contains 6 alkylphenols to about 12 carbon atoms of having an appointment, dialkyl group phenol, wherein primary, the second month in a season or uncle's Fatty Alcohol(C12-C14 and C12-C18) (or their alkyl-blocked derivative) preferably have 8 to 20 carbon atoms, in alkyl group, have 10 monocarboxylic acids to about 24 carbon atoms, and polyoxytrimethylene.Lipid acid list-and di alkanolamide commonly also, the alkyl group of wherein said fatty acid group contain 10 and have 1 to 3 carbon atom to about 20 carbon atoms and described alkyloyl (alkyloyl) group.Any described list-and the di alkanolamide derivative in, randomly, can have the polyoxyalkylene part of the hydrophobic part of group after connecting and described molecule.Contain in the tensio-active agent of polyoxyalkylene at all, described polyoxyalkylene part preferably is made up of 2 to 20 ethylene oxide groups or oxyethane and propylene oxide group.Among one type of back, particularly preferably be those that describe among EP 225 654 A.The nonionogenic tenside of those ethoxylations further preferably, it is to have the Fatty Alcohol(C12-C14 and C12-C18) of 9 to 18 carbon atoms and the condensation product of 3 to 11 moles of ethylene oxide condensations.These example is C ₉- ₁₈The condensation product of pure and average 3 to 9 moles of ethylene oxide.That preferably use in liquid detergent composition of the present invention is the C that on average has 3 to 9 ethylene oxide groups ₁₂-C ₁₅Straight chain primary alcohol.

Preferably, can be used for nonionogenic tenside of the present invention is C ₁₂-C ₁₈The alcohol of ethoxylation, per molecule contain 3 to 9 ethylene oxide units.More preferably on average have 5 to 9 ethylene oxide groups, more preferably on average have the C of 7 ethylene oxide groups ₁₂-C ₁₅The straight chain primary alcohol of ethoxylation.

For the operable suitable synthetic anion surface active agent of described detergent composition generally is to have to contain to have an appointment 8 to the organic sulfate of the alkyl group of about 22 carbon atoms and the water-soluble alkali metal salts of sulfonate; the term alkyl is used to comprise the moieties of senior carboxyl groups; comprise alkyl-sulphate; sulfated alkyl ether; alkylaryl sulfonate; alkyloyl isethionate (alkanoyl isethionate); alkyl succinate; salts of alkyl sulfosuccinates salt; N-alkyloyl sarcosinate (N-alkoyl sarcosinate); the alkyl ether carboxy acid salt; sulfonated and acyl methyl taurine salt, particularly their sodium; magnesium; ammonium and list-; two-and triethanolamine salt.Described alkyl and carboxyl groups contain 8 to 22 carbon atoms usually, preferably contain 8 to 18 carbon atoms, also more preferably contain 12 to 15 carbon atoms, and can be undersaturated.Described sulfated alkyl ether and alkyl ether carboxy acid salt's per molecule can contain one to ten oxyethane or propylene oxide units and preferably per molecule contain one to three ethylene oxide unit.

The example of the synthetic anion surface active agent that is fit to comprises sodium lauryl sulphate, sodium lauryl tri(oxyethyl) sulfate, dodecyl sulfo-succinic acid ammonium, ammonium lauryl sulfate, ammonium dodecyl ether sulfate, cocoyl sodium isethionate, lauroyl sodium isethionate and N-sarcosyl.Most preferred synthetic anion surface active agent comprises synthetic anion surface active agent linear alkylbenzene sulfonate (LAS).Being fit to another synthetic anion surface active agent of the present invention is alcohol ethoxy-ether sodium sulfate (SAES), preferably contains high-caliber C ₁₂Alcohol ethoxy-ether sodium sulfate.

The preferred surfactants system is synthetic anionic and nonionic detergent active material and the extra positively charged ion or the mixture of amphoterics.Particularly preferably be such surfactant system, it is alcohol ethoxy-ether sulfate (AES) and C ₁₂-C ₁₅Ethoxylation primary alconol 3-9EO ethoxylate and quaternary ammonium cation surfactant mixtures.

The preferred surfactants system is the mixture of synthetic anionic and nonionic detergent active material and soap, has positively charged ion or amphoterics extraly.Synthetic anion surface active agent can be for example exists to the amount of about 70wt% with about 5wt% of total surfactant material.

In a preferred embodiment of the invention, described detergent composition also contains cats product or amphoterics, wherein said positively charged ion or amphoterics are with 1 to 20wt% of total surfactant, be preferably 2 to 15wt%, more preferably 3 to 12wt% concentration exists.

Operable suitable cats product is to replace or the quaternary ammonium salt of unsubstituted, straight chain or branching.Preferably, described cats product meets following formula:

R ¹R ²R ³R ⁴N ⁺X ^-

R wherein ¹Be C ₈-C ₂₂Alkyl, C ₈-C ₂₂Thiazolinyl, C ₈-C ₂₂Alkyl alkenyl amide base propyl group or C ₈-C ₂₂Alkoxyl group thiazolinyl ethyl, R ²Be C ₁-C ₂₂Alkyl, C ₂-C ₂₂Thiazolinyl or formula-A-(OA) _nThe group of-OH, R ³And R ⁴Be C ₁-C ₂₂Alkyl, C ₂-C ₂₁Thiazolinyl or formula-A-(OA) _nThe group of-OH, A are-C ₂H ₄-and/or-C ₃H ₆-and n be that 0 to 20 number and X are negatively charged ion.Enough acquisitions of discussing of such cats product are the compound of following formula, wherein R with preferred example ¹Be C _12/14Alkyl group, R ²Be formula-A-(OA) _nThe group of-OH, wherein A is-C ₂H ₄-and n be zero, and R ³And R ⁴All be-CH ₃(be C ₁Alkyl).Such cats product can be for example commercially available from Clariant with trade(brand)name Praepagen HY.

The both sexes that are fit to and the exemplary of zwitterionics are alkyl betaine, alkyl amido trimethyl-glycine, amine oxide, aminopropionate, amino glycinate, amphoteric imidazoline compound, alkyl dimethyl trimethyl-glycine or alkyl two polyethoxye trimethyl-glycines.

Optional ingredients

The composition of this paper can further contain various optional ingredients.A large amount of other compositions that can be used for detergent composition can be included in the composition of this paper, comprise other activeconstituents, carrier, hydrotropic agent, processing aid, dyestuff or pigment etc.

Carrier

Liquid detergent composition of the present invention can contain all kinds of SOLVENTS as carrier.With methyl alcohol, ethanol, propyl alcohol and Virahol is that the lower molecular weight uncle or the secondary alcohol of example is fit to.Other solid support material that is fit to is a glycol, for example propylene glycol, dipropylene glycol, tripropylene glycol, glycerine and have 200 to 5000 molecular weight polyethylene glycol (PEG).Described composition can contain 1wt% to 50wt%, typically contains 5wt% to 30wt%, preferably contains the examples of such carriers of 2wt% to 10wt%.

Detergent builder compound

Can suitably there be one or more detergent builder compounds in the liquid detergent composition of the present invention.But, do not use phosphate builders.Before described hydrogenated castor oil crystallization, when having the dissolved phosphorus hydrochlorate of high density in the solution, may not form described dendritic structure system in an identical manner.

When existing; the example of the organic detergent builder compound that is fit to comprises basic metal; ammonium and replacement ammonium polyacetic acid salt; carboxylate salt; the multi-carboxylate; many ethanoyl carboxylate salt (polyacetyl carboxylates); carboxyl methyl oxygen base succinate (carboxymethyloxysuccinates); carboxyl methyl oxygen propylmalonic acid salt (carboxymethyloxymalonates); quadrol-N, the N-disuccinate; polyepoxysuccinic acid salt (polyepoxysuccinates); oxydiacetate (oxydiacetates); Triethylenetetramine (TETA) six acetate; N-alkyl imido oxalic acid salt or dipropionate; α sulfo group-soap; dipicolinates; the polysaccharide of oxidation; polyhydroxy sulfonate and their mixture.

Concrete example comprises sodium, potassium, lithium, ammonium and substituted ammonium salt, tartrate monosuccinic acid salt (tartrate mono succinate) and the tartrate disuccinate of ethylenediamine tetraacetic acid (EDTA), nitrilotriacetic acid(NTA), oxygen base disuccinic acid (oxydisuccinic acid), melitic acid, benzene polycarboxylic acid and citric acid.

Antioxidant

Can preferably contain 0.005 antioxidant by the liquid detergent composition that the method according to this invention obtains to 2wt%.Preferably, described antioxidant exists with 0.01 to 0.08wt% concentration.

Antioxidant is Kirk-Othmer(Vol 3, pg424) with Uhlmans Encyclopedia(Vol 3, and pg91) the middle material of describing.Can be used for antioxidant of the present invention a type is the alkylated phenol with following general formula:

Figure 2009801468533100002DEST_PATH_IMAGE001

Wherein R is C ₁-C ₂₂Straight chain or branched-alkyl, the preferably C of methyl or branching ₃-C ₆Alkyl; C ₃-C ₆Alkoxyl group, preferred methoxyl group; R ₁Be C ₃-C ₆Branched-alkyl, the preferred tertiary butyl; X is 1 or 2.Hindered phenol compound is a kind of preferred type according to the alkylated phenol of this formula.Such a kind of preferred hindered phenol compound is 2,6-two-tertiary butyl hydroxytoluene (BHT).

The antioxidant that can be suitable for another type of the present invention is cumarone or the 1-benzopyran derivatives with following formula:

R wherein ¹And R ²Be alkyl or R independently of one another ¹And R ²Can form C together ₅-C ₆The cyclic hydrocarbon radical part; B does not exist or CH ₂R ⁴Be C ₁-C ₆Alkyl; R ⁵Be hydrogen or-C (O) R ³, R wherein ³Be hydrogen or C ₁-C ₁₉Alkyl; R ⁶Be C ₁-C ₆Alkyl; R ⁷Be hydrogen or C ₁-C ₆Alkyl; X is-CH ₂OH or-CH ₂A, wherein A is the phenyl of nitrogenous unit, phenyl or replacement.Preferred nitrogenous A unit comprises amino, pyrrolidyl, piperidino-(1-position only), morpholino, Piperazino and their mixture.

Also can use antioxidant for example tocopherol sorbic acid ester, butylated hydroxy-benzoic acid and their salt, gallic acid and its alkyl ester, uric acid and its salt and alkyl ester, Sorbic Acid and its salt and Dihydroxyfumaric acid and its salt.

Spices

Can preferably contain the perfume composition of the 0.001wt% of whole composition by the liquid detergent composition that the method according to this invention obtains, be preferably 0.01 to 2wt% of whole composition to 3wt%.Described perfume composition preferably contains the fragrance components that is selected from terpenes, ketone, aldehyde and their mixture of 0.01wt% at least based on described liquid composition.Described perfume composition can be made up of described fragrance components fully, but common described perfume composition is the complex fragrance mixture of various distinct fragrance agent types.In this, described perfume composition preferably contains 0.1wt% at least, 1.0wt% at least more preferably, the also more preferably described fragrance components of 5wt% at least.

Contain encapsulated spices such as perfume compound microcapsule to the described fragrance components of small part.Described perfume compound can all provide with this form.The preferred perfume compound microcapsule that adopt among the present invention are nuclear-shell microcapsule.Such as used in this article, term nuclear-shell microcapsule are meant capsule, wherein 40 ℃ basically or complete water-fast shell surround the nuclear (comprising any liquid vehicle that is used for it) that contains perfume compound or form by perfume compound.

A kind of nuclear of preferred type-shell perfume compound microcapsule are included in those disclosed among WO 2006/066654 A1.These contain to have and are dispersed in the nuclear of the about 5wt% of about 95wt% in the solid support material of about 50wt% to the perfume compound of about 50wt%.Solid fatty alcohol that this solid support material is preferably non-polymeric or fatty acid ester solid support material, or their mixture.Preferably, described ester or alcohol have about 100 to about 500 molecular weight and about 37 ℃ and arrive about 80 ℃ fusing point, and water insoluble basically.The nuclear that contains described perfume compound and described solid support material is covered by on their outside surface in the water-fast basically coating.In the context of the present invention, nuclear-shell microcapsule preferably have 0.01 to 200 micron, more preferably 1 to 100 micron d _4,3Average particle size particle size.US 5,154, disclose similar microcapsule in 842, and these are fit to also.

The microcapsule of describing among the US-A-5 066 419 have frangible coating, and it is the aminoplastics polymkeric substance preferably.Preferably, described coating is the amine and the reaction product that is selected from the aldehyde of formaldehyde, acetaldehyde, glutaraldehyde or their mixture that is selected from urea and trimeric cyanamide or their mixture.Preferably, described coating is a particulate 1 to 30wt%.

The nuclear of other kind-shell perfume compound microcapsule also are suitable for the present invention.The method of these other microcapsule of preparation perfume compound is included at the interface for example precipitation and deposited polymer (as disclosed among GB-A-751 600, US-A-3 341466 and the EP-A-385 534) in coacervate, and other for example interface condensation of polymerization route (disclosed as US-A-3 577 515, US-A-2003/0125222, US-A-6 020 066 and WO-A-03/101606).The microcapsule with carbamide resin wall are disclosed among US-A-6 797 670 and the US-A-6 586 107.

Other patent application that is particularly related to the use of carbamide nuclear-shell microcapsule in liquid, aqueous is WO-A-98/28396, WO02/074430, EP-A-1 244 768, US-A-2004/0071746 and US-A-2004/0142868.

Preferably, in the method for the invention at described cooling step d) afterwards perfume compound is added described composition.All perfume compound that add with the form of encapsulated perfume compound all must add in step e) after step d).

Detergency enzymes (detersive enzymes)

" detergency enzymes " used herein is meant any enzyme that has cleaning, decontamination or other beneficial effect in laundry applications.The enzyme that is fit to that can be used in the composition of the present invention comprises any suitable source for example proteolytic enzyme, amylase, lipase, cellulase, peroxidase and their mixture in vegetables, animal, bacterium, fungi and yeast source.The preferred selection influenced by various factors, for example pH activity, thermostability and to the stability of active bleach detergent, washing assistant etc.In this respect, for example bacteria protease and fungal cellulase of preferred bacterium and fungal enzyme.For various purposes, enzyme is comprised in the detergent composition of the present invention, comprise based on proteinic, based on sugar or based on the removal of the spot of tri-glyceride, prevent that flow dye from shifting and restore for fabric.

Usually with the level that " cleaning significant quantity " enough is provided enzyme is added in the detergent composition.Term " cleaning significant quantity " is meant that can produce cleaning, greasiness removal, dirt in processed substrate removes, brightens or vividness is improved any amount of effect (freshness improving effect).In fact, for the normal commercial operation, typical amount is by weight the highest about 50mg of every gram detergent composition, more typically is that 0.01mg is to 30mg.Rephrase the statement, composition of the present invention can typically contain 0.001 to 3wt%, is preferably 0.01 to 1wt% commercial enzyme preparation.

Proteolytic enzyme is usually to be enough to providing 0.005 to 0.1 Anson unit (AU) activity/gram composition levels to be present in this type of commercial formulation.Higher activity level may be an ideal in highly spissated detergent formulations.The suitable example of proteolytic enzyme is the subtilisin from the specific bacterial strain acquisition of Bacillus subtilus (B. subtilis) and Bacillus licheniformis (B. licheniformis).From bacillus ( Bacillis) bacterial strain obtain a kind of suitable proteolytic enzyme, it has maximum activity in the pH of whole 8-12 scope, by NovoZymes of Denmark with Esperase exploitation with sell.

Other proteolytic enzyme that is fit to comprises Alcalase and the Savinase Relase from Novozymes, and from International Bio-Synthetics, Inc., the Maxatase of The Netherlands.

Described composition can contain the enzyme of finding among the WO 01/00768 extraly.

The lipase that is fit to that is used for composition of the present invention comprises by those of the microorganisms of pseudomonas monoid, GB1 for example, disclosed Pseudomonas stutzeri (pseudomonas stutzeri) ATCC 19.154 in 372,034.A kind of fit closely lipase is the lipase that derives from wool shape detritus bacterium (Humicola lanuginosa) and can obtain from Novozymes with trade(brand)name Lipex.

Preferably, in the method for the invention at described cooling step d) afterwards enzyme is added in the described composition.

Suds suppressor (suds suppressors)

The compound that can reduce or suppress foam formation with being used to adds composition of the present invention.At US-A-4, in the what is called of describing in 489,455 and US-A-4,489,574 " high density cleaning method " and foam inhibition in the European washing machine of muzzle-loading may particularly important.

Many materials can be used as suds suppressor, and suds suppressor is well known to those skilled in the art.Referring to for example Kirk Othmer Encyclopedia of Chemical Technology, Third Edition, Volume 7,430-447 page or leaf (John Wiley ﹠amp; Sons, Inc., 1979).An interested especially class suds suppressor comprises unary fatty acid (monocarboxylic fatty acid) and their soluble salt.Referring to US-A-2,954,347.Described unary fatty acid and their salt as suds suppressor typically have 10 to about 24 carbon atoms, the preferably hydrocarbyl chain of 12 to 18 carbon atoms.The salt that is fit to comprises an alkali metal salt for example sodium, potassium and lithium salts, and ammonium and alkanol ammonium salt.The fatty acid mixt that use contains lauric acid, tetradecanoic acid, palmitinic acid, stearic acid, eicosanoic acid He docosoic has obtained the favourable bubble effect that presses down.The trade mark that such a kind of preferred lipid acid is Prifac 5908(Uniqema).

The detergent composition of this paper also can contain the nonsurfactant suds suppressor.These for example comprise: high-molecular-weight hydrocarbons is paraffin, fatty acid ester (for example fatty acid triglyceride), the fatty acid ester of monohydroxy-alcohol, aliphatics C for example ₁₈-C ₄₀Ketone (for example stearone) etc.

The nonsurfactant suds suppressor of preferred kind comprises the silicone suds suppressor.This kind comprises uses for example polydimethylsiloxane of organopolysiloxane oil, the dispersion of organopolysiloxane oil or resin and emulsion, and the combining of organopolysiloxane and silica dioxide granule, wherein said organopolysiloxane chemisorption or merge on silicon-dioxide.The silicone suds suppressor is well known in this area, and for example is disclosed in US-A-4, in 265,779.

For any detergent composition that will be used for automatic washing machine, foam should not be formed into their degree from the washing machine overflow.

When using, suds suppressor preferably exists with " foam inhibition amount "." foam inhibition amount " is meant that the makers-up of described composition can select the amount of this Foam Control, thereby it obtains abundant control foam to be used for the low foaming detergent for washing clothes of automatic washing machine.The composition of this paper will contain 0.1% to about 5% suds suppressor usually.

If wish highly foaming, can be with suds booster C for example ₁₀-C ₁₆Alkylolamide adds in the described composition, typically with the concentration of 1%-10%.Described C ₁₀-C ₁₄Monoethanolamine and diglycollic amide have illustrated a kind of typical types of this type of suds booster.If desired, can be typically with the concentration of 0.1%-2% with soluble magnesium salts MgCl for example ₂, MgSO ₄Deng adding, extra foam to be provided and to improve grease and remove performance.

Sequestrant

The liquid detergent composition of this paper can also randomly contain one or more iron, copper and/or manganese sequestrant.This type of sequestrant can be selected from the group of being made up of the fragrant chelating agent of aminocarboxylate, amino phosphonates do, multifunctional replacement and their mixture, all such as hereinafter definition.

If use, about 0.1wt% that these sequestrants will constitute the detergent composition of this paper usually arrives about 10wt%.More preferably, if use, described sequestrant will constitute about 0.1wt% of this based composition to about 3.0wt%.

Clay dirt removal/anti redeposition agent

Composition of the present invention can also randomly contain the amine of the water miscible ethoxylation with the removal of clay dirt and antiredeposition performance.Liquid detergent composition typically contains 0.01% to about 5% these reagent of having an appointment.

A kind of preferred decontamination and anti redeposition agent are the tetrens of ethoxylation.The amine of exemplary ethoxylation is at US-A-4, further described in 597,898.

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

Whitening agent

Any white dyes known in the art or other brightening agent or whitening agent can typically add in the liquid detergent composition of this paper to the level of about 1.2wt% with about 0.05wt%.Can be categorized as subclass with being used for commercial optical brighteners of the present invention, it is including but not necessarily limited to stilbene, pyrazoline, tonka bean camphor, carboxylic acid, methyne cyanines class (methinecyanines), dibenzothiophene-5,5-dioxide, azole, 5-and 6-unit ring heterocycle, and the derivative of other different types of reagent.The example of this type of whitening agent is disclosed in " The Production and Application of Fluorescent Brightening Agents ", M. Zahradnik, John Wiley ﹠amp; Sons publishes, among the New York (1982).

Fabric softener

Various washable (through-the-wash) fabric softener, US-A-4 particularly, 062,647 the montmorillonitic clay that can not feel (impalpable smectite clays) and other tenderizer clay known in the art can be randomly be used in the composition of the present invention to the level of about 10wt% with about 0.5wt% typically, so that the fabric softener benefit to be provided in clean fabric.The clay softening agent can with for example US-A-4, disclosed amine and cationic softening agent are used in combination in 375,416 and US-A-4,291,071.

Dye transfer inhibitor

Composition of the present invention can also comprise that one or more effectively suppress the material that dyestuff shifts to another part fabric from a fabric during cleaning course.Usually, this type of dye transfer inhibitor comprises multipolymer, manganese phthalocyanine, peroxidase and their mixture of polyvinyl pyrrolidone polymers, polyamines N-oxide polymer (polyamine N-oxide polymer), N-vinyl pyrrolidone and N-vinyl imidazole.If use, these reagent typically constitute about 0.01wt% of described composition to about 10wt%, and preferably about 0.01wt% is to about 5wt% and more preferably about 0.05 to about 2wt%.

SYNTHETIC OPTICAL WHITNER

Randomly, can contain SYNTHETIC OPTICAL WHITNER or bleach systems according to composition of the present invention.This SYNTHETIC OPTICAL WHITNER or bleach systems can for example be: (a) separately and/or with bleach-activating agent and/or transition-metal catalyst bonded peroxygen bleach thing class; (b) transition-metal catalyst in the composition that does not have peroxide thing class basically.

Develop the bleaching catalyst that is used for decontamination in recent years and can be used for the present invention.The example of operable transition metal bleach catalyzer for example is found among WO-01/48298, WO-00/60045, WO-02/48301, WO-00/29537 and the WO-00/12667.Described catalyzer or can be used as free ligand and provide, its original position forms complex compound.

Bleach-activating agent is also known by the people in this area.For peroxy bleaching compound, the definite binding mode of bleach-activating agent is unknown, but it is believed that the reaction by activator and inorganic peroxy compounds forms peracid, and this peracid discharges active oxygen by decomposing then.They normally contain N-acyl group or O-acyl residue in the molecule and apply the compound of their activation in washing lotion when contacting with peralcohol on described peralcohol.

The exemplary of the activator in these classifications is many acidylates Alkylenediamine, N for example, N, N ¹, N ¹-tetra acetyl ethylene diamine (TAED) and N, N, N ¹, N ¹-tetra-acetylated methylene diamine (TAMD); The glycoluril of acidylate, for example tetra-acetylated glycoluril (TAGU); Triacetyl cyanurate and sulfo group phenylethyl carbonic ether sodium (sodium sulphophenyl ethyl carbonic acid ester).

Peroxygen bleach is also known by the people in the art, for example peracid (for example PAP), perborate, percarbonate, peroxyhydrate (peroxyhydrate) and their mixture.Concrete preferred example comprises: Sodium peroxoborate (can with-and the form of four-hydrate is commercially available) and yellow soda ash peroxyhydrate (sodium carbonate peroxyhydrate).Other example and other transition-metal catalyst of hydroperoxide class and activator find in WO 02/077145.

In described composition, also preferably include the stablizer that is used for SYNTHETIC OPTICAL WHITNER or bleach systems, for example ethylenediamine tetramethylene phosphonic acid and diethylenetriamine pentamethylenophosphonic acid(DTPP) or other organic phospho acid that is fit to or their salt.These stablizers can use with the form of acid or salt, and it is calcium, magnesium, zinc or aluminium salt form.Described stablizer can preferably exist to the level of about 0.5wt% with about 0.1wt% with the most about 1wt%.

Since many SYNTHETIC OPTICAL WHITNER and bleach systems in aqueous liquid detergent unstable and/or with described composition in other component for example enzyme interact unfriendly; therefore they for example can be protected; for example by encapsulated or by the preparation structurized liquid composition, they suspend with solid form thus.

Also can use optical white, comprise singlet oxygen optical white (singlet oxygen photobleaches).

Embodiment

Following indefiniteness embodiment shows according to embodiment of the present invention.

Method

Use " X-test " to measure translucent material

The black of the about 1cm of printed dimensions intersection (X) on blank sheet of paper; 100 milliliters of flat graduated cylinders are placed on the described X; Liquid detergent composition is added described graduated cylinder up to no longer seeing described X; Height/the volume of the required preparation of described X is covered in measurement.

Measure the shearing curve (shear profiles) of structurized liquid

Anton Paar ASC is the automatization rheometer that is used for measuring liquid viscosity under different shearing conditions.It is equipped with the DSR301 measuring head, and has stainless steel cup and measure hammer (measuring bob) BCC27/TI(that it places the sample cup that contains 20-50ml sample washing composition) the CC27 of coaxial cylinders system be suitable for measuring the liquid washing agent shearing curve of (comprising structurized liquid).In order to measure required sample: treat that with 28g sample being measured fills described cup and be put in carousel/water-bath of 25 ℃.By pressing the program of bringing into operation, this will move described hammer the into shape in the sample, will implement there to measure and kept 5 minutes so that described sample reaches balance, and described instrument will be measured the viscosity that arrives the shear-stress material of 250Pa 0.01 then.Then, whether have the shear shinning curve, shearing curve and the typical curve of measuring compared in order to assess described detergent liquid.

The visually rank of the physical stability of detergent product

To place the sample in a week on the freeze-thaw cycle (3F/T circulation) to remove, and make it to reach room temperature, be separated and color change with respect to 5 ℃ of sample visually ranks of standard then from bunkerage.

To remove from bunkerage at the sample of 5 ℃ of storages, and make it to reach room temperature, assessment is separated then, implements this test after storing for 4,8 and 12 weeks.

To remove from bunkerage at the sample that room temperature (about 21 ℃) is stored, and make it to reach room temperature, then with respect to 5 ℃ of sample assessments of standard Xiang Fenli ﹠amp; Colour-change is implemented this test after storing for 4,8 and 12 weeks.

To remove from bunkerage at the sample of 37 ℃ of storages, and make it to reach room temperature, then with respect to 5 ℃ of sample assessments of standard Xiang Fenli ﹠amp; Colour-change is implemented this test after storing for 4,8 and 12 weeks.

To remove from bunkerage at the sample of 50 ℃ of storages, and make it to reach room temperature, then with respect to 5 ℃ of sample assessments of standard Xiang Fenli ﹠amp; Colour-change is implemented this test after storing for 4 weeks.

Measure viscosity

Can use (25 ℃) Haake VT500 of temperature control and be used for 106 s ^-1MV1 cup and the hammer of measuring (32g sample) and be used for 21s ^-1MV2 cup of measuring and hammer (48g sample) are measured the viscosity of sample.In order to implement to measure, described sample is put in the described cup, be placed on described cup on the instrument then and keep 1 minute to reach the temperature of wanting, start described instrument then and implements measurement after 30 seconds in stable reading.

Table 1: basic ingredient tabulation

Composition	Supplier	Explanation
			Water	United utility	Water
Glycerine	Univar	Solvent (hydrotropic agent)
			Propylene glycol	Dow	Solvent (hydrotropic agent)
Tinopal 5BM-GX	Ciba	White dyes (fluorescent agent)
			Hydrogenated castor oil	Thixcin R is from Elementis or HCO, from Hindustan Lever	Structural agent
NaOH	Univar	Alkali
			Trolamine	Univar	Alkali
Neodol 25-7	Shell	Nonionogenic tenside, alcohol ethoxylate C _12-157EO
			Citric acid	Albian Chemicals	Sequestrant
LAS acid	Uniliver, PortSunlight(GB) factory	Anion surfactant (linear alkylbenzene sulfonate)
			Coconut oil (Coco acid)	Croda	Anion surfactant
SLES 3EO	Uniliver, PortSunlight(GB) factory	Anion surfactant
			Prifac 5908	Uniqema	Saturated hydrogenation fatty acid distribution of coconut oil
Dequest 2066	Thermphos	Diethylenetriamine five (methylene phosphonic acid) sequestrant
			Savinase，Stainzyme	Novozymes	Enzyme, proteolytic enzyme and amylase
Enzyme stabilizers 4-FPBA	Novozymes	4-formalphenol boric acid

Embodiment 1

The method according to this invention preparation is according to following typical liquid detergent composition 1 of the present invention and 2.

Table 2: liquid detergent composition 1

Composition	Concentration (wt%)
		Synthetic anion surface active agent (linear alkylbenzene sulphonic acid)	12.8%
Nonionogenic tenside (Neodol 25-7, alcohol ethoxylate C _12-157EO is from Shell)	20.0%
		Sodium lauryl tri(oxyethyl) sulfate, 3EO	8.0%
Soap-coconut oil sodium	1.1%
		Trolamine	3.0%
Dyestuff/tinting material	0.003%
		White dyes (Tinopal 5BM-GX is from Ciba)	0.3%
Propylene glycol	1.2%
		Citric Acid, usp, Anhydrous Powder sodium	1.3%
Ethanol	1.0%
		Hydrogenated castor oil (Thixcin R is from Elementis)	0.2%
Encapsulated spices (1-100 micron)	0.6%
		Spices (absolute oil)	0.6%
Water	49.9%

The viscosity of said preparation is at 21s ^-1Be 250mPa.s, pH is 8.

At lay up period in differing temps by time assessment said composition 1(and following composition 2) stability, as shown in the table.In each measurement point the stability of liquid is carried out visually rank (seek wild effect such as creaming of emulsion, be separated), and measures shearing curve and pH, and with standard value relatively (with shearing curve and shear shinning curve ratio, and pH is preferably 7 to 9).

Table 3: the analytical results of liquid detergent composition 1

¹VA: visually rank

²SP: shearing curve

Table 4: liquid detergent composition 2

Composition	Concentration (wt%)
		Water	30.1
White dyes (Tinopal 5BM-GX)	0.1
		Glycerine	5.0
Single propylene glycol	9.0
		NaOH	2.7
Trolamine	3.2
		Trisodium Citrate	1.0
Anion surfactant (Neodol 25-7)	20.1
		Anion surfactant (LAS sodium)	13.4
Prifac 5908	4.8
		SLES 3EO	6.7
HCO is from Hindustan Lever	0.25
		Dequest 2066	0.5
Enzyme (proteolytic enzyme, amylase)	1.8
		Enzyme stabilizers 4-FPBA	0.1
Fragrance oil	1.3
		Dyestuff	0.001

The viscosity of said preparation is at 21s ^-1Be 250mPa.s, pH is a 8(scope 7 to 9).

Table 5: the analytical results of liquid detergent composition 2

¹VA: visually rank

²SP: shearing curve

These analyze demonstration, and the liquid detergent composition that contains the lower concentration hydrogenated castor oil according to the present invention presents satisfactory stability.

Obtain liquid detergent composition 1 by the method according to this invention in following mode:

Pre-composition 1

Under the stirring of 150rpm, use the cantilevered stirrer, join the 200g deionized water in 3 liters of beakers and be heated to 30 ℃.Then 1.47g Tinopal 5BM-GX and 50g glycerine, 90g propylene glycol and neutralization bases 57.5g sodium hydroxide and 31.5g trolamine are added in this solution together.Then, one after the other add 201g Neodol 25-7,128g linear alkyl benzene sulphonic acid and 20g citric acid fast, produce a large amount of neutralization heat and temperature is elevated to 65-70 ℃.The base temperature that keeps this 65-70 ℃ is up to adding pre-composition 2.

Pre-composition 2

Utilize the stirring of 100rpm and be heated to 70-75 ℃ 47g Prifac 5908 is dissolved in the independent 500ml beaker.Then, 2g hydrogenated castor oil (Thixcin R is from Elementis) is dissolved in this hot lipid acid.This pre-composition is stirred other 5-10 minute to guarantee dissolving fully and the mixing of described external structure agent (external structurant).When described pre-composition 2 solution complete when transparent this dissolving finish.

Main mixture (pre-composition 1+ pre-composition 2)

Now by with pre-composition 2(70-75 ℃) add 1(65-70 ℃ of pre-composition) in conjunction with described two kinds of pre-compositions, stirring is increased to 200rpm and described two kinds of pre-compositions was thoroughly mixed 10 minutes.Add sequestrant (Dequest 2066 of 16g) then, then add the 96g sodium lauryl tri(oxyethyl) sulfate, and before being cooled to 30 ℃, make it remix 10 minutes.Cooling is carried out in the following manner: through the naturally cooling of 2 hour time, perhaps can use plate-type heat exchanger to cool off main batch of material (main batch) as selecting, described main mixture is cooled to 30 ℃ being less than in 1 minute from 60-65 ℃, and it was kept 10 minutes at this low temperature.

Subsequently, add dyestuff (0.07g patent blue V 85 and 0.01g acid yellow 23), and 10.5g enzyme (proteolytic enzyme and amylase) and 10g perfume compound, and before amount discharge container, made it remix 10 minutes, and use paddle formula mixing tank to add the encapsulated perfume compound slurry of 15g.

Prepared liquid detergent composition by these methods, wherein said hydrogenated castor oil is with the form crystallization of dendrimers.Use opticmicroscope can observe this structure, and the diameter of described dendrimers is about 50 to about 100 microns.Utilize described " X-test ", during cooling described preparation become muddy and whole solution no longer transparent.Obtained required shear shinning curve and described encapsulated perfume compound is suspended equably.The test that ins all sorts of ways has the described liquid composition of the encapsulated perfume compound of suspension.After each test, measure shearing curve, to check any destruction that whether has described structurizing system.Also assess described preparation, whether exist with identification to be separated or whether described capsule remains monodispersed by naked eyes and microscopic visual measurement.5 ℃ of 12 weeks of test, 37 ℃ of 12 weeks of test with after 50 ℃ of 4 weeks of test, described composition does not present the forfeiture or the change of structurizing or capsules disperse.

Claims

1. be used to prepare the phosphate-free liquid detergent method for compositions, it may further comprise the steps:

B) thus described hydrogenated castor oil is dissolved in preparation second pre-composition in the described liquid non aqueous organic solvent by under agitation hydrogenated castor oil being added at least 70 ℃ temperature in the liquid non aqueous organic solvent;

D) mixture with step c) is cooled to be lower than 50 ℃ temperature, and store subsequently this mixture up to described hydrogenated castor oil from solution crystallization and

E) under mixing, will have then in the liquid of encapsulated spices adding from the refrigerative external structureization of step d) of the highest 200 microns particle size.

2. according to the process of claim 1 wherein in step d) the described mixture of step c) is cooled to be lower than 50 ℃ temperature with maximum 1 ℃/minute rate of cooling.

3. according to the method for claim 2, wherein in step d) with the described mixture of step c) with maximum 1 ℃/minute, preferred maximum 0.5 ℃/minute rate of cooling is cooled to be lower than 40 ℃, preferred 30 ℃ temperature.

According to the process of claim 1 wherein in step d) described mixture with step c) at 5 minutes internal cooling to the temperature that is lower than 40 ℃, then this mixture was stored 5 minutes in the temperature that is lower than 40 ℃ at least.

5. according to the method for claim 4, wherein in step d) with the described mixture of step c) in 5 minutes, preferably at 3 minutes internal cooling to the temperature that is lower than 30 ℃, then this mixture was stored 5 minutes in the temperature that is lower than 30 ℃ at least.

6. the method any according to claim 1 to 5, wherein temperature described in the step a) is 55 to 70 ℃, temperature described in the step b) is 70 to 75 ℃ and is 55 to 70 ℃ in temperature described in the step c), is preferably 55 to 65 ℃.

7. the method any according to claim 1 to 6, wherein said encapsulated spices has 0.01 to 100 micron average particle size particle size.

8. the method any according to claim 1 to 7, surfactant concentrations is 20 to 65wt% in wherein said first pre-composition.

9. the method any, wherein b by weight according to claim 1 to 8) be that 1:30 is to 1:15 than a) ratio.

10. the method any according to claim 1 to 9, wherein the described solvent in the step b) comprises free fatty acids or nonionogenic tenside or their mixture.

11. according to the method for claim 10, wherein said solvent is a free fatty acids.

12. the method any according to claim 1 to 10, the concentration of hydrogenated castor oil is the 1.5-20wt% of described pre-composition in wherein said second pre-composition.

13. can be by the liquid detergent composition that obtains according to any one method of claim 1 to 12, wherein said hydrogenated castor oil exists with 0.15 to 0.5wt% concentration of whole composition, and has that fiber wherein twines and the reduced size of described fiber is the dendritic structure of 40nm at the most.

14. according to the liquid detergent composition of claim 13, wherein total surfactant concentration is 20 to 65wt% of a whole composition.