CN1367820A - Process for preparing granular detergent compositions - Google Patents

Abstract

A process for the preparation of medium to low bulk density granular detergent compositions in which a liquid binder is contacted with a solid starting material in a high-speed mixer and the resulting mixture treated in a medium- or low-speed mixer and finally in a gas fluidisation granulator, where more liquid binder is added.

Description

The method for preparing granular detergent composition

Invention field

The present invention relates in a kind of preparation to the method for the granular detergent composition of low bulk density.More particularly; the present invention refers to such method: liquid adhesive is contacted in high-speed mixer with solid raw material; then the mixture that produces is handled in middling speed or low speed mixer; in gas fluidized granulator, handle at last, in gas fluidized granulator, add more liquid adhesive.

Background of invention

Recently, in detergent industry, the existing sizable interest exploitation of people has the production method of the granulating detergent powder of specific tap density.Usually, can produce detergent composition, in the method, each component of composition be mixed the formation hydrous slurry with water, then the hydrous slurry spraying be entered in the tower, contact with warm air to remove and anhydrate by spray-drying process.The spray-dried powders that produces is highly porous, and generally has the tap density of 300-550g/l.

Spray-dired powder has good powder transmission characteristic usually, as distributing and dissolving.Yet, the initial cost of spray-drying process and productive expense height.Yet, also have very big consumers demand for this low-density powder.

Only being difficult to tap density with powder by spraying drying is increased to and is much higher than 600g/l, and the while does not produce detrimental action to the performance of detergent composition, for example can add high-load sodium sulfate to improve tap density in slip, still this composition can not help decontamination.Therefore, the handiness of sizable tap density can only realize by using additional " back tower " operation to increase powder density.

In recent years, for main use mechanically mixing rather than use spray-dired method to produce Betengent product, caused the interest that people are very big.In these class methods, various component dry mixing mix, and optional and liquid adhesive granulating.The liquid adhesive that generally is used for this granulation process is acidic precursor, nonionogenic tenside or its any mixture of anion surfactant, anion surfactant.Use these granulation process, the granulated detergent product of having produced has very high-bulk-density, generally greater than 700 or 800g/l.

The granulated product of high-bulk-density has lower packaging volume, and this helps storing and batch operation, also helps the human consumer.And if do not use the spraying drying step, initial cost and productive expense are generally much lower, and this method consumption energy still less, thereby have environmental benefit.

Yet this high density product generally has the porosity more much lower than traditional spray-dried powders, and this may harm the transmission of product to washings.For example, the concentrated powder of high-bulk-density may dissolve in washings slowly and/or not exclusively, cause undissolved product residue on the fabric of washing.More particularly, there is such problem in the known concentrated powder that contains zeolite: the undissolved powder that contains zeolite can be stayed in the fabric fibre.This white dot that demonstrates itself is high-visible, and not pleasing.

People have made great efforts to use the hybrid system that does not have the spraying drying step to produce material than low bulk density.Yet these method inclinations are in using unconventional detergent ingredients as, burkeite for example, and it is expensive, has therefore increased the cost of product.

Therefore, to the method for the granulated product of low bulk density, for example, its tap density was less than about 900g/l, for example less than 800g/l, preferably less than 750g/l during detergent industry was being sought always and do not needed the spraying drying step to produce to have.To the method for the powder that contains zeolite of low bulk density, this method should not used the spraying drying step, uses traditional initial composition, and produces the product with good powder property in particularly needing to produce.

Prior art

Up to date, people are for low shear mixer/granulator, and are also less as the applied research of gas fluidized granulator.

WO98/58046, WO98/58047, WO98/58048 and WO99/00475 (Unilever) relate to the low granulation process of shearing, and wherein, liquid adhesive are sprayed on the fluidized particles material, preferably carry out in gas fluidized granulator.They have described how the granulated processing parameter of pilot-gas fluidisation is to obtain desirable powder property, for example size-grade distribution, tap density, flowability, and even obtain desirable productive rate to a certain extent.

The low granulating technology of shearing is easy to obtain having the more powder of low bulk density, for example generally is lower than 650g/l.For the tap density greater flexibility is provided, WO97/22685 (Unilever) discloses a kind of method, this method is before low shearing granulating step, the part granulating in high speed or middling speed mixing machine with particle starting material and liquid adhesive, for example in fluidized-bed, add liquid adhesive again and finish granulating.

WO98/58046, WO98/58047, WO98/58048 and WO99/00475 (Unilever) also disclose the use of part granulating step in advance, and as the description of WO97/22685 (Unilever), this is for the tap density greater flexibility is provided.Yet mixing/granulating step of using more than one is not all described or illustrated to these reference clearly before gas fluidized granulating step.

WO98/14551, WO98/14552, WO98/14553, WO98/14556, WO98/14557 and WO98/14558 (Procter and Gamble) all relate to the non-tower method of preparation high-bulk-density granular detergent composition.In first mixing machine, under the operational condition that limits, with tensio-active agent, be that the fine powder of 0.1-500 micron disperses preferably with mashed prod or liquid form and diameter, the further agglomeration of the agglomerate that in one or more mixing steps, will form so then, its condition limits, at last in fluidized-bed, granulating under given conditions.Between the granulation of the nodulizing of mixing machine and fluidized-bed, there is tangible difference.Term " granulating " is defined as free-pouring in order to produce, round granulating agglomerate and fluidisation agglomeration fully.Therefore, though can carry out the growth of agglomerate in fluidized-bed, for example by the bag quilt, these examples point out that clearly the agglomerate that has formed will agglomeration can not take place.

EP 264,049 (Bayer) has described a kind of organic substance that is used for, the granulated continuation method of the growth of preferred coloring agent.This method comprises: in high-speed mixer with pulverulent material with granulating liquid granulating, further granulating in the middling speed mixing machine preferably adds granulating liquid once more, desciccate in fluidized-bed sprays shaping assistant simultaneously then.In last step, material is preferably dry in first part of fluidized-bed, sprays " shaping assistant ", for example sugar soln then in another part of drying installation.In other words, the exsiccant material is as carrier, and shaping assistant may be adsorbed on the carrier with the form of dressing.In EP 264,049, do not point out in fluidized-bed, reagglomeration to take place.

WO99/03964, WO99/03966 and WO99/03967 (Procter ﹠amp; Gamble) described a kind of method that is used to produce the detergent powder with 300-550g/l tap density, this method comprises: in first high-speed mixer, with anion surfactant mashed prod or its acidic precursor with the agglomeration of exsiccant starting material; In second high-speed mixer, detergent agglomerate is mixed, with the agglomerate that obtains to increase; Then, in fluid-bed drier, that the agglomerate that increases is with further agglomeration of tackiness agent, and dry in fluid-bed drier.Disclose by the nozzle height in the stoke exponential sum control fluidized-bed agglomeration step in the control fluidized-bed agglomeration step or controlled the granularity of all these three steps, obtained low bulk density.

We find, the method that is used for producing low bulk density powder described in the prior relates to mechanically mixing and gas is fluidized to being used in combination of a step, and there is such problem in these methods: the fraction of particle in the product powder is far from optimal values.For example, at WO99/03964, WO99/03966 and WO99/03967 (Procter ﹠amp; Gamble) method described in generates 14% particulate (being defined as those particles less than 150 microns) in product.In fact, like the preferred characteristics of these inventions well than higher fraction of particle.Particulate with appropriate size can be used as the starting material of present method, therefore is recycled and gets back to first high-speed mixer.

Be surprisingly, we have found that, can in the method that may further comprise the steps, produce to low bulk density and powder with powder property of improvement in having: in high-speed mixer, liquid adhesive is contacted with the particle starting material and mix; Subsequently, in middling speed or low speed mixer, mix; At last, in gas fluidized granulator, mix with more liquid adhesive.More particularly, compare, obtained significantly lower fraction of particle with the method for prior art.And the powder that the powder that this method produces is produced than prior art has better flowability.

The definition of invention

Aspect first, the invention provides a kind of method that is used to prepare the granulated detergent product, this method may further comprise the steps:

(i) in high-speed mixer, liquid adhesive is mixed with solid raw material and agglomeration;

(ii) in middling speed or low speed mixer, with the mixture mixing of step (i) gained;

(iii) with step (ii) the mixture and the liquid adhesive of gained be fed in the gas fluidized granulator, and further agglomeration and

(iv) choose wantonly and carry out drying and/or cooling.

Aspect second of the present invention, the granulated detergent product that provides a kind of the method according to this invention to obtain, its tap density that has is less than 900g/l.

Detailed Description Of The Invention

Definition

Below, in the context of the present invention, term " granulated detergent product " comprises the granular finished product of sale, and the granular component or the additive that are used to form finished product, for example by forming to batching thereafter or forming with batching thereafter, perhaps any other the form of mixtures that forms with more component or additive.Thereby Ding Yi granulated detergent product can contain or not contain detergent active material here, as synthetic tensio-active agent and/or soap.Minimum requirements is, it should contain the general type material of at least a granulated detergent product traditional components, as tensio-active agent (comprising soap), washing assistant, SYNTHETIC OPTICAL WHITNER or bleach system component, enzyme, enzyme stabilizers or enzyme stabilising system component, dirt anti redeposition agent, white dyes or optical whitening agent, sanitas, defoamer, spices or tinting material.

Yet in a preferred embodiment of the invention, the granulated detergent product contains detergent active material, and as synthetic tensio-active agent and/or soap, its content is at least 5 weight % of this product, preferably at least 10 weight %.

The term of Shi Yonging " powder " is meant the material of being made up of single-material particle and this particulate mixture basically hereinafter.The term of Shi Yonging " particle " referred to agglomeration more short grained small-particle, for example agglomerant powder particle hereinafter.According to the finished product of the inventive method granulometric composition, or contain the particle of high per-cent by high per-cent.Yet, can choose wantonly in this product of preparing burden behind the other granular and/or powdered material.

According to the present invention, " particulate " is defined as diameter less than 180 microns particle.

According to the present invention, " coarse grain " material is defined as diameter greater than those particles of 1400 microns.

Can use the screening analytical method to measure particulate and coarse grained content.

For purposes of the present invention, the flowability of granulated product defines according to dynamic flow (DFR), is unit with ml/s, measures with following step.With an internal diameter is that 35mm, length are that the cylindrical glass tube of 600mm clamps firmly, and its longitudinal axis is in vertical position.Its lower end is 15 ° with the cone end-blocking of a polyvinyl chloride, cone interior angle, and the diameter of its lower end outlet is 22.5mm.First beam sensor is positioned at 150mm place, outlet top, and second beam sensor is positioned at first 250mm place, transmitter top.

In order to measure dynamic flow, described outlet is temporarily sealed, and load described cylinder to about 10cm place more than the transmitter of top with the granulated detergent product.Open outlet, and the electronic measurement powder level is fallen the used flowing time t (second) of transmitter of below from the transmitter of top.Repeat 2 or 3 times, and get its mean time.If V is the pipe volume (ml) between two transmitters up and down, DFR is V/t so.

Use Froude number (Fr) to estimate the relative influence of gravity and centrifugal force on the particle that puts in the concrete mixing device.The used Froude number of the present invention is defined as:

Fr＝ω ²d/2g

Wherein, the rotating speed of ω=agitator [rad/s]

The diameter of d=agitator [m]

G=universal gravity constant [m/s ²]

Except as otherwise noted, these values are relevant with powder property, as tap density, DFR, water content or the like, and also relevant with aged granulated detergent product.

Method

Method of the present invention is undertaken by using high-speed mixer, middling speed or low speed mixer and gas to be fluidized to a machine.

High speed and middling speed or low speed mixer:

Step (i) and (ii)

No matter be used for the mixing machine of the inventive method and be at a high speed, middling speed or low speed, all forms basically by the stationary cylinder or the bowl of hollow, preferred horizontal, rotating shaft is equipped with in its centre, and several accessories has been installed in the rotating shaft.

Annex on the high-speed mixing arbor should provide fully solid to be mixed in this step and liquid, the mixing effect of high energy.In this respect, this annex can be for example shaft-like, shovel shape or combined shaped, or any as known for those skilled in the art other unitized construction of suitable design.

The high-speed mixer that is fit to is any one in the commercially available various mixing machines, for example those that obtain from L dige, Schugi and Drais.Particularly preferred machine comprises L dige (trade mark) CB recirculation machine and Drais (trade mark) K-TTP.

The example that middling speed or low speed mixer are fit to is L dige (trade mark) KM mixing machine, is also referred to as L dige Ploughshare.This device is equipped with various plow-shape annexes on its axle.Choosing wantonly to use one or more high speed scissors tools to prevent to form excessive or caked material.Another machine that is fit to that is applicable to this step is Drais (trade mark) K-T for example.

The minimum tip speed of high-speed mixer annex preferably is at least 5m/s, more preferably is at least 10m/s, most preferably 15m/s at least.The maximum value of tip speed preferably is not more than 60m/s, more preferably no more than 55m/s, yet more preferably no more than 50m/s, most preferably is not more than 45m/s.

High-speed mixer preferably turns round under the Froude number of minimum, and its minimum Froude number is at least 5, more preferably is at least 20, yet more preferably is at least 40, and most preferably is at least 50.The maximum value of Froude number preferably is not more than 750, more preferably no more than 500, and more preferably no more than 400.

The tip speed maximum value of middling speed or low speed mixer annex is more preferably less than 10m/s preferably less than 15m/s, yet is more preferably less than 8m/s, and most preferably less than 6m/s.The minimum value of tip speed preferably is at least 1m/s, more preferably is at least 1.5m/s, and most preferably is at least 2m/s.

Middling speed or low speed mixer preferably in the maximum value of Froude number less than 30, be more preferably less than 15, yet be more preferably less than 5, and most preferably less than 4 times runnings.The minimum value of Froude number preferably is at least 0.15, more preferably is at least 0.30, yet more preferably is at least 0.50, and most preferably is at least 0.60.

Should be pointed out that no matter be for high-speed mixer or middling speed or low speed mixer herein, when specifying any particularly preferred tip speed or Froude number scope, concrete tip speed maximum value and any concrete tip speed minimum value are that it doesn't matter.Similarly, also it doesn't matter for concrete Froude number maximum value and any concrete Froude number minimum value.

In the method for the invention, the essential distinction between middling speed or low speed mixer and the high-speed mixer is, middling speed or low speed mixer move under lower tip speed and/or lower Froude number, preferably move under the lower situation of both.

The rotating shaft rotating speed that annex has been installed on it depends on the specification of used mixing machine to a great extent.For example, high speed L dige CB 100 machines preferably have the axle rotating speed be 100-1100rpm, more preferably 200-750rpm.Similarly, the axle rotating speed that middling speed L dige KM 10000 machines preferably have is 20-200rpm, more preferably 25-120rpm, yet more preferably 30-100rpm, most preferably 30-70rpm.Under other mixing machine specification, adjust preferred rotating speed so as to keep the tip speed of annex and Froude number in the above preferable range that provides.

Except that the stirring effect of annex, middling speed or low speed mixer can mounting cutters, and the driving of cutter can be independent of axle and annex.These cutters can be used for preventing to form caked or excessive material.If use these cutters, preferably the speed with 200-3000rpm turns round, more preferably 2000-3000rpm.

During the steady-state operation, the residence time in mixing machine is depended on Several Parameters, comprises rotating speed, through-put, the position amount of annex and the weir plate in exit of axle.The residence time in the high-speed mixer should be shorter relatively, is preferably about 1-60 second, more preferably 5-30 second, yet more preferably 5-20 second.The residence time in middling speed or the low speed mixer usually should be longer than the residence time in the high-speed mixer.Be preferably about 30 seconds to 10 minutes, more preferably 30 seconds to 5 minutes, most preferably 30 seconds to 3 minutes.

Machine or high-speed mixer or middling speed or low speed mixer that other that can use in the method for the invention is fit to comprise mixing machine Fukae ^RFS-G series; Diosna ^RV series, German Dierks ﹠amp; Sohne produces; Pharma Matrix ^R, Britain T.K.Fielder Ltd produces; Fuji ^RVG-C series, Japanese Fuji Sangyo Co. produces; Roto ^R, Italian Zanchetta ﹠amp; Co.srl produces and Schugi ^RThe Flexomix granulator.

Can be by means of any suitable equipment, heating/cooling jacket for example raises and/or reduces at a high speed and the temperature in middling speed or the low speed mixer.

Technological process in this mixing machine can intermittently or be carried out continuously, yet preferably carries out continuously.

Gas fluidized granulator: step (iii)

The 3rd step of the inventive method used a kind of gas fluidized granulator.In this device, gas (normally air) is blown over the main body of particulate solids, in this particulate solids main body or be sprayed with liquid ingredient on it.Sometimes gas fluidized granulator is called " fluidized-bed " granulator or mixing machine.But strictly speaking this and imprecise because this mixing machine can operate with very high gas flow rate, to such an extent as to do not form traditional " bubbling " fluidized-bed.

Preferably, the carrying out of gas fluidized granulating and agglomeration processes as described in WO98/58046 and the WO98/58047 (Unilever), its content is hereby incorporated by basically.

Gas fluidized device mainly comprises a chamber, gas stream wherein (hereinafter referred to as fluidizing agent), normally air be used for producing solid particulate turbulent flow, to form " cloud and mist " of solid particulate, be sprayed onto liquid adhesive on the cloud and mist then or be sprayed onto in the cloud and mist, so that liquid adhesive contacts with individual particle.When this process was carried out, because the effect of liquid adhesive, the individual particle of solid raw material began agglomeration, formed particle.

The general operational requirement(GOR) of gas fluidized granulator is: the top layer air velocity is about 0.1-1.2ms ^-1, under the plus or minus relative pressure, air inlet temperature (being the fluidizing agent temperature) for-10 ℃ or 5 ℃ up to 100 ℃.Sometimes can be up to 200 ℃.

As the description among the WO98/58048, in the granulating process, can change the fluidizing agent temperature, thereby preferably change bed temperature.For the fs, this temperature can raise, for example up to 100 ℃ or even up to 200 ℃, then one or more other stages (before or after), can only be reduced to and be higher than, be equal to or less than room temperature, for example 30 ℃ or lower, preferred 25 ℃ or lower, or even low to 5 ℃ or lower, or-10 ℃ or lower.

In a preferred embodiment, for the fs, rising fluidizing agent temperature, and the bed temperature that preferably also raises reduce in subordinate phase subsequently.

When this method periodical operation, temperature changes in time.If during operate continuously, temperature will change along " path " of granulating lathe (promptly along the direction of flow of powder) by the granulating lathe.Under latter event, use the granulator handled easily of " plug flow " type, promptly material flows through the type of reactor therein from start to finish.

In intermittent process, the fluidizing agent temperature can reduce in one short relatively period, for example the process period of 10-50%.Usually, gas temperature can reduce at 0.5-15 minute.In successive processes, gas temperature can reduce along one section of granulating lathe " path " short relatively distance, for example along the path of 10-50%.In both cases, gas can be pre-cooled.

Preferably, the agglomeration up to having finished the granulated solid materials of fluidisation basically just reduces the fluidizing agent temperature, and preferably also reduces bed temperature at this moment.

Except that fluidizing agent, gas fluidized granulator also can use a kind of atomization air flow.Auxiliary with this atomization air flow with on liquid adhesive is from the nozzle atomization to the fluidization solid particle or enter in the fluidization solid particle.If the use atomization air flow is operated under the pressure of 2-5bar usually.Atomization air flow is air normally, also can heat.

In a preferred embodiment, but bed temperature is maintained approximately or take out temperature (as hereinafter definition) near the pump of liquid adhesive, at least the part-time that is sprayed onto the process on the fluidization solid particle at liquid adhesive is kept this temperature, preferably keeps this temperature in whole process basically.When liquid adhesive is structurizing mixture (as mentioned below), preferably so do especially.

Perhaps can be preferred, in rising fluidizing agent temperature and the atomizing gas temperature one and preferred two, to reach within 15 ℃ of the pumpable temperature of liquid adhesive (more or less), within preferred 10 ℃, particularly when this liquid adhesive is the structurizing mixture.During being sprayed onto the liquid adhesive agent composition on the fluidisation material, part-time elevated temperature that at least should be therein is preferably basically at whole process elevated temperature.

In a preferred embodiment, in rising fluidizing agent temperature and the atomizing gas temperature one and preferred two, to reach the pumpable temperature of liquid adhesive at least, particularly when this liquid adhesive is the structurizing mixture.

Terminology used here " bed temperature " refers to the fluidizing agent temperature around the solid particle material.For example, can use thermocouple probe to measure bed temperature.Have discernible powder bed or do not have discernible powder bed no matter be (promptly because the gas flow rate of mixing machine operation is too high, so that do not form traditional " bubbling " fluidized-bed), " bed temperature " should be the temperature of being surveyed on the point of the about 15cm of gas distribution plate in fluidising chamber.

Gas fluidized granulator can be chosen any type that vibrating bed is housed wantonly, especially for the type of continuous mode.

Drying and/or cooling: step (iv)

For using, handle and storing, the granulated detergent product must be in free-flowing.Therefore, in the step in the end, if necessary can be with particle drying and/or cooling.This step can be carried out in any known manner, and for example in fluidizer (dry and cooling), or in air lift (cooling).By changing employed processing condition, just can in the used same fluidizer of last agglomeration step, carry out drying and/or cooling, simply as known to those skilled in the art.For example, after finishing the interpolation liquid adhesive, rheomorphism can be continued for some time, and can reduce the gas feed temperature.

In a preferred embodiment, whole process is a successive.

Liquid adhesive

In the method for the invention, add liquid adhesive in step (i) with (iii).Also can add liquid adhesive in (ii), but preferably add small amount of liquid or do not add in the step of this method.If liquid adhesive adds in (ii) in step, preferably step (ii) in 10 weight % of the liquid adhesive total amount that adds in less than this method of the liquid adhesive dosage of adding, preferably less than 5 weight %.

The liquid adhesive that adds in each step can be identical or different, can add more than a kind of liquid adhesive in any one step.

The binder wt ratio that the tackiness agent that adds in the step (i) and step add in (iii) is preferably 20: 1-1: 20, preferred 10: 1-1: 10, more preferably 9: 1-1: 2.Preferably the liquid adhesive that adds in step (i) and (iii) is at least 5 weight % of total amount, more preferably at least 10 weight % be step (iii) in adding.

Usually, for identical processing condition, the weight ratio of the liquid adhesive that step (i) and step add in (iii) is high more, and the tap density of generation is high more.Therefore, by changing the ratio that tackiness agent adds, can change and control the tap density of granulated detergent product to a certain extent.

Can simply liquid adhesive be pumped into the mixing machine of step (i), and optional pump into step mixing machine (ii), perhaps can be used as spraying and introducing.The liquid adhesive spraying is entered step gas fluidized granulator (iii).

Liquid adhesive can contain one or more components of granulated detergent product.The liquid ingredient that is fit to comprises anion surfactant and acidic precursor, nonionogenic tenside, lipid acid, water and organic solvent.

Liquid adhesive can also contain and is dissolved in or is dispersed in solid ingredient in the liquid ingredient, for example inorganic neutralizing agent and washing assistant.Unique restriction is, no matter be with or without dissolved or dispersed solids, but liquid adhesive all should take out by pump, and can comprise the pasty state form with liquid form, be sent in mixing machine and/or the granulator.

Preferably, liquid adhesive comprises anion surfactant.The content of anion surfactant can be high as much as possible in the liquid adhesive, for example is at least 98 weight % of liquid adhesive, perhaps can be less than 75 weight %, is less than 50 weight % or is less than 25 weight %.Certainly, it can account for 5 weight % or still less, does not perhaps exist fully.

The anion surfactant that is fit to is known in those skilled in the art.The example that is suitable for adding this liquid adhesive comprises that alkylbenzene sulfonate particularly has C ₈-C ₁₅The linear alkylbenzene sulfonate of alkyl chain length; Primary and secondary alkyl-sulphate, particularly C ₁₂-C ₁₅Primary alkyl sulphates; Sulfated alkyl ether; Alkene sulfonate; Alkylxylene sulfonate; The dialkyl sulfosuccinate succinate; And fatty sulfonate.Common particular certain cancers.

Very preferably, in this liquid adhesive, form the part or all of of any anion surfactant on the spot by suitable acidic precursor and alkaline material such as for example NaOH reaction of alkali metal hydroxide.Because the latter must prepare burden as the aqueous solution usually, so bring some water inevitably into.In addition, the reaction of alkali metal hydroxide and acidic precursor also generates water byproduct.

Yet in principle, any alkaline inorganic material may be used to neutralizing effect, but preferably water dissolubility alkaline inorganic material.Another kind of preferred feed is a yellow soda ash, and it uses separately, or with one or more other water miscible inorganic materials, for example sodium bicarbonate or silicate are used in combination.If wish, can use the excessive neutralizing agent of stoichiometry to guarantee that neutralization fully, maybe can provide another function, for example as washing assistant, if for example neutralizing agent comprises yellow soda ash.Also can use organic neutralizer.

Certainly; if liquid adhesive contains the acidic precursor of anion surfactant; can the acidic precursor in mixing machine and/or the granulator be neutralized on the spot or neutralization fully by contacting with the solid alkaline material or in mixing machine and/or granulator, adding independent liquid neutralizing agent.Yet the neutralizing effect in mixing machine and/or granulator is not a preferred feature of the present invention.

The liquid acidic precursor can be selected from: linear alkylbenzene sulphur (LAS) acids, alhpa olefin sulfonic acid class, inner olefin sulfonic acid class, fatty acid ester sulfonic acid class and composition thereof.For passing through corresponding alkyl benzene sulphonate (ABS), for example the composition that contains alkyl benzene sulphonate (ABS) with production is reacted in the Dobanoic acid of Shell product, and method of the present invention is particularly useful.Also can use straight or branched primary alkyl sulphates (PAS) with 10-15 carbon atom.

In a preferred embodiment, liquid adhesive contains anion surfactant and nonionogenic tenside.The weight ratio of anion surfactant and nonionogenic tenside is 10: 1-1: 15, be preferably 10: 1-1: 10, more preferably 10: 1-1: 5.If liquid adhesive contains the acidic precursor and the nonionogenic tenside of at least some anion surfactants, anion surfactant comprises that the weight ratio of its acidic precursor and nonionogenic tenside can be higher, for example 15: 1 so.

The non-ionic surfactant component of liquid adhesive can be any or multiple liquid nonionic surfactants, and it is selected from: the primary and secondary alcohol ethoxylate, particularly every mol of alcohol is with the C of average 1-20 moles of ethylene oxide ethoxylation ₈-C ₂₀Fatty alcohol, more especially every mol of alcohol is with the C of average 1-10 moles of ethylene oxide ethoxylation ₁₀-C ₁₅The primary and secondary fatty alcohol.The ionic surfactant pack of non-ethoxylatedization is drawn together alkyl polyglycoside, glycerol monoethers and polyhydroxy amides (glucamide).

In a preferred embodiment, liquid adhesive is anhydrous basically.Just, wherein the total amount of water is no more than 20 weight % of liquid adhesive, preferably is no more than 15 weight %, and more preferably no more than 10 weight %.Yet if wish, the water that can add manipulated variable is beneficial to neutralization.Usually, the water yield of adding can be the 0.5-2 weight % of final Betengent product.Usually, the 3-4 weight % of liquid adhesive can be the water as byproduct of reaction, and the water of all the other existence will be the solvent of dissolving alkaline material.Very preferably liquid adhesive is except the water of mentioning later, and is anhydrous fully, unless may be trace/impurity.

Additionally, can use liquid, aqueous tackiness agent.This is particularly suitable for making the product as additive, these additives subsequently with other component fusion to form the Betengent product be made into fully.Usually, this additive mainly is made up of a kind of or a few component that is used in usually in the detergent composition except containing the component that is produced by liquid adhesive, and for example tensio-active agent or washing assistant are as zeolite or tripoly phosphate sodium STPP.Yet this does not get rid of the granulating of the product that liquid, aqueous tackiness agent is used for being made into fully basically.In a word, typical liquid, aqueous tackiness agent comprises aqueous solution, water-soluble acrylic/toxilic acid polymkeric substance (for example Sokalan CP5) of alkalimetal silicate etc.

This liquid adhesive can be chosen wantonly and contain the dissolved solid and/or be dispersed in wherein fine particle solid.Unique restriction is, no matter be with or without dissolved or dispersed solids, but liquid adhesive all should take out by pump, and at 50 ℃ or higher temperature or be at least 60 ℃ or higher, for example it can be sprayed under 75 ℃.Preferred it be lower than 50 ℃, preferably at 25 ℃ or be solid when lower.Preferably at least 50 ℃, more preferably under at least 60 ℃ the temperature liquid adhesive is sent into mixing machine or gas fluidized granulator.

According to the present invention, if at 50s ^-1Shearing rate and pump take out that the viscosity of liquid adhesive is not more than 1Pa.s under the temperature, think that then the easy pump of liquid adhesive takes out.Have more full-bodied liquid adhesive and still can take out by pump in principle, but at 50s ^-1Shearing rate under viscosity upper limit 1Pa.s be in order to represent that easy pump takes out.

For example, can use Haake VT500 rotary viscosity measuring viscosity.Viscosity measurement can followingly be carried out.A SV2P measuring sensor is connected in the water bath with thermostatic control with refrigerating unit.The float of measuring sensor is with 50s ^-1Shearing rate rotation.Curing mixture is heated to 95 ℃ in microwave, and pours in the sample cup.98 ℃ of down conditionings after 5 minutes, sample is with the speed cooling of per minute+/-1 ℃.Observed temperature note was done " pump is taken out temperature " when viscosity was 1Pa.s.

Therefore, " pump is taken out temperature " of this liquid adhesive is defined as this liquid adhesive at 50s herein ^-1Temperature when demonstrating 1Pa.s viscosity down.

The solid definition is referring to the Handbook of Chemistry and Physics, CRCPress, Boca Raton, Florida, the 67th edition, 1986.

The structurizing mixture

In a preferred embodiment of the invention, liquid adhesive contains structurising agent, and the liquid adhesive that contains structurising agent is called as the structurizing mixture here.Here the disclosure all about liquid adhesive all is equally applicable to the structurizing mixture.

In the context of the present invention, term " structurising agent " is meant and anyly liquid ingredient can be finished solidify in granulator and therefore fine granulated component, even this solid ingredient has low liquid supporting capacity.

Can classify according to structurizing (curing) mechanism of action of structurising agent, its mechanism is as follows, that is: recrystallization (for example silicate or phosphoric acid ester); Form the reticulated structure (for example silica or clay) of solid particulate in small, broken bits; And at those (for example soap class or polymkeric substance) of molecular level performance steric effect, as usually as those types of washing assistant.Can use one or more structurising agents.

The advantage that the structurizing mixture provides is, under lower envrionment temperature, they is sprayed on the solid particulate, and they can solidify this solid particulate and thereby make solid particulate have structure and intensity.Therefore, importantly, but the structurizing mixture should be taken out by pump, and it is sprayable when temperature raises, for example under at least 50 ℃, preferred at least 60 ℃ temperature, yet also should be lower than 50 ℃, preferably be lower than under 35 ℃ the temperature and solidify, so that embody its advantage.

Usually, at a high speed and in middling speed or the low speed mixer, temperature is than this mixture of preparation and that this mixture is pumped into the temperature of granulator is low more than 10 ℃, preferably hangs down more than 20 ℃.

Preferably in the liquid adhesive component, the curing that structurising agent produces can produce following mixture intensity.The intensity of solidified liquid component (hardness) can be measured with the Instron pressure testing device.With before solid ingredient contacts, will form diameter from the solidified liquid component of described method and be 14 millimeters, high 19 millimeters small pieces.Then, move flat board and move to fixed flat planar, these small pieces are destroyed between fixed flat planar and mobile flat board.Move dull and stereotyped speed and be set to 5mm/min, this makes Measuring Time be about 2 seconds.Pressure curve is recorded on computers.Thereby, can provide peak pressure (when die crack), and calculate the E-modulus by slope meter.

For the solidified liquid ingredient, P in the time of 20 ℃ _MaxPreferred minimum value is 0.1MPa, more preferably 0.2MPa, for example 0.3-0.7MPa.Representative value in the time of 55 ℃ is 0.05-0.4MPa.At 20 ℃, for liquid mixture, E _ModPreferred minimum value is 3MPa, for example 5-10MPa.

The structurizing mixture preferably prepares in shearing power mixer, and its component of pre-mixing is also finished any neutralizing effect of the acid precursor of negatively charged ion.

The soap class is represented a preferred type of structured agent, particularly when the structurizing mixture contains liquid nonionic surfactants.Under many circumstances, wish mean chain length that soap kind product has mean chain length greater than liquid nonionic surfactants, but less than the twice of latter's mean chain length.

Very preferably, react by suitable fatty acidic precursor and alkaline material such as alkali metal hydroxide such as NaOH, in this liquid adhesive, form on the spot the agent of any soap type of structured partly or entirely.Yet in principle, any alkaline inorganics may be used to neutralization, but preferred water-soluble alkaline inorganics.In the liquid adhesive that contains anion surfactant and soap, preferably form anion surfactant and soap from their acidic precursors separately.Here about form all disclosures of anion surfactant by the acidic precursor in the neutralising fluid tackiness agent on the spot, be equally applicable to the formation of soap in the structurizing adulterant.

If desired, can in the structurizing mixture, dissolve or the dispersible solid component.Weight % with the structurizing mixture represents that the typical content of basic each composition of structurizing component of mixture is as follows:

The anion surfactant of preferred 98-10 weight %, more preferably 70-30%, particularly 50-30 weight %;

The nonionogenic tenside of preferred 10-98 weight %, more preferably 30-70 weight %, particularly 30-50 weight %;

The structurising agent of preferred 2-30 weight %, more preferably 2-20 weight %, yet more preferably 2-15 weight %, particularly 2-10 weight %.

Except that anion surfactant or its precursor, nonionogenic tenside and structurising agent, the structurizing mixture also can contain other organic solvent.

Solid raw material

Solid raw material of the present invention is a particle, can be Powdered and/or granulous.Similarly, solid raw material can be any granulated detergent product component that obtains with particle form.Preferably contain washing assistant with liquid adhesive blended solid raw material.In a particularly preferred embodiment of the present invention, the washing assistant that solid raw material contains is selected from crystalline and amorphous aluminosilicate.

If solid raw material contains or be made up of the silico-aluminate washing assistant basically, the weight ratio of liquid adhesive and solid ingredient preferred 0.2 so: 1-0.8: 1.If solid ingredient contains or be made up of the phosphoric acid ester washing assistant basically, this ratio preferred 0.2 so: 1-5: 1.

Product

The present invention also comprises the granulated detergent product that is produced by the inventive method (before any back batching waits).

The tap density that granulated detergent product of the present invention has is less than 900g/l, preferably less than 800g/l,, be more preferably less than 750g/l, be more preferably less than 700g/l.Tap density can be low to moderate 450g/l, yet is preferably greater than 550g/l.Be preferably 550-800g/l, more preferably 550-750g/l, yet more preferably 550-700g/l.

The tap density of product determined by the accurate attribute of this method, but can be to a certain extent by change in step (i) and (iii) the ratio of the liquid adhesive of adding control.

The amount that the granulated detergent product of the inventive method contains particulate is low, and has good flowability.

More particularly, the granulated detergent product that the inventive method provides is compared with the like powder of producing by art methods, has the fraction of particle of improvement.Preferably, the particle diameter that is no more than 10 weight % is less than 180 microns, more preferably 8 weight % at the most.And preferably the diameter that contains of this granulated detergent product is no more than 10 weight % greater than 1400 microns particle, and is higher than this boundary more preferably no more than the particle of 5 weight %.

If the DFR value of granulated product is at least 80ml/s, think that so this granulated product is free-pouring.The DFR value of preferred granulated product of the present invention is at least 80ml/s, preferably is at least 90ml/s, more preferably is at least 100ml/s, and most preferably is at least 110ml/s.These DFR values are applicable to the aged product, and preferably also are applicable to not aged product.

At last, this particle can be with different by means of the particle that uses mercury porosimetry to produce by other method.For by relating to the characterization particle of gas fluidized agglomeration method preparation, the latter's technology is an ideal.

Detergent composition and composition

As previously mentioned, the granulated detergent product itself by the inventive method preparation can be the detergent composition of preparing fully, perhaps can be component or the additive that only forms a part of this composition.This part is relevant with detergent composition final, that be completed into.

The total amount of washing assistant is suitably for 10-80 weight % in the finished product detergent composition, preferred 15-60 weight %.This washing assistant can be present in the additive with other component, perhaps, so can use the independent lotion-aid particle that contains one or more washing assistant materials if wish.

The present invention is specially adapted to solid raw material and contains and be selected from crystalline and the situation amorphous aluminosilicate washing assistant, for example disclosed zeolite in GB-A-1473201; Disclosed amorphous aluminosilicate in GB-A-1473202; In GB 1470250 disclosed blended crystalline/amorphous aluminosilicate; And in EP-B-164514 disclosed layered silicate.

Based on the finished product detergent composition, no matter use and/or mix in the particle main body as layering reagent, the total amount that silico-aluminate is fit to is 10-60 weight %, preferred 15-50 weight %.The zeolite that the most commercial granular detergent composition is used is zeolite A.Yet, advantageously, can the also aluminium zeolite P (zeolite MAP) of prescription be described the use of maximum ground in EP-A-384070.Zeolite MAP is a kind of alkali metal aluminosilicate of P type, and the ratio of its siloxanes and aluminium is no more than 1.33, preferably is no more than 1.15, and more preferably no more than 1.07.

Other washing assistant that is fit to comprises hydratable salt, preferred a large amount of the adding, as be at least 25 weight % of solid ingredient, preferably be at least 10 weight %.Hydratable solid comprises mineral sulfates class and carbonate, and inorganic phosphate builders, for example sodium orthophosphate, pyrophosphate salt and tri-polyphosphate.

Other inorganic builders that can exist comprises yellow soda ash (as mentioned above, a hydratable solid example), if wish, can be used in combination with the lime carbonate crystal seed, as disclosed in GB-A-1437950.As mentioned above, this yellow soda ash can be the remnants that are used for forming on the spot the inorganic alkaline neutralizing agent of anion surfactant.

The organic washing-assisting detergent that can exist comprises polycarboxylic acid ester polymer such as polyacrylate(s), vinylformic acid/maleic acid and vinylformic acid phosphinate; Monomeric polycarboxylate class such as citrate, gluconate, oxygen di-succinate, glycerine list-, two-and three succinates, carboxy methoxy-succinic acid ester, carboxymethoxyl malonic ester, pyridine dicarboxylate, hydroxyethyliminodiacetic acid ester, aminopolycarboxylic ester such as nitrilotriacetate (NTA), ethylenediamine tetraacetic acid (EDTA) (EDTA) and iminodiacetic acid (salt) acid esters, alkyl and alkenyl malonic ester and succinate; And sulfonated fatty acid salt.The multipolymer of preferred especially toxilic acid, vinylformic acid and vinyl-acetic ester because it is biodegradable, thereby caters to the need on environment.What these were listed is not exhaustive.

Particularly preferred organic washing-assisting detergent is a Citrate trianion, and suitable consumption is 2-30 weight %, preferred 5-25 weight %; And acrylic polymers, vinylformic acid/maleic acid more especially, suitable consumption is 0.5-15 weight %, preferred 1-10 weight %.Washing assistant preferably exists with alkali metal salt, particularly sodium-salt form.

Except that any negatively charged ion and/or nonionogenic tenside of liquid adhesive, this granular detergent composition can contain one or more other detergent active materials, and it can be selected from soap and non-soap anionic, positively charged ion, nonionic, both sexes and zwitterionic tensio-active agent and composition thereof.These can be before present method or during any appropriate step in feed intake.Many suitable detergent active compounds are obtainable, and abundant description is arranged in the literature, and for example at Schwartz, Perry and Berch " Surface-Active Agentsand Detergents ", I and II roll up.The preferred detergent active compound that can be used is soap class and synthetic soap anionic and non-ionic compound.

This detergent composition also can contain bleach systems, wishes to contain peroxy bleaching compound, for example can produce the inorganic persalt or the organic peroxide acid of hydrogen peroxide in the aqueous solution.This peroxy bleaching compound can be used in combination with bleach-activating agent (bleach precursor), so that improve the bleaching action under low wash temperature.Particularly preferred bleach system contains peroxy bleaching compound (preferred SPC-D), chooses wantonly and uses with bleach-activating agent.

Usually, after granulating, any SYNTHETIC OPTICAL WHITNER and other responsive composition such as enzyme and spices are with other submember back batching.

Typical submember comprises water glass; Inhibiter comprises silicate; Anti redeposition agent such as cellulose polymer compound; White dyes; Inorganic salt such as sodium sulfate, Foam Control that depends on the circumstances or profoamer; Hydrolysising protease and lipolytic enzyme; Dyestuff; Colored spot decorations; Spices; Foaming regulator; And fabric softening compound.What these were listed is not exhaustive.

In the method for the invention, can choose wantonly in any appropriate step introducing " layering agent " or " glidant ".This will improve the granularity of product, for example by preventing particle agglomeration and/or caking.The suitable content of any layering agent, glidant is the 0.1-15 weight % of this granulated product, more preferably 0.5-5 weight %.

Layering agent/the glidant that is suitable for comprises crystalline or amorphous alkali metal silicate, silico-aluminate comprise for example sedimentary silica of zeolite, Citrate trianion, Dicamol, calcite, diatomite, silicon-dioxide, muriate such as sodium-chlor, vitriol such as sal epsom, carbonate such as lime carbonate, and phosphoric acid salt such as tripoly phosphate sodium STPP.According to the mixture that requires also can use these materials.

Zeolite MAP is a kind of preferred washing assistant, and is also particularly useful as the layering agent.The SKS-6 that stratified silicate such as Clariant produce is also as the layering agent.

Powder flowbility also may be improved by adding a small amount of other pulverized structure agent, for example lipid acid (or fatty acid soaps), sugar, acrylate or acrylate/maleic acid ester polymkeric substance, or water glass, and its suitable amount is 1-5 weight %.

Usually, other component can add liquid adhesive or mix with the solid parent material in this method proper step.Yet solid ingredient can be prepared burden later in the granulated detergent product.

This granular detergent composition also may contain particulate filler (or any other component that washing process is not acted on), and it is suitable for comprising inorganic salt, for example sodium sulfate and sodium-chlor.The content that exists of filler can be the 5-70 weight % of this granulated product.

Illustrate the present invention in further detail by following indefiniteness embodiment, except as otherwise noted, wherein umber and percentage ratio are all calculated by weight.Embodiment with numeral flag is of the present invention, and is comparative examples with those of letter sign.

Embodiment

Embodiment 1-6, Comparative Examples A and B:

The base materials powder of the granulated detergent product of the prescription shown in detail in the preparation table 1.

The base materials powder of embodiment 1-6 is prepared as follows:

(i) in L dige recirculator (CB 30), will mix with liquid adhesive by the solid starting raw material that zeolite, Soda Ash Light 99.2min. ash content, Xylo-Mucine (SCMC) and Citrate trianion are formed and granulation

(ii) this material is transferred to L dige Ploughshare (KM300) mixing tank from recirculator;

(iii) above-mentioned material is transferred to as Vometec (trade mark) fluidized-bed of gas fluidized granulator from Ploughshare, add again liquid adhesive and agglomeration and

(iv) this product of final drying/cooling in this fluidized-bed.

The condition of step (i)-(iii) is as follows:

(i) L dige recirculator (CB 30)

The residence time: about 15 seconds

Axle rotating speed: 1000rpm

Tip speed: 15.7m/s

Froude number (Froude number): 168

(ii)Ldige?Ploughshare(KM?300)

The residence time: about 3 minutes

Axle rotating speed: 100rpm

Chopper: close

Tip speed: 2.62m/s

Froude number: 2.8

Liquid adhesive: do not add

(iii) fluidized-bed (intermittent type Vomotec device, be 10kg in batches)

Airflow on surface speed: 1.0m/s

Fluidizing agent temperature: 75 ℃

Atomizing gas temperature: heat

Atomization air pressure: 3.5bar

Nozzle height (batching dish top): 47cm

The spray rate of tackiness agent: 800g/min

Except omitting step (ii), the base materials powder of Comparative Examples A and B prepares in the same way.

The structurizing mixture of anion surfactant, nonionogenic tenside and the soap component that is used for step (i) and liquid adhesive (iii) and is containing base materials powder.This mixture is by mixing in the loop wire at one, in the presence of the nonionogenic tenside of 41.60 weight parts, the lipid acid precursor of the soap of the LAS acidic precursor of 38.44 weight parts and 5.20 weight parts is mixed, and with in 14.75 parts the sodium hydroxide solution with prepare.Mixing temperature in the ring is controlled by interchanger.Neutralizing agent is a sodium hydroxide solution.The gained mixture has following composition:

％

Linear alkylbenzene sulphonic acid 39.9

Nonionogenic tenside (7EO) 41.6

Soap 5.6

Water 12.9

Add the mixture of recirculator and the weight ratio of the mixture that adds gas fluidized granulator and change, as the detailed description in the table 1.

Provide the tap density and the DFR value of the product and the aged product of new system in the table 1, similarly, provided the content of fine particle and coarse particulate matter in the product.

The DFR value aging and new system granulated detergent product of embodiment 1-6 is at least 100ml/s.In fact, minimum DFR value is viewed 108ml/s among the embodiment 1.

Fraction of particle in all embodiment 1-6 is all less than 10 weight %.

The product of Comparative Examples A and B respectively by with embodiment 1 and the preparation of 2 used same procedure, except in embodiment A and B, having omitted second step in the middling speed mixing machine.Comparative Example A An and embodiment 1, and Comparative Examples B and embodiment 2, for better DFR value of granulated detergent product (not only for the new system product but also for ageing prod) and the fraction of particle that reduces, use middling speed mixing machine (be step (ii)) to have obvious benefit.

Result in the table 1 illustrates clearly that also the tap density of product can reduce usually along with tackiness agent that adds in the step (i) and the (ii) ratio reduction of the middle tackiness agent that adds of step.Observed tap density is 739-579g/l.

Table 1

Embodiment	????1	????A	????2	????B	????3	????4	????5	????6
									Base materials powder
Na-LAS	????11.35	????11.35	????11.66	????11.66	????12.08	????12.23	????12.77	????13.30
									Nonionic 7EO	????11.72	????11.72	????12.04	????12.04	????12.47	????12.63	????13.19	????13.73
Soap	????1.58	????1.58	????1.62	????1.62	????1.68	????1.70	????1.78	????1.85
									Zeolite A24	????37.47	????37.47	????37.07	????37.07	????36.53	????36.32	????35.63	????34.95
The Soda Ash Light 99.2min. ash content	????25.90	????25.90	????25.63	????25.63	????25.25	????25.12	????24.64	????24.17
									SCMC	????0.84	????0.84	????0.83	????0.83	????0.82	????0.81	????0.80	????0.78
Citrate trianion	????3.45	????3.45	????3.41	????3.41	????3.36	????3.35	????3.28	????3.22
									Moisture, salt, NDOM	????7.69	????7.69	????7.74	????7.74	????7.81	????7.84	????7.91	????8.00
	????100.00	????100.00	????100.00	????100.00	????100.00	????100.00	????100.00	????100.00
									Processing condition
Mixture in the recirculator (%)	????80	????80	????78	????78	????74	????68	????55	????40
									Mixture in the fluidized-bed (%)	????20	????20	????22	????22	????26	????32	????45	????60
Whether use Ploughshare	Be	Not	Be	Not	Be	Be	Be	Be
									New product character
BD(g/l)	????740	????665	????703	????685	????712	????639	????612	????571
									DFR(ml/s)	????108	????100	????115	????100	????122	????123	????125	????115
Aging product character
									BD(g/l)	????739	????674	????719	????690	????658	????655	????615	????579
DFR(ml/s)	????115	????85	????110	????95	????122	????130	????120	????112
									RRd	????626	????442	????546	????561	????496	????519	????524	????557
RRn	????1.77	????1.7	????1.96	????1.66	????2.07	????2.21	????2.55	????2.39
									Particulate (＜180) (%)	????8.3	????17.5	????8.6	????11.7	????9.1	????6.7	????4.2	????4.2
Coarse grain (＞1400) (%)	????2.6	????0.4	????1.5	????2.3	????1	????0.9	????1	????1.8

Claims (18)

1. method for preparing the granulated detergent product, this method may further comprise the steps:

(i) in high-speed mixer, liquid adhesive is mixed with solid raw material and agglomeration;

(ii) in middling speed or low speed mixer, mix material from step (i);

(iii) will be fed in the gas fluidized granulator from step material and liquid adhesive (ii), and further agglomeration and

(iv) choose wantonly and carry out drying and/or cooling.

2. the annex tip speed when the process of claim 1 wherein the high-speed mixing machine operation is at least 5m/s, preferably is at least 10m/s, more preferably is at least 15m/s.

3. the method for claim 1 or claim 2, wherein the Froude number during the high-speed mixing machine operation is at least 5, preferably is at least 20, more preferably is at least 40, yet more preferably is at least 50.

4. aforesaid right requires each method, and wherein the annex tip speed when middling speed or low speed mixing machine operation preferably less than 10m/s, is more preferably less than 8m/s, yet is more preferably less than 6m/s less than 15m/s.

5. aforesaid right requires each method, and wherein the Froude number when middling speed or low speed mixing machine operation preferably less than 15, is more preferably less than 8 less than 30, is more preferably less than 5, yet is more preferably less than 4.

6. aforesaid right requires each method, and wherein the 10 weight % that are less than of the liquid adhesive total amount that adds in this method add in (ii) in step.

7. the method for claim 6 does not wherein add liquid adhesive in step in (ii).

8. aforesaid right requires each method, wherein the tackiness agent that adds in the step (i) and step (iii) in the weight ratio of tackiness agent of adding be 20: 1-1: 20, preferred 10: 1-1: 10.

9. aforesaid right requires each method, and wherein this liquid adhesive comprises one or more anion surfactants or its acidic precursor.

10. aforesaid right requires each method, and wherein this liquid adhesive contains one or more nonionogenic tensides.

11. aforesaid right requires each method, wherein liquid adhesive is sent into mixing machine or gas fluidized granulator under at least 50 ℃ temperature.

12. aforesaid right requires each method, wherein this liquid adhesive is the structurizing mixture.

13. the method for claim 12, wherein this structurizing mixture contains the soap structurising agent.

14. aforesaid right requires each method; wherein the liquid adhesive that adds in (iii) in step is the structurizing mixture; and the fluidizing agent temperature and/or the atomizing gas temperature of the gas fluidized granulator that when adding the structurizing mixture, raises; but take out with the pump that reaches this liquid adhesive within 35 ℃ of temperature; within preferred 25 ℃, more preferably within 15 ℃.

15. the method for claim 14, but wherein fluidizing agent temperature and/or the atomizing gas temperature pump that is approximately the structurizing mixture is taken out temperature.

16. aforesaid right requires each method, wherein solid raw material contains the silico-aluminate washing assistant.

17. the method for claim 16, wherein this silico-aluminate washing assistant contains zeolite MAP.

18. the granulated detergent product that the method according to this invention obtains, its tap density that has is less than 900g/l.