CN1276006A

CN1276006A - Method for manufacturing washing and detergent particulates

Info

Publication number: CN1276006A
Application number: CN97182399.5A
Authority: CN
Inventors: K·帕茨; W·拉斯; P·桑德库勒
Original assignee: Henkel AG and Co KGaA
Current assignee: Henkel AG and Co KGaA
Priority date: 1997-09-11
Filing date: 1997-10-28
Publication date: 2000-12-06
Also published as: ATE317003T1; JP2001515955A; ES2224224T3; WO1999013045A1; EP1012221B1; ATE269399T1; EP1012221A1; DE59711728D1; CN1275160A; WO1999013046A1

Abstract

The purpose of the present invention is to create particulate detergents or compounds or treated raw materials which have a spherical shape (bead shape) and exhibit improved disintegration properties upon dissolution in an aqueous bath even when they have a reduced surface area. The method of the present invention is economical and allows for the suppression of costly drying steps. To this end, the complex particulate detergents or mixtures or the treated raw materials have an apparent density of more than 600 g/l and are prepared by assembling detergent compounds and/or raw materials with simultaneous or subsequent forming. This method first comprises preparing a premix containing individual raw materials and/or compounds in a solid phase at room temperature and under a pressure of 1 bar. The premix is then converted into granules by compacting forces and optionally retreated, said premix being essentially an anhydrous one. This method further includes using a liquid forming builder under forming conditions, particularly also at room temperature and under a pressure of 1 bar, wherein said builder consists of polymer swollen in a non-aqueous solution.

Description

The preparation method of granulated detergent or clean-out system

The present invention relates to prepare the method for granulated detergent or clean-out system or multicomponent component by means of fit closely prilling process, and the washing composition or the clean-out system of preparation thus.Described multicomponent component and other composition mix to divide and constitute described washing composition or clean-out system.

For a long time, there has been bulk density to be higher than granulated detergent or the clean-out system of 600g/l in the prior art.In recent years, be accompanied by the increase of bulk density, concentrating of detergent active composition and cleaning active composition occur, make that the volume of human consumer's required washing composition that is metered in each washing or cleaning process is littler, and quality also still less.The raising of laundry active or cleaning active material concentration in the raising of bulk density, especially washing composition or the clean-out system from human consumer's angle, is a cost with solubleness variation (reason is that the dissolution rate of employed washing composition is slack-off) normally.This undesirable delay dissolving is easy to form due to the gel phase when especially being dissolved in water by negatively charged ion commonly used in a series of reality and nonionogenic tenside and especially corresponding surfactant mixture.This gelation has produced when the content of tensio-active agent is 10 weight % (based on the washing composition total amount), that is to say, will produce gelation under the conventional surfactants content in washing composition or clean-out system.Rule of thumb, along with the particulate structure is fine and close more, the tendency of this formation gel is also big more.

EP 0 486 592B1 disclose particle or extruding washing composition or the clean-out system that a kind of bulk density is higher than 600g/l, and they contain at least 15 weight %, the negatively charged ion of about at the most 35 weight % and/or nonionogenic tenside.It can prepare as follows: solid-state, free flowable premixture is pressed into pencil under the high pressure of 25 to 200 crust, by means of cutting unit, bundle after will discharging from the porous stripper plate cut into predetermined granular size and rounding and make, and wherein said premixture contains the softening agent and/or the lubricant of tensio-active agent aqueous slurry preferably and/or aqueous solutions of polymers.Premixture to small part is made up of solid state component, mixes with the nonionogenic tenside that liquid parts for example at room temperature is in a liquid state in case of necessity.As mentioned above, in preferred embodiment, use aqueous compositions as softening agent and/or lubricant.But, also can use the higher organic liquid of boiling point, again they are mixed use with water in case of necessity.Yet, the processing condition in this patent unexposed anhydrous when extruding.Made extrudate or can be used as washing composition or clean-out system uses perhaps also can be then be processed to the washing composition or the clean-out system that can use with other granular or powdered components.Because particulate high compactness and relative high surfactant content, also owing to sphere or pearl (they are compared with the particle of routine, much smaller surface-area) that the human consumer liked, therefore, depend on the combination of selected tensio-active agent, above mentioned trouble may occur.

Known by International Patent Application WO-A-93/15180, the dissolution rate of this extruding washing composition can improve in the following manner, promptly uses the alkyl-sulphate of short chain in solid-state premixture, preferred C ₈-to maximum C ₁₆-alkyl-sulphate, and they are joined in the premixture in kind and the mode of determining.But, want to make in all cases the dissolution rate of all washing composition all to bring up to the degree of expection, so this measure just seems unable to do what one wishes.

German patent application DE 195 19 139A1 have recommended a kind of solution to improve individual particle on the one hand, especially the intensity of compression of extrudate, can use washing composition or clean-out system quick on request and still make on the other hand, gelation especially can not take place be not dissolved in the water lotion method of contradiction between the two, bulk density is higher than the negatively charged ion that contains at least 15 weight % of 600g/l and/or the granulated detergent or the clean-out system of nonionogenic tenside uses at least two kinds of different granular components, wherein at least a grain fraction is extruded, and another kind of not being extruded comprises the highest 15 weight % (based on various extruding component meters) that should be of content of tensio-active agent of the extruding component of soap class.Other surface active agent composition of washing composition of making or clean-out system then joins in the washing composition by the component that one or more are not extruded.Although this method has solved the problem that is easy to gelation in water lotion when the washing composition of high compactness and high surface agent content or clean-out system use, brought series of new problems again.The washing that promptly can occur decomposing and make every effort to accordingly reach or the reproducible fluctuation of cleaning performance.In addition, the detergent component through pushing is the density height not only, and dried extrudate is simultaneously also harder.Under the condition of transportation, storage and use, do not push the softer grain fraction of component and therefore bear mechanical force, the part particle is by wearing and tearing, and particle diameter diminishes, and meanwhile forms dust and fine particle.

According to a conventional method, both can use solid also can use washing composition or clean-out system composition liquid under the room temperature usually; Also the aqueous solution and/or dispersion liquid can be widely used as granulating assistant or as be used as softening agent and/or lubricant in EP 0 486592B1.The danger that this method exists is in preparing washing agent or clean-out system, has produced when dissolving in water lotion to promote the dissolved gel-like structure of delaying time again.In addition, the shortcoming that wherein water, the aqueous solution or aqueous dispersions is used as the method existence of granulating assistant especially is, in most of the cases, obtain free-pouring and the finished product stable storing, the dry aftertreatment that must waste energy, and, often to carry out necessary pulverizing and/or screening (referring to " through agglomeration and increased in size " (Size Enlargement by Agglomeration) to formed very thick agglomerate, W.Pietsch, John Wiley﹠amp; Sons, 1990, the 180 pages).Another shortcoming of this method is because the water that solid-state and water miscible component is passed through to be comprised particularly dissolves the pressure influence lower section when extruding, cause producing that particle increases and crystallization, this exerts an adverse impact to the solvability of the washing composition made again usually.

Heavy particulate one method of preparation is two step shottings in the presence of moisture granulating assistant; it wherein at first is the initial agglomerate that preparation still is plasticity in the mixing tank/pelletizer of routine; then such as nodulizer; the vane coating machine; in the device such as Marumerizer; with liquid adhesive and/or dust disposal, carry out drying subsequently usually.Granulation and the balling-up process of carrying out simultaneously for example can be carried out in being equipped with the fluid bed granulation device of rotating-disk.Here, solid-state starting raw material is fluidisation in fluidized-bed at first, join liquid adhesive in the fluidized-bed with the nozzle that points to through tangent line then and carry out agglomeration (referring to " through agglomeration and increased in size " (Size Enlargement byAgglomeration), W.Pietsch, John Wiley﹠amp; Sons, 1990, the 450 to 451 pages).In principle, this method also can be used for (fusion coating method) in the anhydrous process, and still, the advantage that can play the device of desiccation in this case simultaneously is not utilized.

At technical literature (referring to " through agglomeration and increased in size " (Size Enlargement byAgglomeration), W.Pietsch, John Wiley﹠amp; Sons, 1990, the 440-441 pages or leaves) in, two kinds of methods of under high pressure carrying out granulation are only disclosed, they can carry out under anhydrous situation fully.Described method is included in compressing tablet and roll compaction in the tabletting machine, in the method for in the end mentioning, can form compressing tablet usually, and when carrying out granulation subsequently, it is broken and the irregular product that forms.Based on this reason, in some systems, adopt so-called prebreaker, so that it is more even to carry out the shape of initial product of actual granulation or grinding steps.Then undesirable fine particle and/or coarse particles in the particle for preparing thus fallen in screening, is recycled in case of necessity in this process.

International Patent Application WO-A-93/02176 has described the solid-state washing composition with high bulk density or the preparation method of clean-out system, wherein the raw material of solid-state and liquid detergent or clean-out system is mixed and simultaneously or then carry out moulding, employed solids fraction is anion surfactant and washing assistant, liquid composition is a nonionogenic tenside, wherein nonionogenic tenside normally with structure deteriorate agent for example polyoxyethylene glycol or polypropylene glycol or have 20 to 45EO ethoxylation C ₈-C ₁₈-Fatty Alcohol(C12-C14 and C12-C18) intimate mixture form exists.Liquid non-ionic surfactant preferably ethoxylation straight chain or on 2, have the alcohol of methyl branch, its carbochain has 8 to 20 carbon atoms, every mol of alcohol on average has 1 to 15 moles of ethylene oxide.Except that above-mentioned structure deteriorate agent, in principle, water also is described to be suitable as the structure deteriorate agent, but, preferably not making water, this is because when washing composition is stored, because its inner dry washing composition meeting dehydration, therefore, by the utilization structure disrupting agent, do not reach or completely lose with the desired effects that improves dissolution rate.According to this international patent application, in all known granulating methods of mixture that uses separately preparation and/or raw material, can use the nonionogenic tenside that exists with solution or dispersion and the mixture of structure deteriorate agent.Also may even preferably in according to the described pressing method of International Patent Application WO-A-91/02047 (or European patent application EP 0 486 592B1), use.Correspondingly also the aqueous solution, slurry or aqueous dispersions are used in suggestion, and as mentioned above, water does not use as the structure deteriorate agent, usually after extruding, be dried evaporation and remove.This patent does not spell out dry extrusion process; Even in an embodiment, also additionally add the aqueous solution dividually with nonionogenic tenside-structure deteriorate agent composition; Especially, the processing condition that the document is not mentioned when pushing under anhydrous situation.

European patent application EP 0 337 330 has been described under the situation that adds non-ionic compound; by granulation in mixing tank; improve the method for spray-dried detergent bulk density; described non-ionic compound is ethoxylation and/or propenoxylated nonionogenic tenside; for example has the primary alconol or the secondary alcohol that have 2 to 20 moles of alkylene oxides in 8 to 20 carbon atoms and the every mol of alcohol; especially in mixing tank, use have 2 to 6EO and the HLB value 11 or following nonionogenic tenside, also can make spent glycol and propylene glycol as non-ionic compound.

In European patent application EP 0 711 828, described the preparation method of tablet, comprised the granulated product of compacting through parcel.Encapsulate substances is water-soluble binder or the disintegrating agent of melt temperature between 35 to 90 ℃.But the principal character of this method is that compression/compressing tablet is the temperature at least 28 ℃, and in all cases, is lower than that the tackiness agent melt temperature carries out.

By the known a kind of particulate preparation method of International Patent Application WO-A-96/10071 with at least 650 grams per liter bulk densities; its surfactant content is at least 40 weight %; wherein granulating is in having the mixing tank of high shear rate; next step is finished in the temperature of room temperature to 60 ℃; the particulate granularity of using as solid feed is 0.1 to 500 micron; wherein the particulate particle size of at least 15 weight % is greater than 50 microns; but also there is very little fine particle to exist, makes solid feed have extra high surface-area.What use as tackiness agent is that (its weight ratio is 2: 8-8: 2), and can contain the water of 20 weight % at the most, nonionogenic tenside is to have 3 to 7EO C for the surfactant mixture of anion surfactant and nonionogenic tenside ₁₂-C ₁₅Primary alconol.Particularly preferably be, in the scope of described method, surfactant mixture contains the water of 20 weight % at the most, because can improve the viscosity of mixture thus, is easy to CONTROL PROCESS.In addition, surfactant mixture also can contain polyoxyethylene glycol.

US Patent specification US 5 108 646 has described the preparation method of builder agglomerates, and wherein the tackiness agent of the silico-aluminate of 50 to 75 weight parts or crystalline layered silicate and 20 to 35 weight parts carries out agglomeration.Suitable binder mainly is full-bodied anion surfactant slurry, and they can contain the water of 90 weight % at the most.But also can use molecular weight is 1000 to 20000 polymkeric substance, and for example polyoxyethylene glycol can use these materials and conventional nonionogenic tenside equally, for example has 4 to 8EO C ₉-C ₁₆The mixture of alcohol, as long as their melt temperature is not less than 35 or 45 ℃, agglomeration is to carry out in what is called has the strong mixer of specific higher-energy input.When intake surpasses designated value, excessive agglomeration then takes place, form pasty material, when intake is lower than described amount, then can only obtain the extremely light agglomerate of fine powder or undesirable wide size-grade distribution.

In contrast, the objective of the invention is to prepare the method for a kind of granulated detergent or clean-out system or multicomponent component, described multicomponent component is mixed described washing composition of formation or clean-out system with other composition.They in addition when surface-area diminishes, especially when their (pearl shapes) spherical in shape, in the time of also being to dissolve in the water lotion, show the disintegrating property that improves.In addition, this method is economical, and need not to adopt expensive drying step.

Therefore, the purpose of this invention is to provide the preparation method that a kind of bulk density is higher than the granulated detergent of 600g/l or clean-out system or multicomponent component or treated raw material, described multicomponent component or treated raw material mix described washing composition of formation or clean-out system with other composition, wherein with washing composition or clean-out system mixture and/or raw material mixes and simultaneously or the shaping of then carrying out, wherein, at first prepare a kind of premixture, described premixture contains single raw material and/or mixture of planting, they exist with solid form under the pressure of room temperature and 1 crust, applying under the condition of force of compression subsequently, this premixture is made a kind of particle, and then further handle in case of necessity or process, it is characterized in that premixture is anhydrous basically, and use a kind of under molding condition, particularly room temperature and the shaping additive that under the pressure of 1 crust, is in a liquid state and exists with the polymer form of swelling in non-aqueous solution.

To this, within the scope of the invention, term " anhydrous basically " is meant liquid content, promptly is not to be respectively that the basis is below 2 weight % with the premixture in the liquid water that water of hydration and/or water of constitution form exist, preferably below 1 weight %, below 0.5 weight %.Therewith correspondingly, in the preparation process of premixture, water only can be introduced with chemistry and/or physical bond form or as the composition (but not being with liquid, solution or dispersion liquid) of raw material that exists with solid-state form under the pressure of temperature below 45 ℃ and 1 crust or mixture basically.Preferably, the total water content of premixture is no more than 15 weight %, neither exist with liquid free form at this this water, but exist with the form of chemistry and/or physical bond, particularly preferably be, in solid-state premixture, the water-content that is not attached on zeolite and/or the silicate is no more than 10 weight %, preferably be lower than 7 weight %, more preferably at most in 2 to 5 weight % scopes.

Within the scope of the invention, term " granulated detergent or clean-out system " preferably is meant there is not powdery particle, and especially granular size is less than the product of 200 micron particle.It is preferred that the particulate diameter of at least 90 weight % is at least 400 microns size distribution.In the particularly preferred embodiment of the present invention, made washing composition or clean-out system, mixture or treated raw material at least 70 weight %, preferred at least 80 weight %, more preferably reach 100 weight % and be by spherical (pearl) granulometric composition, and its particle size dispersion is that the grain diameter of at least 80 weight % is in the 0.8-2.0mm scope.In the scope of the invention, granular detergent or clean-out system also comprise the sheet body, and this sheet body has the stock size of household detergent or clean-out system, and for example weight is 15 to 40 grams, particularly 20 to 30 restrains, and diameter is about 35 to 40 millimeters.

The anhydrous swelling polymkeric substance that uses as shaping additive is those polymkeric substance that cause the gel state in anhydrous liq in the present invention.The specially suitable system that those are made up of anhydrous liq and polymkeric substance, at room temperature, in the presence of polymkeric substance, at least 20 times of this heights of viscosity ratio anhydrous liq of this system, particularly 300 to 5000 times.For example by means of the Brookfield rotational viscometer, at room temperature preferably 200 to 10000mPas, particularly 400 to 6000mPas for the viscosity of the composition that the shaping additive of mensuration promptly is made up of anhydrous liq and polymkeric substance.Under higher temperature, for example under 60 ℃, viscosity preferably with room temperature under viscosity number only different slightly, and preferably 250 to 2500mPas.Suitable liquid is that the boiling point that at room temperature is in a liquid state (under 1 crust) is above 80 ℃, particularly surpass 120 ℃ one, two or trivalent alcohol, for example n-propyl alcohol, Virahol, propyl carbinol, sec-butyl alcohol, isopropylcarbinol, ethylene glycol, 1,2-or 1, ammediol, glycerol, two-or three-ethylene glycol or-propylene glycol or its mixture, particularly glycerol and/or ethylene glycol, and the representative of the nonionogenic tenside of hereinafter mentioning that at room temperature is in a liquid state.Though known this class nonionogenic tenside has the tendency of gelation when contacting with water, when the non-aqueous solvent as the polymkeric substance in the shaping additive used in the present invention used, the finished product can not have viscosity.The polymkeric substance that produces the swelling system in this class anhydrous liq is multipolymer, polyvinyl alcohol, xanthane, starch, alginate, the amylopectin of partial hydrolysis, the starch that carries methyl ether, hydroxyethyl ether, hydroxypropyl ether and/or hydroxyl butyl ether group or the Mierocrystalline cellulose of polyvinylpyrrolidone, polyacrylic acid, vinylformic acid and toxilic acid, the starch such as the bisphosphate starch of phosphorylation, also can be inorganic polymer such as layered silicate (Schichtsilikate) and their mixture.Polyvinylpyrrolidone preferably those relative molecular weights is up to 30000, and especially the average molecular weight range is 3000 to 30000, those of for example about 10000.The preferred polymkeric substance that uses is hydroxypropylated starch and bisphosphate starch.The concentration of polymkeric substance 5 weight % to 20 weight % preferably in anhydrous liq, particularly about 6 weight % to 12 weight %.

Based on premixture to be compressed, the content of shaping additive preferably is 2 weight % at least, but is lower than 20 weight %, particularly is lower than 15 weight %, and particularly preferred content range is 3 weight % to 10 weight %.In further describing process of the present invention, for the sake of simplicity, shaping additive is represented with a kind of shaping additive or this shaping additive.Yet can use the mixture of multiple different types of shaping additive and differing formed auxiliary agent obviously.

" washing composition or clean-out system " be meant and they can be used for washing or clean, and need not mixing of common and other composition.Otherwise multicomponent mixture or mixture be meant by at least two kinds of one-tenth that usually use in washing composition or clean-out system and be grouped into, still, mixture usually only with other composition, preferably be mixed together use with other mixture." treated raw material " of the present invention is meant the raw material that particle is thinner, and they are transformed into than coarse particles by method of the present invention.Strictly speaking, in this article, when treatment agent was a kind of composition that usually uses in washing composition or clean-out system, treated raw material was a kind of mixture.

The composition of Shi Yonging is except the nonionogenic tenside that is in a liquid state under the pressure of temperature below 45 ℃ and 1 crust that exists if desired in the methods of the invention, can be powdery or granular (carefully to the coarse particles) mixture for preparing respectively, but also can be raw material, but, in all cases, under the pressure of room temperature and 1 crust, they are to exist with solid-state form.For instance, granular particle can be the pearl of spray-dried preparation or the agglomerate of prilling process etc.Except water-content, the composition of mixture is unimportant for the present invention, and water-content will limit so as mentioned above, makes premixture be substantially free of water, preferably contains the water of hydration and/or the water of constitution that are lower than 10 weight %.One preferred embodiment in, in premixture, use the mixture of overdrying.This mixture for example can prepare by spraying drying, and wherein temperature control should be regulated like this, makes the tower temperature out be higher than 100 ℃, for example 110 ℃ or more than.Can in premixture, use solid state composite equally, as liquid component, the carrier of liquid non-ionic surfactant or silicone oil and/or paraffin for example.These mixtures can contain the water of above-mentioned limited range, and wherein mixture is free-pouring, preferably also are free-pouring under minimum 45 ℃ comparatively high temps, perhaps can be transferred at least.But, particularly preferably be in premixture, use to contain 12 weight % at most, preferably contain the mixture of the water (based on premixture) of 9 weight % at most.Preferably in premixture, do not contain free-water fully, promptly not to be combined on the solid in any form, thereby the water of " existing " with liquid form because even extremely low water-content, for example counting 0.2 or 0.5 weight % based on premixture just is enough to be partly dissolved water miscible tackiness agent.Consequently reduced the fusing point or the softening temperature of the finished product and made the finished product lose free-flowing property and bulk density.

Shown that surprisingly water is attached to the sort of solid feed or is combined in is inessential anything but in the sort of solid state composite.Therefore, think to be attached to hereinafter for example water on zeolite or the silicate of the washing assistant described in detail that the water that especially is attached in zeolite A, zeolite P or MAP and/or the X zeolite is not very crucial.On the contrary preferably, in premixture, preferably contain water in other solid state component that is attached to non-described washing assistant below the 3 weight %.Therefore, in embodiments of the present invention, preferably the content of combination water should be no more than 10 weight % and/or should not be no more than 7 weight % with the content of zeolite and/or silicate bonded water in the premixture, is preferably 2 to 5 weight % at the most.Here, particularly advantageous is that premixture does not contain not and washing assistant bonded water fully.But, be difficult to technically realize that reason is in the ordinary course of things, always can be brought into the water of trace by raw material and mixture.

In the solid state composite that in premixture, uses, except at room temperature liquid shaping additive, the components contents that is non-water liquid state under the temperature below 45 ℃ is preferably to reaching 10 weight %, preferably to reaching 6 weight % (in each case based on the premixture meter).In premixture; the preferred solid state composite that contains the nonionogenic tenside that under the pressure of temperature below 45 ℃ and 1 crust, is in a liquid state usually that uses; they can prepare separately by any known method, for example the spray method of spray-drying process, shotting or carrier pearl.But by this method preparation example as containing about 10 weight % at the most, below the preferred 10 weight %, more preferably 8 weight %, for example premixture of the nonionogenic tenside of 1-5 weight % (based on final washing composition meter) at the most.

Contain above-mentioned form water and/or as liquid vehicle, especially as the mixture of nonionogenic tenside carrier liquid under the room temperature (be it contain at room temperature be in a liquid state composition and can use according to the present invention) preferably do not have and be lower than 45 ℃ softening temperature.Similarly, the single raw material of using separately preferably has at least 45 ℃ softening temperature.Preferably the fusing point that has of single raw material of all that use in premixture and mixture or softening temperature preferably are at least 50 ℃ all more than 45 ℃.

In one of the present invention preferred embodiment, mixture that all use in premixture and single raw material at least 80 weight %, preferred at least 85 weight %, more preferably the softening temperature of at least 90 weight % or fusing point are more much higher than the temperature that is issued in the forming technology condition.In the reality, single from the economic angle consideration, forming temperature all is not higher than 150 ℃, preferably is not higher than 120 ℃.Therefore, the employed mixture of at least 80 weight % and single softening temperature or fusing point of planting raw material are higher than 150 ℃ under normal pressure (1 crust).

Except solid is formed and the shaping additive that at room temperature is in a liquid state, premixture can contain the nonionogenic tenside that 10 weight % at the most are in a liquid state under the pressure of temperature below 45 ℃ and 1 crust, especially be generally used for the alcohol alcoxylates of washing composition or clean-out system, the C chain length that for example has is 8 to 20, and particularly every mol of alcohol on average has the Fatty Alcohol(C12-C14 and C12-C18) or the oxo alcohol of 3 to 7 ethylene oxide units.The addition of liquid non-ionic surfactant should guarantee that premixture still exists with free flowable form.If add this liquid non-ionic surfactant in premixture, adding so preferably will be separated from each other the shaping additive of a liquid non-ionic surfactant and a disintegration in technology.In one of the present invention preferred embodiment, liquid non-ionic surfactant is in the successive production process, especially adds to flow of powder by nozzle and is absorbed.

But premixture also contains at least a raw material or the mixture that plays above-mentioned shaping additive effect.The shaping additive that exists with anhydrous swelling polymer form can mix with all the other components of premixture before forming step.When forming by pressing steps or by means of compressing tablet or other pressing process, this is especially preferred.Also can be at shaping, be sprayed at shaping additive on the premixture or be added drop-wise in the premixture, by granulation formation the time, this is especially preferred especially.The temperature of shaping is room temperature or the temperature that energy input produced by former preferably, yet premixture and the shaping additive that separately adds at shaping if desired can be heated to higher temperature equally, for example 35 to 80 ℃, wherein 45 to 65 ℃ temperature is particularly advantageous.

Proof advantageously, in the processing step of compression molding, shaping additive uniform distribution as much as possible in material to be compressed.Do not wish to be confined to this theory, the inventor's viewpoint is, by under the processing condition of compression, make shaping additive (binder form) uniform distribution in premixture, make solid state composite and the single raw material that exists in case of necessity so be wrapped up by tackiness agent, then adhere to each other, almost these are little by a lot of to cause the finished product made, be made up of the individual particle that tackiness agent adheres to each other, tackiness agent then plays the preferred thin sealing coat between these individual particles.In the ideal pattern, this structure image is cellular, has filled up solid matter (mixture or single raw material of planting) in the nest chamber of honeycomb.With water, cold water when contact for example, for example in the initial stage of machine washing process, the almost moment dissolving or decompose of this thin sealing coat; Surprisingly, when shaping auxiliary agent itself at room temperature can not be dissolved in the water fast, also such situation can appear.But, preferably use such shaping additive, promptly they are in following test method, and the concentration in 1 premium on currency is under the situation of 8 shaping additives that restrain, and they are 30 ° of almost all dissolvings in 90 seconds.Yet it is favourable in some cases, controlling i.e. delay dissolving by additive.

Shaping additive must be this class material that has adhesion characteristic under forming temperature.This point also is important for the kind of the shaping additive that select to use and consumption in addition, promptly after forming step, the bonding characteristic of the finished product inside can not lost, guarantee the bonding of the finished product thus, but the finished product originally there is not viscosity under common storage and transportation conditions.Surprisingly, when being in a liquid state shaping additive under using room temperature, no matter the finished product of acquisition still under 30 ℃ of the temperature that raises slightly, promptly all can not become agglutinating at summer temp with under storage and transportation conditions at room temperature.

The mixing of washing composition or clean-out system mixture and/or raw material and while or the shaping of carrying out subsequently can be undertaken by general method, wherein apply for example granulation of compression pressure, compacting as roll-in or extruding or compressing tablet (adding under the conventional disintegrating agent situation in case of necessity) or granulation.Wherein, also spray-dired particle can be used as the prefabricated mixture in the premixture, but the present invention is not limited thereto.On the contrary, preferably do not use spray-dired particle according to method of the present invention, this is because having the superfine raw material of dust-like component according to the present invention also is easy-to-handle, and need not to carry out compound in advance, spraying drying for example.

Basically anhydrous processing method not only can make peroxygen bleach loss of activity not when handling, and can be therefore peroxygen bleach and bleach activator be processed in the particle together, and can seriously not lose its activity.

In the preferred embodiment of the invention, the compression molding of this method is undertaken by agglomeration step, wherein makes premixture carry out the agglomeration granulation in to this equipment that is fit to, and the shaping additive of above-mentioned definition plays tackiness agent.This granulation process can be carried out continuously or intermittently.Preferably the solids fraction with premixture to be compressed is placed on earlier in the tablets press (mixing tank also can be used as tablets press), if desired by adding the dust that the liquid non-ionic surfactant bonding may exist, and introduces shaping additive in tablets press.For example determine by revolution and the residence time and temperature by the kind of shaping additive and amount and machinery and operating parameters for desirable particulate average particle size particle size.Suitable tablets press for example is granulation dish, going barrel, have ploughshare mixing tank (the Pflugscharmischer) (manufacturers: Firma Loedige of knife mill ^), have rotation mixing vessel and vortex generator superpower mixing tank (Firmen Laeis Bucher for example ^Or Eirich ^), have intensive mixer (the Firma LIPP Mischtechnik for example of cutting head ^Or Imcatec ^-, Drais ^-, Fukae ^-or the Forberg-mixing tank) and the so-called Rotorcoater that has level and tilt to 50 ° rotating disk ^(Firma Glatt ^).Taking second place suitable is Loedige ^CB-mixing tank, FirmaPK-Niro ^Sawtooth mixing tank, Ballestra ^Chain type mixing tank and Hosokawa ^-or Schugi ^-mixing tank.Fluidized-bed or horizontal mixer instance such as Nautamixer ^Also be relatively to be fit to.In this embodiment; method of the present invention is preferably carried out in room temperature or under the temperature definite by the energy input of mixing tank or tablets press; that is to say no independent heating steps, as for example international patent application WP 94/13779 and wherein quote described in the prior.In this respect; the advantage of the inventive method is to adopt two step comminution granulations; the method of in European patent application EP 0 367 339, describing for example; wherein at first in super mixer, suppress saccharoid; compressed granulate in slow-speed mixer and tablets press then, and use anhydrous swollen polymkeric substance can in single stage, compress granulation.

Detergent tablet of the present invention can prepare by conventional tabletting method, for example 200 * 10 ⁵Pa to 1500 * 10 ⁵Eccentric or rotation compacting under the Pa pressing pressure.

In the preferred embodiment of the inventive method; at first under the temperature that room temperature extremely raises slightly; preferably under the temperature of room temperature to 35 ℃, the solids that will be used for preparing solid-state and free flowable premixture at first mixes mutually at the mixing tank and/or the tablets press of routine.Compression step of the present invention is finished by the extruding to the premixture of such acquisition, as for example described in European patent EP 0,486 592 B1 or International Patent Application WO-A-93/02176 and the WO-A-94/09111.Wherein, under pressure, premixture is pressed into pencil, the bundle that will discharge from porous nozzle plate (Lochform) cuts into predetermined granular size with cutting unit.All even solid-state premixture contain usually make mixture pressure or under the effect of specific operation plasticity softening and become squeezable softening agent and/or lubricant.The especially anion surfactant that can mention this according to European patent EP 0486 592B1 is alkylbenzene sulfonate and/or (fat) alkyl-sulphate for example, but also can be for example polymeric polycarboxylate of polymkeric substance.Yet the method according to this invention can be abandoned using this known solid plasticizer and/or lubricant fully, because shaping additive defined above can be fulfiled the function of lubricant.Shaping additive is avoided or has been reduced adhesion on appts wall and compression set at least.This is not only applicable to the processing in forcing machine, and is equally applicable to for example in the mixing tank/tablets press of continuous operation or the processing in the roll.

To this, in above-mentioned patent and patent application, clearly explained actual pressing method.In a preferred embodiment of the present invention; preferred continuously premixture be transported to planetary rolling extrusion machine or double-shafted extruder or be furnished with in the twin-screw extruder of running in the same way or antiport, wherein its housing and its extruding granulation head can be heated to predetermined extrusion temperature.Under the shearing action of extruder screw, at pressure, under the preferred at least 25 bar pressure effects with premixture according to equipment therefor with high, also may hang down a little throughputs and compress, plastify, and be squeezed into the pencil shape by the porous nozzle plate in the extruder head, then, preferably extrudate is chopped near spherical to columned granular particle by means of the chopping mechanism of rotation.In this case, the Shu Changdu of the aperture of porous nozzle plate and cutting is determined by selected size.In this embodiment, can successfully prepare the particle that predetermined particle size is arranged basically uniformly, can adapt with the application target of expection in this absolute granular size.Generally, particle diameter preferably is 0.8 centimetre to the maximum.Here, importantly provide a kind of millimetre-sized, for example 0.5 to 5 millimeter, preferred 0.8 to 3 millimeter preparation with single-size size.In an important embodiment, the length of the primary granule of chopping is about 1 with the diameter ratio: 1-3: 1.In addition, extruding/compacting also can be at the low pressure extrusion machine, for example Kahl press or Bextruder ^In carry out.

In addition, preferably provide further shaping procedure of processing to compliant primary granule still; Wherein, after compression step, be not spherical near the globular particle if also form in this first compression molding step, existing corner angle of the original extrudate of rounding so are so that obtain finally to be spherical near the globular particle.In case of necessity, can in this step, use for example zeolite powder of a spot of dry powder, as zeolite NaA powder.This manufacturing process can carry out in commercially available balling machine.To this, note in this step, only forming a spot of fine particle.The drying of describing as preferred implementation in the document of above-mentioned prior art seems unnecessary within the scope of the invention, because method of the present invention is anhydrous basically, promptly not have to add and dissociates, carries out under the situation of unbound water.

What principal character preferred embodiment of the present invention was the particle size distribution that makes premixture than the present invention's preparation is much wide with the finished product of the present invention.At this, premixture can contain much more fines fraction, even dust-like component, also can contain the coarse particles component in case of necessity, but changing into, the fine grain premixture that preferably, will have the particle size distribution of broad and higher amount has narrower particle size distribution and the fine grain the finished product of low amount.

Because the inventive method is anhydrous basically, promptly except the water content (" existing ") of employed solid material with impurity, under anhydrous condition, implement, danger that not only will tensio-active agent raw material gelation in preparation process minimizes or gets rid of fully, and provide valuable method on ecology, because saved the drying step that carries out subsequently, not only save the energy, and avoided main distributing of in the traditional drying method, occurring.

Show, opposite with the washing composition of traditional method preparation, only depend on the solvability of single component now basically according to the solvability again of the washing composition of the present invention's preparation or clean-out system; Contain and dissolve that component is many more faster, the dissolving of so made washing composition is also just fast more; It is many more to contain the slower component of dissolving, and the dissolving of washing composition is also just slow more so.In the methods of the invention, and, for example be higher than in the washing composition or clean-out system of 750 and 800 grams per liters, obviously playing the part of any role such as undesirable interactions such as gelations between breaking-in period again in very high density.Therefore, although thus Zhi Bei washing composition, mixture and treated raw material with have same final composition, but not by the inventive method, promptly do not compare as this class washing composition, mixture and treated raw material that shaping additive prepares under anhydrous condition by means of no water-swelling polymer, solvability is improved.

Correspondingly, another object of the present invention provides a kind of granulated detergent prepared according to the methods of the invention or clean-out system, and its solvability only depends on employed single solvability of planting raw material and mixture.Do not wish to be confined to this theory, the inventor infers that this specific solvability is owing to the particulate polynuclear plane, has wherein filled up solid matter in the nest chamber of honeycomb.

Another object of the present invention provides mixture and treated raw material, for example lotion-aid particle, bleach activator particle or the enzyme granulate according to the inventive method preparation.Especially, treated raw material shows wonderful high dissolution rate in water, and is particularly when using fines, particularly like this when the levigated raw material in case of necessity.

Particularly preferred base particle, mixture and the treated raw material that provides sphere or pearl shape.

The bulk density that the finished product that prepare according to the inventive method have preferably is higher than 700 grams per liters, especially between 750 to 1000 grams per liters.Even use other composition of low bulk density that particle is carried out aftertreatment, the bulk density of the finished product can not reduced to the degree of being expected usually yet.It is contemplated that washing composition, especially extrudate according to the subglobular of the inventive method preparation, and according to ordinary method, especially the washing composition of aqueous method preparation is compared with extrudate, and easier the elephant has desirable sphere smooth, " lubricate " surface.Can realize causing the better space of high bulk density to fill thus, even if mixed neither spherical also be like this when not having the component of this high bulk density again.

The final granulated product that the inventive method obtains can directly be used as washing composition or clean-out system, perhaps at first carries out aftertreatment and/or processing according to ordinary method.The example of conventional aftertreatment be with the fine particle detergent ingredients for example zeolite washing composition or clean-out system are beaten powder, further improve bulk density thus.But, a kind of preferred aftertreatment is German patent application DE 195 24 287 and DE 19,547 457 disclosed methods, wherein dust-like or at least the composition of fine particulate (described thin component) be bonded in the granular the finished product of the inventive method preparation of nuclei of origin core effect, form such washing composition thus, it has this so-called thin component as shell.Advantageously, this can be undertaken by nodulizing again, wherein uses shaping additive in the inventive method as tackiness agent.For with thin component melts agglomeration on base particle of the present invention and base particle according to the present invention preparation, disclosing referring to German patent application DE-A-19524287 and DE-A-19547457 in detail.

The granular the finished product that the term aftertreatment typically refers to according to the inventive method preparation are used as mixture, to wherein mixing other composition, also comprise other mixture in case of necessity.Here, can be referring to patent application of quoting and patent specification, especially European patent EP 0 486 592 B1 and German patent application DE 195 19 139, DE 195 24 287 and DE 195 47 457.In aftertreatment, dezymotize, outside bleach activator and the defoamer, especially add salt, for example comprise silicate (crystal or amorphous), carbonate, supercarbonate, vitriol, hydrosulfate, Citrate trianion or other polycarboxylate, organic acid such as the citric acid of metasilicate.Here, particularly preferably be, the composition that is added is granular, and has the particle size distribution that the particle size distribution with the washing composition of the present invention preparation and mixture adapts.

In a preferred embodiment of the invention, a kind of granular washing composition is provided, wherein at least 80 weight % are made up of the mixture of the inventive method preparation and/or treated raw material.Especially, at least 80 weight % are made up of the base particle of the present invention's preparation.Remaining component can and be mixed according to the various known method preparation.But preferably, these remaining components (it can be mixture and/or treated raw material) also prepare according to the inventive method.But can prepare base particle and all the other components especially thus with same basically free-flowing property, bulk density, particle size and particle size distribution.Equally, mix with above-mentioned all the other compositions by the mixture of the present invention preparation and/or treated raw material and can prepare bigger molding.Sheet body for example.Yet particularly advantageously, by means of the inventive method, all components that can use complete washing composition or clean-out system is as premixture, and is granulated into the bead ball under anhydrous condition.

The detailed description presumable composition of washing composition of the present invention and the component of use now in the methods of the invention.

The important component of washing composition of the present invention and the important component of using in the methods of the invention are tensio-active agents, and anion surfactant especially, its consumption account for washing composition of the present invention or at least according to 0.5 weight % of the washing composition of the present invention's preparation.Here preferably use sulfonate and vitriol, but also use the soap class.

Sulfonate surfactant preferably includes C _9-13-alkylbenzene sulfonate, alkene sulfonate, i.e. the mixture of alkene sulfonate and hydroxyalkylated sulfonic acid salt and stilbene-4,4'-bis-(1-azo-3, 4-dihydroxy-benzene)-2,2'-disulfonate is for example by having the C of two keys with SO 3 sulfonated end of gasiform or mid-way _12-18-monoolefine then obtains with alkali formula or acid hydrolysis sulfonated products.Can pass through chlorosulphonation or sulfoxidation C _12-18-alkane, then hydrolysis or neutralization and the alkylsulfonate that obtains also is fit to.What be fit to equally is alpha-sulfo fatty acid ester (sulfonated ester), for example hydrogenant fatty acid distribution of coconut oil, palm are examined the α-sulfonated formate of lipid acid or tallow fatty acid, they are by α-sulfonation plant and/or the zoogenous methyl esters that has the lipid acid of 8 to 20 carbon atoms in fatty acid molecule, then are neutralized into water miscible single salt and prepare.Here, preferably α-the sulfonated ester of hydrogenant fatty acid distribution of coconut oil, PALM FATTY ACID, palm nuclear lipid acid or tallow fatty acid wherein also can exist on a small quantity, preferably is no more than the unsaturated fatty acids of about 2 to 3 weight %, for example oleic sulfonated products.Particularly preferably be and on ester group, have the alpha-sulfo-fatty acid alkyl ester that carbon atom is no more than 4 alkyl chain, for example methyl esters, ethyl ester, propyl ester and butyl ester.The particularly advantageous methyl esters (MES) that is to use alpha-sulfo-fatty acid, but also can use its saponified disalt.Other anion surfactant that is fit to is the sulfonated glycerin fatty acid ester.Glycerin fatty acid ester is an ester, diester and three esters and composition thereof, for example in the preparation, and by the tri-glyceride transesterification being obtained with the single glycerine of 1-3 moles of fatty acids esterification or with the 0.3-2 mole of glycerin.

Alkyl (thiazolinyl) vitriol is C preferably _12-18-Fatty Alcohol(C12-C14 and C12-C18) (for example coconut oil fat alcohol, tallow fatty alcohol, lauryl alcohol, tetradecyl alcohol, hexadecanol or stearyl alcohol) or C _10-20-oxo alcohol sulfate hemiester or an alkali metal salt, the especially sodium salt of corresponding half ester of the secondary alcohol of same chain length arranged.In addition, alkyl (thiazolinyl) vitriol of described chain length is arranged preferably, they contain synthetic, according to the straight chained alkyl of petroleum chemistry preparation, and have and based on the similar resolution characteristic of the respective compound of oil chemistry raw material.Angle from washing technology particularly preferably is C _12-16-alkyl-sulphate and C _12-15-alkyl-sulphate and C _14-15-alkyl-sulphate.For example according to US Patent specification US3,2 of 234,258 or 5,075,041 preparation, 3-alkyl-sulphate and the commodity DAN by name that sells by Shell Oil Company ^Product also be the anion surfactant that is fit to.Straight or branched C with 1 to 6 moles of ethylene oxide ethoxylation _7-21-alcohol, the C that for example on average has the 2-methyl-branched of 3.5 moles of ethylene oxide (EO) _9-11-alcohol or have 1 to 4EO C _12-18The sulfuric acid monoester of-Fatty Alcohol(C12-C14 and C12-C18) also is suitable for.Because they have high foaminess, therefore, the consumption in washing composition is lower usually, for example is 1 to 5 weight %.Other preferred anionic surfactants tensio-active agent can also be the salt of salts of alkyl sulfosuccinates, is also referred to as sulfosuccinic ester or sulfosuccinate and sulfo-succinic acid and alcohol, an ester and/or the diester of the Fatty Alcohol(C12-C14 and C12-C18) of preferred fat alcohol, especially ethoxylation.Preferred sulfosuccinic ester contains C _8-18-Fatty Alcohol(C12-C14 and C12-C18) group or its mixture.Particularly preferably be, sulfosuccinic ester contains by ethoxylized fatty alcohol (itself is considered to nonionogenic tenside) deutero-Fatty Alcohol(C12-C14 and C12-C18) group.Wherein, the sulfosuccinic ester with the ethoxylized fatty alcohol deutero-Fatty Alcohol(C12-C14 and C12-C18) group that is distributed by the close limit homologue is particularly preferred.Can use alkyl (thiazolinyl) Succinic Acid or its salt that on alkyl (thiazolinyl) chain, preferably have 8 to 18 carbon atoms equally.Other anion surfactant is an amino acid, for example the derivative of fatty acid of N methyl taurine (tauride) and/or sarcosine (sarkosine).To this, particularly preferably be sarkosine or sarcosinate, the sarcosinate of especially preferably higher and optional single or multiple unsaturated fatty acids, for example sarkosine oil base ester.Other anion surfactant is the soap class particularly, and its preferable amount is 0.2 to 5 weight %.Particularly suitable is the saturated fatty acid soap, the for example salt of lauric acid, tetradecanoic acid, palmitinic acid, stearic acid, hydrogenant erucic acid and mountain Yu acid and especially by natural acid, for example fatty acid distribution of coconut oil, palm nuclear lipid acid or tallow fatty acid deutero-soap class mixture.Can use or also have known alkenyl succinate with this soap as its surrogate.

Anion surfactant (comprising the soap class) can its sodium, potassium or ammonium salt and organic bases, and for example the form of the soluble salt of Monoethanolamine MEA BASF, diethanolamine or trolamine exists.Preferably, anion surfactant is with its sodium salt or sylvite, and especially the form with its sodium salt exists.In washing composition of the present invention or the inventive method, preferably use 1 to 30 weight %, the particularly anion surfactant of 5 to 25 weight %.

Except anion surfactant and positively charged ion, zwitter-ion and amphoterics, especially preferably use nonionogenic tenside.

Preferably use alkoxylate as nonionogenic tenside, preferred ethoxylation, especially has the primary alconol that 8 to 18 carbon atoms and every mol of alcohol on average have 1 to 12 moles of ethylene oxide (EO), wherein alcohol radical can be straight chain or preferably be methyl-branched on 2 or contain the group of straight chain or methyl-branched with form of mixtures, and they are present in the oxo process alcohol groups usually.But, the preferred especially alcohol that uses the natural source with 12 to 18 carbon atoms is the alcohol ethoxylate of the straight chain group of lauric alcohol, palmityl alcohol, tallow alcohol or oleyl alcohol for example, wherein every mol of alcohol on average has 2 to 8 moles EO, and the example of preferred ethoxylated alcohol is the C with 3EO or 4EO _12-14-alcohol has the C of 7EO _9-11-alcohol has the C of 3EO, 5EO, 7EO or 8EO _13-15-alcohol, has the C of 3EO, 5EO or 7EO _12-18-pure and mild their mixture for example has the C of 3EO _12-14-pure and mild C with 7EO _12-18The mixture of-alcohol.Shown ethoxylation degree is a statistical average value, for certain products, can be an integer or mark.Preferred alcohol ethoxylate have narrow homologue distribute (ethoxylate of close limit, NRE).Also can use have be higher than 12EO Fatty Alcohol(C12-C14 and C12-C18) as nonionogenic tenside.Example to this is (butter) Fatty Alcohol(C12-C14 and C12-C18) with 14EO, 16EO, 20EO, 25EO, 30EO or 40EO.

In addition, general formula R O (G) _xAlkylglycoside can be used as nonionogenic tenside and use, wherein R represents to have 8 to 22 carbon atoms, the uncle's straight chain or the methyl-branched of preferred 12 to 18 carbon atoms, especially the aliphatic group of methyl-branched on 2, G represents to have the glucose unit (Glykoseeinheit) of 5 or 6 carbon atoms, preferred glucose.The oligomeric degree x that represents the distribution of single glycosides or oligomeric glycosides is 1 to 10 any number; Preferred x is 1.2 to 1.4.That be fit to equally is the polyhydroxy fatty acid amide of formula (I), wherein R ²CO represents to have the aliphatic acyl of 6 to 22 carbon atoms, R ³Expression hydrogen, have the alkyl or the hydroxyalkyl of 1 to 4 carbon atom, [Z] expression has the straight or branched polyhydroxy alkyl of 3 to 10 carbon atoms and 3 to 10 hydroxyls.

Preferred polyhydroxy fatty acid amide is by having the reducing sugar of 5 or 6 carbon atoms, and particularly glucose obtains.Belong to the compound that polyhydroxy fatty acid amide also has formula (II)

R wherein ⁴Be straight or branched alkyl or alkenyl with 7 to 12 carbon atoms, R ⁵Expression has straight chain, side chain or cyclic alkyl or the aryl of 2 to 8 carbon atoms, R ⁶Be straight chain, side chain or cyclic alkyl or aryl or oxygen base alkyl, wherein C with 1 to 8 carbon atom _1-4-alkyl or phenyl is preferred, and [Z] represents the straight chain polyhydroxy alkyl that its alkyl chain is replaced by at least two hydroxyls, or alkoxylate, the derivative of preferred ethoxylation or propenoxylated these groups.Preferably by sugar, for example the reduction amination of glucose, fructose, maltose, lactose, semi-lactosi, seminose or wood sugar obtains [Z].Then, for example according to the instruction of International Patent Application WO-A-95/07331, by in the presence of the alkoxide as catalyzer, compound and fatty acid methyl ester that N-alkoxyl group or N-aryloxy are replaced react, and are converted into required polyhydroxy fatty acid amide.Can use separately or use with other nonionic surfactant combinations, particularly other class preferred nonionic surfactants of using together with oxyalkylated Fatty Alcohol(C12-C14 and C12-C18) and/or alkylglycoside is an alkoxylate, preferred ethoxylation or ethoxylation and propenoxylated fatty acid alkyl ester, preferably has 1 to 4 carbon atom at alkyl chain, especially fatty acid methyl ester, for example disclosed in Japanese patent application JP58/217598, or preferably prepare according to International Patent Application WO-A-90/13533 disclosed method.Nonionogenic tenside preferably on average has 3 to 15EO, preferred 5 to 12EO C _12-18-fatty acid methyl ester.

The amine oxide type, N-cocounut oil alkyl-N for example, N-dimethyl amine oxide compound and N-tallow alkyl-N, the nonionogenic tenside of N-dihydroxy ethyl amine oxide and Marlamid type also are suitable for.The consumption of this nonionogenic tenside preferably is not higher than the consumption of ethoxylized fatty alcohol, especially is not higher than its half.

Other tensio-active agent is so-called geminus (Gemini) tensio-active agent.In this respect, typically refer to the sort of compound that on its each molecule, has two hydrophilic group and two hydrophobic groupings.These groups generally separate each other by so-called " spacer ".This spacer generally is a carbochain, and carbochain is answered sufficiently long, makes hydrophilic group that enough spacings be arranged, and therefore works independently of one another.The feature of this tensio-active agent is to have unusual low micelle-forming concentration and the obvious ability that reduces water surface tension.But under the situation of exception, the geminus tensio-active agent not only is appreciated that into the tensio-active agent of dimerization, and can be the trimeric tensio-active agent.Suitable geminus tensio-active agent for example be according to the sulfation hydroxyl mixed ether of German patent application DE 43 21 022 A1 or according to two polyalcohols of German patent application DE 195 03 061 A1-two-and three polyalcohols-three-vitriol and-ether sulfate.According to German patent application DE 195 13 391, the feature of end capped dimerization and trimerization mixed ether is its difunctionality and multi-functional.Therefore, this known end capped tensio-active agent has good wettability and low foam, and this makes them be particularly suitable for using in machine washing or purging method.Also can use the geminus polyhydroxy fatty acid amide or the poly-polyhydroxy fatty acid amide that are described among International Patent Application WO-A-95/19953, WO-A-95/19954 and the WO-A-95/19955.

Except tensio-active agent, be inorganic and the organic washing-assisting detergent material as washing composition or the most important composition of clean-out system.

Thin crystalline substance, synthetic that uses and the zeolite that contains combination water be zeolite A and/or zeolite P preferably.Particularly preferred zeolite P is a zeolite MAP ^(sell goods of Crosfield company).Yet the mixture of X zeolite and zeolite A, X and/or P also is fit to.Both can use the zeolite of spray-drying powder powder, also can use drying, from the still zeolite of humidity, steady suspension form of its preparation.Under the situation of the zeolite that uses form of suspension, can add a spot of nonionogenic tenside as stablizer, for example based on the ethoxylation C of zeolite meter 1 to 3 weight % with 2 to 5 ethylene oxide groups _12-18-Fatty Alcohol(C12-C14 and C12-C18), has the C of 4 to 5 ethylene oxide groups _12-14The different tridecyl alcohol of-Fatty Alcohol(C12-C14 and C12-C18) or ethoxylation.The average particle size particle size that suitable zeolite has is less than 10 microns (volume distributed median; Measuring method: the Coulter counter) also preferably contain 18 to 22 weight %, the more preferably combination water of 20 to 22 weight %.

The surrogate or the part surrogate that are suitable for as phosphoric acid salt and zeolite are general formula NaMSi _xO _2x+1YH ₂The crystallization of O, lamina sodium silicate, wherein M represents sodium and hydrogen, and x represents 1.9 to 4 number, and y is 0 to 20 number, and preferred x represents 2,3 or 4.This crystallization, layered silicate are for example by open among European patent application EP-A-0164514.The crystallization of preferred above-mentioned general formula, layered silicate are that wherein M represents that sodium, x represent those of 2 or 3.Preferred β-or δ-sodium disilicate Na ₂Si ₂O ₅YH ₂O.

Preferred builder material is an amorphous sodium silicate, its modulus N a ₂O: SiO ₂Be 1: 2 to 1: 3.3, preferred 1: 2 to 1: 2.8, preferred especially 1: 2 to 1: 2.6, it had the dissolving of delay and secondary washing characteristic.Compare with traditional amorphous sodium silicate, this delay dissolution characteristics can be obtained by variety of way, for example obtains by surface treatment, compound, compression/compression or by over-drying.Within the scope of the invention, term " amorphous " also refers to " X ray is amorphous ".Promptly in the X-ray diffraction test, silicate is the reflection of typical X ray for the crystalline state material for example, but has the peak value of one or more scattered x-rays at most not significantly that it has the width of several years diffraction angle to meaning.But, when in electron diffraction test, silicate granules have fuzzy or even clearly during diffraction peak, they very likely provide good washing assistant characteristic so.This may be interpreted as product and has the 10 crystallite scopes to the hundreds of nanometer, and wherein preferred this value maximum is 50 nanometers, especially is 20 nanometers to the maximum.For example in German patent application DE-A-44 00 024, disclose this and conventional water glass and compared, had the so-called X ray amorphous silicate that postpones dissolution characteristics equally.Particularly preferably be amorphous silicate, compound amorphous silicate and the over-drying X ray amorphous silicate of compression/compression.

Certainly also can use common known phosphate as washing assistant, as long as this use can thereby not be restricted owing to the former of ecological aspect.Suitable is ortho-phosphoric acid, tetra-sodium and the sodium salt of tri-polyphosphate especially.Usually be no more than 25 weight % based on final washing composition meter under every kind of situation of its content, preferably be no more than 20 weight %.In some cases, the result shows tri-polyphosphate mixed with other washing assistant, in addition when the content of tri-polyphosphate lower, the most nearly during 10 weight % (based on final washing composition meter), the collaborative improvement just arranged at the secondary washing aspect of performance.

For zeolite, suitable surrogate or part surrogate are natural or the synthetic layered silicate.This layered silicate for example is disclosed by patent application DE 23 34 899, EP 0 026 529 and DE 35 26 405, and its workability is not limited by concrete composition or structure formation.But, preferably terre verte, especially wilkinite.The suitable layered silicate that belongs to chance water swollen terre verte class for example is montmorillonite, hectorite or saponite.In addition, in the lattice of the layered silicate of above-mentioned general formula, can introduce a spot of iron.And according to its ion exchangeable, layered silicate can contain hydrogen, basic metal, alkaline-earth metal ions, especially Na ⁺And Ca ⁺⁺The content of water of hydration is 8 to 20 weight % normally, and depend on degree of swelling or treatment process.Spendable layered silicate for example is disclosed among US 3 966 629, EP 0 026 529 and the EP 0 028 432.Preferably use the layered silicate that does not have calcium ion and strong painted iron ion by alkaline purification basically.

Spendable organic washing-assisting detergent for example is the poly carboxylic acid that can its sodium-salt form uses, for example citric acid, hexanodioic acid, succsinic acid, pentanedioic acid, tartrate, saccharic acid, aminocarboxylic acid, nitrilotriacetic acid(NTA) (NTA), as long as this use can be because of ecology reason be restricted, and their mixture.Preferred salt be poly carboxylic acid for example citric acid, hexanodioic acid, succsinic acid, pentanedioic acid, tartrate, saccharic acid salt with and composition thereof.Also can use acid itself.This acid also has the characteristic of souring ingredients except having typical washing assistant effect, can be used for setting up the low and medium pH value in washing composition or the clean-out system thus.In this respect, optimization citric acid, Succinic Acid, pentanedioic acid, hexanodioic acid, glyconic acid and these sour any mixture.When in premixture of the present invention, using this acid and not being when mixing subsequently, preferably use anhydrous acid.Other suitable organic washing-assisting detergent material is a dextrin, for example oligopolymer of carbohydrate or polymkeric substance, and they obtain by partially hydrolysed starch.Hydrolysis can ordinary method, and for example acid catalysis or enzymatic process carry out.Preferably has molecular-weight average and is 400 to 500000 hydrolysate.At this, a kind of to have glucose equivalent (DE) be 0.5 to 40, and preferred 2 to 30 polysaccharide is preferred, and wherein DE is to be that 100 glucose is compared the yardstick commonly used of polysaccharide reductive action with DE.Can use not only that to have DE be 3 to 20 maltodextrin and to have DE be 20 to 37 dried grape sugar syrup, and can use so-called yellow starch gum and white dextrin with higher molecular weight of 2000 to 30000.Preferred dextrin is disclosed in European patent application EP 0 703 292 A1.For example in the oxidized derivatives of the oligose of this class dextrin, what relate to is the reaction product of dextrin and oxygenant, and this oxygenant can make the alcohol functional group of sugar ring be oxidized to carboxylic acid functional at least.Among European patent application EP 0 232 202, EP 0 427 349, EP 0 472 042 and EP 0 542 496 and International Patent Application WO 92/18542, WO93/08251, WO94/28030, WO95/07303, WO95/12619 and the WO95/20608 this oxidation dextrin and its preparation method are disclosed for example.A kind of C at the sugar ring ₆The product of last oxidation is particularly preferred.Oxidation oligose according to German patent application DE 196 00 018 also is fit to equally.Other second washing assistant that is fit to is other derivative of oxo disuccinic acid ester and disuccinic acid ester (Disuccinate), preferred ethylene diamine disuccinic acid ester.Particularly preferably be glycerine disuccinic acid ester and glycerine three succinates, as in US Patent specification US4 524 009, US 4 639 325, European patent application EP 0 150 930 and Japanese patent application JP 93/339896, describing.Containing zeolite and/or containing in the preparation of silicate, suitable amounts is 3 to 15 weight %.Other spendable second washing assistant for example is acetylizad hydroxycarboxylic acid or its salt; its in case of necessity also can lactone form exist; and it contains at least 4 carbon atoms and at least 1 hydroxyl and 2 acidic groups at the most, has described the example of this second washing assistant in International Patent Application WO 95/20029.The polymer poly-carboxylate's who is fit to example is the sodium salt of polyacrylic acid or polymethyl acrylic acid, and for example having relative molecular weight is this base polymer of 800 to 150000 (by acid).The multipolymer of preferred vinylformic acid of the polycarboxylate of suitable copolymerization and methacrylic acid and acrylic or methacrylic acid and toxilic acid.Specially suitable is to contain 50 to 90 weight % vinylformic acid and the vinylformic acid of 50 to 10 weight % toxilic acids and the multipolymer of toxilic acid.Its relative molecular weight is by free acid normally 5000 to 200000, and is preferred 10000 to 120000, and more preferably 50000 to 100000.(copolymerization) polymer poly-carboxylate's content is conventional amount used in the washing composition, preferred 1 to 10 weight %.Particularly preferably be by the biological decomposable polymkeric substance of monomeric unit polymeric different more than two kinds, for example contain the salt of vinylformic acid and toxilic acid and vinyl alcohol or vinyl alcohol derivatives and contain the salt of vinylformic acid and 2-alkyl allyl sulphonic acid and sugar derivatives as polymer of monomers as monomer with according to German patent DE 42 21 381 according to German patent application DE 43 00 772.Other preferred multipolymer is described in German patent application DE 43 03 320 and DE 44 17 734, and preferably contains propenal and vinylformic acid/acrylate or propenal and vinyl-acetic ester as monomer.Equally, other preferred washing assistant is polymeric dibasic amino acid, its salt or its precursor.Particularly preferably be disclosed poly aspartic acid or its salt or derivatives thereof among the German patent application DE 195 40 086, they also have the bleach stability effect except the characteristic with second washing assistant.Other washing assistant that is fit to is a polyacetal, and they are to obtain by dialdehyde is reacted with the multi-hydroxy carboxy acid with 5 to 7 carbon atoms and 3 hydroxyls at least, for example describe in European patent application EP 0 280 223.Preferred polyacetal be by dialdehyde for example oxalic dialdehyde, glutaraldehyde, terephthalaldehyde with and composition thereof and the multi-hydroxy carboxy acid, for example glyconic acid and/or glucoheptonic acid obtain.

In addition, washing composition also can contain other component that deoiling property and degrease to fabric have active effect.When having been made dirty with the detergent washing of the present invention fabric repeatedly that contains this molten oil or fat melting component in advance, this effect is obvious especially.Preferred molten oil and fat melting component for example are non-ionic ether of cellulose, for example methylcellulose gum and the methoxy content that has respectively based on the nonionic cellulose ether meter are that 15 to 30 weight %, propoxyl content are the methylhydroxypropylcellulose of 1 to 15 weight %, and by the polyester of the known phthalic acid of prior art and/or terephthalic acid and monomer and/or polymer diol or derivatives thereof, polymkeric substance or its negatively charged ion and/or the nonionic modified derivative of preferred ethylene glycol terephthalate and/or polyethyleneterephthalate.Particularly preferably be the sulfonated derivative of phthalic acid and terephthaldehyde's acid polymer.

Other appropriate ingredients is water miscible inorganic salt in the washing composition, for example supercarbonate, carbonate, amorphous silicate, for example above-mentioned delay dissolved silicate or their mixture; Preferred alkali metal carbonate and amorphous alkali metal silicate especially have mol ratio Na ₂O: SiO ₂Be 1: 1 to 1: 4.5, preferred 1: 2 to 1: 3.5 water glass, the content of yellow soda ash is preferably to reaching 20 weight %, preferred 5 to 15 weight % in the washing composition.If not using as washing assistant, the content of washing composition mesosilicic acid sodium is general to 10 weight % nearly, preferred 2 to 8 weight %, otherwise also comparable this is higher.According to the instruction of International Patent Application WO 94/01222, alkaline carbonate also available no sulphur, have 2 to 11 carbon atoms and have other carboxyl in case of necessity and/or amino amino acid and/or its salt replaces.Within the scope of the present invention, available glycine or glycinate part is to all replacing alkaline carbonates.

Other detergent component is again sedimentation inhibitor, defoamer, SYNTHETIC OPTICAL WHITNER and bleach activator, optical whitening agent, enzyme, fabric softener, dyestuff and spices and neutral salt, for example the vitriol of sodium or potassium and muriate.

In order to reduce the pH value of washing composition or clean-out system, also can add acid-salt or slightly be alkaline salt.To this, preferably use hydrosulfate and/or supercarbonate or also can make above-mentioned organic poly carboxylic acid that washing assistant uses simultaneously as souring ingredients.Particularly preferably be and in the solid premixture, use the citric acid that is impregnated in (ordinary method) or anhydrous form subsequently.

In water, provide H as SYNTHETIC OPTICAL WHITNER ₂O ₂Compound, the particularly important is sodium perborate tetrahydrate and Sodium peroxoborate monohydrate.The example of other spendable SYNTHETIC OPTICAL WHITNER is SPC-D, pyrophosphate peroxide, Citrate trianion perhydrate and H is provided ₂O ₂Persalt or peracid, for example peroxybenzoic acid salt, peroxide phthalate, twoly cross nonane diacid, phthaloyl imino peracid or two is crossed dodecanedioic acids.The content of SYNTHETIC OPTICAL WHITNER 5 to 25 weight % preferably are more preferably 10 to 20 weight % in the washing composition, wherein preferably use perborate monohydrate or percarbonate.

Can use crossing to form under the hydrolysising condition as bleach activator and preferably to have 1 to 10 carbon atom, the more preferably aliphatic peroxycarboxylic acid of 2 to 4 carbon atoms, and/or the compound of the peroxybenzoic acid that is substituted in case of necessity.Suitable is has the O-acyl group of described carbonatoms and/or N-acyl group and/or the compound of the benzoyl that is substituted in case of necessity.Preferred bleach activator is the Alkylenediamine of multiple acidylate; especially tetra acetyl ethylene diamine (TAED); the pyrrolotriazine derivatives of acidylate; especially 1; 5-diacetyl-2; 4-dioxo six hydrogen-1; 3; 5-triazine (DADHT); the glycoluril of acidylate; especially tetra-acetylated glycoluril (TAGU); N-acyl group imide; especially N-nonanoyl succinimide (NOSI); the phenolsulfonate of acidylate; especially positive nonanoyl-or different nonanoyl oxygen base benzene sulfonate (just-or different-NOBS); carboxylic acid anhydride; especially Tetra hydro Phthalic anhydride; the polyvalent alcohol of acidylate; especially triactin; diacetate glycol ester; 2; 5-diacetoxyl-2; 5-dihydrofuran and by German patent application DE-A-196 16 693 and DE-A-196 16 767 known enol esters and acetylizad Sorbitol Powder and mannitol or its mixture of describing at European patent application EP-A-0 525 239 (SORMAN); the sugar derivatives of acidylate; especially five acetyl glucose (PAG); five acetyl fructose; tetrem acyl wood sugar and octoacetyl lactose and acetylize; alkylating glycosamine of N-and glucono-lactone in case of necessity; and/or N-acetylize lactan; N-benzoyl caprolactam for example, they are by International Patent Application WO-A-94/27970; WO-A-94/28102; WO-A-94/28103; WO-A-95/00626; open among WO-A-95/14759 and the WO-A-95/17498.Equally also preferably use hydrophilic acyl group acetal and the German patent application DE-A-196 16 770 and the disclosed acyl lactam of International Patent Application WO-A-95/14075 of German patent application DE-A-196 16 769 disclosed replacements.Also can use the mixture of German patent application DE-A-44 43 177 disclosed conventional bleaching promoting agents.The consumption of this bleach activator is a conventional amount used, and based on washing composition total amount meter, preferably 1 to 10 weight % is more preferably 2 to 8 weight %.

When being used for the machine washing method, preferably in washing composition, add conventional defoamer.Suitable defoamer for example is natural or synthetic soap class, and they contain high-load C _18-24-lipid acid.The example of the defoamer of suitable non-ionic surface active is organopolysiloxane and they and fine, in case of necessity the mixture of the silicic acid of silanization and paraffin, wax, Microcrystalline Wax and they and the silicic acid of silanization or the mixture of distearyl ethylene diamide.Preferably use the mixture of various defoamers, for example the mixture of silicone, paraffin or wax.Preferably with defoamer, the defoamer that especially contains silicone and/or paraffin is combined on the carrier of granular, water-soluble or water dispersible.Particularly preferably be the mixture of paraffin and distearyl ethylene diamide here.

The preferred polyphosphonic acid salt that uses is such as 1-hydroxyl ethane-1, and the sodium salt of the neutralization reaction of 1-di 2 ethylhexyl phosphonic acid, diethylenetriamine pentamethylenophosphonic acid(DTPP) or ethylenediamine tetramethylene phosphonic acid, its consumption are 0.1 to 1.5 weight %

The preferred enzyme that uses is a lytic enzyme, for example proteolytic enzyme, lipase, lipolytic enzyme, amylase, cellulase or their mixtures, and same oxydo-reductase (Oxireduktase) also is suitable for.Particularly suitable is by bacterial strain or fungi, and for example the enzyme of subtilis, Bacillus licheniformis, streptomyces griseus and Humicola insolens acquisition is urged active substance.The proteolytic enzyme of subtilysin type preferably, the especially proteolytic enzyme that obtains by bacillus lentus.Here, particularly preferred proteolytic enzyme and amylase or the enzyme mixture of proteolytic enzyme and lipase or proteolytic enzyme and cellulase or the enzyme mixture of cellulase and lipase of being to use.In some cases, peroxidase or oxydase also are suitable for.Suitable amylase is α-Dian Fenmei, isoamylase, Starch debranching enzyme and polygalacturonase.Preferred cellulase for example is fiber biological lytic enzyme (Cellobiohydrolase), endoglucanase and the beta-glucosidase enzyme that is called cellobiase, perhaps their mixture.Because the difference of various types of cellulases only is the activity of its CMC enzyme and avicelase, therefore can reach desired activity by suitable cellulose mixture enzyme.These enzymes can be adsorbed on the carrier and/or be embedded in in the shell material, decompose in advance to prevent them.The content of enzyme, enzyme mixture or enzyme granulate for example is about 0.1 to 5 weight %, preferred 0.1 to 2 weight %.

Except above mentioned phosphonate, also can contain other enzyme stabilizers in the washing composition, the sodium formiate of for example available 0.5 to 1 weight %.Also can use with the stable proteolytic enzyme of soluble calcium salt, calcium contents is based on the preferably about 1.2 weight % of enzyme meter.Except that calcium salt, also can use magnesium salts as stablizer.But, preferably use boron compound, for example boric acid, boron oxide, borax and other alkali metal borate, for example orthoboric acid (H ₃BO ₃), metaboric acid (HBO ₂) and pyroboric acid (tetraboric acid H ₂B ₄O ₇).

The effect of sedimentation inhibitor is that the dirt that will come off from fiber keeps being suspended in the water lotion and prevents that dirt from passing through washing and absorption more again.To this, what be suitable for is most of organic water-soluble colloids, for example salt of the acid sulfate of the water-soluble salt of polymerization of carboxylic acid, gelatin, gelatin, starch or cellulosic ether carboxylate or ether sulfonate or Mierocrystalline cellulose or starch.The water soluble polyamide that contains acidic-group also is suitable for this purpose.In addition, can use the starch preparation of solubility and be different from above-mentioned starch products, for example Jiang Xie starch, starch aldehyde etc.Polyvinylpyrrolidone also is suitable for.But, ether of cellulose preferably, for example carboxymethyl cellulose (Na salt), methylcellulose gum, hydroxy alkyl cellulose and mixed ether, for example methyl hydroxyethylcellulose, methylhydroxypropylcellulose, methyl carboxymethyl cellulose and their mixture, and polyvinylpyrrolidone, its consumption is 0.1 to 5 weight % based on the washing composition meter.

Can contain the derivative of diaminostilbene disulfonic acid or their an alkali metal salt in the washing composition as optical whitening agent.What be suitable for for example is 4,4 '-two (2-anilino-4-morpholino-1,3,5-triazines base-6-amino) stilbene-2, the compound of 2 '-stilbene-4,4'-bis-(1-azo-3, 4-dihydroxy-benzene)-2,2'-disulfonate or homogeneous structure, morpholino group wherein replaces with diethanolamino, methylamino, anilino or 2-methoxy ethyl are amino.In addition, also can use the whitening agent of the biphenyl vinylbenzene fundamental mode of replacement, for example 4,4 '-two (2-sulfo group styryl) biphenyl, 4,4 '-an alkali metal salt of two (4-chloro-3-sulfo group styryl) biphenyl or 4-(4-chloro-styrene base)-4 '-(2-sulfo group styryl) biphenyl.Also can use the mixture of above-mentioned whitening agent.

Embodiment

Embodiment 1

Be prepared as follows washing composition E1 to E5 and be used for correlated non-washing composition V1 of the present invention and V2 (composition sees Table 1).

A batch mixer that is equipped with cutter head-breaking unit (knife mill) (20 liters, Loedige ^The ploughshare mixing tank) premixture list in the table 1 is formed in preparation in, wherein nonionogenic tenside through nozzle spray in flow of powder.Then, this mixture of uniform mixing is 2 minutes.Subsequently they being transported to the granulation head has been preheating in 50 to 65 ℃ the twin-screw extruder.Under the shearing action of extruder screw, the plasticizing premixture, pass through the porous nozzle plate of extruder head then, under the relevant pressure that in table 1, provides they are squeezed into diameter and are 1.4 millimeters bundle, after leaving the porous nozzle plate, by means of cutting unit they are cut into the particle (long and diameter than about 1, thermal cutting) of subglobular.With the hot particle that produces at commercially available Marumerizer ^Rounding is 1 minute in the balling machine, applies a kind of fine powder in case of necessity.

The bulk density of the extrudate of preparation with and the solubility test (L test) that is described below in analog value also list in the table 1.

Can see with removing, when using no water-swelling polymer WQP1 to WQP4 of the present invention, even compare under the lower usage quantity, under the squeeze pressure of obviously low (at least 30%), obtain high-quality product with the softening agent of routine.

In order to measure residue or dissolution characteristics (L test), under agitation (with centering, stirring-head is starched with 800 rev/mins of stirrings with agitator/rotation in 1.5 centimetres laboratory at the bottom of the beaker), in one 2 liters beaker, be sprinkled into 8 grams washing composition to be tested, and stirred 1.5 minutes down at 30 ℃.With hardness is that the water of 16 ° of d is tested.Then washing lotion is sieved (80 microns), the cold water of using minute quantity is at the dillying beaker.Dry sieve weighs up the residual quantity of washing composition to constant weight in 40 ℃ ± 2 ℃ loft drier.Mensuration is carried out 2 times; Residual quantity is the mean value (%) that secondary is measured separately., further tested usually greater than 20% o'clock in each result's deviation each other; But in present test, do not need.

In order to compare, prepared the washing composition V3 that in the finished product, contains with the E2 identical component, but wherein multipolymer not with anhydrous swelling form but adds with the form of about 30 weight % aqueous solution.Then drying is removed excessive water in fluidized-bed.The bulk density of extrudate V3 is 770 grams per liters, and the result of L-test is 28%.

The composition of spray-dired powder SP1 and SP2: the C of spray-dried powders 1:26.00 weight % ₉-C ₁₃-alkylbenzene sulfonate

8.50 the yellow soda ash of weight %

41.33 the zeolite A of weight % is based on the anhydrous active substance meter

9.50 the multipolymer sodium salt of the vinylformic acid of weight % and toxilic acid

1.00 the phosphonate of weight %

12.00 the water of weight %

0.42 the optical whitening agent of weight %

All the other are from the C of the salt spray dried powder 2:26.00 weight % of solution ₉-C ₁₃-alkylbenzene sulfonate

42.83 the zeolite A of weight % is based on the anhydrous active substance meter

5.50 the multipolymer sodium salt of the vinylformic acid of weight % and toxilic acid

1.00 the phosphonate of weight %

5.00 the yellow soda ash of weight %

6.00 the sodium sulfate of weight %

12.00 the water of weight %

0.42 the optical whitening agent of weight %

All the other are from the salt of solution

Table 1

Form	??E1	??E2	??E3	??E4	??E5	??V1	??V2
Form	??E1	??E2	??E3	??E4	??E5	??V1	??V2	Spray-dried powders 1	??62	??-	??62	??62	??64	??62	??-
Spray-dried powders 2	??-	??62	??-	??-	??-	??-	??62	Spray-dried powders 1	??62	??-	??62	??62	??64	??62	??-
Spray-dried powders 2	??-	??62	??-	??-	??-	??-	??62	?C _12/18-Fatty Alcohol(C12-C14 and C12-C18)+7EO	??6	??6	??6	??6	??5	??6	??6
Sodium peroxoborate-hydrate	??20	??20	??20	??20	??20	??20	??20	?C _12/18-Fatty Alcohol(C12-C14 and C12-C18)+7EO	??6	??6	??6	??6	??5	??6	??6
Sodium peroxoborate-hydrate	??20	??20	??20	??20	??20	??20	??20	?C _12/18-fatty alkyl vitriol ^a)	??7	??7	??7	??7	??6	??7	??7
Salt composite ^b)	??-	??-	??-	??-	??7	??-	??-	?C _12/18-fatty alkyl vitriol ^a)	??7	??7	??7	??7	??6	??7	??7
Salt composite ^b)	??-	??-	??-	??-	??7	??-	??-	?WQP1 ^c)	??5	??-	??-	??-	??-	??-	??-
?WQP2 ^d)	??-	??5	??-	??-	??-	??-	??-	?WQP1 ^c)	??5	??-	??-	??-	??-	??-	??-
?WQP2 ^d)	??-	??5	??-	??-	??-	??-	??-	?WQP3 ^e)	??-	??-	??5	??-	??-	??-	??-
?WQP4 ^f)	??-	??-	??-	??4	??6	??-	??-	?WQP3 ^e)	??-	??-	??5	??-	??-	??-	??-
?WQP4 ^f)	??-	??-	??-	??4	??6	??-	??-	Polyoxyethylene glycol (4000)	??-	??-	??-	??-	??-	??7,5	??7,5
Extrusion pressure [bar]	??70	??70	??70	??60	??50	??120	??100	Polyoxyethylene glycol (4000)	??-	??-	??-	??-	??-	??7,5	??7,5
Extrusion pressure [bar]	??70	??70	??70	??60	??50	??120	??100	Bulk density [g/l]	??780	??790	??780	??810	??800	??780	??790
The L-test	??8	??7	??4	??12	??9	??7	??5	Bulk density [g/l]	??780	??790	??780	??810	??800	??780	??790

A) active substance of 92 weight %, other of the sodium sulfate of 3.70 weight %, 2.80 weight % is from the salt of raw material and unsulfonated component, the water of 1.50 weight %

B) forming is sodium sulfate, the 10 weight % water of the yellow soda ash of 42.5 weight %, the water glass of 2.5 weight % (modulus 3.3), 45 weight %

C) polyvinylpyrrolidone (Luviskol of 10 weight % ^K30, the BASF of manufacturers) and the mixture of 90 weight % glycerine

D) 10 weight % vinylformic acid/maleic acid sodium salt (Sokalan ^CP5, the BASF of manufacturers) and the mixture of 90 weight % glycerine

E) mixture of 10 weight % bisphosphate starch and 90 weight % glycerine composition

F) mixture of forming by the ethylene glycol of the hydroxypropylated starch of 6 weight % and 94 weight %

Embodiment 2

Component listed in the table 2 (is removed no water-swelling polymer, outside the WQP) add in the ploughshare mixing tank (the Firma Loedige of manufacturers) of band knife mill with the temperature shown in the table 2 (temperature " all the other "), and they are mixed mutually, wherein, add liquid non-ionic surfactant as last component for the dust that bonds.Then add the no water-swelling polymer that has the listed temperature of table 2 (temperature WQP) equally respectively, after about 2 minutes, material begins to agglomerate into particle.After the remix 8 to 10 minutes, the saccharoid G1 to G11 that provides in the acquisition table 2, it has bulk density shown in the table 2 and solvability (measuring method is with embodiment 1) and has particle size distribution listed in the table 3.It should be noted that all components that can mix in the conventional washing composition especially, comprise enzyme, soil release polymer, foaming regulator and bleach activator (TAED) particle (G10 and G11).Table 2

Form	??G1	??G2	??G3	??G4	??G5	??G6	??G7	??G8	??G9	??G10	??G11
Form	??G1	??G2	??G3	??G4	??G5	??G6	??G7	??G8	??G9	??G10	??G11	SP?1 ^a)	??55	??56	??60	??58	??60	??58	??59	??52	??52	??45	??45
Sodium peroxoborate 1 H ₂O	??19	??19	??20	??20	??20	??20	??20	??17	??18	??15	??15	SP?1 ^a)	??55	??56	??60	??58	??60	??58	??59	??52	??52	??45	??45
Sodium peroxoborate 1 H ₂O	??19	??19	??20	??20	??20	??20	??20	??17	??18	??15	??15	C _12/18-fatty alkyl vitriol ^a)	??7	??7	??7	??7	??7	??7	??7	??7	??7	??8	??8
Fatty Alcohol(C12-C14 and C12-C18)+7EO ^a)	??5	??5	??6	??5	??6	??5	??6	??5	??5	??5	??5	C _12/18-fatty alkyl vitriol ^a)	??7	??7	??7	??7	??7	??7	??7	??7	??7	??8	??8
Fatty Alcohol(C12-C14 and C12-C18)+7EO ^a)	??5	??5	??6	??5	??6	??5	??6	??5	??5	??5	??5	Zeolite Na-A (powder)	??3	??3	??-	??-	??-	??-	??-	??3	??3	??3	??3
The enzyme granulate thing	??-	??-	??-	??-	??-	??-	??-	??-	??-	??2	??3	Zeolite Na-A (powder)	??3	??3	??-	??-	??-	??-	??-	??3	??3	??3	??3
The enzyme granulate thing	??-	??-	??-	??-	??-	??-	??-	??-	??-	??2	??3	Soil release polymer	??-	??-	??-	??-	??-	??-	??-	??-	??-	??1	??1
Foaming regulator	??-	??-	??-	??-	??-	??-	??-	??-	??-	??4	??4	Soil release polymer	??-	??-	??-	??-	??-	??-	??-	??-	??-	??1	??1
Foaming regulator	??-	??-	??-	??-	??-	??-	??-	??-	??-	??4	??4	Bleach activator	??-	??-	??-	??-	??-	??-	??-	??-	??-	??7	??7
Spices	??-	??-	??-	??-	??-	??-	??-	??-	??-	??1	??1	Bleach activator	??-	??-	??-	??-	??-	??-	??-	??-	??-	??7	??7
Spices	??-	??-	??-	??-	??-	??-	??-	??-	??-	??1	??1	WQP?5 ^b)	??-	??-	??-	??-	??-	??10	??-	??-	??-	??-	??-
WQP?4 ^c)	??11	??-	??7	??9	??7	??-	??-	??16	??-	??-	??-	WQP?5 ^b)	??-	??-	??-	??-	??-	??10	??-	??-	??-	??-	??-
WQP?4 ^c)	??11	??-	??7	??9	??7	??-	??-	??16	??-	??-	??-	WQP?6 ^d)	??-	??-	??-	??-	??-	??-	??8	??-	??-	??-	??-
WQP?7 ^e)	??-	??10	??-	??-	??-	??-	??-	??-	??15	??9	??9	WQP?6 ^d)	??-	??-	??-	??-	??-	??-	??8	??-	??-	??-	??-
WQP?7 ^e)	??-	??10	??-	??-	??-	??-	??-	??-	??15	??9	??9	Temperature WQP	??20	??20	??59	??40	??20	??20	??20	??20	??20	??20	??68
Temperature " all the other "	??20	??20	??20	??20	??58	??20	??20	??45	??45	??20	??68	Temperature WQP	??20	??20	??59	??40	??20	??20	??20	??20	??20	??20	??68
Temperature " all the other "	??20	??20	??20	??20	??58	??20	??20	??45	??45	??20	??68	Bulk density [g/l]	??661	??650	??710	??690	??740	??680	??690	??783	??790	??748	??730
The L-test	??7.6	??15.9	??3.9	??7.9	??7.6	??4.3	??6.8	??5.4	??5.4	??10.0	??5.5	Bulk density [g/l]	??661	??650	??710	??690	??740	??680	??690	??783	??790	??748	??730

A) form with embodiment 1

B) mixture of forming by 4 weight % hydroxypropylated starchs and 96 weight % ethylene glycol

C) with embodiment 1, the mixture of forming by 6 weight % hydroxypropylated starchs and 94 weight % ethylene glycol

D) mixture of forming by 8 weight % hydroxypropylated starchs and 92 weight % ethylene glycol

E) mixture of forming by 10 weight % hydroxypropylated starchs and 90 weight % ethylene glycol

Table 3: measure the size test of particle size distribution

	??G1	??G2	??G3	??G4	??G5	??G6	??G7	??G8	??G9	??G10	??G11
	??G1	??G2	??G3	??G4	??G5	??G6	??G7	??G8	??G9	??G10	??G11	On the 1.60mm sieve [%]	??16	??16	??3	??6	??7	??7	??8	??9	??5	??5	??5
On the 1.25mm sieve [%]	??24	??27	??11	??16	??14	??19	??16	??13	??10	??15	??8	On the 1.60mm sieve [%]	??16	??16	??3	??6	??7	??7	??8	??9	??5	??5	??5
On the 1.25mm sieve [%]	??24	??27	??11	??16	??14	??19	??16	??13	??10	??15	??8	On the 1.0mm sieve [%]	??16	??22	??11	??14	??12	??16	??12	??13	??13	??29	??18
On the 0.8mm sieve [%]	??21	??21	??23	??22	??22	??24	??24	??22	??16	??28	??26	On the 1.0mm sieve [%]	??16	??22	??11	??14	??12	??16	??12	??13	??13	??29	??18
On the 0.8mm sieve [%]	??21	??21	??23	??22	??22	??24	??24	??22	??16	??28	??26	On the 0.4mm sieve [%]	??19	??13	??47	??38	??41	??29	??38	??39	??49	??22	??40
By 0.4mm sieve [%]	??4	??1	??5	??4	??4	??5	??2	??4	??7	??1	??3	On the 0.4mm sieve [%]	??19	??13	??47	??38	??41	??29	??38	??39	??49	??22	??40

Embodiment 3

Prepare other granulated detergent G12 to G14 with embodiment 2, but be to use the intensive mixer (Fa.Eirich of manufacturers) that has inclined plate and whirlpool to replace the ploughshare mixing tank as granulating equipment.

Table 4

Form	G12	G13	G14
Form	G12	G13	G14	SP?1 ^a)	47	47	45
Sodium peroxoborate 1 H ₂O	16	16	15	SP?1 ^a)	47	47	45
Sodium peroxoborate 1 H ₂O	16	16	15	C _12/18-fatty alkyl vitriol ^a)	8	8	8
C _12/18-Fatty Alcohol(C12-C14 and C12-C18)+7EO ^a)	6	6	6	C _12/18-fatty alkyl vitriol ^a)	8	8	8
C _12/18-Fatty Alcohol(C12-C14 and C12-C18)+7EO ^a)	6	6	6	Zeolite Na-A (powder)	3	3	4
The enzyme granulate thing	3	3	3	Zeolite Na-A (powder)	3	3	4
The enzyme granulate thing	3	3	3	Soil release polymer	1	1	1
Foaming regulator	4	4	4	Soil release polymer	1	1	1
Foaming regulator	4	4	4	Bleach activator TAED	7	7	-
Bleach activator TAED ^b)	-	-	7	Bleach activator TAED	7	7	-
Bleach activator TAED ^b)	-	-	7	WQP?7 ^c)	5	5	7
Temperature WQP	20	48	20	WQP?7 ^c)	5	5	7
Temperature WQP	20	48	20	Temperature " all the other "	20	48	20
Bulk density [g/l]	813	784	737	Temperature " all the other "	20	48	20
Bulk density [g/l]	813	784	737	The L-test	3.8	3.6	4.9

A) form with embodiment 1

B) in aftertreatment, add

C) form with embodiment 2 tables 5: measure the size test of particle size distribution

	??G1	??G2	??G3
	??G1	??G2	??G3	On the 1.60mm sieve [%]	??4	??5	??5
On the 1.25mm sieve [%]	??8	??10	??13	On the 1.60mm sieve [%]	??4	??5	??5
On the 1.25mm sieve [%]	??8	??10	??13	On the 1.0mm sieve [%]	??12	??15	??20
On the 0.8mm sieve [%]	??17	??17	??20	On the 1.0mm sieve [%]	??12	??15	??20
On the 0.8mm sieve [%]	??17	??17	??20	On the 0.4mm sieve [%]	??47	??41	??35
By 0.4mm sieve [%]	??12	??12	??7	On the 0.4mm sieve [%]	??47	??41	??35

Claims

1. a bulk density is higher than the preparation method of the granulated detergent of 600g/l or clean-out system or multicomponent component or treated raw material, described multicomponent component or treated raw material mix described washing composition of formation or clean-out system with other composition, comprise washing composition or clean-out system mixture and/or raw material mixes and simultaneously or then form, wherein, at first prepare a kind of premixture, described premixture contains single raw material and/or mixture of planting, they exist with solid form under the pressure of room temperature and 1 crust, applying under the condition of force of compression subsequently, this premixture is made a kind of particle, and then be further processed in case of necessity or process, it is characterized in that premixture is anhydrous basically, and use a kind of under molding condition, particularly at room temperature and the shaping additive that under the pressure of 1 crust, is in a liquid state and exists with swollen polymer form in non-aqueous solution.

2. the method for claim 1 is characterized in that, the system that no water-swelling polymer is made up of anhydrous liq and polymkeric substance, wherein at room temperature, and in the presence of polymkeric substance, at least 20 times of this heights of viscosity ratio anhydrous liq of this system, particularly 300 to 5000 times.

3. claim 1 or 2 method is characterized in that, the viscosity of shaping additive at room temperature is 200 to 10000mPas, and particularly 400 to 6000mPas.

4. the method for claim 3 is characterized in that, under higher temperature, the viscosity of shaping additive is only different slightly with the viscosity number under the room temperature, and 60 ℃ down its viscosity be 250 to 2500mPas.

5. the method for one of claim 1 to 4, it is characterized in that, the anhydrous liq component of shaping additive be selected from room temperature be in a liquid state, boiling point (under 1 crust) surpasses 80 ℃, particularly surpasses 120 ℃ one, two or trivalent alcohol and the nonionogenic tenside that at room temperature is in a liquid state.

6. the method for claim 5, it is characterized in that, the anhydrous liq component of shaping additive is selected from n-propyl alcohol, Virahol, propyl carbinol, sec-butyl alcohol, isopropylcarbinol, ethylene glycol, 1,2-or 1, ammediol, glycerol, two-or three-ethylene glycol or-propylene glycol or its mixture.

7. the method for one of claim 1 to 6, it is characterized in that the polymkeric substance that produces the swelling system in anhydrous liq is selected from multipolymer, polyvinyl alcohol, xanthane, starch, alginate, the amylopectin of partial hydrolysis, the starch that carries methyl ether, hydroxyethyl ether, hydroxypropyl ether and/or hydroxyl butyl ether group or the Mierocrystalline cellulose of polyvinylpyrrolidone, polyacrylic acid, vinylformic acid and toxilic acid, starch such as bisphosphate starch and inorganic polymer such as the layered silicate and their mixture of phosphorylation.

8. the method for one of claim 1 to 7 is characterized in that, in shaping additive, the concentration of polymkeric substance in anhydrous liq is 5 weight % to 20 weight %, particularly 6 weight % to 12 weight %.

9. the method for one of claim 1 to 8 is characterized in that, based on premixture meter to be compressed, the content of shaping additive is below 2 weight % to the 20 weight %, particularly 3 weight % to 10 weight %.

10. the method for one of claim 1 to 9 is characterized in that, the shaping additive of use under the concentration of 8 grams, at least almost completely dissolved in 90 seconds in 1 premium on currency under 30 ℃.

11. the method for one of claim 1 to 10, it is characterized in that, the total water content of premixture is no more than 15 weight %, and wherein water does not exist with the free form, and preferably should not be no more than 10 weight % and particularly be lower than 7 weight % with zeolite and/or silicate bonded water-content.

12. the method for one of claim 1 to 11, it is characterized in that, compression molding is undertaken by agglomeration step, wherein make premixture carry out the agglomeration granulation in to this equipment that is fit to, and the shaping additive that exists with no water-swelling polymer form plays tackiness agent.

13. the method for claim 12; it is characterized in that the solids fraction of premixture to be compressed is placed in the tablets press, and mixing tank also can be used as tablets press; if desired by adding the dust that the liquid non-ionic surfactant bonding may exist, and in tablets press, introduce shaping additive.

14. the method for claim 12 or 13 is characterized in that, in agglomeration process, the kind and the amount of control machinery and operating parameters and the shaping additive that exists with no water-swelling polymer form are with the acquisition granular solid of approaching spherical (pearl) at least structurally.

15. the method for one of claim 1 to 11, it is characterized in that, form by extruding, wherein premixture is in pressure lower compression, plasticizing, porous nozzle plate by the extrusion machine head is squeezed into the pencil shape, and then the chopping mechanism by means of rotation preferably is cut into approximate spherical (pearl) to cylindrical pellet.

16. the method for one of claim 1 to 15 is characterized in that, the premixture that will have broad particle size distribution and higher fine particle per-cent is transformed into the finished product with narrower particle size distribution and low fine particle per-cent.

17. the preparation of the method for one of claim 1 to 16, bulk density is higher than granulated detergent or the clean-out system of 600g/l, be used for this mixture or treated raw material, wherein, at first prepare a kind of premixture, described premixture contains single raw material and/or mixture of planting, they exist with solid form under the pressure of room temperature and 1 crust, applying under the condition of force of compression subsequently, this premixture is made a kind of particle, and then be further processed in case of necessity or process, wherein premixture is anhydrous basically, and use a kind of under molding condition, particularly at room temperature and the shaping additive that under the pressure of 1 crust, is in a liquid state and exists with swollen polymer form in non-aqueous solution, it is characterized in that the solvability of granulated detergent or clean-out system depends on employed single solvability of planting raw material and mixture.

18. the composition of claim 17 is characterized in that they have polynuclear plane, has filled up solid matter in the nest chamber of honeycomb.

19. claim 17 or 18 granulation or the washing composition of extruding; it is characterized in that; its at least 80 weight % is made up of the mixture of the present invention's preparation and/or treated raw material; and especially at least 80 weight % are made up of the base particle or the basic extrudate of the present invention preparation, wherein particularly advantageous be when remaining component be the mixture for preparing of the method by one of claim 1 to 15 or treated raw material equally.

20. the washing composition of one of claim 17 to 19 is characterized in that, it contains the dust-like that adheres to by the fusion agglomeration or fine grain at least composition (so-called fine particle) as shell.