WO1999013045A1 - Verfahren zur herstellung teilchenförmiger wasch- oder reinigungsmittel - Google Patents

Verfahren zur herstellung teilchenförmiger wasch- oder reinigungsmittel Download PDF

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Publication number
WO1999013045A1
WO1999013045A1 PCT/EP1997/005945 EP9705945W WO9913045A1 WO 1999013045 A1 WO1999013045 A1 WO 1999013045A1 EP 9705945 W EP9705945 W EP 9705945W WO 9913045 A1 WO9913045 A1 WO 9913045A1
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WO
WIPO (PCT)
Prior art keywords
premix
weight
shaping
raw materials
compounds
Prior art date
Application number
PCT/EP1997/005945
Other languages
German (de)
English (en)
French (fr)
Inventor
Kathleen Paatz
Wilfried Rähse
Peter Sandkühler
Original Assignee
Henkel Kommanditgesellschaft Auf Aktien
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from PCT/EP1997/004975 external-priority patent/WO1998012299A1/de
Priority to EP97913181A priority Critical patent/EP1012221B1/de
Priority to JP2000510835A priority patent/JP2001515955A/ja
Priority to AT97913181T priority patent/ATE269399T1/de
Priority to DE59711728T priority patent/DE59711728D1/de
Priority to KR1020007002623A priority patent/KR20010023926A/ko
Application filed by Henkel Kommanditgesellschaft Auf Aktien filed Critical Henkel Kommanditgesellschaft Auf Aktien
Priority to EP98947499A priority patent/EP1015550B1/de
Priority to CN98810071.1A priority patent/CN1275160A/zh
Priority to KR1020007002612A priority patent/KR20010023917A/ko
Priority to DE59813373T priority patent/DE59813373D1/de
Priority to PCT/EP1998/005548 priority patent/WO1999013046A1/de
Priority to AT98947499T priority patent/ATE317003T1/de
Publication of WO1999013045A1 publication Critical patent/WO1999013045A1/de

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D11/00—Special methods for preparing compositions containing mixtures of detergents
    • C11D11/0082—Special methods for preparing compositions containing mixtures of detergents one or more of the detergent ingredients being in a liquefied state, e.g. slurry, paste or melt, and the process resulting in solid detergent particles such as granules, powders or beads
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/06—Powder; Flakes; Free-flowing mixtures; Sheets
    • C11D17/065—High-density particulate detergent compositions

Definitions

  • the invention relates to a process for the production of particulate detergents or cleaning agents or multi-component components which, when mixed with other ingredients, give such agents, with the aid of a specially adapted granulation process, and detergents or cleaning agents produced in this way.
  • Particulate detergents or cleaning agents with bulk densities above 600 g / 1 have been state of the art for some time.
  • the increase in the bulk density has been accompanied by a concentration of the detergent and cleaning active ingredients, so that the consumer not only had to dispense less volume but also less mass per washing or cleaning process.
  • the increase in the bulk density and, in particular, the higher concentration of the detergent or cleaning agent in the detergent was generally paid for by a subjectively poorer solubility from the point of view of the consumer, which was caused by the generally slower dissolving rate of the detergent used.
  • European patent EP 0 486 592 B1 describes granular or extruded detergents or cleaning agents with bulk densities above 600 g / l, the anionic and / or nonionic surfactants in amounts of at least 15% by weight and up to about 35% by weight. % contain. They are produced by a process in which a solid, free-flowing premix, which contains a plasticizer and / or lubricant from preferably aqueous surfactant pastes and / or aqueous polymer solutions, is extruded at high pressures between 25 and 200 bar and the extrudate exits the hole shape is cut and rounded to the predetermined granule dimension by means of a cutting device.
  • a solid, free-flowing premix which contains a plasticizer and / or lubricant from preferably aqueous surfactant pastes and / or aqueous polymer solutions
  • the premix consists at least in part solid ingredients, to which liquid ingredients such as nonionic surfactants that are liquid at room temperature are mixed.
  • liquid ingredients such as nonionic surfactants that are liquid at room temperature are mixed.
  • aqueous preparations are used as plasticizers and / or lubricants in preferred embodiments.
  • comparatively high-boiling organic liquids can also be used, if appropriate again in a mixture with water.
  • the patent does not disclose any process conditions to be observed in the case of an anhydrous extrusion.
  • the extrudates produced can either already be used as detergents or cleaning agents or can be subsequently processed with other granules or powder components to produce finished detergents or cleaning agents.
  • the German patent application DE 195 19 139 AI proposes to solve the conflict between the high degree of compaction of the individual grain, in particular the extrudate, on the one hand and the rapid and, in particular, non-gelling-free redissolubility of the finished washing or cleaning agent in aqueous liquors, particulate washing - or cleaning agents with a bulk density above 600 g / 1, which contain anionic and / or nonionic surfactants in amounts of at least 15% by weight, in such a way that at least two different granular components are used, of which at least one is extruded and at least one one is not extruded, the surfactant content of the extruded component including the soaps not exceeding 15% by weight, based on the respective extruded component.
  • non-extruded component s
  • This method does solve the problem of gelling highly compressed and high-surfactant washing or cleaning agents. agent when used in an aqueous liquor, but it also involves a number of new problems. Separation processes and accordingly fluctuations in the reproducibility of the desired washing or cleaning result can occur.
  • the extruded portion of the compositions is not only of high density, but the extrudates that are dried on are also comparatively hard. Under the conditions of transport, storage and use, the comparatively softer granulate fraction of the non-extruded component (s) can thus be exposed to mechanical forces, which in part lead to its reduction and thus to the formation of dust and fine particles through abrasion.
  • a method for the production of heavy granules with the aid of an aqueous granulating aid is the two-stage granulation, in which plastic primary agglomerates are first produced in a conventional mixer / granulator, which are then subsequently used in apparatus such as a rounder, rotocoater, marumerizer etc. with liquid binder and / or dust subsequently treated and usually then be dried.
  • the granulation and simultaneous rounding can be carried out, for example, in fluidized bed granulators which contain a rotating disk.
  • Solid starting materials are first fluidized in the fluidized bed and then agglomerated with liquid binder which is introduced into the fluidized bed via tangentially aligned nozzles ("Size Enlargement by Agglomeration", W. Pietsch, John Wiley & Sons, 1990, pages 450 to 451).
  • this method can also be used for non-aqueous processes (melt coating process), but in this case the advantage of the apparatus that it can cause simultaneous drying is not exploited.
  • the international patent application WO-A-93/02176 describes a process for the production of solid detergents or cleaning agents with high bulk densities by joining solid and liquid detergent or cleaning agent raw materials with simultaneous or subsequent shaping, with anionic surfactants and builder substances as solid constituents and liquid ones Components nonionic surfactants are used, the latter being provided in an intimate mixture with a structure breaker such as polyethylene glycol or polypropylene glycol or ethoxylated C 8 -C ] 8 fatty alcohols with 20 to 45 ethylene oxide groups (EO).
  • a structure breaker such as polyethylene glycol or polypropylene glycol or ethoxylated C 8 -C ] 8 fatty alcohols with 20 to 45 ethylene oxide groups (EO).
  • Preferred liquid nonionic surfactants are ethoxylated linear or methyl-branched alcohols in the 2-position which have 8 to 20 carbon atoms in the carbon chain and an average of 1 to 15 moles of ethylene oxide per mole of alcohol.
  • water is also described as a structure breaker which is suitable in principle, the use of which is less preferred, however, since the agents can become poor in water during storage due to the internal drying of the agents and thus the desired effect of the improved The release speed would no longer or not be fully effective due to the use of a structure breaker.
  • the mixtures of nonionic surfactants and structure breakers which are present either as a solution or as a dispersion, can be used in all known granulation processes in which separately produced compounds and / or raw materials are used.
  • Use in an extrusion process according to international patent application WO-A-91/02047 (or European patent EP 0 486 592 B1) is also possible and even preferred.
  • the use of aqueous solutions, pastes or aqueous dispersions is also suggested, the water, as stated above, not being used as a structure breaker and usually being dried off after the extrusion.
  • European patent application EP 0 337 330 describes a method for increasing the bulk density of a spray-dried detergent by granulation in a mixer with the addition of nonionic compounds.
  • nonionic compounds include ethoxylated and / or propoxylated nonionic surfactants such as primary or secondary alcohols with 8 to 20 carbon atoms and 2 to 20 moles of alkylene oxide per mole of alcohol, with nonionic surfactants in particular having 2 to 6 EO and HLB values of 11 or less being added to the mixer become.
  • Ethylene glycols and propylene glycols can also be used there as nonionic compounds.
  • European patent application EP 0 711 828 describes a process for the production of tablets, in which a coated particulate product is pressed.
  • the coating substance is a water-soluble binding or disintegrating agent with melting temperatures between 35 and 90 ° C. It is stated here as an essential feature that the compacting / tableting should be carried out at temperatures which are at least 28 ° C. but below the melting temperature of the binder.
  • Suitable nonionic surfactants are primary C ⁇ -C are indicated l5 alcohols having 3 to 7 EO.
  • Surfactant mixtures which contain up to 20% by weight of water are particularly advantageous in the context of the stated process, since this increases the viscosity of the mixture and makes the process more controllable.
  • the surfactant mixture can also contain polyethylene glycols.
  • builder agglomerates The production of builder agglomerates is described in US Pat. No. 5,108,646, 50 to 75 parts by weight of aluminosilicates or crystalline phyllosilicates being agglomerated with 20 to 35 parts by weight of a binder.
  • Suitable binders there are primarily highly viscous anionic surfactant pastes, which can contain up to 90% by weight of water.
  • polymers such as polyethylene glycols with molecular weights between 1000 and 20,000 are also possible, as are mixtures of these and customary nonionic surfactants such as Cg-Ci ö alcohols with 4 to 8 EO, as long as their melting range is not below 35 ° C or below 45 ° C begins.
  • the agglomeration takes place in a so-called intensive mixer with a very specific, relatively high energy input. With energy inputs above the specified values, over-agglomeration up to a dough-like mass occurs, with lower energy inputs only finely divided powders or very light agglomerates with an undesirably broad grain spectrum are obtained.
  • the object of the invention was to produce particulate detergents or cleaning agents or multicomponent components which, when mixed with other ingredients, produce such agents which, even with a reduced surface area, in particular with a spherical shape (pearl shape), improve disintegration when dissolved in the aqueous solution Have fleet.
  • the process should be economically favorable and be able to do without expensive drying steps.
  • the invention therefore relates to a process for the production of particulate detergents or cleaning agents or multicomponent components or treated raw materials which, when mixed with other ingredients, give such agents, with bulk densities above 600 g / 1, by combining detergent or cleaning agent compounds and / or raw materials with simultaneous or subsequent shaping, first of all producing a premix which contains individual raw materials and / or compounds which are in the form of solids at room temperature and a pressure of 1 bar, and then converting this premix into a grain using compression forces and, if appropriate, using it then further processed or prepared, which is characterized in that the premix is essentially water-free and a molding which is liquid under the molding conditions, in particular also at room temperature and a pressure of 1 bar aids in the form of a polymer swollen in non-aqueous solution.
  • essentially water-free is understood to mean a state in which the content of liquid water, ie water not present in the form of hydrate water and / or constitutional water, is below 2% by weight, preferably below 1% by weight. % and in particular even less than 0.5% by weight, based in each case on the premix, and accordingly water can essentially only be in chemically and / or physically bound form or as a constituent of at temperatures below 45 ° C. at a pressure of 1
  • Raw materials or compounds which are present as a solid, but not as a liquid, solution or dispersion, are advantageously introduced into the process for producing the premix.
  • the premix has a total water content of not more than 15% by weight, so this water is not in liquid free form, but is chemically and / or physically bound, and it is particularly preferred that the go old of water not bound to zeolite and / or silicates in the solid premix is not more than 10% by weight, preferably less than 7% by weight and, with particular preference, not more than 2% by weight to 5% by weight.
  • Particle-shaped detergents or cleaning agents in the context of the invention are preferably understood to mean those which have no dust-like constituents and in particular no particle sizes below 200 ⁇ m.
  • those particle size distributions are preferred which have at least 90% by weight of particles with a diameter of at least 400 ⁇ m.
  • the washing or cleaning agents, compounds or treated raw materials consist of at least 70% by weight, advantageously at least 80% by weight and, with particular preference, up to 100% by weight of spherical (pearl-shaped) particles with a particle size distribution which has at least 80% by weight of particles between 0.8 and 2.0 mm.
  • Particulate detergents or cleaning agents within the meaning of the present invention can also be tablets with dimensions customary for detergent or cleaning agent tablets for household applications, for example with weights from 15 g to 40 g, in particular from 20 g to 30 g, with a diameter of approximately 35 mm to 40 mm.
  • Anhydrously swollen polymers which are used as shaping aids in the context of the present invention are those which lead to gel-like states in non-aqueous liquids.
  • Systems of non-aqueous liquid and polymer are particularly suitable which, at room temperature in the presence of the polymer, have a viscosity which is at least 20 times, in particular 300 to 5000 times, higher than that of the non-aqueous liquid alone.
  • the viscosity of the shaping aid is preferably in the range from 200 mPas to 100,000 mPas at room temperature, in particular from 400 mPas to 6,000 mPas, measured, for example, using a Brookfield rotational viscometer.
  • the viscosity preferably deviates only slightly from the values at room temperature and is preferably in the range from 250 mPas to 2500 mPas.
  • Suitable liquids include mono-, di- or trihydric alcohols which are liquid at room temperature and have boiling points (at 1 bar) above 80 ° C, in particular above 120 ° C, such as n-propanol, iso-propanol, n-butanol, see -Butanol, iso-butanol, ethylene glycol, 1,2- or 1,3-propylene glycol, glycerin, di- or triethylene or propylene glycol or mixtures thereof, in particular glycerol and / or ethylene glycol, and the representatives of the liquid at room temperature nonionic surfactants listed below.
  • nonionic surfactants are known to tend to gel when they come into contact with water, when used as a non-aqueous solvent for the polymer in the molding aid used according to the invention there is no stickiness of the end product.
  • Suitable polymers which lead to swollen systems in such anhydrous liquids are polyvinylpyrrolidone, polyacrylic acid, copolymers of acrylic acid and maleic acid, polyvinyl alcohol, xanthan, partially hydrolyzed starches, alginates, amylopectin, methyl ether, hydroxyethyl ether, hydroxypropyl ether and / or hydroxybutyl ether.
  • Group-bearing starches or celluloses phosphated starches such as starch disphosphate, but also inorganic polymers such as layered silicates and their mixtures.
  • polyvinylpyrrolidones those with relative molecular weights of up to a maximum of 30,000 are preferred. Relative molecular weight ranges between 3000 and 30,000, for example around 10,000, are particularly preferred here.
  • the preferred polymers also include hydroxypropyl starch and starch diphosphate.
  • the concentration of the polymers in the anhydrous liquids is preferably 5% by weight to 20% by weight. in particular about 6% to 12% by weight.
  • the content of shaping aids is preferably at least 2% by weight, but less than 20% by weight, in particular less than 15% by weight, with particular preference for amounts in the range of 3% by weight up to 10% by weight.
  • only one or the shaping aid will be mentioned for the sake of simplicity. However, it should be made clear that the use of several different shaping aids and mixtures of different shaping aids is always possible.
  • Detergents or cleaning agents are understood to mean compositions of this type which can be used for washing or cleaning without usually having to add further ingredients.
  • a multicomponent mixture or compound consists of at least 2 components usually used in detergents or cleaning agents; However, compounds are normally only used in a mixture with other components, preferably together with other compounds.
  • a treated raw material is a relatively finely divided raw material which has been converted into a coarser particle by the process according to the invention. Strictly speaking, a treated raw material in the context of the invention is a compound if the treatment agent is an ingredient usually used in washing or cleaning agents.
  • the ingredients used in the process according to the invention can be separately produced compounds, but also raw materials which are powdery or particulate (fine-particle to coarse), but in any case at room temperature and a pressure of 1 bar - with the exception of those which may be present at temperatures below 45 ° C and a pressure of 1 bar liquid non-ionic surfactants - in solid form.
  • Particles can be used, for example, beads produced by spray drying or agglomerates of a granulation process etc.
  • the composition of the compounds per se is not essential to the invention with the exception of the water content, which must be such that the premix is essentially anhydrous as defined above and preferably not more than 10% by weight of water of hydration and / or water of constitution contains.
  • over-dried compounds are used in the premix.
  • Such compounds can be obtained, for example, by spray drying, the temperature control being regulated in such a way that the tower outlet temperatures are above 100 ° C., for example at 110 ° C. or above.
  • solid compounds in the premix which serve as carriers for liquid components, for example liquid nonionic surfactants or silicone oil and / or paraffins.
  • These compounds can contain water within the scope specified above, the compounds being free-flowing and preferably remaining free-flowing or at least conveyable even at higher temperatures of at least 45 ° C.
  • the water which is to be regarded as less critical on builder substances such as zeolite or silicates, in particular if the water is bound to zeolite A, zeolite P or MAP and / or zeolite X, is less critical.
  • builder substances such as zeolite or silicates, in particular if the water is bound to zeolite A, zeolite P or MAP and / or zeolite X, is less critical.
  • water which is bound to solid constituents other than the builder substances mentioned is preferably present in the premix in amounts of less than 3% by weight.
  • the content of bound water in the premix is not more than 10% by weight and / or the content of water not bound to zeolite and / or silicates is less than 7% by weight. and is in particular a maximum of 2 to 5% by weight. It is particularly advantageous if the premix contains no water at all, which is not bound to the builder substances. However, this is difficult to achieve from a technical point of view, since traces of water are usually always brought in by the raw materials and compounds.
  • the content of the solid compounds used in the premix at non-aqueous liquid components at temperatures below 45 ° C., excluding the shaping aid which is liquid at room temperature, is preferably up to 10% by weight, advantageously up to 6% by weight, in each case based on the premix.
  • solid compounds are used in the premix, which contain customary nonionic surfactants which are liquid at temperatures below 45 ° C. and a pressure of 1 bar and which have been produced separately by all known production methods, for example by spray drying, granulation or spraying of carrier beads.
  • premixes can be prepared which, for example, allow up to about 10% by weight, preferably below, in particular up to a maximum of 8% by weight and, for example, between 1 and 5% by weight of nonionic surfactants, based on the finished composition .
  • the melting point or the softening point of all the individual raw materials and compounds used in the premix is preferably above 45 ° C. and advantageously at least 50 ° C.
  • the shaping temperatures will not be above 150 ° C, preferably not above 120 ° C.
  • at least 80% by weight of the Compounds and individual raw materials used have a softening point or melting point above 150 ° C at normal pressure (1 bar).
  • the premix can contain up to 10% by weight of liquid nonionic surfactants at temperatures below 45 ° C. and a pressure of 1 bar, in particular the alkoxylated alcohols usually used in detergents or cleaning agents. such as fatty alcohols or oxo alcohols with a carbon chain length between 8 and 20 and in particular 3 to 7 ethylene oxide units per mole of alcohol.
  • the liquid nonionic surfactants can be added in amounts which still ensure that the premix is in free-flowing form. If such liquid nonionic surfactants are introduced into the premix, it is preferred that liquid nonionic surfactants and the disintegrating shaping aid are introduced into the process separately from one another.
  • the liquid surfactants are applied to the powder stream in a continuous production process, in particular by means of nozzles, and are sucked up by the latter.
  • the premix also contains at least one raw material or at least one compound which, as stated above, serves as a shaping aid.
  • the shaping aid in the form of the water-swollen polymer can be mixed with the other constituents of the premix before the shaping step. This is particularly preferred if the shaping is carried out by an extrusion step or with the aid of a tableting or other pressing process. It can also be sprayed onto the premix during the shaping or added dropwise to the premix, which is particularly preferred during shaping by means of build-up granulation.
  • the temperature during the shaping step is preferably at room temperature or the temperature resulting from the energy input of the shaping device, but it is also possible to increase the premix and, if appropriate, the shaping aid to be added separately during shaping to higher temperatures, for example 35 ° C. to 80 ° C. to heat, temperatures in the range of 45 ° C to 65 ° C can be particularly advantageous.
  • the shaping aid in the densifying shaping process step is as homogeneous as possible in the is well distributed.
  • the applicant is of the opinion that by homogeneously distributing the shaping aid in the sense of a binder within the premix under the process conditions of compression, the solid compounds and any individual raw materials present are surrounded by the binder and then together are glued that the finished end products are built almost exactly from these many small individual particles, which are held together by the binder, which takes over the function of a preferably thin partition between these individual particles.
  • a honeycomb-like structure can be assumed, whereby these honeycombs are filled with solids (compounds or individual raw materials).
  • the shaping aid must therefore be of the type that the adhesive properties come into play at the temperatures of the shaping.
  • it is also essential for the choice of the type and the amount of the shaping aid used that, although the binding properties are not lost after the shaping step within the end product, the cohesion of the end product is thus ensured, but that the end product itself is stored under normal storage and transport conditions not glued. It must be surprising that when the shaping aid which is liquid at room temperature is used, an end product is nevertheless obtained which does not tend to stick either at room temperature or at slightly elevated temperatures of around 30 ° C., that is to say at summer temperatures and under storage or transport conditions.
  • the assembly of the detergent or cleaning agent compounds and / or raw materials with simultaneous or subsequent shaping can be carried out by conventional methods in which compaction forces such as granulation, compacting, for example Roll compacting or extruding, or tableting, optionally with the addition of conventional disintegrants, and pelleting.
  • Spray-dried granules can also be used as prefabricated compounds in the premix, but the invention is by no means restricted to this. Rather, it is advisable in the method according to the invention not to use spray-dried granules, since even very finely divided raw materials with dust-like fractions can be processed without problems according to the invention without being pre-compounded, for example spray-dried.
  • the essentially water-free procedure not only enables peroxy bleaching agents to be processed without loss of activity, it also enables peroxy bleaching agents and bleach activators to be processed together in one particle without fear of serious loss of activity.
  • the densifying shaping of the process is carried out with the aid of an agglomeration step, the premix being granulated in a suitable device and the shaping aid defined above assumes the role of a binder.
  • the granulation process can be carried out continuously or batchwise. The procedure is preferably such that the solid constituents of the premix to be compacted are placed in a granulator, in which a mixer can also be used, optionally by adding a liquid nonionic surfactant to bind any dusts present and the shaping aid is introduced into the granulator .
  • the desired average particle size of the granulate can be set via the type and amount of shaping aid and via the machine and operating parameters, such as speed and residence time as well as temperature.
  • Suitable pelletizers include, for example, pelletizers, rotary drums, ploughshare mixers with choppers from Lödige®, high-performance mixers with rotating mixing tanks and whirlers, for example from Laeis Bucher® or Eirich®, intensive mixers with shaving heads, for example from LIPP Mischtechnik® or Imcatec®-, Drais ®, Fukae® or Forberg® mixers and the so-called Rotorcoater® from Glatt® with a horizontal and inclined turntable up to 50 °.
  • Lödige® CB mixers, Zig-Zag mixers from PK-Niro®, a Ballestra® chain mix and Hosokawa® or Schugi® mixers are less suitable.
  • a fluid bed or a horizontal mixer for example a Nautamixer®, is also less suitable.
  • the process is preferably carried out at room temperature or the temperature resulting from the energy input from the mixer or granulator, that is to say without a separate heating step, as described, for example, in international patent application WO 94/13779 and the prior art cited therein.
  • An advantage of the process according to the invention is that there is no need to rely on a two-stage granulation process, for example described in European patent application EP 0 367 339, in which granules are first compressed in a high-speed mixer and then in a slow-running mixer and granulator. but can use the anhydrous swollen polymer to carry out the compacting granulation in just one step.
  • Agents in tablet form according to the invention can be produced by means of conventional tablet presses, for example eccentric presses or rotary presses, with compression pressures in the range from, for example, 200 10 5 Pa to 1 500 10 5 Pa.
  • the solids for producing the solid and free-flowing premix are first mixed together at room temperature to slightly elevated temperatures, which are preferably in the range from room temperature to 35 ° C., in a conventional mixing and / or granulating device.
  • the compression step of the process according to the invention is then carried out by extrusion of the premix obtained in this way, as described, for example, in European patent EP 0486 592 B1 or international patent applications WO-A-93/02176 and WO-A-94/0911 1.
  • the premix is pressed under the form of a strand under pressure and the strand is cut to the predeterminable size of the granulate after it has emerged from the hole shape by means of a cutting device.
  • the homogeneous and solid premix usually contains a plasticizer and / or lubricant, which causes the premix to become plastically softened and extrudable under the pressure or under the entry of specific work.
  • a plasticizer and / or lubricant which causes the premix to become plastically softened and extrudable under the pressure or under the entry of specific work.
  • these include in particular anionic surfactants such as alkylbenzenesulfonates and / or (fatty) alkyl sulfates, but also polymers such as polymeric polycarboxylates.
  • anionic surfactants such as alkylbenzenesulfonates and / or (fatty) alkyl sulfates
  • polymers such as polymeric polycarboxylates.
  • the premix is preferably fed continuously to a planetary roller extruder or a 2-screw extruder or 2-screw extruder with co-rotating or counter-rotating screw guide, the housing and the extruder pelletizing head of which can be heated to the predetermined extrusion temperature.
  • the premix is compressed, plasticized, extruded in the form of fine strands through the perforated die plate in the extruder head and finally, under pressure, which is preferably at least 25 bar, but can also be lower at extremely high throughputs depending on the apparatus used the extrudate is preferably reduced to approximately spherical to cylindrical granules by means of a rotating knife.
  • the hole diameter of the perforated nozzle plate and the strand cut length are matched to the selected granulate dimension.
  • the production of granules of an essentially uniformly predeterminable particle size succeeds, and in particular the absolute particle sizes can be adapted to the intended use.
  • particle diameters up to at most 0.8 cm are preferred.
  • Important embodiments provide for the production of uniform granules in the millimeter range, for example in the range from 0.5 to 5 mm and in particular in the range from approximately 0.8 to 3 mm.
  • the length / diameter ratio of the chipped primary granules is in the range from about 1: 1 to about 3: 1.
  • extrusions / pressings can also be carried out in low-pressure extruders, in the Kahl press or in the Bextruder®.
  • any edges present on the primary granulate after the compression step are rounded off, so that ultimately spherical to approximately spherical grains can be obtained if these do not already arise in the first compacting shaping step.
  • small amounts of dry powder for example zeolite powder such as zeolite NaA powder, can also be used in this step. This shape can be done in standard rounding machines. Care should be taken to ensure that only small amounts of fine grain are produced in this stage. Drying, which is described as a preferred embodiment in the abovementioned documents of the prior art, is unnecessary in the context of the present invention, since the process according to the invention is essentially water-free, that is to say without the addition of free, non-bound water.
  • the particle size distribution of the premix is designed to be substantially wider than that of the end product produced according to the invention and according to the invention.
  • the premix can contain much larger fine-grained fractions, even dust, and possibly also coarser-grained fractions, although it is preferred that a premix with a relatively broad particle size distribution and relatively high fractions of fine-grained material in an end product with a relatively narrow particle size distribution and relatively small fractions of fine-grain is transferred.
  • the method of the invention is essentially anhydrous - i.e. with the exception of water contents ("impurities") of the solid raw materials used, water-free, not only is the risk of gelling of the surfactant raw materials minimized to ruled out in the manufacturing process, in addition, an ecologically valuable process is also provided, since by dispensing with one subsequent drying step not only saves energy but also emissions, as they occur mainly with conventional drying methods, can be avoided.
  • agents, compounds and treated raw materials thus produced have an improved dissolution rate compared to agents, compounds and treated raw materials which, although they have the same final Have composition, but were not produced by the process according to the invention, that is, were not produced under anhydrous conditions using an anhydrously swollen polymer as a shaping aid.
  • the invention further relates to a particulate washing or cleaning agent which was produced by the process according to the invention and whose dissolving behavior is only dependent on the dissolving behavior of the individual raw materials and compounds used.
  • this particular dissolving behavior is brought about by a honeycomb-like structure of the particles, these honeycombs being filled with solid.
  • the invention further provides compounds and treated raw materials, for example builder granules, bleach activator granules or enzyme granules, produced using the method according to the invention.
  • Treated raw materials in particular show an astonishingly high dissolution rate in water, especially when the raw material itself has been used in a very finely divided, optionally ground form.
  • base granules, compounds and treated raw materials are provided which are spherical or pearl-shaped.
  • the bulk density of process end products produced according to the invention is preferably above 700 g / 1, in particular between 750 and 1000 g / 1. Even if the granules are processed with other ingredients that have lower bulk densities, the bulk density of the end product does not decrease to the extent that would normally have been expected. It is believed that approximately spherical agents and especially extrudates made by the process of the present invention are more like the ideal shape of a sphere with a smooth, "smeared" surface than the agents and extrudates made by conventional and especially aqueous processes Space filling is achieved, which leads to a higher bulk density, even if components are mixed that have neither spherical structure nor such a high bulk density.
  • the particulate process end products obtained can either be used directly as detergents or cleaning agents or aftertreated beforehand by customary methods and / or be processed.
  • the usual aftertreatments include, for example, powdering with finely divided ingredients from detergents or cleaning agents, for example zeolites, which may further increase the bulk density.
  • a preferred aftertreatment is also the procedure according to German patent applications DE 195 24 287 and DE 195 47 457, dusty or at least fine-particle ingredients (the so-called fine particles) being adhered to the particle-shaped end products of the process, which serve as the core, and thus Means are created which have these so-called fines as an outer shell.
  • Processing is generally understood to mean that the particulate process end products produced according to the invention serve as a compound to which other constituents, if appropriate also other compounds, are admixed.
  • bleach activators and foam inhibitors especially salts such as silicates (crystalline or amorphous) including metasilicate, carbonate, bicarbonate, sulfate, bisulfate, citrate or other polycarboxylates, but also organic acids such as citric acid are mixed in the preparation.
  • the admixing components are used in granular form and with a particle size distribution which is matched to the particle size distribution of the agents and compounds prepared according to the invention.
  • a particulate detergent which consists of at least 80% by weight of compounds and / or treated raw materials produced according to the invention. In particular, it consists of at least 80% by weight of a base granulate produced according to the invention.
  • the remaining ingredients can be prepared and admixed by any known method. However, it is it is preferred that these remaining constituents, which may be compounds and / or treated raw materials, were also produced by the process according to the invention. In particular, this enables basic granules and remaining constituents to be produced with approximately the same pourability, bulk density, size and particle size distribution.
  • surfactants in particular anionic surfactants, which are preferably present in the agents according to the invention or the agents produced according to the invention at least in amounts of 0.5% by weight.
  • anionic surfactants include in particular sulfonates and sulfates, but also soaps.
  • Preferred surfactants of the sulfonate type are C 3 -C 3 -alkylbenzenesulfonates, olefin sulfonates, that is to say mixtures of alkene and hydroxyalkanesulfonates, and disulfonates such as are obtained, for example, from C 2 -C 8 monoolefins with an end or internal double bond by sulfonation with gaseous sulfur trioxide and subsequent alkaline or acidic hydrolysis of the sulfonation products.
  • alkanesulfonates which are obtained from -C 8 alkanes, for example by sulfochlorination or sulfoxidation with subsequent hydrolysis or neutralization.
  • esters of ⁇ -sulfofatty acids for example the ⁇ -sulfonated methyl esters of hydrogenated coconut, palm kernel or tallow fatty acids, which by ⁇ -sulfonation of the methyl esters of fatty acids of vegetable and / or animal origin with 8 to 20 C- Atoms in the fatty acid molecule and subsequent neutralization to water-soluble mono-salts are considered.
  • ⁇ -sulfonated esters of hydrogenated coconut, palm, palm kernel or tallow fatty acids with sulfonation products of unsaturated fatty acids, for example oleic acid, in small amounts Amounts, preferably in amounts not above about 2 to 3% by weight, can be present.
  • ⁇ -sulfofatty acid alkyl esters are preferred which have an alkyl chain with no more than 4 carbon atoms in the ester group, for example methyl esters, ethyl esters, propyl esters and butyl esters.
  • the methyl esters of ⁇ -sulfofatty acids (MES), but also their saponified disalts, are used with particular advantage.
  • Suitable anionic surfactants are sulfonated fatty acid glycerol esters, which are mono-, di- and triesters and mixtures thereof, as obtained in the preparation by esterification by a monoglycerol with 1 to 3 mols of fatty acid or in the transesterification of triglycerides with 0.3 to 2 mols of glycerol .
  • alk (en) yl sulfates the alkali and in particular the sodium salts of the sulfuric acid semiesters of the C 2 -C 8 fatty alcohols, for example from coconut fatty alcohol, tallow fatty alcohol, lauryl, myristyl, cetyl or stearyl alcohol or the C 1 -C 2 o-oxo alcohols and those half-esters of secondary alcohols of this chain length are preferred.
  • alk (en) yl sulfates of the chain length mentioned which contain a synthetic, straight-chain alkyl radical prepared on a petrochemical basis and which have a degradation behavior analogous to that of the adequate compounds based on oleochemical raw materials.
  • the sulfuric acid monoesters of the straight-chain or branched C 7 -C 2 i -alcohols ethoxylated with 1 to 6 mol of ethylene oxide such as 2-methyl-branched C -Cu -alcohols with an average of 3.5 mol of ethylene oxide (EO) or C ⁇ 2 -C] 8 -Fatty alcohols with 1 to 4 EO are suitable. Because of their high foaming behavior, they are normally only used in relatively small amounts in detergents, for example in amounts of 1 to 5% by weight.
  • anionic surfactants are also the salts of alkylsulfosuccinic acid, which are also referred to as sulfosuccinates or as sulfosuccinic acid esters and which are monoesters and / or diesters of sulfosuccinic acid with alcohols, preferably fatty alcohols and especially ethoxylated fatty alcohols.
  • Preferred sulfosuccinates contain C 8 to C 8 fatty alcohol residues or mixtures thereof.
  • Particularly preferred sulfosuccinates contain a fatty alcohol residue which is derived from ethoxylated fatty alcohols, which are nonionic surfactants in themselves.
  • sulfosuccinates whose fatty alcohol residues differ from ethoxylated fatty alcohols with a narrow homolog distribution derive, particularly preferred. It is also possible to use alk (en) ylsuccinic acid with preferably 8 to 18 carbon atoms in the alk (en) yl chain or salts thereof. Fatty acid derivatives of amino acids, for example of N-methyl taurine (taurides) and / or of N-methyl glycine (sarcosides) are suitable as further anionic surfactants.
  • the sarcosides or sarcosinates, and in particular sarcosinates of higher and optionally mono- or polyunsaturated fatty acids such as oleyl sarcosinate, are particularly preferred.
  • Other suitable anionic surfactants are, in particular, soaps, preferably in amounts of 0.2 to 5% by weight.
  • Saturated fatty acid soaps are particularly suitable, such as the salts of lauric acid, myristic acid, palmitic acid, stearic acid, hydrogenated erucic acid and behenic acid, and in particular soap mixtures derived from natural fatty acids, for example coconut, palm kernel or tallow fatty acids.
  • the known alkenylsuccinic acid salts can also be used together with these soaps or as a substitute for soaps.
  • the anionic surfactants can be present in the form of their sodium, potassium or ammonium salts and as soluble salts of organic bases, such as mono-, di- or triethanolamine.
  • the anionic surfactants are preferably in the form of their sodium or potassium salts, in particular in the form of the sodium salts.
  • the anionic surfactants are contained or used in the agents according to the invention or in the method according to the invention preferably in amounts of 1 to 30% by weight and in particular in amounts of 5 to 25% by weight.
  • nonionic surfactants are particularly preferred.
  • the nonionic surfactants used are preferably alkoxylated, advantageously ethoxylated, in particular primary alcohols having preferably 8 to 18 carbon atoms and an average of 1 to 12 moles of ethylene oxide (EO) per mole of alcohol, in which the alcohol radical can be linear or preferably methyl-branched in the 2-position or may contain linear and methyl-branched radicals in the mixture, as are usually present in oxo alcohol radicals.
  • EO ethylene oxide
  • alcohol ethoxylates with linear residues of alcohols of native origin with 12 to 18 carbon atoms, for example from coconut, palm, tallow or oleyl alcohol, and an average of 2 to 8 EO per mole of alcohol are particularly preferred.
  • the preferred ethoxylated alcohols include, for example, -C 2 -C 4 alcohols with 3 EO or 4 EO, C 9 -Cn alcohols with 7 EO, C ⁇ 3 -C ⁇ 5 alcohols with 3 EO, 5 EO, 7 EO or 8 EO, C ⁇ 2 -C ⁇ 8 alcohols with 3 EO, 5 EO or 7 EO and mixtures of these, such as mixtures of C 2 -C ) alcohol with 3 EO and C 2 -C 8 alcohol with 7 EO.
  • the degrees of ethoxylation given represent statistical averages, which can be an integer or a fraction for a specific product.
  • Preferred alcohol ethoxylates have a narrow homolog distribution (narrow range ethoxylates, NRE).
  • fatty alcohols with more than 12 EO can also be used. Examples of these are (tallow) fatty alcohols with 14 EO, 16 EO, 20 EO, 25 EO, 30 EO or 40 EO.
  • the nonionic surfactants also include alkyl glycosides of the general formula RO (G) x , in which R is a primary straight-chain or methyl-branched, in particular methyl-branched aliphatic radical having 8 to 22, preferably 12 to 18, carbon atoms and G is the symbol which stands for a glycose unit with 5 or 6 carbon atoms, preferably for glucose.
  • the degree of oligomerization x which indicates the distribution of monoglycosides and oligoglycosides, is any number between 1 and 10; x is preferably 1.2 to 1.4.
  • polyhydroxy fatty acid amides of the formula (I) in which R 2 CO is an aliphatic acyl radical having 6 to 22 carbon atoms, R 3 is hydrogen, an alkyl or hydroxyalkyl radical having 1 to 4 carbon atoms and [Z] is a linear or branched polyhydroxyalkyl radical with 3 to 10 carbon atoms and 3 to 10 hydroxyl groups.
  • the polyhydroxy fatty acid amides are preferably derived from reducing sugars with 5 or 6 carbon atoms, in particular from glucose.
  • the group of polyhydroxy fatty acid amides also includes compounds of the formula (II)
  • [Z] is also preferably obtained here by reductive amination of a sugar such as glucose, fructose, maltose, lactose, galactose, mannose or xylose.
  • a sugar such as glucose, fructose, maltose, lactose, galactose, mannose or xylose.
  • the N-alkoxy- or N-aryloxy-substituted compounds can then, for example according to the teaching of international patent application WO-A-95/07331, be converted into the desired polyhydroxy fatty acid amides by reaction with fatty acid methyl esters in the presence of an alkoxide as catalyst.
  • nonionic surfactants which are used either as the sole nonionic surfactant or in combination with other nonionic surfactants, in particular together with alkoxylated fatty alcohols and / or alkyl glycosides, are alkoxylated, preferably ethoxylated or ethoxylated and propoxylated, fatty acid alkyl esters, preferably with 1 to 4 carbon atoms in the alkyl chain, in particular fatty acid methyl esters, as described for example in Japanese patent application JP 58/217598 or which are preferably prepared by the process described in international patent application WO-A-90/13533.
  • nonionic surfactants C 8 -C 8 fatty acid methyl esters with an average of 3 to 15 EO, in particular with an average of 5 to 12 EO, are preferred.
  • Nonionic surfactants of the amine oxide type for example N-coconut alkyl-N, N-dimethylamine oxide and N-tallow alkyl-N, N-dihydroxyethylamine oxide, and the fatty acid alkanol amides can also be suitable.
  • the amount of such nonionic surfactants is preferably not more than that of the ethoxylated fatty alcohols, in particular not more than half of them.
  • gemini surfactants can be considered as further surfactants. These are generally understood to mean those compounds which have two hydrophilic groups and two hydrophobic groups per molecule. These groups are usually separated from one another by a so-called “spacer”. This spacer is usually a carbon chain which should be long enough that the hydrophilic groups are sufficiently far apart that they can act independently of one another. Such surfactants are generally characterized by an unusually low critical micelle concentration and the ability to greatly reduce the surface tension of the water. In exceptional cases, however, the term gemini surfactants means not only dimeric but also trimeric surfactants.
  • Suitable gemini surfactants are, for example, sulfated hydroxy mixed ethers according to German patent application DE 43 21 022 AI or dimer alcohol bis and trimeral alcohol tris sulfates and ether sulfates according to German patent application DE 195 03 061 AI.
  • End group-capped dimeric and trimeric mixed ethers according to German patent application DE 195 13 391 are distinguished in particular by their bi- and multifunctionality.
  • the end-capped surfactants mentioned have good wetting properties and are low-foaming, so that they are particularly suitable for use in machine washing or cleaning processes.
  • Gemini polyhydroxy fatty acid amides or poly polyhydroxy fatty acid amides, as described in the international patent applications WO-A-95/1953, WO-A-95/19954 and WO95-A- / 19955, can also be used.
  • the inorganic and organic builder substances are among the most important ingredients of detergents or cleaning agents.
  • the finely crystalline, synthetic and bound water-containing zeolite used is preferably zeolite A and / or P.
  • zeolite P for example, zeolite MAP® (commercial product from Crosfield) is used.
  • zeolite X and mixtures of A, X and / or P are also suitable.
  • the zeolite can be used as a spray-dried powder or as an undried stabilized suspension which is still moist from its production.
  • the zeolite may contain minor additions of nonionic surfactants as stabilizers, for example 1 to 3% by weight, based on zeolite, of ethoxylated C) 2 -C 8 fatty alcohols with 2 to 5 Ethylene oxide groups, -C 2 -C] fatty alcohols with 4 to 5 ethylene oxide groups or ethoxylated isotridecanols.
  • Suitable zeolites have an average particle size of less than 10 ⁇ m (volume distribution; measurement method: Coulter Counter) and preferably contain 18 to 22% by weight, in particular 20 to 22% by weight, of bound water.
  • Suitable substitutes or partial substitutes for phosphates and zeolites are crystalline, layered sodium silicates of the general formula NaMSi x 0 2x + ⁇ yH 2 0, where M is sodium or hydrogen, x is a number from 1.9 to 4 and y is a number from 0 to 20 and preferred values for x are 2, 3 or 4.
  • Such crystalline layered silicates are described, for example, in European patent application EP-A-0 164 514.
  • Preferred crystalline layered silicates of the formula given are those in which M represents sodium and x assumes the values 2 or 3. In particular, both ⁇ - and ⁇ -sodium disilicates Na Si 0 5 yH 2 0 are preferred.
  • the preferred builder substances also include amorphous sodium silicates with a modulus Na 2 0: Si0 2 of 1: 2 to 1: 3.3, preferably 1: 2 to 1: 2.8 and in particular 1: 2 to 1: 2, 6, which are delayed release and have secondary washing properties.
  • the delay in dissolution compared to conventional amorphous sodium silicates can be caused in various ways, for example by surface treatment, compounding, compacting / compression or by overdrying.
  • the term “amorphous” is also understood to mean “X-ray amorphous”.
  • silicates in X-ray diffraction experiments do not provide sharp X-ray reflections, as are typical for crystalline substances, but at most one or more maxima of the scattered X-rays, which have a width of several degree units of the diffraction angle.
  • it can very well lead to particularly good builder properties if the silicate particles deliver washed-out or even sharp diffraction maxima in electron diffraction experiments. This is to be interpreted as meaning that the products have microcrystalline areas in the size 10 nm to a few hundred nm, values up to max. 50 nm and in particular up to max. 20 nm are preferred.
  • Such so-called X-ray amorphous silicates which also have a delay in dissolution compared to conventional water glasses, are described, for example, in German patent application DE 44 00 024 AI.
  • Compacted / compacted amorphous silicates, compounded amorphous silicates and over-dried X-ray amorphous silicates are particularly preferred.
  • phosphates As builders, provided that such use should not be avoided for ecological reasons.
  • the sodium salts of orthophosphates, pyrophosphates and in particular tripolyphosphates are particularly suitable. Their content is generally not more than 25% by weight, preferably not more than 20% by weight, based in each case on the finished composition. In some cases, it has been shown that tripolyphosphates in particular, even in small amounts up to a maximum of 10% by weight, based on the finished composition, in combination with other builder substances lead to a synergistic improvement of the secondary washing ability.
  • Suitable substitutes or partial substitutes for the zeolite are also layer silicates of natural and synthetic origin.
  • Layered silicates of this type are known, for example, from patent applications DE 23 34 899, EP 0 026 529 and DE 35 26 405. Their usability is not limited to a special composition or structural formula. However, smectites, in particular bentonites, are preferred here.
  • Suitable layered silicates, which belong to the group of water-swellable smectites, are, for example, montmorrilonite, hectorite or saponite.
  • small amounts of iron can be incorporated into the crystal lattice of the layered silicates according to the above formulas.
  • the layered silicates can contain hydrogen, alkali, alkaline earth ions, in particular Na + and Ca -1 ⁇ .
  • the amount of water of hydration is usually in the range from 8 to 20% by weight and depends on the swelling condition or the type of processing.
  • Layer silicates which can be used are known, for example, from US Pat. No. 3,966,629, EP 0 026 529 and EP 0 028 432.
  • Layered silicates are preferably used which are largely free of calcium ions and strongly coloring iron ions due to an alkali treatment.
  • Usable organic builders are, for example, the polycarboxylic acids that can be used in the form of their sodium salts, such as citric acid, adipic acid, succinic acid, glutaric acid, tartaric acid, sugar acids, aminocarboxylic acids, nitrilotriacetic acid (NTA), as long as such use is not objectionable for ecological reasons, and mixtures of these.
  • Preferred salts are the salts of polycarboxylic acids such as citric acid, adipic acid, succinic acid, glutaric acid, tartaric acid, sugar acids and mixtures of these. The acids themselves can also be used.
  • the acids typically also have the property of an acidifying component and thus also serve to set a lower and milder pH value for detergents or cleaning agents.
  • Citric acid, succinic acid, glutaric acid, adipic acid, gluconic acid and any mixtures thereof can be mentioned in particular. If they are used in the premix according to the invention and are not subsequently added, these acids are preferably used in anhydrous form.
  • Other suitable organic builder substances are dextrins, for example oligomers or polymers of carbohydrates, which can be obtained by partial hydrolysis of starches. The Hydrolysis can be carried out by customary, for example acid or enzyme-catalyzed, processes.
  • DE dextrose equivalent
  • Both maltodextrins with a DE between 3 and 20 and dry glucose syrups with a DE between 20 and 37 as well as so-called yellow dextrins and white dextrins with higher molar masses in the range from 2000 to 30000 can be used.
  • a preferred dextrin is described in European patent application EP 0 703 292 AI .
  • the oxidized derivatives of oligosaccharides are their reaction products with oxidizing agents which are capable of oxidizing at least one alcohol function of the saccharide ring to the carboxylic acid function.
  • oxidizing agents capable of oxidizing at least one alcohol function of the saccharide ring to the carboxylic acid function.
  • Such oxidized dextrins and processes for their preparation are known, for example, from European patent applications EP 0 232 202, EP 0 427 349, EP 0 472 042 and EP 0 542496 and international patent applications WO 92/18542, WO 93/08251, WO 94/28030, WO 95/07303, WO 95/12619 and WO 95/20608 are known.
  • a product oxidized at C of the saccharide ring can be particularly advantageous.
  • Oxidized oligosaccharides according to German patent application DE 196 00 018 are also suitable.
  • Other suitable cobuilders are oxydisuccinates and other derivatives of disuccinates, preferably ethylenediamine disuccinate.
  • glycerol disuccinates and glycerol trisuccinates are also particularly preferred in this context, such as are described, for example, in US Pat. Nos. 4,524,009, 4,639,325, European Patent Application EP 0 150 930 and Japanese Patent Application JP 93/339896.
  • Suitable amounts used in formulations containing zeolite and / or silicate are 3 to 15% by weight.
  • Suitable organic cobuilders are, for example, acetylated hydroxycarboxylic acids or their salts, which may also be in lactone form and which contain at least 4 carbon atoms and at least one hydroxyl group and a maximum of two acid groups.
  • Such cobuilders are described, for example, in international patent application WO 95/20029.
  • Suitable polymeric polycarboxylates are, for example, the sodium salts of polyacrylic acid or polymethacrylic acid, for example those with a relative molecular weight of 800 to 150,000 (based on acid).
  • Suitable copolymeric polycarboxylates are, in particular, those of acrylic acid with methacrylic acid and of acrylic acid or methacrylic acid with maleic acid.
  • Copolymers of acrylic acid with maleic acid have been found to contain 50 to 90% by weight of acrylic acid and 50 to 10% by weight of maleic acid.
  • Their relative molecular weight, based on free acids, is generally 5,000 to 200,000, preferably 10,000 to 120,000 and in particular 50,000 to 100,000.
  • the content of (co) polymeric polycarboxylates in the compositions is within the usual range and is preferably 1 to 10% by weight. %.
  • biodegradable polymers composed of more than two different monomer units, for example those which, according to German patent application DE 43 00 772, are monomers as salts of acrylic acid and maleic acid as well as vinyl alcohol or vinyl alcohol derivatives or according to German patent DE 42 21 381 Monomeric salts of acrylic acid and 2-alkylallylsulfonic acid as well as sugar derivatives.
  • Other preferred copolymers are those which are described in German patent applications DE 43 03 320 and DE 44 17 734 and which preferably contain acrolein and acrylic acid / acrylic acid salts or acrolein and vinyl acetate as monomers.
  • polymeric aminodicarboxylic acids, their salts or their precursor substances are also particularly preferred.
  • polyaspartic acids or their salts and derivatives are particularly preferred, of which it is disclosed in German patent application DE 195 40 086 that, in addition to cobuilder properties, they also have a bleach-stabilizing effect.
  • Other suitable builder substances are polyacetals, which can be obtained by reacting dialdehydes with polyolcarboxylic acids which have 5 to 7 carbon atoms and at least 3 hydroxyl groups, for example as described in European patent application EP 0 280 223.
  • Preferred polyacetals are obtained from dialdehydes such as glyoxal, glutaraldehyde, terephthalaldehyde and their mixtures and from polyol carboxylic acids such as gluconic acid and / or glucoheptonic acid.
  • the agents can also contain components which have a positive effect on the oil and fat washability from textiles. This effect becomes particularly clear when a textile is soiled that has already been washed several times beforehand with a detergent according to the invention which contains this oil and fat-dissolving component.
  • the preferred oil- and fat-dissolving components include, for example, non-ionic cellulose ethers such as methyl cellulose and methyl hydroxypropyl cellulose with a proportion of methoxy groups of 15 to 30% by weight and of hydroxypropoxyl groups of 1 to 15% by weight.
  • % in each case based on the nonionic cellulose ether, and also the polymeric esters of phthalic acid and / or terephthalic acid known from the prior art monomeric and / or polymeric diols or their derivatives, in particular polymers of ethylene terephthalates and / or polyethylene glycol terephthalates or anionically and / or nonionically modified derivatives thereof.
  • the sulfonated derivatives of phthalic acid and terephthalic acid polymers are particularly preferred.
  • Suitable ingredients of the agents are water-soluble inorganic salts such as bicarbonates, carbonates, amorphous silicates such as the above-mentioned dissolving-delayed silicates or mixtures thereof;
  • alkali carbonate and amorphous alkali silicate especially sodium silicate with a Na 2 0: Si0 molar ratio of 1: 1 to 1: 4.5, preferably 1: 2 to 1: 3.5, are used.
  • the sodium carbonate content of the agents is preferably up to 20% by weight, advantageously between 5 and 15% by weight.
  • the content of sodium silicate in the agents is, if it is not to be used as builder substance, generally up to 10% by weight and preferably between 2 and 8% by weight, otherwise it can also be higher.
  • alkali metal carbonates can also be replaced by sulfur-free, 2 to 11 carbon atoms and, if appropriate, an amino acid and / or salts thereof having a further carboxyl and / or amino group.
  • the alkali metal carbonates it is possible for the alkali metal carbonates to be partially or completely replaced by glycine or glycinate.
  • the other detergent ingredients include graying inhibitors, foam inhibitors, bleaching agents and bleach activators, optical brighteners, enzymes, fabric softening agents, colorants and fragrances as well as neutral salts such as sulfates and chlorides in the form of their sodium or potassium salts.
  • Acidic salts or slightly alkaline salts can also be used to reduce the pH of detergents or cleaning agents.
  • Preferred acidifying components are bisulfates and / or bicarbonates or the above-mentioned organic polycarboxylic acids, which can also be used as builder substances at the same time.
  • Particular preference is given to the use of citric acid, which is either added subsequently (customary procedure) or - in anhydrous form - in the solid premix.
  • citric acid which is either added subsequently (customary procedure) or - in anhydrous form - in the solid premix.
  • sodium perborate tetrahydrate and sodium perborate monohydrate are of particular importance.
  • bleaching agents which can be used are, for example, sodium percarbonate, peroxypyrophosphate, citrate perhydrates and H 2 0-providing peracidic salts or peracids, such as perbenzoates, peroxophthalates, diperazelaic acid, phthaloiminoperic acid or diperdodecanedioic acid.
  • the bleach content of the agents is preferably 5 to 25% by weight and in particular 10 to 20% by weight, advantageously using perborate monohydrate or percarbonate.
  • Bleach activators which can be used are compounds which, under perhydrolysis conditions, give aliphatic peroxocarboxylic acids having preferably 1 to 10 C atoms, in particular 2 to 4 C atoms, and / or optionally substituted perbenzoic acid. Suitable substances are those which carry O- and / or N-acyl groups of the number of carbon atoms mentioned and / or optionally substituted benzoyl groups.
  • hydrophilically substituted acylacetals known from German patent application DE-A-196 16 769 and the acyl lactams described in German patent application DE-A-196 16 770 and international patent application WO-A-95/14075 are also preferably used.
  • the combinations of conventional bleach activators known from German patent application DE-A-44 43 177 can also be used. Such bleach activators are in the usual range, preferably in Amounts of 1 wt .-% to 10 wt .-%, in particular 2 wt .-% to 8 wt .-%, based on the total agent.
  • Suitable foam inhibitors are, for example, soaps of natural or synthetic origin, which have a high proportion of C 1 -C 2 fatty acids.
  • Suitable non-surfactant-like foam inhibitors are, for example, organopolysiloxanes and their mixtures with microfine, optionally silanized silica, and paraffins, waxes, microcrystalline waxes and their mixtures with silanized silica or bistearylethylenediamide. Mixtures of various foam inhibitors are also used with advantages, for example those made of silicones, paraffins or waxes.
  • the foam inhibitors, in particular silicone and / or paraffin-containing foam inhibitors are preferably bound to a granular, water-soluble or dispersible carrier substance. Mixtures of paraffins and bistearylethylenediamides are particularly preferred.
  • the salts of polyphosphonic acids which are preferably used are the neutral sodium salts of, for example, l-hydroxyethane-l, l-diphosphonate, diethylenetriaminepentamethylenephosphonate or ethylenediaminetetramethylenephosphonate in amounts of 0.1 to 1.5% by weight.
  • Particularly suitable enzymes are those from the class of hydrolases, such as proteases, lipases, cutinases, amylases, cellulases or mixtures thereof. Oxireductases are also suitable. Enzymes obtained from bacterial strains or fungi such as Bacillus subtilis, Bacillus licheniformis, Streptomyces griseus and Humicola insolens are particularly suitable. Proteases of the subtilisin type and in particular proteases which are obtained from Bacillus lentus are preferably used. Enzyme mixtures, for example of protease and amylase or protease and lipase or protease and cellulase or of cellulase and lipase, are of particular interest.
  • Peroxidases or oxidases have also proven to be suitable in some cases. Suitable amylases include in particular ⁇ -amylases, iso-amylases, pullulanases and pectinases. Cellobiohydrolases, endoglucanases and ⁇ -glucosidases, which are also called cellobiases, or mixtures thereof, are preferably used as cellulases. Since the different cellulase types differ in their CMCase and avicelase activities, the cellulases can be mixed in a targeted manner desired activities. The enzymes can be adsorbed on carriers and / or embedded in coating substances in order to protect them against premature decomposition. The proportion of the enzymes, enzyme mixtures or enzyme granules can be, for example, about 0.1 to 5% by weight, preferably 0.1 to about 2% by weight.
  • the agents can also contain further enzyme stabilizers.
  • enzyme stabilizers For example, 0.5 to 1% by weight sodium formate can be used. It is also possible to use proteases which are stabilized with soluble calcium salts and a calcium content of preferably about 1.2% by weight, based on the enzyme.
  • proteases which are stabilized with soluble calcium salts and a calcium content of preferably about 1.2% by weight, based on the enzyme.
  • magnesium salts also serve as stabilizers.
  • boron compounds for example boric acid, boron oxide, borax and other alkali metal borates such as the salts of orthoboric acid (H 3 B0 3 ), metaboric acid (HB0 2 ) and pyrobic acid (tetraboric acid H 2 B 0 7 ).
  • Graying inhibitors have the task of keeping the dirt detached from the fiber suspended in the liquor and thus preventing the dirt from being re-absorbed.
  • Water-soluble colloids of mostly organic nature are suitable for this, for example the water-soluble salts of polymeric carboxylic acids, glue, gelatin, salts of ether carboxylic acids or ether sulfonic acids of starch or cellulose or salts of acidic sulfuric acid esters of cellulose or starch.
  • Water-soluble polyamides containing acidic groups are also suitable for this purpose. Soluble starch preparations and starch products other than those mentioned above can also be used, e.g. degraded starch, aldehyde starches, etc. Polyvinylpyrrolidone can also be used.
  • cellulose ethers such as carboxymethyl cellulose (sodium salt), methyl cellulose, hydroxyalkyl cellulose and mixed ethers such as methyl hydroxyethyl cellulose, methyl hydroxypropyl cellulose, methyl carboxymethyl cellulose and mixtures thereof, and also polyvinylpyrrolidone, for example in amounts of 0.1 to 5% by weight, are preferred on the means.
  • the agents can contain derivatives of diaminostilbenedisulfonic acid or its alkali metal salts. Suitable are, for example, salts of 4,4'-bis (2-anilino-4-morpholino-1,3,5-triazinyl-6-amino) stilbene-2,2'-disulfonic acid or compounds of the same structure which instead of the morpholino- Group carry a diethanolamino group, a methylamino group, an anilino group or a 2-methoxyethylamino group.
  • NEN brightener of the type of the substituted diphenyl be present, for example the alkali metal salts of 4,4 '-bis- (2-sulfostyryl), 4,4' -bis (4-chloro-3-sulfostyryl) or 4- ( 4- chlorostyryl) -4 * - (2-sulfostyryl) diphenyl. Mixtures of the aforementioned brighteners can also be used.
  • the premix was plasticized and, at the respective pressure given in Table 1, extruded through the extruder head perforated die plate into fine strands with a diameter of 1.4 mm, which were chopped into approximately spherical granules by means of a knock-out knife ( Length / diameter ratio about 1, hot cut). The resulting warm granules were rounded off for one minute in a Marumerizer® type rounding machine and, if necessary, coated with a fine-particle powder.
  • compositions of the spray-dried powders SP1 and SP2 are Compositions of the spray-dried powders SP1 and SP2:
  • Spray-dried powder 1 26.00% by weight of C 9 -C] 3 -alkylbenzenesulfonate
  • Spray-dried powder 2 26.00% by weight of C 9 -C 3 -alkylbenzenesulfonate
  • Example 1 Composition as in Example 1 b) Mixture of 4% by weight of hydroxypropyl starch and 96% by weight of ethylene glycol c) Mixture of 6% by weight of hydroxypropyl starch and 94% by weight of ethylene glycol as in Example 1 d) Mixture of 8 % By weight of hydroxypropyl starch and 92% by weight of ethylene glycol e) mixture of 10% by weight of hydroxypropyl starch and 90% by weight of ethylene glycol Table 3: Sieve analysis to determine the grain size distribution

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PCT/EP1997/005945 1996-09-20 1997-10-28 Verfahren zur herstellung teilchenförmiger wasch- oder reinigungsmittel WO1999013045A1 (de)

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Application Number Priority Date Filing Date Title
EP97913181A EP1012221B1 (de) 1997-09-11 1997-10-28 Verfahren zur herstellung teilchenförmiger wasch- oder reinigungsmittel
JP2000510835A JP2001515955A (ja) 1997-09-11 1997-10-28 粒状洗剤の製法
AT97913181T ATE269399T1 (de) 1997-09-11 1997-10-28 Verfahren zur herstellung teilchenförmiger wasch- oder reinigungsmittel
DE59711728T DE59711728D1 (de) 1997-09-11 1997-10-28 Verfahren zur herstellung teilchenförmiger wasch- oder reinigungsmittel
KR1020007002623A KR20010023926A (ko) 1996-09-20 1997-10-28 입상 세척제의 제조방법
EP98947499A EP1015550B1 (de) 1996-09-20 1998-09-02 Verfahren zur herstellung teilchenförmiger wasch- oder reinigungsmittel
AT98947499T ATE317003T1 (de) 1997-09-11 1998-09-02 Verfahren zur herstellung teilchenförmiger wasch- oder reinigungsmittel
CN98810071.1A CN1275160A (zh) 1997-09-11 1998-09-02 粒状洗涤剂或清洗剂的制备方法
KR1020007002612A KR20010023917A (ko) 1996-09-20 1998-09-02 세정 및 세척용 입자 제조 방법
DE59813373T DE59813373D1 (de) 1997-09-11 1998-09-02 Verfahren zur herstellung teilchenförmiger wasch- oder reinigungsmittel
PCT/EP1998/005548 WO1999013046A1 (de) 1997-09-11 1998-09-02 Verfahren zur herstellung teilchenförmiger wasch- oder reinigungsmittel

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Cited By (2)

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Publication number Priority date Publication date Assignee Title
WO2008015055A1 (de) * 2006-08-04 2008-02-07 Henkel Ag & Co. Kgaa Teilchenförmiges wasch- oder reinigungsmittel
DE102015206547A1 (de) 2015-04-13 2016-10-13 Henkel Ag & Co. Kgaa Flüssiges Wasch- oder Reinigungsmittel mit suspendierten Partikeln

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE19848024A1 (de) * 1998-10-17 2000-04-20 Henkel Kgaa Verfahren zur Herstellung extrudierter Formkörper
TWI409328B (zh) * 2006-01-25 2013-09-21 Kao Corp Bleach activator granules
WO2010008712A1 (en) * 2008-07-14 2010-01-21 3M Innovative Properties Company Method of making a cleaning solution from hydrogel cleaning concentrate and packaged cleaning concentrate
EP3241889B1 (en) * 2016-05-03 2019-03-20 The Procter and Gamble Company Cleaning composition

Citations (6)

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DD251044A3 (de) * 1984-07-20 1987-11-04 Fettchemie Verfahren zur herstellung von granulierten wasch- und reinigungsmitteln
WO1992002608A1 (de) * 1990-08-03 1992-02-20 Henkel Kommanditgesellschaft Auf Aktien Bleichaktivatoren in granulatform
DE4124701A1 (de) * 1991-07-25 1993-01-28 Henkel Kgaa Verfahren zur herstellung fester wasch- und reinigungsmittel mit hohem schuettgewicht und verbesserter loesegeschwindigkeit
EP0622454A1 (en) * 1993-04-30 1994-11-02 The Procter & Gamble Company Structuring liquid nonionic surfactants prior to granulation process
DE4319666A1 (de) * 1993-06-14 1994-12-15 Henkel Kgaa Verfahren zur Herstellung fester Wasch- oder Reinigungsmittel mit hohem Schüttgewicht und verbesserter Rheologie
WO1997009415A1 (en) * 1995-09-04 1997-03-13 Unilever Plc Detergent compositions and process for preparing them

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DD251044A3 (de) * 1984-07-20 1987-11-04 Fettchemie Verfahren zur herstellung von granulierten wasch- und reinigungsmitteln
WO1992002608A1 (de) * 1990-08-03 1992-02-20 Henkel Kommanditgesellschaft Auf Aktien Bleichaktivatoren in granulatform
DE4124701A1 (de) * 1991-07-25 1993-01-28 Henkel Kgaa Verfahren zur herstellung fester wasch- und reinigungsmittel mit hohem schuettgewicht und verbesserter loesegeschwindigkeit
EP0622454A1 (en) * 1993-04-30 1994-11-02 The Procter & Gamble Company Structuring liquid nonionic surfactants prior to granulation process
DE4319666A1 (de) * 1993-06-14 1994-12-15 Henkel Kgaa Verfahren zur Herstellung fester Wasch- oder Reinigungsmittel mit hohem Schüttgewicht und verbesserter Rheologie
WO1997009415A1 (en) * 1995-09-04 1997-03-13 Unilever Plc Detergent compositions and process for preparing them

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2008015055A1 (de) * 2006-08-04 2008-02-07 Henkel Ag & Co. Kgaa Teilchenförmiges wasch- oder reinigungsmittel
DE102015206547A1 (de) 2015-04-13 2016-10-13 Henkel Ag & Co. Kgaa Flüssiges Wasch- oder Reinigungsmittel mit suspendierten Partikeln
WO2016165841A1 (de) 2015-04-13 2016-10-20 Henkel Ag & Co. Kgaa Flüssiges wasch- oder reinigungsmittel mit suspendierten partikeln

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ATE317003T1 (de) 2006-02-15
EP1012221A1 (de) 2000-06-28
CN1275160A (zh) 2000-11-29
EP1012221B1 (de) 2004-06-16
ES2224224T3 (es) 2005-03-01
DE59711728D1 (de) 2004-07-22

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