EP1015550A1 - Procede de production de nettoyants et detergents particulaires - Google Patents

Procede de production de nettoyants et detergents particulaires

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Publication number
EP1015550A1
EP1015550A1 EP98947499A EP98947499A EP1015550A1 EP 1015550 A1 EP1015550 A1 EP 1015550A1 EP 98947499 A EP98947499 A EP 98947499A EP 98947499 A EP98947499 A EP 98947499A EP 1015550 A1 EP1015550 A1 EP 1015550A1
Authority
EP
European Patent Office
Prior art keywords
weight
premix
shaping
compounds
raw materials
Prior art date
Legal status (The legal status 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 status listed.)
Granted
Application number
EP98947499A
Other languages
German (de)
English (en)
Other versions
EP1015550B1 (fr
Inventor
Kathleen Paatz
Wilfried Rähse
Peter Sandkühler
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Henkel AG and Co KGaA
Original Assignee
Henkel AG and Co KGaA
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/EP1997/005945 external-priority patent/WO1999013045A1/fr
Application filed by Henkel AG and Co KGaA filed Critical Henkel AG and Co KGaA
Priority to EP98947499A priority Critical patent/EP1015550B1/fr
Publication of EP1015550A1 publication Critical patent/EP1015550A1/fr
Application granted granted Critical
Publication of EP1015550B1 publication Critical patent/EP1015550B1/fr
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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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
    • 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, result in 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, which contain anionic and / or nonionic surfactants in amounts of at least 15% by weight and up to about 35% by weight . They are produced by a process in which a solid, free-flowing premix consisting of a plasticizer and / or lubricant preferably contains aqueous surfactant pastes and or aqueous polymer solutions, extruded in the form of strands at high pressures between 25 and 200 bar, and the strand is cut and rounded to the predetermined granule dimension by means of a cutting device after exiting the hole shape.
  • the premix consists at least in part of 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 give 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, at least one of which is extruded and at least one is not extruded, the surfactant content of the extruded Component including the soaps should be a maximum of 15 wt .-%, based on the respective extruded component.
  • non-extruded component s
  • this method solves the problem of gelling highly compressed and high-surfactant detergents or cleaning agents when used in an aqueous liquor, 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 is subsequently treated and usually then 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 then the advantage of the apparatus that it can cause simultaneous drying is not exploited.
  • 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 therefore no longer have the desired effect of improved dissolution rate by using a structure breaker or would no longer be fully effective.
  • 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 binder or disintegrant with melting temperatures between 35 and 90 ° C.
  • the compacting / tableting should be carried out at temperatures which are at least 28 ° C. but below the melting temperature of the binder lie.
  • Primary C 2 -C 15 - are used as nonionic surfactants Alcohols specified with 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.
  • European patent application EP 0 622 454 A1 discloses the conversion of a surfactant paste into granules with bulk densities of at least 650 g / l by the agglomeration of fine particles, which may include zeolites, carbonates, sulfates and citrates.
  • the surfactant paste contains structuring agents in the form of polymeric alcohols, polyacrylic acid or polyvinylpyrrolidone and has a viscosity above 350 mPa.s but below 100,000 mPa.s at processing temperature.
  • the granules obtainable by this process have a high proportion of nonionic surfactant due to the manufacturing process, which means that the incorporation of other detergent raw materials is only possible to a limited extent.
  • the same disadvantage arises in the process known from international patent application WO-A-97/09415, which involves the agglomeration of finely divided particles with the aid of an anhydrous mixture of nonionic surfactant and polymeric builder substance for the production of particulate detergents with bulk densities of at least 600 g / l provides soil release polymer.
  • 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 C 9 -C 16 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 occurs up to a dough-like mass, with lower energy inputs only finely divided powders or very light agglomerates with an undesirably wide 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, give such agents which, even with a reduced surface area, in particular with a spherical shape (bead 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, in which case a premix is first prepared 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 this premix is converted into a grain using compression forces and, if appropriate, thereon 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 essentially 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 wt .-%, each based on the Premix.
  • Water can therefore essentially only in chemically and / or physically bound form or as a constituent of the raw materials or compounds present as a solid at temperatures below 45 ° C. at a pressure of 1 bar, but only in subordinate quantities as a liquid. Solution or dispersion are introduced into the process for producing the premix.
  • the premix has a total water content of not more than 20% by weight, the majority of this water not being in liquid free form but being chemically and / or physically bound, and it is particularly preferred that the content of not of zeolite and / or water bound to silicates in the solid premix is not more than 15% by weight, preferably less than 12% by weight and, with particular preference, not more than 5% by weight to H% by weight.
  • an "essentially non-aqueous solution" in which the polymer is swollen is understood to mean a solution which is either completely water-free or contains only enough water that, when the liquid shaping aid is used, the content of liquid water in the premix of the shaping agent is below the limit of 2% by weight indicated above. In relation to the shaping agent alone, this can mean the presence of water in a not insignificant amount, as long as it is observed that the shaping agent is only used in such amounts that the limit value of 2% by weight of additional liquid water in the premix is not reached.
  • Particulate 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 80% by weight of particles with a diameter of at least 400 ⁇ m.
  • the washing or cleaning agents, compounds or treated raw materials produced consist of at least 70% by weight, advantageously at least 80% by weight and, with particular preference, up to 100% by weight of spherical (perlenf 'shaped) particles having a particle size distribution which is at least 80 wt .-% 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. act with a diameter of about 35 mm to 40 mm.
  • Swollen polymers which are used in the context of the present invention as a component of the shaping aid are those which lead to gel-like states in essentially non-aqueous liquids.
  • Systems of essentially non-aqueous liquid and polymer are particularly suitable which, at room temperature and 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 essentially 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 50,000 mPas, measured, for example, using a Brookfield rotary viscometer. At higher temperatures, for example 60 ° C., the viscosity preferably deviates only relatively little from the values at room temperature and is preferably in the range from 250 mPas to 40,000 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.
  • 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
  • these liquids which are referred to as essentially non-aqueous, can also contain water, as long as it is observed that the shaping agent is used in the process according to the invention only in such amounts that the above-mentioned limit value of 2% by weight of additional liquid water in the premix is not is achieved.
  • a liquid which is essentially non-aqueous in this sense preferably contains not more than 20% by weight, in particular not more than 15% by weight, water, in a particularly preferred embodiment liquids with water contents below 1% by weight, for example 0.5% to 0.8% by weight, can be used.
  • Suitable polymers which lead to swollen systems in such essentially non-aqueous liquids are polyvinylpyrrolidone, polyacrylic acid, copolymers of acrylic acid and maleic acid, polyvinyl alcohol, xanthan, partially hydrolyzed starches, for example maltodextrins.
  • 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 shaping aid is preferably 1% by weight to 80% by weight, in particular approximately 2% by weight to 60% by weight.
  • the content of shaping aids is preferably at least 2% by weight, but less than 25% by weight, in particular less than 20% by weight, with particular preference for amounts in the range of 3% by weight up to 15% 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 manufactured 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.
  • beads or agglomerates of a granulation process etc. produced by spray drying can be used as particulate particles.
  • 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 demanding 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 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 to silicates is less than 7% by weight and is in particular a maximum of 2 to 5% by weight.
  • the premix contains no water which is not bound to the builder substances.
  • 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 .
  • Compounds which contain water in the form specified above and / or serve as a carrier for liquids, in particular for nonionic surfactants which are liquid at room temperature, that is to say which contain ingredients which are liquid at room temperature and can be used according to the invention preferably have no softening point below 45 ° C. .
  • the individual raw materials used separately have a melting point of preferably at least 45 ° C.
  • 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 will 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 ones commonly used in washing or cleaning agents Alcohols, 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 on average 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 molding aid are introduced into the process separately from each other.
  • 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 polymer swollen in substantially non-aqueous liquid can be mixed with the other components 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 is distributed as homogeneously as possible in the material to be compacted in the process step of compacting shaping.
  • 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 be glued that the finished end products are built almost exactly from these many small individual particles, which by the binder, which is the task of a preferably thin partition between them Individual particles takes over, are held together.
  • a honeycomb-like structure can be assumed, whereby these honeycombs are filled with solids (compounds or individual raw materials). In contact with water.
  • 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 does not stick under normal storage and 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 are exerted, such as granulating, compacting, for example roller compacting or extruding, or tableting, optionally with the addition of conventional disintegrants, and pelleting.
  • Spray-dried granules can also be used as pre-made compounds in the premix the invention is in no way limited 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 method 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 as well as the so-called Rotorcoater® from Glatt® with horizontal and inclined turntables up to 50 °.
  • Lödige® CB mixers, Zig-Zag mixers from PK-Niro®, a Ballestra® chain mix and Hosokawa® or are less suitable Schugi® mixer.
  • a fluid bed or a horizontal mixer for example a Nautamixer®, is also less suitable.
  • 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, using the polymer swollen in essentially non-aqueous liquid, can carry out the compacting granulation in only 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 the production of 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 0 486 592 B1 or international patent applications WO-A-93/02176 and WO-A-94/09111.
  • the premix is pressed in the form of a strand under pressure and the strand is cut to the predeterminable size of the granulate by means of a cutting device after it has emerged from the hole shape.
  • the homogeneous and solid premix usually contains a plasticizer or lubricant, which causes the premix under the pressure or under the entry more specific Work plastically softens and becomes extrudable.
  • a plasticizer or lubricant which causes the premix under the pressure or under the entry more specific Work plastically softens and becomes extrudable.
  • 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-shaft 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 see 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 of about 0.8 up 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 / pressing 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, unbound 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 process according to the invention is carried out essentially water-free, not only is the risk of gelling of the surfactant raw materials minimized or ruled out in the production process, but also an ecologically valuable process is provided, since a subsequent one is dispensed with Drying step not only saves energy but also emissions, as they occur mainly with conventional types of drying, can be avoided.
  • agents, compounds and treated raw materials thus produced thus have an improved dissolution rate compared to agents, compounds and treated raw materials which, although having the same final composition, were not produced by the process according to the invention, that is to say not under essentially anhydrous conditions using an in essentially non-aqueous liquid swollen polymers were prepared as molding aids.
  • 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. Especially show treated raw materials an astonishingly high dissolving rate in water, especially when the raw material was used in a very finely divided, possibly 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, which were produced by the method according to the invention, more closely resemble the ideal shape of a sphere with a smooth, "smeared" surface than the agents and extrudates produced by conventional and in particular aqueous methods. This achieves a better filling of the space, which leads to a higher bulk density, even if components are mixed in which have neither spherical structure nor such a high bulk density.
  • the particulate end products of the process obtained can either be used directly as detergents or cleaning agents or aftertreated and / or prepared beforehand by customary methods.
  • 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, where dusty or at least fine-particle ingredients (the so-called fine particles) are adhered to the particulate end products of the process, which serve as the core, and thus means arise which have these so-called fine particles as the outer shell.
  • Processing is generally understood to mean that the particulate end products of the process produced according to the invention serve as a compound to which other ingredients, 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 tunnels 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 50% by weight of compounds and / or treated raw materials produced according to the invention. In particular, it consists of at least 60% 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 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. It is also possible to mix larger moldings from the mixture of the compounds and / or raw materials treated according to the invention with the remaining constituents mentioned, for example tablets.
  • a particular advantage, however, is the fact that with the aid of the method according to the invention it is possible to actually use all the constituents of a complete washing or cleaning agent as a premix and to granulate water-free into beads.
  • 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.
  • the surfactants of the sulfonate type are preferably C 9 -C 13 -alkylbenzenesulfonates, olefin sulfonates, that is to say mixtures of alkene and hydroxyalkanesulfonates and disulfonates such as are obtained, for example, from C 12 -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 I2 -C 18 alkanes, for example by sulfochlorination or sulfoxidation and subsequent hydrolysis or neutralization.
  • esters of ⁇ -sulfo fatty acids esters of ⁇ -sulfo fatty acids (ester sulfonates), 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 carbon atoms in the Fatty acid molecule and subsequent neutralization to water-soluble mono-salts are considered.
  • Preferred ⁇ -sulfofatty acid alkyl esters 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) are particularly advantageous. but also used their saponified salts.
  • Suitable anionic surfactants are sulfonated fatty acid glycerol esters, which are mono-, di- and triesters as well as their mixtures, such as those produced by esterification by a monoglycerol with 1 to 3 moles of fatty acid or in the transesterification of triglycerides with 0.3 to 2 moles of glycerol be preserved.
  • Alk (en) yl sulfates are the alkali and especially the sodium salts of the Schwefelhoffreschester C I2 -C 18 fatty alcohols, for example, from coconut fatty alcohol, tallow fatty alcohol, lauryl, myristyl, cetyl or stearyl alcohol, or C 10 -C 20 oxo alcohols, and be those half-esters of secondary alcohols of this chain length are preferred. Also preferred are 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.
  • C 12 -C I6 alkyl sulfates and C 12 -C ! 5 alkyl sulfates and C 14 -C 15 alkyl sulfates are particularly preferred from the point of view of washing technology.
  • 2,3-Alkyl sulfates which are produced, for example, according to US Pat. Nos. 3,234,258 or 5,075,041 and can be obtained as commercial products from the Shell Oil Company under the name DAN®, are also suitable anionic surfactants.
  • the sulfuric acid monoesters of the straight-chain or branched C 7 -C 21 alcohols ethoxylated with 1 to 6 mol of ethylene oxide such as 2-methyl-branched C 9 -C u alcohols with an average of 3.5 mol of ethylene oxide (EO) or C 12 -C 18 -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 18 fatty alcohol residues or mixtures thereof.
  • Particularly preferred sulfosuccinates contain a fatty alcohol residue that differs from ethoxylated fatty alcohols derived, which are considered non-ionic surfactants.
  • 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 in the form of their sodium, potassium or ammonium salts and also 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 aluminum alcohol residue may be linear or preferably methyl-branched in the 2-position or may contain linear and methyl-branched radicals in the mixture, such as are usually present in oxo alcohol residues.
  • 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 12 -C 14 alcohols with 3 EO or 4 EO, C 9 -C "alcohols 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 denotes a primary straight-chain or methyl-branched, in particular methyl-branched aliphatic radical having 8 to 22, preferably 12 to 18 C atoms and G is the symbol is 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.
  • R 3 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
  • [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)
  • R 4 is a linear or branched alkyl or alkenyl radical having 7 to 12 carbon atoms
  • R 5 is a linear, branched or cyclic alkylene radical or an arylene radical is 2 to 8 carbon atoms
  • R 6 is a linear, branched or cyclic alkyl radical or Aryl radical or an oxy-alkyl radical having 1 to 8 carbon atoms, C 1 -C 4 -alkyl or phenyl radicals being preferred, and [Z] for a linear polyhydroxyalkyl radical whose alkyl chain is substituted by at least two hydroxyl groups, or alkoxylated, preferably ethoxylated or propoxylated derivatives of this radical.
  • [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 preferably according to that in international patent application WO-A-90/13533 described methods are produced.
  • Nonionic surfactants are C 12 -C 18 fatty acid methyl esters with an average of 3 to 15 EO, in particular with an average of 5 to 12 EO.
  • 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 have a sufficient distance so 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 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 in the event that the zeolite is used as a suspension, it can contain minor additions of nonionic surfactants as stabilizers, for example 1 to 3% by weight, based on zeolite, of ethoxylated C 12 -C 8 fatty alcohols with 2 to 5 Ethylene oxide groups, C 2 -C 14 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 O 2x + 1 yH 2 O, 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.
  • both ⁇ - and ⁇ -sodium disilicates Na 2 Si 2 O 5 'yH 2 O are preferred.
  • the preferred builder substances also include amorphous sodium silicates with a modulus Na 2 0: SiO 2 from 1: 2 to 1: 3.3, preferably from 1: 2 to 1: 2.8 and in particular from 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. in the Within the scope of this invention, 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 regions with a size of 10 nm to a few hundred ⁇ m, 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.
  • 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 agent, in combination with other builder substances lead to a synergistic improvement in 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.
  • smectites in particular bentonites, are preferred here.
  • Suitable layered silicates belonging to the group with water swellable smectites include, 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 ++ .
  • 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 of 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 processes, for example acid-catalyzed or enzyme-catalyzed.
  • 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 0 542 496 and international patent applications WO 92/18542, WO 93/08251, WO 94/28030 , WO 95/07303, WO 95/12619 and WO 95/20608.
  • a product oxidized at C 6 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 which contain 50 to 90% by weight of acrylic acid and 50 to 10% by weight of maleic acid have proven to be particularly suitable.
  • 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.
  • Further 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 to be mentioned as further preferred builder substances.
  • 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 builders are polyacetals which have by reaction of dialdehydes with polyol comprising 5 to 7 carbon atoms and at least 3 hydroxyl groups, Preferred polyacetals are obtained for example as described in European "patent application EP 0,280,223.
  • the agents can also contain components which have a positive effect on the oil and fat washability from textiles. This effect is particularly evident if a textile is soiled that has already been washed several times with a detergent according to the invention which contains this oil and fat-dissolving component. was washed.
  • 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 methoxyl 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 the polymeric esters of phthalic acid and / or terephthalic acid known from the prior art with 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 of this.
  • 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 molar ratio Na 2 O: SiO 2 from 1: 1 to 1: 4.5, preferably from 1: 2 to T: 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 having a further carboxyl and / or amino group and or their salts.
  • 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.
  • Acidic salts or slightly alkaline salts can also be used to lower 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.
  • the use of citric acid is particularly preferred. which is either added subsequently (customary procedure) or - in anhydrous form - used in a solid premix.
  • bleaching agents that can be used are, for example, sodium percarbonate, peroxypyrophosphates, citrate perhydrates and H 2 O 2 -supplying peracidic salts or peracids, such as perbenzoates, peroxophthalates, diperazelaic acid, phthaloiminoperic acid or diperdodecanedioic acid.
  • the bleaching agent 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.
  • polyacylated alkylenediamines especially tetraacetylethylenediamine (TAED), acylated triazine derivatives, especially 1,5-diacetyl-2,4-dioxohexahydro-1,3,5-triazine (DADHT), acylated glycolurils, especially tetraacetylglycoluril (TAGU), N- Acylimides, in particular N-nonanoylsuccinimide (NOSI), acylated phenolsulfonates, in particular n-nonanoyl- or isononanoyloxybenzenesulfonate (n- or iso-NOBS), carboxylic acid anhydrides, in particular phthalic anhydride, acylated polyhydric alcohols, in particular triacetyloxy, 2,5-acetiacetyl, ethylene glycol 2,5-dihydrofuran and the enol esters known from
  • WO-A-94/28102, WO-A-94/28103, WO-A-95/00626, WO-A-95/14759 and WO-A-95/17498 are known.
  • 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.
  • Bleach activators of this type are present in the customary quantitative range, preferably in amounts of 1% by weight to 10% by weight, in particular 2% by weight to 8% by weight, based on the total agent.
  • Suitable foam inhibitors are, for example, soaps of natural or synthetic origin, which have a high proportion of C 18 -C 24 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 paraffm-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 are preferably the neutral sodium salts of, for example, l-hydroxyethane-l, l-diphosphonate.
  • Diethylenetriaminepenta- methylene phosphonate or ethylenediaminetetramethylene phosphonate used in amounts of 0.1 to 1.5 wt .-%.
  • 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 desired activities can be set by targeted mixtures of the cellulases.
  • 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.
  • calcium salts magnesium salts also serve as stabilizers.
  • boron compounds for example boric acid, boron oxide, borax and other alkali metal borates such as that, is particularly advantageous Salts of orthoboric acid (H 3 BO 3 ), metaboric acid (HBO 2 ) and pyrobic acid (tetraboric acid H 2 B 4 O 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, based on the Means used.
  • 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-l, 3,5-triazinyl-6-amino) stilbene-2,2'-disulfonic acid or compounds of similar structure which instead of the morpholino- Group carry a diethanolamino group, a methylamino group, anilino group or a 2-methoxyethylamino group.
  • Brighteners of the substituted diphenylstyryl type may also be present, for example the alkali salts of 4,4'-bis (2-sulfostyryl) diphenyl, 4,4'-bis (4-chloro-3-sulfostyryl) diphenyl, or 4- (4-chlorostyryl) -4 '- (2-sulfostyryl) diphenyl. Mixtures of the aforementioned brighteners can also be used. Examples
  • a premix was made from the components shown in Table 1, the addition of the nonionic surfactant to the powder stream being carried out by spraying through nozzles, manufactured.
  • the mixture was then homogenized for a further 2 minutes and then fed to a twin-screw extruder whose pelletizing head had been preheated to temperatures between 50 ° C. and 65 ° C.
  • 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.
  • a further agent V3 was prepared which contained the same ingredients in the end product as E2, but in which the copolymer had not been introduced into the process in a form which was not swollen in essentially non-aqueous liquid, but rather as an approximately 30% by weight aqueous solution. The excess water was then dried off in a fluidized bed. The bulk weight of extrudate V3 was 770 g / 1, the L test gave a value of 28%.
  • compositions of the spray-dried powders SPl and SP2 are Compositions of the spray-dried powders SPl and SP2:
  • Spray-dried powder 1 26.00% by weight of C 9 -C I3- alkylbenzenesulfonate
  • Spray dried powder 2 26.00% by weight of C 9 -C 13 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
  • composition of spray product 3 SP3: 22% by weight C 9 -C 13 -alkylbenzenesulfonate, 1.1% by weight soap, 48.88% by weight zeolite A (based on anhydrous active substance), 6, 9% by weight of copolymeric sodium salt of acrylic acid and maleic acid, 0.78% by weight of phosphonate, 3% by weight of sodium carbonate, 14.45% by weight of water, 0.39% by weight of optical brightener, the remainder to 100 % Salts from solutions b) mixture of 3% by weight of hydroxypropyl starch and 97% by weight of glycerin (water content 0.5% by weight) c) mixture of 3% by weight of hydroxypropyl starch and 97% by weight of glycerin (water content 14% by weight)
  • the bulk density of the granules G15 or G16 could be reduced to values of 780 g / 1 or by treatment in a Marumerizer®, known as rounding 753 g / 1 are increased, whereas with the same treatment of the granules G17.
  • G18 and G19 only showed a significantly smaller increase in bulk density to values of 805 g / 1, 805 g / 1 and 800 g / 1, respectively.

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Detergent Compositions (AREA)
  • Manufacturing Of Micro-Capsules (AREA)
  • Physical Or Chemical Processes And Apparatus (AREA)
EP98947499A 1996-09-20 1998-09-02 Procede de production de nettoyants et detergents particulaires Expired - Lifetime EP1015550B1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
EP98947499A EP1015550B1 (fr) 1996-09-20 1998-09-02 Procede de production de nettoyants et detergents particulaires

Applications Claiming Priority (7)

Application Number Priority Date Filing Date Title
DE19638599A DE19638599A1 (de) 1996-09-20 1996-09-20 Verfahren zur Herstellung eines teilchenförmigen Wasch- oder Reinigungsmittels
WOPCT/EP97/04975 1997-09-11
PCT/EP1997/004975 WO1998012299A1 (fr) 1996-09-20 1997-09-11 Procede de production d'un detergent ou nettoyant particulaire
PCT/EP1997/005945 WO1999013045A1 (fr) 1997-09-11 1997-10-28 Procede pour la production de detergents particulaires
WOPCT/EP97/05945 1997-10-28
EP98947499A EP1015550B1 (fr) 1996-09-20 1998-09-02 Procede de production de nettoyants et detergents particulaires
PCT/EP1998/005548 WO1999013046A1 (fr) 1997-09-11 1998-09-02 Procede de production de nettoyants et detergents particulaires

Publications (2)

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EP1015550A1 true EP1015550A1 (fr) 2000-07-05
EP1015550B1 EP1015550B1 (fr) 2006-02-01

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EP98947499A Expired - Lifetime EP1015550B1 (fr) 1996-09-20 1998-09-02 Procede de production de nettoyants et detergents particulaires

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JP (1) JP2001500557A (fr)
KR (3) KR20010029500A (fr)
CN (1) CN1187435C (fr)
AT (1) ATE256176T1 (fr)
CZ (1) CZ296295B6 (fr)
DE (2) DE19638599A1 (fr)
ES (1) ES2213222T3 (fr)
PL (1) PL331987A1 (fr)
RU (1) RU2200190C2 (fr)
SK (1) SK285376B6 (fr)
TR (1) TR199900582T2 (fr)
UA (1) UA64724C2 (fr)
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Publication number Priority date Publication date Assignee Title
DE19723616A1 (de) * 1997-06-05 1998-12-10 Henkel Kgaa Granulares Waschmittel
DE19746781A1 (de) * 1997-10-23 1999-04-29 Henkel Kgaa Verfahren zur Herstellung duftverstärkter Wasch- oder Reinigungsmittel
DE19753310A1 (de) * 1997-12-02 1999-06-10 Henkel Kgaa Rohstoff-Compounds mit hohem Schüttgewicht
DE19808758A1 (de) * 1998-03-02 1999-09-09 Henkel Kgaa Verfahren zur Herstellung von Wasch- und Reinigungsmittelformkörpern
CN1346400A (zh) * 1998-09-25 2002-04-24 宝洁公司 溶解性改进的粒状洗涤剂组合物
DE19848024A1 (de) * 1998-10-17 2000-04-20 Henkel Kgaa Verfahren zur Herstellung extrudierter Formkörper
DE19858887A1 (de) * 1998-12-19 2000-06-21 Henkel Kgaa Kompaktat mit silicatischem Builder
DE10031619A1 (de) 2000-06-29 2002-01-10 Cognis Deutschland Gmbh Tensidgranulate mit verbesserter Auflösegeschwindigkeit
DE10137925A1 (de) 2001-08-07 2003-02-20 Cognis Deutschland Gmbh Geminitenside und Polyethylenglycol
DE10242222A1 (de) * 2002-09-12 2004-03-25 Henkel Kgaa Unter Druck kompaktiertes Wasch- oder Reinigungsmittel
WO2008054335A1 (fr) * 2006-10-30 2008-05-08 Eduard Valerievich Belinskiy Moyen de lavage granulé synthétique et cabine de douche associée
US8119112B2 (en) * 2008-01-31 2012-02-21 Bausch & Lomb Incorporated Ophthalmic compositions with an amphoteric surfactant and hyaluronic acid
GB0915572D0 (en) * 2009-09-07 2009-10-07 Reckitt Benckiser Nv Detergent composition
ES2632282T3 (es) * 2013-03-22 2017-09-12 Basf Se Alquil glicósidos como surfactantes
CN104152293A (zh) * 2014-07-28 2014-11-19 张洪山 洗涤用碱性蛋白彩色粒子成套生产线
USD762486S1 (en) 2015-02-18 2016-08-02 Henkel Ag & Co. Kgaa Solid state detergent in a transparent container
USD784819S1 (en) 2015-02-18 2017-04-25 Henkel Us Iv Corporation Container for a solid state detergent
US9512388B2 (en) 2015-02-18 2016-12-06 Henkel Ag & Co. Kgaa Solid state detergent in a transparent container
DE102015002877B4 (de) 2015-03-09 2024-09-12 Henkel Ag & Co. Kgaa Wasch- oder reinigungsaktive Extrudate, deren Herstellung und Verwendung in granularen Wasch- oder Reinigungsmitteln
WO2020050426A1 (fr) * 2018-09-03 2020-03-12 주식회사 프랜드 Procédé de préparation de billes de gommage à propriétés antibactériennes à base d'amidon

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DE4024759A1 (de) * 1990-08-03 1992-02-06 Henkel Kgaa 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
DE4319666A1 (de) * 1993-06-14 1994-12-15 Henkel Kgaa Verfahren zur Herstellung fester Wasch- oder Reinigungsmittel mit hohem Schüttgewicht und verbesserter Rheologie
GB9422924D0 (en) * 1994-11-14 1995-01-04 Unilever Plc Detergent compositions

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EP1015550B1 (fr) 2006-02-01
UA64724C2 (uk) 2004-03-15
CZ296295B6 (cs) 2006-02-15
ATE256176T1 (de) 2003-12-15
ES2213222T3 (es) 2004-08-16
CN1187435C (zh) 2005-02-02
JP2001500557A (ja) 2001-01-16
DE59711115D1 (de) 2004-01-22
EP0931137B1 (fr) 2003-12-10
RU99108122A (ru) 2001-02-20
SK35299A3 (en) 1999-07-12
SK285376B6 (sk) 2006-12-07
KR20010023917A (ko) 2001-03-26
KR20010023926A (ko) 2001-03-26
KR20010029500A (ko) 2001-04-06
CN1230984A (zh) 1999-10-06
EP0931137A1 (fr) 1999-07-28
CZ97799A3 (cs) 1999-09-15
WO1998012299A1 (fr) 1998-03-26
DE19638599A1 (de) 1998-03-26
TR199900582T2 (xx) 1999-06-21
PL331987A1 (en) 1999-08-16
RU2200190C2 (ru) 2003-03-10

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