EP0931137A1 - Procede de production d'un detergent ou nettoyant particulaire - Google Patents

Procede de production d'un detergent ou nettoyant particulaire

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Publication number
EP0931137A1
EP0931137A1 EP97942019A EP97942019A EP0931137A1 EP 0931137 A1 EP0931137 A1 EP 0931137A1 EP 97942019 A EP97942019 A EP 97942019A EP 97942019 A EP97942019 A EP 97942019A EP 0931137 A1 EP0931137 A1 EP 0931137A1
Authority
EP
European Patent Office
Prior art keywords
premix
weight
compounds
raw materials
binder
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
EP97942019A
Other languages
German (de)
English (en)
Other versions
EP0931137B1 (fr
Inventor
Wilfried Rähse
Norbert Kühne
Dieter Jung
Peter Sandkühler
Bernd Larson
Kathleen Paatz
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
Application filed by Henkel AG and Co KGaA filed Critical Henkel AG and Co KGaA
Publication of EP0931137A1 publication Critical patent/EP0931137A1/fr
Application granted granted Critical
Publication of EP0931137B1 publication Critical patent/EP0931137B1/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
    • 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
    • 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 rapidly soluble, compressed particulate detergents or cleaning agents or compounds or treated raw materials therefor, and detergents or cleaning agents produced in this way or the like.
  • Compounds or treated raw materials for this, which from the point of view of the consumer have a significantly better quality.
  • 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 once again the higher concentration of the detergent or cleaning agent in the agent was generally paid for by a subjectively poorer solubility from the point of view of the consumer, since the dissolving rate of the agent used was slower.
  • EP-B-0 486 592 describes granular or extruded washing 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 which contains a plasticizer and / or lubricant composed of preferably aqueous surfactant pastes and / or aqueous polymer solutions at high pressures between 25 and 200 bar extruded and the strand is cut and rounded after exiting the hole shape by means of a cutting device to the predetermined granule size.
  • a solid, free-flowing premix which contains a plasticizer and / or lubricant composed of preferably aqueous surfactant pastes and / or aqueous polymer solutions at high pressures between 25 and 200 bar extruded and the strand is cut and rounded after exiting the hole shape by means of a cutting
  • 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 cleaners, or they can be subsequently processed with other granules or powder components to produce finished detergents or cleaners.
  • German patent application DE 195 19 139.0 proposes, in order 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-gelation-based redissolvability of the finished detergents or cleaning agents in aqueous liquors, particulate detergents.
  • surfactant content being extruded Component including the soaps should be a maximum of 15 wt .-%, based on the respective extruded component.
  • Further surfactant components of the finished washing or cleaning agent are introduced into the agent through one or more non-extruded component (s).
  • 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 tangent-oriented 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.
  • 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 in an intimate mixture with a Structural breakers such as polyethylene glycol or polypropylene glycol or ethoxylated C e - C 18 fatty alcohols with 20 to 45 EO were provided.
  • a Structural breakers such as polyethylene glycol or polypropylene glycol or ethoxylated C e - C 18 fatty alcohols with 20 to 45 EO were provided.
  • 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, but its use is less preferred 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, for example, European patent EP-B-0486 592) 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-A-0337 330 describes a process 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 as nonionic compounds.
  • European patent application EP-A-0 711 828 describes a process for producing 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.
  • the compacting / tableting should be carried out at temperatures which are at least at 28 ° C., but in any case below the melting temperature of the binder.
  • 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.
  • 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 sheet silicates being agglomerated with 20 to 35 parts by weight of a binder.
  • Suitable binders are, in particular, highly viscous anionic surfactant pastes, which can contain between 0 and 90% by weight of water.
  • polymers such as polyethylene glycols with molecular weights between 1,000 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 the 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 instead.
  • intensive mixer with a very specific, relatively high energy input instead.
  • 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 compounds or treated raw materials therefor which, even with a reduced surface area, in particular with a spherical shape (pearl shape), have improved disintegration when dissolved in the aqueous liquor.
  • 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 the like.
  • Compounds or treated raw materials for this purpose with bulk weights above 600 g / 1 by joining detergent or cleaning agent compounds and / or raw materials with simultaneous or subsequent shaping initially producing a premix comprising individual raw materials and / or compounds which are produced at room temperature and a pressure of 1 bar as a solid and have a melting point or softening point not below 45 ° C, and optionally up to 10% by weight at temperatures below 45 ° C and a pressure of 1 bar, contains liquid nonionic surfactants, and using compression forces at Temperatures of at least 45 ° C are converted into a grain and, if necessary, subsequently processed or processed.
  • the premix is essentially water-free and in the premix at least one raw material or compound that is in solid form at a pressure of 1 bar and temperatures below 45 ° C., but is present as a melt under the processing conditions ,
  • This melt serves as a polyfunctional, water-soluble binder, which in the preparation of the agents performs both the function of a lubricant and an adhesive function for the solid detergent or cleaning agent compounds or raw materials, when the agent is redissolved in aqueous fleet, however, has a disintegrating effect.
  • essentially water-free is understood to mean a state in which the content of liquid water, ie water not present in the form of hydrated 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 at temperatures below 45 ° C.
  • the premix which advantageously has a total water content of not more than 15% by weight, ie this water is not in liquid free form, but is chemically and / or physically bound, and it is particularly preferred that the content of not zeolite and / or water bound to 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 to 5% by weight.
  • 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 90% by weight of particles with a diameter of at least 400 ⁇ m.
  • the detergents or cleaning agents, compounds or treated raw materials produced consist of spherical at least 70% by weight, advantageously at least 80% by weight and, with particular preference, up to 100% by weight (Pearl-shaped) particles with a particle size distribution which has at least 80% by weight of particles between 0.8 and 2.0 mm.
  • 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 compound on the other hand, consists of at least 2 commonly used in washing or cleaning agents Ingredients; 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 - with the exception of any nonionic surfactants which are liquid at temperatures below 45 ° C and a pressure of 1 bar - can be separately manufactured compounds, but also raw materials which are powdery or particulate (fine to coarse), in any case in solid form at room temperature and a pressure of 1 bar.
  • any nonionic surfactants which are liquid at temperatures below 45 ° C and a pressure of 1 bar
  • raw materials which are powdery or particulate (fine to coarse), in any case in solid form at room temperature and a pressure of 1 bar.
  • beads or (fluidized bed) granules etc. produced by spray drying can be used as particulate particles.
  • the composition of the compounds per se is insignificant for the invention with the exception of the water content, which must be such that the premix is essentially water-free as defined above and preferably contains no more than 10% by weight of water of hydration and / or constitutional water .
  • 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 liquids, 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 remaining free-flowing or at least conveyable even at higher temperatures of at least 45 ° C.
  • the water that is bound to builder substances such as zeolite or silicates (for a description of the substances see below), in particular if the water is bound to zeolite A, zeolite P or MAP and / or zeolite X, is to be regarded as 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 in particular is a maximum of 2 to 5% by weight. It is particularly advantageous if the premix contains no water that 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 liquids at temperatures below 45 ° C. is preferably also or additionally up to 10% by weight, advantageously up to 6% by weight, again 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 prepared 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 .
  • At least 80% by weight, in particular at least 85% by weight and, with particular preference, at least 90% by weight of the compounds and individual raw materials used in the premix have a significantly higher softening point or melting point than the temperatures, which are achieved under the process conditions.
  • the process temperatures will not be above 150 ° C., preferably not above 120 ° C., for economic reasons alone.
  • at least 80% by weight of the compounds and individual raw materials used will have a softening point or melting point above 150 ° C. As a rule, the softening point or melting point is even far above this temperature.
  • the decomposition temperature of these ingredients is also significantly above 45 at a pressure of 1 bar and in particular at higher pressures which are present in the inventive and preferred extrusion processes ° C.
  • 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 C chain length between 8 and 20 and in particular an average of 3 to 7 ethylene oxide units per mole of alcohol (for a more detailed description see below).
  • the liquid nonionic surfactants can be added in amounts which still ensure that the premix is free-flowing Form is present. If such liquid nonionic surfactants are introduced into the premix, it is preferred that liquid nonionic surfactants and the disintegrating binder are introduced into the process separately from one another.
  • the liquid nonionic 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 serves as a binder, although it is solid at room temperature, but is present in liquid form in the form of a melt under the process conditions.
  • the binder itself can be melted once sprayed onto the premix or added dropwise to the premix.
  • it has also proven advantageous to introduce the binder in solid form as a powder into the premix.
  • the melting point or softening point at a pressure of 1 bar is at least 45 ° C. and (in particular for economic reasons) preferably below 200 ° C., in particular up to a maximum of 150 ° C. If the binder is introduced into the premix in the form of a melt, the temperature in the melting vessel is also more than 45 ° C. to a maximum of about 200 ° C., the temperature in the melting vessel being the melting temperature or the temperature of the softening point of the binder or can exceed the binder mixture significantly.
  • suitable binder and the temperature in the compression process step are interdependent. Since it has proven to be advantageous if the binder is distributed as homogeneously as possible in the material to be compacted in the compression step, temperatures must be present in the compression step at which the binder at least softens, but preferably completely and not only partially is in molten form. If a binder with a high melting point or high softening point is selected, then a temperature must be set in the compression process step, which ensures that the binder melts. In addition, depending on the desired composition of the end product, temperature-sensitive raw materials should also be able to be processed.
  • the upper temperature limit is determined by the Given the decomposition temperature of the sensitive raw material, it is preferred to work significantly below the decomposition temperature of this raw material.
  • the lower limit for the melting point or softening point is of such great importance, since at melting points or softening points below 45 ° C, an end product is usually obtained which is already at room temperature and slightly elevated temperatures of 30 ° C, So at summer temperatures and under camp or Transport conditions tend to stick. It has proven to be particularly advantageous if a few degrees, for example 2 to 20 ° C., are used above the melting point or above the softening point
  • the applicant is of the opinion that the homogeneous distribution of the binder within the premix under the process conditions of compression compresses the solid compounds and any individual raw materials that may be present in the binder and subsequently glues them together the finished end products are made 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).
  • these thin partitions dissolve or disintegrate almost immediately; Surprisingly, this is also the case if the binder itself is not readily soluble in water at room temperature, for example due to a crystal structure.
  • binders are preferably used which can be almost completely dissolved within 90 seconds in a test method as described below in a concentration of 8 g of binder in 1 liter of water at 30 ° C.
  • the binder or binders must therefore be such that the adhesive properties are retained even at temperatures which are significantly above the melting point or the softening point.
  • a binder which is already completely present as a melt at temperatures of up to 130 ° C., preferably up to 100 ° C. and in particular up to 90 ° C.
  • the binder must therefore be selected depending on the process and process conditions, or the process conditions, in particular the process temperature, must - if a particular binder is desired - be adapted to the binder.
  • Preferred binders which can be used alone or in a mixture with other binders, are polyethylene glycols, 1,2-polypropylene glycols and modified polyethylene glycols and polypropylene glycols.
  • the modified polyalkylene glycols include in particular the sulfates and / or the disulfates of polyethylene glycols or polypropylene glycols with a relative molecular weight between 600 and 12000 and in particular between 1000 and 4000.
  • Another group consists of mono- and / or disuccinates of the polyalkylene glycols, which in turn have relative molecular weights between 600 and 6000, preferably between 1000 and 4000.
  • polyethylene glycols include those polymers which, in addition to ethylene glycol, also produce C 3 -
  • C 5 glycols and glycerol and mixtures of these can be used as starting molecules. Also included are ethoxylated derivatives such as trimethylol propane with 5 to 30 EO.
  • the polyethylene glycols preferably used can have a linear or branched structure, linear polyethylene glycols being particularly preferred.
  • the particularly preferred polyethylene glycols include those with relative molecular weights between 2000 and 12000, advantageously around 4000, polyethylene glycols with relative molecular weights below 3500 and above 5000 especially in combination with polyethylene glycols with a relative molecular weight around 4000 can be used and such combinations advantageously to more than 50% by weight, based on the total amount of the polyethylene glycols, have polyethylene glycols with a relative molecular weight between 3500 and 5000.
  • polyethylene glycols which are in the liquid state at room temperature and a pressure of 1 bar can also be used as binders; Here we are mainly talking about polyethylene glycol with a relative molecular mass of 200, 400 and 600. However, these per se liquid polyethylene glycols should only be used in a mixture with at least one further binder, this mixture again having to meet the requirements according to the invention, that is to say having a melting point or softening point of at least above 45 ° C.
  • the modified polyethylene glycols also include polyethylene glycols which are end group-capped on one or more sides, the end groups preferably being C 1 -C 2 -alkyl chains which can be linear or branched.
  • the end groups have the alkyl chains between C 1 and C 6 , especially between C 4 and C 4 , isopropyl and isobutyl or tert-butyl also being possible alternatives.
  • binders are low molecular weight polyvinylpyrrolidones and derivatives thereof with relative molecular weights up to a maximum of 30,000. Relative molecular weight ranges between 3,000 and 30,000, for example around 10,000, are preferred here. Polyvinylpyrrolidones are preferably not used as sole binders but in Combination with others, especially in combination with polyethylene glycols.
  • binders have been found to be raw materials which, as raw materials, have washing or cleaning properties per se, for example nonionic surfactants with melting points of at least 45 ° C. or mixtures of nonionic surfactants and other binders.
  • nonionic surfactants with melting points of at least 45 ° C. or mixtures of nonionic surfactants and other binders.
  • Surfactants include alkoxylated fatty or oxo alcohols, especially C 12 -C 18 alcohols. Degrees of alkoxylation, in particular degrees of ethoxylation, of on average 18 to 100 AO, in particular EO per mole of alcohol and mixtures thereof have proven to be particularly advantageous. In particular, fatty alcohols with an average of 18 to 35 EO, in particular with an average of 20 to 25 EO, show advantageous binder properties in the sense of the present invention. Binder mixtures may also contain ethoxylated alcohols with an average of fewer EO units per mole of alcohol, for example tallow fatty alcohol with 14 EO.
  • these relatively low ethoxylated alcohols only in a mixture with higher ethoxylated alcohols.
  • the binder content of these relatively low ethoxylated alcohols is advantageously less than 50% by weight, in particular less than 40% by weight, based on the total amount of binder used.
  • nonionic surfactants such as C 12 -C 18 alcohols with an average of 3 to 7 EO, which are usually used in detergents or cleaning agents and which are liquid per se at room temperature, are preferably only present in the binder mixtures in amounts that are less than 10 % By weight, in particular less than 8% by weight and advantageously less than 2% by weight, of these nonionic surfactants, in each case based on the end product of the process.
  • nonionic surfactants which are liquid at room temperature in the binder mixtures.
  • such nonionic surfactants are therefore not a component of the binder mixture, since they not only lower the softening point of the mixture, but can also contribute to the stickiness of the end product and, furthermore, also due to their tendency to cause gelling upon contact with water The requirement for the rapid dissolution of the binder / the dividing wall in the end product is often not to the desired extent are enough.
  • conventional anionic surfactants or their precursors, the anionic surfactant acids, used in washing or cleaning agents are contained in the binder mixture.
  • nonionic surfactants which are suitable as binders are the fatty acid methyl ester ethoxylates which do not tend to gel, in particular those with an average of 10 to 25 EO (for a more detailed description of this group of substances, see below). Particularly preferred representatives of this group of substances are predominantly on C 16 -C 18 -
  • Fatty acid-based methyl esters for example hardened beef tallow methyl ester with an average of 12 EO or with an average of 20 EO.
  • ethoxylated fatty acids with 2 to 100 EO, the “fatty acid” residues of which can be linear or branched in the context of this invention.
  • Ethoxylates which, in particular, are preferred are those have a narrowed homolog distribution (NRE) and / or a melting point above 50 ° C.
  • NRE narrowed homolog distribution
  • Such fatty acid ethoxylates can be used as the sole binder or in combination with other binders, while the non-ethoxylated sodium and potassium soaps are less preferred and only in combination with other binders can be used.
  • hydroxy mixed ethers which can be obtained according to the teaching of European patent application EP-A-0 754 667 (BASF) by ring opening of epoxides of unsaturated fatty acid esters, are also suitable as binders, in particular in combination with polyethylene glycols, the aforementioned fatty acid methyl ester ethoxylates or the fatty acid ethoxylates .
  • Cellulose / glycerin for example hydroxypropyl cellulose / glycerin, have proven to be excellently usable binders. 5 to 20% by weight “solutions” are the Polymers in glycerol, in particular about 10% by weight “solutions”, are particularly advantageous.
  • a mixture is used as the binder which contains C 12 -C 18 fatty alcohol based on coconut or tallow with an average of 20 EO and polyethylene glycol with a relative molecular weight of 400 to 4000.
  • a mixture is used as the binder which is predominantly methyl ester-based C 16 -C 18 fatty acids with an average of 10 to 25 EO, in particular hardened beef tallow methyl ester with an average of 12 EO or an average of 20 EO, and a C 12 - Contains C 18 fatty alcohol based on coconut or tallow with an average of 20 EO and / or polyethylene glycol with a relative molecular weight of 400 to 4000.
  • binders either alone on polyethylene glycols with a relative molecular weight around 4000 or on a mixture of C 2 -C 18 fatty alcohol based on coconut or tallow with an average of 20 EO and one of the fatty acid methyl ester ethoxylates described above or on a mixture of C 2 -C 18 fatty alcohol
  • binder mixtures in particular in a mixture with polyethylene glycols; however, they cannot be used as the sole binder, since they have a binding / adhesive function, but do not have a disintegrating effect.
  • other binders can be used alone or in combination with others
  • Binders are also used 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.
  • Alkyl glycosides which have a degree of softening above 80 ° C. and a melting point above 140 ° C. are particularly suitable.
  • alkyl glycosides are also suitable. Using high shear forces, the melt aggravation and in particular the melt extrusion with such highly concentrated compounds can already be carried out at temperatures which are above the softening point but still below the melting temperature.
  • alkyl glycosides can also be used as the sole binder, it is preferred to use mixtures of alkyl glycosides and other binders. In particular, here are mixtures of polyethylene glycols and alkyl glycosides, advantageously in weight ratios from 25: 1 to 1: 5, with particular preference from 10: 1 to 2: 1.
  • binders particularly in combination with polyethylene glycols and / or alkyl glycosides, are 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 up to 4 carbon atoms and [Z] represents a linear or branched polyhydroxyalkyl radical having 3 to 10 carbon atoms and 3 to 10 hydroxyl groups.
  • 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 up to 4 carbon atoms
  • [Z] represents a linear or branched polyhydroxyalkyl radical having 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)
  • Aryl radical with 2 to 8 carbon atoms and R represents a linear, branched or cyclic alkyl radical or an aryl radical or an oxyalkyl radical with 1 to 8 carbon atoms, C 1 -C 4 alkyl or phenyl radicals being preferred, and [Z] for a linear polyhydroxyalkyl radical, the alkyl chain of which 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.
  • 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.
  • Particularly preferred giucamides already melt at 95 to 105 ° C. But here too - as with the alkyl glycosides - working temperatures which are above the softening temperature but below the melting temperature are normally sufficient in the process according to the invention.
  • the content of binder or binders in the premix is preferably at least 2% by weight, but less than 15% by weight, in particular less than 10% by weight, with particular preference from 3 to 6% by weight, in each case based on the premix.
  • the water-swollen polymers are used in amounts below 10 % By weight, advantageously in amounts of 4 to 8% by weight, preferably 5 to 6% by weight.
  • the solids for the preparation of the solid and free-flowing premix are firstly at room temperature to slightly elevated temperatures, which are preferably below the melting temperature or the softening point of the binder and in particular at temperatures up to 35 ° C. in a customary mixture. and / or pelletizer mixed together.
  • These solids also include those which, according to European patent EP-B-0 486 592, can serve as plasticizers and / or lubricants.
  • the function of a lubricant can also be performed by the binder or the binders or the binder mixtures.
  • the binders are preferably added as the last component. As already stated above, they can be added as a solid, that is to say at a processing temperature which is below their melting point or their softening point, or as a melt. However, the admixture is advantageously carried out under conditions such that the most homogeneous possible distribution of the binder in the solid mixture is achieved. In the case of very finely divided binders, this can be accomplished at temperatures below 40 ° C., for example at temperatures of the binder between 15 and 30 ° C. However, the binder advantageously has temperatures at which it is already in the form of a melt, that is to say above the softening point, in particular in the form of a complete melt.
  • Preferred temperatures of the melt are at 60 to 150 ⁇ C, with particular preference the temperature range of 80 to 120 ° C.
  • the melt solidifies almost instantaneously, and the premix is, according to the invention, in solid, free-flowing form.
  • the mixing process is advantageously as long in any case continued until the melt has solidified and the premix is in solid, free-flowing form.
  • the detergent or cleaning agent compounds and / or raw materials can be joined together with simultaneous or subsequent shaping by customary processes 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 prefabricated compounds in the premix, but the invention is by no means restricted to this. Rather, the method according to the invention lends itself 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 actual granulation, compacting, tableting, pelleting or extrusion process takes place according to the invention at processing temperatures which, at least in the compression step, correspond at least to the temperature of the softening point, if not even the temperature of the melting point of the binder.
  • the process temperature is significantly above the melting point or above the temperature at which the binder is in the form of a melt.
  • the process temperature in the compression step is not more than 20 ° C. above the melting temperature or the upper limit of the melting range of the binder. It is technically possible to set even higher temperatures; However, it has been shown that a temperature difference of 20 ° C.
  • thermoly sensitive raw materials for example peroxy bleaching agents such as perborate and / or percarbonate, but also enzymes, increasingly without serious Active substance losses can be processed.
  • the duration of the temperature effect is preferably between 10 seconds and a maximum of 5 minutes, in particular it is a maximum of 3 minutes.
  • 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 (for a detailed description see below) to be processed together without fear of serious loss of activity.
  • the method according to the invention is carried out by means of an extrusion, as described, for example, in European patent EP-B-0486 592 or international patent applications WO-A-93/02176 and WO-A-94/09111.
  • a solid premix is pressed in 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 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.
  • Preferred plasticizers and / or lubricants are surfactants and / or polymers which, in the context of the present invention, with the exception of the nonionic surfactants mentioned above, are not introduced into the premix in liquid and in particular not in aqueous, but in solid form.
  • the premix is preferably continuously fed to a planetary roller extruder or a 2-shaft extruder or 2-screw extruder fed with co-rotating or counter-rotating screw guide, the housing and the .Extruder pelletizing head can be raised to the predetermined extrusion temperature.
  • the premix is compressed, plasticized, and extruded in the form of fine strands through the perforated die plate in the extruder head under pressure, which is preferably at least 25 bar, at extremely high throughputs depending on the apparatus used and finally 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 application. In general, diameter of up to 0.8 cm is 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 chopped-off primary granules is in the range from about 1: 1 to about 3: 1.
  • 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.
  • extrusions / pressings can also be carried out in low-pressure extruders, in the Kahl press or in the extruder.
  • the invention now provides that the temperature control in the transition area of the screw, the pre-distributor and the nozzle plate is designed such that the melting temperature of the binder or the upper limit of the melting range of the binder is at least reached, but preferably exceeded.
  • the duration of the temperature influence in the compression range of the extrusion is preferably less than 2 minutes and in particular in a range between 30 seconds and 1 minute.
  • the binder used has a melting temperature or a melting range of up to 75 ° C .; Process temperatures which are at most 10 ° C. and in particular at most 5 ° C. above the melting temperature or the upper temperature limit of the melting range of the binder have then proven to be particularly favorable.
  • the binder also functions as a lubricant and at least prevents or at least reduces sticking to apparatus walls and compaction tools. This applies not only to processing in the extruder, but also equally to processing, for example in continuously operating mixers / granulators or rollers.
  • the compressed material preferably has temperatures not above 80 ° C., temperatures between 35 and 75 ° C. being particularly preferred. It has been found that exit temperatures - especially in the extrusion process - from 40 to 70 ° C, for example up to 60 ° C, are particularly advantageous. Just as in the extrusion process, it is also preferred in the other production processes to feed the resulting primary granules / compactates to a further shaping processing step, in particular to round them, so that ultimately spherical to approximately spherical (pearl-shaped) grains can be obtained.
  • the particle size distribution of the premix is substantially broader 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 having the same final composition, were not produced by the process according to the invention, that is to say were not produced by means of a melt under anhydrous conditions.
  • 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.
  • a granular or extruded detergent which consists of at least 80% by weight of compounds and / or raw materials treated according to the invention.
  • a granular or extruded detergent consists of at least 80% by weight of a base granulate or base extrudate produced according to the invention.
  • the remaining ingredients may have been 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.
  • the invention further provides compounds and treated raw materials produced according to the invention, for example builder granules (extrudates), bleach activator granules (extrudates) or enzyme granules (extrudates).
  • 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 end products of the process produced according to the invention have a very high bulk density.
  • the bulk density is preferably above 700 g / 1, in particular between 750 and 1000 g / l. Even if the extrudates are processed with other ingredients that have lower bulk densities, the bulk density of the final product does not decrease to the extent that would normally be expected.
  • 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 washing or cleaning agents, which generally further increases the bulk density.
  • a preferred aftertreatment is also the procedure according to German patent applications DE-A-195 24 287 and DE-A-195 47 457, dusty or at least finely divided ingredients (the so-called fine fractions) of the particulate end products of the process, which are the core serve, be glued and thus funds are created which have these so-called fines as an outer shell. This advantageously takes place in turn by melt agglomeration, the same binders as can be used in the process according to the invention.
  • bleach activators and foam inhibitors especially salts such as silicates (crystalline or amorphous) including metasilicate, carbonate, bicarbonate, sulfate, bisulfate, citrate or other polycarboxyates, but also organic acids such as citric acid (see below) are mixed in the preparation. It is particularly preferred that 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.
  • salts such as silicates (crystalline or amorphous) including metasilicate, carbonate, bicarbonate, sulfate, bisulfate, citrate or other polycarboxyates, but also organic acids such as citric acid (see below) are mixed in the preparation. It is particularly preferred that 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.
  • surfactants in particular anionic surfactants, which should be present in the agents according to the invention or agents manufactured 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 9 -C 13 alkylbenzene sulfonates, olefin sulfonates, ie mixtures of alkene and hydroxyalkane sulfonates, and disulfonates such as are obtained, for example, from C 12 -C 18 monoolefins having an end or internal double bond by sulfonating with gaseous Sulfur trioxide and subsequent alkaline or acidic hydrolysis of the sulfonation products is considered.
  • alkanesulfonates obtained from C 12 -C 18 alkanes, for example by sulfochlorination or sulfoxidation with subsequent hydrolysis or neutralization.
  • esters of ⁇ -sulfo fatty acids e.g. the ⁇ -sulfonated methyl esters of hydrogenated coconut, palm kernel or tallow fatty acids which are prepared by ⁇ -sulfonation of the methyl esters of fatty acids of plant and / or animal origin with 8 to 20 C atoms in the fatty acid molecule and subsequent neutralization to form water-soluble mono salts, into consideration.
  • ⁇ -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 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 the alkali and especially the sodium salts of the sulfuric acid half esters of the C 12 -C 18 fatty alcohols, for example from coconut fatty alcohol, tallow fatty alcohol, lauryl, myristyl, cetyl or stearyl alcohol or the C 10 -C 20 oxo alcohols, and those Half-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.
  • C 12 -C 16 alkyl sulfates and C 12 -C 15 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, for example, according to US Pat. Nos. 3,234,258 or 5,075,041 and can be obtained as commercial products from Shell Oil Company under the name DAN (R) are suitable anitone 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 Cg-C , 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 used in detergents only in relatively small amounts, for example in amounts of 1 to 5% by weight.
  • Preferred anionic surfactants are also the salts of alkylsulfosuccinic acid, which are also referred to as sulfosuccinates or as sulfosuccinic acid esters and which represent monoesters and / or diesters of sulfosuccinic acid with alcohols, preferably fatty alcohols and in particular 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 which is derived from ethoxylated fatty alcohols, which in themselves are nonionic surfactants (description see below).
  • 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.
  • 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.
  • soaps or the known alkenylsuccinic acid salts can also be used as a substitute for soaps.
  • the anionic surfactants can be 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, preferably having 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 residue 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 otyl 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, with 7 EO, C 13 -C 1s alcohols with 3 EO, 5 EO, 7 EO or 8 EO, C 12 -C 18 alcohols with 3 EO, 5 EO or 7 EO and mixtures thereof, such as mixtures of C 12 -C 14 alcohol with 3 EO and C 12 -C ⁇ 8 alcohol with 7 EO.
  • the degrees of ethoxylation given are 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, as described above. 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 the alkyl glycosides of the general formula RO (G) x already described in detail above and the polyhydroxy fatty acid amides of the formulas (I) and (II).
  • 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.
  • 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, are preferred as nonionic surfactants, while, as described above, especially higher ethoxylated fatty acid methyl esters are advantageous as binders.
  • C 12 -C 18 fatty acid methyl esters with 10 to 12 EO can be used both as surfactants and as binders.
  • 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 these 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 generally separated from one another by a so-called “spacer”. This spacer is generally 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 distinguished generally due to an unusually low critical micelle concentration and the ability to greatly increase the surface tension of the water reduce, out. 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-A-43 21 022 or dimer alcohol bis- and trimeral alcohol tris-sulfates and ether sulfates according to German patent application DE-A-195 03 061.
  • End group-blocked dimer and trimeric mixed ethers According to German patent application DE-A-195 13 391, they are particularly characterized by their bi- and multifunctionality.
  • the end-capped surfactants 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 (R) (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. In the event that the zeolite is used as a suspension, it may contain minor additions of nonionic surfactants as stabilizers, for example 1 to 3% by weight, based on zeolite, of ethoxylated C 12 -C 18 -
  • 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 Is 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 ⁇ -
  • the preferred builder substances also include amorphous sodium silicates with a modulus Na 2 O: 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.
  • 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 of size 10 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-A-44 00 024.
  • Compacted / compacted amorphous silicates, compounded amorphous silicates and over-dried X-ray amorphous silicates are particularly preferred.
  • the generally known 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 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 layer silicates of natural and synthetic origin.
  • Layered silicates of this type are known, for example, from patent applications DE-B-23 34 899, EP-A-0 026 529 and DE-A-35 26 405.
  • Their usability is not limited to a special composition or structural formula. However, smectites, in particular be ⁇ tonites, 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, due to their ion exchange
  • Properties contain hydrogen, alkali, alkaline earth ions, in particular Na + and Ca ++ .
  • the amount of water of hydration is usually in the range of 8 to 20% by weight and depends on the swelling condition or the type of processing.
  • Useful sheet silicates are known, for example, from US-A-3,966,629, EP-A-0 026 529 and EP-A-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 citro- Nenoic 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.
  • 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. They are preferably hydrolysis products with average molecular weights in the range from 400 to 500,000.
  • 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 British patent application 94 19091.
  • the oxidized derivatives of such dextrins 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.
  • Such oxidized dextrins and processes for their preparation are known, for example, from European patent applications EP-A-0232 202, EP-A-0427 349, EP-A-0472 042 and EP-A-0542496 as well as international patent applications WO-A-92/18542 , WO-A-93/08251, WO-A-94/28030, WO-A-95/07303, WO-A-95/12619 and WO-A-95/20608.
  • a product oxidized at C 6 of the saccharide ring can be particularly advantageous.
  • 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.
  • Suitable amounts used in formulations containing zeolite and / or silicate are 3 to 15% by weight.
  • organic cobuilders are, for example, acetylated hydroxycarboxylic acids or their salts, which may optionally 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-A-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 DE-A-4300772, are salts of acrylic acid and maleic acid as well as vinyl alcohol or vinyl alcohol derivatives or according to DE-C-4221 381 as monomers contain 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-A-4303320 and DE-A-44 17734 and preferably contain acrolein and acrylic acid / acrylic acid salts or acrolein and vinyl acetate as monomers.
  • Suitable builder substances are oxidation products of carboxyl group-containing polyglucosans and / or their water-soluble salts, as are described, for example, in international patent application WO-A-93/08251 or whose preparation is described, for example, in international patent application WO-A-93/16110 .
  • Oxidized oligosaccharides according to German patent application DE-A-19600018 are also suitable.
  • polymeric aminodicarboxylic acids their salts or their precursor substances.
  • Particularly preferred are polyaspartic acids or their salts and derivatives, of which it is disclosed in German patent application DE-A-195 40 086 that, in addition to cobuilder properties, they also have a bleach-stabilizing effect.
  • 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-A-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 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 ethers, as well as the polymers of phthalic acid and / or terephthalic acid or their derivatives known from the prior art, in particular polymers of ethylene terephthalates and / or polyethylene glycol terephthalates or anionically and / or nonionically modified derivatives thereof. Of these, 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; in particular, alkali carbonate and amorphous
  • Alkali silicate especially sodium silicate with a molar Na 2 O: SiO 2 ratio of 1: 1 to 1: 4.5, preferably 1: 2 to 1: 3.5, is used.
  • the content of sodium carbonate in the agent is preferably up to 20 wt .-%, advantageously z. wipe 5 and 15 wt .-%.
  • 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 more.
  • alkali metal carbonates can also be replaced by sulfur-free amino acids having 2 to 11 carbon atoms and optionally an additional carboxyl and / or amino group and / or by their salts.
  • the alkali metal carbonates it is possible for the alkali metal carbonates to be partially or completely replaced by glycine or glycine.
  • the other detergent ingredients include graying inhibitors (dirt carriers), foam inhibitors, bleaching agents and bleach activators, optical brighteners, enzymes, fabric softening agents, dyes 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 at the same time are also used as builder substances can be.
  • 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.
  • sodium perborate tetrahydrate and sodium perborate monohydrate are of particular importance.
  • Other bleaches that can be used include sodium percarbonate,
  • Peroxypyrophosphates citrate perhydrates and H 2 O 2 -supplying acidic salts or peracids, such as perbenzoates, peroxophthalates, diperazelaic acid, phthaloiminoperacid 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.
  • aliphatic peroxocarboxylic acids with preferably 1 to 10 C atoms, in particular 2 to 4 C atoms, and / or optionally substituted perbenzoic acid can be used as bleach activators.
  • 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 in particular tetraacetylethylene diamine (TAED), acylated triazine derivatives, in particular 1,5-diacetyl-2,4-dioxohexahydro-1,3,5-triazine (DADHT), acylated glycolurils, in particular tetraacetylglycoluril (TAGU), N- Acylimides, especially N-nonanoylsuccinimide (NOSI), acylated phenolsulfonates, especially n-nonanoyl- or isononanoyloxybenzenesulfonate (n- or iso-NOBS), carboxylic acid anhydrides, especially phthalic anhydride, acylated polyhydric alcohols, especially triacetin Diacetoxy-2,5-dihydrofuran and the enol esters known from German patent applications DE-A-196 16 693 and DE-A-
  • hydrophilically substituted acylacetals known from German patent application DE-A-196 16769 and the acyl lactams described in German patent application DE-A-196 16770 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-4443 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 -
  • 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 different foam inhibitors are also used with advantages, e.g. those made of silicone, 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 neutral-reacting sodium salts of, for example, 1-hydroxyethane-1,1-diphosphonate, diethylenetriaminepentamethylenephosphonate or ethylenediaminetetramethylenephosphonate in amounts of 0.1 to 1.5% by weight are preferably used as salts of polyphosphonic acids.
  • Particularly suitable enzymes are those from the class of hydrolases, such as proteases, lipases or lipolytically active enzymes, 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. Active ingredients. Proteases of the subtilisin type and in particular proteases which are obtained from Bacillus lentus are preferably used.
  • Enzyme mixtures for example from protease and amyiase or protease and lipase or lipolytically active enzymes or protease and cellulase or from cellulase and lipase or lipolytically active enzymes or from protease, amyiase and lipase or lipolytically active enzymes or protease, lipase or lipolytic enzymes and cellulase, but especially protease- and / or lipase-containing mixtures or mixtures with lipolytic enzymes of particular interest.
  • Known cutinases are examples of such lipolytically active enzymes.
  • 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.
  • 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 the salts of orthoboric acid (H 3 BO 3 ), metaboric acid (HBO 2 ) and pyrobic acid (tetraboric acid H 2 B 4 O 7 ), is particularly advantageous.
  • 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 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, for example 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 polyvinylpyrrolidone, for example in amounts of 0.1 to 5% by weight, based on the detergent, are preferred used.
  • the agents can, as optical brighteners, derivatives of diaminostilbenedisulfonic acid or the like. whose alkali metal salts contain. 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 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.
  • Means M1 and M2 were produced according to the following procedure:
  • a solid premix was made from the solid ingredients, including the binder, which in this case was added in solid form.
  • the binder was sprayed into the premix in the form of a sprayable melt; however, this did not lead to end products with significantly different properties.
  • the melt solidified within a short time after application to the solid mixture. The usual residence time in the mixer was sufficient for this
  • the mixture was then homogenized for a further 2 minutes and then fed to a twin-screw extruder, the pelletizing head of which had been preheated to temperatures between 50 and 65 ° C., preferably to 62 ° C.
  • the non-ionic surfactants that were optionally present at temperatures below 45 ° C. and a pressure of 1 bar were added to the powder stream by spraying through nozzles.
  • the premix was plasticized and then extruded at a pressure between 50 and 100 bar, preferably around 78 bar, through the extruder head perforated die plate into fine strands with a diameter of 1.4 mm, which, after the die outlet, was removed by means of a knock-out knife were crushed into approximately spherical granules (length / diameter ratio about 1, hot cut).
  • the resulting warm granulate was rounded off for one minute in a Marumerizer ® type rounding machine and, if necessary, coated with a finely divided powder.
  • the bulk density of the extrudates produced was 800 ⁇ 50 g / l.
  • a homogeneous premix consisting of 61% by weight of spray-dried granules 1 (for composition see below), 6% by weight of C 12 -C 18 fatty alkyl sulfate (composition 92.00% by weight of active substance, 3 , 70% by weight sodium sulfate, 2.80% by weight other salts from raw materials and unsulfonated components and 1.50% by weight water), 3% by weight copolymeric sodium salt of acrylic acid and maleic acid (powder form), 20 % By weight sodium perborate monohydrate and 6% by weight po- made of ethylene glycol as a binder with a molecular weight of 4000.
  • Grade 2 tolerable, isolated, not yet disturbing residues, very finely divided, not gelling when water is added
  • Grade 3 recognizable residues that are already annoying when critically assessed, from grade 4: clearly recognizable and disturbing residues in increasing numbers and
  • M1 achieved grades of 1-2 in both the towel test and the bowl test.
  • an agent V1 was prepared which contained the same ingredients in the end product, but in which the copolymer had not been introduced into the process in powder form but as an approximately 30% strength by weight aqueous solution. The excess water was then dried off in a fluidized bed. The bulk density of the extrudate was 770 g / l, the L test gave a value of 28%. In the towel test, V1 got the grade 3-4, in the bowl test even the grade 4.
  • the detergent M2 turned out to be particularly cheap for washing colored textiles.
  • 65.71% by weight of spray-dried granules 2 (for composition see below) were mixed with 11.83% by weight of an alkyl sulfate compound prepared in the fluidized bed (composition: 75% by weight C 12 -C 18 - Alkyl sulfate, 17% by weight sodium sulfate, 3% by weight sodium carbonate, 1% by weight water, remainder salts from solutions), 2.96% by weight copolymeric sodium salt of acrylic acid and maleic acid (powder form), 6.99 % By weight of trisodium citrate dihydrate, 3.59% by weight of polyethylene glycol with a relative molecular weight of 4000 and 8.92% by weight of C 12 -C 18 fatty alcohol mixed an average of 7 EO as described above to a premix and extruded.
  • the extrudate had a bulk density of 811 g / l and achieved a value of 2% in the solubility test (L test) described above.
  • the bowl test gave a grade of 1-2.
  • an agent V2 was again produced, which contained the same ingredients in the end product, but in which the copolymer had not been introduced into the process in powder form but as an approximately 30% by weight aqueous solution. The excess water was then dried off in a fluidized bed. The bulk density of the extrudate was clearly below 800 g / l, the L test gave a value of above 20%. If the alkyl sulfate compound was not co-extruded, but was subsequently mixed in according to the teaching of German patent application DE-A-195 19 139, the bulk density of the extrudate was 780 g / l, the L test gave a value of 7% and the bowl test a grade of 1-2.
  • Agents according to the invention were also prepared by introducing 3 to 5% by weight of nonionic surfactant via a spray-dried compound which had subsequently been processed with the nonionic surfactant.
  • Agents according to the invention were also produced, for example, by using a binder mixture of polyethylene glycol with a relative molecular weight of 4000 and a cetylstearyl alcohol with an average of 20 EO in a weight ratio of 1: 2 to 5: 1.
  • Products according to the invention were also manufactured by using as an alkybenzenesulfonate
  • the extrudates had values in the described L test of less than 15% or less than 10%. If, in the comparative examples, a concentrated aqueous alkylbenzenesulfonate paste was used instead of the alkylbenzenesulfonate powder and the water was subsequently dried off, all the products in the L test had a value above 20%.
  • composition of the spray-dried granules Composition of the spray-dried granules:
  • Spray dried granules 2 12.07% by weight of C 9 -C 13 alkylbenzenesulfonate
  • agents M3 to M10 according to the invention had the following compositions and were prepared as described above:
  • Fatty alcohol C 12 i4 polyglycoside (78 4% by weight of active substance, 18% by weight of water glass module 2.4, 5% by weight of water)
  • Tetraacethylethylene diamine (95% by weight 8.5 TAED, 2% by weight

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  • 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)
EP97942019A 1996-09-20 1997-09-11 Procede de production d'un detergent ou nettoyant particulaire Expired - Lifetime EP0931137B1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE19638599 1996-09-20
DE19638599A DE19638599A1 (de) 1996-09-20 1996-09-20 Verfahren zur Herstellung eines teilchenförmigen Wasch- oder Reinigungsmittels
PCT/EP1997/004975 WO1998012299A1 (fr) 1996-09-20 1997-09-11 Procede de production d'un detergent ou nettoyant particulaire

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EP0931137A1 true EP0931137A1 (fr) 1999-07-28
EP0931137B1 EP0931137B1 (fr) 2003-12-10

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DE102015002877A1 (de) 2015-03-09 2016-09-15 Henkel Ag & Co. Kgaa Granulares Wasch- oder Reinigungsmittel mit verbesserter Lösegeschwindigkeit

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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
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DE4319666A1 (de) * 1993-06-14 1994-12-15 Henkel Kgaa Verfahren zur Herstellung fester Wasch- oder Reinigungsmittel mit hohem Schüttgewicht und verbesserter Rheologie
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Cited By (2)

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Publication number Priority date Publication date Assignee Title
DE102015002877A1 (de) 2015-03-09 2016-09-15 Henkel Ag & Co. Kgaa Granulares Wasch- oder Reinigungsmittel mit verbesserter Lösegeschwindigkeit
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

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ATE256176T1 (de) 2003-12-15
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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
CZ97799A3 (cs) 1999-09-15
WO1998012299A1 (fr) 1998-03-26
EP1015550A1 (fr) 2000-07-05
DE19638599A1 (de) 1998-03-26
TR199900582T2 (xx) 1999-06-21
PL331987A1 (en) 1999-08-16
RU2200190C2 (ru) 2003-03-10

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