EP0931137B1 - Procede de production d'un detergent ou nettoyant particulaire - Google Patents

Procede de production d'un detergent ou nettoyant particulaire Download PDF

Info

Publication number
EP0931137B1
EP0931137B1 EP97942019A EP97942019A EP0931137B1 EP 0931137 B1 EP0931137 B1 EP 0931137B1 EP 97942019 A EP97942019 A EP 97942019A EP 97942019 A EP97942019 A EP 97942019A EP 0931137 B1 EP0931137 B1 EP 0931137B1
Authority
EP
European Patent Office
Prior art keywords
weight
premix
compounds
branched
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.)
Expired - Lifetime
Application number
EP97942019A
Other languages
German (de)
English (en)
Other versions
EP0931137A1 (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

Links

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, compacted particulate Detergents or cleaning agents or compounds or treated Raw materials for this as well as detergents or cleaning agents or Compounds or treated raw materials for this, which from the perspective of the consumer have a significantly better quality.
  • Gelling of this type can already be carried out at a surfactant content of 10% by weight, based on the entire agent, that is to say in the case of detergents or cleaning agents which are customary Amounts of surfactant occur.
  • a surfactant content of 10% by weight, based on the entire agent, that is to say in the case of detergents or cleaning agents which are customary Amounts of surfactant occur.
  • the tendency to form gels decreases also with the increasingly compact grain structure of the particles.
  • EP-B-0 486 592 describes granular or extruded washing or Detergent with bulk weights above 600 g / l, the anionic and / or nonionic surfactants in amounts of at least 15% by weight and up to about 35% by weight contain. They are manufactured using a process in which a solid, free-flowing Premix, which is a plasticizer and / or lubricant, preferably aqueous Contains surfactant pastes and / or aqueous polymer solutions at high pressures between 25 and 200 bar extruded and the extrudate after exiting the hole shape cut to the predetermined granule dimension by means of a cutting device and is rounded.
  • a solid, free-flowing Premix which is a plasticizer and / or lubricant, preferably aqueous Contains surfactant pastes and / or aqueous polymer solutions at high pressures between 25 and 200 bar extruded and the extrudate after exiting the hole shape cut to the predetermined gran
  • the premix consists at least partly of solid Ingredients that may contain liquid ingredients such as at room temperature liquid nonionic surfactants are added.
  • liquid nonionic surfactants are aqueous preparations used.
  • lubricants are aqueous preparations used.
  • the patent does not disclose any procedural conditions to be observed in the event of a anhydrous extrusion.
  • the extrudates produced can either be used as washing or Detergent used or later with other granules or Powder components are processed into finished washing or cleaning agents.
  • German patent application DE 195 19 139.0 proposes to solve the conflict between high degree of compaction of the individual grain, especially the extrudate on the one hand and the required rapid and in particular non-gelatinous redissolubility of the finished washing or cleaning agents in aqueous liquors before, particulate detergents or cleaning agents with a Bulk density above 600 g / l, which contains anionic and / or nonionic surfactants Contain amounts of at least 15 wt .-%, such that at least two various granular components are used, of which at least one extruded and at least one is not extruded, the surfactant content being extruded Component including soaps a maximum of 15 wt .-%, based on the respective extruded component.
  • surfactant components of the finished washing or Detergents are created by one or more non-extruded components introduced into the agent.
  • This method does solve the problem of gelling highly compressed and high-tenside detergent or cleaning agent at Use in an aqueous liquor, but it also includes a number of new ones Problems. Separation processes and corresponding fluctuations can occur the reproducibility of the desired washing or cleaning result.
  • the extruded portion of the media is not only of high density dried extrudates are also comparatively hard. Among the Conditions of transportation, storage and use can be the comparatively softer Granulate portion thus be exposed to mechanical forces that are proportional to its Reduction and thus lead to the formation of dust and fine particles through abrasion.
  • a method for the production of heavy granules with the help of a aqueous granulation aid is the two-stage granulation, wherein initially in plastic primary agglomerates are still produced in a conventional mixer / granulator, which are then used in devices such as a rounder, rotocoater, marumerizer etc. liquid binder and / or dust subsequently treated and usually then be dried.
  • the granulation and simultaneous rounding can for example in fluidized bed granulators that contain a rotating disk, be performed.
  • Solid starting materials are initially in the Fluidized bed fluidized and then with liquid binder that is tangential aligned nozzles are fed into the fluidized bed, agglomerated ("Size Enlargement by Agglomeration ", W.
  • 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 the 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-B-0 486 592) 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-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, in particular Non-ionic surfactants with 2 to 6 EO and HLB values of 11 or less added in the mixer become.
  • Ethylene glycols and propylene glycols can also be used as nonionic compounds be used.
  • German patent application DE-A-43 19 666 discloses a process for the production washable or cleaning active extrudates of high density, being a homogeneous and solid Premix containing certain alkoxinated alcohols, pressed under pressure and then on Granule dimension is cut. Extrusion without the addition of Waser will not In the example section, the mixture contains, for example, almost 5% free water.
  • European patent application EP-A-0 711 828 describes a method for the production described by tablets, wherein a coated particulate product is pressed.
  • the coating substance is a water-soluble binding or disintegrating agent Melting temperatures between 35 and 90 ° C.
  • Primary C 12 -C 15 alcohols with 3 to 7 EO are specified as nonionic surfactants.
  • Surfactant mixtures which contain up to 20% by weight of water are particularly advantageous in the context of the stated process, since this increases the viscosity of the mixture and makes the process more controllable.
  • the surfactant mixture can also contain polyethylene glycols.
  • builder agglomerates The production of builder agglomerates is described in US Pat. No. 5,108,646, 50 to 75 parts by weight of aluminosilicates or crystalline phyllosilicates being agglomerated with 20 to 35 parts by weight of a binder.
  • Suitable binders 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 1000 and 20,000 are also suitable, 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. With energy inputs above the specified values, over-agglomeration up to a dough-like mass occurs, with lower energy inputs only finely divided powders or very light agglomerates with an undesirably broad grain spectrum are obtained.
  • the object of the invention was particulate washing or cleaning agents or to produce compounds or treated raw materials for this, which even with a reduced surface, especially with a spherical shape (pearl shape) an improved one Have disintegration in the dissolution in the aqueous liquor. Besides, should the process should be economical and avoid expensive drying steps can.
  • the content of liquid i.e. not in the form of water of hydration and / or constitutional water
  • the water present is less than 2% by weight, preferably less than 1% by weight and in particular even less than 0.5% by weight, based in each case on the premix. Accordingly, water can essentially only in chemically and / or physically bound form or as Part of the solid at temperatures below 45 ° C at a pressure of 1 bar existing raw materials or compounds, but not as a liquid, solution or dispersion be introduced into the process for producing the premix.
  • the premix has a total water content of not more than 15% by weight, this water So not in free liquid form, but chemically and / or physically bound is present, and it is particularly preferred that the content of not zeolite and / or Silicate-bound water in the solid premix not more than 10% by weight, preferably less than 7% by weight and with particular preference a maximum of 2 to 5% by weight is.
  • Particulate detergents or cleaning agents are used in the context of the invention preferably understood those that have no dust-like portions and in particular none Have particle sizes below 200 microns. Such particle size distributions are in particular preferred, which at least 90 wt .-% particles with a Have a diameter of at least 400 ⁇ m.
  • the laundry or cleaning agents and compounds produced consist of the invention or treated raw materials to at least 70 wt .-%, advantageously at least 80% by weight and, with particular preference, up to 100% by weight spherical (pear-shaped) particles with a particle size distribution which at least Has 80 wt .-% particles between 0.8 and 2.0 mm.
  • Detergents or cleaning agents are understood to mean such compositions which are used for Washing or cleaning can be used without usually other ingredients must be added.
  • a compound consists of at least 2 usually used in washing or cleaning agents components; Compounds are usually only mixed with others Ingredients, preferably used together with other compounds.
  • On treated raw material is a relatively finely divided raw material in the context of this invention, the was 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 usually in detergents or cleaning agents ingredient used.
  • the ingredients used in the process according to the invention can - with the exception the possibly existing at temperatures below 45 ° C and a pressure of 1 bar liquid nonionic surfactants - separately manufactured Compounds, but also raw materials, which are powdery or particulate (fine particles to rough), but in any case at room temperature and a pressure of 1 bar in solid form available. Particulate particles can be produced, for example, by spray drying Beads or (fluidized bed) granules can be used.
  • the Composition of the compounds per se is not essential for the invention with the Except for the water content, which must be such that the premix is like defined above is essentially anhydrous and preferably not more than 10% by weight contains 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 so that the tower outlet temperatures above 100 ° C, for example at 110 ° C or above.
  • solid compounds are used in the premix, which as a carrier of Liquids, for example liquid nonionic surfactants or silicone oil and / or Paraffins. These compounds can contain water in the above Frame included, the compounds are free-flowing and even at higher Temperatures of at least 45 ° C remain free-flowing or at least conveyable.
  • the premix compound with a maximum of 10 wt .-% and with particular preference with a maximum of 7% by weight of water, based on the Premix can be used.
  • Free water water that is not in any Form is bound to a solid and is therefore "in liquid form" preferably not at all in the premix, since very small amounts are already present, for example by 0.2 or 0.5% by weight, based on the premix, are sufficient to to dissolve the water-soluble binder. This would have the consequence that the Melting point or softening point lowered and the end product both Free flowing as well as bulk weight would lose.
  • the bound water content 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 a maximum of 2 to 5% by weight. It is Particularly advantageous if the premix contains no water that does not adhere to the Builder substances is bound. However, this is difficult to achieve technically, because in usually at least always traces of water due to the raw materials and compounds be introduced.
  • the content of the solid compounds used in the premix at at temperatures below 45 ° C non-aqueous liquids 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 is usually liquid at temperatures below 45 ° C and a pressure of 1 bar contain non-ionic surfactants, which according to all known production methods - for example by spray drying, granulating or spraying carrier beads - were made separately.
  • premixes can be made which for example up to about 10 wt .-%, preferably below, in particular up to a maximum of 8% by weight and, for example, between 1 and 5% by weight of nonionic Allow surfactants, based on the finished product.
  • 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 much higher softening point or melting point than the temperatures can be achieved under the process conditions.
  • process temperatures do not exceed 150 ° C, preferably not above 120 ° C.
  • at least 80% by weight of the compounds and individual raw materials used a softening point or Have a melting point above 150 ° C.
  • the softening point lies or the melting point even far above this temperature.
  • ingredients which decompose under the influence of temperature
  • for example Peroxy bleaching agents such as perborate or percarbonate
  • the decomposition temperature of these is Ingredients at a pressure of 1 bar and especially at higher pressures, which in the extrusion processes according to the invention and preferred are also significant above 45 ° C.
  • the premix can add up to 10% by weight Temperatures below 45 ° C and a pressure of 1 bar liquid nonionic surfactants, especially the alkoxylated ones commonly used in washing or cleaning agents Alcohols, 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 (see below for a more detailed description).
  • liquid nonionic surfactants can be done in amounts that still ensure that the premix is pourable Form is present. If such liquid nonionic surfactants are introduced into the premix, it is preferred that liquid nonionic surfactants and the disintegrating binder be introduced separately into the process.
  • the liquid nonionic surfactants are used in a continuous Production process applied in particular to the powder stream by means of nozzles and sucked up by the latter.
  • the premix also contains at least one raw material or at least one compound, which or which serves as a binder is solid at room temperature, during the compression under the process conditions but liquid in the form of a Melt is present.
  • the binder itself can be melted onto the premix once be sprayed on or added dropwise to the premix, but on the other hand it has also proven to be advantageous, the binder in solid form as a powder in the premix contribute.
  • the melting point or softening point is at a pressure of 1 bar at at least 45 ° C and (especially for economic reasons) preferred below 200 ° C, in particular up to a maximum of 150 ° C.
  • the temperature in the Melting vessel also more than 45 ° C to a maximum of about 200 ° C, the temperature in the melting vessel, the melting temperature or the temperature of the Softening point of the binder or binder mixture is quite significant can exceed.
  • the type of suitable binder and the temperature in the compression step are interdependent. Since it has proven to be advantageous if the binder in the compression step as homogeneous as possible in the one to be compressed Temperature is well distributed in the compression process step are present in which the binder at least softens, but preferably completely and is not only partially in the molten form. So is a binder with high melting point or high softening point selected, so must Process step of the compression set a temperature that the Ensures melting of the binder.
  • temperature sensitive raw materials should be able to be processed. Here the upper temperature limit is determined by the Given the decomposition temperature of the sensitive raw material, it being preferred to work significantly below the decomposition temperature of this raw material.
  • the lower limit for the melting point or softening point is therefore of such a kind of great importance, as with melting points or softening points below 45 ° C
  • melting points or softening points below 45 ° C
  • an end product is obtained that is already at room temperature and light increased temperatures by 30 ° C, i.e. in summer temperatures and under storage or transport conditions tend to stick. It has proven to be particularly advantageous if a few degrees, e.g. 2 to 20 ° C, above the melting point or working above the softening point
  • the applicant is of the opinion that due to the homogeneous distribution of the binder within the premix Process conditions of compression of the solid compounds and, if necessary existing individual raw materials in this way enclosed by the binder and then are glued together that the finished end products almost exactly from these many small individual particles that are built up by the binder that the Takes on the role of a preferably thin partition between these individual particles, be held together.
  • the idealized form one can Honeycomb-like structure is assumed, these honeycombs with solids (Compounds or individual raw materials) are filled.
  • the binder or binders must therefore be of the type that the adhesive properties even at temperatures that are significantly above the melting point or the softening point lie, still remain. On the other hand, it is also essential for that Choice of the type and amount of the binder (s) used, that the binding Properties are not lost after re-cooling within the end product, the cohesion of the end product is thus assured, but the end product not glued even under normal storage and transport conditions.
  • a binder is used that at Temperatures up to a maximum of 130 ° C, preferably up to a maximum of 100 ° C and in particular up to 90 ° C is already completely in the form of a melt.
  • the binder must therefore depend on the process and process conditions are selected or the process conditions, in particular the process temperature - if a certain binder is required will - be adapted to the binder.
  • Binders that 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 have between 600 and 6000, preferably between 1000 and 4000.
  • polyethylene glycols include those polymers which, in addition to ethylene glycol, also use C 3 -C 5 glycols and glycerol and mixtures of these as starting molecules. Also included are ethoxylated derivatives such as trimethylol propane with 5 to 30 EO.
  • the preferably used polyethylene glycols can be linear or branched Have structure, with linear polyethylene glycols being preferred in particular.
  • the particularly preferred polyethylene glycols include those with relative molecular weights between 2000 and 12000, advantageously around 4000, with polyethylene glycols with relative molecular weights below 3500 and above 5000 especially in Combination with polyethylene glycols with a molecular weight around 4000 can be used and such combinations advantageously to more than 50 % By weight, based on the total amount of polyethylene glycols, with polyethylene glycols have a relative molecular mass between 3500 and 5000.
  • polyethylene glycols are also used, which in themselves at room temperature and a pressure of 1 bar in the liquid state; here is mostly from Polyethylene glycol with a relative molecular weight of 200, 400 and 600.
  • these per se liquid polyethylene glycols should only be mixed with at least one further binder can be used, this mixture again must meet the requirements of the invention, i.e. a melting point or Must have a 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 12 -alkyl chains which can be linear or branched.
  • the end groups have the alkyl chains between C 1 and C 6 , especially between C 1 and C 4 , isopropyl and isobutyl or tert-butyl also being possible alternatives.
  • Low molecular weight polyvinylpyrrolidones and derivatives are also suitable as binders of these with relative molecular weights up to a maximum of 30,000.
  • Preferred here relative molecular mass ranges between 3000 and 30,000, for example around 10,000.
  • Polyvinylpyrrolidones are preferably not used as the sole binder, but in Combination with others, especially in combination with polyethylene glycols, used.
  • 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.
  • the preferred nonionic surfactants include alkoxylated fatty or oxo alcohols, in particular 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.
  • 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. However, it is preferred to use 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 washing or cleaning agents and which are liquid per se at room temperature, are preferably only present in the binder mixtures in such an amount that 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. As already described above, however, it is less preferred to use nonionic surfactants which are liquid at room temperature in the binder mixtures.
  • nonionic surfactants are therefore not a constituent 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 rapid dissolution of the binder / partition in the end product often does not suffice to the desired extent.
  • conventional anionic surfactants or their precursors, the anionic surfactant acids, which are deposited 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 methyl esters based on C 16 -C 18 fatty acids, for example hardened beef tallow methyl esters with an average of 12 EO or with an average of 20 EO.
  • ethoxylated fatty acids with 2 to 100 EO, their "fatty acid” residues can be linear or branched within the scope of this invention.
  • preferred ethoxylates which have a narrowed homolog distribution (NRE) and / or have a melting point above 50 ° C.
  • NRE narrowed homolog distribution
  • Such fatty acid ethoxylates can used as the sole binder or in combination with other binders are less preferred, while the non-ethoxylated sodium and potassium soaps and are only used in combination with other binders.
  • hydroxy mixed ethers which are, according to the teaching of European, also are Patent application EP-A-0 754 667 (BASF) by ring opening of unsaturated epoxides
  • Fatty acid esters can be obtained as binders, especially in combination with Polyethylene glycols, the aforementioned fatty acid methyl ester ethoxylates or Fatty acid ethoxylates, suitable.
  • anhydrous swollen polymers have also been found, in particular Starch disphosphate / glycerin, polyvinylpyrrolidone / glycerin and modified Cellulose / glycerin, for example hydroxypropyl cellulose / glycerin, as excellent proven binders. 5 to 20% by weight “solutions” are the Polymers in glycerin, especially about 10% by weight “solutions”, especially 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 which are based either solely on polyethylene glycols with a relative molecular weight of around 4000 or on a mixture of C 12 -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 based on a mixture of C 12 -C 18 fatty alcohol based on coconut or tallow with an average of 20 EO, one of the fatty acid methyl ester ethoxylates described above and a polyethylene glycol, in particular with a molecular weight of around 4000.
  • binder mixtures especially in Mixture with polyethylene glycols may be included; however, they cannot act alone Binders are used because they fulfill a binding / adhesive function, but have no disintegrating effect.
  • alkyl glycosides of the general formula RO (G) x can also be used as further binders, alone or in combination with other binders, in which R is a primary straight-chain or methyl-branched, especially in the 2-position methyl-branched aliphatic radical having 8 to 22, preferably 12 to 18 C atoms means and G is the symbol which stands for a glycose unit with 5 or 6 C 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.
  • alkyl glycosides can also be used as the sole binder, it is preferred to use mixtures of alkyl glycosides and other binders.
  • 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 in particular 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, especially from glucose.
  • the group of polyhydroxy fatty acid amides also includes compounds of the formula (II) in which R 3 is a linear or branched alkyl or alkenyl radical having 7 to 12 carbon atoms, R 4 is a linear, branched or cyclic alkyl radical or an aryl radical is 2 to 8 carbon atoms and R 5 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.
  • R 3 is a linear or branched alkyl or alkenyl radical having 7 to 12 carbon atoms
  • R 4 is a linear, branched or cyclic alkyl radical or an
  • [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-arytoxy-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 glucamides 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 particular preference of 3 to 6 wt .-%, each 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 initially at room temperature to slightly elevated temperatures, preferably below the Melting temperature or the softening point of the binder and especially at temperatures up to 35 ° C in a conventional mixing and / or Granulating device mixed together.
  • These solids also include those which according to the European patent EP-B-0 486 592 as plasticizing and / or Lubricants can serve.
  • anionic surfactants such as Alkylbenzenesulfonates and / or (fatty) alkylsulfates, but also polymers such as polymers Polycarboxylates. A more detailed description of the possible anionic surfactants and polymers occurs later in the list of possible ingredients.
  • the function of a lubricant can also from the binder or binders or the Binder mixtures are perceived.
  • the binders are preferably added as the last component.
  • Your offer can, as already explained above, as a solid, i.e. at a processing temperature, which is below its melting point or softening point, or as Melt.
  • the admixture among such is advantageous Conditions carried out that a uniform, homogeneous distribution of the Binder is achieved in the solid mixture. With very finely divided binders this at temperatures below 40 ° C, for example at temperatures of the binder between 15 and 30 ° C.
  • the binder advantageously has but temperatures at which it is already in the form of a melt, i.e. above the Softening point, in particular in the form of a complete melt. Preferred temperatures of the melt are below 60 to 150 ° C.
  • Preference for the temperature range from 80 to 120 ° C.
  • the at room temperature to slightly elevated temperature, but below the Softening point or melting point of the binder takes place, the solidifies Melt almost instantaneously, and according to the invention the premix is in a solid, pourable form.
  • the mixing process is advantageously as long in any case continued until the melt has solidified and the premix in solid, free-flowing form is present.
  • the actual granulation, compacting, tableting, pelleting or extrusion process takes place according to the invention at processing temperatures that at least in the compression step at least the temperature of the softening point, if not even correspond to the temperature of the melting point of the binder.
  • the process temperature is significant above the melting point or above the temperature at which the binder as Melt is present.
  • the process temperature in the Compression step not more than 20 ° C above the melting temperature or the upper one Limit of the melting range of the binder is.
  • Such a temperature control has the further advantage that thermally 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.
  • thermally 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 possibility of accurate Temperature control of the binder, especially in the crucial step of compaction, that is between the mixing / homogenization of the premix and the shaping, allows an energetically very cheap and for the temperature sensitive components of the premix extremely gentle procedure because the premix is only exposed to the higher temperatures for a short time.
  • the duration is preferably the temperature effect between 10 seconds and a maximum of 5 minutes, in particular it is a maximum of 3 minutes.
  • the invention Process carried out by means of an extrusion, such as in the European patent EP-B-0 486 592 or international patent applications WO-A-93/02176 and WO-A-94/09111.
  • This creates a solid premix extruded under pressure and the strand after exiting from the hole shape by means of a cutting device tailored to the predeterminable granule dimension.
  • the homogeneous and solid premix contains a plasticizer and / or lubricant, which causes the premix under the pressure or under the entry of specific work plastically softened and becomes extrudable.
  • Preferred plasticizers and / or lubricants are Surfactants and / or polymers in the context of the present invention with Except for the non-ionic surfactants mentioned above, however, not in liquid and in particular not in an aqueous, but in solid form introduced into the premix become.
  • the premix is preferably continuous a planetary roller extruder or a 2-shaft extruder or 2-screw extruder fed with co-rotating or counter-rotating screw guide, its housing and its extruder pelletizing head is heated to the predetermined extrusion temperature could be.
  • the premix is made under the shear of the extruder screws under pressure, which is preferably at least 25 bar, at extremely high throughputs depending on the apparatus used, but can also be below it, compacted, plasticized, extruded in the form of fine strands through the perforated die plate in the extruder head and finally preferably the extrudate by means of a rotating knife about spherical to cylindrical granules.
  • the hole diameter the perforated nozzle plate and the strand cut length are selected Granule dimension matched.
  • the production of Granules of an essentially uniformly predeterminable particle size wherein in particular, the absolute particle sizes adapted to the intended application could be. In general, particle diameters up to at most 0.8 cm are preferred.
  • chipped primary granules lie in the Range from about 1: 1 to about 3: 1. It is also preferred to use the still plastic primary granulate to supply a further shaping processing step; be there edges present on the crude extrudate are rounded, so that ultimately spherical to approximately spherical extrudate grains can be obtained. If desired you can in this stage small amounts of dry powder, for example zeolite powder such as zeolite NaA powder can also be used. This shape can be found on the market Rondier devices take place.
  • extrusions / pressings can also be carried out in low-pressure extruders, in the Kahl press or be carried out 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 upper limit of the melting range of the binder at least reached, preferably but is exceeded.
  • the duration of the temperature influence is Compression range of the extrusion preferably less than 2 minutes and especially in a range between 30 seconds and 1 minute.
  • the one used Binders have a melting temperature or melting range up to 75 ° C .; Process temperatures which are a maximum of 10 ° C and in particular a maximum of 5 ° C above the melting temperature or the upper temperature limit of the melting range of the Binder is then found to be particularly favorable.
  • the binder exercises in addition to those previously used mentioned modes of action also prevents and prevents the function of a lubricant or at least reduces the risk of sticking to apparatus walls and Compression tools. This applies not only to processing in the extruder, but also equally for processing, for example in continuously working Mixers / granulators or rollers.
  • the compressed material preferably points directly after it leaves the production apparatus Temperatures not above 80 ° C, with temperatures between 35 and 75 ° C are particularly preferred. It has been found that outlet temperatures - especially in the extrusion process - from 40 to 70 ° C, for example up to 60 ° C, especially are advantageous.
  • the resulting primary granules / compactates give another shape
  • To supply processing step, in particular to fillet, so that ultimately spherical to almost spherical (pearl-shaped) grains are obtained can.
  • the particle size distribution of the premix is much broader than that of the invention manufactured and end product according to the invention.
  • the premix can be essential Larger fractions of fine grain, even dust, possibly also contain coarse-grained fractions, but it is preferred that a premix with relatively broad particle size distribution and relatively high proportions of fine grain in one End product with a relatively narrow particle size distribution and relatively small proportions Fine grain is transferred.
  • the process of the invention is essentially anhydrous - i.e. with the exception water-free ("impurities") of the solid raw materials used - is carried out is not only the risk of gelling the surfactant raw materials already minimized to excluded in the manufacturing process, in addition also provided an ecologically valuable process because by not using one subsequent drying step not only saves energy but also emissions, as they occur predominantly with conventional types of drying can be avoided can.
  • Agents, compounds and raw materials treated in this way thus have a improved dissolving speed compared to such agents, compounds and treated raw materials, which have the same final composition, but were not produced by the method according to the invention, i.e. not by means of a melt were produced under anhydrous conditions.
  • another object of the invention is a particulate washing or Detergent, which was produced by the method according to the invention and its loosening behavior only depends on the loosening behavior of those used Individual raw materials and compounds. Without restricting yourself to this theory wanting, the applicant assumes that this special release behavior through a honeycomb-like structure of the particles is effected, these honeycombs with solid are filled.
  • Detergent provided that at least 80 wt .-% from the invention Compounds and / or treated raw materials. In particular consists of at least 80% by weight of a granular or extruded detergent a base granulate or base extrudate produced according to the invention.
  • the remaining Ingredients can be prepared and mixed by any known method his. However, it is preferred that these remaining constituents, which Compounds and / or treated raw materials can be, according to the invention Processes were made. In particular, this enables basic granules and remaining components with approximately the same pourability, bulk density, size and To produce particle size distribution.
  • the invention further relates to compounds produced according to the invention and treated raw materials, for example builder granules (extrudates), Bleach activator granules (extrudates) or enzyme granules (extrudates).
  • treated raw materials for example builder granules (extrudates), Bleach activator granules (extrudates) or enzyme granules (extrudates).
  • builder granules extrudates
  • Bleach activator granules extrudates
  • enzyme granules extrudates
  • Base granules, compounds and treated raw materials are particularly preferred provided which have spherical or pearl shape.
  • the end products of the process produced according to the invention a very high bulk density.
  • the bulk density is preferably above 700 g / l, in particular between 750 and 1000 g / l. Even if the extrudates contain other ingredients, which have lower bulk weights are processed, this drops Bulk weight of the final product not to the extent normally expected would. It is believed that approximately spherical agents, and particularly extrudates, which were produced by the method according to the invention, rather the Ideally, a sphere with a smooth, "smeared" surface resembles the one after Agents and extrudates produced by conventional and in particular aqueous processes. This achieves a better space filling, which leads to a higher bulk density leads, even if components are mixed in, which are neither spherical nor have such a high bulk density.
  • the particulate process end products obtained can either be used directly as Detergents or cleaning agents are used or previously using customary methods aftertreated and / or processed.
  • the usual post-treatments include for example powdering with finely divided ingredients of washing or Detergents, 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, wherein dusty or at least finely divided ingredients (the so-called fines) to the Particulate process end products produced according to the invention, which as the core serve, be glued and thus means arise which these so-called Have fine particles as the outer shell.
  • This is advantageously done by a melting agglomeration, the same binders as in the invention Procedures can be used.
  • For melting agglomeration of the fines on the Basic granules according to the invention and produced according to the invention are expressly stated to the disclosure in German patent applications DE-A-195 24 287 and DE-A-195 47 457
  • Processing is generally understood to mean that the invention produced particulate process end products serve as a compound to which other ingredients, possibly other compounds.
  • 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 (see below) mixed in the preparation.
  • the admixture components in granular form and with a Particle size distribution are used, based on the particle size distribution Agents and compounds produced according to the invention is coordinated.
  • surfactants especially anionic surfactants, at least in amounts of 0.5% by weight in the agents according to the invention or according to the invention manufactured means should be included.
  • anionic surfactants include in particular Sulfonates and sulfates, but also soaps.
  • Preferred surfactants of the sulfonate type are C 9 -C 13 alkylbenzenesulfonates, olefin sulfonates, ie mixtures of alkene and hydroxyalkanesulfonates and disulfonates, such as are obtained, for example, from C 12 -C 18 monoolefins with 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 ⁇ -sulfonation of the methyl esters of fatty acids of plant and / or animal origin with 8 to 20 carbon atoms in the fatty acid molecule and subsequent neutralization water-soluble mono-salts are prepared. It is preferably are the ⁇ -sulfonated esters of hydrogenated coconut, palm, palm kernel or Tallow fatty acids, including sulfonation products of unsaturated fatty acids, for example oleic acid, in small amounts, preferably in amounts not above about 2 to 3% by weight may be present.
  • ⁇ -sulfofatty acid alkyl esters preferred, which is an alkyl chain with no more than 4 carbon atoms in have the ester group, for example methyl ester, ethyl ester, propyl ester and Butyl ester.
  • Suitable anionic surfactants are sulfonated fatty acid glycerol esters, which are mono-, di- and Triesters and their mixtures represent how they are made by Esterification by a monoglycerin with 1 to 3 moles of fatty acid or during the transesterification of triglycerides with 0.3 to 2 moles of glycerol can be obtained.
  • the alk (en) yl sulfates are the alkali and in particular the sodium salts of the sulfuric acid half esters of 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 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, petrochemical-based straight-chain alkyl radical 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 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 (R) , are also 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 C 9 -C 11 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 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, which is derived from ethoxylated fatty alcohols, which in themselves are nonionic surfactants (description see below).
  • sulfosuccinates the fatty alcohol residues of which are derived from ethoxylated fatty alcohols with a narrow homolog distribution, are particularly preferred. It is also possible to use alk (en) ylsuccinic acid with preferably 8 to 18 carbon atoms in the alk (en) yl chain or salts thereof.
  • anionic surfactants are fatty acid derivatives of amino acids, for example of N-methyl taurine (tauride) and / or of N-methyl glycine (sarcoside).
  • the sarcosides or sarcosinates are particularly preferred, and above all Sarcosinates of higher and optionally mono- or polyunsaturated Fatty acids such as oleyl sarcosinate.
  • anionic surfactants include, in particular, soaps, preferably in quantities from 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 from natural fatty acids, e.g. B. coconut, Palm kernel or tallow fatty acids, derived soap mixtures.
  • natural fatty acids e.g. B. coconut, Palm kernel or tallow fatty acids, derived soap mixtures.
  • these soaps or the known alkenyl succinic acid salts can also be used as a substitute for soaps be used.
  • the anionic surfactants can be in the form of their sodium, potassium or ammonium salts as well as soluble salts of organic bases, such as mono-, di- or triethanolamine, available.
  • the anionic surfactants are preferably in the form of their sodium or Potassium salts, especially in the form of the sodium salts.
  • the anionic surfactants are in the agents according to the invention or are in the Process according to the invention preferably in amounts of 1 to 30 wt .-% and Contained or used in particular in amounts of 5 to 25 wt .-%.
  • nonionic surfactants are preferred.
  • the nonionic surfactants used are preferably alkoxylated, advantageously ethoxylated, in particular primary alcohols having preferably 8 to 18 carbon atoms and an average of 1 to 12 moles of ethylene oxide (EO) per mole of alcohol, in which the alcohol 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 fat 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 11 alcohols with 7 EO, C 13 -C 15 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 18 alcohol with 7 EO.
  • the degrees of ethoxylation given represent statistical averages, which can be an integer or a fraction for a specific product.
  • Preferred alcohol ethoxylates have a narrow homolog distribution (narrow range ethoxylates, NRE).
  • fatty alcohols with more than 12 EO can also be used, 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 and the polyhydroxy fatty acid amides of the formulas (I) and (II) which have already been described in detail above.
  • 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-cocoalkyl-N, N-dimethylamine oxide and N-tallow alkyl-N, N-dihydroxyethylamine oxide, and the fatty acid alkanolamides can be suitable.
  • the amount of these nonionic surfactants is preferably not more than that of the ethoxylated fatty alcohols, especially not more than that Half of it.
  • gemini surfactants can be considered as further surfactants.
  • the two hydrophilic groups and two have hydrophobic groups per molecule. These groups are usually by one so-called “spacers” separated from each other. 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 each other.
  • Such surfactants are generally characterized by an unusually low critical Micell concentration and the ability to greatly increase the surface tension of water reduce, out. In exceptional cases, however, the term gemini surfactants understood not only dimeric but also trimeric surfactants.
  • Suitable Gemini surfactants are, for example, sulfated hydroxy mixed ethers according to the German patent application DE-A-43 21 022 or dimeral alcohol bis and trimeral alcohol tris sulfates and ether sulfates according to German patent application DE-A-195 03 061.
  • End group capped dimeric and trimeric mixed ethers according to the German Patent application DE-A-195 13 391 are particularly characterized by their bi- and Mommy functionality.
  • the end groups capped have surfactants good network properties and are low-foaming, so that they are particularly suitable for Suitable for use in machine washing or cleaning processes.
  • Gemini polyhydroxy fatty acid amides or poly polyhydroxy fatty acid amides can also be used. as described in international patent applications WO-A-95/19953, WO-A-95/19954 and WO95-A- / 19955 can be described.
  • the inorganic and organic belong above all Builder substances for the most important ingredients of washing 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.
  • the zeolite in the event that the zeolite is used as a suspension, it can contain small additions of nonionic surfactants as stabilizers, for example 1 to 3% by weight, based on zeolite, of ethoxylated C 12 -C 18 fatty alcohols with 2 to 5 ethylene oxide groups , C 12 -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. In particular, 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 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” also means “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 provide 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 sodium salts are particularly suitable Orthophosphate, the pyrophosphate and especially the tripolyphosphate.
  • Your salary generally not more than 25% by weight, preferably not more than 20% by weight, each based on the finished product.
  • tripolyphosphates in small amounts up to a maximum of 10% by weight, based on the finished agent, in combination with other builder substances to form one lead to synergistic improvement of secondary washing ability.
  • Suitable substitutes or partial substitutes for the zeolite are layered silicates natural and synthetic origin.
  • Layered silicates of this type are known, for example, from US Pat Patent applications DE-B-23 34 899, EP-A-0 026 529 and DE-A-35 26 405 are known. Your Applicability is not based on a special composition or structural formula limited. However, smectites, in particular bentonites, are preferred here.
  • Suitable sheet silicates which belong to the group of water-swellable smectites, are, for example, montmorrilonite, hectorite or saponite.
  • small amounts of iron can be incorporated into the crystal lattice of the layered silicates according to the above formulas.
  • the layered silicates can contain hydrogen, alkali, alkaline earth ions, in particular Na + and Ca ++ .
  • 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.
  • 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.
  • Useful organic builders are, for example, those in the form of their sodium salts usable polycarboxylic acids, such as citric acid, adipic acid, succinic acid, Glutaric acid, tartaric acid, sugar acids, aminocarboxylic acids, nitrilotriacetic acid (NTA), if 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 from these.
  • the acids themselves can also be used.
  • the acids have a builder effect typically also the property of an acidifying component and serve thus also for setting a lower and milder pH value of washing or Detergents.
  • dextrins for example oligomers or polymers of carbohydrates, which can be obtained by partial hydrolysis of starches.
  • the hydrolysis can be carried out by customary, for example acid or enzyme-catalyzed, processes. 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 19 091.
  • 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-0 232 202, EP-A-0 427 349, EP-A-0 472 042 and EP-A-0 542 496 and international patent applications WO- A-92/18542, WO-A-93/08251, WO-A-94128030, 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.
  • Suitable cobuilders are oxydisuccinates and other derivatives of disuccinates, preferably ethylenediamine disuccinate.
  • glycerol disuccinates and glycerol trisuccinates such as those found in the United States Patent specifications US 4,524,009, US 4,639,325 in the European patent application EP-A-0 150 930 and Japanese patent application JP 93/339896 become.
  • Suitable amounts are in zeolite and / or formulations containing silicate at 3 to 15% by weight.
  • organic cobuilders are, for example, acetylated hydroxycarboxylic acids or their salts, which may also be present in lactone form and which have at least 4 carbon atoms and at least one hydroxy group as well contain a maximum of two acid groups.
  • Such cobuilders are used, for example, in the 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 mass from 800 to 150,000 (based on acid).
  • Suitable copolymers Polycarboxylates are in particular those of acrylic acid with methacrylic acid and Acrylic acid or methacrylic acid with maleic acid. Have proven to be particularly suitable Copolymers of acrylic acid with maleic acid have proven to be 50 to 90% by weight of acrylic acid and contain 50 to 10% by weight of maleic acid.
  • Their relative molecular mass, based on free acids is generally 5,000 to 200,000, preferably 10,000 to 120,000 and especially 50,000 to 100,000.
  • the content of (co) polymeric polycarboxylates in the compositions is in the usual range and is preferably 1 to 10% by weight.
  • biodegradable polymers made from more than two different ones Monomer units, for example those which according to DE-A-43 00 772 as Monomeric salts of acrylic acid and maleic acid as well as vinyl alcohol or vinyl alcohol derivatives or according to DE-C-42 21 381 as monomer salts of acrylic acid and the 2-alkylallylsuifonic acid and sugar derivatives.
  • copolymers are those described in the German patent applications DE-A-43 03 320 and DE-A-44 17 734 are described and as monomers preferably acrolein and acrylic acid / acrylic acid salts or acrolein and vinyl acetate exhibit.
  • Suitable builder substances are oxidation products of carboxyl-containing ones Polyglucosans and / or their water-soluble salts, such as those in the international patent application WO-A-93/08251 or their Manufactured, for example, in international patent application WO-A-93/16110 is described. Oxidized oligosaccharides according to the German patent application DE-A-196 00 018.
  • further preferred builder substances are polymeric aminodicarboxylic acids, to name their salts or their precursors.
  • Polyaspartic acids are particularly preferred or their salts and derivatives, of which in the German Patent application DE-A-195 40 086 discloses that in addition to cobuilder properties also have a bleach-stabilizing effect.
  • polyacetals which are obtained by converting Dialdehydes with polyol carboxylic acids, which have 5 to 7 carbon atoms and at least 3 Have hydroxyl groups, for example as in the European patent application EP-A-0 280 223 can be obtained.
  • Preferred polyacetals will be from dialdehydes such as glyoxal, glutaraldehyde, terephthalaldehyde and mixtures thereof and obtained from polyol carboxylic acids such as gluconic acid and / or glucoheptonic acid.
  • the agents can also contain components that make the oil and fat washable made of textiles. This effect is particularly evident if a textile is soiled that has already been washed several times with one 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 wt .-% and Hydroxypropoxyl groups from 1 to 15 wt .-%, each based on the nonionic Cellulose ether, as well as the polymers known from the prior art Phthalic acid and / or terephthalic acid or their derivatives, in particular Polymers from ethylene terephthalates and / or polyethylene tycoterephthalates or anionically and / or nonionically modified derivatives of these. Particularly preferred of these are the sulfonated derivatives of phthalic acid and terephthalic acid polymers.
  • 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 ratio Na 2 O: SiO 2 of 1: 1 to 1: 4.5, preferably of 1: 2 to 1: 3.5, are used.
  • the sodium carbonate content of the agents is preferably up to 20% by weight, advantageously between 5 and 15% by weight.
  • the content of sodium silicate in the agents is - if it is not to be used as builder substance - generally up to 10% by weight and preferably between 2 and 8% by weight, otherwise more.
  • Alkali carbonates also by sulfur-free, 2 to 11 carbon atoms and optionally a further carboxyl and / or amino group having amino acids and / or by the salts of which are replaced.
  • a partial to complete replacement of the alkali carbonates by glycine or glycinate he follows.
  • the other detergent ingredients include graying inhibitors (dirt carriers), Foam inhibitors, bleaches 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.
  • Acid can also be used to reduce the pH of detergents or cleaning agents Salts or slightly alkaline salts can be used.
  • citric acid which is particularly preferred either added subsequently (customary procedure) or - in anhydrous form - Is used in a solid premix.
  • bleaching agents which can be used are, for example, sodium percarbonate, peroxypyrophosphates, citrate perhydrates and H 2 O 2 -producing 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.
  • 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.
  • Substances containing O and / or N-acyl groups of the number of carbon atoms mentioned are suitable and / or optionally substituted benzoyl groups.
  • polyacylated alkylenediamines especially tetraacetylethylenediamine (TAED), acylated triazine derivatives, in particular 1,5-diacetyl-2,4-dioxohexahydro-1,3,5-triazine (DADHT), acylated glycolurils, especially tetraacetylglycoluril (TAGU), N-acylimides, especially N-nonanoylsuccinimide (NOSi), acylated phenol sulfonates, especially n-nonanoyl or isononanoyloxybenzenesulfonate (n- or iso-NOBS), Carboxylic anhydrides, especially phthalic anhydride, acylated polyvalent Alcohols, especially triacetin, ethylene glycol diacetate, 2,5-diacetoxy-2,5-dihydrofuran and those from German patent applications DE-A-196 16 693 and DE
  • 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 different foam inhibitors are also used with advantages, for example those made of silicones, paraffins or waxes.
  • the foam inhibitors, in particular silicone and / or paraffin-containing foam inhibitors are preferably bound to a granular, water-soluble or dispersible carrier substance. Mixtures of paraffins and bistearylethylenediamides are particularly preferred.
  • the salts of polyphosphonic acids are preferably the neutral sodium salts for example, 1-hydroxyethane-1,1-diphosphonate, diethylenetriaminepentamethylenephosphonate or ethylenediaminetetramethylenephosphonate in amounts of 0.1 to 1.5 wt .-% used.
  • enzyme mixtures for example from protease and amylase or protease and lipase or lipolytic enzymes or protease and cellulase or from cellulase and Lipase or lipolytic enzymes or from protease, amylase and lipase or lipolytic enzymes or protease, lipase or lipolytic enzymes and cellulase, but especially protease- and / or lipase-containing mixtures or Mixtures with lipolytically active enzymes of particular interest.
  • lipolytic enzymes are the well-known cutinases. Peroxidases too or oxidases have been found to be suitable in some cases.
  • Amylases include in particular ⁇ -amylases, iso-amylases, pullulanases and pectinases.
  • Cellobiohydrolases, endoglucanases and ⁇ -glucosidases are preferably used as cellulases, which are also called cello bias, or mixtures of these used. Since the different cellulase types are characterized by their CMCase and Avicelase activities can be distinguished by targeted mixtures of the cellulases the desired activities are set.
  • the enzymes can be adsorbed on carriers and / or embedded in coating substances to protect them against premature decomposition.
  • the proportion of enzymes, enzyme mixtures or enzyme granules can, 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 removing the dirt detached from the fiber in the Keep the liquor suspended and thus prevent the dirt from re-opening.
  • Water-soluble colloids of mostly organic nature are suitable for this purpose, 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, acidic Group-containing polyamides are suitable for this purpose.
  • Polyvinylpyrrolidone can also be used.
  • cellulose ethers such as carboxymethyl cellulose (Na salt) are preferred, 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 wt .-%, based on the Means used.
  • the agents can be derivatives of diaminostilbenedisulfonic acid or whose alkali metal salts contain. Suitable are e.g. Salts of 4,4'-bis (2-anilino-4-morpholino-1,3,5-triazinyl-6-amino) stilbene-2,2'-disulfonic acid or similarly constructed Compounds which instead of the morpholino group a diethanolamino group, a Carry a methylamino group, an anilino group or a 2-methoxyethylamino group. Brighteners of the substituted diphenylstyryl type may also be present, e.g.
  • Means M1 and M2 were produced according to the following procedure:
  • a solid premix was made from the solid components, including the binder, which in this case was added in solid form, manufactured.
  • the binder was injected into the premix in the form of a sprayable melt; however, this did not result End products with significantly different properties.
  • the melt froze application to the solid mixture within a short time. The usual dwell time in Mixer was sufficient for this.
  • the mixture was then homogenized for a further 2 minutes and then fed to a 2-screw extruder, the pelletizing head on Temperatures between 50 and 65 ° C, preferably to 62 ° C, was preheated.
  • 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 of sodium perborate monohydrate and 6% by weight of polyethylene glycol as binder with a molecular weight of 4000.
  • an agent V1 was produced, which has the same ingredients in the end product contained, but in which the copolymer is not in powder form, but as about 30 wt .-% aqueous solution had been introduced into the process. The excess Water was then dried away in a fluidized bed. The bulk density of the Extrudate was 770 g / l, the L test gave a value of 28%. Received in the towel test V1 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.
  • spray-dried granulate 2 composition see below
  • 11.83% by weight of an alkyl sulfate compound produced 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 with an average of 7 EO, mixed to a premix as described above and extruded ,
  • an agent V2 was again produced, which has the same ingredients in the end product contained, but in which the copolymer is not in powder form, but as about 30 % By weight aqueous solution had been introduced into the process. The excess Water was then dried away in a fluidized bed. The bulk density of the Extrudate was well below 800 g / l, the L test showed a value above 20 %. If the alkyl sulfate compound was not co-extruded, but according to the teaching of German patent application DE-A-195 19 139 subsequently mixed, that was it Bulk weight of the extrudate at 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 produced by introducing 3 to 5% by weight non-ionic surfactant over a spray-dried compound, which then with the nonionic surfactant had been processed.
  • Agents according to the invention were also produced, for example, by using a mixture of binders made of polyethylene glycol with a 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 prepared by using a sodium C 9 -C 13 -alkylbenzenesulfonate powder of 85% by weight alkylbenzenesulfonate, 4.5% by weight sodium carbonate, 3.5% by weight sodium sulfate, 2% by weight as alkylbenzenesulfonate.
  • -% sodium chloride and 4 wt .-% water and unsulphated components were used in the premix.
  • the extrudates had values in the described L test of less than 15% or less than 10%.
  • composition of the spray-dried granules Composition of the spray-dried granules:
  • composition M3 M4 M5 M6 Spray dried granules 1 57 60 64 55 sodium perborate 20 23 - 25 Polyethylene glycol (4000) 5 - - - Polyethylene glycol (2000), capped on one side with methyl end groups - - - 7 Fatty acid methyl ester C 16/18 + 12 EO - - 6 - C 12/18 fatty alcohol + 7 EO 6 6 7 7 C 12/18 fatty alkyl sulfate (92% by weight of active substance, 3.70% by weight of sodium sulfate, 2.80% by weight of other salts from raw materials and unsulfated components, 1.50% by weight of water) 7 5 8th 6 Fatty alcohol C 12/14 polyglycoside (78% by weight active substance, 18% by weight water glass module 2.4, 5% by weight water) 5 - - - C 16/18 fatty acid ethoxylate + 80 EO - 6 - -

Landscapes

  • 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)
  • Physical Or Chemical Processes And Apparatus (AREA)
  • Manufacturing Of Micro-Capsules (AREA)

Claims (24)

  1. Procédé de production de détergents ou nettoyants particulaires, respectivement de compositions ou de matières premières traitées à cet effet avec des densités apparentes supérieures à 600 g/l par combinaison de compositions et/ou de matières premières de détergents ou nettoyants avec formage simultané ou ultérieur, caractérisé en ce qu'on produit tout d'abord un prémélange fluide, solide, qui contient des matières premières individuelles et/ou compositions qui se présentent à la température ambiante et sous une pression de 1 bar comme ,solides et qui présentent un point de fusion, respectivement un point de ramollissement qui n'est pas inférieur à 45°C, et qui le cas échéant contiennent jusqu'à 10 % en poids d'agents tensioactifs non ioniques, liquides à des températures inférieures à 45°C et à une pression de 1 bar, le processus de mélange s'effectuant à la température ambiante et jusqu'à des températures inférieures au point de fusion, respectivement aux points de ramollissement des matières premières individuelles et/ou compositions mentionnées, ce prémélange étant transformé ou préparé avec utilisation de forces de compression à des températures d'au moins 45°C en un grain, et pouvant le cas échéant subir un traitement ou une préparation ultérieure, sous réserve que
    (a) la teneur en eau libre, par rapport au prémélange, se situe en dessous de 2 % en poids et une teneur en eau globale de 15 % en poids, par rapport au prémélange, n'étant pas dépassée et
    (b) dans le prémélange, un ou plusieurs agents tensioactifs anioniques sont utilisés en une quantité minimale de 0,5 % en poids, par rapport à l'agent, et au moins une matière première et une composition se présentant sous forme solide à une pression de 1 bar et à des températures inférieures à 45°C, mais se présentant dans les conditions de traitement sous la forme d'une masse fondue, cette masse fondue servant de liant polyfonctionnel soluble dans l'eau qui dans la production des agents joue le rôle d'un lubrifiant tout en remplissant une fonction d'adhérence pour les compositions ou matières premières de détergents ou de nettoyants, mais agissant de manière désintégrante lors de la redissolution de l'agent dans le bain aqueux, cette matière première ou composition étant choisie dans le groupe des polyéthylèneglycols linéaires, ramifiés et modifiés, des polypropylèneglycols modifiés, des 1,2-polypropylèneglycols, des polyvinylpyrrolidones à faible poids moléculaire et de leurs dérivés ayant des masses moléculaires relatives allant au maximum jusqu'à 30 000, des alcools gras et oxoalcools alcoxylés, des éthoxylates d'esters méthyliques d'acides gras, des acides gras éthoxylés ramifiés et linéaires comportant de 2 à 100 OE, des hydroxyéthers mixtes, des polymères gonflés anhydres, des alkylglycosides de formule RO(G)x, dans laquelle
       R représente un alkyle en C8 à C22 primaire, à chaíne droite ou à ramifications méthyles,
       G représente une unité glycose comportant 5 ou 6 atomes de carbone,
       x représente un nombre compris entre 1 et 10,
       des amides de polyhydroxy(acides gras) de formule (I)
    Figure 00800001
       dans laquelle
       R2CO représente un acyle en C6 à C22,
       R3 représente un hydrogène, un alkyle en C1 à C4, un hydroxyalkyle en C1 à C4,
       [Z] représente un polyhydroxy(alkyle en C3 à C10) linéaire ou ramifié comportant de 3 à 10 groupes hydroxyle,
       des amides de polyhydroxy(acides gras) de formule (II)
    Figure 00810001
       dans laquelle
       R4 représente un alkyle en C7 à C12 linéaire ou ramifié, un alcényle en C7 à C12 linéaire ou ramifié,
       R5 représente un alkyle en C2 à C8 linéaire ou ramifié, un cycloalkyle comportant de 2 à 8 atomes de carbone, un aryle comportant de 2 à 8 atomes de carbone,
       R6 représente un alkyle en C1 à C8 linéaire ou ramifié, un oxyalkyle en C1 à C8, un cycloalkyle comportant de 1 à 8 atomes de carbone, un aryle comportant de 1 à 8 atomes de carbone,
       [Z'] représente un polyhydroxyalkyle linéaire éventuellement alcoxylé comportant au moins deux groupes hxdroxyle dans la chaíne alkyle,
       et leurs mélanges.
  2. Procédé selon la revendication 1, caractérisé en ce que la teneur en eau non liée à des zéolithes et/ou des silicates dans le prémélange ne dépasse pas 10 % en poids et en particulier est inférieure à 7 % en poids.
  3. Procédé selon la revendication 1 ou 2, caractérisé en ce que le prémélange présente, outre les constituants solides, jusqu'à 10 % en poids, des agents tensioactifs non ioniques liquides, à des températures inférieures à 45°C et sous une pression de 1 bar, en particulier les alcools alcoxylés habituellement utilisés dans les détergents ou nettoyants, comme des alcools gras ou des oxoalcools ayant une longueur de chaíne carbonée comprise entre 8 et 20 et en particulier en moyenne de 3 à 7 unités oxyde d'éthylène par mole d'alcool, l'addition des agents tensioactifs non ioniques liquides et du liant à action désintégrante dans le prémélange s'effectuant de préférence de façon séparée.
  4. Procédé selon l'une des revendications 1 à 3, caractérisé en ce que le point de fusion des matières premières individuelles utilisées dans le prémélange, respectivement le point de ramollissement des compositions utilisées dans le prémélange est situé au-dessus de 45°C et de préférence à au moins 50°C.
  5. Procédé selon l'une des revendications 1 à 4, caractérisé en ce qu'on utilise dans le prémélange des compositions et des matières premières qui présentent à 80 % en poids, de préférence à au moins 85 % en poids et de façon particulièrement préférée à au moins 90 % en poids, un point de ramollissement, respectivement un point de fusion nettement plus élevé que les températures qui sont atteintes dans les conditions du procédé.
  6. Procédé selon l'une des revendications 1 à 5, caractérisé en ce que dans l'étape de compression on travaille dans un intervalle de température de quelques degrés, par exemple de 2 à 20°C, au-dessus du point de fusion, respectivement au-dessus du point de ramollissement.
  7. Procédé selon l'une des revendications 1 à 6, caractérisé en ce qu'on utilise un ou plusieurs liants qui se dissolvent presque entièrement à une concentration de 8 g de liant pour un litre d'eau à 30°C en 90 secondes.
  8. Procédé selon l'une des revendications 1 à 7, caractérisé en ce qu'on utilise des liants qui se présentent déjà à des températures allant au maximum jusqu'à 130°C, de préférence allant au maximum jusqu'à 100°C et en particulier à 90°C, entièrement sous forme de masse fondue.
  9. Procédé selon l'une des revendications 1 à 8, caractérisé en ce que les solides pour la production du prémélange solide et fluide sont introduits tout d'abord à la température ambiante jusqu'à des températures légèrement augmentées, qui se situent de préférence en dessous de la température de fusion, respectivement de l'intervalle de fusion du liant et en particulier à des températures allant jusqu'à 35°C, dans un dispositif de mélange et/ou de granulation habituel.
  10. Procédé selon l'une des revendications 1 à 9, caractérisé en ce que les liants sont ajoutés en tant que dernier composant au prémélange, leur addition au mélange s'effectuant dans des conditions telles que l'on atteint une répartition aussi régulière et homogène que possible du liant - sous la forme d'une masse fondue figée ou sous la forme d'une poudre - dans le mélange de solides.
  11. Procédé selon l'une des revendications 1 à 10, caractérisé en ce que l'intégration du liant s'effectue à des températures auxquelles le liant se présente sous la forme d'une masse fondue, les températures préférées de la massé fondue se situant entre 60 et 150°C, en particulier dans un intervalle de température allant de 80 à 120°C.
  12. Procédé selon l'une des revendications 1 à 11, caractérisé en ce qu'on poursuit le processus de mélange jusqu'à ce que la masse fondue soit figée et que le prémélange se présente sous une forme solide et fluide.
  13. Procédé selon l'une des revendications 1 à 12, caractérisé en ce qu'on utilise un prémélange dont la teneur en liant, respectivement liants, est au moins de 2 % en poids, mais est inférieure à 15 % en poids, de préférence inférieure à 10 % en poids et est de façon particulièrement préférée comprise entre 3 et 6 % en poids, toujours par rapport au prémélange.
  14. Procédé selon l'une des revendications 1 à 13, caractérisé en ce qu'on établit une température du procédé dans le processus proprement dit de granulation, de compactage, de compression, de réduction en boulettes ou d'extrusion au-dessus du point de fusion, respectivement au-dessus de la température à laquelle le ou les liants se présentent sous la forme d'une masse fondue, la température du procédé ne dépassant cependant pas 20°C au-dessus de la température de fusion, respectivement de l'intervalle de fusion du liant.
  15. Procédé selon l'une des revendications 1 à 14, caractérisé en ce que le liant présente une température de fusion, respectivement un intervalle de fusion allant au maximum jusqu'à 150°C, de préférence allant au maximum jusqu'à 100°C et en particulier jusqu'à 75°C, et en ce que la température du procédé se situe à 10°C et en particulier au maximum à 5°C au-dessus de la température, de fusion, respectivement de la limite supérieure de température de l'intervalle de fusion du liant.
  16. Procédé selon l'une des revendications 1 à 15, caractérisé en ce que la durée d'action de la température entre le mélange/homogénéisation du prémélange et le formage, donc dans l'intervalle de compression, est comprise entre 10 secondes et au maximum 5 minutes, et est en particulier d'au maximum 3 minutes.
  17. Procédé selon l'une des revendications 1 à 16, caractérisé en ce que la production s'effectue par extrusion, le prémélange étant comprimé sous pression, plastifié, extrudé sous la forme de brins fins à travers la plaque de buse à trous dans la tête d'extrusion et réduit enfin au moyen d'un couteau rotatif, de préférence à des grains de granulés approximativement sphériques (en forme de perles) à cylindriques, et en ce que la régulation de la température dans la zone de transition de la vis d'extrusion, du prérépartiteur et de la plaque de buse est établie de manière à ce que la température de fusion du liant, respectivement la limite supérieure de l'intervalle de fusion du liant soit au moins atteinte, mais de préférence dépassée.
  18. Procédé selon la revendication 17, caractérisé en ce que la durée de l'action de la température dans l'intervalle de compression de l'extrusion s'élève au maximum à 2 minutes et se situe en particulier dans un intervalle compris entre 30 secondes et 1 minute.
  19. Procédé selon l'une des revendications 1 à 18, caractérisé en ce que la matière comprimée, directement après la sortie de l'appareil de fabrication, présente des températures ne dépassant pas 80°C, de préférence comprises entre 35 et 75°C et en particulier entre 40 et 70°C, par exemple allant jusqu'à 60°C.
  20. Procédé selon l'une des revendications 1 à 19, caractérisé en ce qu'on transforme un prémélange ayant une répartition granulométrique relativement large et des proportions relativement élevées de grains fins en un produit final ayant une répartition granulométrique relativement étroite et des proportions relativement faibles de grains fins.
  21. Agent détergent ou nettoyant particulaire, composition ou matière première traitée à cet effet avec des densités apparentes supérieures à 600 g/l, produit selon l'une des revendications 1 à 20, où l'on produit à partir de compositions et/ou de matières premières à cet effet tout d'abord un prémélange solide. et fluide, qui présente des matières premières individuelles et/ou des compositions se présentant sous forme de solides à la température ambiante et sous une pression de 1 bar, et ayant un point de fusion, respectivement un point de ramollissement qui n'est pas inférieur à 45°C, et qui que le cas échéant contiennent jusqu'à 10 % en poids d'agents tensioactifs non ioniques liquides à des températures inférieures à 45°C et à une pression de 1 bar, le processus de mélange se déroulant à la température ambiante et jusqu'à des températures inférieures au point de fusion, respectivement de ramollissement des matières premières individuelles et/ou compositions mentionnées, et ce prémélange étant transformé en un grain avec utilisation de forces de compression à des températures d'au moins 45°C, puis transformé ou préparé, sous réserve que la teneur en eau libre dans le prémélange, par rapport au prémélange, se situe en dessous de 2 % en poids, et qu'une teneur globale en eau de 15 % dans le prémélange, par rapport à ce prémélange, ne soit pas dépassée, caractérisé en ce que le prémélange contient un ou plusieurs agents tensioactifs anioniques en une quantité minimale de 0,5 % en poids; par rapport à l'agent, au moins une matière première ou une composition qui est introduite par le prémélange et se présentant sous forme solide à une pression de 1 bar et à des températures inférieures à 45°C, mais se présentant dans les conditions de traitement sous la forme d'une masse fondue, cette masse fondue servant de liant polyfonctionnel soluble dans l'eau, qui dans la production des agents joue le rôle d'un lubrifiant tout en remplissant une fonction d'adhérence pour les compositions, respectivement matières premières de détergents ou de nettoyants, mais agissant de manière désintégrante lors de la redissolution de l'agent dans le bain aqueux, et cette matière première ou composition étant choisie dans le groupe des polyéthylèneglycols linéaires, ramifiés et modifiés, des polypropylèneglycols modifiés, des 1,2-polypropylèneglycols, des polyvinylpyrrolidones à faible poids moléculaire et de leurs dérivés ayant des masses moléculaires relatives allant au maximum jusqu'à 30 000, des alcools gras et oxoalcools alcoxylés, des éthoxylates d'esters méthyliques d'acides gras, des acides gras éthoxylés ramifiés et linéaires comportant de 2 à 100 OE, des hydroxyéthers mixtes, des polymères gonflés anhydres, des alkylglycosides de formule RO(G)x, dans laquelle
       R représente un alkyle en C8 à C22 primaire, à chaíne droite ou à ramifications méthyles,
       G représente une unité glycose comportant 5 ou 6 atomes de carbone,
       x représente un nombre compris entre 1 et 10,
       des amides de polyhydroxy(acides gras) de formule (I)
    Figure 00860001
       dans laquelle
       R2CO représente un acyle en C6 à C22,
       R3 représente un hydrogène, un alkyle en C1 à C4, un hydroxyalkyle en C1 à C4,
       [Z] représente un polyhydroxy(alkyle en C3 à C10) linéaire ou ramifié comportant de 3 à 10 groupes hydroxyle,
       des amides de polyhydroxy(acides gras) de formule (II)
    Figure 00870001
       dans laquelle
       R4 représente un alkyle en C7 à C12, linéaire ou ramifié, un alcényle en C7 à C12 linéaire ou ramifié,
       R5 représente un alkyle en C2 à C8 linéaire ou ramifié, un cycloalkyle comportant de 2 à 8 atomes de carbone; un aryle comportant de 2 à 8 atomes de carbone,
       R6 représente un alkyle en C1 à C8 linéaire ou ramifié, un oxyalkyle en C1 à C8, un cycloalkyle comportant de 1 à 8 atomes de carbone, un aryle comportant de 1 à 8 atomes de carbone,
       [Z'] représente un polyhydroxyalkyle linéaire éventuellement alcoxylé comportant au moins deux groupes hydroxyle dans la chaíne alkyle,
       et leurs mélanges, et présentant une structure en nids d'abeilles, les nids d'abeilles étant remplis de solide.
  22. Détergent granulé ou extrudé selon la revendication 21, caractérisé en ce qu'il se compose à au moins 80 % en poids de compositions produites et/ou de matières premières traitées selon l'invention, et en particulier à au moins 80 % en poids de granulé de base ou produit d'extrusion de base produit selon l'invention, où il est particulièrement avantageux que le reste des composants soit également constitué de compositions ou de matières premières traitées qui ont été produites selon l'une des revendications 1 à 20.
  23. Agent selon l'une des revendications 21 ou 22, caractérisé en ce qu'il présente comme enveloppe extérieure des constituants en forme de poussière ou du moins fins (ce qu'on appelle les fines), qui ont été collés par une agglomération à l'état fondu.
  24. Articles moulés, en particulier comprimés, que l'on peut obtenir selon l'une des revendications 1 à 20, où l'on produit tout d'abord à partir de compositions et/ou de matières premières à cet effet un prémélange solide et fluide, qui contient des matières individuelles et/ou des compositions se présentant à la température ambiante et à une pression de 1 bar sous forme de solide et présentant un point de fusion, respectivement un point de ramollissement qui n'est pas inférieure à 45°C, et qui que le cas échéant contiennent jusqu'à 10 % en poids d'agents tensioactifs non ioniques liquides à des températures inférieures à 45°C et à une pression de 1 bar, le processus de mélange se déroulant à la température ambiante et jusqu'à des températures inférieures au point de fusion, respectivement de ramollissement des matières premières individuelles et/ou compositions mentionnées, et ce prémélange étant transformé en un grain avec utilisation de forces de compression à des températures d'au moins 45°C, puis transformé ou préparé, sous réserve que la teneur en eau libre dans le prémélange, par rapport au prémélange, se situe en dessous de 2 % en poids, et qu'une teneur globale en eau de 15 % dans le prémélange, par rapport à ce prémélange, ne soit pas dépassée, caractérisé en ce que l'article moulé contient un ou plusieurs agents tensioactifs anioniques en une quantité minimale de 0,5 % en poids, par rapport à l'agent, au moins une matière première ou une composition qui est introduite par le prémélange et se présentant sous forme solide à une pression de 1 bar et à des températures inférieures à 45°C, mais se présentant dans les conditions de traitement sous la forme d'une masse fondue, cette masse fondue servant de liant polyfonctionnel soluble dans l'eau, qui dans la production des agents joue le rôle d'un lubrifiant tout en remplissant une fonction d'adhérence pour les compositions, respectivement matières premières de détergents ou de nettoyants, mais agissant de manière désintégrante lors de la redissolution de l'agent dans le bain aqueux, et cette matière première ou composition étant choisie dans le groupe des polyéthylèneglycols linéaires, ramifiés et modifiés, des polypropylèneglycols modifiés, des 1,2-polypropylèneglycols, des polyvinylpyrrolidones à faible poids moléculaire et de leurs dérivés ayant des masses moléculaires relatives allant au maximum jusqu'à 30 000, des alcools gras et oxoalcools alcoxylés, des éthoxylates d'esters méthyliques d'acides gras, des acides gras éthoxylés ramifiés et linéaires comportant de 2 à 100 OE, des hydroxyéthers mixtes, des polymères gonflés anhydres, des alkylglycosides de formule RO(G)x, dans laquelle
       R représente un alkyle en C8 à C22 primaire, à chaíne droite ou à ramifications méthyles,
       G représente une unité glycose comportant 5 ou 6 atomes de carbone,
       x représente un nombre compris entre 1 et 10,
       des amides de polyhydroxy(acides gras) de formule (I)
    Figure 00890001
       dans laquelle
       R2CO représente un acyle en C8 à C22,
       R3 représente un hydrogène, un alkyle en C1 à C4, un hydroxyalkyle en C1 à C4,
       [Z] représente un polyhydroxy alkyle en C3 à C10 linéaire ou ramifié comportant de 3 à 10 groupes hydroxyle,
       des polyhydroxyamides d'acides gras de formule (II)
    Figure 00900001
       dans laquelle
       R4 représente un alkyle en C7 à C12, linéaire ou ramifié, un alcényle en C7 à C12 linéaire ou ramifié,
       R5 représente un alkyle en C2 à C8 linéaire ou ramifié, un cycloalkyle comportant de 2 à 8 atomes de carbone, un aryle comportant de 2 à 8 atomes de carbone,
       R6 représente un alkyle en C1 à C8 linéaire ou ramifié, un oxyalkyle en C1 à C8, un cycloalkyle comportant de 1 à 8 atomes de carbone, un aryle comportant de 1 à 8 atomes de carbone,
       [Z'] représente un polyhydroxyalkyle linéaire éventuellement alcoxylé comportant au moins deux groupes hydroxyle dans la chaíne alkyle,
       et leurs mélanges, ainsi qu'un ou plusieurs agents désagrégeants.
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

Publications (2)

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

Family

ID=7806359

Family Applications (2)

Application Number Title Priority Date Filing Date
EP97942019A Expired - Lifetime EP0931137B1 (fr) 1996-09-20 1997-09-11 Procede de production d'un detergent ou nettoyant particulaire
EP98947499A Expired - Lifetime EP1015550B1 (fr) 1996-09-20 1998-09-02 Procede de production de nettoyants et detergents particulaires

Family Applications After (1)

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

Country Status (14)

Country Link
EP (2) EP0931137B1 (fr)
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)
WO (1) WO1998012299A1 (fr)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
USD762486S1 (en) 2015-02-18 2016-08-02 Henkel Ag & Co. Kgaa Solid state detergent in a transparent container
US9512388B2 (en) 2015-02-18 2016-12-06 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

Families Citing this family (17)

* Cited by examiner, † Cited by third party
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
JP2003527455A (ja) * 1998-09-25 2003-09-16 ザ、プロクター、エンド、ギャンブル、カンパニー 改善された溶解度特性を有する粒状洗剤組成物
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
RU2673078C2 (ru) * 2013-03-22 2018-11-22 Басф Се Алкилгликозиды в качестве поверхностно-активных веществ
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
DE102015002877A1 (de) 2015-03-09 2016-09-15 Henkel Ag & Co. Kgaa Granulares Wasch- oder Reinigungsmittel mit verbesserter Lösegeschwindigkeit
WO2020050426A1 (fr) * 2018-09-03 2020-03-12 주식회사 프랜드 Procédé de préparation de billes de gommage à propriétés antibactériennes à base d'amidon

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
USD762486S1 (en) 2015-02-18 2016-08-02 Henkel Ag & Co. Kgaa Solid state detergent in a transparent container
US9512388B2 (en) 2015-02-18 2016-12-06 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
USD799327S1 (en) 2015-02-18 2017-10-10 Henkel IP & Holding GmbH Container for a solid state detergent
USD799324S1 (en) 2015-02-18 2017-10-10 Henkel IP & Holding GmbH Container for a solid state detergent
USD799326S1 (en) 2015-02-18 2017-10-10 Henkel IP & Holding GmbH Container for a solid state detergent

Also Published As

Publication number Publication date
JP2001500557A (ja) 2001-01-16
DE59711115D1 (de) 2004-01-22
RU99108122A (ru) 2001-02-20
CZ296295B6 (cs) 2006-02-15
KR20010023917A (ko) 2001-03-26
EP1015550A1 (fr) 2000-07-05
TR199900582T2 (xx) 1999-06-21
ES2213222T3 (es) 2004-08-16
SK35299A3 (en) 1999-07-12
DE19638599A1 (de) 1998-03-26
PL331987A1 (en) 1999-08-16
CN1187435C (zh) 2005-02-02
KR20010023926A (ko) 2001-03-26
KR20010029500A (ko) 2001-04-06
CZ97799A3 (cs) 1999-09-15
EP1015550B1 (fr) 2006-02-01
CN1230984A (zh) 1999-10-06
RU2200190C2 (ru) 2003-03-10
EP0931137A1 (fr) 1999-07-28
WO1998012299A1 (fr) 1998-03-26
SK285376B6 (sk) 2006-12-07
UA64724C2 (uk) 2004-03-15
ATE256176T1 (de) 2003-12-15

Similar Documents

Publication Publication Date Title
EP0931137B1 (fr) Procede de production d'un detergent ou nettoyant particulaire
EP1235897B1 (fr) Pastilles de detergent
EP1025198B1 (fr) Procede servant a preparer un produit lavant ou detergent au parfum renforce
DE19956803A1 (de) Tensidgranulate mit verbesserter Auflösegeschwindigkeit
EP1253193A2 (fr) Compositions solides de détergents, leur procédé de préparation et leur utilisation
EP0804529B1 (fr) Compose silicate alcalin amorphe
EP1842900A1 (fr) Procédé destiné à la fabrication de granulés et leur utilisation dans des agents de lavage et/ou de nettoyage
DE19941934A1 (de) Detergentien in fester Form
EP1012221B1 (fr) Procede pour la production de detergents particulaires
EP0839178B1 (fr) Compose amorphe de silicate alcalin
EP0724620B1 (fr) Procede de production d'extrudes de lavage ou de nettoyage a pouvoir ameliore de redispersion
EP1036158B1 (fr) Procede de production de melanges de matieres premieres de masse volumique apparente elevee
EP0845028B1 (fr) Procede de production d'un silicate alcalin amorphe soumis a une impregnation
WO1997034977A1 (fr) Procede de production de silicates granulaires a masse volumique apparente elevee
EP0888450B2 (fr) Additif pour produits de lavage ou de nettoyage, et procede de fabrication associe
EP0846758A2 (fr) Additif détergent
EP0836641A1 (fr) Granules detergents et nettoyants de masse volumique apparente elevee, exempts de poudre et de fractions fines
WO2016142209A1 (fr) Détergent ou produit de nettoyage granulaire à solubilité améliorée
WO2000022076A1 (fr) Granules renfermant du phosphonate
DE19911570A1 (de) Aniontensid-Granulate
DE10108573A1 (de) Feste Waschmittelzusatzstoffe, deren Herstellung und Verwendung
DE102004053385A1 (de) Kugelförmige Agglomerate
DE19632284A1 (de) Wasch- oder Reinigungsmitteladditiv sowie ein Verfahren zu seiner Herstellung
WO1997018290A1 (fr) Procede de preparation de detergents et de nettoyants granulaires ou constituants utilises pour les preparer

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

17P Request for examination filed

Effective date: 19990311

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): AT BE DE ES FR GB IT NL

17Q First examination report despatched

Effective date: 20020903

GRAH Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOS IGRA

RIC1 Information provided on ipc code assigned before grant

Ipc: 7C 11D 11/00 B

Ipc: 7C 11D 17/06 A

GRAS Grant fee paid

Free format text: ORIGINAL CODE: EPIDOSNIGR3

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

AK Designated contracting states

Kind code of ref document: B1

Designated state(s): AT BE DE ES FR GB IT NL

REG Reference to a national code

Ref country code: GB

Ref legal event code: FG4D

Free format text: NOT ENGLISH

REF Corresponds to:

Ref document number: 59711115

Country of ref document: DE

Date of ref document: 20040122

Kind code of ref document: P

GBT Gb: translation of ep patent filed (gb section 77(6)(a)/1977)

Effective date: 20040319

REG Reference to a national code

Ref country code: ES

Ref legal event code: FG2A

Ref document number: 2213222

Country of ref document: ES

Kind code of ref document: T3

ET Fr: translation filed
PLBE No opposition filed within time limit

Free format text: ORIGINAL CODE: 0009261

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT

26N No opposition filed

Effective date: 20040913

REG Reference to a national code

Ref country code: FR

Ref legal event code: PLFP

Year of fee payment: 20

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: DE

Payment date: 20160921

Year of fee payment: 20

Ref country code: NL

Payment date: 20160920

Year of fee payment: 20

Ref country code: GB

Payment date: 20160920

Year of fee payment: 20

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: FR

Payment date: 20160921

Year of fee payment: 20

Ref country code: AT

Payment date: 20160921

Year of fee payment: 20

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: BE

Payment date: 20160920

Year of fee payment: 20

Ref country code: ES

Payment date: 20160916

Year of fee payment: 20

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: IT

Payment date: 20160922

Year of fee payment: 20

REG Reference to a national code

Ref country code: DE

Ref legal event code: R071

Ref document number: 59711115

Country of ref document: DE

REG Reference to a national code

Ref country code: NL

Ref legal event code: MK

Effective date: 20170910

REG Reference to a national code

Ref country code: GB

Ref legal event code: PE20

Expiry date: 20170910

REG Reference to a national code

Ref country code: AT

Ref legal event code: MK07

Ref document number: 256176

Country of ref document: AT

Kind code of ref document: T

Effective date: 20170911

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: GB

Free format text: LAPSE BECAUSE OF EXPIRATION OF PROTECTION

Effective date: 20170910

REG Reference to a national code

Ref country code: BE

Ref legal event code: MK

Effective date: 20170911

REG Reference to a national code

Ref country code: ES

Ref legal event code: FD2A

Effective date: 20180508

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: ES

Free format text: LAPSE BECAUSE OF EXPIRATION OF PROTECTION

Effective date: 20170912