EP0847440A1 - Produits de lavage et de nettoyage comprimes et mis en forme de figures geometriques - Google Patents

Produits de lavage et de nettoyage comprimes et mis en forme de figures geometriques

Info

Publication number
EP0847440A1
EP0847440A1 EP96929282A EP96929282A EP0847440A1 EP 0847440 A1 EP0847440 A1 EP 0847440A1 EP 96929282 A EP96929282 A EP 96929282A EP 96929282 A EP96929282 A EP 96929282A EP 0847440 A1 EP0847440 A1 EP 0847440A1
Authority
EP
European Patent Office
Prior art keywords
mixture
components
solid
shaped
range
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.)
Withdrawn
Application number
EP96929282A
Other languages
German (de)
English (en)
Inventor
Wilfried Rähse
Johann-Friedrich Fues
Norbert Kühne
Bernd Larson
Peter Sandkühler
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Henkel AG and Co KGaA
Original Assignee
Henkel AG and Co KGaA
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Henkel AG and Co KGaA filed Critical Henkel AG and Co KGaA
Publication of EP0847440A1 publication Critical patent/EP0847440A1/fr
Withdrawn legal-status Critical Current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
    • C11D17/065—High-density particulate detergent compositions
    • 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
    • C11D17/0047—Detergents in the form of bars or tablets

Definitions

  • the forms of multicomponent detergents and cleaning agents currently on the market, in particular from the field of textile detergents with a compact good structure, are on the one hand pourable and free-flowing granules or agglomerates with at least predominant proportions of the multicomponent goods in the fine grain range and on the other hand in particular spherical extrudate grains with average Ball diameters in the millimeter range.
  • Also known for use as machine dishwashing detergents are compact tablets in the form of a spatially much larger formation with tablet thickness and diameter in the centimeter range.
  • the technical teaching of the invention described below is based on the objective of giving solid, compacted multi-component mixtures from the field of detergents and cleaners a spatial configuration which is not known to this day in the subject area concerned.
  • the teaching according to the invention intends to form multi-component mixtures from the area mentioned here and in particular from the area of more solidly compacted laundry detergents as a pourable and free-flowing mixture of the coarse particle area, but is not restricted to the spherical structure or rounded cylinder shape which is customary today.
  • the teaching of action according to the invention described below aims to open up the possibility of condensing the roughly particulate To design multicomponent goods in a figurable manner in a viable manner and thus, for example, to enable the mixed goods to be visually identified by the consumer.
  • the teaching according to the invention relates to solid, compacted multicomponent mixtures from the field of detergents and cleaning agents, in particular textile detergents, and in an important embodiment these multicomponent mixtures are at least predominantly present as a pourable and free-flowing mix in the coarse particle range.
  • the teaching according to the invention is characterized here in that the coarse particulate material is at least partially formed in a figurally shaped plate or disk structure, the following being true in particular: the ratio of the greatest length or width of the respective individual particle of the coarse particle area designed according to the invention to the latter average platelet or disk thickness is above 1.2 for numerical values.
  • the symbol “L” is used for determining the greatest length or width of the individual particle and the symbol “1" for the associated plate or disk thickness.
  • the coarse particles with a platelet or disk structure which are shaped figuratively according to the teaching of the invention are characterized by numerical values of at least 1.5 in relation to the ratio (L) / (l).
  • the compact form according to the invention in a predetermined manner can make up the multicomponent mixture of valuable substances in its entirety, but it is also possible for the coarse particulate compact form according to the invention to be mixed with it non-figuratively shaped portions of the multi-component mixture are present. For details, see below.
  • the new teaching relates to a multicomponent pourable and free-flowing detergent and cleaning agent, in particular textile detergent, which combines high density with good dissolvability even in cold water and thereby allows greater freedom in the choice of valuable and possibly auxiliary substances .
  • the teaching according to the invention is characterized here in that it is designed as an abrasion-resistant material free of dust and fine particles of the following spatial structure:
  • Strongly compressed core made from a number of valuable and / or auxiliary substances which are soluble and / or finely dispersed insoluble in an aqueous liquor, this core being provided with a platelet or disk base structure and designed in a predetermined manner as a figure - hereinafter also called " Core material "designated -,
  • this core material is at least partially encased by a mixture of the same and / or further valuable and auxiliary substances with - based on the diameter of the core material - smaller individual particle size - also referred to below as "envelope substance" -,
  • binder which is soluble in cold water and solid at room temperature - hereinafter also referred to as "binder”.
  • the teaching according to the invention relates in a further embodiment to the method for producing the In the sense of the previous definition, shaped or figuratively formed, compressed multi-component mixtures from the field of valuable and / or auxiliary substances of detergents and cleaning agents, in particular corresponding textile detergents.
  • a preparation of the corresponding fine material which is flowable under pressure is preferably pressed in a mixture with liquid flow agents, lubricants and / or binders - by hole shapes of the desired figurative design.
  • the emerging strand is comminuted by chipping granulation and the granules formed are dried without substantial rounding.
  • figure-shaped coarse particles of the compressed multicomponent mixture are formed, which have the predeterminable shape in a vertical view of the platelet-shaped or disk-shaped basic structure of the individual particles.
  • the teaching according to the invention is largely free, taking into account the general knowledge of the specialist in the field concerned.
  • the predeterminable figure-like design is determined by the shape of the hole for pressing out the primary material compacted in the form of a strand.
  • Appropriate techniques are available to experts from completely different areas - for example in the area of Production of figurative pasta - well known.
  • the invention now uses this knowledge for the spatially aesthetic design of compacted multicomponent mixtures from the field of detergents and cleaning agents and in particular textile detergents.
  • the particular spatial shape selected can correspond to concrete and / or abstract figure templates, as is generally known for the technology mentioned here in the completely different areas mentioned.
  • the multicomponent mixture In use, the multicomponent mixture must meet the required performance requirements, for example in textile washing.
  • the composition of the recyclable material is thus shaped by the extensive specialist knowledge available today in this special area.
  • the multicomponent material compacted by the shaping processing process must have sufficient spontaneous solubility when water enters - preferably even in the cold wash liquor. Nevertheless, the sufficiently solid cohesion of the dry multicomponent material is necessary in order to give these comparatively complex, figure-shaped particles sufficient stability of the primary shape under the stresses of the packaging, the mixing with other, possibly coarse-grained materials as well as the stresses during transport and use.
  • the value range concerned in the invention also applies here important requirement that the solid material should be designed to be essentially tack-free in the region of the room temperature even in the case of prolonged storage in order to rule out undesirable caking and thus obstructions in the metering.
  • the following presentation of essential parameters of the teaching according to the invention shows how the objective according to the invention can be achieved technically without having to give up the desired degree of freedom in the spatially aesthetic configuration of the individual multi-component particles.
  • the greatest length or width (L) of the individual particle in plan view should be in the range of about 1. 2 to 20 mm, further preferred ranges for this parameter (L) being in the range from approximately 1.5 to 12 mm and in particular in the numerical range from 4 to 10 mm.
  • the respectively associated disk or plate thickness (1) is below and expediently clearly below the associated parameter (L) in the individual particle, with numerical values for (1) expediently below in adaptation to the size of the figure-shaped surface 5 mm and preferably in the range of about 0.5 to 3 mm.
  • numerical values for (1) expediently below in adaptation to the size of the figure-shaped surface 5 mm and preferably in the range of about 0.5 to 3 mm.
  • the thickness of the individual shaped particle is at most about 1.5 to 2 mm.
  • Particularly preferred values for (1) can be in the range from 0.8 to 1.5 mm.
  • the ratio of the parameters of (L) / (l) can be of importance, in particular, for the sufficiently trouble-free producibility and / or the sufficient storage stability of the dried individually shaped particles.
  • Preferred Numerical values for this ratio (L) / (l) are at least 2 and expediently in the range from about 3 to 20. Numerical values in the range from 4 to 15 and in particular from about 4 to 10 - for example numerical values of the ratio discussed here in the range from 4 to 8 - are particularly preferred.
  • the compression of the multicomponent mixture in the extrusion step is preferably carried out under conditions such that the true density of the individual particle concerned is at least 1 g / cm 3 and preferably above this number limit.
  • Particularly preferred ranges for the true density of the respective individual particle are, for example, in the range from 1.2 to 2.5 g / cm 3 and in particular in the range from approximately 1.35 to 1.55 g / cm 3 .
  • the individual figure-like interior design of these compacted individual particles determines the bulk densities of the individual solid material based on a large number of such identically shaped particles, precisely because of their comparatively more complex spatial configuration.
  • the teaching according to the invention provides in particular to set bulk densities of at least 350 g / l for the figure-shaped, coarse particulate material, with corresponding bulk densities in the range from 400 to 900 g / l and in particular those in the range from 500 to 750 g / l being particularly preferred can.
  • These last-mentioned determination parameters are particularly important when the finished goods intended for distribution and use are formed exclusively or at least for the most part from appropriately figured multi-component compactates.
  • the teaching according to the invention is not restricted to this.
  • mixtures of substances in which coarse particulate fractions formed according to the invention account for at least about 10 to 25% by weight and preferably at least 35 to about 50% by weight of the mixture are generally more important.
  • Corresponding mixtures of substances in which the amount of particles figuratively designed according to the invention represents the at least predominant amount can be particularly important.
  • the teaching according to the invention comprises mixtures of substances in which figurally shaped coarse particulate fractions in the sense of the embodiment shown here are present in a mixture with non-figurative fractions of the multi-component mixture. These further portions can be present as fine particulate - in particular powdery - and / or also as coarse particulate, for example in the form of conventional granules, agglomerates and / or in particular rounded extrudates. Embodiments may be of particular importance in which, according to the invention, figuratively shaped coarse particulate fractions are preferred. minor amounts of spherical trained portions of the total multi-component mixture required are combined and, if necessary, portions of fine-grained material are also added. This is immediately understandable with the following example:
  • the applicant's older German patent application according to DE 195 19 139 suggests, on the one hand, to solve the conflict between the high degree of compression of the mixture of materials, in particular by extrusion, and the rapid, in particular gelation-free, dissolvability of this material even in the early phase a washing process before to design granular detergents or cleaning agents with a bulk density above 600 g / 1 in such a way that at least two different granular components are provided in the multi-substance mixture to be used, at least one of which extrudes and at least one does not is extruded.
  • the extruded component (s) should be present in amounts of 30 to 85% by weight, based on the total agent.
  • an important possibility for the teaching according to the invention is to mix these extrudates shaped according to the invention with non-extruded good portions, which may have fine grain structure or coarse grain structure.
  • the mixing ratios of the respective fractions can be regulated within wide limits, whereby reference can be made to the numerical ranges already given.
  • the decisive factor for the design according to the invention in all of the embodiments concerned here is that the visual impression of the multicomponent mixture - with a suitable choice of the figuratively predetermined proportion of coarse particles according to the invention - is decisively determined by this figuratively shaped proportion of recyclable material. For the characteristic character of a corresponding multicomponent product, a previously unknown form of offer is thus created in the work area concerned here.
  • the components of the solid detergents and cleaning agents which are not specifically shaped can be present as a mixing component (s) which are separate from the figurative portion.
  • a mixing component which are separate from the figurative portion.
  • additional portions are at least partially bonded to the figurally shaped coarse portions. It is understandable that this is particularly the case corresponding portions of the non-specifically shaped fine particulate area.
  • embodiments are preferred in the sense of the teaching according to the invention which are characterized by a coarse particulate content of the mixed material of at least 50% by weight and preferably at least 60 to 70% by weight.
  • the percentages or ranges by weight given relate to the total weight of the multicomponent mixture.
  • the figure-shaped coarse particulate material in the sense of the definition according to the invention is present at least 50% by weight and preferably at least 70% by weight - however,% by weight here based on the coarse particulate Proportion of.
  • the teaching according to the invention is not limited to this, and the presence of only a subordinate amount of the figurative material - in particular for the visual identifiability of the mixed material - in admixture with other components of the mixture falls within the scope of the teaching according to the invention.
  • the solid parts embodied according to the invention can be uniform or at least in the respective mixture of valuable materials according to shape, size, composition and / or color one of these parameters should be non-uniform. It is immediately clear that this opens up a wide range of options for the individual design of mixed products that meet the specified technical requirements catalogs and / or aesthetic requirements. Details of particularly important embodiments are given below.
  • the figurative multicompact compacts in the sense of the teaching according to the invention can, for example, be star-shaped or in the spatial form of other celestial bodies, in particular the moon. Numerous special designs fall into these two collective terms.
  • Representations of plants or parts of plants can be the basis for interesting spatial forms. Examples include: leaf and / or flower shape, mushrooms, tree profiles and the like.
  • a large and very varied area for the figure-like configuration of the compact in the sense of the invention are spatial forms which are based on the representation of animals. Examples include: fish, butterflies, birds, rabbits, elephants or shells.
  • a completely different area in a simple spatial representation is accessible through everyday objects, for example shirts and / or trousers, shoes and the like.
  • striking spatial shapes can also correspond to abstract representations, examples of which are: diamonds, cylinders, pyramids, ovals, drops and the like.
  • the teaching according to the invention it can be interesting to provide one or more hole shapes in the interior of the figure-shaped surface, which can be circular but can also have any other shape.
  • the star shape which has a circular hole in its center, is only taken here as an example.
  • Other examples of this are, for example, ladder-shaped compacts, panes with a hole shape (s) in the inside of the pane and the like.
  • the technical realization of such figure-shaped spatial bodies by means of extrusion is possible in a known manner; reference is made to the relevant specialist knowledge.
  • the last-mentioned configuration of the figure-shaped compact may be of particular interest for a number of reasons: First of all, this additional hole shape in the interior of the particle enlarges the surface of the compressed particle even more, thus providing an additional solution for the early phase of the Use of the extrudate particles ensured.
  • a completely different point of view can have at least the same or even greater technical significance:
  • this spatial shape of the figurative fractions mentioned here can increase stability against undesired segregation processes in the state storage and transport of the solid mixtures.
  • disk-shaped or platelet-shaped portions with a hole shape in the interior of the disk can be spherical when mixed trained solid components contribute to an effective stabilization of a once set mixing state of the solid components.
  • the even distribution of separate solid fines and the preferred at least partial solidification of these fines on the figure-shaped particle space form described below can be facilitated by the additional configuration of these last-mentioned particles mentioned here.
  • a particularly interesting application of the working principle according to the invention can lie in the following configuration: Solid, free-flowing detergent and cleaning agent mixtures and, in particular, corresponding textile detergents are known to be highly complex mixtures of a large number of valuable substances with a predetermined effect within the scope of the overall work process process.
  • the main components such as builders / cobuilders, surfactants, alkali agents are added to a large number of other active ingredients or valuable substances such as defoamers or agents to dampen foam formation, so-called soil repellents, bleaches containing H 2 0 2, for example of the type of perborate compounds and / or percarbonate compounds, bleach activators, which as a rule form intermediate peracids by reaction with the H 2 0 2 in the aqueous washing liquor, the enzymes already mentioned and the like.
  • Recyclable materials of this type are either added to the multicomponent mixture as such or are often also mixed in the form of so-called compounds with proportions of other recyclable materials.
  • the practically unlimited possibility, according to the invention, in terms of its variety, of visually identifying certain portions of the mixture of valuable materials makes it possible here to make the type and / or amount of certain identifiable mixture components of the overall mixture visually perceptible.
  • the different mixture components or corresponding compounds can be shaped and / or color can be configured differently from one another. This opens up the possibility for the viewer, who is adequately informed about the composition of the individual particles, to make statements about the composition of the multicomponent mixture and its potential effect.
  • the method for producing the granules figuratively predetermined and shaped according to the invention is based on the information in EP-B-0 486 592, the disclosure of which is hereby also expressly made the subject of the present invention disclosure. Described in this basic property right for the production of densified multi-substance mixtures of the subject area concerned according to the invention by means of extrusion and knockdown granulation with subsequent rounding, granular, extruded detergents or cleaning agents with bulk densities above 600 g / 1, the anionic and / or non-ionic surfactants in amounts of at least 15% by weight and up to about 35% by weight.
  • a solid, free-flowing premix which contains a plasticizer and / or lubricant, is extruded in the form of strands at high pressures of between 25 and 200 bar, the strand is cut to the predetermined granule dimension after exiting the hole shape by means of a cutting device and then the rounding step subjected to ball formation.
  • the method according to the invention is based on the disclosure of this prior publication.
  • the strand pressed by hole shapes of the desired figurative design is comminuted by knock-off granulation, taking into account the previously defined ratio numbers of (L) / (l).
  • the granulate thus formed is now dried without substantial rounding off.
  • This drying is preferably carried out in the fluidized bed.
  • General technical knowledge applies here to the process parameters to be used in the individual case.
  • This older property right describes the possibility of combining a comparatively coarse and in particular spherical core of the multi-material material with additionally required fine fractions of the multi-material mixtures in the sense of shell agglomeration.
  • the fine fractions are used as a coating substance with the use of a preferably cold water-soluble binder on a pre-formed, relatively coarse-particle carrier core of the multicomponent mixture solidified.
  • the teaching according to the invention extends the disclosure of the above-mentioned application according to DE 195 24 287.4 (H 1988) in such a way that the primary material produced in a predetermined figurative embodiment is now used as the carrier core, at least with the fine grain fractions of the multicomponent mixture (coating substance) still required, using the water-soluble binder ( Binder) is firmly bonded.
  • Binder water-soluble binder
  • carrier grain designed according to the invention in a figurative manner is also referred to as "core material”.
  • envelopeing substance The more finely divided components applied to at least a portion of the surface of the core material are referred to as "enveloping substance” and the binder used to solidify them, which is solid at room temperature and preferably also soluble in cold water, is referred to as "binder”.
  • the teaching according to the invention provides that at least a predominant part of the multicomponent mixtures which form gel and / or only slowly dissolve when water enters, are components of the coating substance, these components being incorporated into the coating substance with a predeterminable individual particle size.
  • Their cohesion is here due to the moderately elevated temperatures that occur at room temperature and in practice solid binder guaranteed. If water enters the binder, it will dissolve at the usual cold tap water.
  • the slowly soluble and possibly gelling solid particles isolated and separated from one another by the binder in the coating substance disperse in the liquor without coagulating or in any other way impairing the flushing-in process and / or the washing process.
  • This process of disintegration of the coating substance into individualized fine particles can be promoted almost arbitrarily by the additional measures described below - for example the use of dispersing and / or dissolving aids.
  • the nature and, in particular, the solubility of the core material, which is present as a highly compressed material, are chosen so that there are no obstacles to the dissolvability and dispersion of the multicomponent mixture.
  • any fine-particle to dust-like components can be introduced and solidified, in particular in the coating substance, which, after their release by the primary step of dissolving the binder, can then perform the sub-task they are to do as part of the washing and cleaning process. It immediately makes sense that not only selected individual components are suitable as constituents of the coating substance, in particular any selected and compiled multicomponent compounds can be used here, which are separated from neighboring particles in the form of the preferably spherical dry material and are thus protected against undesired interaction.
  • Such fine-particle multicomponent compounds in the coating substance can be coordinated with one another in such a way that predetermined technical effects can take place in an optimized form when and / or after their dissolution in the wash liquor.
  • the compilation of the solid core material - the carrier grain - is also variable and selectable within a comparatively wide range within the multicomponent mixtures available here.
  • the selection of the component (s) is dominated here on the one hand by the requirement of sufficient dissolvability in the course of the washing process - without, for example, triggering difficulties due to the formation of gels - and on the other hand by overarching concepts of a washing and cleaning process that is multi-stage, for example with regard to the pH value of the washing liquor.
  • the carrier grain can consist of a specifically selected component, but in particular also of appropriately selected and compressed multicomponent mixtures. Further details can be found in the following details on the teaching according to the invention.
  • the core material - also referred to as "carrier grain” -
  • the coating substance or the components to be used as coating substance and finally the binder / binder for the bowl-shaped covering of the carrier grain.
  • This inner core of the respective individual grain of the multicomponent mixture according to the invention can in turn be of 1-component or multicomponent design. Since, as a rule, a substantial proportion - preferably the predominant proportion - of the total grain is formed by the carrier grain, its sufficient compaction is a determining factor. Bulk densities of at least 450 g / 1 and in particular of at least 500 to 600 g / 1 are preferred for the core material. Upper limits can be, for example, at 1,300 to 1,500 g / 1 or also lie above it. Nonetheless, the predeterminable water solubility of this core material is adjustable.
  • the core material makes up at least about 35 to 40% by weight of the total mixture.
  • the amount by weight of the core material is at least about 50% by weight of the total mixture, with particular importance being able to be in the range from about 55 to 90% by weight - here as well, based on the total, as before Multi-component mix
  • the core material is 1-component or multi-component and is formed at least substantially by water-soluble and / or finely dispersed water-insoluble inorganic and / or organic components of conventional washing and cleaning agents.
  • Corresponding builders and / or cobuilders, alkalizing agents, temperature-stable bleaching agents based on hydrogen peroxide, such as perborate compounds, may be mentioned here by way of example only from the field of textile detergents.
  • Further examples are at least largely gelling-free soluble surfactant compounds, in particular corresponding anionic surfactants and / or nonionic surfactants, but also a large number of other customary small components made of textile detergents, which can be safely exposed to the stresses of a sufficient compression step, for example by extrusion.
  • the carrier grain in the sense of the invention can be constructed from the group of valuable materials which are provided as components for the extrusion in the earlier German patent application DE 195 19139 (H 1795) mentioned above and there with other non-extruded granular components of the Detergent and cleaning agent mixtures are mixed.
  • the individual components should be soluble and / or finely dispersed insoluble in the aqueous phase.
  • inorganic soluble or finely dispersed insoluble detergent components such as main builder components, for example zeolite compounds of the Zeoiith A, X and / or P type, alkalizing agents such as soda and water glass, sufficiently stable carrier salts for hydrogen peroxide, for example sodium perborate salts, but also inorganic salts as auxiliary components, for example Sodium sulfate.
  • Suitable organic components can be sufficiently soluble anionic surfactants, for example of the alkylbenzoisulfonate type, or also comparatively short-chain alkyl sulfate salts.
  • Nonionic surfactant compounds in limited quantities, which in particular combine fatty alcohol residues with oligo-EO residues, are also suitable mixture components for the core material. Compounds of this type are generally flowable components at room temperature and, accordingly, are only mixed into the solid core material in limited amounts. Soap as a further surfactant compound is also a suitable component for the construction of the core material.
  • organic mixture components of the carrier grain are, for example, cobuilder components which, when mixed with the main builder component, form the builder system.
  • cobuilder components which, when mixed with the main builder component, form the builder system.
  • Typical examples of this are compounds of the type of trisodium citrate and / or polymeric polycarboxylates, such as sodium salts of polyacrylic acid or polymethacrylic acid, their copolymers and / or their copolymers with maleic acid.
  • constituents of the core material can be readily water-soluble and / or solubilizing organic components such as polyethylene glycol and / or its derivatives, which in turn are multifunctional in the production of the high-density preparation forms of the core material and its redissolution in the aqueous fleet. But also small components, which can be used under the comparatively harsh conditions of compression of the core material.
  • Carrier material is harmless, can be part of the core material / carrier grain.
  • the well-known brighteners from the field of textile detergents are only mentioned here as examples.
  • the coating substance can be bonded directly to the carrier grain.
  • the multi-stage textile washing with timing of the introductory work stage (s) should be mentioned here only as an example.
  • Separating layers of the type concerned here can also have a completely different practical meaning: with a suitable selection of the separating layer material, this can promote or accelerate the dissolution of the carrier grain in the aqueous liquor. This can be particularly valid for those carrier materials that are not free from gel-forming surfactant compounds and that have formed a solution-inhibiting gelled surfactant layer in the production of the carrier material at least in the outer shell of the carrier grain.
  • the immediate application of the coating substance to the carrier grain will be provided.
  • the coating substance can be applied in one coat or in multiple coats.
  • the coating substance applied to the carrier grain consists, on the other hand, of the solid valuable substances and possibly auxiliary substances, which are generally more finely divided than the carrier grain, the flowable valuable substances and / or auxiliary substances to be mixed therewith, as well as the one used as agglomeration aid in cold Binder soluble in water and solid at room temperature.
  • This last component is described in detail in a separate treatise below, so that only the valuable and, if necessary, auxiliary substances of the coating substance are discussed here, which are solidified on the carrier grain by means of the binder.
  • One or more of the following representatives can in particular be present as solid components of the coating substance: dust and / or fine particles or portions of the core material comminuted to fine particles; slowly soluble and / or gelling components in the form of selected 1-substances and / or in the form of pre-formed multi-substance compounds; usual components, in particular also small components of detergents and cleaning agents, insofar as they are not to be exposed to the working conditions of the compression of the core material; if necessary, quickly soluble components in cold water for the rapid conditioning of the washing liquor and / or the items to be cleaned in an early phase of the washing process; Reactive components for the subsequent reaction with further reactive components of the multicomponent mixture, which are to be stored with sufficient certainty in the storage in the solid matter from the corresponding reactive components.
  • the various groups shown here for the solid components of the coating substance are explained below by way of example. Taking general knowledge into account This leads to further teachings for the structure of the material mixtures according to the invention.
  • the solid components of the coating substance are formed by the core material or at least by substantial portions of the core materials.
  • the shell substance differs from the core material in the size of the solid particles to be compared with one another.
  • This embodiment can become important, for example, if mixtures of detergents and cleaning agents known per se are to be converted into specifically shaped spatial bodies. Textile detergent mixtures are still largely offered in the form of free-flowing and free-flowing powders or partial agglomerates, which comprise a very wide range of particles. Textile detergent mixtures of this type in particular frequently contain substantial amounts of dust which can lead to undesired nuisance in practical use.
  • the fines present at the same time promote - for example under conditions of increased air humidity - the undesired clumping process of the dry material mixture which, for example, can hinder or complicate the portioning of household detergents when a detergent package is used for a long time.
  • the proposed form of supply of the multi-material mixtures with a firm and preferably non-sticky outer surface with simultaneous selection of the individual particle size and shape in the millimeter range excludes disabilities of the type described.
  • the teaching according to the invention provides for the use of only slowly soluble and / or gelling components and / or multi-component compounds as a solid component of the coating substance.
  • the teaching according to the invention here provides for the adequately finely dispersed distribution of these portions in the aqueous liquor to be ensured even if no additional measures of solubilization are provided, via the separate storage of these problem portions in the coating substance and the selection and predetermination according to the invention of the individual particle size of these problem ingredients or restrictions on retaliation.
  • a next group of possible mixture components of the coating substance are further conventional components, in particular also small components of detergents and cleaning agents, which should not be exposed to the working conditions of the compression of the core material.
  • Components of this type are often obtained in the form of the finest solid products. Their incorporation into the coating substance eliminates any other problems that may arise. A peculiarity in this connection is already discussed here: Corresponding, in particular dusty or very finely divided components of the multicomponent mixture of valuable substances can be added to the flowable preparation of the binder and dissolved, dispersed and / or emulsified therein and introduced into the coating substance in this form.
  • Another example of possible mixture components of the coating substance is given when the washing and cleaning process is to be carried out in several stages.
  • step-by-step configuration lie in a prior conditioning of the washing liquor and / or the textile goods to be cleaned by using particularly fast-acting binders for the water hardness, the release of particularly strongly wetting and deaerating surfactant components in the early phase of the washing process and the like.
  • teaching according to the invention taking into account the general specialist knowledge, opens up the technically particularly simple possibility of realizing these variants.
  • the amount of coating substance in the embodiments mentioned here is preferably at least about 5 to 10% by weight and in particular at least about 20 to 25% by weight. - Weight? based on the entire multi-component mixture. If the coating substance can also make up more than half of the total mixture, it can nevertheless be assumed in important embodiments that the coating substance forms a maximum of about 50% by weight of the multicomponent mixture. In specific embodiments, for example, corresponding amount ranges of the coating substance of about 20 to 45% by weight and in particular of about 25 to 35% by weight have proven to be very advantageous. as previously defined.
  • the solid components of the coating substance are used with average particle sizes - determined as sieve numbers - which are smaller than the average particle size or the individual particle size of the core material / carrier grain. In this way it is ensured that during the process of coating the core material the shell substance is formed around the carrier core in the sense of a shell agglomeration.
  • Suitable average particle sizes (sieve numbers) for the solid components of the coating substance are - in coordination with the particle sizes of the carrier grain used - in particular the following values: preferably ⁇ than 0.8 mm, preferably ⁇ than 0.6 mm and in particular ⁇ than 0.5 mm.
  • a downward particle size limit for these solid particles of the coating substance is usually out. Even the finest dust particles can be part of the coating substance and / or can be introduced into the coating substance using the flowable binder.
  • fractions of recyclable material which are flowable at room temperature in the solid components of the coating substance.
  • examples here are corresponding liquid nonionic surfactant compounds, but also auxiliaries of a completely different kind.
  • One example here is silicone oils, which are known to be used as a foam brake or as a component of the foam brake in textile detergent mixtures.
  • it can be preferred to prevent premature spreading of such flowable auxiliaries by their preparation and incorporation in the form of selected multicomponent compounds. In this way, an undesirable delay in dissolution of the anionic surfactants, which are already slowly soluble and / or soluble by gelling, can be counteracted.
  • the solid and, where appropriate, flowable valuable and / or auxiliary substances from the coating substance are intimately mixed in the finished preparation form of the figure-shaped granulate in intimate admixture with the binder which is solid at room temperature and, in particular, at least for the most part covered.
  • This binding of the shell substance particles to one another is preferably designed to be sufficiently stable that a noteworthy abrasion of fine material is eliminated under the conditions of transport, storage and use of the granular material.
  • this preferred embodiment of the coating substance in certain embodiments is not mandatory.
  • the application of the finely divided coating substance components to the surface of the carrier core and their connection thereon and to one another, with the use of the binder substance (s) described below, is expediently carried out in such a way that the finely divided components of the coating substance are used by means of granulation or, respectively, a flowable binder phase Agglomeration applied to the carrier grain and solidified there. It is particularly suitable here to carry out this process step in the sense of melt agglomeration or melt granulation, the binder heated and melted to higher temperatures being used as the flowable phase. Details of this are given below.
  • the application method of the coating substance is not restricted to this melting agglomeration or granulation, other wet methods are also suitable.
  • the coating substance can be formed, for example, by using a binder phase in which aqueous preparations - solutions and / or emulsions - of the binder are used. A subsequent drying step then usually follows the formation of the coating layer. See the details below.
  • the binder used in the formation of the coating substance is the binder used in the formation of the coating substance
  • the binder should be a component that is solid at room temperature, but at the same time soluble in cold water. The following also applies:
  • binders which the poly- the functional and initially described importance of this component.
  • binders are, in particular, organic components and, in turn, in particular film-forming organic components which can be used as such or as a mixture with auxiliaries, such as dispersants and / or solubilizers.
  • auxiliaries such as dispersants and / or solubilizers.
  • the components used as binders can have their own function in the context of customary washing and cleaning agent mixtures - for example as cobuilders or as solution and dispersion auxiliaries - but components in the sense according to the invention are also suitable as binders which do not contain any conventional components of washing and / or Are detergents.
  • a particularly suitable class of organic and preferably film-forming binders are water-soluble and / or water-dispersible oligomer and / or polymer compounds of synthetic, semisynthetic and / or natural origin.
  • the relevant literature has dealt in particular with water-soluble polymer compounds from the recent past in detail with reference to the US patent literature.
  • For the purpose of the disclosure here are the most important classes of water-soluble polymer compounds summarized, which can also be used in principle in the sense of the use according to the invention as a binder component - taking into account general specialist knowledge.
  • Acrylamide polymers acrylic acid and / or methacrylic acid polymers and copolymers with further components containing in particular free carboxy groups, such as maleic acid, ethylene oxide polymers or polyethylene glycols and their reaction products, polymer compounds based on carbohydrate compounds of the guar gum type and hetropolysaccharides of the type .des Gum Arabic or gum tragacanth, galactomannan polymers of the locust bean gum type, water-soluble cellulose derivatives, for example of the type of alkyl celluloses, hydroxyalkyl celluloses, carboxymethyl celluloses and the like.
  • polystyrene resin Polyethylenimine, polyvinyl alcohol and water-soluble vinyl alcohol copolymers, polyvinyl pyrrolidone and starch and water-soluble starch derivatives.
  • polymer compounds defined here includes corresponding oligomer compounds of comparatively lower molecular weight in all cases, insofar as these components meet the requirements for the binder and its properties described in the context of the disclosure of the invention. In this respect, too, reference can be made to the general specialist knowledge.
  • binder components which are soluble in cold water and nevertheless solid at room temperature can be used in the field of starch degradation products known as cobuilders and / or (meth) acrylic acid polymer compounds or
  • Copolymer compounds with, for example, maleic acid Another particularly suitable area for the selection of binders or binder components in the sense according to the invention is poly-EO components or corresponding derivatives with reactive and possibly also oleophilic molecular components, insofar as the overall structure of the poly or oligo-EO derivative fulfills the basic conditions defined for the binder.
  • Suitable adhesives are in principle melts, emulsions and, in particular, aqueous solutions of the binder substances, and here in particular corresponding organic oligomer or polymer compounds, components which form adhesive films being of particular importance here.
  • control of the solubility of the binder in cold water can influence the dissolution mechanism of the solid multicomponent mixture according to the invention.
  • very easily water-soluble oligo-EO derivatives - such as those of the fatty alcohol ethoxylates with 30 or 40 EO units in the molecule - can be modified in their dissolving behavior by using them in a mixture with more hydrophobic components - for example fatty alcohols become.
  • the setting of the cold solubility and the solid state at room temperature or only slightly elevated temperatures must also be ensured here.
  • the use of the oleophilic mixture component makes it possible to control the cold water solubility and thus the water solubility as a whole, so that a further possibility of specifically influencing the multicomponent product in its entirety is possible here.
  • Binders are particularly important because, in terms of their molecular structure, they fall within the range of valuable and auxiliary substances for use in detergents and cleaning agents. Any remaining slight stickiness of the dried binder component in the region of room temperature can be compensated in a simple manner by powdering known per se. This can be considered, for example, in the case of binders based on oligo or poly-EO compounds.
  • the flowable binder can in turn also be a carrier for very finely divided and / or dissolved valuable and / or auxiliary substances which are introduced into the multicomponent material together with the carrier.
  • auxiliaries can also be added to the flowable preparation of the binder as additives, in order to influence the visual appearance of the finished goods, and can be added to the coating substance in this form.
  • auxiliaries include dyes, pigments, brighteners and the like. This opens up the technically easy-to-implement option of giving the figure-shaped, dry multi-component mixtures a particularly attractive appearance.
  • the following modification also opens up here: if, for example, soluble and / or finely insoluble dyes or pigments are used to color the outer shell of the multicomponent balls, a corresponding final application shell of the cold water-soluble binder can ensure this finish of the outer surface. In this way it is possible to ensure, if necessary, strongly pronounced visual effects with a minimum addition of optically perceptible auxiliary substance.
  • soluble and / or finely insoluble dyes or pigments are used to color the outer shell of the multicomponent balls, a corresponding final application shell of the cold water-soluble binder can ensure this finish of the outer surface. In this way it is possible to ensure, if necessary, strongly pronounced visual effects with a minimum addition of optically perceptible auxiliary substance.
  • there is an important modification here compared to previously customary detergent preparations with a broad grain spectrum and fine particle size.
  • the respective amount of the binder to be used is also determined, inter alia, by the mixing ratio of core material and coating substance. Nevertheless, generally limited amounts of binder substance are sufficient, the shell agglomeration of the coating substances ensure on the carrier grain. Accordingly, the binder contents in the dry recyclable preparations according to the invention are usually at most about 15 to 20% by weight. and preferably not more than 10% by weight. -% by weight in each case calculated as solid substance and based on the sum of core material and shell substance. In particularly important embodiments, significantly lower binder levels are again provided in the dry material. The amounts of this substance generally do not exceed values of 5 to 6% by weight.
  • the shell agglomeration with a binder melt already with amounts of the binder in the range of approximately 1 to 3% by weight. -% is to be realized.
  • the corresponding solid products are characterized by their complete absence of dust with high abrasion resistance and at the same time excellent washability and solubility in the cold or only moderately heated wash liquor.
  • the technology to be used to apply the coating substance to the carrier grain falls in the area of shell agglomeration or shell aggregation.
  • the suitable production processes are characterized in that the core material in the form of a preformed carrier is agglomerated or granulated enveloping or granulated and the binder solidified in the form of a preformed carrier with the finely divided material of the husk substance in the presence of the binder in flowable preparation form.
  • aqueous preparations of the binder substances are suitable as the flowable binder phase, in particular solutions and / or emulsions being considered here, but the use of the binder as a flowable melt is particularly preferred.
  • the two types of processes mentioned here can be carried out in such a way that the flowable preparation of the binder is sprayed into the material to be agglomerated or granulated, core material and the finely divided solid particles of the coating substance being added to the agglomeration zone at the same time, and preferably here be moved sufficiently.
  • the coating of the carrier grains can be carried out in known manner in rounders, in other mixing devices, but also in the fluidized bed.
  • the core material is sprayed with the sticky flow phase of the binder in a mixer.
  • the particles, which are finer than the core material stick to the surface of the core material, which is moved in a rolling manner, and form the desired shell covering there.
  • Other suitable devices are rounders (spheronizers), coating pears, rotating drums and the fluidized bed apparatuses already mentioned.
  • this coating step is usually followed by a drying step.
  • the use of melts of the binder or binder mixture can dispense with this additional work step.
  • the use of a propellant gas using multi-component nozzles is provided for spraying the flowable binder preparation.
  • the procedure can be as follows: in addition to the binder melt introduced in particular with a propellant gas, a further hot gas phase - usually hot air - is blown into the material to be agglomerated. This enables the short-term setting and optimization of the microclimate in the area of the solid surfaces and thus the optimization of the application and spreading of the binder melt on the surfaces to be brought into contact with one another.
  • the temperature control in particular in the solid material in the course of melting agglomeration, is largely determined by the temperature sensitivity of the materials or parts of materials to be brought into contact with one another.
  • the temperature of the solid material is kept at a maximum in the range up to 45 or 60 ° C. and thus at most in the range of the melting temperature of the binder.
  • the total content of surfactants, including soaps, in the detergents is preferably 15 to 40% by weight and in particular 18 to 30% by weight.
  • Suitable surfactants are - in particular also in the carrier grain - both anionic surfactants and also anionic and nonionic surfactants together.
  • Preferred surfactants of the sulfonate type are C 9 -C 3 alkylbenzenesulfonates, olefin sulfonates, ie mixtures of alkene and hydroxyalkanesulfonates and disulfonates such as are obtained, for example, from C 2 -C 1 -monoolefins with a terminal or internal double bond Sulfonation with gaseous sulfur trioxide and subsequent alkaline or acid hydrolysis of the sulfonation products is considered.
  • alkane sulfonates are suitable, chlorination or Ci ⁇ -cis-alkanes, for example by sulfo sulfoxidation be recovered and subsequent hydrolysis or neutralization.
  • esters of ⁇ -sulfofatty acids for example the ⁇ -sulfonated methyl esters of hydrogenated coconut, palm kernel or tallow fatty acids, and their salts.
  • Sulfated fatty acid glycerol esters are also suitable.
  • Fatty acid glycerol esters are to be understood as the mono-, di- and triesters as well as their mixtures as they are produced by esterification of a monoglycerin with 1 to 3 moles of fatty acid or in the transesterification of triglycerides with 0.3 to 2 moles Glycerin can be obtained.
  • Preferred sulfated fatty acid glycerol esters are the sulfonation products of saturated fatty acids having 6 to 22 carbon atoms, for example caproic acid, caprylic acid, capric acid, myristic acid, lauric acid, palmitic acid, stearic acid or behenic acid.
  • the sulfonation products represent a complex mixture that contains mono-, di- and triglyceride sulfonates with a ⁇ -position and / or internal sulfonic acid grouping.
  • Sulfonated fatty acid salts, glyceride sulfates, glycerol sulfates, glycerol and soaps are formed as by-products. If one starts from the sulfonation of saturated fatty acids or hardened fatty acid glycerol ester mixtures, then the
  • the proportion of the ⁇ -sulfonated fatty acid disalts can be up to about 60% by weight.
  • alk (en) yl sulfates the alkali and in particular the sodium salts of the sulfuric acid half-esters of the C ⁇ 2 -C 8 fatty alcohols, for example from coconut oil alcohol, tallow fatty alcohol, lauryl, myristyl, cetyl or stearyl alcohol or the C 0 -C 2 o-oxo alcohols and those half-esters of secondary alcohols of this chain length are preferred.
  • alk (en) yl sulfates of the chain length mentioned which contain a synthetic, straight-chain alkyl radical prepared on a petrochemical basis and which have a degradation behavior analogous to that of the adequate compounds based on oleochemical raw materials.
  • C 6 -C 8 alk (en) yl sulfates are particularly preferred for washing technology reasons. It can also be particularly advantageous and particularly advantageous for machine detergents to use C 6 -C 8 -alk (en) yl sulfates in combination with lower melting anionic surfactants and in particular with those anionic surfactants which have a lower Krafft point and at relatively low ones Washing temperatures of, for example, room temperature to 40 ° C. show a low tendency to crystallize.
  • the agents therefore contain mixtures of short-chain and long-chain fatty alkyl sulfates, preferably mixtures of C 2 -C 4 fatty alkyl sulfates or C 2 -C 8 fatty alkyl sulfates with C 6 -C 18 fatty alkyl sulfates or C 2 -C 6 fatty alkyl sulfates with C ⁇ 6 -C ⁇ 8 fatty alkyl sulfates.
  • saturated alkyl sulfates but also unsaturated alkenyl sulfates with an alkenyl chain length of preferably Cie to C 22 are used.
  • mixtures of saturated, predominantly C 6 sulfated fatty alcohols and unsaturated, mainly C 8 existing sulfated fatty alcohols are preferred, for example those which are derived from solid or liquid fatty alcohol mixtures of the HD-Ocenol (R) type (commercial product of the applicant).
  • Weight ratios of alkyl sulfates to alkenyl sulfates from 10: 1 to 1: 2 and in particular from about 5: 1 to 1: 1 are preferred.
  • 2,3-Alkyl sulfates which are produced, for example, in accordance with 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 anionic surfactants.
  • the sulfuric acid monoesters of the straight-chain or branched C7-C 2 ⁇ alcohols ethoxylated with 1 to 6 moles of ethylene oxide such as 2-methyl-branched Cg-Cu alcohols with an average of 3.5 moles of ethylene oxide (EO) or C 2 -C 8 -Fatty alcohols with 1 to 4 EO are suitable. Because of their high foaming behavior, they are 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 in particular ethoxylated fatty alcohols.
  • Preferred sulfosuccinates contain C 8 to C 8 fatty alcohol residues or mixtures thereof.
  • Particularly preferred sulfosuccinates contain a fatty alcohol residue, which is derived from ethoxylated fatty alcohols, which in themselves are nonionic surfactants (for a 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.
  • preferred anionic surfactants are alkyl benzene sulfonates and / or both straight-chain and branched alkyl sulfates.
  • soaps can also be used, preferably in amounts of 0.1 to 5% by weight, based on the total agent.
  • saturated fatty acid soaps 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. Coconut, palm kernel or tallow fatty acids, derived soap mixtures.
  • the anionic surfactants and soaps can be present in the form of their sodium, potassium or ammonium salts and as soluble salts of organic bases, such as mono-, di- or triethanolamine.
  • the anionic surfactants are preferably in the form of their sodium or potassium salts, in particular in the form of the sodium salts.
  • the nonionic surfactants used are preferably alkoxylated, advantageously ethoxylated, in particular primary alcohols having preferably 8 to 18 carbon atoms and an average of 1 to 12 moles of ethylene oxide (EO) per mole of alcohol, in which the alcohol radical has a methyl or linear branching in the 2-position may be or may contain linear and methyl-branched radicals in the mixture, as are usually present in oxo alcohol radicals.
  • alcohol ethoxylates with linear residues of alcohols of native origin with 12 to 18 carbon atoms, for example from coconut, palm, tallow or oleyl alcohol, and an average of 2 to 8 EO per mole of alcohol are particularly preferred.
  • the preferred ethoxylated alcohols include, for example, -C 2 -C 4 alcohols with 3 EO or 4 EO, C 9 -Cn- Alcohols with 7 EO, C ⁇ 3 -C 15 alcohols with 3 EO, 5 EO, 7 EO or 8 EO, C ⁇ 2 -C ⁇ alcohols with 3 EO, 5 EO or 7 EO and mixtures of these, such as mixtures of Ci ⁇ -Cn alcohol with 3 EO and C ⁇ 2 -C ⁇ 8 - alcohol with 5 EO.
  • the degrees of ethoxylation given represent statistical averages, which can be an integer or a fraction for a specific product.
  • Preferred alcohol ethoxylates have a narrow homolog distribution (narrow range ethoxylates, NRE).
  • fatty alcohols with more than 12 EO can also be used. Examples of this are tallow fatty alcohol with 14 EO, 25 EO, 30 EO or 40 EO.
  • alkyl glycosides of the general formula RO (G) x can also be used as further nonionic surfactants, in which R is a primary straight-chain or methyl-branched, in particular 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 carbon atoms, preferably for glucose.
  • the degree of oligomerization x which indicates the distribution of monoglycosides and oligoglycosides, is any number between 1 and 10; x is preferably 1.2 to 1.4.
  • 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 having 1 to 4 carbon atoms in the alkyl chain, in particular fatty acid methyl esters, as described, for example, in Japanese patent application JP 58/217598 or which are preferably prepared by the process described in international patent application WO-A-90/13533.
  • Nonionic surfactants of the amine oxide type for example N-coconut alkyl-N, N-dimethylamine oxide and N-tallow alkyl-N, N-dihydroxyethylamine oxide, and the fatty acid alkanolamides can also be suitable.
  • the amount of these nonionic surfactants is preferably not more than that of the ethoxylated fatty alcohols, in particular not more than half of them.
  • Suitable surfactants are polyhydroxy fatty acid amides of the formula (I),
  • the polyhydroxy fatty acid amides are known substances which can usually be obtained by reductive amination of a reducing sugar with ammonia, an alkylamine or an alkanolamine and subsequent acylation with a fatty acid, a fatty acid alkyl ester or a fatty acid chloride.
  • the polyhydroxy fatty acid amides are preferably derived from reducing sugars with 5 or 6 carbon atoms, in particular from glucose.
  • the invention covers the embodiment that the composition of the carrier material on the one hand and that of the coating substance (s) are identical or practically the same, and differ only by the particle sizes of the solid particles present in the respective material fraction differentiate. In important and preferred embodiments, however, there are definitely differences in the composition of the valuable substances or the mixtures of valuable substances - on the one hand in the carrier grain, on the other hand in the coating substance.
  • the granular agents contain an extrudate-based carrier grain, the proportion of the extruded component (s) being 50 to 80% by weight, based on the total agent. It may further be preferred that this extruded component contains surfactants, the anionic surfactant content in the extruded component preferably being not more than 20% by weight and preferably up to 15% by weight, based on the extruded component.
  • the detergents contain extruded carrier components containing surfactants in quantities such that 0.5 to 12% by weight, based on the detergent as a whole, of surfactants are provided.
  • the coating substance (s) contains anionic surfactants or anionic and nonionic surfactants, preferably in amounts of 30 to 95% by weight, based on the coating substance.
  • the coating substance contains anionic surfactants, but is free of non-ionic surfactants.
  • Alkylbenzenesulfonates and / or straight-chain and / or branched alkylsulfates are advantageously used as anionic surfactants.
  • the non-extruded granular and surfactant-containing components are preferably contained in the compositions in such a way that they contain 2 to 30% by weight, in particular 5 to 25% by weight, in each case based on the total agent, of surfactants are provided.
  • the non-extruded components in particular the surfactant-containing components, can have been produced by any of the processes known today, for example by means of spray drying, superheated steam drying, spray neutralization or granulation.
  • components containing anionic surfactants which are preferred by spray neutralization in accordance with the older German patent application P 44 25 968.9 or by granulation and, if appropriate, simultaneous drying in a fluidized bed in accordance with the teaching of international applications WO-A-93/04162 and WO-A- 94/18303 can be obtained.
  • the grain size distribution of the non-extruded surfactant-containing valuable substances - also in the form of granules - should meet the requirement specified above: at least smaller on average than the carrier grain in order to ensure its coating.
  • granules of almost any particle size and particle size distribution can be produced in the fluidized bed.
  • other granular components for example an enzyme granulate, a foam inhibitor granulate, a bleach activator granulate for their incorporation into the coating substance.
  • Suitable enzymes are those from the class of proteases, lipases or lipolytically active enzymes, amylases, cellulases or mixtures thereof. Enzymes obtained from bacterial strains or fungi such as Bacillus subtilis, Bacillus licheniformis, Streptomyces griseus and Humicola insolens are particularly suitable. Proteases of the subtilisin type and in particular proteases which are obtained from Bacillus lentus are preferably used.
  • Enzyme mixtures for example of protease and amylase or protease and lipase or lipolytically active enzymes or protease and Cellulase or from cellulase and lipase or lipolytically active enzymes or from protease, amylase and lipase or lipolytically active enzymes or protease, lipase or lipolytically acting enzymes and cellulase, but especially protease and / or lipase-containing mixtures or Mixtures with lipolytically active enzymes of particular interest.
  • Known cutinases are examples of such lipolytically active enzymes.
  • Peroxidases or oxidases have also proven to be suitable in some cases.
  • the enzymes are preferably adsorbed on carriers and / or embedded in coating substances in order to protect them against premature decomposition.
  • the proportion of the enzymes, enzyme mixtures or enzyme granules can be, for example, about 0.1 to 5% by weight, preferably 0.1 to about 2% by weight.
  • Suitable foam inhibitors are, for example, soaps of natural or synthetic origin, which have a high proportion of C 8 -C 24 fatty acids.
  • Suitable non-surfactant-like foam inhibitors are, for example, organopolysiloxanes and their mixtures with microfine, optionally silanized silica, and paraffins, waxes, microcrystalline waxes and their mixtures with silanized silica or bistearylethylenediamide. Mixtures of various foam inhibitors, for example those made of silicones, paraffins or waxes, are also used with advantages.
  • the foam inhibitors in particular silicone and / or paraffin-containing foam inhibitors, are preferably bound to a granular, water-soluble or dispersible carrier substance.
  • a granular, water-soluble or dispersible carrier substance Mixtures of paraffins and bistearylethylenediamides and mixtures of paraffins and silicones on inorganic carriers are particularly preferred.
  • Granules which contain mixtures of paraffins and silicones in a weight ratio of 1: 1 to 3: 1 are particularly preferred.
  • bleach activators can be incorporated into the preparations.
  • N-acyl or O-acyl compounds which form organic peracids with H 2 0 2 , preferably N, N'-tetraacylated diamines, p- (alkanoyloxy) benzenesulfonates, furthermore carboxylic acid anhydrides and esters of polyols such as gluco- sepenta acetate.
  • Further known bleach activators are acetylated mixtures of sorbitol and mannitol, as are described, for example, in European patent application EP-A-0 -525 239.
  • bleach activators are N, N, N 1 , N'-tetraacetylethylene diamine (TAED), 1, 5-diacetyl-2, 4-dioxo-hexahydro-l, 3, 5-triazine (DADHT) and acetylated sorbitol-mannitol mixtures (SORMAN).
  • the bleach activators contain bleach activators in the usual range.
  • the bleach activators are introduced into the agents according to the invention in amounts such that the agents contain 1 to 10% by weight and preferably 3 to 8% by weight, based in each case on the total agent, of bleach activator.
  • ingredients of the agents according to the invention are preferably inorganic and organic builder substances, bleaching agents, substances which have a positive influence on the washability of oil and fat, graying inhibitors, possibly substances which have an effect on the solubility and dissolving rate of the individual granular components and / or the whole Improving agents, fabric softening agents, optical brighteners, dyes and fragrances as well as alkaline and / or neutral salts in the form of their sodium and / or potassium salts.
  • Suitable inorganic builder substance is, for example, fine crystalline, synthetic and bound water-containing zeolite in detergent quality.
  • the following are particularly suitable special Zeoiith A and / or P and optionally Zeoiith X and mixtures of A, X and / or P.
  • the Zeoiith can be used as a spray-dried powder or as an undried stabilized suspension that is still moist from its production.
  • the Zeoiith in the event that the Zeoiith is used as a suspension, it can contain small additions of nonionic surfactants as stabilizers, for example 1 to 3% by weight, based on Zeoiith, of ethoxylated C 2 -C 8 fatty alcohols with 2 to 5 ethylene oxide groups , -C 2 -C 4 fatty alcohols with 4 to 5 ethylene oxide groups or ethoxylated isotridecanols.
  • Suitable zeolites have an average particle size of less than 10 mm (volume distribution; measurement method: Coulter Counter) and preferably contain 18 to 22% by weight, in particular 20 to 22% by weight, of bound water. Zeolites can be contained both in the extruded components and in the non-extruded components.
  • Suitable substitutes or partial substitutes for phosphates and zeolites are crystalline, layered sodium silicates of the general formula NaMSi x ⁇ 2X + ⁇ "yH 2 0, where M is sodium or hydrogen, x is a number from 1.9 to 4 and y is a number from 0 to 20 is 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 is sodium and x is Assumes values 2 or 3.
  • both ⁇ - and d-sodium disilicate Na2Si 2 0 5 * yH2 ⁇ are preferred, with ⁇ -sodium disilicate being able to be obtained, for example, by the method described in international patent application WO-A-91/08171 Crystalline layered sodium silicates can be contained both in the extruded and in the non-extruded components.
  • Amorphous silicates so-called X-ray amorphous silicates, which 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, can have secondary washing power and can be used as builder substances. It can even 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.
  • Silicates and silicate compounds according to the older German patent application P 44 00 024.3 or silicates and silicate compounds are particularly preferred, for example those which are commercially available under the names Nabion 15 (R1 and Britesil (R) (Akzo-PQ).
  • Particularly preferred are also spray-dried sodium carbonate-sodium silicate compounds, which can additionally contain surfactants, in particular anionic surfactants such as alkylbenzenesulfonates or alkyl sulfates, including 2,3-alkyl sulfates.
  • Amorphous silicates and silicate compounds such as the silicate-carbonate compounds mentioned can also be present in the carrier grain and in the coating substance be included.
  • Sodium silicate with a molar ratio Na 2 0: Si0 2 of 1: 1 to 1: 4.5 is used primarily as amorphous silicate, and preferably from 1: 2 to 1: 3.0 as amorphous silicate with secondary washing power.
  • the content of sodium carbonate and / or sodium bicarbonate in the agents is preferably up to 20% by weight, advantageously between 5 and 15% by weight.
  • the sodium silicate content of the compositions is generally up to 30% by weight and preferably between 2 and 25% by weight.
  • Usable organic builders are, for example, the polycarbonates preferably used in the form of their sodium salts, such as citric acid, adipic acid, succinic acid, glutaric acid, tartaric acid, sugar acids, aminocarboxylic acids, nitrilotriacetic acid (NTA), provided that such use is not objectionable for ecological reasons is, and mixtures of these.
  • Preferred salts are the salts of polycarboxylic acids such as citric acid, adipic acid, succinic acid, glutaric acid, tartaric acid, sugar acids and mixtures of these.
  • Suitable polymeric polycarboxylates are, for example, the sodium salts of polyacrylic acid or polymethacrylic acid, for example those with a relative molecular weight of 800 to 150,000 (based on acid).
  • Suitable copolymeric polycarbonate are, in particular, those of acrylic acid with methacrylic acid and of acrylic acid or methacrylic acid with maleic acid. Copolymers of acrylic acid with maleic acid, which contain 50 to 90% by weight of acrylic acid and 50 to 10% by weight of maleic acid, have proven to be particularly suitable.
  • Their relative molecular weight, based on free acids is generally 5,000 to 200,000, preferably 10,000 to 120,000 and in particular 50,000 to 100,000.
  • Terpolymers and quadropolymers are also particularly preferred, for example those described in DE-A-43 00 772 contain 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 monomeric salts of acrylic acid and 2-A1-alkylallylsulfonic acid as well as sugar derivatives.
  • Suitable builder systems are oxidation products of carboxyl-containing polyglucosans and / or their water- soluble salts, as described, for example, in international patent application WO-A-93/08251 or whose preparation is described, for example, in international patent application WO-A-93/16110.
  • polyaspartic acids or their salts and derivatives are also to be mentioned as further preferred builder substances.
  • polyacetals which can be obtained by reacting dialdehydes with polyolcarboxylic acids which have 5 to 7 carbon atoms and at least 3 hydroxyl groups, for example as described in European patent application EP-A-0 280 223.
  • Preferred polyacetals are obtained from dialdehydes such as glyoxal, glutaraldehyde, terephthalaldehyde and their mixtures and from polyol carboxylic acids such as gluconic acid and / or glucoheptonic acid.
  • the organic builder substances can be used both in the carrier grain and in the coating substance, the use in the carrier grain being preferred.
  • bleaching agents are, for example, sodium percarbonate, peroxypyrophosphates, citrate perhydrates and H 2 0 2 -supplying peracidic salts or peracids, such as perbenzoates, peroxophthalates, diperazelaic 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, with perborate monohydrate being advantageously used.
  • the bleaching agents can be contained both in the carrier grain and in the coating substance of the agent. It is preferred to use perborates over the Introducing carrier grain into the agent, while percarbonates are preferably used in the coating substance.
  • the agents can also contain components which have a positive influence on the oil and fat washability from textiles. This effect becomes particularly clear when a textile is soiled that has already been washed several times beforehand with a detergent according to the invention which contains this oil and fat-dissolving component.
  • the preferred oil and fat-dissolving components include, for example, nonionic cellulose ethers such as methyl cellulose and methyl hydroxypropyl cellulose with a proportion of methoxyl groups of 15 to 30% by weight and of hydroxypropoxyl groups of 1 to 15% by weight, based in each case the nonionic cellulose ether, and the polymers of phthalic acid and / or terephthalic acid or their derivatives known from the prior art, in particular polymers of ethylene terephthalates and / or polyethylene glycol terephthalates or anionically and / or nonionically modified derivatives thereof. These substances can be contained both in the core and in the shell, their content in the shell being preferred.
  • Graying inhibitors have the task of keeping the dirt detached from the fiber suspended in the liquor and thus preventing the dirt from being picked up again.
  • water-soluble colloids of mostly organic nature are suitable, for example the water-soluble salts of polymeric carboxylic acids, glue, gelatin, salts of ether carboxylic acids or ether sulfonic acids of starch or cellulose or salts of acidic sulfuric acid esters of cellulose or starch.
  • Water-soluble polyamides containing acidic groups are also suitable for this purpose. Soluble starch preparations and starch products other than those mentioned above can also be used, for example degraded starch, aldehyde starches, etc. Also Polyvinyl pyrrolidone is useful.
  • cellulose ethers such as carboxymethyl cellulose (sodium salt), methyl cellulose, hydroxyalkyl cellulose and mixed ethers, such as methyl hydroxyethyl cellulose, methyl hydroxypropyl cellulose, methyl carboxymethyl cellulose and mixtures thereof, and polyvinylpyrrolidone, for example in amounts of 0.1 to 5% by weight, based on the means used.
  • These substances can also be contained both in the core and in the shell, but in particular also in the binder.
  • the agents can also contain components which increase the dissolution rate of the individual components and / or of the entire agent.
  • the components preferably used include, in particular, C 8 -C 8 alcohols with 10 to 80 moles of ethylene oxide per mole of alcohol, for example tallow alcohol with 30 EO and tallow alcohol with 40 EO, but also fatty alcohols with 14 EO, and polyethylene glycols with a relative molecular weight between 200 and 2000.
  • Other suitable substances are described, for example, in international patent application WO-A-93/02176.
  • the agents can contain derivatives of diamino-stilbene disulfonic acid or its alkali metal salts. Suitable are, for example, salts of 4,4'-bis (2-anilino-4-morpholino-1,3,5-triazinyl-6-amino) stilbene-2,2'-disulfonic acid or compounds of the same structure which instead of the Mor- pholino group carry a diethanolamino group, a methylamino group, an anilino group or a 2-methoxyethylamino group.
  • Brighteners of the substituted diphenylstyryl type may also be present, for example the alkali salts of 4,4'-bis (2-sulfostyryl) diphenyl, 4, 4'-bis (4-chloro-3-sulfostyryl) diphenyl, or 4- (4-chlorostyryl) -4'- (2-sulfostyryl) diphenyl. Mixtures of the aforementioned brighteners can also be used. Above all, sulfates may be present as neutral salts, and chlorides may also be present, and in particular in cleaning agents.
  • Some fine-grained components can also be used to powder off existing granules, thereby, for example, reducing the stickiness of the granules and increasing the bulk densities of the individual granules and of the entire composition.
  • Suitable surface modifiers of this type are known from the prior art.
  • suitable, finely divided zeolites, silicas, amorphous silicates, fatty acids or fatty acid salts for example calcium stearate, but especially precipitated silicas, mixtures of zeolite and silicas or mixtures of zeolite and calcium stearate are preferred.
  • composition in weight ? Composition in weight ?.
  • the mixed and compacted strand of the extrusion was extruded with a figure-shaped cross-sectional shape.
  • the granules formed from the extruded strand by knock-off granulation were fed to the fluidized-bed drying without prior rounding of the granules formed.
  • this assessment relates to the behavior of the multi-component mixtures in the hand wash test, their performance for machine textile washing is not affected.

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  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Detergent Compositions (AREA)

Abstract

L'invention concerne des mélanges de plusieurs composants solides et comprimés dans le domaine des produits de lavage et de nettoyage, notamment des produits de lavage pour textiles, qui existent au moins principalement sous la forme d'un mélange, dans le domaine des grosses particules, coulants et en vrac. Les mélanges de plusieurs composants de l'invention sont caractérisés en ce que le produit à grosses particules est conçu au moins en partie sous forme de figure géométrique, une plaquette ou un disque, dont le rapport entre la plus grande longueur ou largeur (L) et l'épaisseur moyenne de la plaquette (1) est supérieur à 1,2 et présente de préférence la valeur de 1,5. L'invention concerne en outre le procédé de fabrication de ces mélanges à plusieurs composants conçus à la manière de figures géométriques ainsi que les produits de lavage et de nettoyage correspondants, notamment de produits de lavage pour textiles, qui sont coulants et en vrac, sont résistants à l'abrasion, comportent plusieurs composants et sont exempts de particules de poussière et de particules fines.
EP96929282A 1995-08-29 1996-08-20 Produits de lavage et de nettoyage comprimes et mis en forme de figures geometriques Withdrawn EP0847440A1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE1995131690 DE19531690A1 (de) 1995-08-29 1995-08-29 Figurenhaft ausgestaltete feste und verdichtete Mehrkomponentengemische aus dem Bereich der Wasch- und Reinigungsmittel sowie Verfahren zu ihrer Herstellung
DE19531690 1995-08-29
PCT/EP1996/003654 WO1997008290A1 (fr) 1995-08-29 1996-08-20 Produits de lavage et de nettoyage comprimes et mis en forme de figures geometriques

Publications (1)

Publication Number Publication Date
EP0847440A1 true EP0847440A1 (fr) 1998-06-17

Family

ID=7770630

Family Applications (1)

Application Number Title Priority Date Filing Date
EP96929282A Withdrawn EP0847440A1 (fr) 1995-08-29 1996-08-20 Produits de lavage et de nettoyage comprimes et mis en forme de figures geometriques

Country Status (3)

Country Link
EP (1) EP0847440A1 (fr)
DE (1) DE19531690A1 (fr)
WO (1) WO1997008290A1 (fr)

Families Citing this family (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE69812403T2 (de) 1997-11-10 2004-01-29 Procter & Gamble Verfahren zur herstellung einer waschmitteltablette
WO1999024548A1 (fr) 1997-11-10 1999-05-20 The Procter & Gamble Company Detergent en pastille
ES2244096T3 (es) 1997-11-26 2005-12-01 THE PROCTER & GAMBLE COMPANY Pastilla detergente.
BR9807007A (pt) 1997-11-26 2000-03-14 Procter & Gamble Tablete de detergentes de múltiplas camadas tendo tanto porções comprimiidas quanto não comprimidas
EP1051476A1 (fr) 1998-01-26 2000-11-15 The Procter & Gamble Company Pastille detergente multicouches
DE19848024A1 (de) * 1998-10-17 2000-04-20 Henkel Kgaa Verfahren zur Herstellung extrudierter Formkörper
DE19850983A1 (de) * 1998-11-05 2000-05-11 Henkel Kgaa Wasch- und Reinigungsmittelformkörper mit Entschäumergranulat

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB545118A (en) * 1940-11-02 1942-05-11 Harry William Kilby Pears Improvements in soap products formed by extrusion and subsequent treatment
FR2035622A5 (fr) * 1969-02-18 1970-12-18 Lion Fat Oil Co Ltd
DK132898A (fr) * 1969-10-24
GB2231579A (en) * 1989-05-09 1990-11-21 Unilever Plc Spray-dried detergent
DE4100306A1 (de) * 1991-01-08 1992-07-09 Henkel Kgaa Kornfoermige, leicht loesliche trockenkonzentrate von inhaltsstoffen aus wasch- und/oder reinigungsmitteln und verfahren zu ihrer herstellung

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO9708290A1 *

Also Published As

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DE19531690A1 (de) 1997-03-06
WO1997008290A1 (fr) 1997-03-06

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