WO1997018290A1 - Procede de preparation de detergents et de nettoyants granulaires ou constituants utilises pour les preparer - Google Patents

Procede de preparation de detergents et de nettoyants granulaires ou constituants utilises pour les preparer Download PDF

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Publication number
WO1997018290A1
WO1997018290A1 PCT/EP1996/004841 EP9604841W WO9718290A1 WO 1997018290 A1 WO1997018290 A1 WO 1997018290A1 EP 9604841 W EP9604841 W EP 9604841W WO 9718290 A1 WO9718290 A1 WO 9718290A1
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WIPO (PCT)
Prior art keywords
granules
weight
acid
cleaning agents
components
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PCT/EP1996/004841
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German (de)
English (en)
Inventor
Manfred Greger
Karl-Martin Faeser
Volker Bauer
Norbert Kühne
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Henkel Kommanditgesellschaft Auf Aktien
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Priority to EP96938109A priority Critical patent/EP0876469A1/fr
Publication of WO1997018290A1 publication Critical patent/WO1997018290A1/fr

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2/00—Processes or devices for granulating materials, e.g. fertilisers in general; Rendering particulate materials free flowing in general, e.g. making them hydrophobic
    • B01J2/22—Processes or devices for granulating materials, e.g. fertilisers in general; Rendering particulate materials free flowing in general, e.g. making them hydrophobic by pressing in moulds or between rollers
    • 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 almost spherical to cylindrical detergent or cleaning agent granules, granules which are obtained thereafter, and detergents and cleaning agents which contain these granules
  • Homogenizing devices conventional granulating devices, for example pellet press extruders with one or two shafts, planetary roller extruders and other apparatuses, can be used.
  • a continuously operating twin-screw extruder is preferred.
  • the premix which is plasticized in the extruder, emerges in the form of fine strands through a perforated die plate.
  • the extrudate is then removed by means of a rotating cutting knife into almost spherical to cylindrical granules and this still plastic PMR granulate preferably rounded off in a conventional rounding machine, if necessary using small amounts of dry powder.
  • other active ingredients in particular temperature-sensitive recipe components, can be added to the dried-on granulate, or sprayed on and sprayed on formed grain can be mixed to form a multigrain mixture
  • the extrusion is carried out by means of a circular plate provided with nozzle bores.
  • the hole nozzles can be arranged vertically or horizontally.
  • the fine strands of approximately 0.5 to 5 mm, typically of 0.8, emerging through the hole shapes mm to 2.0 mm diameter are in a hot cut from a single or multi-bladed Rotating cutter head crushed into almost spherical to cylindrical granules.
  • the knife sheaths of the cut-off day device either lie on the nozzle plate with a low contact pressure or form a gap with the plate that is very small compared to the diameter of the perforated nozzles.
  • the homogeneous and solid, ⁇ eselfahiges premix must be of such consistency that it is plastically softened and extrudable under the pressure or under the entry of specific work, but that at the time of the exit from the hole shape, at which no more shear forces act on the system , the viscosity of the system is suddenly reduced in such a way that the extruded strand can be cut, to be precise cut to predetermined dimensions
  • a disadvantage of this prior art method is that energy losses in the form of temperature increases occur under the high working pressure, so that the extruder housing, including the extruder pelletizing head, normally has to be cooled in order to prevent the viscosity of the premix from being so already during the extrusion drops sharply that an actual extrusion is no longer possible. Too high temperature increases also lead to the fact that temperature-sensitive ingredients, for example bleaching agents such as perborate or percarbonate, could not be used without cooling the housing
  • gear press rolls are commercially available.For example, they can be purchased as granulate molding machines, in particular of the G series from Bepex GmbH, Leingart, Federal Republic of Germany.
  • the granulate molding by means of a gear press roll takes place in such a way that the feed material is drawn in by the toothed rolls and through which Nozzle holes are pressed as part of this Press rollers use hollow gears with nozzle holes in the tooth base. Scraper blades fitted inside the wheel cut off the emerging pellets.
  • the compression that can be achieved in addition to shaping is determined by the number of nozzles, the nozzle pressure and the ratio of nozzle diameter to nozzle length.
  • the gear wheels used in the press roll according to the invention for molding the granules are hollow and have nozzle bores in the tooth base.
  • a pressure of 10 to 200 bar, preferably 10 to 130 bar, in particular 30 to 60 bar, builds up within the press rolls, and the scraper blades present in the interior of the wheel or in the outlet of the press roll produce a granulate content of 0.5 to 10 mm, preferably 1 to 5 mm.
  • plasticized premixes are supplied to the gear press rolls, which are 2 to 100% by weight, preferably 10 to 45% by weight and in particular above 10% by weight, for example 15 to 40% by weight .-% returned shares. It is not necessary to grind the coarse particles into smaller grains beforehand.
  • the premix consists at least in part of solid, preferably finely divided, conventional ingredients of detergents and cleaning agents, to which liquid constituents may have been added.
  • the solid ingredients can be spray dried Extracted tower powders, but also agglomerates and granules, the mixture components selected in each case as pure substances which are mixed with one another in the finely divided state, and mixtures of these.
  • liquid ingredients are optionally added and selected plasticizers and / or lubricants are mixed in.
  • aids are of polyfunctional importance in the context of the present invention.
  • they enable the formation of the primary granulate granule by causing the premix to be converted into a mass compressed under high pressure and, if desired, subsequent shaping processing, which consists in particular of the formation of the granule granule formed primarily.
  • subsequent shaping processing which consists in particular of the formation of the granule granule formed primarily.
  • they contribute to the stabilization of the granulate, they maintain its predetermined spatial shape, in particular when mixing with other components, if necessary, during filling, during transport and storage of the granules, and in particular prevent the formation of undesirable, dust-like components.
  • the auxiliaries discussed here can have an intrinsic effect in the washing and cleaning process, in particular in interaction with others
  • plasticizers and / or lubricants used as auxiliaries can be solid, flowable, gel-like or pasty at room temperature without the need to use an additional liquid phase.
  • Preferred plasticizers and / or lubricants are preparations based on surfactant components and / or based on water-soluble or water-emulsifiable or water-dispersible
  • plasticizers and / or lubricants examples include numerous types of the nonionic surfactants commonly used in detergents and cleaning agents.
  • Substances with a low melting point for example higher molecular weight polyethylene glycol ethers with molecular weights between 4,000 and 20,000 can be used as plasticizers and / or lubricants which are solid at room temperature
  • plasticizers and / or lubricants are used which have been produced using limited amounts of auxiliary liquids.
  • Organic liquid phases which are water-soluble or water-miscible are preferably used here.
  • water-based preparations of the plasticizers and / or lubricant preferred
  • the surfactants and / or polymer compounds used as plasticizers and / or lubricants are advantageously introduced into the process in such a concentrated form that the nature of the plastic, slidably compressible mass can be adjusted in small amounts of these auxiliaries
  • the pastes are preferably used in amounts not exceeding 12% by weight, in particular in amounts between 0.5 and 10% by weight, and with particular advantage between 3 and 8% by weight, based on the total mixture. At least 30 are particularly suitable % By weight, preferably 40% by weight pastes and gels
  • surfactant preparations with a surfactant content of at least 50% by weight, in particular from 50 to 70% by weight, are used.
  • the present invention takes advantage of the fact that, in particular, these highly concentrated, aqueous surfactant mixtures show a state that can be described as a paste-like or gel-like preparation form with a lubricant character.
  • the surfactant components so formed form in which the granules formed dry Binder-like top and intermediate layers, which are jointly responsible for the cohesion of the grains can be anionic surfactant salts, in particular sulfates and sulfonates, from the wide range of compounds proposed here for detergents and cleaning agents, optionally in admixture with customary, nonionic compounds Particular importance is to be taken as an example in the production of textile detergents, a feed mixture of at least two solid components (spray-dried granules / fatty alkyl sulfate compound) with or without the addition of sodium piperborate (monohydrate and / or tetrahydrate) with the addition of 2 to 5% by weight of water and 4 to 8% by weight of a 55 to 65% Cg to C 3 alkylbenzenesulfonate paste (ABS paste) instead of the aforementioned combination of spray-dried granules and a fatty alkyl
  • ABS paste 55 to 65% C
  • APG alkyl polyglycoside
  • plasticizers and / or lubricants based on surfactants are mixtures of ABS and APG pastes, as well as mixtures of ABS pastes and ethoxylated C ⁇ to C ⁇ 8 fatty alcohols, mixtures of ethoxylated fatty alcohols and water as well as mixtures of APG ethoxylated fatty alcohol water in the ratio of (0.5 - 1) 1 (1, 5 - 1), in which case the APG content is counted as an active substance and not as a paste
  • polymer compounds in numerous detergents and cleaning agents is common today because the polymer compounds act, for example, as scaffolding substances with the ability to bind the water hardness.
  • polymers with a carboxyl group which in the salt form, for example, as an alkali salt can be present like the sodium or potassium salts of homopolymeric or copolymeric polycarboxylates, for example polyacrylates, polymethacrylates and in particular copolymers of acrylic acid with maleic acid, preferably those composed of 50% to 10% maleic acid.
  • the molecular weight of the homopolymers is generally between 1000 and 100000, that of the copolymers between 2000 and 200000, preferably 50,000 to 120,000, based on the free acid
  • Suitable, albeit less preferred compounds of this class are copolymers of acrylic acid or methacrylic acid with vinyl ethers, such as vinyl methyl ether, methyl esters, Ac rylamide and methacrylamide, ethylene, propylene and styrene, in which the proportion of acid is at least 50%.
  • vinyl ethers such as vinyl methyl ether, methyl esters, Ac rylamide and methacrylamide, ethylene, propylene and styrene, in which the proportion of acid is at least 50%.
  • Polymer compounds used include carboxymethyl cellulose (CMC) and / or methyl cellulose (MC).
  • polymer compounds are distinguished by a pronounced lubricating character, which provides the decisive processing aid in the processes according to the invention.
  • these polymer components dry out in the formation of the granulate granules according to the invention into polymer films which, on the one hand, promote the connection of the grain and, on the other hand, easily return to the state of the solution or emulsification or dispersion when aqueous media are added.
  • liquid phase (s) are used that, when mixed simply, a free-flowing, powdery structure of the premix is retained even after the addition of the plasticizer and / or lubricant.
  • the content of the respective mixture of free water not bound as crystal water or in comparable form in this processing stage is preferably up to 12% by weight, preferably up to 10% by weight and in particular in the range from about 4 to 8% by weight. %. Included in this amount is the amount of water that is entered via the plasticizing aid with a lubricating character. If desired, further solids can also be added to the premix after the addition of the plasticizer and / or lubricant. The total mass is briefly mixed in, a solid, free-flowing premix being obtained which is suitable for feeding the gear press roller used in accordance with the invention.
  • the granules can then be fed to a rounding step as in international patent application WO-A-91/02047.
  • Usual rounding devices such as Marumerizer, but also sieve mills, as are commercially available from Bepex GmbH, for example, can be used here.
  • Sieve mills of this type have the advantage that any coarse particles that may have occurred are reduced to a maximum grain size limit and the fractions of finer granules that are produced in this way can also be returned to the premix.
  • the finally formed granulate granulate is preferably fed to a drying step, for example a fluidized bed dryer, in which, at moderately raised supply air temperatures, in particular up to a maximum of 80 ° C., correspondingly moderate final product temperatures of, for example, between 55 to 60 ° C. are set, but then not exceeded become.
  • a drying step for example a fluidized bed dryer, in which, at moderately raised supply air temperatures, in particular up to a maximum of 80 ° C., correspondingly moderate final product temperatures of, for example, between 55 to 60 ° C. are set, but then not exceeded become.
  • the product is cooled with cold air, for example.
  • the content of free water in the granulate can be reduced.
  • Preferred residual contents of unbound water are about 1% by weight, preferably in the range of about 0.1 to 0.5% by weight.
  • the resulting, very low-dust product can be classified, for example sieved, to remove small coarse particles.
  • the proportion of coma to be set according to the invention is generally above 90%, preferably above 95%, of the granulated material. In some cases it is possible to carry out this drying step directly after the pressing of the primary granulate and thus before the final shaping, if desired, in a rounding device.
  • the "internal drying" of the granules is also possible: by using moisture-binding components in the premix in the short processing time, the plasticizing effect of the liquid components presented can be used. Then, by binding at least partial components of these liquid components through the mixed-in components, the granules are dried "from the inside out", so that the external drying can be shortened or omitted entirely.
  • Components which are able to bind water in the form of stall water are, for example, sodium sulfate and / or sodium carbonate in anhydrous or low-water form or else a zeolite which has been partially freed from water of crystallization
  • the p ⁇ mar-formed and still plastic granule comers can be applied before, during and / or after any rounding off of the further active ingredients, but preferably, for example, sensitive, in particular temperature-sensitive, formulation constituents can also be added to the dried granulate, for example sprayed on and / or be mixed as a separately formed grain with formation of a multigrain mixture.
  • the invention covers both the area of ready-to-use multicomponent mixtures in the form of uniform granulate bodies and also partial products which require recipe completion after mixing with other constituents of the respective detergent and cleaning agent.
  • granule systems are used which represent a combination of granules of different compositions.This way, the storage-stable combination of potentially reactive or at least only partially compatible components is achieved.
  • this is conventional textile detergents, but now in this preparation form at least two Using granulate types in a mixture with one another
  • the bleaching agent component in particular perborate or sodium carbonate containing water from the water, is pelletized with the use of a proportion of the plasticizers and / or lubricants.
  • the zeolite optionally used as detergent builder substance in particular zeolite and / or zeolite P, pressed with the rest of the detergent components.
  • the interaction between peroxy bleach and zeolite which has a substantial influence on the storage stability of the mixed product, as is to be taken into account in powdery preparations, is excluded.
  • the use of granulate systems made of differently composed granules can be used in almost any combination.
  • the granules according to the invention can be recycled, i. that is, they can be used in the first process step in combination with other steps to make the plasticized premix.
  • the material densities in the grain and thus also the bulk density of the granules are largely determined by the working pressures used in pressing the homogenized material through the perforated plates.
  • Bulk densities in the range from 850 to 980 g / l can be set on the basis of commercially available textile detergent formulations, with good flowability and a preferably high, uniform, spherical grain structure.
  • free-flowing granules in the dry state with uniform bulk densities of 950 to 980 g / l were achieved with an average particle size of the spherical granules in the range of, for example, about 1 mm.
  • the method according to the invention is characterized by a very low proportion of returned goods.
  • This portion of the return material after sieving the granules through a 1.6 mm sieve was in each case in the range of at most 10% by weight.
  • sensitive formulation components for example activators for bleaching agents, enzymes, defoamers, in particular silicone defoamers, perfume and the like, can be added to the granules. Even then, detergent products with bulk densities in the range of about 900 g / l are still obtained.
  • the textile detergents which are customary on the market today in the form of free-flowing powders and / or granules generally contain a combination of anionic-surfactant and non-surfactant active detergent components.
  • the anionic surfactant components make up the largest proportion and the nonionic surfactants make up the smaller proportion of the surfactant mixture.
  • textile detergent concentrates with surfactant contents can be up to 35% by weight and preferably in the range from about 15 to 25% by weight.
  • the bleaching agent in particular sodium numperborate in the form of the monohydrate and / or the tetrahydrate, can already be processed in the raw material to be classified and then compressed, without substantial losses of perborate, so that each granulate contains the predetermined amount Granulate content of peroxy bleaching agent
  • the use of spray-dried granules with vanabler admixture is possible.
  • neither spray-dried powders / granules nor pre-formed powders with a bead structure are required to produce the raw materials to be compressed.
  • nonionic surfactants usually used in detergents and cleaning agents are no problem, the pluming effects occurring in the spray drying, see definition in Rompp chemical lexicon, 4 edition, volume 5, page 3488, are omitted.
  • the nonionic surfactants are easily added by incorporation into the mixture of substances before the press step, they can even provide valuable process help in the manner described here as a highly concentrated, aqueous gel or paste
  • the invention relates to universal detergents for textiles which are present in this form of the free-flowing granules with bulk densities above 750 g / l, in particular above 800 g / l, for example in the range from 850 to 950 g / l and in a particularly important one Embodiment are characterized by a uniform particle shape and size.
  • the preferred particle shape is spherical. Preferred particle sizes here are in the range from 0.5 to 10 mm ball diameter, in particular in the range from approximately 1 to 5 mm.
  • the formulation components can correspond to the textile detergents that are commonly used today.
  • Suitable anionic surfactants are, for example, those of the sulfonate and sulfate type.
  • the surfactants of the sulfonate type are alkylbenzenesulfonates (Cg to C 13 alkyl), olefin sulfonates, ie mixtures of alkene and hydroxyalkanesulfonates and disulfonates, such as those obtained from C 2 to C 18 monoolefins with a terminal or internal double bond by sulfonation Gaseous sulfur trioxide and subsequent alkaline or acidic hydrolysis of the sulfonation products.
  • alkanesulfonates which are obtainable from C1 2 - to Ciralkanes by sulfochlorination or sulfoxidation and subsequent hydrolysis or neutralization or by bisulfite addition to olefins, and in particular the esters of ⁇ -sulfofatty acids (ester sulfonates), for.
  • esters of ⁇ -sulfofatty acids esters of ⁇ -sulfofatty acids (ester sulfonates)
  • B. the ⁇ -sulfonated methyl esters of hydrogenated coconut, palm kernel or tallow fatty acids for.
  • Suitable surfactants of the sulfate type are the sulfuric acid monoesters from primary alcohols of natural or synthetic origin, in particular from fatty alcohols, e.g. B. from coconut fatty alcohol, tallow fatty alcohol, oleyl alcohol, lauryl, myristyl, cetyl or stearyl alcohol or the C 10 -C 2 o-oxo alcohols, and those secondary alcohols of this chain length.
  • the sulfuric acid monoesters with 1 to 6 moles of ethylene oxide ethoxylated alcohols, such as 2-methyl-branched C 9 -Cn alcohols with an average of 3.5 moles of ethylene oxide, are also suitable.
  • Preferred fatty alkyl sulfates are derived from fatty alcohol mixtures obtained from coconut oil, palm and palm kernel oil, which additionally contain proportions of unsaturated alcohols, e.g. B. oleyl alcohol, may contain. Mixtures in which the proportion of the alkyl radicals is 30 to 70 find a preferred use % By weight on C 12 to 18 to 30% by weight on C 14 , 5 to 15% by weight on C 16 , less than 3% by weight on C 10 and 0 to 40% by weight on C 18 are distributed. Sulfated fatty acid monoglycerides are also suitable.
  • anionic surfactants are 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 Ci ⁇ fatty alcohol residues or mixtures thereof.
  • Particularly preferred sulfosuccinates contain a fatty alcohol residue which is derived from ethoxylated fatty alcohols, which are nonionic surfactants in themselves.
  • sulfosuccinates the fatty alcohol residues of which are derived from ethoxylated fatty alcohols with a narrow homolog distribution, are particularly preferred.
  • Suitable anionic surfactants are especially soaps, preferably in amounts of 0.5 to 5% by weight.
  • Saturated fatty acid soaps such as the salts of lauric acid, myristic acid, palmitic acid or stearic acid, and in particular from natural fatty acids, e.g. B. coconut, palm kernel or taig fatty acids, derived soap mixtures.
  • the anionic surfactants can be present in the form of their sodium, potassium or ammonium salts and as soluble salts of organic bases, such as mono-, di- or triethanolamine.
  • the anionic surfactants are preferably present in the form of their sodium or potassium salts.
  • the content of anionic surfactants or anionic surfactant mixtures in detergents according to the invention is preferably 5 to 40% by weight, in particular 8 to 30% by weight.
  • Addition products of 1-40, preferably 2-20 moles of ethylene oxide to one mole of an aliphatic compound having essentially 10-20 carbon atoms from the group of alcohols, carboxylic acids, fatty amines, carboxamides and alkanesulfonamides can be used as nonionic surfactants.
  • Liquid ethoxylated and / or propoxylated alcohols which differ from primary alcohols with preferably 8 to 18, are preferably used as nonionic surfactants Derive carbon atoms and an average of 1 to 12 moles of alkylene oxide in which the alcohol radical may be linear or methyl-branched in the 2-position, or may contain linear or methyl-branched radicals in the mixture, as are usually present in oxo alcohol radicals.
  • linear residues of alcohols of native origin with 12 to 18 carbon atoms are preferred, such as. B. from coconut, tallow or oleyl alcohol.
  • C 12 -C 14 alcohols with three moles of ethylene oxide or four moles of ethylene oxide C ⁇ -Cn alcohol with 7 moles of ethylene oxide
  • C 13 -C 15 alcohols with three moles of ethylene oxide five moles of ethylene oxide, seven moles of ethylene oxide or eight moles
  • Ethylene oxide C 12 -C 18 alcohols with three moles of ethylene oxide, five moles of ethylene oxide or seven moles of ethylene oxide or mixtures thereof, such as mixtures of C 12 to C 14 alcohol with three moles of ethylene oxide and C 12 to C 8 alcohol used with five moles of ethylene oxide.
  • 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).
  • NRE narrow range ethoxylates
  • alcohol ethoxylates are preferred which have an average of 2 to 8 ethylene oxide groups.
  • alkyl polyglycosides of the general formula RO (G) x can also be used as further nonionic surfactants, in which R denotes a primary, straight-chain or aliphatic radical with 8 to 22, preferably 12 to 18, C-atoms branched methyl and G denotes Is symbol which stands for a glucose unit with 5 or 6 carbon atoms, preferably for glucose.
  • the degree of oligomerization x which indicates the distribution of monoglycosides or oligoglycosides, is any number between 1 and 10.
  • Suitable surfactants are polyhydroxy fatty acid amides of the general formula
  • R 2 - CO - N - [Z] in which R 2 - CO stands for an aliphatic acyl radical with 6 to 22 carbon atoms, R 3 for hydrogen, an alkyl or hydroxyalkyl radical with 1 to 4 carbon atoms and [Z] for a linear or branched polyhydroxyalkyl radical with 3 to 10 carbon atoms and 3 to 10 Hydroxyl groups.
  • Preferably used as polyhydroxyfatty acid amides are fatty acid alkyl glucamides in which R 3 is hydrogen or an alkyl group, R 2 - CO is the acyl radical of a saturated or unsaturated fatty acid and [Z] is a glucose radical.
  • bleaching agents sodium perborate tetrahydrate, sodium perborate monohydrate. and sodium percarbonate is of particular importance.
  • Other useful bleaching agents are, for example, peroxypyrophosphates, citrate perhydrates and hydrogen peroxide-providing peracid salts or peracids, such as perbenzoates, peroxophthalates, diperazelaic acid or diperdodecanedioic acid.
  • the bleach content of the agents is preferably 5 to 25% by weight and in particular 10 to 20% by weight, with perborate monohydrate or percarbonate advantageously being used.
  • bleach activators can be incorporated into the preparations.
  • these are N-acyl or O-acyl compounds which form organic peracids with hydrogen peroxide, preferably N, N'-tetraacylated diamines, furthermore carboxylic acid anhydrides and esters of polyols such as glucose pentaacetate.
  • the bleach activator content of the bleach-containing agents is in the usual range, preferably between 1 and 10% by weight and in particular between 2 and 8% by weight.
  • bleach activators are N.N.N'.N'-tetraacetylethylene diamine, 1,4-diacetyl-2,4-dioxo-hexahydro-1,3,5-triazine, furthermore carboxylic acid anhydrides and esters of polyols, such as glucose pentaacetate.
  • water-soluble polyglycol ethers with 2 to 7 ethylene glycol ethers in the molecule are also of interest, in particular if they are used together with water-soluble, nonionic or anionic surfactants.
  • Suitable organic or inorganic builders are weakly acidic, neutral or alkaline reacting soluble and / or insoluble components, the calcium ions failures or complex ties.
  • Suitable and, in particular, ecologically harmless substances such as finely crystalline, synthetic water-containing zeolites of the NaA type, which have a calcium binding capacity in the range from 100 to 200 mg CaO / g (according to the specifications in DE 24 12 837), and / or zeolite P are preferred Use.
  • Their average particle size is usually in the range from 1 to 10 micrometers (measurement method: Coulter Counter; volume distribution).
  • Their content is generally 0-40, preferably 10-30% by weight, based on the anhydrous substance.
  • Zeolite NaA is produced in the form of a water-containing slurry (masterbatch), which is subjected to drying, in particular spray drying, using the processes customary today for the production of textile detergents.
  • Their water content is preferably between 19 and 22% by weight. They have practically no particles larger than 30 ⁇ m and preferably consist of at least 80% particles smaller than 10 ⁇ m.
  • Zeolite A and zeolite P are particularly suitable, as are zeolite X and mixtures of A and X and / or P. Quantities and weight ratios that affect the builders are based on the anhydrous active substance in the context of the present invention, unless stated otherwise .
  • Suitable substitutes or partial substitutes for phosphates and zeolite are crystalline, layered silicates of the general formula NaMSi x O 2 _ * ⁇ yH 2 O, where M is sodium or hydrogen, x is a number from 1, 9 - 4 and y is a number from 0 - 20 is.
  • Layered silicates of this type are described, for example, in European patent application 0164514.
  • both ⁇ - and ⁇ -sodium disilicates Na 2 Si 2 ⁇ 5 • yH 2 O are preferred.
  • Further builder substances are amorphous silicates with secondary washing power, for example those according to DE-P44 00 024.3, DE-P44 19 745.4 and DE-P44 46 363.4.
  • zeolite and / or the crystalline sheet silicate and / or the amorphous silicate are preferably used either alone or with a zeolite to crystalline layered silicate or amorphous silicate weight ratio with secondary washing power of 10: 1 to 1: 3 and in particular 3: 1 to 1: 1.
  • Usable organic builders are, for example, polycarboxylates, the polycarboxylic acids preferably used in the form of their sodium salts, such as Citric acid, adipic acid, succinic acid, glutaric acid, aminocarboxylic acid, nitrilotriacetic acid (NTA), provided that such use is not objectionable for ecological reasons, and mixtures of these and (co) -polymeric polycarboxylic acids and polycarboxylates, such as the sodium salts of polyacrylic acids or polymethacrylic acids, For example, those with a relative molecular weight of 800 to 150,000 (based on acid) and in particular those of acrylic acid with methacrylic acid and of acrylic acid or methacrylic acid with maleic acid are preferred.
  • polycarboxylates the polycarboxylic acids preferably used in the form of their sodium salts, such as Citric acid, adipic acid, succinic acid, glutaric acid, aminocarboxylic acid, nitrilotriacetic
  • 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.
  • biodegradable polymers for example those which, according to DE-A-43 00 772, are salts of monomers acrylic acid and maleic acid as well as vinyl alcohols or vinyl alcohol derivatives or according to DE-C-42 21 381 as monomers salts of acrylic acid and 2-alkyiallylsulfonic acid and sugar derivatives.
  • copolymers are those which are described in German patent applications DE-A-43 03 320 and P 44 17 734.8 and which preferably contain acrolein and acrylic acid / acrylic acid salts or acrolein and vinyl acetate as monomers.
  • phosphate can also be used, in particular pentasodium triphosphate, optionally also pyrophosphates such as orthophosphates, which act primarily as precipitants for lime salts.
  • pentasodium triphosphate optionally also pyrophosphates such as orthophosphates, which act primarily as precipitants for lime salts.
  • the phosphate content based on pentasodium triphosphate, is below 30% by weight.
  • agents without a phosphate content are preferably used here.
  • Suitable inorganic, non-complexing salts are the bicarbonates, carbonates, borates or silicates of the alkalis, which are also referred to as washing alkalis; Of the alkali silicates, especially the sodium silicates with a Na 2 O: SiO 2 ratio of 1: 1 to 1: 3.5 can be used (see above).
  • the other detergent components include graying inhibitors (dirt carriers), foam inhibitors, optical brighteners, enzymes, fabric softening substances, colorants and fragrances as well as neutral salts.
  • Graying inhibitors have the task of keeping the dirt detached from the fiber suspended in the liquor and thus preventing graying.
  • Water-soluble colloids of mostly organic nature are suitable for this, for example the water-soluble salts of polymeric carboxylic acids, glue, gelatin, salts of ether carboxylic acids or ether sulfonic acids of starch and the cellulose, ether sulfonic acids or salts of acidic sulfuric acid esters of cellulose or starch.
  • Water-soluble polyamides containing acidic groups are also suitable for this purpose.
  • Soluble starch preparations and starch products other than those mentioned above can also be used, e.g. B. degraded starch, strong aldehyde, etc.
  • Polyvinylpyrrolidone is also useful.
  • carboxymethyl cellulose (sodium salt), methyl cellulose, methyl hydroxyethyl cellulose and their mixtures and polyvinylpyrrolidone, for example in amounts of 0.1 to 5% by weight, based on the composition, are preferably used
  • the foaming power of the surfactants can be increased or decreased by combining suitable types of surfactants, a reduction can also be achieved by adding powerful surfactant-like substances.
  • a reduced foaming capacity which is desirable when working in machines, can often be achieved by combining different types of surfactants, e.g. B of sulfates and / or sulfonates with nonionic surfactants and / or with soaps
  • the foam-dampening effect increases with the degree of saturation and the C number of the fatty acid salt. Soaps of natural or synthetic origin, which have a high proportion, are therefore suitable as foam-inhibiting soaps C 8 -C 24 fatty acids.
  • Suitable non-active foam inhibitors are, for example, organopolysiloxanes and mixtures thereof with microfine, optionally silanized silica and also paraffins, waxes, Mikrok ⁇ stallinwachse and mixtures thereof with silanized silica also of C 12 - to C ⁇ o-alkylamines and Cr to C ⁇ .
  • Bisacylamides derived from dicarboxylic acids can be used.
  • Mixtures of various foam inhibitors for example those of silicones, paraffins or waxes, are also advantageously used.
  • the foam inhibitors are preferably bound to a granular, water-soluble or dispersible carrier substance or are admixed with the plasticizers and / or lubricants
  • the agents can contain enzyme stabilizers.
  • enzyme stabilizers For example, 0.5 to 1% by weight sodium formate can be used. It is also possible to use proteases with soluble calcium salts and a calcium content of preferably about 1.2 % By weight, based on the enzyme, are stabilized.
  • 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. .
  • the detergents can contain, as optical brighteners, derivatives of diaminostilbenedisulfonic acid or its alkali metal salts.
  • Suitable are, for example, salts of 4,4'-bis (2-anilino-4-mo ⁇ holino-1, 3,5-triacin-6-yl-amino) -stilbene-2,2'-disulfonic acid or compounds of the same structure which instead the morpholino group carry a diethanolamino group, a methylamino group, an aniline group or a 2-methoxyamino group.
  • Brighteners of the substituted 4,4'-distyryl-diphenyl type may also be present; for example the compounds 4,4'-bis (4-chloro-3-sulfostyryl) diphenyl. Mixtures of the aforementioned brighteners can also be used.
  • Enzymes from the class of proteases, lipases, cutinases, cellulases and amylases or mixtures thereof are possible. Enzymes obtained from bacterial strains or fungi such as Bacillus subtilis, Bacillus licheniformis or Streptomyces griseus are particularly suitable. Proteases of the Sulbtilis type and in particular proteases obtained from Bacillus Lentus are preferably used in a mixture with other enzymes. The enzymes can be adsorbed on carriers and / or embedded in coating substances in order to protect them against premature decomposition. Their proportion can be about 0.2 to 2% by weight.
  • the salts of polyphosphonic acids, hydroxyethane-1, 1-diphosphonic acid (HEDP) and. Can be used as stabilizers, in particular for per-compounds or enzymes
  • Ethylenediaminetetramethylenephosphonic acid ETMP
  • Diethyle ⁇ triamin- pentamethylenephosphonic acid DTPMP or DETPMP
  • the present invention therefore also relates to granules which have been obtained in accordance with the abovementioned type and which are characterized in that they have a bulk density of above 700 g / l, preferably 750 to 1,000 g / l and in particular 850 to 980 g / l, and as a ready-to-use multi-substance mixture in the form of uniform granules or as a combination of granules of different compositions or as a partial product, which, to complete the recipe, still requires mixing with other components of conventional detergents and cleaning agents.
  • the present invention relates to washing and cleaning agents containing granules of the aforementioned type, which are characterized in that they contain a surfactant content of up to 35% by weight, preferably 15 to 25% by weight.
  • a plastifiable, solid, free-flowing premix was obtained by reacting 61.6% by weight of a spray-dried granulate, 5% by weight of an alkyl sulfate compound, 20.7% by weight.
  • C ⁇ rC 18 fatty alcohol with 7 EO 1.7% by weight polyethylene glycol (PEG 400) 1.8% by weight soda (anhydrous) and 5.6% of a 30% aqueous polycarboxylate solution ( Sokalan ® CP5) mixed and worked up.
  • Composition of the spray-dried granules Composition of the spray-dried granules:
  • the solid components were placed in a batch mixer of 130 l, which was equipped with a cutter head shredder, and then with the mixer running, the premixed nonionic surfactant / PEG 400 mixture and then the carboxylate solution were added and the mixture was mixed for 30 seconds.
  • the premix obtained was free-flowing and could be fed to the granulating system according to the invention, a gear press roll.
  • the inventive Zahnradpreßwalze used as part of the granulation was one of the Bepex GmbH, Germany, under the name granular machine GCS 200/40 available model, typically a flow rate of 0.2 s m per hour in a typical hole nozzle diameter of 1, 5 mm was carried out, product outlet or discharge temperatures of 58 ° C were used. It was not necessary to cool the apparatus.
  • the subsequent batch rounding was carried out optimally within a batch time of 1 min at a rotor peripheral speed of 8 m / s in the presence of 3.2% by weight of zeolite NaA powder. After sieving through a 1.6 mm sieve, a granulate with a granular bulk density of about 820 g / l was obtained in a granulate yield of 90%.
  • the Grobkom could be returned without grinding.

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

Abstract

L'invention concerne un procédé permettant de comprimer des prémix solides coulants, selon lequel le processus peut se dérouler dans des conditions impliquant moins de risques d'altération des produits, comparativement aux procédés similaires classiques. A cette fin, les moules perforés à travers lesquels les prémix sont comprimés, sont disposés dans deux rouleaux de compression à roues dentées tournant en sens contraire et en prise. D'éventuelles fractions à gros grains peuvent le cas échéant être renvoyées sans broyage.
PCT/EP1996/004841 1995-11-15 1996-11-06 Procede de preparation de detergents et de nettoyants granulaires ou constituants utilises pour les preparer WO1997018290A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
EP96938109A EP0876469A1 (fr) 1995-11-15 1996-11-06 Procede de preparation de detergents et de nettoyants granulaires ou constituants utilises pour les preparer

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE19542570.7 1995-11-15
DE1995142570 DE19542570A1 (de) 1995-11-15 1995-11-15 Verfahren zur Herstellung von granularen Wasch- oder Reinigungsmitteln oder Komponenten hierfür

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WO1997018290A1 true WO1997018290A1 (fr) 1997-05-22

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EP (1) EP0876469A1 (fr)
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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112138606A (zh) * 2020-10-22 2020-12-29 安徽环态生物能源科技开发有限公司 一种生物质燃料颗粒成型机

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR1569996A (fr) * 1968-04-23 1969-06-06
US3947938A (en) * 1974-01-22 1976-04-06 Iu Conversion Systems, Inc. Roll-pelletizer and rolls therefor for making uniform particle size pellets
EP0363975A1 (fr) * 1988-10-12 1990-04-18 Gebr. Kaiser Maschinenfabrik Dispositif pour obtenir des granules ou pastilles à partir d'une matière fluide
DE4336548A1 (de) * 1992-11-14 1994-05-19 Degussa Verfahren zur Herstellung kugelförmiger Granulate aus pulverförmigen Feststoffen und damit hergestellte granulierte Feststoffe
DE4329064A1 (de) * 1993-08-28 1995-03-02 Henkel Kgaa Gerüststoffkomponente für Wasch- oder Reinigungsmittel
DE4415362A1 (de) * 1994-05-02 1995-11-09 Henkel Kgaa Verfahren zur Herstellung silikatischer Buildergranulate mit erhöhtem Schüttgewicht

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR1569996A (fr) * 1968-04-23 1969-06-06
US3947938A (en) * 1974-01-22 1976-04-06 Iu Conversion Systems, Inc. Roll-pelletizer and rolls therefor for making uniform particle size pellets
EP0363975A1 (fr) * 1988-10-12 1990-04-18 Gebr. Kaiser Maschinenfabrik Dispositif pour obtenir des granules ou pastilles à partir d'une matière fluide
DE4336548A1 (de) * 1992-11-14 1994-05-19 Degussa Verfahren zur Herstellung kugelförmiger Granulate aus pulverförmigen Feststoffen und damit hergestellte granulierte Feststoffe
DE4329064A1 (de) * 1993-08-28 1995-03-02 Henkel Kgaa Gerüststoffkomponente für Wasch- oder Reinigungsmittel
DE4415362A1 (de) * 1994-05-02 1995-11-09 Henkel Kgaa Verfahren zur Herstellung silikatischer Buildergranulate mit erhöhtem Schüttgewicht

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112138606A (zh) * 2020-10-22 2020-12-29 安徽环态生物能源科技开发有限公司 一种生物质燃料颗粒成型机

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DE19542570A1 (de) 1997-05-22
EP0876469A1 (fr) 1998-11-11

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