EP0486592A1 - Fabrication de granules comprimes pour produits de lavage. - Google Patents

Fabrication de granules comprimes pour produits de lavage.

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Publication number
EP0486592A1
EP0486592A1 EP90912777A EP90912777A EP0486592A1 EP 0486592 A1 EP0486592 A1 EP 0486592A1 EP 90912777 A EP90912777 A EP 90912777A EP 90912777 A EP90912777 A EP 90912777A EP 0486592 A1 EP0486592 A1 EP 0486592A1
Authority
EP
European Patent Office
Prior art keywords
granules
weight
water
premix
mixture
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
EP90912777A
Other languages
German (de)
English (en)
Other versions
EP0486592B1 (fr
Inventor
Franz-Josef Carduck
Hubert Pawelczyk
Wilfried Raehse
Jochen Jacobs
Eduard Smulders
Guenther Vogt
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Henkel AG and Co KGaA
Original Assignee
Henkel AG and Co KGaA
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from DE19893926253 external-priority patent/DE3926253A1/de
Priority claimed from DE4010533A external-priority patent/DE4010533A1/de
Application filed by Henkel AG and Co KGaA filed Critical Henkel AG and Co KGaA
Publication of EP0486592A1 publication Critical patent/EP0486592A1/fr
Application granted granted Critical
Publication of EP0486592B1 publication Critical patent/EP0486592B1/fr
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/0047—Detergents in the form of bars or tablets
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D11/00—Special methods for preparing compositions containing mixtures of detergents
    • C11D11/0082—Special methods for preparing compositions containing mixtures of detergents one or more of the detergent ingredients being in a liquefied state, e.g. slurry, paste or melt, and the process resulting in solid detergent particles such as granules, powders or beads
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/0047—Detergents in the form of bars or tablets
    • C11D17/0065—Solid detergents containing builders
    • C11D17/0073—Tablets
    • 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 compacted granules, the granules obtained by using the process and storage-stable and free-flowing detergent concentrates containing them and having a long shelf life.
  • the prerequisites for such a modification of the recipe are understandably that, on the one hand, the washing and cleaning-technical performance required by the consumer is at least maintained compared to the products currently available on the market, but on the other hand, the storage stability of pourable and pourable products is guaranteed. Like through one extensive state of the art is documented, the fulfillment of this requirement profile poses not inconsiderable technological problems.
  • German patent application 20 50 560 a process for the production of particulate detergents and cleaning agents ("Nuform") with bulk densities between 500 and 900 g / l is known, in which a premix compresses a very specific composition "under pressure” and then is extruded. No information was given regarding the amount of pressure to be applied. In order to prevent the strands from sticking together, they must be cooled by means of an air stream before they are then shredded into pieces of a certain length. The bulk density is inversely proportional to the length of the pieces.
  • German patent application 21 62 353 describes a process for the production of enzyme granules and detergent granules containing enzymes, which have a bulk density of between 300 and 1,000 g / l.
  • a mechanically pre-processed mass is pressed into a long strand under pressure which is approximately between 7 and 35 bar.
  • they In order to prevent the threads from sticking together to form larger aggregates when they emerge from the extrusion press, they must be "deplastified". This is done either by cooling or by evaporating the moisture, the solvent or the plasticizer (surface hardening). Only then can the thread strands be broken into smaller sections of the desired length.
  • European patent application 351 937 describes a process for producing detergent and cleaning agent granules with bulk densities of at least 650 g / l, which in turn is dependent on the formulation.
  • Agents containing 12 to 70% by weight of surfactants must contain at least 15% by weight of water-soluble, crystalline inorganic salts, and the ratio of crystalline salt: surfactant must not be less than 0.4.
  • the agents are dry mixed and granulated in known mixers.
  • European patent application 352 135 describes a process for the production of granular detergents with bulk densities above 650 g / 1, which assumes that a solid alkaline material is placed in a mixer or granulator with a cutting device and liquid anionic surfactant in the acid form does not exceed at temperatures 55 ° C is added so slowly that the mixture remains solid throughout the neutralization process.
  • the alkaline material must be used in excess. Only after complete neutralization can a liquid binder, for example water, liquid nonionic surfactant or an aqueous polycarboxylate solution, be added to the mixture. The granulation takes place in known mixers and granulators.
  • 3,188,291 discloses the production of soap carriers and detergents in granular form with low bulk densities between about 16 and 480 g / l.
  • the mass is extruded at pressures between about 82 and 165 bar.
  • the mass was too viscous for prints beyond this and could no longer be extruded.
  • the bulk density was too high. This patent thus teaches that low bulk densities are achieved when using higher pressures during extrusion, while the bulk density increases when the pressure is reduced.
  • the object of the invention was to develop a process for the production of compacted granules which are used in detergents and cleaners and in particular in textile detergents and detergent concentrates.
  • the granules should be stable in storage and pourable and free-flowing.
  • the object was to provide a method which allows the shape of the individual, compacted granulate to be predetermined.
  • the invention relates in a first embodiment to the process for the production of compacted granules which are used in washing and cleaning agents.
  • a homogeneous premix is extruded in the form of a strand using hole molds with opening widths of the predetermined granule dimension at high pressures between 25 and 200 bar with the addition of a plasticizer and / or lubricant.
  • the strand is cut to the predetermined granule dimension directly after it leaves the hole shape by means of a cutting device.
  • the application of the high working pressure causes the premix to be plasticized during the formation of the granulate and ensures the cutting ability of the freshly extruded strands.
  • the premix consists at least in part of solid, preferably finely divided common ingredients of detergents and cleaning agents, which may contain liquid components are mixed.
  • the solid ingredients can be tower powders obtained by spray drying, but also agglomerates, the respectively selected mixture components as pure substances which are mixed with one another in a finely divided state, and mixtures of these.
  • liquid ingredients are added, if appropriate, and then the plasticizer and / or lubricant selected according to the invention is mixed in.
  • these aids are of polyfunctional importance.
  • they enable the formation of the primary granulate by causing the premix to be converted into a mass which can be pressed under high pressure, and, if desired, subsequent shaping processing, which in particular consists of rounding off the primarily formed granule.
  • subsequent shaping processing which in particular consists of rounding off the primarily formed granule.
  • they contribute to the stability 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 other mixture components.
  • the plasticizers and / or lubricants used as auxiliaries can be fluid, 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 polymer compounds. Examples of a plasticizer and / or lubricant that can be used without the use of an additional liquid phase are numerous types of the nonionic surfactants commonly used in detergents and cleaning agents.
  • 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.
  • aqueous preparations of the plasticizers and / or lubricants are 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 properties of the plastic, slidably compressible mass can be adjusted even with small amounts of these auxiliaries.
  • the pastes are preferably used in quantities of not more than 12% by weight, in particular in quantities of between 0.5 and 10% by weight, and with particular advantage between 3 and 8% by weight, based on the total mixture, used. At least 30% by weight, preferably at least 40% by weight pastes and gels are particularly suitable.
  • surfactant preparations with a surfactant content of at least 50% by weight, in particular 50 to 70% by weight, are used.
  • the invention takes advantage of the fact that, in particular, these highly concentrated aqueous surfactant mixtures show a state that is in the form of a pasty or gel-like preparation Lubricant character can be called.
  • the surfactant components thus introduced form cover and intermediate layers which act like binders and which are jointly responsible for the grain cohesion.
  • 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, can be of particular importance.
  • a mixture of at least two powder components tower powder / carrier bead
  • sodium perborate monohydrate and / or tetrahydrate
  • % of a 55 to 65% Cg-C ⁇ alkylbenzenesulfonate paste named.
  • Equally preferred is the use of 3 to 8% by weight of a 50 to 60% by weight aqueous paste of an alkyl polyglycoside (APG) of the general formula R0 (G) x , in which R is a primary straight-chain or in 2 Position methyl-branched aliphatic radical with 8 to 22, preferably 8 to 18 carbon atoms, G is a symbol which represents a glycose unit with 5 or 6 carbon atoms, and the degree of oligomerization x is between 1 and 10.
  • APG alkyl polyglycoside
  • plasticizers and / or lubricants on a tenside basis are mixtures of ABS and APG pastes, and mixtures of ABS pastes and ethoxylated Cg-Ciß fatty alcohols, mixtures of ethoxylated fatty alcohols and water, and mixtures of APG: ethoxylated fatty alcohol: water in the ratio 0.5-1: 1-1.5: 1, the APG content being calculated in this case as an active substance and not as a paste.
  • polymer compounds in numerous washing and cleaning agents is common today, since the polymer compounds act, for example, as scaffolding substances with the ability to bind water hardness.
  • polymers containing carboxyl groups which are also used in the salt form, for. B. present as an alkali salt can, 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 from 50% to 10% maleic acid.
  • the molecular weight of the homopolymers is generally between 1,000 and 100,000, that of the copolymers between 2,000 and 200,000, 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 ethers, vinyl esters, acrylamide or methacrylamide, ethylene, propylene and styrene, in which the proportion of acid is at least 50%.
  • vinyl ethers such as vinyl methyl ethers, vinyl esters, acrylamide or methacrylamide, ethylene, propylene and styrene, in which the proportion of acid is at least 50%.
  • polymer compounds are also used to improve the dirt-carrying capacity of an aqueous washing liquor. Examples include carboxymethyl cellulose (CMC) and / or methyl cellulose (MC).
  • aqueous preparation forms of these polymer compounds are distinguished by a pronounced lubricating character which gives the decisive processing aid in the process according to the invention.
  • these polymer components dry out into polymer films which, on the one hand, promote the cohesion of the granules and, on the other hand, easily change back to the state of the solution or emulsification or dispersion when added in aqueous media in particular.
  • a polymer in particular a copolymer of acrylic acid and maleic acid
  • a plasticizer and / or lubricant it is particularly preferred to use 3 to 8% by weight of a 30 to 50% by weight solution of a polymer, in particular a copolymer of acrylic acid and maleic acid, in water as a plasticizer and / or lubricant. Mixtures of these polymer solutions and the surfactant, in particular anionic, plasticizers and / or lubricants are also advantageous.
  • plasticizers and / or lubricants include gelatin, starch and starch derivatives and polyvinyl alcohol.
  • 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 free water not bound as crystal water or in comparable form in the respective substance mixture 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 proportion of water which is introduced via the plasticizing aid with a lubricating character.
  • 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, preferably free-flowing premix being obtained which is suitable for feeding a homogenization system.
  • Kneaders of any configuration for example twin-screw kneaders, can preferably be selected as the homogenizing device.
  • the intensive mixing process can in itself lead to the desired temperature increase.
  • Moderately elevated temperatures of, for example, a maximum of about 60 to 70 ° C. are generally not exceeded.
  • compliance with lower temperatures for example about 40 to 45 ° C.
  • the premix is mixed and kneaded so intensively that the mixture, which previously appeared solid and dry, became compressed, plastified and shaping compressible mass is worked up. At the same time, the cutting ability of the homogenized mixture is ensured.
  • the free-flowing premix is preferably fed continuously to a twin-screw kneader (extruder), the housing and the extruder granulation head of which are heated to the predetermined extrusion temperature, for example heated to 40 to 60 ° C are.
  • the premix is compressed at pressures from 50 to 200 bar, in particular at pressures from 80 to 180 bar, plasticized, extruded in the form of fine strands through the perforated die plate in the extruder head, and finally the extrudate by means of a rotating cutting knife preferably comminuted to spherical to cylindrical granules.
  • the hole diameter in the perforated nozzle plate and the strand cut length are matched to the selected granule dimension.
  • the production of granules of an essentially uniformly predeterminable particle size succeeds, and in particular the absolute particle sizes can be adapted to the intended use.
  • Absolute particle sizes can be, for example, in the range from a few tenths of a millimeter to a few centimeters, for example in the range from about 0.3 mm up to 1 to 2 cm. In general, however, particle diameters of up to at most 0.8 cm will be preferred.
  • Important embodiments of the invention provide for the production of the uniform granule grain with diameters in the millimeter range, for example in the range from 0.5 to 5 mm and in particular in the range from approximately 0.8 to 3 mm.
  • the length / diameter ratio of the chopped-off primary granules is in the range from about 1: 1 to about 3: 1.
  • the granulation in this first homogenizing process step is, however, not restricted to the processing of the plasticized premix via extruder screws and perforated plates of the type described, which are arranged in the extruder head. Also by similar, conventional granulating devices, for example pellet presses, 1- and 2-shaft extruders, planetary roller extruders, According to the invention, plasticized, compacted and homogenized material can be granulated into granular material.
  • the still plastic, moist primary granulate is first fed to a further shaping processing step.
  • the edges present on the raw granulate are rounded off, so that ultimately spherical or at least approximately spherical granules can be obtained.
  • Dry powders suitable for detergents and cleaning agents can be pulverulent materials or corresponding inert materials.
  • a particularly useful material in this connection is, for example, zeolite powder such as zeolite NaA powder.
  • This final shaping of the still moist granulate from the extruder granulation can be carried out batchwise or continuously in standard rounding machines.
  • Corresponding rounding devices with a rotating base plate are suitable, for example, the desired degree of rounding being able to be set by varying the granulate residence time in the rounding device and / or the speed of rotation of the device plate.
  • the finally formed granulate grain is preferably fed to a drying step, for example a fluidized bed dryer, in which, with moderately raised supply air temperatures, in particular up to a maximum of 80 ° C., corresponding final product temperatures of, for example, between 55 to 60 ° C set, but then not exceeded.
  • a drying step for example a fluidized bed dryer, in which, with moderately raised supply air temperatures, in particular up to a maximum of 80 ° C., corresponding final product temperatures of, for example, between 55 to 60 ° C set, but then not exceeded.
  • the product is cooled, for example, with cold air.
  • Preferred residual amounts of unbound water are up to about 1% by weight, preferably in the range from about 0.1 to 0.5% by weight.
  • the resulting very low-dust Product can be classified to remove small coarse particles formed, for example, sieved.
  • the grain proportion to be set according to the invention is generally above 90%, preferably above 95%, of the granulated material.
  • the "internal drying" of the granules is also possible: by using moisture-binding components in the premix, the plasticizing effect of the liquid components present can be exploited in the short processing time; then by binding at least partial portions of these liquid portions by means of 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 water of crystallization 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 primarily formed and still plastic granules can be loaded with further active ingredients before, during and / or after a rounding, if appropriate.
  • sensitive, in particular temperature-sensitive, formulation constituents can also be added to the dried granulate, e.g. B. sprayed and / or mixed as a separately formed grain to form a multigrain mixture.
  • the invention encompasses both the area of ready-to-use multi-substance mixtures in the form of uniform granules and also partial products which, in order to complete the recipe, also mix with other constituents of the detergent and cleaning agent concerned need.
  • more than 60% by weight and in particular more than 70% by weight of the total mixture of substances are granules obtained by the process according to the invention with a highly compressed and solid grain structure.
  • granule systems are used which represent a combination of granules of different compositions.
  • the storage-stable combination of potentially reactive or at least only partially compatible components is achieved.
  • An example of this are conventional textile detergents, which, however, now use at least two types of granules in a mixture with one another in the new preparation form.
  • the bleaching agent component in particular perborate and sodium carbonate containing water of crystallization, is pelletized with the use of a proportion of the plasticizers and / or lubricants.
  • the zeolite used as detergent builder in particular zeolite NaA, is used in a separate second granulate pressed with the rest of the detergent ingredients. Interactions between perborate and zeolite which have a substantial influence on the storage stability of the mixed product - as are to be taken into account in powdery formulations - are excluded in this way. This possibility of using granulate systems made up of granules of different compositions can be used in almost any combination.
  • the granules according to the invention can be "recycled", i. H. in the first process step they can be used in combination with other substances to produce 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 when the homogenized material is pressed through the perforated plates.
  • Bulk weights in the range from 850 to 980 g / l can be set on the basis of commercially available textile detergent formulations, with good free-flowing properties and a preferably homogeneous, spherical grain structure.
  • free-flowing granules in the dry state with uniform bulk weights of 950 to 980 g / l have been realized with an average particle size of the spherical granules in the range of approximately 1 mm.
  • the method according to the invention is characterized by a very low proportion of return goods.
  • the proportion of return material after sieving the granulate through a 1.6 mm sieve was in each case in the range of at most 3%.
  • sensitive formulation constituents - 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 weights 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 and nonionic detergent active components.
  • the anionic surfactant components make up the larger proportion and the nonionic surfactants make up the smaller proportion of the surfactant mixture.
  • the total surfactant content for powdery, free-flowing household detergents is about 12 to a maximum of 15% by weight, based on the total detergent. This also applies to the detergents with increased bulk density which are currently on the market.
  • the invention allows the use of the described method for the production of detergent concentrates, in particular corresponding concentrates, which are essentially free of adhesive and free-flowing and free-flowing, storage-stable for textile detergents with a significantly increased content of detergent surfactants.
  • textile detergent concentrates with surfactant contents of up to about 35% by weight and preferably in the range from about 15 to 25% by weight can be produced without the fear of sticking and / or product softening, as is the case in the powdery mixtures available on the market Elevation of the surfactant content occur.
  • the goal of space-saving and low-packaging detergent preparations is optimally achieved without making the area more pourable having to leave detergent preparations that are stable in storage and meet all other requirements.
  • the bleach in particular sodium perborate in the form of the monohydrate and / or the tetrahydrate
  • the bleach can already be processed in the raw material to be plasticized and then pressed, without substantial losses of perborate occurring.
  • Each granulate thus contains the predetermined percentage of perborate.
  • the use of spray-dried powders with variable admixtures is possible.
  • neither spray-dried powders nor pre-formed powders with a bead structure are required to produce the raw materials to be compressed.
  • the use or addition of heavy powder of the individual raw materials is not necessary.
  • the processing of the nonionic surfactants commonly used in detergents and cleaning agents is no problem, and the pluming problems that usually occur in spray drying are eliminated.
  • the nonionic surfactants are easily added by incorporation into the mixture before extrusion, they can even be used here highly concentrated aqueous gel or paste provide valuable process help in the manner described.
  • the invention relates to universal detergents for textiles which are present in the new form of the free-flowing granules with bulk densities above 750 g / 1, in particular above 800 g / 1, for example in the range from 850 to 950 g / 1 and in one particularly important 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 about 0.5 to 5 mm ball diameter, in particular in the range from about 0.8 to 2 mm.
  • the formulation components can correspond to the textile detergents that are customary today. The following is general information on the composition of suitable active ingredient mixtures, the components of textile detergents which are common today, in particular, being summarized here.
  • Suitable anionic surfactants are, for example, those of the sulfonate and sulfate type.
  • the surfactants of the sulfonate type are alkylbenzenesulfonates (Cg-Ci5-alkyl), olefin sulfonates, ie mixtures of alkene and hydroxyalkanesulfonates and disulfonates, such as are obtained, for example, from Ci2-C ⁇ 8-monoolefins with a terminal or internal double bond by sulfonating with gaseous Sulfur trioxide and subsequent alkaline or acid hydrolysis of the Receives sulfonation products.
  • Dialkanesulfonates made from are obtainable 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), e.g. B. the ⁇ -sulfonated methyl esters of hydrogenated coconut, palm kernel or tallow fatty acids.
  • Suitable surfactants of the sulfate type are the sulfuric acid monoesters from primary alcohols of natural and synthetic origin, ie from fatty alcohols, e.g. B. coconut fatty alcohols, Taigfettalko ⁇ fetch, oleyl alcohol, lauryl, myristyl, palmityl or stearyl alcohol, or unc * those secondary alcohols of this chain length.
  • the sulfuric acid monoesters of the alcohols ethoxylated with 1 to 6 mol of ethylene oxide, such as 2-methyl-branched Cg-Cn alcohols with an average of 3.5 mol of ethylene oxide, are also suitable.
  • Sulfated fatty acid onoglycerides are also suitable.
  • saturated fatty acids are useful.
  • natural fatty acids e.g. B. coconut, palm kernel or taig fatty acids derived soap mixtures.
  • Preferred are those which are composed of 50 to 100% of saturated C ⁇ 2-Ci8 fatty acid soaps and 0 to 50% of oleic acid soap.
  • anionic surfactants can be present in the form of their sodium, potassium and ammonium salts and as soluble salts of organic bases, such as mono-, di- or triethanolamine.
  • the detergent content according to the invention of anionic surfactants or of anionic surfactant mixtures is preferably 5 to 40, in particular 8 to 30,% by weight.
  • Addition products of 1 to 40, preferably 2 to 20 moles of ethylene oxide with 1 mole of an aliphatic compound having essentially 10 to 20 carbon atoms from the are nonionic surfactants Group of alcohols, carboxylic acids, fatty amines, carboxamides or alkanesulfonamides can be used.
  • water-soluble nonionics In addition to the water-soluble nonionics, non-fully or not completely water-soluble polyglycol ethers with 2 to 7 ethylene glycol ether residues in the molecule are also of interest, in particular if they are used together with water-soluble, nonionic or anionic surfactants.
  • alkyl glycosides of the general formula R-0- (G) x can also be used as nonionic surfactants, in which R is a primary straight-chain or aliphatic radical having 8 to 22, preferably 12 to 18, C atoms and methyl-branched in the 2-position ⁇ indicates that G is a symbol which stands for a glycose unit with 5 or 6 C atoms, and the degree of oligomerization x is between 1 and 10.
  • Suitable and, in particular, ecologically harmless builder 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 information in DE 24 12837) are used with preference.
  • Their average particle size is usually in the range from 1 to 10 ⁇ m (measurement method: Coulter Counter, volume distribution).
  • Their content is generally 0 to 40, preferably 10 to 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.
  • masterbatch water-containing slurry
  • Further builder constituents which can be used in particular together with the zeolites are (co) polymeric polycarboxylates, such as 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 100,000, that of the copolymers between 2,000 and 200,000, preferably 50,000 to 120,000, based on free acid.
  • a particularly preferred acrylic acid-maleic acid copolymer has a molecular weight of 50,000 to 100,000.
  • Suitable, albeit less preferred, compounds of this class are copolymers of acrylic acid or methacrylic acid with vinyl ethers, such as vinyl methyl ethers, in which the proportion of acid is at least 50%.
  • vinyl ethers such as vinyl methyl ethers
  • polyacetal carboxylic acids as described, for example, in US Pat. Nos. 4,144,226 and 4,146,495, and polymeric acids which are obtained by polymerizing acrolein and subsequent disproportionation by means of alkalis and are composed of acrylic acid units and vinyl alcohol units or acrolein units.
  • Usable organic builders are, for example, the polycarboxylic acid preferably used in the form of their sodium salts, such as citric acid and nitrilotriacetate (NTA), provided that such use is not objectionable for ecological reasons.
  • NTA nitrilotriacetate
  • phosphates can also be used, in particular pentasodium tri-phosphate, optionally also pyrophosphates and orthophosphates, which act primarily as precipitants for lime salts.
  • the phosphate content based on pentasodium triphosphate, is below 30% by weight. However, agents without a phosphate content are preferably used.
  • 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 ⁇ : Si ⁇ 2 ratio of 1: 1 to 1: 3.5 can be used.
  • the other detergent ingredients include graying inhibitors (dirt carriers), foam inhibitors, bleaching agents and bleach activators, optical brighteners, enzymes, fabric softening agents, dyes and fragrances as well as neutral salts.
  • Graying inhibitors have the task of keeping the dirt detached from the fiber suspended in the liquor and thus preventing graying.
  • Water-soluble colloids are suitable for this, such as, for example, the water-soluble salts of polymeric carboxylic acids, glue, gelatin, salts of ether carboxylic acids or ether sulfonic acids of starch or cellulose or salts of acidic sulfuric acid esters of cellulose or starch.
  • Water-soluble polyamides containing acidic groups are also suitable for this purpose.
  • Soluble starch preparations and starch products other than those mentioned above can also be used, e.g. B. degraded starch, aldehyde starches, etc.
  • Polyvinylpyrrolidone is also useful.
  • Carboxymethyl cellulose (sodium salt), methyl cellulose, methyl hydroxyethyl cellulose and mixtures thereof 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 non-surfactant-like organic substances.
  • a reduced foaming power, which is desirable when working in machines, is often achieved by combining different types of surfactants, e.g. B. of sulfates and / or sulfonates with nonionics and / or with soaps. Soap rises the foam-suppressing effect with the degree of saturation and the C number of the fatty acid residue. Soaps of natural and synthetic origin that contain a high proportion of cig - ⁇ - fatty acids are therefore suitable as foam-inhibiting soaps.
  • Suitable non-surfactant-like foam inhibitors are organopolysiloxanes and their mixtures with microfine, optionally silanized silica, paraffins, waxes, microcrystalline waxes and their mixtures with silanized silica.
  • Bisacylamides derived from Ci2-C20 _A ⁇ * ⁇ y ⁇ a ' ' nen and C2-Cö-dicarboxylic acids are also useful.
  • Mixtures of different foam inhibitors are also advantageously used, e.g. B. from silicone and paraffins or waxes.
  • the foam inhibitors are preferably bound to a granular, water-soluble or dispersible carrier substance or are admixed with the plasticizer and / or lubricant.
  • sodium perborate tetrahydrate NaB02 • H2O2 • 3 H2O
  • sodium perborate monohydrate NaB ⁇ 2. H2O2
  • Other bleaching agents that can be used are, for example, peroxycarbonate (a2CO3. 1.5 H2O2), peroxypyrophosphates, citrate perhydrates and H2O2-providing peracidic salts or peracids, such as perbenzoates, peroxaphthalates, diperazelaic acid or diperdodecetoacetic acid.
  • bleach activators can be incorporated into the preparations.
  • these are N-acyl or O-acyl compounds which form organic peracids with H2O2, preferably N, N'-tetraacylated diamines, such as N, N, N ', N'-tetraacetylethylenediamine, furthermore carboxylic acid anhydrides and esters of polyols such as glucose pentaacetate.
  • the detergents can contain, as optical brighteners, derivatives of diaminostilbenedisulfonic acid or its alkali metal salts.
  • B salts of 4,4'-bis (2-anilino-4-morpholino-l, 3,5-triazin-6-yl-amino) -stilbene-2,2'-disulfonic acid or Compounds of the same structure which carry a diethanolamino group, a methylamino group, an anilino group or a 2-methoxyethylamino group instead of the morpholino group.
  • brighteners of the substituted 4,4'-distyryl-diphenyl type can be present; z.
  • B the compound 4,4'-bis (4-chloro-3-sulfostyryl) diphenyl. Mixtures of the aforementioned brighteners can also be used.
  • Enzymes from the class of proteases, lipases and amylases or their mixtures are possible. Enzymatic active ingredients obtained from bacterial strains or fungi such as Bacillus subtilis, Bacillus licheniformis and Streptomyces griseus are particularly suitable. The enzymes can be adsorbed on carriers and / or embedded in coating substances in order to protect them against premature decomposition.
  • the salts of polyphosphonic acids such as l-hydroxyethane-1,1-diphosphonic acid (HEDP) and aminotrimethylenephosphonic acid (ATP) or diethylenetriamine-pentamethylenephosphonic acid (DTPMP or DETPMP) come into consideration as stabilizers, in particular for per-compounds and enzymes.
  • HEDP l-hydroxyethane-1,1-diphosphonic acid
  • ATP aminotrimethylenephosphonic acid
  • DTPMP or DETPMP diethylenetriamine-pentamethylenephosphonic acid
  • the first blend component was a spray dried powder
  • Acrylic acid copolymer (Sokalan CP ⁇ ( R )) 10% by weight
  • Surfactant mixture I consisted of Na-dodecylbenzenesulfonate (ABS) and of tallow fatty alcohol reacted with 5 ethylene oxide groups (E0) in a ratio of 11.5: 1.
  • the second mixture component was a carrier bead containing nonionic surfactant, which was composed of the following main components:
  • Ci2-C ⁇ 8 fatty alcohol with 5 E0 22% by weight
  • Acrylic acid copolymer (Sokalan CP5 ( R )) 3% by weight
  • the free-flowing material thus obtained was fed to the homogenizing compression and plasticization.
  • the mass formed was extruded in the form of a strand, chopped into cylindrical granulate particles, rounded off and dried.
  • the tower powder (TP) and the carrier bead (TB) were placed in a batch mixer (20 liters) equipped with a cutter head shredder and 0.5 min. mixed. With the mixer and cutter head chopper running, the required amount of water and then the entire ABS paste were pumped in via a slot nozzle (2.5 min.). Finally, if necessary, the entire amount of Na perborate monohydrate was added and 1 min. nachge ⁇ mixed. The resulting premix was free-flowing and could be used to feed the continuous kneader-extruder system.
  • the premix obtained was fed continuously to a 2-screw kneader (extruder), the housing of which, including the extruder pelletizing head, was heated to about 45 to 50 ° C. Under the action of the shear of the extruder screws, the premix was plasticized and then extruded through the extruder head perforated die plate into fine strands (1.0 and 1.2 mm in diameter) which, after the die outlet, were comminuted into cylindrical granules by means of a knock-out knife (Length / diameter ratio about 1, hot cut).
  • extruder 2-screw kneader
  • the warm and moist granules obtained from the extruder granulation were rounded off in batches or continuously in a commercially available rounding device of the Marumerizer type with the addition of zeolite NaA powder as the powdering agent.
  • the desired degree of rounding was set by varying the granulate dwell time in the rounding device and the speed of rotation of the device disc.
  • the moist granules from the rounding device were dried in a discontinuously operating fluidized bed dryer at an air temperature of 75 to 80 ° C. to a product temperature of 55 to 60 ° C. for 15 minutes. After the product had been cooled to 30 ° C. with cold air, a free-flowing product was obtained.
  • the very low-dust product was sieved through a sieve with a mesh width of 1.6 mm.
  • the proportion of return material above 1.6 mm was in the range of maximum 3% in all cases.
  • the sieved gut grain was used as a starting basis for the blending of detergent end products.
  • a tower powder (ABS 9%, calcined soda 25%, zeolite NaA (anhydrous substance) 38%, acrylic acid copolymer 8%, water 15%, the rest of the usual detergent components) was used in one amount of 88.5% by weight with 2.5% by weight of water, 5% by weight of nonionic surfactant based on Ci2-Ci8 fatty alcohol • 5 EO and 4% by weight of 55% ABS Na paste sets and worked up.
  • Free-flowing granules with a bulk density of 950 g / 1 were obtained.
  • Free-flowing tower powder based on the following main components: 22% by weight of surfactant mixture I, 2.5% by weight of sodium soap based on sebum, 15% by weight of calcined soda, 7% by weight of water glass, 26.5% by weight % Zeolite NaA (anhydrous substance), 7.5% by weight acrylic copolymer, 12% by weight water, the rest of the usual co-formulants.
  • Carrier bead based on the following main components: 22% by weight Ci2-Ci8 fatty alcohol • 5 EO, sodium soap based on sebum 2% by weight, Zeolite NaA (anhydrous substance) 55% by weight, acrylic acid copolymer 3% by weight, water 15% by weight.
  • the comminuted and mixed material according to the working instructions from Examples 1 to 5 was mixed with approximately 11% by weight (based on the total mixture) of 60% ABS paste and homogenized.
  • the resulting material was plastically compressed by kneading and pressed to give shape.
  • ABS 12.5% by weight ABS and 7.5% by weight Ci2-Ci8 fatty alcohol • 5 EO, 25% by weight soda, 40% by weight zeolite (anhydrous substance) and 12% by weight % bound water and several small components were prepared in a mixer and then sprayed with 5% by weight of a 55% ABS paste, based on the sum of the mixture and ABS paste.
  • the premix prepared as described above was introduced into the annular space of the pellet press via a screw conveyor.
  • the press consisted of a rotating wooden roller into which radial holes were made, distributed over the entire circumference. A press roll was arranged eccentrically in this ring die. In this experiment, a ring die with a diameter of approx. 80 mm and approx. 500 holes was used. The bore diameter was 1.5 mm.
  • a continuous feeding of the product was achieved through the screw dosing.
  • the product was compacted in the gap between the roller and the die.
  • the pressure defined by the extrudability of the mass was reached, the product was pressed through the radial channels of the die and the entire strand was pushed out by the appropriate length.
  • the strand was cut to a length of 1.5 mm by a knife attached to the outside of the die.
  • the cylindrical granules produced in this way were rounded off in a further process step. This was done by rolling off in a rounding machine. Depending on the residence time (between 15 and 120 seconds) in this rounding device, either rounded or spherical granules were obtained only at the corners.
  • the strength of the granules could be improved by adding 3% by weight of zeolite NaA in the rounding step.
  • Abrasion-resistant and very free-flowing granules with a bulk density of the dry products of 950 g / 1 were obtained.

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

Abstract

Des granulés comprimés constitués de particules d'une dimension préalablement déterminée sont obtenus à partir des prémélanges de constituants, au moins en partie solides, de produits de lavage et de nettoyage avec addition de plastifiants et/ou de lubrifiants solubles, émulsionnables ou dispersibles dans l'eau, les prémélanges étant transfomés en une masse homogène et pressés sous forme de boudins, sous des pressions de 25 à 200 bars, à travers des formes dont les orifices ont un diamètre correspondant à la dimension fixée pour les granulés. A leur sortie des formes, les boudins comprimés sont réduits à la dimension fixée pour les granulés. Le procédé convient pour la fabrication de concentrés stables et non collants, destinés aux produits de lavage et de nettoyage à usage domestique ou industriel sous forme de granulés fortement comprimés pulvérulents et coulants.
EP90912777A 1989-08-09 1990-07-31 Fabrication de granules comprimes pour produits de lavage Expired - Lifetime EP0486592B1 (fr)

Applications Claiming Priority (5)

Application Number Priority Date Filing Date Title
DE19893926253 DE3926253A1 (de) 1989-08-09 1989-08-09 Verdichtete wasch- und reinigungsmittel in granulatform, verfahren zu ihrer herstellung und anwendung des verfahrens zur gewinnung lagerstabil rieselfaehiger waschmittel-konzentrate
DE3926253 1989-08-09
DE4010533A DE4010533A1 (de) 1990-04-02 1990-04-02 Tablettierte wasch- und/oder reinigungsmittel fuer haushalt und gewerbe und verfahren zu ihrer herstellung
DE4010533 1990-04-02
PCT/EP1990/001247 WO1991002047A1 (fr) 1989-08-09 1990-07-31 Fabrication de granules comprimes pour produits de lavage

Publications (2)

Publication Number Publication Date
EP0486592A1 true EP0486592A1 (fr) 1992-05-27
EP0486592B1 EP0486592B1 (fr) 1994-06-15

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EP (1) EP0486592B1 (fr)
JP (1) JPH05500076A (fr)
KR (1) KR927003783A (fr)
AT (1) ATE107352T1 (fr)
DE (1) DE59006160D1 (fr)
DK (1) DK0486592T3 (fr)
ES (1) ES2055441T3 (fr)
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US6409770B1 (en) 1995-12-08 2002-06-25 Henkel Kommanditgesellschaft Auf Aktien Bleaching and washing agents with enzyme bleaching system
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US6200946B1 (en) 1996-04-01 2001-03-13 Henkel Kommanditgesellschaft Auf Aktien Transition metal ammine complexes as activators for peroxide compounds
US6235695B1 (en) 1996-04-01 2001-05-22 Henkel Kommanditgesellschaft Auf Aktien Cleaning agent with oligoammine activator complexes for peroxide compounds
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US6211136B1 (en) 1996-08-31 2001-04-03 Henkel Kommanditgesellschaft Auf Aktien Process for preparing granular detergent components
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US6541233B1 (en) 1997-07-30 2003-04-01 Henkel Kommanditgesellschaft Auf Aktien β-glucanase from a bacillus
US6534471B1 (en) 1998-01-15 2003-03-18 Henkel Kommanditgesellschaft Auf Aktien Method for producing colored detergents and cleaning agents
US6380147B1 (en) 1998-06-03 2002-04-30 Henkel Kommanditgesellschaft Auf Aktien Detergents containing amylase and protease
US6391838B1 (en) 1999-03-31 2002-05-21 Henkel Kommanditgesellschaft Auf Aktien Detergents containing enzymes and bleach activators
US6610752B1 (en) 1999-10-09 2003-08-26 Cognis Deutschland Gmbh Defoamer granules and processes for producing the same
US7199096B1 (en) 1999-11-09 2007-04-03 Cognis Deutschland Gmbh & Co. Kg Detergent tablets
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US6756351B2 (en) 2000-04-18 2004-06-29 Cognis Deutschland Gmbh & Co. Kg Detergents and cleaning agents
US6479452B2 (en) 2000-06-29 2002-11-12 Cognis Deutschland Gmbh & Co. Kg Surfactant granules with an improved dissolving rate comprising alky and alkenyl sulfates
US6616705B2 (en) 2000-09-08 2003-09-09 Cognis Deutschland Gmbh & Co. Kg Laundry detergent compositions
US6620209B2 (en) 2000-09-08 2003-09-16 Cognis Deutschland Gmbh & Co. Kg Laundry detergent compositions
US6649085B2 (en) 2000-11-25 2003-11-18 Clariant Gmbh Cyclic sugar ketones as catalysts for peroxygen compounds
US6746996B2 (en) 2001-01-19 2004-06-08 Clariant Gmbh Use of transition metal complexes having oxime ligands as bleach catalysts
US6897192B2 (en) 2001-07-14 2005-05-24 Clariant Gmbh Process for the preparation of bleach activator granules
US7122511B2 (en) 2001-07-25 2006-10-17 Clariant Gmbh Process for the preparation of bleach activator granules
WO2004027009A1 (fr) * 2002-09-12 2004-04-01 Henkel Kommanditgesellschaft Auf Aktien Produits de lavage ou de nettoyage comprimes sous l'effet d'une pression
US6875734B2 (en) 2003-02-03 2005-04-05 Clariant Gmbh Use of transition metal complexes as bleach catalysts
US8080401B2 (en) 2004-10-01 2011-12-20 Henkel Ag & Co. Kgaa Alpha-amylase variants having an elevated solvent stability, method for the production thereof and detergents and cleansers containing these alpha-amylase variants
US8785365B2 (en) 2004-10-01 2014-07-22 Basf Se Alpha-amylase variants stabilized against dimerization and/or multimerization, method for the production thereof, and detergents and cleansers containing these alpha-amylase variants
US9353361B2 (en) 2004-10-01 2016-05-31 Basf Se Alpha-amylase variants stabilized against dimerization and/or multimerization, method for the production thereof, and detergents and cleansers containing these alpha-amylase variants
WO2007054203A2 (fr) 2005-11-08 2007-05-18 Henkel Ag & Co. Kgaa Systeme pour produire du peroxyde d'hydrogene par voie enzymatique
DE102007016391A1 (de) 2007-04-03 2008-10-09 Henkel Ag & Co. Kgaa Farbschützendes Wasch- oder Reinigungsmittel
DE102007028310A1 (de) 2007-06-20 2008-12-24 Clariant International Ltd. Tensidmischungen mit synergistischen Eigenschaften
DE102008013606A1 (de) 2008-03-11 2009-09-17 Clariant International Ltd. Verfahren zur Herstellung fester Erdalkalimetallsalze sekundärer Paraffinsulfonsäuren
US8426635B2 (en) 2008-03-11 2013-04-23 Clariant Finance (Bvi) Limited Process for preparing solid alkaline earth metal salts of secondary paraffinsulphonic acids
WO2012107187A1 (fr) 2011-02-10 2012-08-16 Clariant International Ltd Utilisation de complexes de métaux de transition en tant que catalyseurs de blanchiment dans des produits détergents et nettoyants
DE102011010818A1 (de) 2011-02-10 2012-08-16 Clariant International Ltd. Verwendung von Übergangsmetallkomplexen als Bleichkatalysatoren in Wasch- und Reinigungsmitteln
DE102014009836A1 (de) 2014-07-03 2016-01-07 Weylchem Wiesbaden Gmbh Natriumsalze sekundärer Alkansulfonate enthaltende Compounds, ihre Herstellung und Verwendung sowie Wasch-, Desinfektion- und Reinigungsmittel enthaltend diese

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US5318733A (en) 1994-06-07
DE59006160D1 (de) 1994-07-21
WO1991002047A1 (fr) 1991-02-21
ES2055441T3 (es) 1994-08-16
EP0486592B1 (fr) 1994-06-15
DK0486592T3 (da) 1994-07-18
ATE107352T1 (de) 1994-07-15
JPH05500076A (ja) 1993-01-14
KR927003783A (ko) 1992-12-18

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