EP0595946A1 - Procede de fabrication de produits de lavage a densite apparente elevee et a vitesse de dissolution amelioree. - Google Patents

Procede de fabrication de produits de lavage a densite apparente elevee et a vitesse de dissolution amelioree.

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Publication number
EP0595946A1
EP0595946A1 EP92916049A EP92916049A EP0595946A1 EP 0595946 A1 EP0595946 A1 EP 0595946A1 EP 92916049 A EP92916049 A EP 92916049A EP 92916049 A EP92916049 A EP 92916049A EP 0595946 A1 EP0595946 A1 EP 0595946A1
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EP
European Patent Office
Prior art keywords
liquid
solid
agents
surfactants
breaker
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Application number
EP92916049A
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German (de)
English (en)
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EP0595946B1 (fr
Inventor
Norbert Kuehne
Hubert Pawelczyk
Jochen Jacobs
Guenther Vogt
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Henkel AG and Co KGaA
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Henkel AG and Co KGaA
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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
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66—Non-ionic compounds
    • C11D1/72—Ethers of polyoxyalkylene glycols
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/06—Powder; Flakes; Free-flowing mixtures; Sheets
    • C11D17/065—High-density particulate detergent compositions
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/37—Polymers
    • C11D3/3703—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/3707—Polyethers, e.g. polyalkyleneoxides

Definitions

  • the invention relates to a process for the production of solid detergents and cleaning agents and to the detergents and cleaning agents produced by this process, which are distinguished by an improved dissolving rate, in particular at low temperatures.
  • Solid detergents and cleaning agents with a high bulk density i.e. Agents with a bulk density above 500 g / 1 often have a lower dissolving rate due to their compact shape and the resulting lower surface area, especially at low temperatures around 15 to 60 ° C, than agents with a comparable composition, but have a bulk density of, for example, only 300 g / 1.
  • EP 208534 describes spray-dried granules with improved solute content. This is achieved in that the aqueous slurry which is spray dried contains polyacrylate and in particular a mixture of polyacrylate, polyethylene glycol and nonionic surfactant.
  • the object of the invention was to produce a solid washing and cleaning agent with a high bulk density, which contains conventional ingredients, including ethoxylated alcohols as nonionic surfactants, and which has an improved dissolution rate at temperatures between 15 and 60 ° C.
  • the invention accordingly relates to a process for the production of solid detergents and cleaners with a high bulk density by combining solid and liquid detergent raw materials with simultaneous or subsequent shaping and, if desired, drying, anionic surfactants, builder substances and alkalizing agents being used as solid constituents, and nonionic surfactants as liquid constituents is used, and in which the liquid nonionic surfactants are used in an intimate mixture with a structure breaker in a weight ratio of liquid nonionic surfactant: structure breaker of 10: 1 to 1: 2 to improve the dissolution behavior and to facilitate incorporation.
  • the liquid nonionic surfactants are preferably derived from ethoxylated fatty alcohols with 8 to 20 carbon atoms and an average of 1 to 15 moles of ethylene oxide per mole of alcohol and in particular from primary alcohols with preferably 9 to 18 carbon atoms and an average of 1 to 12 moles of ethylene oxide per mole of alcohol, in which the alcohol residue may be linear or methyl-branched in the 2-position, or may contain linear and methyl-branched residues in the mixture, such as are usually present in oxo alcohol residues.
  • linear residues of alcohols of native origin with 12 to 18 carbon atoms such as, for example, coconut oil, tallow fat or oleyl alcohol, are particularly preferred.
  • the degrees of ethoxylation given represent statistical mean values which can be an integer or a fraction for a special product.
  • Preferred alcohol ethoxylates have a restricted 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.
  • the preferred ethoxylated alcohols include, for example, Cg-Cn-oxo alcohol with 7 E0, Ci3-Ci5-oxo alcohol with 3 E0, 5 E0 or 7 E0 and in particular Ci2-Ci4 alcohols with 3 E0 or 4 E0, Ci2-Ci8 alcohols 3 E0, 5 E0 or 7 E0 and mixtures of these, such as mixtures of Ci2-Ci4 alcohol with 3 E0 and Ci2-Ci8 alcohol with 5 E0.
  • a number of both solid and liquid substances which are hydrophilic, water-soluble or water-dispersible are suitable as structure breakers.
  • Suitable are, for example, lower polyalkylene glycols which are derived from straight-chain or branched glycols having 2 to 6 carbon atoms, preferably polyethylene glycol or polypropylene glycol, and have a relative molecular weight between 200 and 12,000.
  • polyethylene glycols with a relative molecular weight of between 200 and 4000 are preferred, the liquid polyethylene glycols with a relative molecular weight of up to 2,000 and in particular between 200 and 600 having particularly advantageous properties.
  • the sulfates and in particular the disulfates of lower polyalkylene glycol ethers are suitable.
  • the sulfates and / or disulfates which are derived from polyethylene glycols and Derive polypropylene glycols with a relative molecular mass between 600 and 6000 and in particular between 1,000 and 4,000.
  • the disulfates generally originate from polyglycol ethers, such as those which can be caused by the slight traces of water in the alkoxylation of alcoholic components.
  • Another group of suitable structure breakers consists of the water-soluble salts of mono- and / or disulfosuccinates of the lower polyalkylene glycol ethers.
  • the corresponding polyethylene glycol ether and polypropylene glycol ether compounds are of particular importance, sulfosuccinates and disulfosuccinates of polyglycol ethers having a relative molecular weight between 600 and 6,000, in particular between 1,000 and 4,000, being particularly preferred.
  • any salts but preferably the alkali metal salts, in particular the sodium and potassium salts, and ammonium salts and / or salts of organic amines, for example triethanolamine, can be used as structure breakers for the use of the anionically modified polyalkylene glycol ethers .
  • the most important salts for practical use are the sodium and potassium salts of sulfates, disulfates, sulfosuccinates and disulfosuccinates of polyethylene glycol and polypropylene glycol.
  • Mixtures of the polyalkylene glycol ethers and their anionically modified derivatives are preferably also used in any mixing ratio.
  • a mixture of polyalkylene glycol ether and the sulfosuccinates and / or disulfosuccinates of the polyalkylene glycol ether is preferred.
  • a mixture of polyalkylene glycol ether and the corresponding sulfates and / or disulfates and a mixture of polyalkylene glycol ether and the corresponding sulfates and / or disulfates and the corresponding sulfosuccinates and / or sulfodisuccinates are also suitable.
  • suitable and preferably used structure breakers are the addition products of about 20 to about 80 moles of ethylene oxide with 1 mole of an aliphatic alcohol with essentially 8 up to 20 carbon atoms, which have long been known ingredients of detergents and cleaning agents.
  • Examples of particularly preferred structure breakers from the group of highly ethoxylated alcohols are tallow fatty alcohol with 30 E0 and tallow alcohol with 40 E0. It is also preferred to use mixtures which contain highly ethoxylated alcohols, for example mixtures of tallow fatty alcohol with 40 E0 and water or of tallow fatty alcohol with 40 E0 and polyethylene glycol with a relative molecular weight between 200 and 2000.
  • Further suitable structure breakers are ethoxylated, vicinal internal alkanediols or 1,2-alkanediols with a carbon chain with 8 to 18 carbon atoms and 4 to 15 moles of ethylene oxide per mole of diol. It is possible for only one of the two OH groups or both OH groups of the alkanediol to be ethoxylated.
  • Modified nonionic surfactants with a terminal acid group are also suitable as structure breakers. These are nonionic surfactants, especially fatty alcohols, in which a 0H group has been converted into a group with a carboxyl group.
  • Nonionic surfactants with a terminal acid group thus include esters or partial esters of a nonionic surfactant with a polycarboxylic acid or a polycarboxylic anhydride.
  • acid-terminated nonionic surfactants are the known polyether carboxylic acids and esters or semi-esters of C 1 -C 6-alcohols with succinic anhydride, maleic anhydride, maleic acid or citric acid.
  • Suitable structure breakers consists of alkylene glycol monoalkyl ethers of the general formula RO (CH2CH2 ⁇ ) n H, in which R represents a radical with 2 to 8 carbon atoms and n represents a number from 1 to 8.
  • R represents a radical with 2 to 8 carbon atoms
  • n represents a number from 1 to 8.
  • additives are ethylene glycol monoethyl ether and diethylene glycol onobutyl ether.
  • Water is also a suitable structural breaker in principle. However, the use of water as a structure breaker is less preferred. In most cases, the aim is to keep the free water content in the agents as low as possible in order to achieve the highest possible active ingredient concentrations in the agents.
  • anhydrous ingredients for example anhydrous soda or at least partially dewatered zeolite, are often used which are able to bind free water. It is therefore obvious that water is a less suitable structural breaker, since the agents become poorer in water during storage due to the internal drying of the agent, so that the positive effect of the improved dissolution rate after a period of use no longer applies or is no longer fully effective.
  • the liquid nonionic surfactants in particular the ethoxylated fatty alcohols, are used in intimate mixing with the structure breaker.
  • This intimate mixing is achieved by either producing a homogeneous solution or a dispersion from the liquid nonionic surfactants used according to the invention and the hydrophilic, water-soluble or water-dispersible structure breakers.
  • the additives even in very small amounts, for example around 8% by weight, based on the sum of liquid nonionic surfactant and structure breaker, bring about the desired improvement in the dissolving speed of the finished washing and cleaning agents, so that they are preferably in one Weight ratio of liquid nonionic surfactant: structure breaker from 8: 1 to 1: 1.5 can be used.
  • liquid nonionic surfactant and structure breaker can be used in all known processes in which detergents and cleaners have a high bulk density, ie a bulk density above 500 g / 1, preferably above 600 g / 1 and in particular between 700 and 1,000 g / l, and which contain liquid ethoxylated alcohols as nonionic surfactants according to the definition of the invention, are used.
  • Ver ⁇ examples of such known and preferred Ver ⁇ are granulation, in which either the ingredient 'e a synthetic detergent or a spray-dried detergents and Cleaning agents or a mixture of spray-dried and non-spray-dried ingredients of detergents and cleaning agents are compacted in a high-speed mixer and simultaneously in this mixer or subsequently in another device, for example in a fluidized bed, with the solution or dispersion according to the invention .
  • a method is also preferred in which spray-dried and / or non-spray-dried ingredients of detergents and cleaning agents are granulated together with the solution or dispersion used according to the invention, which has been applied to a carrier, in particular to a zeolite-containing carrier.
  • a method is preferred, which is described in detail in international patent application WO 91/02047.
  • a solid, homogeneous premix is extruded in the form of a strand, with the addition of a plasticizer and / or lubricant, through hole shapes with opening widths of the predetermined granule dimension at high pressures between 25 and 200 bar.
  • the strand is cut to the predetermined granule dimension directly after it emerges from 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, conventional ingredients of detergents and cleaning agents, to which liquid constituents are optionally added.
  • the solid ingredients can be tower powders obtained by spray drying, but also agglomerates, 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.
  • the liquid ingredients are optionally added and then the plasticizer and / or lubricant selected according to the invention is mixed in.
  • Preferred plasticizers and / or lubricants are aqueous solutions of polymeric polycarboxylates, as well as highly concentrated anionic surfactant pastes and nonionic surfactants.
  • the solutions or dispersions of liquid nonionic surfactants and hydrophilic, water-soluble or water-dispersible structure breakers can either be added to the solid premix as a liquid constituent or as a plasticizer and / or lubricant, or they are part of a solid mixture component of the premix, this solid mixture component consisting of a carrier bead which has been charged with the solution or the dispersion.
  • the addition of the solution according to the invention or the dispersion in liquid form, that is to say not bound to a carrier bead, can be carried out at any point in the process, for example when preparing the premix, but also when processing the plasticized premix before passing through the perforated shape (perforated nozzle plate).
  • solutions or dispersions according to the invention are preferably used in the production of washing and cleaning agents by extrusion under high pressure, the weight ratio of liquid nonionic surfactant: structure breaker in the solutions or dispersions being 10: 2 to 1: 1 and in particular 10: 3 to 10 : 8 is.
  • Kneaders of any configuration can preferably be selected as the homogenizing device.
  • the intensive mixing process can itself lead to a desired temperature increase. Moderately elevated temperatures of, for example, 60 to 70 ° C. are generally not exceeded.
  • the premix is preferably fed continuously to a 2-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.
  • the premix is compressed at pressures from 25 to 200 bar, preferably above 30 bar and in particular at pressures from 50 to 180 bar, plasticized, extruded in the form of fine strands through the perforated die plate in the extruder head and finally by means of the extrudate of a rotating knives preferably reduced to spherical to cylindrical granules.
  • the hole diameter in the perforated nozzle plate and the strand cut length are reduced to selected granule dimension.
  • Important embodiments provide for the production of uniform granules 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. It is further preferred that the still plastic, moist primary granules undergo a further shaping processing step feed; edges present on the raw granulate are rounded off so that ultimately spherical or at least approximately spherical granules can be obtained.
  • small amounts of dry powder for example zeolite powder such as zeolite NaA powder, can also be used in this step.
  • This shaping can take place in standard rounding devices, for example in rounding devices with a rotating base plate.
  • the granules are then preferably fed to a drying step, for example a fluidized bed dryer.
  • a drying step for example a fluidized bed dryer.
  • extruded granules which contain peroxy compounds as bleaching agents for example perborate monohydrate
  • the free water content of the dried granules is preferably up to about 3% by weight, in particular between 0.1 to 1% by weight.
  • dry powders are again zeolite-NaA powder, but also precipitated or pyrogenic silica, as are commercially available, for example, as Aerosil ( R ) or Sipernat ( R ) (products from ' Degussa').
  • Highly preferred Concentrated, at least 90% by weight fatty alcohol sulfate powder which essentially, ie at least 90%, consist of particles with a particle size smaller than 100 ⁇ m. Mixtures of zeolite and fatty alcohol sulfate powder are particularly preferred.
  • solid washing and cleaning agents are claimed which are produced by the process according to the invention. These washing and cleaning agents show an improved dissolving speed at temperatures between 15 and 60 ° C. and in particular between 20 and 45 ° C.
  • detergents produced by the process according to the invention which contain 20 to 45% by weight of surfactants are preferred.
  • 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. H. Mixtures of alkene and hydroxyalkanesulfonates and disulfonates, such as those obtained, for example, from Ci2 ⁇ Ci8 monoolefins with terminal and internal double bonds by sulfonation with gaseous sulfur trioxide and subsequent alkaline or acidic hydrolysis of the sulfonation products.
  • dialcan sulfonates which are obtainable from Ci2-Ci8-alkanes 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 example those Oc-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, in particular from fatty alcohols, for example coconut oil alcohols, tallow fatty alcohols, oleyl alcohol, lauryl, myristyl, cetyl or stearyl alcohol, or the Cl0 ⁇ C20 ⁇ 0 ⁇ oaoils and 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 monoglycerides are also suitable.
  • Soaps from natural or synthetic, preferably saturated, fatty acids can also be used.
  • Soap mixtures derived from natural fatty acids for example coconut, palm kernel or tallow fatty acids, are particularly suitable.
  • Preferred are those which are composed of 50 to 100% of saturated Ci2-Ci8 fatty acid soaps and 0 to 50% of oleic acid soaps.
  • the anionic surfactants can be in the form of their sodium, potassium and ammonium salts and also 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 35,% by weight. It is particularly advantageous if the content of sulfonates and / or sulfates in the compositions is 10 to 35% by weight, in particular 15 to 30% by weight, and the soap content is up to 8% by weight. , in particular 0.5 to 5 wt .-%.
  • the anionic surfactants can be used in solid form, for example in spray-dried or granulated form, or in liquid to pasty form. Thus, it is preferred to incorporate the anionic surfactants used as plasticizers and / or lubricants in the form of an aqueous surfactant paste.
  • the content of the agents in ethoxylated alcohols used according to the invention as nonionic surfactants is preferably 1 to 15% by weight and in particular 2 to 10% by weight.
  • the content of the structure breakers used according to the invention inevitably results from this.
  • the compositions preferably contain up to 5% by weight, in particular 1 to 3% by weight, of polyethylene glycol with a relative molecular weight between 200 and 1,500.
  • the weight ratio of anionic surfactant: nonionic surfactant is preferably at least 1: 1 and in particular 1: 1 to 6: 1, for example 2: 1 to 6: 1.
  • alkyl glycosides of the general formula R-0- (G) x in which R is a primary straight-chain or in 2-position methyl-branched aliphatic radical with 8 to 22, preferably 12 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 , is preferably between 1 and 2 and in particular is significantly smaller than 1.4, for example in amounts of 1 to 10% by weight.
  • Suitable and, in particular, ecologically safe 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 12 837), are used with preference.
  • Their average particle size is usually in the range from 1 to 10 ⁇ m (measurement method: Coulter Counter, volume distribution).
  • the zeolite content of the compositions is generally up to 50% by weight, preferably at least 10% by weight and in particular 20 to 40% by weight, based on the anhydrous substance.
  • Zeolite NaA is obtained in its production as 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. It is possible to use the zeolite or at least zeolite fractions in the form of the undried masterbatch or an only partially dried masterbatch.
  • 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 from 50% to 10% maleic acid.
  • the relative 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 free acid.
  • a particularly preferred acrylic acid-maleic acid copolymer has a relative 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 ether, in which the proportion the acidity is at least 50%.
  • polyacetal carboxylic acids such as those described in US Pat. Nos. 4,144,226 and 4,146,495, and polymeric acids which are obtained by polymerizing acrolein and subsequent disproportionation using alkalis and are composed of acrylic acid units and vinyl alcohol units or acrolein units.
  • the (co) polymeric polycarboxylates are introduced into the process in solid form or in liquid form, ie in the form of an aqueous solution, preferably in the form of a 30 to 55% strength by weight aqueous solution.
  • the content of the agents in (co) polymeric polycarboxylates is preferably up to 10% by weight and in particular 2 to 8% by weight.
  • Usable organic builders are, for example, the polycarboxylic acids 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
  • alkali carbonate and alkali silicate especially sodium silicate with a molar ratio Na2 ⁇ : Si ⁇ 2 of 1: 1 to 1: 4.0, are used.
  • the alkalizing agents are preferably introduced into the process in solid form. However, it is also possible to use at least some of the alkalizing agents in the form of an aqueous solution, e.g. in the form of an aqueous alkali silicate solution or a mixture of solid alkali carbonate and an alkali silicate solution.
  • the sodium carbonate content of the agents is preferably up to 20% by weight, advantageously between 5 and 15% by weight.
  • the sodium silicate content of the agents is generally up to 10% by weight and preferably between 2 and 8% by weight.
  • the other detergent components include graying inhibitors (dirt carriers), foam inhibitors, bleaching agents and bleach activators, optical brighteners, enzymes, fabric softening agents, colorants and fragrances as well as neutral salts.
  • graying inhibitors dirty carriers
  • foam inhibitors foam inhibitors
  • bleaching agents and bleach activators optical brighteners
  • enzymes fabric softening agents
  • colorants and fragrances colorants and fragrances as well as neutral salts.
  • sodium perborate tetrahydrate and sodium perborate monohydrate are of particular importance.
  • Further bleaching agents that can be used are, for example, peroxycarbonate, peroxypyrophosphates, citrate perhydrates and H2O2-providing peracid salts or peracids, such as perbenzoates, peroxaphthalates, diperazelaic acid or diperdodecanedioic acid.
  • the bleaching agent content of the agents is preferably 5 to 25% by weight and in particular 10 to 20% by weight, with perborate monohydrate being advantageously used
  • 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, further carboxylic 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 3 and 8% by weight.
  • 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, 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, for example degraded starch, aldehyde starches, etc.
  • Polyvinylpyrrolidone can also be used.
  • Carboxymethyl cellulose (sodium salt), methyl cellulose, methyl hydroxyethyl cellulose and mixtures thereof and polyvinylpyrrolidone are preferably used, in particular in amounts of 0.5 to 5% by weight, based on the composition.
  • 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, for example sulfates and / or sulfonates with nonionic surfactants and / or with 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-alkylamines and C2-Co-dicarboxylic acids can also be used.
  • foam inhibitors are also advantageously used, for example those made from silicones 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.
  • the detergents can contain, as optical brighteners, derivatives of diaminostilbenedisulfonic acid or its alkali metal salts.
  • derivatives of diaminostilbenedisulfonic acid or its alkali metal salts for example, 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 are suitable 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-di-phenyl type may also be present; for example the compound 4,4'-bis (4-chloro-3-sulfostyryl) diphenyl. Mixtures of the aforementioned brighteners can also be used.
  • uniformly white granules are obtained if, apart from the customary optical brighteners, the agents are present in customary amounts, for example between 0.1 and 0.5, preferably around 0.1 to 0.3, by weight. -%, even small quantities, for example, 10 " ⁇ to 10" 3 wt .-%, preferably around 10 ⁇ 5 wt .-%, of a blue dye.
  • a particularly preferred dye is Tinolux ( R ) (product name of Ciba-Geigy).
  • Enzymes from the class of proteases, lipases and amylases or mixtures thereof can be used. Enzymes obtained from bacterial strains or fungi such as Bacillus subtilis, Bacillus licheniformis and Streptomyces griseus are particularly suitable. Proteases of the subtilisin type and in particular proteases obtained from Bacillus lentus are preferably used.
  • the enzyme * can be adsorbed on carrier substances and / or embedded in coating substances in order to protect them against premature decomposition.
  • the salts of polyphosphonic acids are suitable as stabilizers, in particular for per-compounds and enzymes.
  • the detergents and cleaning agents can be produced uniformly from extrudates which have the above-mentioned ingredients.
  • the agents can also be obtained from a mixture of several different granules, of which the extrudates according to the invention form the main component.
  • the bleach activator, the enzymes, and colorants and fragrances can be subsequently added to the extrudates. It is preferred to use the bleach activator and the enzymes in each case in compacted granular form, for example as extrudates produced separately in each case, which are obtained by means of a kneader of the configuration described above or via a pellet press.
  • the premix was plasticized and then extruded at a pressure of 120 bar through the extruder head perforated die plate into fine strands with a diameter of 1.2 mm, which after the die outlet were comminuted into approximately spherical granules by means of a knock-out knife (Length / diameter ratio about 1, hot cut).
  • the resulting warm granulate was rounded off for 1 minute in a Maru erizer-type rounding device available on the market and then dried at a supply air temperature of 120 ° C. in a fluidized bed dryer.
  • the low-dust product was sieved through a sieve with a mesh size of 1.6 mm. The proportion above 1.6 mm was below 3%.
  • the granules obtained had a bulk density of 820 g / l.
  • the dissolving rate of the granules was determined using the conductivity measurement method:
  • the dissolving time of the granules according to the invention was 2.20 minutes at 20 ° C. and 90% resolution.
  • a premix of the same composition as in the example according to the invention was produced, but the ethoxylated alcohols and the polyethylene glycol were not added in a mixture, but separately in succession.
  • the premix was extruded, cut, rounded, dried and sieved.
  • the bulk density of the granules VI was approximately 820 g / l.
  • the dissolving time of the granules VI at 20 ° C. and 90% resolution was 3.77 minutes.
  • a premix was prepared which contained the same constituents in the same amounts as in the example according to the invention, with the exception that the additive polyethylene glycol was dispensed with.
  • the premix was as in the invention Example extruded, cut, rounded, dried and sieved.
  • the bulk density of the granules V2 was about 820 g / 1.
  • the dissolving time of the Granules V2 was 3.85 minutes at 20 ° C and 90% resolution.

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  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
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  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Detergent Compositions (AREA)

Abstract

L'invention concerne un procédé de fabrication de produits de lavage et de produits détergents à densité apparente élevée et à vitesse de dissolution améliorée consistant à rassembler des matières premières détergentes solides et liquides, tout en les façonnant simultanément ou ultérieurement, avec séchage éventuel, et en utilisant comme constituants solides, des agents tensioactifs anioniques, des adjuvants et des agents d'alcalinisation et, comme constituants liquides, des agents tensioactifs non ioniques. En vue d'améliorer le pouvoir de dissolution et de simplifier la mise en oeuvre, on obtient de tels produits en mélangeant intimement les agents tensioactifs non ioniques liquides avec un fractionneur de structure, dans un rapport pondéral agent tensioactif non ionique liquide: fractionneur de structure de 10:1 à 1:2. Les fractionneurs de structure utilisés de préférence sont des polyéthylèneglycols ou des polypropylèneglycols de masse moléculaire relative comprise entre 200 et 12000, des produits d'addition d'environ 20 à 80 moles d'oxyde d'éthylène sur 1 mole d'un alcool aliphatique renfermant essentiellement de 8 à 20 atomes de carbone, ainsi que des mélanges de ces composés.
EP92916049A 1991-07-25 1992-07-16 Procede de fabrication de produits de lavage a densite apparente elevee et a vitesse de dissolution amelioree Expired - Lifetime EP0595946B1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE4124701A DE4124701A1 (de) 1991-07-25 1991-07-25 Verfahren zur herstellung fester wasch- und reinigungsmittel mit hohem schuettgewicht und verbesserter loesegeschwindigkeit
DE4124701 1991-07-25
PCT/EP1992/001616 WO1993002176A1 (fr) 1991-07-25 1992-07-16 Procede de fabrication de produits de lavage a densite apparente elevee et a vitesse de dissolution amelioree

Publications (2)

Publication Number Publication Date
EP0595946A1 true EP0595946A1 (fr) 1994-05-11
EP0595946B1 EP0595946B1 (fr) 1997-03-12

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EP92916049A Expired - Lifetime EP0595946B1 (fr) 1991-07-25 1992-07-16 Procede de fabrication de produits de lavage a densite apparente elevee et a vitesse de dissolution amelioree

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EP (1) EP0595946B1 (fr)
JP (1) JPH06509369A (fr)
AT (1) ATE150084T1 (fr)
DE (2) DE4124701A1 (fr)
ES (1) ES2098520T3 (fr)
WO (1) WO1993002176A1 (fr)

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Also Published As

Publication number Publication date
EP0595946B1 (fr) 1997-03-12
DE4124701A1 (de) 1993-01-28
WO1993002176A1 (fr) 1993-02-04
JPH06509369A (ja) 1994-10-20
DE59208196D1 (de) 1997-04-17
ES2098520T3 (es) 1997-05-01
ATE150084T1 (de) 1997-03-15

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