EP0674703B1 - Procede de fabrication d'un detergent et nettoyant granule - Google Patents

Procede de fabrication d'un detergent et nettoyant granule Download PDF

Info

Publication number
EP0674703B1
EP0674703B1 EP94902690A EP94902690A EP0674703B1 EP 0674703 B1 EP0674703 B1 EP 0674703B1 EP 94902690 A EP94902690 A EP 94902690A EP 94902690 A EP94902690 A EP 94902690A EP 0674703 B1 EP0674703 B1 EP 0674703B1
Authority
EP
European Patent Office
Prior art keywords
granules
weight
acid
stage
preferred
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.)
Revoked
Application number
EP94902690A
Other languages
German (de)
English (en)
Other versions
EP0674703A1 (fr
Inventor
Wolfgang Seiter
René-Andres ARTIGA GONZALEZ
Adolf Wiche
Sönke TAMS
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
Family has litigation
First worldwide family litigation filed litigation Critical https://patents.darts-ip.com/?family=25921330&utm_source=***_patent&utm_medium=platform_link&utm_campaign=public_patent_search&patent=EP0674703(B1) "Global patent litigation dataset” by Darts-ip is licensed under a Creative Commons Attribution 4.0 International License.
Priority claimed from DE4304475A external-priority patent/DE4304475A1/de
Application filed by Henkel AG and Co KGaA filed Critical Henkel AG and Co KGaA
Publication of EP0674703A1 publication Critical patent/EP0674703A1/fr
Application granted granted Critical
Publication of EP0674703B1 publication Critical patent/EP0674703B1/fr
Anticipated expiration legal-status Critical
Revoked legal-status Critical Current

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/06—Powder; Flakes; Free-flowing mixtures; Sheets
    • C11D17/065—High-density particulate detergent compositions
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D11/00—Special methods for preparing compositions containing mixtures of detergents
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D11/00—Special methods for preparing compositions containing mixtures of detergents
    • C11D11/0082—Special methods for preparing compositions containing mixtures of detergents one or more of the detergent ingredients being in a liquefied state, e.g. slurry, paste or melt, and the process resulting in solid detergent particles such as granules, powders or beads
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/06—Powder; Flakes; Free-flowing mixtures; Sheets

Definitions

  • the invention relates to a method for producing granulated detergents and cleaning agents, in particular those with high bulk density, or a component therefor, the have a special morphology, which is in a - macroscopic seen - expresses almost spherical structure.
  • EP 367 339 is modified by 0.1 to 40 % By weight of a powder either in the second granulation stage or between be added to the first and second pelletizing stages. Lay here thus optimal conditions for a build-up granulation.
  • the powder agglomerates in the moist, sticky areas of the primary agglomerates and causes a further formation of raspberry-like structures.
  • adding large amounts of powder will make the sticky surface of the primary granules covered quickly and completely, the build-up granulation comes to a standstill and, depending on the time of adding the powder, it becomes relative receive small agglomerates.
  • the addition of only small amounts of powder however, only partially covers the adhesive surface, so that it is combined into larger agglomerates.
  • the object of the invention was to provide granules with a - macroscopic seen - almost spherical surface and an almost monodisperse internal granulate structure, which so far has only been possible through an extrusion process could be produced, to be provided by a Granulation processes can be produced.
  • the invention accordingly relates to a process for the production a granulated detergent or cleaning agent or a component for this, the granules having a certain morphology with almost spherical and smooth surface and an almost monodisperse inner Has structure and is a roll granulate.
  • the washing and cleaning agent obtained or the component therefor, which one (s) is produced by a granulation process stands out in particular by a certain surface morphology. Macroscopic seen the granules are almost spherical; microscopic seen the granules are characterized by a surprisingly "smooth" Surface that shows some cracks, but without it sharp, protruding edges or protruding protrusions. The difference in the surface morphology is very clear the figures, wherein Figures 3 and 4, the invention Granules with a "smooth" surface and Figures 1 and 2 die conventional raspberry structure-like, obtained by structural granulation Show granules.
  • the special morphology of the granules according to the invention causes them to move against each other on a rolling basis. This can be shown by a simple test, with the granules poured become. While pouring conventional granules granulate layers only slip, rolls with the granules according to the invention in each case the upper granulate layer over the granulate layer underneath from. Because of this property, the invention Granules called roll granules below.
  • the preferred composition of the roll granules is characterized in that they contain at least 10% by weight of anionic and / or nonionic surfactants, in particular 10 to 45% by weight of anionic and nonionic surfactants contain. Roll granules with 15 contain up to 35% by weight of anionic and nonionic surfactants.
  • Preferred anionic surfactants of the sulfonate type are C 9 -C 13 alkylbenzenesulfonates, olefin sulfonates, ie mixtures of alkene and hydroxyalkanesulfonates, and disulfonates such as are obtained, for example, from C 12 -C 18 monoolefins with an end or internal double bond by sulfonating with gaseous Sulfur trioxide and subsequent alkaline or acidic hydrolysis of the sulfonation products is considered.
  • alkanesulfonates obtained from C 12 -C 18 alkanes, for example by sulfochlorination or sulfoxidation with subsequent hydrolysis or neutralization.
  • Preferred anionic surfactants are also the salts of alkylsulfosuccinic acid, which are also referred to as sulfosuccinates or as sulfosuccinic acid esters and which represent monoesters and / or diesters of sulfosuccinic acid with alcohols, preferably fatty alcohols and in particular ethoxylated fatty alcohols.
  • Preferred sulfosuccinates contain C 8 to C 18 fatty alcohol residues or mixtures thereof.
  • Particularly preferred sulfosuccinates contain a fatty alcohol residue which is derived from ethoxylated fatty alcohols, which in themselves are nonionic surfactants (description see below).
  • sulfosuccinates the fatty alcohol residues of which are derived from ethoxylated fatty alcohols with a restricted homolog distribution, are particularly preferred. It is also possible to use alk (en) ylsuccinic acid with preferably 8 to 18 carbon atoms in the alk (en) yl chain or salts thereof.
  • esters of ⁇ -sulfo fatty acids e.g. the ⁇ -sulfonated methyl esters of hydrogenated coconut, palm kernel or tallow fatty acids.
  • Suitable sulfate-type anionic surfactants are the sulfuric acid monoesters from primary alcohols of natural and synthetic origin.
  • Suitable fatty alkyl sulfates are the sulfuric acid monoesters of the C 12 -C 18 fatty alcohols, such as lauryl, myristyl, cetyl alcohol or stearyl alcohol, and the fatty alcohol mixtures obtained from coconut oil, palm and palm kernel oil, which also contain fractions of unsaturated alcohols, for example oleyl alcohol , can contain.
  • Suitable anionic surfactants are, in particular, soaps, preferably in amounts of 0.5 to 8% by weight.
  • Saturated fatty acid soaps are suitable, such as the salts of lauric acid, myristic acid, palmitic acid or stearic acid, and in particular soap mixtures derived from natural fatty acids, for example coconut, palm kernel or tallow fatty acids.
  • soap mixtures are preferred which are composed of 50 to 100% by weight of saturated C 12 -C 18 fatty acid soaps and 0 to 50% by weight of oleic acid soap.
  • the anionic surfactants can be in the form of their sodium, potassium or ammonium salts as well as soluble salts of organic bases, such as mono-, di- or Triethanolamine.
  • the anionic surfactants are preferably in Form of their sodium or potassium salts, especially in the form of the sodium salts in front.
  • the anionic surfactant content of the roll granules is preferably 5 to 20% by weight. However, their content can also exceed 20% by weight, for example up to 25% by weight.
  • Preferred anionic surfactants are fatty alkyl sulfates, Alkylbenzenesulfonates, sulfosuccinates and mixtures thereof, such as mixtures of fatty alk (en) yl sulfates and sulfosuccinates or fatty alkyl sulfates and fatty alk (en) ylbenzenesulfonates, especially in combination with soap.
  • Addition products of 1 to 12 moles of ethylene oxide with primary C 12 -C 18 fatty alcohols and their mixtures such as coconut oil, tallow oil or oleyl alcohol, or with methyl-branched, in particular methyl-branched primary alcohols (oxo alcohols) are preferred as nonionic surfactants in the Contain granules.
  • C 12 -C 14 alcohols with 3 EO or 4 EO C 9 -C 11 alcohol with 7 EO, C 13 -C 15 alcohols with 3 EO, 5 EO, 7 EO or 8 EO, C 12 - C 18 alcohols with 3 EO, 5 EO or 7 EO and mixtures thereof, such as mixtures of C 12 -C 14 alcohol with 3 EO and C 12 -C 18 alcohol with 5 EO.
  • the degrees of ethoxylation given represent statistical averages, which can be an integer or a fraction for a specific product.
  • Preferred alcohol ethoxylates have a restricted homolog distribution (narrow range ethoxylates, NRE).
  • the content of the ethoxylated C 12 -C 18 fatty alcohols in the finished granules is advantageously at least 2% by weight, preferably 5 to 15% by weight, in particular 8 to 15% by weight.
  • the liquid nonionic surfactants are mixed with lower polyalkylene glycols which are derived from straight-chain or branched glycols having 2 to 6 carbon atoms and / or highly ethoxylated fatty alcohols with 20 to 80 EO, in particular tallow fatty alcohol with 30 EO or 40 EO , used.
  • Preferred lower polyalkylene glycols are polyethylene glycols or polypropylene glycols which have a relative molecular mass between 200 and 12,000, in particular between 200 and 4,000, for example up to 2,000.
  • the weight ratio of liquid nonionic surfactant to lower polyalkylene glycol and / or highly ethoxylated fatty alcohol in these mixtures is preferably 10: 1 to 1: 2, in particular 5: 1 to 1: 1.5 and is advantageously in some cases 1.5: 1 to 1 : 1.5, for example by 1: 1.
  • the preferred nonionic surfactants also include alkyl glycosides of the general formula RO (G) x , in which R is a primary straight-chain or aliphatic radical having 8 to 22, preferably 12 to 18, C-atoms and methyl-branched and G is the symbol which stands for a glycose unit with 5 or 6 carbon atoms, preferably for glucose.
  • the degree of oligomerization x which indicates the distribution of monoglycosides and oligoglycosides, is any number between 1 and 10 and is preferably 1.2 to 1.4.
  • non-ionic surfactants that either as the sole nonionic surfactant or in combination with others nonionic surfactants, especially together with alkoxylated Fatty alcohols used are alkoxylated, preferably ethoxylated or ethoxylated and propoxylated fatty acid alkyl esters, preferably with 1 to 4 carbon atoms in the alkyl chain, in particular fatty acid methyl ester, as for example in the Japanese patent application JP 58/217598 are described or which are preferably according to the in the international patent application WO 90/13533 become.
  • nonionic surfactants of the amine oxide type for example N-cocoalkyl-N, N-dimethylamine oxide and N-tallow alkyl-N, N-dihydroxyethylamine oxide, and the fatty acid alkanolamides may be suitable.
  • the amount of this nonionic Surfactants are preferably no more than that of the ethoxylated ones Fatty alcohols, especially not more than half of them.
  • Suitable surfactants are polyhydroxy fatty acid amides of the formula (I), in the R 2 CO for an aliphatic acyl radical having 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 stands.
  • the polyhydroxy fatty acid amides are known substances which can usually be obtained by reductive amination of a reducing sugar with ammonia, an alkylamine or an alkanolamine and subsequent acylation with a fatty acid, a fatty acid alkyl ester or a fatty acid chloride.
  • the polyhydroxy fatty acid amides are preferably derived from reducing sugars with 5 or 6 carbon atoms, in particular from glucose.
  • the preferred polyhydroxy fatty acid amides are therefore fatty acid N-alkylglucamides as represented by the formula (II):
  • the polyhydroxy fatty acid amides used are preferably fatty acid N-alkylglucamides of the formula (II) in which R 3 is hydrogen or an alkyl group and R 2 CO is the acyl radical of caproic acid, caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, palmoleic acid, stearic acid, Isostearic acid, oleic acid, elaidic acid, petroselinic acid, linoleic acid, linolenic acid, arachic acid, gadoleic acid, behenic acid or erucic acid or their technical mixtures.
  • Fatty acid N-alkylglucamides of the formula (II) which are obtained by reductive amination of glucose with methylamine and subsequent acylation with lauric acid or C 12/14 coconut fatty acid or a corresponding derivative are particularly preferred.
  • the roll granules obtained according to the invention can be any known Contain ingredients of washing and / or cleaning agents.
  • Preferred further constituents are builder substances, alkaline substances and neutral salts, bleaches, graying inhibitors, foam inhibitors and optical brighteners.
  • Suitable inorganic builders are, for example, phosphates, preferably tripolyphosphates, but also orthophosphates and pyrophosphates, as well as zeolite and crystalline layered silicates.
  • the finely crystalline, synthetic and bound water-containing zeolite used is preferably zeolite NaA in detergent quality.
  • zeolite NaX and mixtures of NaA and NaX are also suitable.
  • the zeolite can be used as a spray-dried powder or as an undried stabilized suspension that is still moist from its manufacture.
  • the zeolite may contain minor additions of nonionic surfactants as stabilizers, for example 1 to 3% by weight, based on zeolite, of ethoxylated C 12 -C 18 fatty alcohols with 2 to 5 ethylene oxide groups .
  • Suitable zeolites have an average particle size of less than 10 ⁇ m (volume distribution; measurement method: Coulter Counter) and preferably contain 20 to 22% by weight of bound water.
  • Suitable substitutes or partial substitutes for phosphates and zeolites are crystalline, layered sodium silicates of the general formula (III) NaHSi x O 2x + 1 .yH 2 O, where M is sodium or hydrogen, x is a number from 1.9 to 4 and y is a number Number is from 0 to 20 and preferred values for x are 2, 3 or, 4.
  • Such crystalline layered silicates are described, for example, in European patent application 164 514.
  • Preferred crystalline sheet silicates of the formula (III) are those in which M represents sodium and x assumes the values 2 or 3. In particular, both ⁇ - and ⁇ -sodium disilicates Na 2 Si 2 O 5 .yH 2 O are preferred.
  • Useful organic builder substances are preferred, for example polycarboxylic acids used in the form of their sodium salts, such as citric acid, Adipic acid, succinic acid, glutaric acid, tartaric acid, sugar acids, Aminocarboxylic acids, nitrilotriacetic acid (NTA), provided such use is not objectionable for ecological reasons, as well as mixtures from these.
  • Preferred salts are the salts of polycarboxylic acids such as citric acid, Adipic acid, succinic acid, glutaric acid, tartaric acid, sugar acids and mixtures of these.
  • Suitable polymeric polycarboxylates are, for example, the sodium salts polyacrylic acid or polymethacrylic acid, for example those with a relative molecular weight of 800 to 150,000 (based on acid).
  • Suitable copolymeric polycarboxylates are, in particular, those of acrylic acid with methacrylic acid and acrylic acid or methacrylic acid with maleic acid. Copolymers of acrylic acid with maleic acid have proven particularly suitable proven that 50 to 90 wt .-% acrylic acid and 50 to 10 wt .-% maleic acid contain.
  • Their relative molecular mass, 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.
  • the content of (co) polymers in the compositions Polycarboxylates is preferably 1 to 8% by weight, in particular 2 to 6 % By weight. In particular, the use of biodegradable polymers prefers.
  • polyacetals which by reaction of dialdehydes with polyol carboxylic acids, which have 5 to 7 carbon atoms and have at least 3 hydroxyl groups, for example as in European Patent application 280 223 can be obtained.
  • Preferred Polyacetals are made from dialdehydes such as glyoxal, glutaraldehyde and terephthalaldehyde as well as their mixtures and from polyol carboxylic acids such as gluconic acid and / or glucoheptonic acid.
  • Suitable ingredients of the agents are water-soluble inorganic salts such as bicarbonates, carbonates, silicates or mixtures of these;
  • alkali carbonate and alkali silicate especially sodium silicate with a molar ratio Na 2 O: SiO 2 of 1: 1 to 1: 4.5, preferably of 1: 1.9 to 1: 3.3, are used.
  • the sodium carbonate content of the agents is preferably up to 20% by weight, advantageously between 2 and 15% by weight, in particular up to 10% by weight.
  • the sodium silicate content of the agents is generally up to 10% by weight and preferably between 2 and 8% by weight.
  • bleaching agents which serve as bleaching agents and supply H 2 O 2 in water
  • sodium perborate tetrahydrate and sodium perborate monohydrate are of particular importance.
  • Further bleaching agents which can be used are, for example, sodium percarbonate, peroxypyrophosphates, citrate perhydrates and H 2 O 2 -producing peracidic salts or peracids, such as perbenzoates, peroxophthalates, diperazelaic acid 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.
  • Graying inhibitors have the task of removing the fiber Keep dirt suspended in the fleet and prevent 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 Starch or the cellulose or salts of acidic sulfuric acid esters Cellulose or starch. Also water-soluble containing acidic groups Polyamides are suitable for this purpose.
  • soluble ones Use starch preparations and other starch products than those mentioned above, e.g. degraded starch, aldehyde starches, etc. Polyvinylpyrrolidone is also useful.
  • cellulose ethers such as carboxymethyl cellulose are preferred.
  • Methyl cellulose, hydroxyalkyl cellulose and mixed ethers such as methyl hydroxyethyl cellulose, Methyl hydroxypropyl cellulose, methyl carboxymethyl cellulose and their mixtures used.
  • Carboxymethyl cellulose (sodium salt), Methyl cellulose, methyl hydroxyethyl cellulose and their mixtures and polyvinyl pyrrolidone are preferred, for example in amounts of 0.1 to 5 % By weight, based on the composition.
  • Suitable foam inhibitors are, for example, soaps of natural or synthetic origin, which have a high proportion of C 18 -C 24 fatty acids.
  • Suitable non-surfactant-like foam inhibitors are, for example, organopolysiloxanes and their mixtures with microfine, optionally silanized silica, and paraffins, waxes, microcrystalline waxes and their mixtures with silanized silica or bistearylethylenediamide. Mixtures of various foam inhibitors are also advantageously used, for example those made of silicone, paraffins or waxes.
  • the foam inhibitors, in particular silicone or paraffin-containing foam inhibitors are preferably bound to a granular, water-soluble or dispersible carrier substance.
  • the neutral reacting agents can preferably be used Sodium salts of, for example, 1-hydroxyethane-1,1-diphosphonate and Diethylenetriaminepentamethylenephosphonate in amounts of 0.1 to 1.5% by weight be included.
  • the agents can contain derivatives of diaminostilbenedisulfonic acid or its alkali metal salts. Suitable are, for example, salts of 4,4'-bis (2-anilino-4-morpholino-1,3,5-triazinyl-6-amino) stilbene-2,2'-disulfonic acid or compounds of similar structure which instead of the morpholino Group carry a diethanolamino group, a methylamino group, anilino group or a 2-methoxyethylamino group.
  • Brighteners of the substituted diphenylstyryl type may also be present, for example the alkali salts of 4,4'-bis (2-sulfostyryl) diphenyl, 4,4'-bis (4-chloro-3-sulfostyryl) diphenyl, or 4- (4-Chlorostyryl-4 '- (2-sulfostyryl) -diphenyls. Mixtures of the aforementioned brighteners can also be used.
  • Uniformly white granules are obtained if, apart from the usual brighteners, the agents are used in customary amounts, for example between 0.1 and 5% by weight, preferably between 0.1 and 0.3% by weight, also in small amounts, for example 10 -6 to 10 -3 % by weight, preferably around 10 -5 % by weight, of a blue dye
  • a particularly preferred dye is Tinolux (R) (commercial product from Ciba-Geigy).
  • the free, ie unbound, content of the roll granules obtained according to the invention Water is in the framework known for granules, it can for example up to 20% by weight. However, preferred granules contain not more than 10% by weight of free, unbound water.
  • the bulk density of the roll granules is generally between about 400 and 1200 g / l. However, preferred roll granules have a bulk density between 600 and 1100 g / l, preferably between 700 and 950 g / l. The Despite possibly high proportions of ethoxylated nonionic surfactants, granules are non-greasy.
  • the diameter of the roll granules is arbitrary and preferably predeterminable, d. H. targeted to a desired value adjustable. So in a preferred embodiment, roll granules preferred, where the maximum of the particle size distribution (weight distribution) is less than 2 mm, preferably between 0.8 and 1.4 mm. In In a further preferred embodiment, roll granules are preferred where the maximum of the particle size distribution (weight distribution) is between 0.2 and 0.6 mm, preferably between 0.3 and 0.5 mm.
  • the roll granules produced according to the invention can either be used directly as washing and Detergents are used, and / or they are mixed with other quantities, preferably small amounts, for example in the range from 2 to 10 % By weight, based on the total amount of the proportions used, of liquid Sprayed nonionic surfactants or nonionic surfactant mixtures in a manner known per se, and / or they are processed in a preparation step with other components, preferably granular and in particular granular and compacted Components of detergents and cleaning agents mixed.
  • granular components include compacted ones Bleaching agent or bleach activator granules, enzyme granules and granular Carrier for colors and fragrances, but also carbonates, zeolite, Layered silicates, polycarboxylates or polycarboxylic acids such as citric acid and / or polymeric polycarboxylates.
  • bleach activators are N-acyl or O-acyl compounds which form organic peracids with H 2 O 2 , preferably N, N'-tetraacylated diamines, furthermore carboxylic acid anhydrides and esters of polyols such as glucose pentaacetate.
  • the addition of bleach activators is in the usual range, preferably between 1 and 10% by weight and in particular between 3 and 8% by weight, based on the finished washing and cleaning agent.
  • Particularly preferred bleach activators are N, N, N ', N'-tetraacetylethylenediamine and 1,5-diacetyl-2,4-dioxo-hexahydro-1,3,5-triazine.
  • Enzymes come from the class of proteases, lipases, amylases, Cellulases or their mixtures in question. Are particularly well suited Strains of bacteria or fungi such as Bacillus subtilis, Bacillus licheniformis and Streptomyces griseus derived enzymatic agents. Preferably become proteases of the subtilisin type and in particular proteases that are obtained from Bacillus lentus. Their share can be about 0.2 amount to about 2 wt .-%, based on the finished detergent.
  • the enzymes can be adsorbed on carrier substances and / or in coating substances embedded to protect them against premature decomposition.
  • the roll granules are after obtained a process, the powdered in a first process stage Starting materials submitted and, if necessary, with liquid components are mixed, the mixture in a second process stage is compressed by the entry of energy and the resulting Granules are rolled compacting against each other, being a smooth surface (microscopic) and an almost monodisperse inner Preserve structure, and roll-up granulation by adding a fine particle Powder is stopped after placing the granules on a given Maximum of the particle size distribution has grown. Of the The diameter of the roll granules that can be produced by this method is thus predeterminable.
  • powdered starting materials are presented and mixed together.
  • Preferred powdered starting materials are anionic surfactants, zeolite, silicate, soda, and in particular also Peroxy bleaches such as perborate.
  • Granular precursors for example spray-dried or granulated surfactant compounds be, but it is preferred that these precursors first be crushed or ground.
  • Foam inhibitors which are bound to a granular carrier substance with the other powdery starting materials mixed in the first process stage.
  • Premixes can, for example, also be used alone and if necessary compressing by increasing the temperature in the second process stage roll against each other.
  • the powdery ones are preferred Starting materials in the first stage of the process with liquid components acted upon.
  • Suitable liquid components are liquid non-ionic surfactants, water and any possible mixture of non-ionic surfactants, lower polyalkylene glycols, highly ethoxylated fatty alcohols, water, aqueous solutions, for example aqueous solutions of (co) polymeric polycarboxylates or water glass solutions, but also aqueous anionic surfactant pastes, and optionally liquid foam inhibitors, for example silicone oil.
  • liquid nonionic surfactants preferably ethoxylated C 12 -C 18 fatty alcohols, and / or water or aqueous solutions or mixtures of the type mentioned above are added as liquid constituents in the first process stage in such amounts that rollable in the second process stage , but non-adhesive granules can be obtained.
  • the optimal amount of liquid components for each recipe can be determined by simply trying them out.
  • the granular foam inhibitor is added preferably only after the powder has been applied Starting materials to moisturize the granular foam inhibitors prevent.
  • the granular foam inhibitor is added before entry in the second stage.
  • the first stage of the process can be used in all mixers, mixing plates, granulators, yes even be carried out in high speed mixers as long as these devices can be operated so that only a mixture and Powder applied, but no granulation or agglomeration takes place. The exception to this is the binding of fine fractions that are in the The opposite is even desirable. Since in a preferred embodiment Processes carried out continuously are also in the first process stage Mixer types that are operated continuously are preferred can.
  • the charged powdery starting materials are then transferred to a second mixer, in which the powdery starting materials are rolled against one another by the energy input of the tools.
  • a second mixer in which the powdery starting materials are rolled against one another by the energy input of the tools.
  • small amounts of liquid can also be added in this process stage, as long as the roll granulation is not affected. However, it is particularly preferred not to introduce any further components in this process stage before the roll granulation is terminated.
  • a large number of granulators are also suitable in this stage, for example pan granulators, plate granulators, rounders such as Marumerizer (R) and Spheronizer (R) , but also, for example, ploughshare mixers or annular layer mixers. A continuously operating ploughshare mixer is preferred at this point.
  • the resulting granules grow in with increasing dwell time the second stage of the process during the compacting roll-up granulation on.
  • the size of the granules is therefore determined by the residence time in the second mixer or by the duration of the compacting roll granulation certainly.
  • the compacting roll granulation by adding a fine particle Powder causes.
  • the resulting granules become like this powdered that the rolling process is stopped abruptly, but the plasticity the resulting granules are not completely lost.
  • Suitable fine-particle Powders are, for example, zeolite powders such as zeolite NaA powder, but also magnesium silicate, silicas, powdered silicone defoamers as well as all powders that are about 90% particle size exist below 30 ⁇ m.
  • the fine-particle powder is then broken off roll-up granulation preferably in amounts of up to 10% by weight, in particular added in amounts of 0.5 to 8 wt .-%. It is particularly advantageous the addition of finely divided powders in amounts of 1 to 5% by weight.
  • the resulting granules can be processed be further processed.
  • the setting of the high bulk density is made once by the rolling compression of the charged powdery raw materials to others also by powdering and by the possible density Bulking of the almost spherical granules seen macroscopically.
  • the existence of finely divided granules usually leads to this a further increase in bulk density.
  • the granules can then be dried, for example be dried in a fluidized bed, or left harden by cooling. There is drying in the fluidized bed also possible when using peroxy bleach. Keep the granules even when drying in the fluidized bed its seen macroscopically almost spherical structure because of the complete powdering of the Granules no further granulation can take place.
  • % aqueous C 9 -C 13 alkylbenzenesulfonate solution mixed in a continuously operating mixer (Schugi) and then with a high energy input in a CB mixer from Lödige with the addition of 4.8 parts by weight of a C 12 -C 18 fatty alcohol with 5 ethylene oxide groups.
  • the throughput was 1 t / h.
  • the bulk density of the granules after drying was 785 g / l. If the roll granulation was broken off according to the invention with about 2% by weight, based on the finished granulate, of zeolite powder, the bulk density of the dried granules was 860 g / l.
  • Example 2 All of the ingredients mentioned in Example 1, being spray-dried Granules are used with a composition according to Example 2 were in a Lödige ploughshare mixer with a Throughput of approx. 2 t / h mixed and then discontinuously in another Lödige mixer FK with an extension of the dwell time granulated.
  • the bulk density of the non-powdered granules from 476 g / l to 690 g / l; stopping the roll granulation powdering with 2% by weight of zeolite caused an increase in bulk density of the undried granules to 818 g / l.
  • the rolled granules dried in a fluidized bed were mixed with bleach activator granules and enzyme granules, introduction of perfume and final powdering with a mixture of zeolite powder and fine particles Silicic acid and / or with a powdered silicone defoamer processed.
  • the granules obtained according to Examples 1 to 4 had almost monodisperse internal granulate structure and a surface as in the Figures 3 and 4 is given.

Landscapes

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

Claims (4)

  1. Procédé de fabrication d'un détergent et nettoyant ou d'un composant pour celui-ci, dont les granules présentent une morphologie déterminée avec une surface quasiment sphérique (à l'oeil nu) et lisse (au microscope), ainsi qu'une structure interne quasiment monodispersée et un diamètre quelconque, car prédéterminable, caractérisé en ce que dans une première étape du procédé, les matières de départ pulvérulentes sont présentées dans un mélangeur et éventuellement mélangées avec les constituants liquides, le mélange est compacté par l'apport d'énergie dans une deuxième étape du procédé dans un deuxième mélangeur et les granules obtenus sont roulés les uns contre les autres afin de les compacter, ce qui leur confère une surface lisse (au microscope) et une structure interne quasiment monodispersée, et la granulation par roulage est arrêtée par l'adjonction d'une poudre à fines particules, après que l'on ait laissé les granules croítre jusqu'à un maximum prédéfini de distribution granulométrique.
  2. Procédé selon la revendication 1, caractérisé en ce que la poudre à fines particules est ajoutée pour interrompre la granulation par roulage en proportions pouvant atteindre 10 % en poids, de préférence en proportions comprises entre 0,5 et 0,8 % en poids et en particulier, en proportions de 1 à 5 % en poids.
  3. Procédé selon la revendication 1 ou 2, caractérisé en ce que les granules sont séchés.
  4. Procédé selon une des revendications 1 à 3, caractérisé en ce que l'on ajoute comme constituants liquides dans la première étape du procédé, des tensioactifs non ioniques liquides, de préférence des alcools gras éthoxylés en C12-C18 et/ou de l'eau ou des solutions aqueuses, ou des mélanges, dans des proportions telles que l'on obtienne dans la seconde étape du procédé des granules roulables, mais non collants.
EP94902690A 1992-12-15 1993-12-06 Procede de fabrication d'un detergent et nettoyant granule Revoked EP0674703B1 (fr)

Applications Claiming Priority (5)

Application Number Priority Date Filing Date Title
DE4242184 1992-12-15
DE4242184 1992-12-15
DE4304475 1993-02-15
DE4304475A DE4304475A1 (de) 1992-12-15 1993-02-15 Granuliertes Wasch- und Reinigungsmittel
PCT/EP1993/003427 WO1994013779A1 (fr) 1992-12-15 1993-12-06 Detergent et nettoyant granule

Publications (2)

Publication Number Publication Date
EP0674703A1 EP0674703A1 (fr) 1995-10-04
EP0674703B1 true EP0674703B1 (fr) 1999-10-20

Family

ID=25921330

Family Applications (1)

Application Number Title Priority Date Filing Date
EP94902690A Revoked EP0674703B1 (fr) 1992-12-15 1993-12-06 Procede de fabrication d'un detergent et nettoyant granule

Country Status (4)

Country Link
EP (1) EP0674703B1 (fr)
AT (1) ATE185839T1 (fr)
ES (1) ES2139064T3 (fr)
WO (1) WO1994013779A1 (fr)

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0390251A2 (fr) * 1989-03-30 1990-10-03 Unilever N.V. Compositions détergentes et procédé pour leur préparation

Family Cites Families (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CA962158A (en) * 1971-03-11 1975-02-04 Unilever Limited Detergent compositions
GB1437076A (en) * 1972-08-15 1976-05-26 Unilever Ltd Preparation of components for detergent formulations
JPH05500076A (ja) * 1989-08-09 1993-01-14 ヘンケル・コマンディットゲゼルシャフト・アウフ・アクチェン 洗剤中で使用する高密度顆粒の製造方法
US4991831A (en) * 1989-08-14 1991-02-12 Green Ronald J Paper sheet feeding apparatus
GB8925621D0 (en) * 1989-11-13 1990-01-04 Unilever Plc Process for preparing particulate detergent additive bodies and use thereof in detergent compositions
DE4024759A1 (de) * 1990-08-03 1992-02-06 Henkel Kgaa Bleichaktivatoren in granulatform

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0390251A2 (fr) * 1989-03-30 1990-10-03 Unilever N.V. Compositions détergentes et procédé pour leur préparation

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
HANS-PETER WILKE, RALF BUHSE, KLAUS GROSS: "MISCHER, Verfahrenstechnische Grundlagen und apparative Anwendungen", VULKAN VERLAG, ESSEN *

Also Published As

Publication number Publication date
EP0674703A1 (fr) 1995-10-04
ES2139064T3 (es) 2000-02-01
WO1994013779A1 (fr) 1994-06-23
ATE185839T1 (de) 1999-11-15

Similar Documents

Publication Publication Date Title
EP0642576B1 (fr) Procede de fabrication continue d'un detergent et/ou d'un nettoyant granulaire
EP0859827B1 (fr) Procede de production d'un silicate alcalin amorphe avec impregnation
EP0665879B1 (fr) Procede de preparation d'extrudats a action lavante et nettoyante
DE4203031A1 (de) Verfahren zur herstellung fester wasch- und reinigungsmittel mit hohem schuettgewicht und verbesserter loesegeschwindigkeit
EP0931137B1 (fr) Procede de production d'un detergent ou nettoyant particulaire
DE19956803A1 (de) Tensidgranulate mit verbesserter Auflösegeschwindigkeit
EP0804529B1 (fr) Compose silicate alcalin amorphe
EP0839178B1 (fr) Compose amorphe de silicate alcalin
EP1167509B1 (fr) Granules d'agent tensio-actif a vitesse de decomposition amelioree
EP0566583B1 (fr) Produits concentres secs facilement solubles, contenant des substances de produits de lavage
EP0724620B1 (fr) Procede de production d'extrudes de lavage ou de nettoyage a pouvoir ameliore de redispersion
EP1012221B1 (fr) Procede pour la production de detergents particulaires
EP0674703B1 (fr) Procede de fabrication d'un detergent et nettoyant granule
WO1996017045A1 (fr) Agents de lavage ou de nettoyage contenant des adjuvants de lavage hydrosolubles
DE4304475A1 (de) Granuliertes Wasch- und Reinigungsmittel
EP1043387A2 (fr) Granules d'alkylbenzènesulfonate
DE19529908A1 (de) Verfahren zur Herstellung eines amorphen Alkalisilikats mit Imprägnierung
EP0919614B1 (fr) Procédé de production des compositions détergentes à haute densité
WO2000039261A1 (fr) Adjuvant de lavage soluble et de faible dosage
EP0936267A2 (fr) Composé de silicate de métal alcalin / tensioactif nonionique
DE19542570A1 (de) Verfahren zur Herstellung von granularen Wasch- oder Reinigungsmitteln oder Komponenten hierfür
DE19911570A1 (de) Aniontensid-Granulate
WO1997023595A1 (fr) Procede pour produire des agents de lavage et/ou de nettoyage et dispositif correspondant
DE4435742A1 (de) Verfahren zur Herstellung wasch- oder reinigungsaktiver Extrudate
EP0871697A1 (fr) Procede de production d'agents de lavage et de nettoyage en granules ou composants utilises a cet effet

Legal Events

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

Free format text: ORIGINAL CODE: 0009012

17P Request for examination filed

Effective date: 19950606

AK Designated contracting states

Kind code of ref document: A1

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

RIN1 Information on inventor provided before grant (corrected)

Inventor name: TAMS, SOENKE

Inventor name: WICHE, ADOLF

Inventor name: ARTIGA GONZALEZ, RENE-ANDRES

Inventor name: SEITER, WOLFGANG

17Q First examination report despatched

Effective date: 19960223

GRAG Despatch of communication of intention to grant

Free format text: ORIGINAL CODE: EPIDOS AGRA

GRAG Despatch of communication of intention to grant

Free format text: ORIGINAL CODE: EPIDOS AGRA

GRAH Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOS IGRA

GRAH Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOS IGRA

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

AK Designated contracting states

Kind code of ref document: B1

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

REF Corresponds to:

Ref document number: 185839

Country of ref document: AT

Date of ref document: 19991115

Kind code of ref document: T

REF Corresponds to:

Ref document number: 59309840

Country of ref document: DE

Date of ref document: 19991125

ET Fr: translation filed
ITF It: translation for a ep patent filed

Owner name: STUDIO JAUMANN P. & C. S.N.C.

REG Reference to a national code

Ref country code: ES

Ref legal event code: FG2A

Ref document number: 2139064

Country of ref document: ES

Kind code of ref document: T3

PLBQ Unpublished change to opponent data

Free format text: ORIGINAL CODE: EPIDOS OPPO

PLBI Opposition filed

Free format text: ORIGINAL CODE: 0009260

PLBF Reply of patent proprietor to notice(s) of opposition

Free format text: ORIGINAL CODE: EPIDOS OBSO

26 Opposition filed

Opponent name: THE PROCTER & GAMBLE COMPANY

Effective date: 20000719

NLR1 Nl: opposition has been filed with the epo

Opponent name: THE PROCTER & GAMBLE COMPANY

PLBF Reply of patent proprietor to notice(s) of opposition

Free format text: ORIGINAL CODE: EPIDOS OBSO

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

Ref country code: BE

Payment date: 20010315

Year of fee payment: 8

PLBQ Unpublished change to opponent data

Free format text: ORIGINAL CODE: EPIDOS OPPO

PLAB Opposition data, opponent's data or that of the opponent's representative modified

Free format text: ORIGINAL CODE: 0009299OPPO

R26 Opposition filed (corrected)

Opponent name: THE PROCTER & GAMBLE COMPANY

Effective date: 20000719

NLR1 Nl: opposition has been filed with the epo

Opponent name: THE PROCTER & GAMBLE COMPANY

RDAH Patent revoked

Free format text: ORIGINAL CODE: EPIDOS REVO

RTI2 Title (correction)

Free format text: PROCES FOR PREPARING A GRANULATED WASHING AND CLEANING AGENT

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

Ref country code: FR

Payment date: 20011212

Year of fee payment: 9

Ref country code: AT

Payment date: 20011212

Year of fee payment: 9

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

Ref country code: NL

Payment date: 20011228

Year of fee payment: 9

Ref country code: ES

Payment date: 20011228

Year of fee payment: 9

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

Ref country code: DE

Payment date: 20020109

Year of fee payment: 9

RDAG Patent revoked

Free format text: ORIGINAL CODE: 0009271

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

Free format text: STATUS: PATENT REVOKED

27W Patent revoked

Effective date: 20011010

NLR2 Nl: decision of opposition
NLR2 Nl: decision of opposition

Effective date: 20011010