EP0678573A1 - Procédé de préparation de granules s'écoulant librement - Google Patents

Procédé de préparation de granules s'écoulant librement Download PDF

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Publication number
EP0678573A1
EP0678573A1 EP94201090A EP94201090A EP0678573A1 EP 0678573 A1 EP0678573 A1 EP 0678573A1 EP 94201090 A EP94201090 A EP 94201090A EP 94201090 A EP94201090 A EP 94201090A EP 0678573 A1 EP0678573 A1 EP 0678573A1
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EP
European Patent Office
Prior art keywords
acid
paste
process according
weight
spray dried
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
EP94201090A
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German (de)
English (en)
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EP0678573B1 (fr
Inventor
Achille Jules Edmond Doumen
Luc Goovaerts
Jose Luis Vega
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Procter and Gamble Co
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Procter and Gamble Co
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 to ES94201090T priority Critical patent/ES2152286T3/es
Application filed by Procter and Gamble Co filed Critical Procter and Gamble Co
Priority to EP94201090A priority patent/EP0678573B1/fr
Priority to AT94201090T priority patent/ATE197811T1/de
Priority to DE69426356T priority patent/DE69426356T2/de
Priority to JP7527733A priority patent/JP2763403B2/ja
Priority to BR9507325A priority patent/BR9507325A/pt
Priority to PE1995266823A priority patent/PE4996A1/es
Priority to AU23892/95A priority patent/AU2389295A/en
Priority to PH50365A priority patent/PH31632A/en
Priority to CA002187516A priority patent/CA2187516C/fr
Priority to CN95193542A priority patent/CN1078246C/zh
Priority to US08/722,089 priority patent/US5703037A/en
Priority to PCT/US1995/004798 priority patent/WO1995029215A1/fr
Publication of EP0678573A1 publication Critical patent/EP0678573A1/fr
Application granted granted Critical
Publication of EP0678573B1 publication Critical patent/EP0678573B1/fr
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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
    • C11D17/06—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
    • 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
    • C11D11/00—Special methods for preparing compositions containing mixtures of detergents
    • C11D11/04—Special methods for preparing compositions containing mixtures of detergents by chemical means, e.g. by sulfonating in the presence of other compounding ingredients followed by neutralising
    • 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
    • C11D3/3746—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/3757—(Co)polymerised carboxylic acids, -anhydrides, -esters in solid and liquid compositions
    • C11D3/3761—(Co)polymerised carboxylic acids, -anhydrides, -esters in solid and liquid compositions in solid 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
    • C11D3/3746—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/3769—(Co)polymerised monomers containing nitrogen, e.g. carbonamides, nitriles or amines
    • C11D3/3776—Heterocyclic compounds, e.g. lactam

Definitions

  • the present invention is concerned with a process for the manufacture of free flowing detergent granules having a bulk density of at least 600 g/l which comprises the addition of a spray dried powder comprising anionic polymer and cationic surfactant.
  • Cationic surfactants are well-known detergent ingredients which are used, in particular, for imparting a soft feel to fabrics after they have been washed.
  • the most commonly used cationic surfactants are commercially available as aqueous solutions, typically with a surfactant activity of about 35% or 40%.
  • Anionic polymers such as polycarboxylates are also well-known detergent ingredients. It has been found to be particularly beneficial to incorporate such polymers into surfactant pastes during the process of preparing high density detergent granules.
  • EP508543 published on 12th April 1991 describes a process in which a surfactant paste is structured (or "conditioned") with various agents, including polycarboxylate, prior to an agglomeration step. The addition of the polymer enables higher surfactant activities to be achieved in this process whilst still providing free-flowing, high bulk density detergent granules with a rapid rate of dissolution.
  • the present invention provides a process for incorporating aqueous solutions of cationic surfactants into free-flowing, high bulk density, high active detergent granules.
  • the objective of the present invention is achieved by complexing anionic polymer with cationic surfactant in solution.
  • the solution is then spray dried and mixed with high active surfactant pastes, preferably in a twin screw extruder, prior to agglomeration resulting in high active surfactant agglomerates of desirable properties.
  • the present invention provides a process for the manufacture of free flowing detergent granules having a bulk density of at least 600 g/l, comprising the steps of:
  • step b) comprises the steps of:
  • the spray dried powder which is added in step (b) preferably comprises:
  • the spray-dried powder comprises less than 10% by weight, preferably less than 5% by weight, (on anhydrous basis) of inorganic components. If however inorganic components are present, the spray dried component should comprise less than 5% by weight (on anhydrous basis) of aluminosilicate, carbonate and tripolyphosphate. It is also preferred that the spray dried powder comprises less than 10%, more preferably less than 1% by weight of anionic surfactant.
  • a useful anionic polymer (II) is one which comprises carboxylate functional groups.
  • Such a polymer may be selected from the group consisting of water-soluble salts of homo-and copolymers of aliphatic carboxylic acids such as acrylic acid, maleic acid, vinylic acid, itaconic acid, mesaconic acid, fumaric acid, aconitic acid, citraconic acid, methylenemalonic acid, aspartic acid and mixtures thereof.
  • hydrophobically modified polycarboxylates partially esterfied with long chain alcohols).
  • anionic polymer (II) is a copolymer of maleic and acrylic acid having a molecular weight of from 2 000 to 100 000.
  • a useful cationic surfactant (I) is a quaternary ammonium salt such as ditallow dimethyl ammonium chloride or coco dimethyl ethoxy ammonium chloride.
  • One or various aqueous pastes of the salts of anionic surfactants, and optionally nonionic surfactants are preferred for use in the present invention, preferably comprising the sodium salt of the anionic surfactant.
  • the anionic surfactant, or anionic / nonionic surfactant mix is preferably as concentrated as possible, (that is, with the lowest possible moisture content that allows it to flow in the manner of a liquid) so that it can be pumped at temperatures at which it remains stable.
  • a surfactant must be part of the paste in a concentration of preferably from 40% to 95%, more preferably from 60% to 85% by weight.
  • the moisture in the surfactant aqueous paste is as low as possible, while maintaining paste fluidity, since low moisture leads to a higher concentration of the surfactant in the finished particle.
  • the paste contains between 0 and 40% water, more preferably between 5 and 30% water and most preferably between 5% and 20% water.
  • high active surfactant pastes it is preferable to use high active surfactant pastes to minimize the total water level in the system during mixing, granulating and drying.
  • Lower water levels allow for: (1) a higher active surfactant to builder ratio, e.g., 1:1; (2) higher levels of other liquids in the formula without causing dough or granular stickiness; and (3) less granular drying to meet final moisture limits.
  • Viscosity is a function, among others, of concentration and temperature, with a range in this application up to about 10,000 Pas.
  • the viscosity of the paste entering the system is from about 1 Pas to about 100 Pas. and more preferably from about 10 Pas to about 70 Pas.
  • the viscosity of the paste of this invention is measured at a temperature of 70°C and a shear rate of 25 s ⁇ 1.
  • the paste can be introduced into the mixer at an initial temperature between its softening point (generally in the range of 20-60°C) and its degradation point (depending on the chemical nature of the paste, e.g. alkyl sulphate pastes tend to degrade above 75-85°C).
  • High temperatures reduce viscosity simplifying the pumping of the paste but result in lower active agglomerates.
  • the use of in-line cooling steps are preferred ways to increase agglomerate activity.
  • the use of in-line moisture reduction steps e.g. flash drying), however, require the use of higher temperatures (above 100°C).
  • the activity of the agglomerates is maintained high due to the elimination of moisture.
  • the introduction of the paste into the mixer can be done in many ways, from simply pouring to high pressure pumping through small holes at the end of the pipe, before the entrance to the mixer. While all these ways are viable to manufacture agglomerates with good physical properties, it has been found that in a preferred embodiment of the present invention the extrusion of the paste results in a better distribution in the mixer which improves the yield of particles with the desired size.
  • the use of high pumping pressures prior to the entrance in the mixer results in an increased activity in the final agglomerates.
  • the activity of the aqueous surfactant paste is at least 40% and can go up to about 95%; preferred activities are 60% to 85%, most preferred are 70% to 85%. At the higher active concentrations, little or no builder is required for cold granulation of the paste.
  • the resultant high active surfactant granules can be added to dry builders or powders or used in conventional agglomeration operations.
  • the aqueous surfactant paste contains an organic surfactant selected from the group consisting of anionic, nonionic, zwitterionic, ampholytic and cationic surfactants, and mixtures thereof. Anionic surfactants, and mixtures of anionic and nonionic surfactants are preferred.
  • Surfactants useful herein are listed in U.S. Pat. No. 3,664,961, Norris, issued May 23, 1972, and in U.S. Pat. No. 3,919,678, Laughlin et al., issued Dec. 30, 1975. The following are representative examples of surfactants useful in the present composition
  • Water-soluble salts of the higher fatty acids are useful anionic surfactants in the compositions herein.
  • Soaps can be made by direct saponification of fats and oils or by the neutralization of free fatty acids.
  • Particularly useful are the sodium and potassium salts of the mixtures of fatty acids derived from coconut oil and tallow, i.e., sodium or potassium tallow and coconut soap.
  • Useful anionic surfactants also include the water-soluble salts, preferably the alkali metal, ammonium and alkylolammonium salts, of organic sulfuric reaction products having in their molecular structure an alkyl group containing from about 10 to about 20 carbon atoms and a sulfonic acid or sulfuric acid ester group.
  • alkyl is the alkyl portion of acyl groups.
  • this group of synthetic surfactants are the sodium and potassium alkyl sulfates, especially those obtained by sulfating the higher alcohols (C8-C18 carbon atoms) such as those produced by reducing the glycerides of tallow or coconut oil; and the sodium and potassium alkyl benzene sulfonates in which the alkyl group contains from about 9 to about 15 carbon atoms, in straight or branched chain configuration, e.g., those of the type described in U.S. Pat. Nos. 2,220,099 and 2,477,383.
  • Especially valuable are linear straight chain alkyl benzene sulfonates in which the average number of carbon atoms in the alkyl group is from about 11 to 13, abbreviated as C11-C13 LAS.
  • Suitable anionic surfactants herein include the water-soluble salts of esters of alpha-sulfonated fatty acids containing from about 6 to 20 carbon atoms in the fatty acid group and from about 1 to 10 carbon atoms in the ester group; water-soluble salts of 2-acyloxy-alkane-1-sulfonic acids containing from about 2 to 9 carbon atoms in the acyl group and from about 9 to about 23 carbon atoms in the alkane moiety; alkyl ether sulfates containing from about 10 to 20 carbon atoms in the alkyl group and from about 1 to 30 moles of ethylene oxide; watersoluble salts of olefin sulfonates containing from about 12 to 24 carbon atoms; and beta-alkyloxy alkane sulfonates containing from about 1 to 3 carbon atoms in the alkyl group and from about 8 to about 20 carbon atoms in the alkane moiety.
  • the acid salts are typically discussed and used, the
  • Water-soluble nonionic surfactants are also useful as surfactants in the compositions of the invention. Indeed, preferred processes use anionic/nonionic blends.
  • a particularly preferred paste comprises a blend of nonionic and anionic surfactants having a ratio of from about 0.01:1 to about 4:1.
  • Such nonionic materials include compounds produced by the condensation of alkylene oxide groups (hydrophilic in nature) with an organic hydrophobic compound, which may be aliphatic or alkyl aromatic in nature. The length of the polyoxyalkylene group which is condensed with any particular hydrophobic group can be readily adjusted to yield a water-soluble compound having the desired degree of balance between hydrophilic and hydrophobic elements.
  • Suitable nonionic surfactants include the polyethylene oxide condensates of alkyl phenols, e.g., the condensation products of alkyl phenols having an alkyl group containing from about 6 to 16 carbon atoms, in either a straight chain or branched chain configuration, with from about 4 to 25 moles of ethylene oxide per mole of alkyl phenol.
  • Preferred nonionics are the water-soluble condensation products of aliphatic alcohols containing from 8 to 22 carbon atoms, in either straight chain or branched configuration, with from 2 to 25 moles of ethylene oxide per more of alcohol. Particularly preferred are the condensation products of alcohols having an alkyl group containing from about 9 to 15 carbon atoms with from about 2 to 25 moles of ethylene oxide per mole of alcohol; and condensation products of propylene glycol with ethylene oxide.
  • Other preferred nonionics are polyhydroxy fatty acid amides, such as tallow N-methyl glucose amide, and alkyl poly glucoside.
  • Semi-polar nonionic surfactants include water-soluble amine oxides containing one alkyl moiety of from about 10 to 18 carbon atoms and 2 moieties selected from the group consisting of alkyl groups and hydroxyalkyl groups containing from 1 to about 3 carbon atoms; water-soluble phosphine oxides containing one alkyl moiety of about 10 to 18 carbon atoms and 2 moieties selected from the group consisting of alkyl groups and hydroxyalkyl groups containing from about 1 to 3 carbon atoms; and water-soluble sulfoxides containing one alkyl moiety of from about 10 to 18 carbon atoms and a moiety selected from the group consisting of alkyl and hydroxyalkyl moieties of from about 1 to 3 carbon atoms.
  • Ampholytic surfactants include derivatives of aliphatic or aliphatic derivatives of heterocyclic secondary and tertiary amines in which the aliphatic moiety can be either straight or branched chain and wherein one of the aliphatic substituents contains from about 8 to 18 carbon atoms and at least one aliphatic substituent contains an anionic water-solubilizing group.
  • Zwitterionic surfactants include derivatives of aliphatic quaternary ammonium phosphonium, and sulfonium compounds in which one of the aliphatic substituents contains from about 8 to 18 carbon atoms.
  • Preferred cationic surfactants are water soluble quartenary ammonium salts containing one or two long alkyl groups containing from 10 to 14 carbon atoms and 2 or 3 short alkyl groups each of which contain no more than 2 carbon atoms and optionally have ethoxy groups.
  • Useful cationic surfactants include water-soluble quaternary ammonium compounds of the form R4R5R6R7N+X ⁇ , wherein R4 is alkyl having from 10 to 20, preferably from 12-18 carbon atoms, and R5 is C1 to C20 , R6 and R7 are each C1 to C7 alkyl preferably methyl; X ⁇ is an anion, e.g. chloride.
  • Examples of such trimethyl ammonium compounds include C12 ⁇ 14 alkyl trimethyl ammonium chloride, C12 ⁇ 14 alkyl dimethyl ethoxy ammonium chloride and cocalkyl trimethyl ammonium methosulfate.
  • Other useful cationic surfactants are described in US Pat No. 4,222,905, Cockrell, issued Sept 16, 1990 and in US Pat No 4,239,659, Murphy, issued Dec. 16, 1980.
  • Useful organic polymers may also function as builders to improve detergency. Included among such polymers may be mentioned sodium carboxy-lower alkyl celluloses, sodium lower alkyl celluloses and sodium hydroxy-lower alkyl celluloses, such as sodium carboxymethyl cellulose, sodium methyl cellulose and sodium hydroxypropyl cellulose, polyacrylates and various copolymers, such as those of maleic and acrylic acids. Molecular weights for such polymers vary widely but most are within the range of 2,000 to 100,000.
  • Polymeric polycarboxyate builders are set forth in U.S. Patent 3,308,067, Diehl, issued March 7, 1967. Such materials include the water-soluble salts of homo-and copolymers of aliphatic carboxylic acids such as acrylic acid, maleic acid, vinylic acid, itaconic acid, mesaconic acid, fumaric acid, aconitic acid, citraconic acid methylenemalonic acid, and aspartic acid.
  • aliphatic carboxylic acids such as acrylic acid, maleic acid, vinylic acid, itaconic acid, mesaconic acid, fumaric acid, aconitic acid, citraconic acid methylenemalonic acid, and aspartic acid.
  • the spray dried powder comprising the cationic surfactant and anionic polymer may be prepared by any conventional method, such as spray drying using pressure nozzle, two-fluid nozzle or spinning disc atomiser.
  • the spinning disc atomiser and the two fluid nozzle are preferred.
  • the spray dried powder is preferably mixed with the high active surfactant paste to form a uniform pasty mixture.
  • the high active paste may also be thickened or "structured". Suitable thickening or structuring agents are fatty acids, fatty acid soaps, silicates and polymers. It is preferred that the mixing of this processing step is carried out in an extruder.
  • the extruder fulfills the functions of pumping and mixing the viscous surfactant paste on a continuous basis.
  • a basic extruder consists of a barrel with a smooth inner cylindrical surface. Mounted within this barrel is the extruder screw. There is an inlet port for the high active paste which, when the screw is rotated, causes the paste to be moved along the length of the barrel. Additional ports in the barrel may allow other ingredients, including the spray dried powder to be added directly into the barrel.
  • a preferred extruder is the twin screw extruder. This type of extruder has two screws mounted in parallel within the same barrel, which are made to rotate either in the same direction (co-rotation) or in opposite directions (counter-rotation). The co-rotating twin screw extruder is the most preferred piece of equipment for use in this invention.
  • Suitable twin screw extruders for use in the present invention include those supplied by : APV Baker, (CP series); Werner and Pfleiderer, (Continua Series); Wenger, (TF Series); Leistritz, (ZSE Series); and Buss, (LR Series).
  • high shear mixing means mixing and/or granulation of the above pasty mixture with powders in a high shear mixer at a blade tip speed of from about 5m/sec. to about 50 m/sec., unless otherwise specified.
  • the total residence time of the mixing and granulation process is preferably in the order of from 0.1 to 10 minutes, more preferably 0.1-5 and most preferably 0.2-4 minutes.
  • the more preferred mixing and granulation tip speeds are about 10-45 m/sec. and about 15-40 m/sec.
  • the ratio of pasty mixture to powder should be chosen in order to maintain discrete particles at all stages of the process. These particles may be sticky but must be substantially free flowing so that the mixing and granulation steps can be carried out simultaneously, or immediately sequentially without causing blockage of the mixer/granulator.
  • Suitable apparatus includes, for example, falling film sulphonating reactors, digestion tanks, esterification reactors, etc.
  • any of a number of mixers/agglomerators can be used.
  • the process of the invention is continuously carried out.
  • mixers of the Fukae R FS-G series manufactured by Fukae Powtech Kogyo Co., Japan are especially preferred.
  • this apparatus is essentially in the form of a bowl-shaped vessel accessible via a top port, provided near its base with a stirrer having a substantially vertical axis, and a cutter positioned on a side wall.
  • the stirrer and cutter may be operated independently of one another and at separately variable speeds.
  • the vessel can be fitted with a cooling jacket or, if necessary, a cryogenic unit.
  • mixers found to be suitable for use in the process of the invention inlcude Diosna R V series ex Dierks & Söhne, Germany; and the Pharma Matrix R ex T K Fielder Ltd., England.
  • Other mixers believed to be suitable for use in the process of the invention are the Fuji R VG-C series ex Fuji Sangyo Co., Japan; and the Roto R ex Zanchetta & Co srl, Italy.
  • Other preferred suitable equipment can include Eirich R , series RV, manufactured by Gustau Eirich Hardheim, Germany; Lödige R , series CB and KM in series for continuous mixing/agglomeration, manufactured by Lödige Machinenbau GmbH, Paderborn Germany; Drais R T160 series, manufactured by Drais Werke GmbH, Mannheim Germany; and Winkworth R RT 25 series, manufactured by Winkworth Machinery Ltd., Bershire, England.
  • the Littleford Mixer, Model #FM-130-D-12, with internal chopping blades and the Cuisinart Food Processor, Model #DCX-Plus, with 7.75 inch (19.7 cm) blades are two examples of suitable mixers. Any other mixer with fine dispersion mixing and granulation capability and having a residence time in the order of 0.1 to 10 minutes can be used.
  • the "turbine-type" impeller mixer, having several blades on an axis of rotation, is preferred.
  • the invention can be practiced as a batch or a continuous process.
  • Preferred operating temperatures should also be as low as possible since this leads to a higher surfactant concentration in the finished particle.
  • the temperature during the agglomeration is less than 100°C, more preferably between 10 and 90°C, and most preferably between 25 and 80°C.
  • Lower operating temperatures useful in the process of the present invention may be achieved by a variety of methods known in the art such as nitrogen cooling, cool water jacketing of the equipment, addition of solid CO2, and the like; with a preferred method being solid CO2, and the most preferred method being nitrogen cooling.
  • powders are suitable for use in the granulation step of the present process.
  • Prefered powders for use in the process and compositions of the present invention are compatible detergency builder or combination of builders or powder.
  • the detergent compositions herein can contain crystalline aluminosilicate ion exchange material of the formula Na z [(A1O2) z ⁇ (SiO2) y ] ⁇ xH2O wherein z and y are at least about 6, the molar ratio of z to y is from about 1.0 to about 0.4 and z is from about 10 to about 264.
  • Amorphous hydrated aluminosilicate materials useful herein have the empirical formula M z (zA1O2 ⁇ ySiO2) wherein M is sodium, potassium, ammonium or substituted ammonium, z is from about 0.5 to about 2 and y is 1, said material having a magnesium ion exchange capacity of at least about 50 milligram equivalents of CaCO3 hardness per gram of anhydrous aluminosilicate. Hydrated sodium Zeolite A with a particle size of from about 1 to 10 microns is preferred.
  • the aluminosilicate ion exchange builder materials herein are in hydrated form and contain from about 10% to about 28% of water by weight if crystalline, and potentially even higher amounts of water if amorphous. Highly preferred crystalline aluminosilicate ion exchange materials contain from about 18% to about 22% water in their crystal matrix.
  • the crystalline aluminosilicate ion exchange materials are further characterized by a particle size diameter of from about 0.1 micron to about 10 microns. Amorphous materials are often smaller, e.g., down to less than about 0.01 micron.
  • Preferred ion exchange materials have a particle size diameter of from about 0.2 micron to about 4 microns.
  • particle size diameter herein represents the average particle size diameter by weight of a given ion exchange material as determined by conventional analytical techniques such as, for example, microscopic determination utilizing a scanning electron microscope.
  • the crystalline aluminosilicate ion exchange materials herein are usually further characterized by their calcium ion exchange capacity, which is at least about 200 mg equivalent of CaCO3 water hardness/g of aluminosilicate, calculated on an anhydrous basis, and which generally is in the range of from about 300 mg eq./g to about 352 mg eq./g.
  • the aluminosilicate ion exchange materials herein are still further characterized by their calcium ion exchange rate which is at least about 2 grains Ca++/gallon/minute/gram/gallon of aluminosilicate (anhydrous basis), and generally lies within the range of from about 2 grains/gallon/minute/gram/gallon to about 6 grains/gallon/minute/gram/gallon, based on calcium ion hardness.
  • Optimum aluminosilicate for builder purposes exhibit a calcium ion exchange rate of at least about 4 grains/gallon/minute/gram/gallon.
  • the amorphous aluminosilicate ion exchange materials usually have a Mg++ exchange of at least about 50 mg eq. CaCO3/g (12 mg Mg++/g) and a Mg++ exchange rate of at least about 1 grain/gallon/minute/gram/gallon. Amorphous materials do not exhibit an observable diffraction pattern when examined by Cu radiation (1.54 Angstrom Units).
  • Aluminosilicate ion exchange materials useful in the practice of this invention are commercially available.
  • the aluminosilicates useful in this invention can be crystalline or amorphous in structure and can be naturally occurring aluminosilicates or synthetically derived.
  • a method for producing aluminosilicate ion exchange materials is discussed in U.S. Pat. No. 3,985,669, Krummel et al., issued Oct. 12, 1976, incorporated herein by reference.
  • Preferred synthetic crystalline aluminosilicate ion exchange materials useful herein are available under the designations Zeolite A, Zeolite B, Zeolite P, Zeolite MAP and Zeolite X.
  • the crystalline aluminosilicate ion exchange material has the formula Na12[(A1O2)12(SiO2)12] ⁇ xH2O wherein x is from about 20 to about 30, especially about 27 and has a particle size generally less than about 5 microns.
  • the granular detergents of the present invention can contain neutral or alkaline salts which have a pH in solution of seven or greater, and can be either organic or inorganic in nature.
  • the builder salt assists in providing the desired density and bulk to the detergent granules herein. While some of the salts are inert, many of them also function as detergency builder materials in the laundering solution.
  • neutral water-soluble salts examples include the alkali metal, ammonium or substituted ammonium chlorides, fluorides and sulfates.
  • the alkali metal, and especially sodium, salts of the above are preferred.
  • Sodium sulfate is typically used in detergent granules and is a particularly preferred salt.
  • Citric acid and, in general, any other organic or inorganic acid may be incorporated into the granular detergents of the present invention as long as it is chemically compatible with the rest of the agglomerate composition.
  • water-soluble salts include the compounds commonly known as detergent builder materials.
  • Builders are generally selected from the various water-soluble, alkali metal, ammonium or substituted ammonium phosphates, polyphosphates, phosphonates, polyphosphonates, carbonates, silicates, borates, citrates, silicas and polyhyroxysulfonates.
  • alkali metal especially sodium, salts of the above.
  • inorganic phosphate builders are sodium and potassium tripolyphosphate, pyrophosphate, polymeric metaphosphate having a degree of polymerization of from about 6 to 21, and orthophosphate.
  • polyphosphonate builders are the sodium and potassium salts of ethylene diphosphonic acid, the sodium and potassium salts of ethane 1-hydroxy-1,1-diphosphonic acid and the sodium and potassium salts of ethane, 1,1,2-triphosphonic acid.
  • Other phosphorus builder compounds are disclosed in U.S. Pat. Nos. 3,159,581; 3,213,030; 3,422,021; 3,422,137; 3,400,176 and 3,400,148, incorporated herein by reference.
  • nonphosphorus, inorganic builders are sodium and potassium carbonate, bicarbonate, sesquicarbonate, tetraborate decahydrate, and silicate having a molar ratio of SiO2 to alkali metal oxide of from about 0.5 to about 4.0, preferably from about 1.0 to about 2.4.
  • Highly preferred materials within the silicate class are crystalline layered sodium silicates of general formula : NaMSiO 2x+1 .yH2O wherein M is sodium or hydrogen, x is a number from 1.9 to 4 and y is a number from 0 to 20. Crystalline layered sodium silicates of this type are disclosed in EP-A-0164514 and methods for their preparation are disclosed in DE-A-3417649 and DE-A-3742043.
  • x in the general formula above has a value of 2, 3 or 4 and is preferably 2. More preferably M is sodium and y is 0 and preferred examples of this formula comprise the ⁇ and ⁇ forms of Na2Si2O5. These materials are available from Hoechst AG FRG as respectively NaSKS-11 and NaSKS-6. The most preferred material is ⁇ -Na2Si2O5, (NaSKS-6). Crystalline layered silicates are incorporated either as dry mixed solids, or as solid components of agglomerates with other components.
  • compositions made by the process of the present invention does not require excess carbonate for processing, and preferably does not contain over 2% finely divided calcium carbonate as disclosed in U.S. Pat. No. 4,196,093, Clarke et al., issued Apr.1, 1980, and is preferably free of the latter.
  • the composition was prepared by mixing a 40% active solution of the sodium salt of the copolymer and a 40% active solution of fatty alkyldimethylhydroxethylamoniumchloride to give a well mixed slurry. The slurry was then processed through a continuous spray dryer with concurrent air inlet and a rotating disc (15000 rpm) at the top of the tower. After the exit from the bottom of the tower, the product is further dried and cooled in a fluid bed dryer and fluid bed cooler in series.
  • the resulting spray dried powder After classification (removal of fines and oversize particles) by vibrating screens, the resulting spray dried powder had an apparent bulk density of 250 g/l.
  • An aqueous surfactant paste comprising : 62.5% by weight sodium alkyl sulphate having substantially C12, C14 and C15 alkyl chains ; 15.5% by weight sodium alkyl ethoxy sulphate having substantially C12 to C15 alkyl chains and an average of 3 ethoxy groups per molecule ; 17% by weight of water and the balance being mainly comprised of unreacted alcohol and sulphates.
  • aqueous surfactant paste and the powder compound described in example one were intimately mixed in a twin screw extruder (manufactured by Werner & Pfleiderer, C170).
  • the resulting viscous paste was extruded (at a temperature of 60°C) directly into a Loedige CB30 (trade name) high speed mixer containing a mixture of 2 part zeolite A to 1 part finely divided light carbonate.
  • the mixer operates on a continuous basis and discharges directly into a Loedige KM 3000 (trade name) continuous ploughshare mixer.
  • the resulting agglomerates were transferred to a fluid bed drier, cooled in a fluid bed cooler and then classified through mesh sieves to remove oversize and fine particles.
  • the agglomerates formed have an anionic surfactant content of 40% by weight, a polymer level of 14%, a cationic surfactant level of 7% and an equilibrium relative humidity level of 10% at room temperature.
  • the granules have an apparent bulk density of 680 g/l and have excellent flow and handling properties.
  • This powder was then incorporated into a free flowing, high density particle, by the same process as described in example 1 (b), (except that the composition of the powder mixture entering the high speed mixer was: Zeolite A, 42%; light sodium carbonate 58%) to give a free flowing granular product having an anionic surfactant content of 40%, a polymer content of 7%, a cationic surfactant level of 7%, and an equilibrium relative humidity level of 10% at room temperature.
  • the granules have an apparent bulk density of 700 g/l and have excellent flow and handling properties.

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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)
EP94201090A 1994-04-20 1994-04-20 Procédé de préparation de granules s'écoulant librement Expired - Lifetime EP0678573B1 (fr)

Priority Applications (13)

Application Number Priority Date Filing Date Title
EP94201090A EP0678573B1 (fr) 1994-04-20 1994-04-20 Procédé de préparation de granules s'écoulant librement
AT94201090T ATE197811T1 (de) 1994-04-20 1994-04-20 Verfahren zur herstellung von rieselfähigen waschmittelgranulaten
DE69426356T DE69426356T2 (de) 1994-04-20 1994-04-20 Verfahren zur Herstellung von rieselfähigen Waschmittelgranulaten
ES94201090T ES2152286T3 (es) 1994-04-20 1994-04-20 Procedimiento de fabricacion de granulos de detergente que fluyen libremente.
US08/722,089 US5703037A (en) 1994-04-20 1995-04-20 Process for the manufacture of free-flowing detergent granules
PE1995266823A PE4996A1 (es) 1994-04-20 1995-04-20 Procedimiento para la manufactura de granulos detergentes fluidos
JP7527733A JP2763403B2 (ja) 1994-04-20 1995-04-20 自由流動性洗剤粒状物の製法
PH50365A PH31632A (en) 1994-04-20 1995-04-20 Process for the manufacture of free-flowing detergent granules.
CA002187516A CA2187516C (fr) 1994-04-20 1995-04-20 Procede de fabrication de granules detersives coulantes
CN95193542A CN1078246C (zh) 1994-04-20 1995-04-20 生产自由流动洗涤粒的方法
BR9507325A BR9507325A (pt) 1994-04-20 1995-04-20 Processo para a fabrição de grânulos detergentes com livre escoamento
PCT/US1995/004798 WO1995029215A1 (fr) 1994-04-20 1995-04-20 Procede de fabrication de granules detersives coulantes
AU23892/95A AU2389295A (en) 1994-04-20 1995-04-20 Process for the manufacture of free-flowing detergent granules

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
EP94201090A EP0678573B1 (fr) 1994-04-20 1994-04-20 Procédé de préparation de granules s'écoulant librement

Publications (2)

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EP0678573A1 true EP0678573A1 (fr) 1995-10-25
EP0678573B1 EP0678573B1 (fr) 2000-11-29

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EP (1) EP0678573B1 (fr)
JP (1) JP2763403B2 (fr)
CN (1) CN1078246C (fr)
AT (1) ATE197811T1 (fr)
AU (1) AU2389295A (fr)
BR (1) BR9507325A (fr)
CA (1) CA2187516C (fr)
DE (1) DE69426356T2 (fr)
ES (1) ES2152286T3 (fr)
PE (1) PE4996A1 (fr)
PH (1) PH31632A (fr)
WO (1) WO1995029215A1 (fr)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0745662A1 (fr) * 1994-12-15 1996-12-04 Nippon Shokubai Co., Ltd. Adjuvant pour detergent, son procede de fabrication et composition detergente le contenant
US6468957B1 (en) 1998-09-29 2002-10-22 Henkel Kommanditgesellschaft Auf Aktien Granulation method
DE102012217877A1 (de) 2012-10-01 2013-08-14 Henkel Ag & Co. Kgaa Nontower-Verfahren

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE19721885A1 (de) † 1997-05-26 1998-12-03 Henkel Kgaa Verfahren zur Herstellung kationtensidhaltiger Granulate
DE10163603B4 (de) 2001-12-21 2006-05-04 Henkel Kgaa Verfahren zur Herstellung builderhaltiger Tensidgranulate
DE102008059447A1 (de) * 2008-11-27 2010-06-02 Henkel Ag & Co. Kgaa Wasch- und Reinigungsmittel enthaltend Proteasen aus Bacillus pumilus

Citations (4)

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Publication number Priority date Publication date Assignee Title
DE3521498A1 (de) * 1984-06-20 1986-01-16 Lion Corp., Tokio/Tokyo Additiv fuer waschmittel-granulat
JPS6272799A (ja) * 1985-09-26 1987-04-03 ライオン株式会社 粒状洗剤用添加剤
DE3643334A1 (de) * 1985-12-19 1987-07-09 Lion Corp Zusatz fuer ein koerniges wasch- und reinigungsmittel
EP0508543A1 (fr) * 1991-04-12 1992-10-14 The Procter & Gamble Company Structuration chimique de pâtes tensio-actives pour former des granulés tensio-actifs avec haute activité

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US4704221A (en) * 1986-10-22 1987-11-03 The Procter & Gamble Company Granular detergents which contain high levels of anionic surfactant that forms a middle-phase, surface treated with a water soluble cationic surfactant
IN170991B (fr) * 1988-07-21 1992-06-27 Lever Hindustan Ltd
CA2017922C (fr) * 1989-06-09 1995-07-11 Frank Joseph Mueller Preparation de granules detergentes a haut pouvoir nettoyant au moyen d'un systeme de neutralisation continue
GB9001285D0 (en) * 1990-01-19 1990-03-21 Unilever Plc Detergent compositions and process for preparing them
US5066425A (en) * 1990-07-16 1991-11-19 The Procter & Gamble Company Formation of high active detergent particles

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Publication number Priority date Publication date Assignee Title
DE3521498A1 (de) * 1984-06-20 1986-01-16 Lion Corp., Tokio/Tokyo Additiv fuer waschmittel-granulat
JPS6272799A (ja) * 1985-09-26 1987-04-03 ライオン株式会社 粒状洗剤用添加剤
DE3643334A1 (de) * 1985-12-19 1987-07-09 Lion Corp Zusatz fuer ein koerniges wasch- und reinigungsmittel
EP0508543A1 (fr) * 1991-04-12 1992-10-14 The Procter & Gamble Company Structuration chimique de pâtes tensio-actives pour former des granulés tensio-actifs avec haute activité

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DATABASE WPI Section Ch Week 8719, Derwent World Patents Index; Class A97, AN 87-132629 *

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0745662A1 (fr) * 1994-12-15 1996-12-04 Nippon Shokubai Co., Ltd. Adjuvant pour detergent, son procede de fabrication et composition detergente le contenant
EP0745662A4 (fr) * 1994-12-15 1999-02-24 Nippon Catalytic Chem Ind Adjuvant pour detergent, son procede de fabrication et composition detergente le contenant
US5962401A (en) * 1994-12-15 1999-10-05 Nippon Shokubai Co., Ltd. Detergent builder process of manufacturing same and detergent composition containing same
US6468957B1 (en) 1998-09-29 2002-10-22 Henkel Kommanditgesellschaft Auf Aktien Granulation method
DE102012217877A1 (de) 2012-10-01 2013-08-14 Henkel Ag & Co. Kgaa Nontower-Verfahren

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DE69426356D1 (de) 2001-01-04
JP2763403B2 (ja) 1998-06-11
WO1995029215A1 (fr) 1995-11-02
PE4996A1 (es) 1996-04-01
BR9507325A (pt) 1997-09-30
PH31632A (en) 1999-01-12
CN1150449A (zh) 1997-05-21
ATE197811T1 (de) 2000-12-15
ES2152286T3 (es) 2001-02-01
DE69426356T2 (de) 2001-06-21
CA2187516C (fr) 2000-02-15
CA2187516A1 (fr) 1995-11-02
JPH09512299A (ja) 1997-12-09
CN1078246C (zh) 2002-01-23
AU2389295A (en) 1995-11-16
EP0678573B1 (fr) 2000-11-29

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