EP1141197B1 - Procedes permettant de preparer une composition detergente en granules contenant de la carboxymethylcellulose modifiee - Google Patents

Procedes permettant de preparer une composition detergente en granules contenant de la carboxymethylcellulose modifiee Download PDF

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Publication number
EP1141197B1
EP1141197B1 EP99966543A EP99966543A EP1141197B1 EP 1141197 B1 EP1141197 B1 EP 1141197B1 EP 99966543 A EP99966543 A EP 99966543A EP 99966543 A EP99966543 A EP 99966543A EP 1141197 B1 EP1141197 B1 EP 1141197B1
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EP
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Prior art keywords
detergent
agglomerates
densifier
density
speed mixer
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EP99966543A
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German (de)
English (en)
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EP1141197A1 (fr
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Ricci John Jones
Teruaki Tatsuno
Jennifer Ann Leupin
Paul Richard Sherrington
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Procter and Gamble Co
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Procter and Gamble Co
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    • 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
    • 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
    • C11D3/20—Organic compounds containing oxygen
    • C11D3/22—Carbohydrates or derivatives thereof
    • C11D3/222—Natural or synthetic polysaccharides, e.g. cellulose, starch, gum, alginic acid or cyclodextrin
    • C11D3/225—Natural or synthetic polysaccharides, e.g. cellulose, starch, gum, alginic acid or cyclodextrin etherified, e.g. CMC

Definitions

  • the present invention generally relates to processes for producing a granular detergent composition. More particularly, the invention is directed to processes during which detergent granules or agglomerates are produced from starting detergent materials, one of which is a modified carboxy methyl cellulose.
  • formulators In an effort to appease consumers' desires to slow, or preferably, eliminate the degradation of a fabric's appearance, formulators have searched for detergent additives that will aid in maintaining a fabric's appearance over its normal life cycle. As new detergent additives are developed, formulators must find a way to incorporate the additives into detergent compositions without adversely affecting the physical or chemical properties of the existing composition. That is, an additive that maintains fabric appearance should not reduce the cleaning efficacy of the detergent, nor should it cause the detergent to clump or otherwise have undesirable physical characteristics in the eyes of the average consumer. Often, the challenges associated with the introduction of a new detergent additive can be met with adjustments to the detergent manufacturing process.
  • the first type of process involves spray-drying an aqueous detergent slurry in a spray-drying tower to produce highly porous detergent granules.
  • the various detergent components are dry mixed after which they are agglomerated with a binder such as a nonionic or anionic surfactant.
  • a binder such as a nonionic or anionic surfactant.
  • surfactants and combinations thereof in detergent compositions.
  • various anionic surfactants especially the alkyl benzene sulfonates, alkyl sulfates, alkyl alkoxy sulfates and various nonionic surfactants, such as alkyl ethoxylates and alkylphenol ethoxylates are commonly used in detergent formulations.
  • Surfactants have found use as detergent components capable of the removal of a wide variety of soils and stains. A consistent effort, however, is made by detergent manufacturers to improve detersive properties of detergent compositions by providing new and improved surfactants.
  • a problem commonly associated with anionic surfactants is their sensitivity to cold water and/or hard water.
  • the present invention meets the aforementioned needs in the art by providing a process for continuously preparing detergent agglomerates comprising the steps of: (A) continuously mixing a liquid binder and dry detergent materials into a high speed mixer/densifier to obtain detergent agglomerates, wherein the ratio of the liquid binder to the dry detergent material is from 1:10 to 10:1, wherein the dry detergent materials comprise modified carboxy methyl cellulose; (B) optionally mixing the detergent agglomerates in a moderate speed mixer/densifier to further density and agglomerate the detergent agglomerates; and (C) drying the detergent agglomerates so as to increase their density.
  • the dry detergent materials consist essentially of modified carboxy methyl cellulose.
  • the liquid binder comprises water and a polymer selected from the group consisting of dye transfer agents, polyamines, homopolymers and copolymers of polyacrylates, homopolymers and copolymers of polyacrylamides, homopolymers and copolymers of polyvinyl alcohol, homopolymers and copolymers of polyvinyl pyrrolidone, polymaleates, aliphatic polyesters, natural proteins, synthetic non-crystalline polyaminoacids, water soluble nylons, polyethylene glycol, polyacrylate and mixtures thereof.
  • the liquid binder comprises a polymer selected from the group consisting of a polyvinyl N-Oxide, a copolymer of epichlorohydrin and a cyclic amine moiety, and mixtures thereof.
  • a preferred aspect of the invention includes the use of a surfactant paste in addition to the polymer-based liquid binder.
  • the paste includes surfactants selected from branched and linear anionics, nonionic, zwitterionic, ampholytic and cationic classes and compatible mixtures thereof.
  • the surfactant paste is selected from the group consisting of linear straight chain alkylbenzene sulfonates in which the average number of carbon atoms in the alkyl group is from 11 to 13, abbreviated as C 11-13 LAS, Sodium ethoxysulphate based on a biodegradable C12/14 synthetic or natural primary alcohol ethoxylate made with a nominal 3 moles of ethylene oxide.
  • second detergent agglomerates can be made by a process comprising the steps of: (A) continuously mixing a detergent surfactant paste and additional dry detergent materials into a high speed mixer/densifier to obtain second detergent agglomerates, wherein the ratio of the surfactant paste to the additional dry detergent material is from 1:10 to 10:1; (B) optionally mixing the second detergent agglomerates in a moderate speed mixer/densifier to increase their density; (C) drying the second detergent agglomerates to further increase their density.
  • the second detergent agglomerates can then be mixed with the first detergent agglomerates to form the high density detergent composition.
  • the surfactant paste can be replaced by, or supplemented with an acid precursor of an anionic surfactant and additional dry detergent materials which contain an alkaline inorganic material capable of neutralizing the acid precursor.
  • detergent granules can be admixed with the modified carboxy methyl cellulose containing agglomerates defined above to form a high density detergent composition.
  • These granules can be formed by spray drying an aqueous slurry containing adjunct detergent ingredients to form spray dried granules. Then the granules and the detergent agglomerates can be blended together to form the high density detergent composition.
  • modified carboxy methyl cellulose materials provide fabric appearance benefits.
  • the modified carboxy methyl cellulose materials are sometimes supplied as a sticky powder, which when added to a detergent composition can cause the resulting detergent agglomerates to be sticky as well.
  • Sticky agglomerates often cause clumps in the detergent composition which is a strong consumer negative.
  • these modified carboxy methyl cellulose materials are not always dispersed satisfactorily, resulting in reduced performance and moreover localised residues of the material in the washing machine and on the fabrics.
  • other detergent ingredients can become entrapped in the cellulosic material, causing further residue problems, reduced performance of these other ingredients.
  • the stickiness and the poor dispersability of the modified carboxy methyl cellulose, and its deleterious effect on the detergent composition can be counter-acted by the processing conditions and constituents defined herein.
  • a first agglomerate is prepared from using a liquid binder comprising a mixture of surfactant selected from the group of LAS, preferably C 11-13 LAS or Sodium ethoxysulphate, wherein the ethoxysulate is preferably based on a biodegradable C12/14 synthetic or natural primary alcohol ethoxylate made with a nominal 3 moles of ethylene oxide and mixtures thereof; this liquid binder is used in combination with a polymer selected from the group of a copolymer of epichlorohydrin and a cyclic amine moiety or polyvinyl N-Oxide, and mixtures thereof in combination with dry detergent materials that include a modified carboxy methyl cellulose.
  • a liquid binder comprising a mixture of surfactant selected from the group of LAS, preferably C 11-13 LAS or Sodium ethoxysulphate, wherein the ethoxysulate is preferably based on a biodegradable C12/14 synthetic or natural primary alcohol ethoxylate
  • a second agglomerate is prepared using a surfactant paste and dry starting materials that do not include modified carboxy methyl cellulose.
  • the two separate agglomerates are admixed to form a detergent composition that is free flowing.
  • the separate detergent particles of this invention can be formed by spray drying techniques which can include further processing of the "post-tower" detergent granules.
  • post-tower detergent granules it is meant those detergent granules which have been processed through a conventional spray-drying tower or. similar apparatus.
  • compositions of the invention contain, in addition to a modified carboxy methyl cellulose material, at least one suitable adjunct dry detergent ingredient which is preferably included in the detergent composition.
  • the resulting detergent composition preferably comprises from 0.01% to 4%, more preferably from 0.05% to 2%, and most preferably from 0.1% to 1%, by weight of the modified carboxy methyl cellulose.
  • the adjunct dry detergent ingredient is preferably selected from the group consisting of builders, enzymes, bleaching agents, bleach activators, suds suppressors, soil release agents, brighteners, perfumes, hydrotropes, dyes, pigments, polymeric dispersing agents, pH controlling agents, chclants, processing aids, crystallization aids, and mixtures thereof.
  • the following disclosure of modified carboxy methyl cellulose materials and adjunct detergent ingredients and mixtures thereof for use in the compositions herein is representative of the detergent ingredients, but is not intended to be limiting.
  • modified carboxy methyl cellulose materials which are in the form of cellulosic based polymers or oligomers, can provide substantive and unexpected cleaning benefits when added to a laundry composition. But these materials can also pose certain processing problems for granular detergent formulators.
  • the modified carboxy methyl cellulose materials that are suitable for use in laundry operations and provide the desired fabric appearance and integrity benefits can be characterized by the following general formula: wherein each R is selected from the group consisting of R 2 , R c , and wherein:
  • carboxy methyl cellulose is modified with an ester linkage, ether linkage or combinations thereof.
  • Modified carboxy methyl cellulose materials suitable for use in this invention are described in greater detail in two applications entitled “Laundry Detergent Compositions With Cellulosic Based Polymers to Provide Appearance and Integrity Benefits to Fabrics Laundered Therewith", WO 99/14245 and WO 99/14295. Both of these applications were filed in the PCT on September 15, 1998, in the name of Jennifer A. Leupin et al.
  • One or more builders can be used to further improve the performance of the compositions described herein.
  • the builder can be selected from the group consisting of aluminosilicates, crystalline layered silicates, MAP zeolites, citrates, amorphous silicates, polycarboxylates, sodium carbonates and mixtures thereof.
  • the sodium carbonate ingredient can serve as the inorganic alkaline material when a liquid acid precursor of the mid-chain branched surfactant is used.
  • suitable auxiliary builders are described hereinafter.
  • Preferred builders include aluminosilicate ion exchange materials and sodium carbonate.
  • the aluminosilicate ion exchange materials used herein as a detergent builder preferably have both a high calcium ion exchange capacity and a high exchange rate. Without intending to be limited by theory, it is believed that such high calcium ion exchange rate and capacity are a function of several interrelated factors which derive from the method by which the aluminosilicate ion exchange material is produced.
  • the aluminosilicate ion exchange materials used herein are preferably produced in accordance with Corkill et al, U.S. Patent No. 4,605,509 (Procter & Gamble).
  • the aluminosilicate ion exchange material is in "sodium" form since the potassium and hydrogen forms of the instant aluminosilicate do not exhibit as high of an exchange rate and capacity as provided by the sodium form.
  • the aluminosilicate ion exchange material preferably is in over dried form so as to facilitate production of crisp detergent agglomerates as described herein.
  • the aluminosilicate ion exchange materials used herein preferably have particle size diameters which optimize their effectiveness as detergent builders.
  • the term "particle size diameter" as used herein represents the average particle size diameter of a given aluminosilicate ion exchange material as determined by conventional analytical techniques, such as microscopic determination and scanning electron microscope (SEM).
  • the preferred particle size diameter of the aluminosilicate is from 0.1 micron to 10 microns, more preferably from 0.5 microns to 9 microns. Most preferably, the particle size diameter is from 1 microns to 8 microns.
  • the aluminosilicate ion exchange material has the formula Na z [(AlO 2 ) z .(SiO 2 ) y ]xH 2 O wherein z and y are integers of at least 6, the molar ratio of z to y is from 1 to 5 and x is from 10 to 264. More preferably, the aluminosilicate has the formula Na 12 [(AlO 2 ) 12 .(SiO 2 ) 12 ]xH 2 O wherein x is from 20 to 30, preferably about 27.
  • These preferred aluminosilicatcs are available commercially, for example under designations Zeolite A, Zeolite B and Zeolite X.
  • naturally-occurring or synthetically derived aluminosilicate ion exchange materials suitable for use herein can be made as described in Krummel et al, U.S. Patent No. 3,985,669.
  • the aluminosilicates used herein are further characterized by their ion exchange capacity which is at least about 200 mg equivalent of CaCO 3 hardness/gram, calculated on an anhydrous basis, and which is preferably in a range from about 300 to 352 mg equivalent of CaCO 3 hardness/gram. Additionally, the instant aluminosilicate ion exchange materials are still further characterized by their calcium ion exchange rate which is at least about 2 grains Ca ++ /gallon/minute/-gram/gallon, and more preferably in a range from 2 grains Ca ++ /gallon/minute/-gram/gallon to 6 grains Ca ++ /gallon/minute/-gram/gallon.
  • the dry starting materials are mixed with a liquid binder.
  • a binder is added for purposes of enhancing agglomeration by providing a "binding" or “sticking” agent for the detergent components.
  • the preferred liquid binder for use in this invention comprises water, surfactant paste and a polymer.
  • the paste includes surfactants selected from branched and linear anionics, nonionic, zwitterionic, ampholytic and cationic classes and compatible mixtures thereof. The viscosity, rheology and chemical composition of the surfactant pastes are described in more detail below.
  • the polymer is selected from the group consisting of dye transfer agents, polyamines, homopolymers and copolymers of polyacrylates, homopolymers and copolymers of polyacrylamides, homopolymers and copolymers of polyvinyl alcohol, homopolymers and copolymers of polyvinyl pyrrolidone, polymaleates, aliphatic polyesters, natural proteins, synthetic non-crystalline polyaminoacids, water soluble nylons, polyethylene glycol, polyacrylate and mixtures thereof.
  • Detergent compositions made with the agglomerates of this invention preferably comprise from 0.01% to 4%, more preferably from 0.05% to 2%, and most preferably from 0.1% to 1%, by weight of the liquid binder.
  • the surfactant paste is selected from the group consisting of linear straight chain alkylbenzene sulfonates, preferably linear straight chain alkylbenzene sulfonates in which the average number of carbon atoms in the alkyl group is from 11 to 13 (abbreviated as C 11-13 LAS), sodium ethoxysulphate, preferably based on a biodegradable C12/14 synthetic or natural primary alcohol ethoxylate made with a nominal 3 moles of ethylene oxide, and mixtures thereof.
  • the dye transfer agent is a polyvinyl N-Oxide such as poly(4-vinylpyridine-N-oxide) "PVNO".
  • PVNO poly(4-vinylpyridine-N-oxide)
  • Copolymers of N-vinylpyrrolidone and N-vinylimidazole are also acceptable for use herein.
  • Polyvinyl N-oxide materials are disclosed in U.S. Patent No. 5,804,543, which issued on September 8, 1998, to Wertz and Panandiker.
  • liquid binders for use in this invention are polyamines, and even more preferred are copolymers of epichlorohydrin and a cyclic amine moiety. Descriptions and example of the preferred polyamines for use in this invention can be found in the following PCT Patent Applications: WO 99/14300, WO 99/14299 and WO 99/14301 all three of these applications were filed internationally on September 15, 1988.
  • the process comprises the step of spraying an additional binder in one or both of the mixer/densifiers.
  • the additional binder is preferably selected from the group consisting of water, anionic surfactants, nonionic surfactants, polyethylene glycol, polyvinyl pyrrolidone polyacrylates, citric acid and mixtures thereof.
  • suitable binder materials including those listed herein are described in Beerse et al, U.S. Patent No. 5,108,646 (Procter & Gamble Co.).
  • the viscoelastic surfactant paste used herein has viscoelastic fluid properties which can be described by a commonly used mathematical model that accounts for the shear thinning nature of the paste.
  • the rate index n varies from 0 to 1. The closer n is to 0, the more shear thinning the fluid. The closer n is to 1, the closer it is to simple Newtonian behavior, i.e. constant viscosity behavior. K can be interpreted as the apparent viscosity at a shear rate of 1 sec -1 .
  • the viscoelastic surfactant paste used in the process has a consistency K at 70°C of from 50,000 to 450,000 cPoise ⁇ sec n-1 (500 to 2,500 Poise ⁇ sec n-1 ), more preferably from 100,000 to 195,000 cPoise ⁇ sec n-1 (1,000 to 1,950 Poise ⁇ sec n-1 ), and most preferably from 120,000 to 180,000 cPoise ⁇ sec n-1 (1,200 to 1,800 Poise ⁇ sec n-1 ).
  • the surfactant paste has a shear index n of from 0.05 to 0.25, more preferably from 0.08 to 0.20 and most preferably from 0.10 to 0.15.
  • the paste includes surfactants selected from branched and linear anionics, nonionic, zwitterionic, ampholytic and cationic classes and compatible mixtures thereof.
  • Detergent surfactants useful herein are described in U.S. Patent 3,664,961, Norris, issued May 23, 1972, and in U.S. Patent 3,919,678, Laughlin et al., issued December 30, 1975.
  • Useful cationic surfactants also include those described in U.S. Patent 4,222,905, Cockrell, issued September 16, 1980, and in U.S. Patent 4,239,659, Murphy, issued December 16, 1980.
  • detergent surfactants useful in the present surfactant paste.
  • Water-soluble salts of the higher fatty acids i.e., "soaps" 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.
  • Additional anionic surfactants that are suitable for use herein include the water-soluble salts, preferably the alkali metal, ammonium and alkylolammonium salts, of organic sulfuric reaction products having in their molecular structure a straight-chain alkyl group containing from 10 to 20 carbon atoms and a sulfonic acid or sulfuric acid ester group.
  • alkyl is the alkyl portion of acyl groups.
  • examples of this group of synthetic surfactants are the sodium and potassium alkyl sulfates, especially those obtained by sulfating the higher alcohols (C 8-18 carbon atoms) such as those produced by reducing the glycerides of tallow or coconut oil; and the sodium and potassium alkylbenzene sulfonates in which the alkyl group contains from 9 to 15 carbon atoms, in straight chain, e.g., those of the type described in U.S. Patents 2,220,099 and 2,477,383.
  • Especially valuable are linear straight chain alkylbenzene sulfonates in which the average number of carbon atoms in the alkyl group is from 11 to 13, abbreviated as C 11-13 LAS.
  • anionic surfactants suitable for use herein are the sodium alkyl glyceryl ether sulfonates, especially those ethers of higher alcohols derived from tallow and coconut oil; sodium coconut oil fatty acid monoglyceride sulfonates and sulfates; sodium or potassium of ethylene oxide per molecule and wherein the alkyl groups contain from 8 to 12 carbon atoms; and sodium or potassium salts of alkyl ethylene oxide ether sulfates containing 1 to 10 units of ethylene oxide per molecule and wherein the alkyl group contains from 10 to 20 carbon atoms.
  • suitable anionic surfactants include the water-soluble salts of esters of alpha-sulfonated fatty acids containing from 6 to 20 carbon atoms in the fatty acid group and from 1 to 10 carbon atoms in the ester group; water-soluble salts of 2-acyloxyalkane-1-sulfonic acids containing from 2 to 9 carbon atoms in the acyl group and from 9 to 23 carbon atoms in the alkane moiety; alkyl ether sulfates containing from 10 to 20 carbon atoms in the alkyl group and from 1 to 30 moles of ethylene oxide; water-soluble salts of olefin and paraffin sulfonates containing from 12 to 20 carbon atoms; and beta-alkyloxy alkane sulfonates containing from 1 to 3 carbon atoms in the alkyl group and from 8 to 20 carbon atoms in the alkane moiety.
  • Preferred adjunct anionic surfactants are C 10-18 linear alkylbenzene sulfonate and C 10-18 alkyl sulfate.
  • low moisture (less than about 25% water) alkyl sulfate paste can be the sole ingredient in the surfactant paste.
  • Most preferred are C 10-18 alkyl sulfates, linear or branched, and any of primary, secondary or tertiary.
  • a preferred embodiment of the present invention is wherein the surfactant paste comprises from 20% to 40% of a mixture of sodium C 10-13 linear alkylbenzene sulfonate and sodium C 12-16 alkyl sulfate in a weight ratio of about 2:1 to 1:2.
  • Another preferred embodiment of the detergent composition includes a mixture of C 10-18 alkyl sulfate and C 10-18 alkyl ethoxy sulfate in a weight ratio of about 80:20.
  • Water-soluble nonionic surfactants are also useful in the instant invention.
  • 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 6 to 15 carbon atoms, in either a straight chain or branched chain configuration, with from 3 to 12 moles of ethylene oxide per mole of alkyl phenol. Included are the water-soluble and water-dispersible condensation products of aliphatic alcohols containing from 8 to 22 carbon atoms, in either straight chain or branched configuration, with from 3 to 12 moles of ethylene oxide per mole of alcohol.
  • nonionics suitable for use herein are semi-polar nonionic surfactants which include water-soluble amine oxides containing one alkyl moiety of from 10 to 18 carbon atoms and two moieties selected from the group of alkyl and hydroxyalkyl moieties of from 1 to 3 carbon atoms; water-soluble phosphine oxides containing one alkyl moiety of 10 to 18 carbon atoms and two moieties selected from the group consisting of alkyl groups and hydroxyalkyl groups containing from 1 to 3 carbon atoms; and water-soluble sulfoxides containing one alkyl moiety of from 10 to 18 carbon atoms and a moiety selected from the group consisting of alkyl and hydroxyalkyl moieties of from 1 to 3 carbon atoms.
  • Preferred nonionic surfactants are of the formula R 1 (OC 2 H 4 ) n OH, wherein R 1 is a C 10 -C 16 alkyl group or a C 8 -C 12 alkyl phenyl group, and n is from 3 to about 80.
  • Particularly preferred are condensation products of C 12 -C 15 alcohols with from 5 to 20 moles of ethylene oxide per mole of alcohol, e.g., C 12 -C 13 alcohol condensed with about 6.5 moles of ethylene oxide per mole of alcohol.
  • Nonionic surfactants include polyhydroxy fatty acid amides. Examples are N-methyl N-1-deoxyglucityl cocoamide and N-methyl N-1-deoxyglucityl oleamide. Processes for making polyhydroxy fatty acid amides are known and can be found in Wilson, U.S. Patent No. 2,965,576 and Schwartz, U.S. Patent No. 2,703,798.
  • Ampholytic surfactants include derivatives of aliphatic derivatives of heterocyclic secondary and tertiary amines in which the aliphatic moiety can be straight chain or branched and wherein one of the aliphatic substituents contains from 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 8 to 18 carbon atoms.
  • Cationic surfactants can also be included in the present invention.
  • Cationic surfactants comprise a wide variety of compounds characterized by one or more organic hydrophobic groups in the cation and generally by a quaternary nitrogen associated with an acid radical. Pentavalent nitrogen ring compounds are also considered quaternary nitrogen compounds. Suitable anions are halides, methyl sulfate and hydroxide. Tertiary amines can have characteristics similar to cationic surfactants at washing solution pH values less than about 8.5. A more complete disclosure of these and other cationic surfactants useful herein can be found in U.S. Patent 4,228,044, Cambre, issued October 14, 1980.
  • Cationic surfactants are often used in detergent compositions to provide fabric softening and/or antistatic benefits.
  • Antistatic agents which provide some softening benefit and which are preferred herein are the quaternary ammonium salts described in U.S. Patent 3,936,537, Baskerville, Jr. et al., issued February 3, 1976.
  • agglomerates refers to particles formed by build-up agglomeration of starting detergent ingredients (particles) which typically have a smaller median particle size than the formed agglomerates. All percentages and ratios used herein are expressed as percentages by weight (anhydrous basis) unless otherwise indicated. All viscosities referenced herein are measured at 70°C ( ⁇ 5°C) and at shear rates of about 10 to 100 sec -1 .
  • the invention entails continuously mixing into a high speed mixer/densifier several streams of starting detergent ingredients which include a liquid binder comprising a mix of a liquid polymer and a surfactant paste. Dry detergent materials, which may include a modified carboxy methyl cellulose material, are also added continuously into the high speed mixer/densifier.
  • the dry starting detergent material comprises from 10% to 50%, preferably from 15% to 45% and, most preferably from 20% to 40% of an aluminosilicate or zeolite builder and from 10% to 40%, preferably from 15% to 30% and, most preferably from 15% to 25% of a sodium carbonate. It should be understood that additional starting detergent ingredients several of which are described hereinafter may be mixed into high speed mixer/densifier without departing from the scope of the invention.
  • the dry starting detergent material comprises from 10% to 50%, preferably from 15% to 45% and, most preferably from 20% to 40% of an aluminosilicate or zeolite builder and from 10% to 40%, preferably from 15% to 30% and, most preferably from 15% to 25% of an ester modified carboxy methyl cellulose. It should be understood that additional starting detergent ingredients several of which are described hereinafter may be mixed into high speed mixer/densifier without departing from the scope of the invention.
  • the ratio of the surfactant paste or liquid binder to the dry starting detergent material is from 1:10 to 10:1, more preferably from 1:4 to 4:1 and, most preferably from 2:1 to 2:3.
  • the first processing step can be successfully completed, under the process parameters described herein, in a high speed mixer/densifier which preferably is a Lödige CB mixer or similar brand mixer.
  • a high speed mixer/densifier which preferably is a Lödige CB mixer or similar brand mixer.
  • These types of mixers essentially consist of a horizontal, hollow static cylinder having a centrally mounted rotating shaft around which several plough-shaped blades are attached.
  • the shaft rotates at a speed of from 300 rpm to 2500 rpm, more preferably from 400 rpm to 1600 rpm.
  • the mean residence time of the detergent ingredients in the high speed mixer/densifier is preferably in range from 2 seconds to 45 seconds, and most preferably from 5 seconds to 15 seconds.
  • the mean residence time can be conveniently and accurately measured by dividing the tear weight of the mixer/densifier by the throughput (e.g., kg/hr).
  • the resulting detergent agglomerates formed in the high speed mixer/densifier are then fed into a lower or moderate speed mixer/densifier during which further agglomeration and densification is carried forth.
  • This particular moderate speed mixer/densifier used in the present process should include liquid distribution and agglomeration tools so that both techniques can be carried forth simultaneously. It is preferable to have the moderate speed mixer/densifier to be, for example, a Lödige KM (Ploughshare) mixer, Drais® K-T 160 mixer or similar brand mixer.
  • the main centrally rotating shaft speed is from 30 to 160 rpm, more preferably from 50 to 100 rpm.
  • the mean residence time in the moderate speed mixer/densifier is preferably from 0.25 minutes to 15 minutes, most preferably the residence time is 0.5 to 10 minutes.
  • This mean residence time also can be conveniently and accurately measured by dividing the tear weight of the mixer/densifier at steady state by the throughput (e.g., kg/hr).
  • the liquid distribution is accomplished by cutters, generally smaller in size than the rotating shaft, which preferably operate at about 3600 rpm.
  • the high speed mixer/densifier and moderate speed mixer/densifier in combination preferably impart a requisite amount of energy to form the desired agglomerates. More particularly, the instant process imparts from 5 ⁇ 10 10 erg/kg to 2 ⁇ 10 12 erg/kg at a rate of from 3 ⁇ 10 8 erg/kg-sec to 3 ⁇ 10 9 erg/kg-sec to form free flowing high density detergent agglomerates.
  • the energy input and rate of input can be determined by calculations from power readings to the moderate speed mixer/densifier with and without granules, residence time of the granules in the mixer/densifier, and the mass of the granules in the mixer/densifier. Such calculations are clearly within the scope of the skilled artisan.
  • the detergent agglomerates are dried in a fluid bed dryer or similar apparatus.
  • the density of the resulting detergent agglomerates exiting the fluid bed dryer is at least 400 g/l, more preferably from 500 g/l to 600 g/l.
  • the particle porosity of the resulting detergent agglomerates of the composition is preferably in a range from 5% to 20%, more preferably at about 10%.
  • a low porosity detergent agglomerate provides a dense or low dosage detergent product, to which the present process is primarily directed.
  • an attribute of dense or densified detergent agglomerates is the relative particle size.
  • the present process typically provides agglomerates having a median particle size of from 400 microns to 700 microns, and more preferably from 475 microns to 600 microns.
  • the phrase "median particle size" refers to individual agglomerates and not individual particles or detergent granules.
  • the detergent agglomerates exiting the fluid bed dryer are further conditioned by cooling the agglomerates in a fluid bed cooler or similar apparatus as are well known in the art.
  • Another optional process step involves adding a coating agent to improve flowability and/or minimize over agglomeration of the detergent composition in one or more of the following locations of the instant process: (I) the coating agent can be added directly after the fluid bed cooler; (2) the coating agent may be added between the fluid bed dryer and the fluid bed cooler; (3) the coating agent may be added between the fluid bed dryer and the moderate speed mixer/densifier; and/or (4) the coating agent may be added directly to the moderate speed mixer/densifier and the fluid bed dryer.
  • the coating agent can be added in any one or a combination of streams, see Capeci et al, U.S. Patent 5,516,448, issued May 14, 1996 and Capeci et al, U.S. Patent 5,489,392, issued February 6, 1996.
  • the coating agent is preferably selected from the group consisting of aluminosilicates, silicates, carbonates and mixtures thereof.
  • the coating agent may be one or more combinations of the builder material, aluminosilicates, carbonates, silicates.
  • the coating agent not only enhances the free flowability of the resulting detergent composition which is desirable by consumers in that it permits easy scooping of detergent during use, but also serves to control agglomeration by preventing or minimizing over agglomeration, especially when added directly to the moderate speed mixer/densifier. As those skilled in the art are well aware, over agglomeration can lead to very undesirable flow properties and aesthetics of the final detergent product.
  • optional steps contemplated by the present process include screening the oversized detergent agglomerates in a screening apparatus which can take a variety of forms including but not limited to conventional screens chosen for the desired particle size of the finished detergent product.
  • Other optional steps include conditioning of the detergent agglomerates by subjecting the agglomerates to additional drying.
  • Another optional step of the instant process entails finishing the resulting detergent agglomerates by a variety of processes including spraying and/or admixing other conventional detergent ingredients.
  • this step encompasses spraying perfumes, brighteners and enzymes onto the finished agglomerates to provide a more complete detergent composition.
  • Such techniques and ingredients are well known in the art.
  • One or more spray drying techniques can be used alone, or in combination with the aforementioned agglomeration processes, to make detergent compositions in accordance with the instant invention.
  • One or more spray-drying towers may be employed to manufacture granular laundry detergents which often have a density of about 500 g/l or less.
  • an aqueous slurry of various heat-stable ingredients in the final detergent composition are formed into homogeneous granules by passage through a spray-drying tower, using conventional techniques, at temperatures of 175°C to 225°C.
  • additional process steps as described herein can be optionally used to obtain the level of density (i.e., > 650 g/l) required by modern compact, low dosage detergent products.
  • spray-dried granules from a tower can be densified further by loading a liquid such as water or a nonionic surfactant into the pores of the granules and/or subjecting them to one or more high speed mixer/densifiers.
  • a suitable high speed mixer/densifier for this process is the aforementioned "Lödige CB 30" or “Lödige CB 30 Recycler” which comprises a static cylindrical mixing drum having a central rotating shaft with mixing/cutting blades mounted thereon.
  • the ingredients for the detergent composition are introduced into the drum and the shaft/blade assembly is rotated at speeds in the range of 100-2500 rpm to provide thorough mixing/densification. See Jacobs et al, U.S. Patent 5,149,455, issued September 22, 1992.
  • Other such apparatus includes the devices marketed under the trade name "Shugi Granulator” and under the tradename "Drais K-TTP 80.”
  • Another process step which can be used to densify further spray-dried granules involves grinding and agglomerating or deforming the spray-dried granules in a moderate speed mixer/densifier so as to obtain particles having lower porosity.
  • Equipment such as the aforementioned "Lödige KM" (Series 300 or 600) or “Lödige Ploughshare” mixer/densifiers are suitable for this process step.
  • Other useful equipment includes the device which is available under the tradename "Drais K-T 160".
  • This process step which employs a moderate speed mixer/densifier e.g. Lödige KM
  • the aforementioned high speed mixer/densifier e.g. Lödige CB
  • Other types of granules manufacturing apparatus useful herein include the apparatus disclosed in U.S. Patent 2,306,898, to G. L. Heller, December 29, 1942.
  • the reverse sequential mixer/densifier configuration is also contemplated by the invention.
  • One or a combination of various parameters including residence times in the mixer/densifiers, operating temperatures of the equipment, temperature and/or composition of the granules, the use of adjunct ingredients such as liquid binders and flow aids, can be used to optimize densification of the spray-dried granules in the process of the invention.
  • adjunct ingredients such as liquid binders and flow aids
  • Patent 5,133,924, issued July 28, 1992 spray-dried granules are brought into a deformable state prior to densification
  • Delwel et al U.S. Patent 4,637,891, issued January 20, 1987 (granulating spray-dried granules with a liquid binder and aluminosilicate); Kruse et al, U.S. Patent 4,726,908, issued February 23, 1988 (granulating spray-dried granules with a liquid binder and aluminosilicate); and, Bortolotti et al, U.S. Patent 5,160,657, issued November 3, 1992 (coating densified spray-dried granules with a liquid binder and aluminosilicate).
  • other aspects of the process invention include admixing additional detergent materials with the various agglomerates, spray dried granules and combinations thereof.
  • This admixing step may be enhanced by combining the agglomerates, granules, or combinations thereof with additional detergent materials and a liquid binder in a mixing drum or other similar device.
  • the additional detergent materials may be coated with a nonionic surfactant or other liquid binder as described previously before the admixing step so as to preclude any deleterious interaction with the other detergent ingredients (e.g. anionic surfactants) prior to immersion in the washing solution (i.e. during processing and storage).
  • This liquid binder or nonionic surfactant coating also improves the flow properties of the detergent composition in which the builder material is included.
  • the high density detergent composition can be produced by feeding a liquid acid precursor of an anionic surfactant, an alkaline inorganic material (e.g. sodium carbonate) and optionally other detergent ingredients into a high speed mixer/densifier (residence time 5-30 seconds) so as to form agglomerates containing a partially or totally neutralized anionic surfactant salt and the other starting detergent ingredients. Subsequently, the contents in the high speed mixer/densifier can be sent to a moderate speed mixer/densifier (e.g. Lödige KM) for further agglomeration resulting in the finished high density detergent composition.
  • a moderate speed mixer/densifier e.g. Lödige KM
  • the surfactant paste is premixed or extruded in a mixing or extruding apparatus such as a twin-screw extruder (e.g., Werner and Pfleiderer, Continua Series) to structure the paste for easier agglomeration.
  • a mixing or extruding apparatus such as a twin-screw extruder (e.g., Werner and Pfleiderer, Continua Series) to structure the paste for easier agglomeration.
  • structuring agents such as polymers, sodium hydroxide, sodium chloride, potassium hydroxide silicates can be used to render the paste more suitable for loading higher amounts of surfactant. See Aouad et al, U.S. Patent 5,451,354, issued September 19, 1995.
  • high density detergent compositions can be produced by blending conventional or densified spray-dried detergent granules with detergent agglomerates in various proportions (e.g. a 60:40 weight ratio of granules to agglomerates) produced by one or a combination of the processes discussed herein.
  • Additional adjunct ingredients such as enzymes, perfumes, brighteners can be sprayed or admixed with the agglomerates, granules or mixtures thereof produced by the processes discussed herein.
  • Another process of the invention involves cooling a molten surfactant paste and forming flakes on a chill roll, after which the flakes are ground to the desired particle size.
  • the cooled flakes can be dried further using a rotary drum dryer.
  • This Example illustrates the process of the invention which produces free flowing, crisp, high density detergent composition.
  • Two feed streams of various detergent starting ingredients are continuously fed, at a rate of 2800 kg/hr, into a Lödige CB-30 mixer/densifier.
  • One stream comprises a liquid binder containing water and PVNO the other stream containing dry detergent materials containing an ester modified carboxy methyl cellulose, aluminosilicate and sodium carbonate.
  • the rotational speed of the shaft in the Lödige CB-30 mixer/densifier is about 1400 rpm and the mean residence time is about 10 seconds.
  • the contents from the Lödige CB-30 mixer/densifer are continuously fed into a Lödige KM 600 mixer/densifer for further agglomeration during which the mean residence time is about 30 seconds.
  • the resulting detergent agglomerates are then fed to a fluid bed dryer and then to a fluid bed cooler, the mean residence time being about 10 minutes and 15 minutes, respectively.
  • a coating agent, aluminosilicate, is fed after the Lödige KM 600 mixer/densifier to control and prevent over agglomeration.
  • the detergent agglomerates are then screened with conventional screening apparatus resulting in a uniform particle size distribution.
  • composition of the detergent agglomerate mixture exiting the fluid bed cooler for three process runs are set forth in Table I below: Component % Weight of Total Feed A B C Ester Modified Carboxy Methyl Cellulose 5.0 5.0 3.0 PVNO 36.0 41.0 22.0 Aluminosilicate 25.4 24.0 34.0 Sodium carbonate 26.3 24.0 34.0 Polyethylene glycol (MW 4000) 1.1 1.7 2.0 Misc. (water) 6.2 4.3 5.0 100.0 100.0 100.0
  • the base granule is prepared by a conventional spray drying process in which the starting ingredients are formed into a slurry and passed though a spray drying tower having a counter current stream of hot air (200-300°C) resulting in the formation of porous granules.
  • the admixed agglomerates are formed from two feed streams of various starting detergent ingredients which are continuously fed, at a rate of 1400 kg/hr, into a Schugi high shear granulator (1000-4000 RPM) or a Lödige CB-30 mixer/densifier, one of which comprises a liquid binder containing either: I ) PVNO and water or 2) a copolymer of epichlorohydrin and a cyclic amine moiety (IME) and water or 3) the IME material, alkyl ethoxy sulfate surfactant paste and water; and the other stream containing starting dry detergent containing a premixed mixture of either: 1) an ester modified carboxy methyl cellulose, aluminosilicate and sodium carbonate or 2) ester modified carboxy methyl cellulose and aluminosilicate.
  • a Schugi high shear granulator 1000-4000 RPM
  • Lödige CB-30 mixer/densifier one of which comprises a liquid
  • the rotational speed of the shaft in the Lödige CB-30 mixer/densifier is about 1400 rpm and the median residence time is about 5-10 seconds.
  • the contents from the Lödige CB-30 mixer/densifier are continuously fed into a Lödige KM-600 mixer/densifier for further agglomeration during which the mean residence time is about 1-2 minutes.
  • the resulting detergent agglomerates are then fed to a fluid bed dryer and to a fluid bed cooler before being admixed with the spray dried granules.
  • These agglomerates are then admixed with agglomerates made with a surfactant paste that contains surfactant and water and dry detergent ingredients containing dry detergent material containing aluminosilicate and sodium carbonate.
  • adjunct detergent ingredients are sprayed on or dry added to the blend of agglomerates and granules.

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Claims (10)

  1. Procédé pour préparer en continu des agglomérats détergents, caractérisé par les étapes consistant à :
    (A) mélanger en continu un liant liquide et des matériaux détergents secs dans un mélangeur/densificateur à grande vitesse pour obtenir des agglomérats détergents, où le rapport du liant liquide au matériau détergent sec est de 1/10 à 10/1, où les matériaux détergents secs comprennent de la carboxyméthylcellulose modifiée ;
    (B) éventuellement mélanger les agglomérats détergents dans un mélangeur/densificateur à vitesse modérée pour densifier encore et agglomérer les agglomérats détergents ; et
    (C) sécher les agglomérats détergents de façon à augmenter leur densité.
  2. Procédé pour préparer une composition détergente haute densité, caractérisé par les étapes consistant à :
    (A) mélanger en continu un liant liquide et des matériaux détergents secs dans un mélangeur/densificateur à grande vitesse pour obtenir des premiers agglomérats détergents, où le rapport du liant liquide au matériau détergent sec est de 1/10 à 10/1, où les matériaux détergents secs comprennent de la carboxyméthylcellulose modifiée ;
    (B) éventuellement mélanger les premiers agglomérats détergents dans un mélangeur/densificateur à vitesse modérée pour augmenter leur densité ;
    (C) sécher les premiers agglomérats détergents pour augmenter encore leur densité ;
    (D) mélanger en continu une pâte de tensioactif détergent et des matériaux détergents secs additionnels dans un mélangeur/densificateur à grande vitesse pour obtenir des deuxièmes agglomérats détergents, où le rapport de la pâte de tensioactif au matériau détergent sec additionnel est de 1/10 à 10/1 ;
    (E) mélanger les deuxièmes agglomérats détergents dans un mélangeur/densificateur à vitesse modérée pour augmenter leur densité ;
    (F) sécher les deuxièmes agglomérats détergents pour augmenter encore leur densité ; et
    (G) mélanger les premiers agglomérats détergents et les deuxièmes agglomérats détergents pour former la composition détergente haute densité.
  3. Procédé selon l'une quelconque des revendications 1 et 2, dans lequel le liant liquide est caractérisé par l'eau, une pâte de tensioactif choisie parmi les classes anionique, non ionique, zwittérionique, ampholyte et cationique, ramifiées et linéaires, et leurs mélanges compatibles, et un polymère choisi dans l'ensemble constitué par les agents de transfert de colorants, les polyamines, les homopolymères et copolymères de polyacrylates, les homopolymères et copolymères de polyacrylamides, les homopolymères et copolymères de poly(alcool vinylique), les homopolymères et copolymères de polyvinylpyrrolidone, les polymaléates, les polyesters aliphatiques, les protéines naturelles, les poly(acides aminés) synthétiques non cristallins, les nylons solubles dans l'eau, le polyéthylèneglycol, le polyacrylate et leurs mélanges.
  4. Procédé selon l'une quelconque des revendications 1 à 3, dans lequel le liant liquide est caractérisé par: (1) un mélange de tensioactifs choisis dans l'ensemble constitué par le LAS, le sulfate de sodium éthoxylé et leurs mélanges ; et (2) un polymère choisi dans l'ensemble constitué par un poly(N-oxyde de vinyle), un copolymère d'épichlorhydrine et d'un fragment amine cyclique, les homopolymères et copolymères de polyacrylates, et leurs mélanges.
  5. Procédé selon l'une quelconque des revendications 1 à 4, dans lequel la pâte de tensioactif a une viscosité, mesurée à 70°C et à des vitesses de cisaillement de 10 à 100 s-1, de 50 000 cPs à 450 000 cPs, et est en outre caractérisée par de l'eau et un tensioactif additif choisi dans l'ensemble constitués par les tensioactifs non ioniques, zwittérioniques, ampholytes et cationiques, et leurs mélanges.
  6. Procédé pour préparer en continu une composition détergente haute densité, caractérisé par les étapes consistant à :
    (A) sécher par pulvérisation une bouillie aqueuse contenant des ingrédients détergents additifs pour former des granules séchés par pulvérisation ;
    (B) mélanger en continu un liant liquide et des matériaux détergents secs dans un mélangeur/densificateur à grande vitesse pour obtenir des agglomérats détergents, où le rapport du liant liquide aux matériaux détergents secs est de 1/10 à 10/1, où les matériaux détergents secs comprennent de la carboxyméthylcellulose modifiée ;
    (C) éventuellement mélanger les agglomérats détergents dans un mélangeur/densificateur à vitesse modérée pour augmenter leur densité ;
    (D) sécher les agglomérats détergents pour augmenter encore leur densité ; et
    (E) mélanger les granules et les agglomérats détergents ensemble de façon à former la composition détergente haute densité.
  7. Procédé pour préparer en continu une composition détergente haute densité, caractérisé par les étapes consistant à :
    (A) mélanger en continu un liant liquide et des matériaux détergents secs dans un mélangeur/densificateur à grande vitesse pour obtenir des premiers agglomérats détergents, où le rapport du liant liquide au matériau détergent sec est de 1/10 à 10/1, où les matériaux détergents secs comprennent de la carboxyméthylcellulose modifiée ;
    (B) éventuellement mélanger les premiers agglomérats détergents dans un mélangeur/densificateur à vitesse modérée pour augmenter leur densité ;
    (C) sécher les premiers agglomérats détergents pour augmenter encore leur densité ;
    (D) mélanger en continu un précurseur acide d'un tensioactif anionique et des matériaux détergents secs additionnels qui contiennent un matériau minéral alcalin capable de neutraliser le précurseur acide dans un mélangeur/densificateur à grande vitesse pour obtenir des deuxièmes agglomérats détergents, où le rapport du tensioactif anionique aux matériaux détergents secs additionnels est de 1/10 à 10/1 ;
    (E) éventuellement mélanger les deuxièmes agglomérats détergents dans un mélangeur/densificateur à vitesse modérée pour augmenter leur densité ;
    (F) sécher les deuxièmes agglomérats détergents pour augmenter leur densité ; et mélanger les premiers agglomérats détergents et les deuxièmes agglomérats détergents pour former la composition détergente haute densité.
  8. Procédé pour préparer en continu des agglomérats détergents, caractérisé par les étapes consistant à :
    (A) mélanger en continu un liant liquide et des matériaux détergents secs dans un mélangeur/densificateur à grande vitesse pour obtenir des agglomérats détergents, où le rapport du liant liquide au matériau détergent sec est de 1/10 à 10/1, où les matériaux détergents secs sont constitués principalement de carboxyméthylcellulose modifiée ;
    (B) éventuellement mélanger les agglomérats détergents dans un mélangeur/densificateur à vitesse modérée pour densifier encore et agglomérer les agglomérats détergents ; et
    (C) sécher les agglomérats détergents de façon à augmenter leur densité.
  9. Procédé selon l'une quelconque des revendications 1 à 8, dans lequel le liant liquide est caractérisé par de l'eau, une pâte de tensioactif choisie parmi les classes anionique, non ionique, zwittérionique, ampholyte et cationique, ramifiées et linéaires, et leurs mélanges compatibles, et un polymère choisi dans l'ensemble constitué par les agents de transfert de colorants, les polyamines, les homopolymères et copolymères de polyacrylates, les homopolymères et copolymères de polyacrylamides, les homopolymères et copolymères de poly(alcool vinylique), les homopolymères et copolymères de polyvinylpyrrolidone, les polymaléates, les polyesters aliphatiques, les protéines naturelles, les poly(acides aminés) synthétiques non cristallins, les nylons solubles dans l'eau, le polyéthylèneglycol, le polyacrylate et leurs mélanges.
  10. Procédé selon l'une quelconque des revendications 1 à 9, dans lequel le liant liquide est caractérisé par : (1) un mélange de tensioactifs choisis dans l'ensemble constitué par le LAS, le sulfate de sodium éthoxylé et leurs mélanges ; et (2) un polymère choisi dans l'ensemble constitué par un poly(N-oxyde de vinyle), un copolymère d'épichlorhydrine et d'un fragment amine cyclique, les homopolymères et copolymères de polyacrylates, et leurs mélanges.
EP99966543A 1998-12-22 1999-12-21 Procedes permettant de preparer une composition detergente en granules contenant de la carboxymethylcellulose modifiee Expired - Lifetime EP1141197B1 (fr)

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WO2001059054A1 (fr) * 2000-02-10 2001-08-16 The Procter & Gamble Company Compositions de detergents a lessive possedant une combinaison d'un polymere d'amine cyclique et d'un inhibiteur de transfert de couleurs
US20050187130A1 (en) * 2004-02-23 2005-08-25 Brooker Alan T. Granular laundry detergent composition comprising an anionic detersive surfactant, and low levels of, or no, zeolite builders and phosphate builders
DE102004020010A1 (de) * 2004-04-21 2005-11-17 Henkel Kgaa Verfahren zur Herstellung von Polymer-Granulaten
US9376648B2 (en) 2008-04-07 2016-06-28 The Procter & Gamble Company Foam manipulation compositions containing fine particles
CN108362166A (zh) * 2018-01-10 2018-08-03 马斌祥 一种空分主板式换热器内部油污清洗方法

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US4441881A (en) * 1982-09-07 1984-04-10 Lever Brothers Company Detergent compositions containing ethoxylated fatty alcohols with narrow ethylene oxide distributions
CN1213137C (zh) * 1996-12-26 2005-08-03 普罗格特-甘布尔公司 含有对所洗涤的织物的外观和整体有利的纤维素类聚合物的洗衣洗涤剂组合物
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BR9916501A (pt) 2001-09-04
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AU2205500A (en) 2000-07-12
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JP2002533530A (ja) 2002-10-08
AR023072A1 (es) 2002-09-04

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