EP0714976B2 - Compositions détergentes contenant un agent tensioactif cationique et procédé pour leur fabrication - Google Patents

Compositions détergentes contenant un agent tensioactif cationique et procédé pour leur fabrication Download PDF

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Publication number
EP0714976B2
EP0714976B2 EP94308960A EP94308960A EP0714976B2 EP 0714976 B2 EP0714976 B2 EP 0714976B2 EP 94308960 A EP94308960 A EP 94308960A EP 94308960 A EP94308960 A EP 94308960A EP 0714976 B2 EP0714976 B2 EP 0714976B2
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EP
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Prior art keywords
weight
composition
anionic
cationic surfactant
component
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EP94308960A
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German (de)
English (en)
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EP0714976A1 (fr
EP0714976B1 (fr
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Anthony Dovey
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Procter and Gamble Co
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Procter and Gamble Co
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Application filed by Procter and Gamble Co filed Critical Procter and Gamble Co
Priority to EP94308960A priority Critical patent/EP0714976B2/fr
Priority to DE69424551T priority patent/DE69424551T3/de
Priority to AT94308960T priority patent/ATE193051T1/de
Priority to TR95/01509A priority patent/TR199501509A2/xx
Priority to BR9509843A priority patent/BR9509843A/pt
Priority to CN95197503.XA priority patent/CN1174566A/zh
Priority to JP8519046A priority patent/JPH10511713A/ja
Priority to MX9704078A priority patent/MX9704078A/es
Priority to PCT/US1995/015548 priority patent/WO1996017042A1/fr
Priority to AU43714/96A priority patent/AU4371496A/en
Priority to CA002206326A priority patent/CA2206326A1/fr
Priority to ZA9510227A priority patent/ZA9510227B/xx
Priority to MA24083A priority patent/MA23734A1/fr
Publication of EP0714976A1 publication Critical patent/EP0714976A1/fr
Publication of EP0714976B1 publication Critical patent/EP0714976B1/fr
Publication of EP0714976B2 publication Critical patent/EP0714976B2/fr
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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
    • C11D10/00—Compositions of detergents, not provided for by one single preceding group
    • C11D10/04—Compositions of detergents, not provided for by one single preceding group based on mixtures of surface-active non-soap compounds and soap
    • C11D10/047—Compositions of detergents, not provided for by one single preceding group based on mixtures of surface-active non-soap compounds and soap based on cationic surface-active compounds and soap
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/38—Cationic compounds
    • C11D1/65—Mixtures of anionic with cationic compounds
    • 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
    • C11D11/02—Preparation in the form of powder by spray drying
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02—Anionic compounds
    • C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
    • C11D1/14—Sulfonic acids or sulfuric acid esters; Salts thereof derived from aliphatic hydrocarbons or mono-alcohols
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02—Anionic compounds
    • C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
    • C11D1/29—Sulfates of polyoxyalkylene ethers
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/38—Cationic compounds
    • C11D1/62—Quaternary ammonium compounds

Definitions

  • the invention relates to granular detergent compositions comprising cationic surfactant and anionic surfactant and/or anionic hydrotrope.
  • Water-soluble cationic surfactants are commercially available as aqueous solutions, typically up to 35% or 40% active (by weight). However any attempts to granulate these aqueous solutions result in granular components having low cationic surfactant content.
  • DE 2449354 discloses dishwashing compositions containing cationic surfactants and anionic suds suppressors.
  • EP 234717 also discloses suds controllers containing cationic compounds, whereby anionic surfactants can be present in the composition.
  • JP 57137397 discloses powders made by blending anionic soaps into a molten cationic softener.
  • EP-A 000 225 published on 10th January 1979, discloses compositions comprising water-soluble cationic surfactant and anionic surfactant.
  • the surfactants are combined together with other detergent ingredients, such as builders, in a crutcher mix and spray-dried. It is an essential feature that there is a molar excess of anionic surfactant over cationic surfactant.
  • the examples disclose up to a maximum of about 8% by weight of cationic surfactant in the spray dried component.
  • EP 547722 discloses spray-dried compositions containing cationic softeners and high levels of urea and additional surfactant.
  • the present invention aims to provide granular detergent components or compositions having a higher level of water-soluble cationic surfactant than prior art components.
  • anionic surfactant This is achieved by mixing small amounts of anionic surfactant with the aqueous solution of the cationic surfactant, and subsequently drying and granulating, either simultaneously or sequentially.
  • the addition of the anionic surfactant permit more concentrated cationic solutions to be processed without entering a viscous gel phase. Consequently more concentrated granular surfactant components or compositions can be produced.
  • the present invention concerns a granular detergent composition or component as defined in claim 1.
  • the granular detergent composition or component preferably comprises the cationic surfactant at a level of at least 30% by weight of the composition or component, and the anionic surfactant at a level of from 1% to 20% by weight the composition or component.
  • a highly preferred granular detergent composition or component is substantially free of anionic polymer, and comprises:
  • Another aspect of the present invention is a process for making the composition or component as defined in claim 4.
  • the granulating step may be subsequentay carried out and comprises the step of mixing the concentrated solution with a detergent builder selected from the group consisting of aluminosilicate, silicate, carbonate, citrate, phosphate or mixtures thereof.
  • a detergent builder selected from the group consisting of aluminosilicate, silicate, carbonate, citrate, phosphate or mixtures thereof.
  • a suds suppressing agent is added to the mixing step (i).
  • the drying step may be carried out by means of an evaporation step.
  • drying and granulating steps may be carried out simultaneously, preferably by means of spray drying.
  • the cationic surfactant component of the composition is water-soluble.
  • water solubility we refer in this context to the solubility of cationic surfactant in monomeric form, the limit of solubility being determined by the onset of micellisation and measured in terms of the critical micelle concentration (CMC).
  • CMC critical micelle concentration
  • the cationic surfactant should thus have a CMC for the pure material greater than about 200ppm and preferably greater than about 500ppm, specified at 30°C and in distilled water (Critical Micelle Concentrations of Aqueous Surfactant Systems, P. Mukerjee and K.J. Mysels, NSRDS-NBS, (1971)).
  • Useful cationic surfactants include water-soluble quaternary ammonium compounds of the form R 1 R 2 R 3 R 4 N + X - , wherein R 1 is alkyl having from 10 to 20, preferably from 12-18 carbon atoms, and R 2 , R 3 and R 4 are each C 1 to C 7 alkyl, or hydroxyalkyl, preferably methyl; X - is an anion, e.g. chloride. Examples of such quaternary ammonium compounds include C 12-14 alkyl trimethyl ammonium chloride, C 12-14 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.
  • Another group of useful cationic compounds are the polyammonium salts of the general formula : wherein R 3 is selected from C 8 to C 20 alkyl, alkenyl and alkaryl groups; each R 4 is C 1 -C 4 alkyl; n is from 1 to 6; and m is from 1 to 3.
  • a further preferred type of cationic component has the formula : wherein R 1 is C 1 to C 4 alkyl; R 2 is C 5 to C 30 straight or branched chain alkyl or alkenyl, alkyl benzene, or wherein s is from 0 to 5, R 3 is C1 to C20 alkyl or alkenyl; a is 0 or 1; n is 0 or 1; m is from 1 to 5; Z- and Z2 are each selected from the group consisting of : and wherein at least one of said groups is selected from the group consisting of ester, reverse ester, amide and reverse amide; and X is an anion which makes the compound water-soluble, preferably selected from the group consisting of amide, methyl sulfate, hydroxide, and nitrate preferably chloride, bromide or iodine.
  • this particular cationic component is evironmentally desirable, since it is biodegradable, both in terms of its long alkyl chain and its nitrogen containing segment.
  • Preferred choline ester derivatives having the following formula : wherein R is a C 5 to C 30 straight chain or branched chain alkyl or alkenyl, group and X is an anion, which makes the compound at least water-dispersible, preferably selected from the group consisting of halide, methyl sulfate, sulfate, and nitrate, preferably methyl sulfate, chloride, bromide or iodide, as well as those wherein the ester linkage in the above formula is replaced with a reverse ester, amide or reverse amide linkage.
  • p may be from 0 to 20.
  • the preferred choline-derivative cationic substances may be prepared by the direct esterification of a fatty acid of the desired chain length with dimethylaminoethanol, in the presence of an acid catalyst. The reaction product is then quaternized with a methyl halide, forming the desired cationic material.
  • the choline-derived cationic materials may also be prepared by the direct esterification of a long chain fatty acid of the desired chain length together with 2-haloethanol, in the presence of an acid catalyst material. The reaction product is then used to quaternize.
  • Trimethylamine forming the desired cationic component.
  • Other suitable choline esters for use herein have the formula: wherein t is 0 or 1, y is from 1 to 20, and R and X are as defined above.
  • the anionic surfactant component of the present invention include water-soluble salts of the higher fatty acids, i.e., "soaps".
  • 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 10 to 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 (C 8 -C 18 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 9 to 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 11 to 13, abbreviated as C 11 -C 13 LAS.
  • Other useful anionic surfactants herein 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-acyloxy-alkane-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; watersoluble salts of olefin sulfonates containing from 12 to 24 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.
  • anionic surfactants useful in the present invention are hydrotropes such as aryl sulphonates.
  • hydrotropes such as aryl sulphonates.
  • Preferred are sodium or potassium salts of benzene, toluene, xylene or cumene sulphonate.
  • a suds suppressing agent is useful in the present invention as a process aid, to control suds at the stage of mixing the cationic surfactant solution with the anionic surfactant.
  • suds suppressing agents such as monocarboxylic fatty acids and their soluble salts, high molecular weight hydrocarbons such as paraffin, fatty acid esters, fatty acid esters of monovalent alcohols, aliphatic C1-C40 ketones, N-alkoxylated amino triazines, propylene oxide, and monstearyl phosphates and phosphate esters.
  • Another preferred category of suds suppressing agents comprises silicone suds suppressors.
  • This category includes the use of polyorganosiloxane oils, such as polydimethyl siloxane, dispersions or emulsions of polyorganosiloxane oils or resins, and combinations of polyorganosiloxane with silica particles wherein the polyorganosiloxane is chemisorbed or fused onto the silica.
  • Silicone suds suppressors are well-known in the art and are, for example, disclosed in US-A-4 265 779, issued May 5th 1981. Other silicone suds suppressors are disclosed in US-A-3 455 839 and German Patent Application DE-A-21 24 526.
  • the detergent compositions herein can contain crystalline aluminosilicate ion exchange material of the formula Na z [(AlO 2 ) z ⁇ (SiO 2 ) y ] ⁇ xH 2 O wherein z and y are at least 6, the molar ratio of z to y is from 1.0 to 0.4 and z is from 10 to 264.
  • Amorphous hydrated aluminosilicate materials useful herein have the empirical formula M z (zAlO 2 ⁇ ySiO 2 ) wherein M is sodium, potassium, ammonium or substituted ammonium, z is from 0.5 to 2 and y is 1, said material having a magnesium ion exchange capacity of at least 50 milligram equivalents of CaCO 3 hardness per gram of anhydrous aluminosilicate. Hydrated sodium Zeolite A with a particle size of from 1 to 10 microns is preferred.
  • the aluminosilicate ion exchange builder materials herein are in hydrated form and contain from 10% to 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 18% to 22% water in their crystal matrix.
  • the crystalline aluminosilicate ion exchange materials are further characterized by a particle size diameter of from 0.1 micrometer to 10 micrometers. Amorphous materials are often smaller, e.g., down to less than 0.01 micrometer.
  • Preferred ion exchange materials have a particle size diameter of from 0.2 micrometer to 4 micrometers.
  • 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 200 mg equivalent of CaCO 3 water hardness/g of aluminosilicate, calculated on an anhydrous basis, and which generally is in the range of from 300 mg eq./g to 352 mg eq./g.
  • the amorphous aluminosilicate ion exchange materials usually have a Mg ++ exchange of at least 50 mg eq. CaCO 3 /g (12 mg Mg ++ /g). 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.
  • 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 Na 12 [(AlO 2 ) 12 (SiO2) 12 ] • xH 2 O wherein x is from 20 to 30, especially 27 and has a particle size generally less than 5 ⁇ m.
  • 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.
  • Specific inorganic phosphate builders are sodium and potassium tripolyphosphate, pyrophosphate and polymeric metaphosphate having a degree of polymerization of from 6 to 21.
  • 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.
  • nonphosphorus, inorganic builders are sodium and potassium carbonate, bicarbonate, sesquicarbonate, tetraborate decahydrate, and silicate having a molar ratio of SiO 2 to alkali metal oxide of from 0.5 to 4.0, preferably from 1.0 to 2.4.
  • the 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.
  • Softening clay is a particularly useful component which may be optionally incorporated into the compositions of the present invention.
  • the clay may be incorporated into the cationic surfactant containing particle of the present invention, however it is preferred that the clay is incorporated into a particle separate from the cationic surfactant.
  • the cationic surfactant containing particles and the clay containing particles may then be mixed together, usually with other particulate components comprising conventional detergent ingredients to give a finished commerial laundry detergent product.
  • Softening clays may be either unmodified or organically modified. Those clays which are not organically modified can be described as expandable, three-layered clays, i.e., aluminosilicates and magnesium silicates, having an ion exchange capacity of at least 50 meq/100g. of clay and preferably at least 60 meq/100 g. of clay.
  • the starting clays for the organically modified clays can be similarly described.
  • the term "expandable" as used to describe clays relates to the ability of the layered clay structure to be swollen, or expanded, on contact with water.
  • the three-layer expandable clays used herein are those materials classified geologically as smectites.
  • the family of smectite (or montmorillonoid) clays includes the following trioctahedral minerals: talc; hectorite; saponite; sauconite; vermiculite; and the following dioctahedral minerals: prophyllite; montmorillonite; volchonskoite and nontronite.
  • the clays employed in these compositions contain cationic counterions such as protons, sodium ions, potassium ions, calcium ions, and lithium ions. It is customary to distinguish between clays on the basis of one cation predominantly or exclusively absorbed. For example, a sodium clay is one in which the absorbed cation is predominantly sodium. Such absorbed cations can become involved in exchange reactions with cations present in aqueous solutions.
  • a typical exchange reaction involving a smectite-type clay is expressed by the following equation : smectite day (Na) + + NH 4 OH ⁇ smectite clay (NH 4 ) + + NaOH.
  • cation exchange capacity (sometimes termed “base exchange capacity") in terms of milliequivalents per 100 g. of clay (meq/100g).
  • base exchange capacity cation exchange capacity
  • the cation exchange capacity of clays can be measured in several ways, including by electrodialysis, by exchange with ammonium ion followed by titration, or by a methylene blue procedure, all as fully set forth in Grimshaw, "The Chemistry and Physics of Clays", pp. 264-265, Interscience (1971).
  • the cation exchange capacity of a clay material relates to such factors as the expandable properties of the clay, the charge of the clay (which in turn is determined at least in part by the lattice structure), and the like.
  • the ion exchange capacity of clays varies widely in the range form 2 meq/100 g. of kaolinites to 150 meq/100 g., and greater, for certain smectite clays.
  • Preferred smectite-type clays are sodium montmorillonite, potassium montmorillonite, sodium hectorite and potassium hectorite.
  • the clays used herein have a particle size range of up to 1 ⁇ m.
  • any of the clays used herein may be either naturally or synthetically derived.
  • composition was made : % by weight Cationic Surfactant 40 Sodium (C12-14) alkyl sulphate 1.6 Sodium (C12-14) alkyl ether (3) sulphate 0.4 Zeolite A (hydrated) 54.9 Suds Suppressing Agent 0.1 Water 3
  • the above composition was prepared by mixing a 40% aqueous solution of the cationic surfactant with a 79% aqueous paste of the mixture of anionic surfactants, and with the antifoam. The mixture was then evaporated to form a 60% cationic surfactant active paste.
  • the paste was fed into a high shear mixer (a Loedige CB®) where it was granulated with the Zeolite A. The resulting granules were further treated in a low shear mixer (a Loedige KM®) and subsequently dried in a fluid bed dryer to a moisture level of 3% (free) water.
  • the above composition was prepared by mixing a 40% aqueous solution of the cationic surfactant with a 79% aqueous paste of the mixture of anionic surfactants.
  • the Zeolite A was also added to the mixture and a homogeneous crutcher mix formed.
  • the crutcher mix was then spray dried using hot air in a conventional counter-current spray dry tower to give the finished granular composition.
  • a 40% aqueous solution of the cationic surfactant was fed into a high shear-mixer (Loedige CB®) and agglomerated with a fixed amount of Zeolite A powder.
  • the feed was stopped just before over-agglomeration occurred (the point where the liquid level exceeds the capacity of the powder, leading to the formation of an un-processable 'dough').
  • the resultant wet agglomerate was then dried in a fluid-bed dryer giving a product with the following composition :- % by weight Cationic Surfactant 15 Sodium (C12-14) alkyl sulphate - Sodium (C12-14) alkyl ether (3) sulphate - Zeolite A (hydrated) 82 Water 3
  • This particle is not suitable for inclusion in 'compact-type' products due to the low cationic surfactant activity.
  • a 40% aqueous solution of the cationic surfactant was dried by evaporation to form a 60% cationic surfactant active paste.
  • the paste became a highly viscous gel and no further useful processing was possible.

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Claims (7)

  1. Composition ou composant détergent(e) granulaire comprenant un agent tensioactif anionique ou un hydrotrope anionique, un agent tensioactif cationique soluble dans l'eau ayant dans sa forme pure une CMC (concentration critique en micelles) de plus de 200 ppm à 30 °C dans de l'eau distillée, et moins de 10% en poids d'un polymère anionique, caractérisé(e) en ce que l'agent tensioactif cationique est présent à un niveau d'au moins 20 % en poids de la composition ou du composant et le rapport molaire de l'agent tensioactif anionique et/ou de l'hydrotrope anionique à l'agent tensioactif cationique est inférieur à 1:1, et la composition ou le composant comprend 10 % à 69 % en poids d'un adjuvant détergent choisi dans le groupe constitué d'un aluminosilicate, d'un silicate, d'un carbonate, d'un citrate, d'un phosphate ou de leurs mélanges, pourvu que n'importe quel phosphate dans la composition ou composant soit choisi parmi le tripolyphosphate, le pyrophosphate et le métaphosphate polymère de sodium et de potassium ayant un degré de polymérisation de 6 à 21.
  2. Composition ou composant détergent(e) granulaire selon la revendication 1, dans laquelle ou lequel l'agent tensioactif cationique est présent à un niveau d'au moins 30 % en poids de la composition ou du composant et l'agent tensioactif anionique est présent à un niveau de 1 % à 20 % en poids de la composition ou du composant et le rapport molaire de l'agent tensioactif anionique à l'agent tensioactif cationique est inférieur à 0,5:1.
  3. Composition ou composant détergent(e) granulaire selon la revendication 2, qui est sensiblement exempt(e) d'un polymère anionique, comprenant :
    (a) 35 % à 50 % en poids d'un agent tensioactif cationique soluble dans l'eau,
    (b) 1 % à 5 % en poids d'un agent tensioactif anionique, et
    (c) 40 % à 60 % en poids d'aluminosilicate de sodium.
  4. Procédé de préparation de la composition ou du composant selon l'une quelconque des revendications 1 à 3, comprenant les étapes consistant :
    (i) à mélanger une solution aqueuse comprenant un agent tensioactif cationique soluble dans l'eau ayant dans sa forme pure une CMC (concentration critique en micelles) de plus de 200 ppm à 30 °C dans de l'eau distillée, un agent tensioactif anionique ou un hydrotrope anionique, de préférence un agent tensioactif anionique, et moins de 10 % en poids d'un polymère anionique,
    (ii) à sécher le mélange pour former une solution concentrée ayant une teneur en solides d'au moins 50 % en poids, et
    (iii) à granuler la solution concentrée,
       caractérisé en ce que l'agent tensioactif cationique est présent à un niveau d'au moins 20 % en poids de la composition ou du composant et le rapport molaire de l'agent tensioactif anionique et/ou de l'hydrotrope anionique à l'agent tensioactif cationique est inférieur à 1:1, et la composition ou le composant comprend 10 % à 69 % en poids d'un adjuvant détergent choisi dans le groupe constitué d'un aluminosilicate, d'un silicate, d'un carbonate, d'un citrate, d'un phosphate ou de leurs mélanges, pourvu que n'importe quel phosphate dans la composition ou composant soit choisi parmi le tripolyphosphate, le pyrophosphate et le métaphosphate polymère de sodium et de potassium ayant un degré de polymérisation de 6 à 21.
  5. Procédé selon la revendication 4, dans lequel un agent suppresseur de mousse est ajouté à l'étape de mélange (i).
  6. Procédé selon l'une quelconque des revendications 4 ou 5, dans lequel l'étape de séchage est effectuée au moyen d'une étape d'évaporation et l'étape de granulation est ensuite effectuée en mélangeant la solution concentrée avec un adjuvant détergent choisi dans le groupe constitué d'un aluminosilicate, d'un silicate, d'un carbonate, d'un citrate, d'un phosphate ou de leurs mélanges.
  7. Procédé selon la revendication 4 dans lequel les étapes de séchage et de granulation sont effectuées simultanément, de préférence par séchage par pulvérisation.
EP94308960A 1994-12-02 1994-12-02 Compositions détergentes contenant un agent tensioactif cationique et procédé pour leur fabrication Expired - Lifetime EP0714976B2 (fr)

Priority Applications (13)

Application Number Priority Date Filing Date Title
EP94308960A EP0714976B2 (fr) 1994-12-02 1994-12-02 Compositions détergentes contenant un agent tensioactif cationique et procédé pour leur fabrication
DE69424551T DE69424551T3 (de) 1994-12-02 1994-12-02 Kationisches Tensid enthaltende Waschmittelzusammensetzungen sowie deren Herstellung
AT94308960T ATE193051T1 (de) 1994-12-02 1994-12-02 Kationisches tensid enthaltende waschmittelzusammensetzungen sowie deren herstellungsverfahren
TR95/01509A TR199501509A2 (tr) 1994-12-02 1995-11-29 Katyonik yüzey aktif cismi iceren deterjan bilesimleri ve bilesimin hazirlanmasi icin bir islem.
PCT/US1995/015548 WO1996017042A1 (fr) 1994-12-02 1995-11-30 Compositions detergentes comprenant un agent tensioactif cationique et processus de fabrication
CN95197503.XA CN1174566A (zh) 1994-12-02 1995-11-30 含有阳离子表面活性剂的洗涤剂组合物及其制备方法
JP8519046A JPH10511713A (ja) 1994-12-02 1995-11-30 カチオン界面活性剤を含んでなる洗剤組成物およびその製造方法
MX9704078A MX9704078A (es) 1994-12-02 1995-11-30 Composiciones detergentes que comprenden agente tensioactivo cationico y procedimiento para hacer la composicion.
BR9509843A BR9509843A (pt) 1994-12-02 1995-11-30 Composição detergente compreendendo tensoatívo catiónico e processo para sua fabricação
AU43714/96A AU4371496A (en) 1994-12-02 1995-11-30 Detergent compositions comprising cationic surfactant and process for making the composition
CA002206326A CA2206326A1 (fr) 1994-12-02 1995-11-30 Compositions detergentes comprenant un agent tensioactif cationique et processus de fabrication
ZA9510227A ZA9510227B (en) 1994-12-02 1995-12-01 Detergent compositions comprising cationic surfactant and process for making the composition
MA24083A MA23734A1 (fr) 1994-12-02 1995-12-01 Compositions detegentes comprenant un agent tensioactif cationique et procede pour fabriquer ladite composition

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
EP94308960A EP0714976B2 (fr) 1994-12-02 1994-12-02 Compositions détergentes contenant un agent tensioactif cationique et procédé pour leur fabrication

Publications (3)

Publication Number Publication Date
EP0714976A1 EP0714976A1 (fr) 1996-06-05
EP0714976B1 EP0714976B1 (fr) 2000-05-17
EP0714976B2 true EP0714976B2 (fr) 2005-03-23

Family

ID=8217930

Family Applications (1)

Application Number Title Priority Date Filing Date
EP94308960A Expired - Lifetime EP0714976B2 (fr) 1994-12-02 1994-12-02 Compositions détergentes contenant un agent tensioactif cationique et procédé pour leur fabrication

Country Status (13)

Country Link
EP (1) EP0714976B2 (fr)
JP (1) JPH10511713A (fr)
CN (1) CN1174566A (fr)
AT (1) ATE193051T1 (fr)
AU (1) AU4371496A (fr)
BR (1) BR9509843A (fr)
CA (1) CA2206326A1 (fr)
DE (1) DE69424551T3 (fr)
MA (1) MA23734A1 (fr)
MX (1) MX9704078A (fr)
TR (1) TR199501509A2 (fr)
WO (1) WO1996017042A1 (fr)
ZA (1) ZA9510227B (fr)

Families Citing this family (9)

* 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
EP0971030A1 (fr) * 1998-07-10 2000-01-12 The Procter & Gamble Company Agglomérats tensio-actifs
GB0009029D0 (en) 2000-04-12 2000-05-31 Unilever Plc Laundry wash compositions
GB0009877D0 (en) * 2000-04-20 2000-06-07 Unilever Plc Granular detergent component and process for its preparation
DE102004018751A1 (de) * 2004-04-17 2005-11-03 Clariant Gmbh Verfahren zur Herstellung von quaternären Hydroxyalkylammonium Granulaten
US20080262129A1 (en) * 2007-04-06 2008-10-23 Kao Corporation Process for producing powder
US20130085093A1 (en) * 2010-05-14 2013-04-04 Yuken Industry Co., Ltd. Aqueous cleaning agent composition
EP2821474A1 (fr) * 2011-01-12 2015-01-07 The Procter and Gamble Company Procédé de contrôle de la plastification d'un film hydrosoluble
CN115895790A (zh) * 2022-11-30 2023-04-04 四川科宏达集团有限责任公司 一种阴-阳离子表面活性剂复配清洗剂及制备方法

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BE833077A (fr) † 1974-09-06 1975-12-31 Composition d'assouplissement des tissus contenant un tamis moleculaire zeolitique
US3936537A (en) † 1974-11-01 1976-02-03 The Procter & Gamble Company Detergent-compatible fabric softening and antistatic compositions
EP0011333A1 (fr) † 1978-11-16 1980-05-28 THE PROCTER & GAMBLE COMPANY Additif pour détergent sous forme de particules contenant un complexe adoucissant anionique-cationique insoluble et des compositions détergentes contenant l'additive
US4292035A (en) † 1978-11-13 1981-09-29 The Procter & Gamble Company Fabric softening compositions
GB2185752A (en) † 1986-01-23 1987-07-29 Procter & Gamble Detergent composition comprising suds control prills

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DE2449354B2 (de) * 1974-10-17 1979-08-23 Basf Ag, 6700 Ludwigshafen Verwendung von Orthophosphorsäureestern als Schaumdämpfer in kationischen Tensidformulierungen
DE2857300A1 (de) * 1977-11-17 1980-06-26 Procter & Gamble Koernige wasch- und reinigungsmittelzusammensetzungen fuer eine verbesserte entfernung von fettigem schmutz
JPS598392B2 (ja) * 1979-06-29 1984-02-24 花王株式会社 洗浄剤組成物
DE3069767D1 (en) * 1979-09-29 1985-01-17 Procter & Gamble Detergent compositions
JPS57137397A (en) * 1981-02-20 1982-08-24 Kao Corp Detergent composition
US4430244A (en) * 1982-03-04 1984-02-07 Colgate-Palmolive Company Silicate-free bleaching and laundering composition
US4622173A (en) * 1984-12-31 1986-11-11 Colgate-Palmolive Co. Non-aqueous liquid laundry detergents containing three surfactants including a polycarboxylic acid ester of a non-ionic
US4637890A (en) * 1986-01-23 1987-01-20 The Procter & Gamble Company Detergent composition providing rinse cycle suds and turbidity control containing a soap, quaternary ammonium salt and a silicone
US5071594A (en) * 1989-10-02 1991-12-10 Ethyl Corporation Free flowing granular laundry detergent comprising tert-amine oxide dihydrate
CZ367592A3 (en) * 1991-12-18 1993-09-15 Colgate Palmolive Co Process for preparing a freely flowing particulate composition for softening textile materials

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BE833077A (fr) † 1974-09-06 1975-12-31 Composition d'assouplissement des tissus contenant un tamis moleculaire zeolitique
US3936537A (en) † 1974-11-01 1976-02-03 The Procter & Gamble Company Detergent-compatible fabric softening and antistatic compositions
US4292035A (en) † 1978-11-13 1981-09-29 The Procter & Gamble Company Fabric softening compositions
EP0011333A1 (fr) † 1978-11-16 1980-05-28 THE PROCTER & GAMBLE COMPANY Additif pour détergent sous forme de particules contenant un complexe adoucissant anionique-cationique insoluble et des compositions détergentes contenant l'additive
GB2185752A (en) † 1986-01-23 1987-07-29 Procter & Gamble Detergent composition comprising suds control prills

Also Published As

Publication number Publication date
MA23734A1 (fr) 1996-07-01
DE69424551T2 (de) 2001-01-18
EP0714976A1 (fr) 1996-06-05
DE69424551T3 (de) 2005-12-29
MX9704078A (es) 1997-08-30
WO1996017042A1 (fr) 1996-06-06
AU4371496A (en) 1996-06-19
JPH10511713A (ja) 1998-11-10
EP0714976B1 (fr) 2000-05-17
ATE193051T1 (de) 2000-06-15
DE69424551D1 (de) 2000-06-21
ZA9510227B (en) 1996-06-12
CN1174566A (zh) 1998-02-25
TR199501509A2 (tr) 1996-07-21
BR9509843A (pt) 1997-11-25
CA2206326A1 (fr) 1996-06-06

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