EP0739977B1 - Process for producing granular detergent components or compositions - Google Patents

Process for producing granular detergent components or compositions Download PDF

Info

Publication number
EP0739977B1
EP0739977B1 EP95302860A EP95302860A EP0739977B1 EP 0739977 B1 EP0739977 B1 EP 0739977B1 EP 95302860 A EP95302860 A EP 95302860A EP 95302860 A EP95302860 A EP 95302860A EP 0739977 B1 EP0739977 B1 EP 0739977B1
Authority
EP
European Patent Office
Prior art keywords
crystalline zeolite
zeolite
weight
process according
mixtures
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
EP95302860A
Other languages
German (de)
English (en)
French (fr)
Other versions
EP0739977A1 (en
Inventor
Peter Rutherford Brougham
George Burgess
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Procter and Gamble Co
Original Assignee
Procter and Gamble Co
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority to AT95302860T priority Critical patent/ATE174954T1/de
Application filed by Procter and Gamble Co filed Critical Procter and Gamble Co
Priority to EP95302860A priority patent/EP0739977B1/en
Priority to DE69506842T priority patent/DE69506842T2/de
Priority to JP8532520A priority patent/JPH11504363A/ja
Priority to CA002216813A priority patent/CA2216813C/en
Priority to CN96194895A priority patent/CN1101463C/zh
Priority to AU53761/96A priority patent/AU5376196A/en
Priority to KR1019970707532A priority patent/KR19990008008A/ko
Priority to BR9608103A priority patent/BR9608103A/pt
Priority to US08/945,434 priority patent/US5925614A/en
Priority to PCT/US1996/004224 priority patent/WO1996034079A1/en
Priority to MX9708235A priority patent/MX9708235A/es
Priority to AR33630096A priority patent/AR001719A1/es
Priority to TW085107775A priority patent/TW327191B/zh
Publication of EP0739977A1 publication Critical patent/EP0739977A1/en
Application granted granted Critical
Publication of EP0739977B1 publication Critical patent/EP0739977B1/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/06—Powder; Flakes; Free-flowing mixtures; Sheets
    • C11D17/065—High-density particulate detergent compositions
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/02—Inorganic compounds ; Elemental compounds
    • C11D3/12—Water-insoluble 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
    • C11D11/0088—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 the liquefied ingredients being sprayed or adsorbed onto solid particles
    • 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
    • C11D3/02—Inorganic compounds ; Elemental compounds
    • C11D3/12—Water-insoluble compounds
    • C11D3/124—Silicon containing, e.g. silica, silex, quartz or glass beads
    • C11D3/1246—Silicates, e.g. diatomaceous earth
    • C11D3/128—Aluminium silicates, e.g. zeolites
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/37—Polymers
    • C11D3/3703—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/373—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds containing silicones
    • 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
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66—Non-ionic compounds

Definitions

  • the present invention relates to a process for the continuous preparation of a granular detergent composition or component having a high bulk density and good flow properties.
  • crystalline Zeolite A which is a water-insoluble, crystalline material well-known in the detergent art as a builder which is particularly suited to removing cations such as calcium and magnesium from hard water.
  • Crystalline Zeolite A is a very finely divided powder. It has been common practice to process the finely divided powder into the form of larger granules (typically 400 to 1000 micrometers) before incorporation into finished products, especially finished detergent compositions. Various granulation processes are known including spray drying and agglomeration. Conventional agglomeration processes in which Zeolite A is used as one of the components have long been known in the prior art :
  • GB2005715 published on 25th April 1979 describes an agglomeration process based upon Zeolite A.
  • the Zeolite A is agglomerated along with carbonate/bicarbonate to make nonionic surfactant agglomerates.
  • WO93/25378 published on 23rd December 1993, discloses a process for making granular detergents comprising Zeolite A.
  • the Zeolite A is agglomerated with a high active, neutralised surfactant paste in a high speed mixer and a moderate speed mixer/agglomerator to make anionic surfactant agglomerates.
  • EP-B-0 342 043 published on 15 th November 1989, discloses detergent powders comprising aluminosilicate ion exchange materials including Zeolite A, Zeolite B, Zeolite X, Zeolite HS and mixtures thereof.
  • EP521635 published on 7th January 1993, discloses granular detergents made using from 10% to 100% of Zeolite MAP.
  • Zeolite MAP has a different chemical composition to Zeolite A.
  • Example 1 of this patent application it is reported that the oil absorbing capacity of Zeolite MAP is 41.6 ml/100g, and that this is higher than measured samples of Zeolite A for which it is 26 to 35.5 ml/100g.
  • modifying the chemical structure of conventional crystalline Zeolite A i.e. modifying the stoichiometric ratios of Si, Al, Na, O, H) is not always desirable because other properties and characteristics of the Zeolite are necessarily affected.
  • the object of the invention is to provide a granulation process for making granular detergents which incorporates highly absorbent crystalline Zeolite into granular agglomerates, without losing any of the builder capabilities, especially calcium exchange capacity and calcium exchange rate.
  • this object is achieved by using a crystalline Zeolite which consists essentially of Zeolite A, P, X,Y, (or mixtures thereof) and Zeolite HS (Hydroxy Sodalite).
  • Zeolite HS Hydro Sodalite
  • the zeolite of the present invention has modified physical characteristics (i.e. crystallinity, surface area characteristics, moisture level) which in turn promotes greater ease and flexibility in processing during the manufacture of detergent powders.
  • the basic chemical structure of the zeolite is unchanged, hence the excellent builder properties of zeolite may still be utilised.
  • a process for the preparation of a granular detergent composition or component having a bulk density greater than 650 g/l which comprises the step of dispersing a liquid binder throughout a powder stream in a high speed mixer to form granular agglomerates, wherein the powder stream comprises a powder consisting essentially of crystalline zeolite A, P, X, Y, or mixtures thereof, and crystalline zeolite HS.
  • the ratio of zeolite A, P, X, Y, or mixtures thereof, to crystalline zeolite HS is from 1:1 to 99:1, preferably from 3:1 to 20:1, and that the powder has an oil absorbing capacity of at least 40 ml/100g, more preferably at least 45ml/100g, most preferably at least 50ml/100g.
  • the granular agglomerates are formed by mixing in the high speed mixer for a residence time of from 2 seconds to 30 seconds, followed by the step of further mixing in a moderate speed mixer/agglomerator for a residence time through the moderate speed mixer of less than 5 minutes, preferably less than 2 minutes, in which, optionally, a finely divided powder may be added.
  • the liquid binder is a surfactant paste, an organic polymer or silicone oil.
  • Surfactant paste may comprise anionic, nonionic, cationic, amphoteric, zwitterionic surfactants, and mixtures thereof; anionic and/or nonionic surfactants being most preferred.
  • Granulation in the context of the present invention is defined as a process of making a granulated product which is an agglomerate of particles that itself behaves as a particle (according to S.A. Kuti, "Agglomeration - The Practical Alternative", published in Journal American Oil Chemists' Society, Volume 55, January 1978).
  • the granular agglomerate is defined herein as the product of such a granulation process.
  • Kuti goes on to state that "the agglomerate is usually formed by blending solids with liquids that serve as adhesive agents. But a lump-free liquid-solids blend is often a difficult task to produce.”
  • the "solids” referred to by Kuti will comprise crystalline zeolite having certain physical characteristics to be defined in more detail below. It has now been found that this choice of “solids” contributes greatly to fulfilling the task of producing a lump-free liquid-solids blend.
  • the essential component of the granular agglomerate of the present invention is crystalline Zeolite HS of the formula : (Na2O) . (Al2O3) . x (SiO2) . wH2O wherein x is 2, and w is about 2.5 (From D.W. Breck, "Zeolite Molecular Sieves", John Wiley & Sons, New York, 1974, page 155).
  • Zeolite HS is also known as Zeolite G, Sodalite Hydrate and Hydroxy Sodalite.
  • the ideal unit cell composition for sodalite hydrate is: Na 6 AlO 6 Si 6 O 24 ⁇ 8 H 2 O (Breck, page 269)
  • NaOH is intercalated during synthesis, the composition varies according to : Na 6 AlO 6 Si 6 O 24 ⁇ xNaOH (8-2x) H 2 O (Breck, page 272) since one NaOH replaces two water molecules. Sodium hydrate has been observed to adsorb water after dehydration.
  • reaction conditions such that crystalline zeolite A (or P, X, Y) is formed in the required ratio to zeolite HS.
  • Preferred ways of doing this are to use sodium-rich gels in the zeolite formation and to carefully control the presence of various anions as well as the crystallisation temperature.
  • Elecron microscopy has shown crystals of zeolite HS "growing" from the surface of the zeolite A. Without wishing to be bound by theory it is suggested that this surface modification effect results in the desired higher oil adsorption values of the zeolite powder.
  • Crystalline zeolites are also essential features of the present invention. Certain crystalline zeolites are of great importance in most currently marketed heavy duty granular detergent compositions on account of their detergent builder capacities.
  • Aluminosilicate builders include those having the empirical formula: M z (zAlO 2 ) y ] ⁇ x H 2 O wherein z and y are integers of at least 6, the molar ratio of z to y is in the range from 1.0 to 0.5, and x is an integer from 15 to 264.
  • aluminosilicate ion exchange materials are commercially available. These aluminosilicates 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 disclosed in US Patent 3,985,669, Krummel et al, issued October 12, 1976. Preferred synthetic crystalline aluminosilicate ion exchange materials useful herein are available under the designations zeolite A, zeolite P(B), (including zeolite MAP), zeolite X and zeolite Y.
  • the crystalline aluminosilicate ion exchange material has the formula : Na 12 [(AlO 2 ) 12 (SiO2) 12 ] ⁇ x H 2 O wherein x is from 20 to 30, especially about 27.
  • This material is known as zeolite A.
  • the "overdried" zeolites are particularly useful when a low moisture environment is required, for example to improve stability of detergent bleaches such as perborate and percarbonate.
  • the aluminosilicate has a particle size of 0.1-10 micrometers in diameter.
  • Preferred ion exchange materials have a particle size diameter of from 0.2 micrometers to 4 micrometers.
  • the term "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 zeolite A 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 zeolite A materials herein are still further characterized by their calcium ion exchange rate which is at least 2 grains Ca ++ /gallon/minute/gram/gallon (0.13g Ca ++ /litre/minute/gram/litre) of aluminosilicate (anhydrous basis), and generally lies within the range of from 2 grains/gallon/minute/gram/gallon(0.13g Ca ++ /litre/minute/gram/litre) to 6 grains/gallon/minute/gram/gallon (0.39g Ca ++ /litre/minute/gram/litre), based on calcium ion hardness.
  • Optimum aluminosilicate for builder purposes exhibit a calcium ion exchange rate of at least 4 grains/gallon/minute/gram/gallon (0.26g Ca ++ /litre/minute/gram/litre).
  • the granular agglomerates of the present invention also comprise other detergent ingredients.
  • Water-soluble salts of the higher fatty acids are useful anionic surfactants in the compositions herein.
  • Soaps can be made by direct saponification of fats and oils or by the neutralization of free fatty acids.
  • Particularly useful are the sodium and potassium salts of the mixtures of fatty acids derived from coconut oil and tallow, i.e., sodium or potassium tallow and coconut soap.
  • Useful anionic surfactants also include the water-soluble salts, preferably the alkali metal, ammonium and alkylolammonium salts, of organic sulfuric reaction products having in their molecular structure an alkyl group containing from 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; and methyl ester sulphonates.
  • 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.
  • anionic surfactants 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 salts of alkyl phenol ethylene oxide ether sulfates containing from 1 to 10 units 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 from 1 to 10 units of ethylene oxide per molecule and wherein the alkyl group contains from 10 to 20 carbon atoms.
  • Suitable 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.
  • the acid salts are typically discussed and used, the acid neutralization can be performed as part of the fine
  • Water-soluble nonionic surfactants are also useful as surfactants in the compositions of the invention. Indeed, preferred processes use anionic/nonionic blends.
  • 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 16 carbon atoms, in either a straight chain or branched chain configuration, with from 4 to 25 moles of ethylene oxide per mole of alkyl phenol.
  • Preferred nonionics are the water-soluble condensation products of aliphatic alcohols containing from 8 to 22 carbon atoms, in either straight chain or branched configuration, with from 1 to 25 moles of ethylene oxide per mole of alcohol, especially 2 to 7 moles of ethylene oxide per mole of alcohol.
  • Particularly preferred are the condensation products of alcohols having an alkyl group containing from 9 to 15 carbon atoms; and condensation products of propylene glycol with ethylene oxide.
  • polyhydroxy fatty acid amides which may be prepared by reacting a fatty acid ester and an N-alkyl polyhydroxy amine.
  • the preferred amine for use in the present invention is N-(R1)-CH2(CH2OH)4-CH2-OH and the preferred ester is a C12-C20 fatty acid methyl ester.
  • Most preferred is the reaction product of N-methyl glucamine (which may be derived from glucose) with C12-C20 fatty acid methyl ester.
  • Semi-polar nonionic surfactants include water-soluble amine oxides containing one alkyl moiety of from 10 to 18 carbon atoms and 2 moieties selected from the group consisting of alkyl groups and hydroxyalkyl groups containing from 1 to 3 carbon atoms; water-soluble phosphine oxides containing one alkyl moiety of 10 to 18 carbon atoms and 2 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.
  • Ampholytic surfactants include derivatives of aliphatic or aliphatic derivatives of heterocyclic secondary and tertiary amines in which the aliphatic moiety can be either straight or branched chain and wherein one of the aliphatic substituents contains from 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.
  • Useful cationic surfactants include water-soluble quaternary ammonium compounds of the form R 4 R 5 R 6 R 7 N + X - , wherein R 4 is alkyl having from 10 to 20, preferably from 12-18 carbon atoms, and R 5 , R 6 and R 7 are each C 1 to C 7 alkyl preferably methyl; X - is an anion, e.g. chloride.
  • Examples of such trimethyl ammonium compounds include C 12-14 alkyl trimethyl ammonium chloride and cocalkyl trimethyl ammonium methosulfate.
  • the granular detergents of the present invention can contain neutral or alkaline salts which have a pH in solution of seven or greater, and can be either organic or inorganic in nature.
  • the builder salt assists in providing the desired density and bulk to the detergent granules herein. While some of the salts are inert, many of them also function as detergency builder materials in the laundering solution.
  • neutral water-soluble salts examples include the alkali metal, ammonium or substituted ammonium chlorides, fluorides and sulfates.
  • the alkali metal, and especially sodium, salts of the above are preferred.
  • Sodium sulfate is typically used in detergent granules and is a particularly preferred salt.
  • Citric acid and, in general, any other organic or inorganic acid may be incorporated into the granular detergents of the present invention as long as it is chemically compatible with the rest of the agglomerate composition.
  • water-soluble salts include the compounds commonly known as detergent builder materials.
  • Builders are generally selected from the various water-soluble, alkali metal, ammonium or substituted ammonium phosphates, polyphosphates, phosphonates, polyphosphonates, carbonates, silicates, borates, and polyhyroxysulfonates.
  • alkali metal especially sodium, salts of the above.
  • inorganic phosphate builders are sodium and potassium tripolyphosphate, pyrophosphate, polymeric metaphosphate having a degree of polymerization of from about 6 to 21, and orthophosphate.
  • polyphosphonate builders are the sodium and potassium salts of ethylene diphosphonic acid, the sodium and potassium salts of ethane 1-hydroxy-1,1-diphosphonic acid and the sodium and potassium salts of ethane, 1,1,2-triphosphonic acid.
  • Other phosphorus builder compounds are disclosed in U.S. Pat. Nos. 3,159,581; 3,213,030; 3,422,021; 3,422,137; 3,400,176 and 3,400,148.
  • 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.
  • organic polymers are also useful as builders to improve detergency. Included among such polymers may be mentioned sodium carboxy-lower alkyl celluloses, sodium lower alkyl celluloses and sodium hydroxy-lower alkyl celluloses, such as sodium carboxymethyl cellulose, sodium methyl cellulose and sodium hydroxypropyl cellulose, polyvinyl alcohols (which often also include some polyvinyl acetate), polyacrylamides, polyacrylates and various copolymers, such as those of maleic and acrylic acids. Molecular weights for such polymers vary widely but most are within the range of 2,000 to 100,000.
  • polymers are polyamine N-oxide polymers, copolymers of N-vinylpyrrolidone and N-vinylimidazole, polyvinylpyrrolidone polymers, polyvinyloxazolidones and polyvinylimidazoles or mixtures thereof.
  • Polymeric polycarboxyate builders are set forth in U.S. Patent 3,308,067, Diehl, issued March 7, 1967. Such materials include the water-soluble salts of homo-and copolymers of aliphatic carboxylic acids such as maleic acid, itaconic acid, mesaconic acid, fumaric acid, aconitic acid, citraconic acid and methylenemalonic acid.
  • Particulate suds suppressors may also be incorporated either directly in the agglomerates herein by way of the powder stream into the agglomerating unit, or in the finished composition by dry adding.
  • the suds suppressing activity of these particles is based on fatty acids or silicones.
  • the silicone oil is adsorbed onto the specified Zeolite A.
  • compositions of the present invention can be included in the compositions of the present invention. These include flow aids, color speckles, bleaching agents and bleach activators, suds boosters or suds suppressors, antitarnish and anticorrosion agents, soil suspending agents, soil release agents, dyes, fillers, optical brighteners, germicides, pH adjusting agents, nonbuilder alkalinity sources, hydrotropes, enzymes, enzyme-stabilizing agents, chelating agents and perfumes.
  • These optional ingredients may be incorporated either directly in the agglomerates herein or may be components of separate particles suitable for dry adding to the agglomerates of the present invention.
  • Zeolite A # has an oil absorption capacity of 36 ml/100g supplied by Degussa under the Trade Name Wessalith®.
  • C12-15AS is sodium alkyl sulphate, the alkyl chains principally comprising C12 to C15.
  • C12-15AE3S is sodium alkyl ether sulphate, the alkyl chains principally comprising C12 to C15, and with an average of 3 ethoxy groups per molecule.
  • Co-polymer is a co-polymer of acrylic and maleic acid.
  • Nonionic surfactant comprises 7 parts of ethoxylated alcohol, the alkyl chains principally comprising C12 to C15, and with an average of 3 ethoxy groups per molecule; and 3 parts of C12-14 polyhydroxy fatty acid amide. Misc is mainly sulphate with some other minor impurities.
  • Granular agglomerates having the composition of Example 1 were prepared by the following process.
  • the powdered raw materials Zeolite A/HS and sodium carbonate
  • the mixer pan was then stopped and preheated surfactant paste (50°C), 80% surfactant active in aqueous solution, was then added in slices into a hollow formed in the middle of the powder. Loose powder being scooped over the paste to completely cover it.
  • the mixer was then started again with pan rotating at 64 rpm, and choppers set at 2500 rpm. The mixing was stopped when granular agglomerates started to form (at this point the current drawn by the Eirich rose from 2.8 to 3 amps.
  • oversized particles be considered as those having particle size of greater than 1600 micrometers.
  • Granular agglomerates having the composition of Examples 2 were prepared by the following process.
  • a paste comprising the surfactants was prepared by sulphating and neutralising appropriate alcohols.
  • the resulting paste had a water content of 18%.
  • the paste was pumped into a high shear mixer (Loedige CB®).
  • Simultaneously Zeolite A/HS and sodium carbonate were fed into the high shear mixer and intimately mixed with the high viscosity paste therein.
  • the resulting mixture was transferred directly to a low shear mixer (Loedige KM®) were agglomerates formed. After exiting from the low shear mixer the agglomerates were screened to remove oversize "lumps" and fines.
  • agglomerates were cooled in a fluid bed and stored prior to dry mixing with other detergent powders in order to form a finished product.
  • the residence time in the high shear mixer was approximately 8 seconds, and the residence time in the low shear mixer was approximately 35 seconds.
  • Granular agglomerates having the composition of Example 3 were prepared by the same process as Example 2, the anionic surfactant paste being replaced by the nonionic surfactant maintained as a viscous paste at 70°C.
  • Granular agglomerates having the composition of Comparative Example A were prepared by the same process as Example 1, using the same time of mixing the powders and paste as that used in Example 1.
  • the resulting granular agglomerates had greater than 25% by weight of oversized particles (oversized particles be considered as those having particle size of greater than 1600 micrometers).

Landscapes

  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Detergent Compositions (AREA)
EP95302860A 1995-04-27 1995-04-27 Process for producing granular detergent components or compositions Expired - Lifetime EP0739977B1 (en)

Priority Applications (14)

Application Number Priority Date Filing Date Title
EP95302860A EP0739977B1 (en) 1995-04-27 1995-04-27 Process for producing granular detergent components or compositions
DE69506842T DE69506842T2 (de) 1995-04-27 1995-04-27 Verfahren zur Herstellung von granularen Waschmittelkomponenten oder Waschmittelzusammensetzungen
AT95302860T ATE174954T1 (de) 1995-04-27 1995-04-27 Verfahren zur herstellung von granularen waschmittelkomponenten oder waschmittelzusammensetzungen
PCT/US1996/004224 WO1996034079A1 (en) 1995-04-27 1996-03-27 Process for producing granular detergent components or compositions
CN96194895A CN1101463C (zh) 1995-04-27 1996-03-27 制备粒状洗涤剂组分或组合物的方法
AU53761/96A AU5376196A (en) 1995-04-27 1996-03-27 Process for producing granular detergent components or compo sitions
KR1019970707532A KR19990008008A (ko) 1995-04-27 1996-03-27 입상 세제 성분 또는 조성물의 제조방법
BR9608103A BR9608103A (pt) 1995-04-27 1996-03-27 Processo para a produção de componentes ou composições detergentes granulares
JP8532520A JPH11504363A (ja) 1995-04-27 1996-03-27 粒状洗剤成分または組成物の製法
CA002216813A CA2216813C (en) 1995-04-27 1996-03-27 Process for producing granular detergent components or compositions
MX9708235A MX9708235A (es) 1995-04-27 1996-03-27 Procedimiento para producir componentes o composiciones detergentes granulares.
US08/945,434 US5925614A (en) 1995-04-27 1996-03-27 Process for producing granular detergent components or compositions
AR33630096A AR001719A1 (es) 1995-04-27 1996-04-26 Proceso para la preparación de componente o composiciones detergentes granulares
TW085107775A TW327191B (en) 1995-04-27 1996-06-27 Process for producing granular detergent components or compositions

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
EP95302860A EP0739977B1 (en) 1995-04-27 1995-04-27 Process for producing granular detergent components or compositions

Publications (2)

Publication Number Publication Date
EP0739977A1 EP0739977A1 (en) 1996-10-30
EP0739977B1 true EP0739977B1 (en) 1998-12-23

Family

ID=8221175

Family Applications (1)

Application Number Title Priority Date Filing Date
EP95302860A Expired - Lifetime EP0739977B1 (en) 1995-04-27 1995-04-27 Process for producing granular detergent components or compositions

Country Status (13)

Country Link
EP (1) EP0739977B1 (ja)
JP (1) JPH11504363A (ja)
KR (1) KR19990008008A (ja)
CN (1) CN1101463C (ja)
AR (1) AR001719A1 (ja)
AT (1) ATE174954T1 (ja)
AU (1) AU5376196A (ja)
BR (1) BR9608103A (ja)
CA (1) CA2216813C (ja)
DE (1) DE69506842T2 (ja)
MX (1) MX9708235A (ja)
TW (1) TW327191B (ja)
WO (1) WO1996034079A1 (ja)

Families Citing this family (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1996034082A1 (en) * 1995-04-27 1996-10-31 The Procter & Gamble Company Process for producing granular detergent components or compositions
US6140301A (en) * 1995-04-27 2000-10-31 The Procter & Gamble Company Process for producing granular detergent components or compositions
GB9913547D0 (en) * 1999-06-10 1999-08-11 Unilever Plc Particulate detergent composition containing zeolite
GB9913546D0 (en) 1999-06-10 1999-08-11 Unilever Plc Granular detergent component containing zeolite map and laundry detergent compositions containing it
EP1505147B1 (en) * 2003-08-06 2008-04-02 Kao Corporation Process for producing granular anionic surfactant
EP2113494B1 (en) * 2008-05-02 2010-07-14 Kaba Rosmalen Holding N.V. Cement additive, cement composition, cement composition comprising waste material, and processes for making and using the same
TWI342932B (en) 2008-08-18 2011-06-01 King Slide Works Co Ltd Damping device
US8933131B2 (en) 2010-01-12 2015-01-13 The Procter & Gamble Company Intermediates and surfactants useful in household cleaning and personal care compositions, and methods of making the same
BR112013019684A2 (pt) 2011-02-17 2016-10-18 Procter & Gamble alquil-fenil-sulfonatos lineares biobaseados
CN103380204B (zh) 2011-02-17 2016-02-03 宝洁公司 包含c10-c13烷基苯基磺酸盐的混合物的组合物
GB201222908D0 (en) 2012-12-19 2013-01-30 Pq Silicas Uk Ltd Curable liquid compositions
GB201406268D0 (en) * 2014-04-08 2014-05-21 Pq Silicas Uk Ltd Particulate zeolite composition

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4264464A (en) * 1977-10-06 1981-04-28 Colgate-Palmolive Company High bulk density particulate heavy duty laundry detergent
GB8811447D0 (en) * 1988-05-13 1988-06-15 Procter & Gamble Granular laundry compositions
GB9113675D0 (en) * 1991-06-25 1991-08-14 Unilever Plc Particulate detergent composition or component
DE69332270T3 (de) * 1992-06-15 2006-08-17 The Procter & Gamble Company, Cincinnati Verfahren zum herstellen von kompakten waschmittelzusammensetzungen
EP0643130B2 (en) * 1993-09-13 2007-09-19 The Procter & Gamble Company Granular detergent compositions comprising nonionic surfactant and process for making such compositions

Also Published As

Publication number Publication date
CN1101463C (zh) 2003-02-12
CN1188505A (zh) 1998-07-22
EP0739977A1 (en) 1996-10-30
BR9608103A (pt) 1999-02-02
AR001719A1 (es) 1997-11-26
WO1996034079A1 (en) 1996-10-31
DE69506842T2 (de) 1999-08-05
CA2216813C (en) 2002-02-19
ATE174954T1 (de) 1999-01-15
JPH11504363A (ja) 1999-04-20
KR19990008008A (ko) 1999-01-25
MX9708235A (es) 1997-12-31
CA2216813A1 (en) 1996-10-31
DE69506842D1 (de) 1999-02-04
TW327191B (en) 1998-02-21
AU5376196A (en) 1996-11-18

Similar Documents

Publication Publication Date Title
US4487710A (en) Granular detergents containing anionic surfactant and ethoxylated surfactant solubility aid
US4136051A (en) Pourable washing compositions containing a luminosilicates and non-ionics and method for their preparation
EP0739977B1 (en) Process for producing granular detergent components or compositions
KR19990036403A (ko) 함침된 무정형의 알칼리 금속 실리케이트의 제조 방법
AU611555B2 (en) Process for preparing detergent compositions
JPH08509775A (ja) 造粒工程前の液体非イオン系界面活性剤の構造化
EP0544365B1 (en) Detergent compositions and process for preparing them
EP0870008B1 (en) Process for producing granular detergent components or compositions
CA1316790C (en) Non-phosphorus detergent bleach compositions
EP0643129A1 (en) Process for preparing detergent compositions
CN1111594C (zh) 制造洗涤剂组合物的方法
US5925614A (en) Process for producing granular detergent components or compositions
US6140301A (en) Process for producing granular detergent components or compositions
CA2231577C (en) Process for making granular detergents
US5998356A (en) Process for making granular detergents
CA2248635C (en) Particulate aluminosilicate-built detergent compositions comprising cogranules of zeolite map and alkali metal silicate
JP3008266B2 (ja) 結晶性アルカリ金属ケイ酸塩顆粒の製造方法及び衣料用の高嵩密度粒状洗剤組成物
EP0892843B1 (en) Modified aluminosilicate
CN1116402C (zh) 含二氧化硅的低密度洗涤剂附聚物的制备
JP3198035B2 (ja) 高密度洗浄剤粒子
US6004921A (en) Process for making granular suds suppressing component
JPH09500168A (ja) 洗剤組成物

Legal Events

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

Free format text: ORIGINAL CODE: 0009012

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): AT BE CH DE DK ES FR GB GR IE IT LI LU NL PT SE

17P Request for examination filed

Effective date: 19970421

17Q First examination report despatched

Effective date: 19970807

GRAG Despatch of communication of intention to grant

Free format text: ORIGINAL CODE: EPIDOS AGRA

GRAG Despatch of communication of intention to grant

Free format text: ORIGINAL CODE: EPIDOS AGRA

GRAH Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOS IGRA

GRAH Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOS IGRA

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

AK Designated contracting states

Kind code of ref document: B1

Designated state(s): AT BE CH DE DK ES FR GB GR IE IT LI LU NL PT SE

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: NL

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 19981223

Ref country code: LI

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 19981223

Ref country code: GR

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 19981223

Ref country code: ES

Free format text: THE PATENT HAS BEEN ANNULLED BY A DECISION OF A NATIONAL AUTHORITY

Effective date: 19981223

Ref country code: CH

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 19981223

Ref country code: BE

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 19981223

Ref country code: AT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 19981223

REF Corresponds to:

Ref document number: 174954

Country of ref document: AT

Date of ref document: 19990115

Kind code of ref document: T

REG Reference to a national code

Ref country code: CH

Ref legal event code: EP

REF Corresponds to:

Ref document number: 69506842

Country of ref document: DE

Date of ref document: 19990204

REG Reference to a national code

Ref country code: IE

Ref legal event code: FG4D

ITF It: translation for a ep patent filed
ET Fr: translation filed
PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: SE

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 19990323

Ref country code: PT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 19990323

Ref country code: DK

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 19990323

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: LU

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 19990427

Ref country code: IE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 19990427

NLV1 Nl: lapsed or annulled due to failure to fulfill the requirements of art. 29p and 29m of the patents act
REG Reference to a national code

Ref country code: CH

Ref legal event code: PL

PLBE No opposition filed within time limit

Free format text: ORIGINAL CODE: 0009261

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

Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT

26N No opposition filed
REG Reference to a national code

Ref country code: IE

Ref legal event code: MM4A

REG Reference to a national code

Ref country code: GB

Ref legal event code: IF02

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

Ref country code: DE

Payment date: 20070430

Year of fee payment: 13

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

Ref country code: IT

Payment date: 20070616

Year of fee payment: 13

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

Ref country code: FR

Payment date: 20070404

Year of fee payment: 13

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: DE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20081101

REG Reference to a national code

Ref country code: FR

Ref legal event code: ST

Effective date: 20081231

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: FR

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20080430

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

Ref country code: GB

Payment date: 20090312

Year of fee payment: 15

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: IT

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20080427

GBPC Gb: european patent ceased through non-payment of renewal fee

Effective date: 20100427

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: GB

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20100427