EP0618289B1 - Hochaktive körnige Reinigungsmittel enthaltend Chelatbildner und Polymere und Verfahren zu ihrer Herstellung - Google Patents

Hochaktive körnige Reinigungsmittel enthaltend Chelatbildner und Polymere und Verfahren zu ihrer Herstellung Download PDF

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Publication number
EP0618289B1
EP0618289B1 EP19930870058 EP93870058A EP0618289B1 EP 0618289 B1 EP0618289 B1 EP 0618289B1 EP 19930870058 EP19930870058 EP 19930870058 EP 93870058 A EP93870058 A EP 93870058A EP 0618289 B1 EP0618289 B1 EP 0618289B1
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Prior art keywords
polymer
paste
chelating agent
high active
weight
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EP19930870058
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English (en)
French (fr)
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EP0618289A1 (de
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Adrian John Waynforth Angell
Yousef Georges Aouad
Jose Luis Vega
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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 EP19930870058 priority Critical patent/EP0618289B1/de
Priority to DE1993620455 priority patent/DE69320455T2/de
Priority to JP6522056A priority patent/JPH08508525A/ja
Priority to CA002159178A priority patent/CA2159178C/en
Priority to US08/532,555 priority patent/US5712242A/en
Priority to PCT/US1994/001917 priority patent/WO1994022992A1/en
Publication of EP0618289A1 publication Critical patent/EP0618289A1/de
Publication of EP0618289B1 publication Critical patent/EP0618289B1/de
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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
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/37—Polymers
    • C11D3/3746—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/3757—(Co)polymerised carboxylic acids, -anhydrides, -esters in solid and liquid compositions
    • C11D3/3761—(Co)polymerised carboxylic acids, -anhydrides, -esters in solid and liquid compositions in solid compositions
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • 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
    • 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
    • C11D3/26—Organic compounds containing nitrogen
    • C11D3/33—Amino carboxylic acids
    • 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
    • C11D3/36—Organic compounds containing phosphorus
    • C11D3/364—Organic compounds containing phosphorus containing nitrogen

Definitions

  • the present invention relates to a high active surfactant paste composition and to high active granular detergent components and compositions which can be made using such paste compositions.
  • the invention also relates to a process for making these pastes, and granular components and compositions.
  • agglomeration This term describes any process in which small particles of the components are processed in such a way that they are built-up (or “agglomerated") to form suitable granular components.
  • the ideal detergent agglomerate should have a high bulk density and a high surfactant content and yet still have good solubility and dispersion properties. It should also be possible to use a manufacturing process which is both efficient and versatile.
  • US-A-5 080 848 published on 14th January, 1992 describes a process for making surfactant granules typically having an anionic surfactant activity of 50% to 75% (see examples 1 to 8).
  • the process involves chilling and granulating a viscous high active surfactant paste.
  • the granulation may be performed with the aid of some detergency builders (see examples 3 and 4), but the emphasis is on reducing the temperature in order to initiate granulation.
  • the finished detergent composition may contain other optional ingredients including chelating agents, but there is no indication of any advantages of adding solutions of chelating agent and polymers directly to the paste.
  • EP-A-0 508 543 published on 14th October, 1992 discloses methods of chemically conditioning high active surfactant pastes in order to achieve high active detergent granules. Phosphonates, polymers and copolymers are disclosed as useful conditioning agents. Conditioning of a paste may be achieved by, for example, increasing paste viscosity and/or drying. An example of paste conditioning by the addition of powdered co-polymer is given. However there is no suggestion of the benefits of using solutions of chelant and polymer together.
  • the present invention addresses the problems of how to make higher active surfactant particles than possible using the disclosures in prior art and how to increase the rate of solubility of the resulting particles. There is no need to cool the paste during the granulation step, and the resulting agglomerates have an activity of at least 35%, preferably at least 50%, and more preferably at least 60%.
  • the present invention allows the handling of paste compositions which contain more water than those of the prior art, which therefore have a correspondingly lower viscosity, and yet still result in granular detergents having a very high surfactant composition.
  • a free-flowing granular detergent component or composition having a bulk density of at least 650 g/l which comprises
  • the high active surfactant paste of the present invention comprises three essential components, a surfactant premix, a chelating agent and a polymer or copolymer. It is also an essential feature of the invention that the chelating agent and the polymer or copolymer are in the form of aqueous solutions. The three essential components may then be mixed together in any convenient order.
  • the ratio of chelating agent to polymer/copolymer has now been found to be essential for making high active agglomerates having a good rate of solubility.
  • the ratio of chelating agent to polymer/copolymer in the present invention should be from 1:100 to 1:1; and preferably from 1:50 to 1:2, and more preferably from 1:20 to 1:5. Most preferably the ratio is about 1:7.
  • One or various aqueous pastes of the salts of anionic surfactants is preferred for use in the present invention, preferably the sodium salt of the anionic surfactant. While granulation using various pure or mixed surfactants is known, for the present invention to be of practical use in industry and to result in particles of adequate physical properties to be incorporated into granular detergents, an anionic surfactant must be part of the paste in a concentration of above 40%, preferably from 40%-95%.
  • the activity of the aqueous surfactant paste premix is at least 40% and can go up to about 95%; preferred activities are : 50-80% and 65-75%.
  • the balance of the paste premix is primarily water but can include a processing aid such as a nonionic surfactant. At the higher active concentrations, little or no builder is required for cold granulation of the paste.
  • the resultant concentrated surfactant granules can be added to dry builders or powders or used in conventional agglomeration operations.
  • the aqueous surfactant paste premix contains an organic surfactant selected from the group consisting of anionic, zwitterionic, ampholytic and cationic surfactants, and mixtures thereof. Anionic surfactants are preferred.
  • Nonionic surfactants are used as secondary surfactants or processing aids and are not included herein as an "active" surfactant.
  • Surfactants useful herein are listed in U.S. Pat. No. 3,664,961, Norris, issued May 23, 1972, and in U.S. Pat. No. 3,919,678, Laughlin et al., issued Dec. 30, 1975.
  • Useful cationic surfactants also include those described in U.S. Pat. No. 4,222,905, Cockrell, issued Sept. 16, 1980, and in U.S. Pat. 4,239,659, Murphy, issued Dec. 16, 1980.
  • cationic surfactants are generally less compatible with the aluminosilicate materials herein, and thus are preferably used at low levels, if at all, in the present compositions. The following are representative examples of surfactants useful in the present compositions.
  • 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.
  • 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; water-soluble 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 cam be performed as part of the
  • the preferred anionic surfactant pastes are mixtures of linear or branched alkylbenzene sulfonates having an alkyl of 10-16 carbon atoms and alkyl sulfates having an alkyl of 10-18 carbon atoms. These pastes are usually produced by reacting a liquid organic material with sulfur trioxide to produce a sulfonic or sulfuric acid and then neutralizing the acid to produce a salt of that acid.
  • the salt is the surfactant paste discussed throughout this document.
  • the sodium salt is preferred due to end performance benefits and cost of NaOH vs. other neutralizing agents, but is not required as other agents such as KOH may be used.
  • Water-soluble nonionic surfactants are also useful as secondary surfactant in the compositions of the invention. Indeed, preferred processes use anionic/nonionic blends.
  • a particularly preferred paste comprises a blend of nonionic and anionic surfactants having a ratio of from 0.01:1 to 1:1, more preferably 0.05:1.
  • Nonionics can be used up to an equal amount of the primary organic surfactant.
  • 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 4 to 25 moles of ethylene oxide per more of alcohol. Particularly preferred are the condensation products of alcohols having an alkyl group containing from 9 to 15 carbon atoms with from 4 to 25 moles of ethylene oxide per mole of alcohol; and condensation products of propylene glycol with ethylene oxide.
  • 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.
  • Particularly preferred surfactants herein include linear alkylbenzene sulfonates containing from 11 to 14 carbon atoms in the alkyl group; tallow alkyl sulfates; coconutalkyl glyceryl ether sulfonates; alkyl ether sulfates wherein the alkyl moiety contains from 14 to 18 carbon atoms and wherein the average degree of ethoxylation is from 1 to 4; olefin or paraffin sulfonates containing from 14 to 16 carbon atoms; alkyldimethylamine oxides wherein the alkyl group contains from 11 to 16 carbon atoms; alkyldimethylammonio propane sulfonates and alkyldimethylammonio hydroxy propane sulfonates wherein the alkyl group contains from 14 to 18 carbon atoms; soaps of higher fatty acids containing from 12 to 18 carbon atoms; condensation products of C9-C15 alcohols with from 3 to 8 moles of
  • Useful cationic surfactants include.
  • 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.
  • Specific preferred surfactants for use herein include: sodium linear C 11 -C 13 alkylbenzene sulfonate; alpha-olefin sulphonates; triethanolammonium C 11 -C 13 alkylbenzene sulfonate; alkyl sulfates, (tallow, coconut, palm, synthetic origins, e.g.
  • Viscosity is a function, among others, of concentration and temperature, with a range in this application from 10,000 cps to 10,000,000 cps.
  • the viscosity of the paste entering the system is from 20,000 to 100,000 cps. and more preferably from 30,000 to 70,000 cps.
  • the viscosity of the paste of this invention is measured at a temperature of 70°C when measured at 25s -1 .
  • a Physica Viscotherm VT100 was used for measuring viscosity.
  • the chelating agents suitable for use in the present invention can be chosen from a wide range of chemicals which are known to the man skilled in the art.
  • suitable chelating agents are phosphonic and succinic acids and their salts.
  • the polyphosphonates 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.
  • particularly suitable chelating agents are ethylene diamine tetra (methylene phosphonic acid) and diethylene triamine penta (methylene phosphonic acid).
  • EDDS ethylenediamine-N,N'-disuccinic acid
  • Preferred EDDS compounds are the free acid form and the sodium or magnesium salt thereof.
  • Examples of such preferred sodium salts of EDDS include NaEDDS, Na 2 EDDS and Na 4 EDDS.
  • Examples of such preferred magnesium salts of EDDS include Mg EDDS and Mg 2 EDDS.
  • the magnesium salts are the most preferred for inclusion in compositions in accordance with the invention.
  • the structure of the acid form of EDDS is as follows : EDDS can be synthesised, for example, from readily available, inexpensive starting material such as maleic anhydride and ethylene diamine as follows :
  • the [S,S] isomer of EDDS can be synthesised from L-aspartic acid and 1,.2-dibromoethane, as follows :
  • the concentration of the aqueous solutions of the chelating agent is not critical in the present invention. However, it is convenient to use solutions which are readily available commercially. Aqueous solutions having a concentration of from 5% to 60% of the chelating agent are suitable.
  • the polymers and co-polymers of the present invention may be chosen from a wide range of organic polymers, some of which also may function as builders to improve detergency. Included among such polymers may be mentioned sodium carboxy-lower alkyl celluloses, sodium lower alkyl celluloses and sodium hydroxy-lower alkyl celluloses, such as sodium carboxymethyl cellulose, sodium methyl cellulose and sodium hydroxypropyl cellulose, polyvinyl alcohols (which often also include some polyvinyl acetate), polyacrylamides, polyacrylates, polyaspartates, polyvinylpyrrolidones and various copolymers, such as those of maleic and acrylic acids. Molecular weights for such polymers vary widely but most are within the range of 2,000 to 100,000.
  • Polymeric polycarboxyate builders are set forth in U.S. Patent 3,308,067, Diehl, issued March 7, 1967. Such materials include the water-soluble salts of homo-and copolymers of aliphatic carboxylic acids such as maleic acid, itaconic acid, mesaconic acid, fumaric acid, aconitic acid, citraconic acid and methylenemalonic acid.
  • copolymers of maleic and acrylic acid having a molecular weight of from 2000 to 100000, carboxymethyl cellulose and mixtures thereof.
  • the concentration of the aqueous solutions of the polymer or copolymer is not critical in the present invention. However, it is convenient to use solutions which are readily available commercially. Aqueous solutions having a concentration of from 5% to 60% of the polymer or copolymer are suitable.
  • the high active surfactant paste described hereinabove may be treated by any suitable process, for example agglomeration with powders to form granular detergent components or compositions.
  • the high active surfactant paste is mixed by fine dispersion mixing and granulation with an effective amount of powder.
  • Any compatible detergency builder or combination of builders or powder can be used in the process and compositions of the present invention.
  • 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 micron to 10 microns. Amorphous materials are often smaller, e.g., down to less than 0.01 micron.
  • Preferred ion exchange materials have a particle size diameter of from 0.2 micron to 4 microns.
  • particle size diameter herein represents the average particle size diameter by weight of a given ion exchange material as determined by conventional analytical techniques such as, for example, microscopic determination utilizing a scanning electron microscope.
  • the crystalline aluminosilicate ion exchange materials herein are usually further characterized by their calcium ion exchange capacity, which is at least 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 aluminosilicate ion exchange materials herein are still further characterized by their calcium ion exchange rate which is at least 13x10 -2 g/l/min/g/l (2 grains Ca ++ /gallon/minute/gram/gallon) of aluminosilicate (anhydrous basis) and generally lies within the range of from 13x10 -2 g/l/min/g/l (2 grains/gallon/minute/gram/gallon) to 39x10 -2 g/l/min/g/l (6 grains/gallon/minute/gram/gallon), based on calcium ion hardness.
  • Optimum aluminosilicate for builder purposes exhibit a calcium ion exchange rate of at least 26x10 -2 g/l/min/g/l (4 grains/gallon/minute/gram/gallon).
  • the amorphous aluminosilicate ion exchange materials usually have a Mg ++ exchange of at least 50 mg eq. CaCO 3 /g (12 mg Mg ++ /g) and a Mg ++ exchange rate of at least 6.5x10 -2 g/l/min/g/l (1 grain/gallon/minute/gram/gallon). Amorphous materials do not exhibit an observable diffraction pattern when examined by Cu radiation (1.54 Angstrom Units).
  • Aluminosilicate ion exchange materials useful in the practice of this invention are commercially available.
  • the aluminosilicates useful in this invention can be crystalline or amorphous in structure and can be naturally occurring aluminosilicates or synthetically derived.
  • a method for producing aluminosilicate ion exchange materials is discussed in U.S. Pat. No. 3,985,669, Krummel et al., issued Oct. 12, 1976.
  • Preferred synthetic crystalline aluminosilicate ion exchange materials useful herein are available under the designations Zeolite A, Zeolite B, 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 microns.
  • the granular detergents of the present invention can contain neutral or alkaline salts which have a pH in solution of seven or greater, and can be either organic or inorganic in nature.
  • the builder salt assists in providing the desired density and bulk to the detergent granules herein. While some of the salts are inert, many of them also function as detergency builder materials in the laundering solution.
  • neutral water-soluble salts examples include the alkali metal, ammonium or substituted ammonium chlorides, fluorides and sulfates.
  • the alkali metal, and especially sodium, salts of the above are preferred.
  • Sodium sulfate is typically used in detergent granules and is a particularly preferred salt.
  • Citric acid and, in general, any other organic or inorganic acid may be incorporated into the granular detergents of the present invention as long as it is chemically compatible with the rest of the agglomerate composition.
  • water-soluble salts include the compounds commonly known as detergent builder materials.
  • Builders are generally selected from the various water-soluble, alkali metal, ammonium or substituted ammonium phosphates, polyphosphates, phosphonates, polyphosphonates, carbonates, silicates, borates, 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 6 to 21, and orthophosphate.
  • 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.
  • powders normally used in detergents such as zeolite, carbonate, silica, silicate, citrate, phosphate or perborate and process acids such as starch, can be used in preferred embodiments of the present invention.
  • the process steps of the present invention comprise:
  • the surfactant paste premix may be prepared by any method which is known to the man skilled in the art. Particularly useful methods include sulphation and/or sulphonation or other reactions to make the desired anionic surfactants e.g. in a falling film sulphonating reactors, digestion tanks, esterification reactors, etc. It is particularly convenient to neutralise the acid precursers of anionic surfactants in a continuous neutralisation loop. In such a piece of equipment the acid precurser is fed into a loop together with a neutralising agent such as aqueous sodium hydroxide. The components are intimately mixed to promote neutralisation and then fed through a heat exchanger to be cooled. A proportion of the neutralised surfactant is removed from the loop, whilst the remainder is fed back to the point of injection of the acid and the alkali, and passes around the loop again.
  • a neutralising agent such as aqueous sodium hydroxide
  • the surfactant paste must then be mixed with a solution of a chelating agent and a solution of a polymer or co-polymer. This may be achieved in any convenient piece of mixing equipment, and may be carried out using any order of addition of the separate or premixed components.
  • the moisture in the surfactant aqueous paste is as low as possible, while maintaining paste fluidity, since low moisture leads to a higher concentration of the surfactant in the finished particle.
  • the paste after drying contains between 5 and 40% water, more preferably between 15 and 35% water and most preferably between 15% and 25% water.
  • a highly attractive mode of operation for lowering the moisture of the paste is the installation, in line, of an atmospheric or a vacuum flash drier, or a scraped surface heat exchanger or a wiped film evaporator.
  • the extruder fulfils the functions of pumping and mixing the viscous surfactant paste on a continuous basis.
  • a basic extruder consists of a barrel with a smooth inner cylindrical surface. Mounted within this barrel is the extruder screw. There is an inlet port for the high active paste which, when the screw is rotated, causes the paste to be moved along the length of the barrel.
  • the detailed design of the extruder allows various functions to be carried out. Firstly additional ports in the barrel may allow other ingredients, including the chemical structuring agents to be added directly into the barrel. Secondly a vacuum pump and a seal around the shaft of the screw allows a vacuum to be drawn which enables the moisture level to be reduced. Thirdly means for heating or cooling may be installed in the wall of the barrel for temperature control.
  • a preferred extruder is the twin screw extruder. This type of extruder has two screws mounted in parallel within the same barrel, which are made to rotate either in the same direction (co-rotation) or in opposite directions (counter-rotation).
  • the co-rotating twin screw extruder is the most preferred piece of equipment for use in this invention.
  • An extruder is particularly useful in this invention because the paste can be effectively cooled by adding liquid nitrogen or solid carbon dioxide into the barrel (this may be considered surprising, because normally an extruder heats its contents as a result of the mechanical energy input to overcome viscous shear forces) and at the same time pumps the increasingly viscous (colder) paste out of the extruder and into the mixer/agglomerator were granulation takes place.
  • Suitable twin screw extruders for use in the present invention include those supplied by : APV Baker, (CP series); Werner and Pfleiderer, (Continua Series); Wenger, (TF Series); Leistritz, (ZSE Series); and Buss, (LR Series).
  • the extruder allows the paste to be conditioned by moisture and temperature reduction. Moisture may be removed under vacuum, preferably between O mmHg (gauge) and -55 mmHg (gauge), (0 - 7.3 kPa below atmospheric pressure).
  • Temperature may be reduced by the addition of solid carbon dioxide or liquid nitrogen directly into the extruder barrel. However, this is not a preferred mode of operation of the present invention.
  • any apparatus, plants or units suitable for the processing of surfactants can be used for carrying out the process according to the invention.
  • any of a number of mixers/agglomerators can be used.
  • the process of the invention is continuously carried out.
  • mixers of the Fukae R FS-G series manufactured by Fukae Powtech Kogyo Co., Japan are essentially in the form of a bowl-shaped vessel accessible via a top port, provided near its base with a stirrer having a substantially vertical axis, and a cutter positioned on a side wall.
  • the stirrer and cutter may be operated independently of one another and at separately variable speeds.
  • the vessel can be fitted with a cooling jacket or, if necessary, a cryogenic unit.
  • mixers found to be suitable for use in the process of the invention include Diosna R V series ex Dierks & Söhne, Germany; and the Pharma Matrix R ex T K Fielder Ltd., England.
  • Other mixers believed to be suitable for use in the process of the invention are the Fuji R VG-C series ex Fuji Sangyo Co., Japan; and the Roto R ex Zanchetta & Co srl, Italy.
  • Other preferred suitable equipment can include Eirich R , series RV, manufactured by Gustau Eirich Hardheim, Germany; Lödige R , series FM for batch mixing, series Baud KM for continuous mixing/agglomeration, manufactured by Lödige Machinenbau GmbH, Paderborn Germany; Drais R T160 series, manufactured by Drais Werke GmbH, Mannheim Germany; and Winkworth R RT 25 series, manufactured by Winkworth Machinery Ltd., Berkshire, England.
  • the Littleford Mixer, Model #FM-130-D-12, with internal chopping blades and the Cuisinart Food Processor, Model #DCX-Plus, with 7.75 inch (19.7 cm) blades are two examples of suitable mixers. Any other mixer with fine dispersion mixing and granulation capability and having a residence time in the order of 0.1 to 10 minutes can be used.
  • the "turbine-type" impeller mixer, having several blades on an axis of rotation, is preferred.
  • the invention can be practiced as a batch or a continuous process.
  • the paste can be introduced into the mixer at an initial temperature between its softening point (generally in the range of 40-60°C) and its degradation point (depending on the chemical nature of the paste, e.g. alkyl sulphate pastes tend to degrade above 75-85°C). High temperatures reduce viscosity simplifying the pumping of the paste but result in lower active agglomerates.
  • the introduction of the paste into the mixer can be done in many ways, from simply pouring to high pressure pumping through small holes at the end of the pipe, before the entrance to the mixer. While all these ways are viable to manufacture agglomerates with good physical properties, it has been found that in a preferred embodiment of the present invention the extrusion of the paste results in a better distribution in the mixer which improves the yield of particles with the desired size.
  • the use of high pumping pressures prior to the entrance in the mixer results in an increased activity in the final agglomerates.
  • the resulting detergent granules may be dried, cooled and/or dusted with a suitable surface coating agent.
  • C45AS/AE3S 80:20
  • This example describes the process in batch mode in a lab scale high shear mixer (food processor manufactured by Braun [Trade Name]). Three hundred grams of powders are added first to the mixer. In this particular case a 1.2:1.0 ratio of Zeolite A to finely divided light density sodium carbonate is used.
  • the surfactant is an aqueous paste of C45AS/AE3S (80:20) with a detergent activity of 78%, and a water content of 16%.
  • the paste is pre-mixed in a batch mixer with a 40% solution of the co-polymer of maleic and acrylic acid , sodium salt and a 20% solution of the sodium salt of the ethylene diamine-N,N-disuccinic acid.
  • the weight ratio of paste : polymer : chelating agent was 1 : 0.64 : 0.09.
  • the mixture is then dried to the original paste moisture of 16%.
  • the paste mixture is placed into an oven at 60 °C until thermal equilibrium is reached.
  • the mixer is then started and paste added at a rate of 500g/min until the onset of agglomeration and formation of granules.
  • the end point is sharp and easily recognized. It is characterized by an increased power draw by the mixer, and a change in the mixer contents from a mixture of finely divided powders and distributed surfactant paste, to agglomerates containing powders and paste having a mean particle size between 400 - 600 micrometers.
  • the activity of the agglomerates formed is 51%.
  • the agglomerates were dried in a fluid bed drier and the rate of surfactant release of the resulting agglomerates was tested in a Sotax bath at 20 °C in distilled water (see section B - test method). The time taken for 50% of the surfactant to dissolve is 78 seconds.
  • This example describes the process in batch mode in a lab scale high shear mixer (food processor) as used in example 1.
  • the powders composition is a 1.2:1.0 ratio of zeolite A to finely divided light density sodium carbonate.
  • the surfactant is an aqueous paste of C45AS/AE3S (80:20) with a detergent activity of 78%, and a water content of 16%.
  • the paste temperature is 60 °C.
  • the mixer is started and paste added at a rate of 500 g/min until the onset of agglomeration and the formation of granules.
  • the activity of agglomerates formed is 40%.
  • the agglomerates were dried in a fluid bed drier and the rate of surfactant release of the resulting agglomerates was tested in a Sotax bath at 20 °C in distilled water (see section B - test method). The time taken for 50% of the surfactant to dissolve is 114 seconds..
  • This example describes the process in batch mode in a lab scale high shear mixer (food processor) as used in example 1.
  • Three hundred grams of powders are added first to the mixer.
  • a 1.2:1.0 ratio of Zeolite A to finely divided sodium carbonate is used.
  • the surfactant is an aqueous paste of C45AS/AE3S (80:20) with a detergent activity of 78%, and a water content of 16%.
  • the paste is pre-mixed in a batch mixer with a 40% solution of the co-polymer of maleic and acrylic acid , sodium salt .
  • the weight ratio of paste:polymer was 1:0.64.
  • the mixture is then dried to the original paste moisture of 16%.
  • the paste mixture is placed into an oven at 60 °C until thermal equilibrium is reached.
  • the mixer is then started and paste added at a rate of 500 g/min until the onset of agglomeration and formation of granules.
  • the activity of the agglomerates formed is 46%.
  • the agglomerates were dried in a fluid bed drier and the rate of surfactant release of the resulting agglomerates was tested in a Sotax bath at 20°C in distilled water (see section B - test method).
  • the time taken for 50% of the surfactant to dissolve is 84 seconds..
  • This example describes the process in batch mode in a lab scale high shear mixer (food processor) as used in example 1.
  • a lab scale high shear mixer food processor
  • Three hundred grams of powders are added first to the mixer.
  • a 1.2:1.0 ratio of Zeolite A to finely divided light density sodium carbonate is used.
  • the surfactant is an aqueous paste of C45AS/AE3S (80:20) with a detergent activity of 78%, and a water content of 16%.
  • the paste is pre-mixed in a batch mixer with a 20% solution of the sodium salt of the ethylene diamine-N,N-disuccinic acid.
  • the weight ratio of paste:chelating agent was 1:0.09.
  • the mixture is then dried to the original paste moisture of 16%.
  • the paste mixture is placed into an oven at 60 °C until thermal equilibrium is reached.
  • the mixer is then started and paste added at a rate of 500 g/min until the onset of agglomeration and formation of granules.
  • the activity of the agglomerates formed is 49%.
  • the agglomerates were dried in a fluid bed drier and the rate of surfactant release of the resulting agglomerates was tested in a Sotax bath at 20 °C in distilled water (see section B - test method). The time taken for 50% of the surfactant to dissolve was 120 seconds.
  • Example 1 illustrates the product of the present invention.
  • Example 2 shows a comparison of a product made without chelant or polymer. The surfactant activity is lower and the rate of solubility is poorer.
  • Example 3 shows a comparison of a product made with polymer only (ie without chelant). Good rate of solubility is achieved, but the particulate activity is lower.
  • Example 4 shows a comparison of a product made with chelant only (ie without polymer). Good surfactant activity is obtained but the rate of solubility is poor.

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Claims (12)

  1. Freifließende granuläre Reinigerkomponente oder -zusammensetzung mit einer Schüttdichte von mindestens 650 g/l, umfassend:
    i) mindestens 35 Gew.-% anionisches Tensid
    ii) 0,5 bis 30 Gew.-% Polymer oder Copolymer
    dadurch gekennzeichnet, daß sie weiterhin umfaßt
    iii) 0,5 bis 10 Gew. -% Chelatbildner, wobei das Gewichtsverhältnis von Chelatbildner zu Polymer/Copolymer 1:100 bis 1:1 beträgt.
  2. Freifließende granuläre Reinigerkomponente oder -zusammensetzung nach Anspruch 1, wobei das Gewichtsverhältnis von Chelatbildner zu Polymer/Copolymer 1:50 bis 1:2, vorzugsweise 1:20 bis 1:5 beträgt.
  3. Freifließende granuläre Reinigerkomponente oder -zusammensetzung nach Anspruch 1 und/oder 2, umfassend mindestens 50 Gew.-% anionisches Tensid.
  4. Freifließende granuläre Reinigerkomponente oder -zusammensetzung nach mindestens einem der vorangehenden Ansprüche, wobei der Chelatbildner aus der Gruppe Bernsteinsäuren, Phosphonsäuren oder deren Salze oder Mischungen dieser gewählt ist.
  5. Freifließende granuläre Reinigerkomponente oder -zusammensetzung nach Anspruch 4, wobei der Chelatbildner Ethylendiamin-N,N'-dibernsteinsäure oder Diethylentriaminpenta(methylenphosphonsäure) oder deren Salze oder Mischungen dieser ist.
  6. Freifließende granuläre Reinigerkomponente oder -zusammensetzung nach Anspruch 1 und/oder 2, wobei das verwendete Polymer oder Copolymer aus den Copolymeren von Malein- und Acrylsäure mit einem Molekulargewicht von 2.000 bis 100.000 oder Carboxymethylcellulose oder Mischungen dieser gewählt ist.
  7. Verfahren zur Herstellung einer hochaktiven Reinigerpaste mit einer bei 70°C gemessenen Viskosität von mindestens 10 Pas und einer Scherrate von 25 s-1, durch :
    i) Herstellen einer Pastenvormischung, welche mindestens 40 Gew.-% eines anionischen Tensids umfaßt und welches dadurch gekennzeichnet ist, daß die Pastenvormischung
    ii) mit einer Lösung, umfassend ein Polymer oder Copolymer. und
    iii) einer Lösung, umfassend einen Chelatbildner, vermischt wird, wobei das Gewichtsverhältnis von Chelatbildner zu Polymer/ Copolymer 1:100 bis 1:1 beträgt.
  8. Verfahren zur Herstellung einer hochaktiven Reinigerpaste nach Anspruch 7, wobei die Lösung des Chelatbildners eine wäßrige Lösung ist, umfassend 5 bis 60 % eines Chelatbildners, gewählt aus der Gruppe der Bernsteinsäuren, Phosphonsäuren oder deren Salze oder Mischungen dieser.
  9. Verfahren zur Herstellung einer hochaktiven Reinigerpaste nach Anspruch 7, wobei die Lösung des Polymeren oder Copolymeren eine wäßrige Lösung ist, umfassend 5 bis 60 % eines Copolymeren von Malein- und Acrylsäure mit einem Molekulargewicht von 2.000 bis 100.000.
  10. Verfahren zur Herstellung eines hochaktiven granulären Reinigers, umfassend die Schritte
    (i) Herstellen einer Pastenvormischung, welche mindestens 40 Gew.-% eines anionischen Tensids umfaßt,
    (ii) Vermischen der Pastenvormischung mit einer Lösung, umfassend ein Polymer oder Copolymer, um eine hochaktive Reinigerpaste vorzusehen, die eine bei 70°C gemessene Viskosität von mindestens 10 Pas und eine Scherrate von 25 s-1 aufweist,
    (iii) Vermischen der Pastenvormischung mit einer einen Chelatbildner umfassenden Lösung,
    (iv) Transportieren der hochaktiven Reinigerpaste aus (iii) zu der Einlaßöffnung eines Hochgeschwindigkeitsmischers;
    (v) Vermischen der hochaktiven Reinigerpaste mit einer wirksamen Menge pulverförmiger Materialien in dem Hochgeschwindigkeitsmischer bei einer Verweilzeit von 1 Sekunde bis 30 Sekunden;
    (vi) wahlweise Trocknen und/oder Kühlen des hochaktiven granulären Reinigers,
    wobei das Gewichtsverhältnis von Chelatbildner (in Schritt (iii)) zu Polymer/Copolymer (in Schritt (ii)) 1:100 bis 1:1 beträgt.
  11. Verfahren zur Herstellung eines hochaktiven granulären Reinigers nach Anspruch 10, wobei in Schritt (iv) des Verfahrens ein Doppelschnecken-Extruder verwendet wird.
  12. Verfahren zur Herstellung eines hochaktiven granulären Reinigers nach Anspruch 1 1, wobei vor dem Doppelschnecken-Extruder ein Trockner verwendet wird.
EP19930870058 1993-03-30 1993-03-30 Hochaktive körnige Reinigungsmittel enthaltend Chelatbildner und Polymere und Verfahren zu ihrer Herstellung Expired - Lifetime EP0618289B1 (de)

Priority Applications (6)

Application Number Priority Date Filing Date Title
EP19930870058 EP0618289B1 (de) 1993-03-30 1993-03-30 Hochaktive körnige Reinigungsmittel enthaltend Chelatbildner und Polymere und Verfahren zu ihrer Herstellung
DE1993620455 DE69320455T2 (de) 1993-03-30 1993-03-30 Hochaktive körnige Reinigungsmittel enthaltend Chelatbildner und Polymere und Verfahren zu ihrer Herstellung
US08/532,555 US5712242A (en) 1993-03-30 1994-02-23 High active granular detergents comprising chelants and polymers, and processes for their preparation
CA002159178A CA2159178C (en) 1993-03-30 1994-02-23 High active granular detergents comprising chelants and polymers, and processes for their preparation
JP6522056A JPH08508525A (ja) 1993-03-30 1994-02-23 キレート化剤と重合体とを含む高活性粒状洗剤およびそれらの製法
PCT/US1994/001917 WO1994022992A1 (en) 1993-03-30 1994-02-23 High active granular detergents comprising chelants and polymers, and processes for their preparation

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
EP19930870058 EP0618289B1 (de) 1993-03-30 1993-03-30 Hochaktive körnige Reinigungsmittel enthaltend Chelatbildner und Polymere und Verfahren zu ihrer Herstellung

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EP0618289B1 true EP0618289B1 (de) 1998-08-19

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US8262852B2 (en) 2006-11-03 2012-09-11 Nalco Company Method for improving fiber quality and process efficiency in mechanical pulping

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GB2285053A (en) * 1993-12-23 1995-06-28 Procter & Gamble Rinse aid composition
BR9711966A (pt) * 1996-08-26 1999-08-24 Procter & Gamble Processo de aglomera-Æo para produ-Æo de composi-{es detergente envolvrndo a pr--mistura de pol¡meros de poliamina modificada
US6046153A (en) * 1996-08-26 2000-04-04 The Procter & Gamble Company Spray drying process for producing detergent compositions involving premixing modified polyamine polymers
GB9618875D0 (en) * 1996-09-10 1996-10-23 Unilever Plc Process for preparing high bulk density detergent compositions
GB9618877D0 (en) * 1996-09-10 1996-10-23 Unilever Plc Process for preparing high bulk density detergent compositions
DE69823668T2 (de) * 1997-07-15 2005-04-07 The Procter & Gamble Company, Cincinnati Verfahren zur herstellung hochkonzentrierter waschmittelagglomerate durch mehrstufige einspritzung von tensidpasten
BR9816085A (pt) * 1998-11-25 2001-08-14 Procter & Gamble Processo para formar uma composição de limpeza
DE102004032320A1 (de) 2004-07-02 2006-01-19 Basf Ag Mischpulver oder Mischgranulat auf Basis von MGDA
EP1803801A1 (de) 2006-01-03 2007-07-04 Basf Aktiengesellschaft Mischpulver oder Mischgranulat auf Basis von Glutaminsäure-N,N-diessigsäure und ihren Salzen

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CA2159178A1 (en) 1994-10-13
CA2159178C (en) 1999-05-11
DE69320455T2 (de) 1999-04-22
JPH08508525A (ja) 1996-09-10
WO1994022992A1 (en) 1994-10-13
DE69320455D1 (de) 1998-09-24

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