EP0653481A1 - Composition de détergent granulaire - Google Patents

Composition de détergent granulaire Download PDF

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Publication number
EP0653481A1
EP0653481A1 EP93309042A EP93309042A EP0653481A1 EP 0653481 A1 EP0653481 A1 EP 0653481A1 EP 93309042 A EP93309042 A EP 93309042A EP 93309042 A EP93309042 A EP 93309042A EP 0653481 A1 EP0653481 A1 EP 0653481A1
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EP
European Patent Office
Prior art keywords
weight
granular
bulk density
anionic
percarbonate
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.)
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EP93309042A
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German (de)
English (en)
Inventor
Andrew Dorset
Robin Gibson Hall
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Procter and Gamble Co
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Procter and Gamble Co
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Publication date
Application filed by Procter and Gamble Co filed Critical Procter and Gamble Co
Priority to EP93309042A priority Critical patent/EP0653481A1/fr
Priority to US08/637,700 priority patent/US5756445A/en
Priority to CN94194702A priority patent/CN1047792C/zh
Priority to BR9408033A priority patent/BR9408033A/pt
Priority to PCT/US1994/011511 priority patent/WO1995013344A1/fr
Priority to CA002174721A priority patent/CA2174721C/fr
Priority to AU10393/95A priority patent/AU1039395A/en
Priority to JP7513824A priority patent/JPH09505097A/ja
Publication of EP0653481A1 publication Critical patent/EP0653481A1/fr
Withdrawn legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • 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
    • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/06—Powder; Flakes; Free-flowing mixtures; Sheets

Definitions

  • the invention concerns a granular detergent component having a bulk density of less than 400 g/l which comprises an anionic surfactant, zeolite, and, optionally, a cofiller.
  • the invention also concerns a granular laundry detergent composition comprising the low bulk density component and, additionally, high density granular components, preferably including percarbonate.
  • EPA289312 published 2nd November 1988 discloses a process for the spray-drying of an aqueous slurry which contains carbonate and a crystal growth modifier.
  • Optional post-treatments include spraying on of nonionic surfactant and mixing with other components including bleach, bleach activator, enzymes, etc.
  • Such components require the presence of relatively high levels of organic materials, in particular anionic surfactants (in this application surfactants are present at a level of at least 5% by weight).
  • WO9303131 published on 18th February 1993 discloses a spray dried component which comprises alkyl sulphate, aluminosilicate and silicate. Certain ratios of the components as well as processing conditions are specified. The spray dried component is then mixed with bleach, bleach activator, foam inhibitor, enzymes etc. The application considers the problem of replacing linear alkyl benzene sulponate (LAS) by the more biodegradable alkyl sulphates. Such components are difficult to spray dry and require the introduction of specific process parameters such as low temperature spray drying.
  • LAS linear alkyl benzene sulponate
  • High bulk density components which are desirable in todays granular detergents, such as carbonate, percarbonate and silicate, do not offer the detergent formulator much flexibility in terms of finished product bulk density.
  • a low bulk density spray-dried component which could be blended with the high bulk density components would offer greatly increased flexibility in terms of achieving the desired final product density.
  • Such flexibility arises from the possibility to vary parameters such as the composition of the aqueous slurry prior to spray drying, the parameters of the spray drying process and the ratio of the low bulk density component to the high bulk density components which may be used.
  • the organic material facilitates the production of spray dried components having good physical properties, and which can be made at a low bulk density without loss of quality.
  • the organic material chosen for use in the present invention is low levels of surfactant, preferably anionic surfactant at a level of from 0.05% to 2% by weight, which has a Krafft point of at least 30°C.
  • a second aspect of the present invention is to provide a finished composition which comprises the low bulk density spray-dried component, together with additional higher bulk density components.
  • a third aspect of the present invention is to provide spray-dried components which are low in moisture content, and which have a high capacity for moisture uptake. Such components, when combined with granular percarbonate offer improved storage stability of the percarbonate, especially in humid conditions.
  • the present invention is concerned with a granular detergent component having a bulk density of less than 400 g/l comprising from 20% to 50% by weight of aluminosilicate, and optionally up to 50% by weight of a co-filler.
  • the granular components of the invention further comprise from 0.05% to 2% by weight of anionic surfactant.
  • the anionic surfactant may be used alone, or it may be combined with non-anionic surfactants.
  • the anionic surfactant, or mixture of anionic and non-anionic surfactants (when present) has a Krafft Point greater than 30°C.
  • the anionic surfactant is present at a level of from 1% to 1.8%, and is C14-C20 alkyl sulphate.
  • the co-filler is a hydratable inorganic salt selected from the group of salts consisting of carbonate, bicarbonate, sesquicarbonate, sulphate, citrate or mixtures of these, and is present at a level of from 10 to 30% by weight of the low bulk density component.
  • the low bulk density component is mixed with other components.
  • Such granular components preferably include those selected from the group consisting of silicate, layered silicate, carbonate, bicarbonate, sesquicarbonate, sulphate, citrate or mixtures of these. It is preferred that the spray-dried component is present in the composition at a level of from 10% to 60% by weight, and that the granular components which individually have a bulk density of greater than 800 g/l are present, when mixed together in the composition at a level of up to 50% by weight, preferably from 10 to 40%.
  • the composition further comprises granular percarbonate having a bulk density of at least 800 g/l.
  • the percarbonate is preferably at a level of greater than 3% by weight of the finished composition, and more preferably from 5% to 50% by weight of the finished composition.
  • the spray dried component is processed so that therein the ratio of total water to aluminosilicate does not exceed 1:3, preferably does not exceed 1:5.
  • the various detergent ingredients are defined in more detail below.
  • the surfactants which are useful as components of the low bulk density component of the present invention are those having a Krafft Point greater than 30°C.
  • 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.
  • Those soaps having a chain length of at least 12 carbon atoms are especially useful in the present invention because they have Krafft points in the required range.
  • Useful anionic surfactants also include the water-soluble salts, preferably the alkali metal, ammonium and alkylolammonium salts, of organic sulfuric reaction products having in their molecular structure an alkyl group containing from about 10 to about 20 carbon atoms and a sulfonic acid or sulfuric acid ester group.
  • this group of synthetic surfactants are the sodium and potassium alkyl sulfates, especially those obtained by sulfating the higher alcohols (C8-C18 carbon atoms) such as those produced by reducing the glycerides of tallow or coconut oil.
  • Those alkyl sulphates having a chain length of at least 14 carbon atoms are especially useful in the present invention because they have Krafft points in the required range.
  • Suitable anionic surfactants herein include the water-soluble salts of esters of alpha-sulfonated fatty acids containing from about 6 to 20 carbon atoms in the fatty acid group and from about 1 to 10 carbon atoms in the ester group; and alkyl ether sulfates containing from about 10 to 20, especially 16 to 20, carbon atoms in the alkyl group and from about 1 to 30 moles of ethylene oxide.
  • MES C16-18 methyl ester sulphonates
  • Particularly preferred surfactants herein include; primary and secondary alkyl sulfates; coconutalkyl glyceryl ether sulfonates; alkyl ether sulfates wherein the alkyl moiety contains from about 16 to 18 carbon atoms and wherein the average degree of ethoxylation is from about 1 to 4; olefin or paraffin sulfonates containing from about 16 carbon atoms; and methyl ester sulphonates.
  • 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 about 9 to 15 carbon atoms with from about 4 to 25 moles of ethylene oxide per mole of alcohol; and condensation products of propylene glycol with ethylene oxide.
  • Nonionic surfactants comprises alkyl polyglucoside compounds of general formula RO (C n H 2n O) t Z x wherein Z is a moiety derived from glucose; R is a saturated hydrophobic alkyl group that contains from 12 to 18 carbon atoms; t is from 0 to 10 and n is 2 or 3; x is from 1.3 to 4, the compounds including less than 10% unreacted fatty alcohol and less than 50% short chain alkyl polyglucosides.
  • Compounds of this type and their use in detergent compositions are disclosed in EP-B 0070074, 0070077, 0075996 and 0094118.
  • Still another class of nonionic surfactants comprises polyhydroxy fatty acid amides which may be produced by reacting a fatty acid ester and an N-alkyl polyhydroxy amine.
  • a preferred amine 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 with C12-C20 fatty acid methyl ester.
  • One class of nonionic surfactants useful in the present invention comprises condensates of ethylene oxide with a hydrophobic moiety, providing surfactants having an average hydrophilic-lipophilic balance (HLB) in the range from 8 to 17, preferably from 9.5 to 13.5, more preferably from 10 to 12.5.
  • HLB hydrophilic-lipophilic balance
  • the hydrophobic (lipophilic) moiety may be aliphatic or aromatic in nature and the length of the polyoxyethylene 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.
  • Especially preferred nonionic surfactants of this type are the C9-C15 primary alcohol ethoxylates containing 3-9 moles of ethylene oxide per mole of alcohol, particularly the C13-C15 primary alcohols containing 6-9 moles of ethylene oxide per mole of alcohol and the C11-C15 primary alcohols containing 3-5 moles of ethylene oxide per mole of alcohol.
  • Surfactants which have a Krafft Point of less than 30°C are not excluded from the present invention, but they should be used in combination with high Krafft point surfactants in surfactant systems at levels whereby the total surfactant system has a Krafft Point in excess of 30°C.
  • Anionic surfactant having a lower Krafft Point which may be used in this way include sodium and potassium alkyl benzene sulfonates in which the alkyl group contains from about 9 to about 15 carbon atoms, in straight or branched chain configuration, e.g., those of the type described in U.S. Pat. Nos. 2,220,099 and 2,477,383. Especially valuable are linear straight chain alkyl benzene sulfonates in which the average number of carbon atoms in the alkyl group is from about 11 to 13, abbreviated as C11-C13 LAS.
  • Useful cationic surfactants include water-soluble quaternary ammonium compounds of the form R4R5R6R7N+X ⁇ , wherein R4 is alkyl having from 10 to 20, preferably from 12-18 carbon atoms, and R5, R6 and R7 are each C1 to C7 alkyl preferably methyl; X ⁇ is an anion, e.g. chloride.
  • Examples of such trimethyl ammonium compounds include C12 ⁇ 14 alkyl trimethyl ammonium chloride and cocalkyl trimethyl ammonium methosulfate.
  • Semi-polar nonionic surfactants include water-soluble amine oxides containing one alkyl moiety of from about 10 to 18 carbon atoms and 2 moieties selected from the group consisting of alkyl groups and hydroxyalkyl groups containing from 1 to about 3 carbon atoms; water-soluble phosphine oxides containing one alkyl moiety of about 10 to 18 carbon atoms and 2 moieties selected from the group consisting of alkyl groups and hydroxyalkyl groups containing from about 1 to 3 carbon atoms; and water-soluble sulfoxides containing one alkyl moiety of from about 10 to 18 carbon atoms and a moiety selected from the group consisting of alkyl and hydroxyalkyl moieties of from about 1 to 3 carbon atoms.
  • Ampholytic surfactants include derivatives of aliphatic or aliphatic derivatives of heterocyclic secondary and tertiary amines in which the aliphatic moiety can be either straight or branched chain and wherein one of the aliphatic substituents contains from about 8 to 18 carbon atoms and at least one aliphatic substituent contains an anionic water-solubilizing group.
  • Zwitterionic surfactants include derivatives of aliphatic quaternary ammonium phosphonium, and sulfonium compounds in which one of the aliphatic substituents contains from about 8 to 18 carbon atoms.
  • the low bulk density component of the present invention comprises other detergent ingredients selected from a wide range of possible ingredients which are commonly used in laundry detergents.
  • the particles will contain from 20 to 50% by weight of aluminosilicate and up to 50% by weight of co-filler, and optionally other components; preferred components being described below.
  • preferred sodium aluminosilicate zeolites have the unit cell formula Na z [(AlO2 ) z (SiO2 ) y ] xH 2O wherein z and y are at least 6; the molar ratio of z to y is from 1.0 to 0.5 and x is at least 5, preferably from 7.5 to 276, more preferably from 10 to 264.
  • the aluminosilicate materials are in hydrated form and are preferably crystalline, containing from 10% to 28%, more preferably from 16% to 22% water in bound form.
  • the above aluminosilicate ion exchange materials are further characterised by a particle size diameter of from 0.1 to 10 micrometers, preferably from 0.2 to 4 micrometers.
  • particle size diameter herein represents the average particle size diameter of a given ion exchange material as determined by conventional analytical techniques such as, for example, microscopic determination utilizing a scanning electron microscope or by means of a laser granulometer.
  • the aluminosilicate ion exchange materials are further characterised by their calcium ion exchange capacity, which is at least 200 mg equivalent of CaCO3 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 characterised by their calcium ion exchange rate which is at least 130 mg equivalent of CaCO3/litre/minute/(g/litre) [2 grains Ca++/gallon/minute/gram/gallon)] of aluminosilicate (anhydrous basis), and which generally lies within the range of from 130 mg equivalent of CaCO3/litre/minute/(gram/litre) [2 grains/gallon/minute/ (gram/gallon)] to 390 mg equivalent of CaCO3/litre/minute/ (gram/litre) [6 grains/gallon/minute/(gram/gallon)], based on calcium ion hardness.
  • Optimum aluminosilicates for builder purposes exhibit a calcium ion exchange rate of at least 260 mg equivalent of CaCO3/litre/ minute/ (gram/litre) [4 grains/gallon/minute/(gram/gallon)].
  • Aluminosilicate ion exchange materials useful in the practice of this invention are commercially available and can be naturally occurring materials, but are preferably synthetically derived. A method for producing aluminosilicate ion exchange materials is discussed in US Patent No. 3,985,669.
  • Preferred synthetic crystalline aluminosilicate ion exchange materials useful herein are available under the designations Zeolite A, Zeolite B, Zeolite X, Zeolite HS, Zeolite MAP and mixtures thereof.
  • the crystalline aluminosilicate ion exchange material is Zeolite A and has the formula Na 12 [(AlO2 ) 12 (SiO2)12 ]. xH2 O wherein x is from 20 to 30, especially 27.
  • Suitable co-fillers can include, but are not restricted to, alkali metal carbonates, bicarbonates, sesquicarbonates, sulphates, monomeric polycarboxylates, salts of homo or copolymeric polycarboxylic acids in which the polycarboxylic acid comprises at least two carboxylic radicals separated from each other by not more than two carbon atoms, organic phosphonates and aminoalkylene poly (alkylene phosphonates) and mixtures of any of the foregoing.
  • hydratable salt it is meant that the salt is in a state in which it may absorb additional water by hydration. That is to say that the salt is present either in its anhydrous form, or in a partially hydrated form.
  • Preferred builder systems are free of boron compounds and any polymeric organic materials are preferably biodegradable.
  • Suitable water-soluble monomeric or oligomeric carboxylate builders include lactic acid, glycolic acid and ether derivatives thereof as disclosed in Belgian Patent Nos. 831,368, 821,369 and 821,370.
  • Polycarboxylates containing two carboxy groups include the water-soluble salts of succinic acid, malonic acid, (ethylenedioxy) diacetic acid, maleic acid, diglycolic acid, tartaric acid, tartronic acid and fumaric acid, as well as the ether carboxylates described in German Offenlegenschrift 2,446,686, and 2,446,687 and U.S. Patent No. 3,935,257 and the sulfinyl carboxylates described in Belgian Patent No. 840,623.
  • Polycarboxylates containing three carboxy groups include, in particular, water-soluble citrates, aconitrates and citraconates as well as succinate derivatives such as the carboxymethyloxysuccinates described in British Patent No. 1,379,241, lactoxysuccinates described in British Patent No. 1,389,732, and aminosuccinates described in Netherlands Application 7205873, and the oxypolycarboxylate materials such as 2-oxa-1,1,3-propane tricarboxylates described in British Patent No. 1,387,447.
  • Polycarboxylates containing four carboxy groups include oxydisuccinates disclosed in British Patent No. 1,261,829, 1,1,2,2-ethane tetracarboxylates, 1,1,3,3-propane tetracarboxylates and 1,1,2,3-propane tetracarboxylates.
  • Polycarboxylates containing sulfo substituents include the sulfosuccinate derivatives disclosed in British Patent Nos. 1,398,421 and 1,398,422 and in U.S. Patent No. 3,936,448, and the sulfonated pyrolysed citrates described in British Patent No. 1,439,000.
  • Another preferred polycarboxylate builder is ethylenediamine-N,N'-disuccinic acid (EDDS) or the alkali metal, alkaline earth metal, ammonium, or substituted ammonium salts thereof, or mixtures thereof.
  • EDDS ethylenediamine-N,N'-disuccinic acid
  • Alicyclic and heterocyclic polycarboxylates include cyclopentane-cis,cis,cis-tetracarboxylates, cyclopentadienide pentacarboxylates, 2,3,4,5-tetrahydrofuran - cis, cis, cis-tetracarboxylates, 2,5-tetrahydrofuran - cis - dicarboxylates, 2,2,5,5-tetrahydrofuran - tetracarboxylates, 1,2,3,4,5,6-hexane - hexacarboxylates and carboxymethyl derivatives of polyhydric alcohols such as sorbitol, mannitol and xylitol.
  • Aromatic polycarboxylates include mellitic acid, pyromellitic acid and the phthalic acid derivatives disclosed in British Patent No. 1,425,343. Of the above, the preferred polycarboxylates are hydroxycarboxylates containing up to three carboxy groups per molecule, more particularly citrates.
  • the parent acids of the monomeric or oligomeric polycarboxylate chelating agents or mixtures thereof with their salts e.g. citric acid or citrate/citric acid mixtures are also contemplated as components of builder systems of detergent compositions in accordance with the present invention.
  • Suitable water soluble organic salts are the homo-or co-polymeric polycarboxylic acids or their salts in which the polycarboxylic acid comprises at least two carboxyl radicals separated from each other by not more than two carbon atoms.
  • Polymers of the latter type are disclosed in GB-A-1,596,756.
  • Examples of such salts are polyacrylates of MWt 2000-5000 and their copolymers with maleic anhydride, such copolymers having a molecular weight of from 20,000 to 70,000, especially about 40,000.
  • Such builder polymeric materials may be identical to the polymeric materials as binder materials and coating materials, as described hereinabove. These materials are normally used at levels of from 0.5% to 10% by weight more preferably from 0.75% to 8%, most preferably from 1% to 6% by weight of the composition.
  • Organic phosphonates and amino alkylene poly (alkylene phosphonates) include alkali metal ethane 1-hydroxy diphosphonates, nitrilo trimethylene phosphonates, ethylene diamine tetra methylene phosphonates and diethylene triamine penta methylene phosphonates, although these materials are less preferred where the minimisation of phosphorus compounds in the compositions is desired.
  • the primary component of the present invention has a bulk density of less than 400 g/l and is preferably prepared by spray drying, although other techniques of preparing low density flowable powders may be used. Following the spray drying route, an aqueous slurry is prepared comprising the solids. The slurry is then pumped at high pressure through atomising nozzles into a drying tower where excess water is driven off, producing a flowable powder. The resulting powder may then be oversprayed with liquid ingredients, especially nonionic surfactants for which the powder has a high adsorption capacity before it loses its good flow characteristics.
  • compositions will include a percarbonate bleach, normally in the form of the sodium salt, as the source of alkaline hydrogen peroxide in the wash liquor.
  • This percarbonate is normally incorporated at a level of from 3% to 50% by weight, more preferably from 5% to 30% by weight and most preferably from 8% to 25% by weight of the total composition.
  • Sodium percarbonate is an addition compound having a formula corresponding to 2Na2CO3.3H2O2, and is available commercially as a crystalline solid. Most commercially available material includes a low level of a heavy metal sequestrant such as EDTA, 1-hydroxyethylidene 1, 1-diphosphonic acid (HEDP) or an amino-phosphonate, that is incorporated during the manufacturing process.
  • a heavy metal sequestrant such as EDTA, 1-hydroxyethylidene 1, 1-diphosphonic acid (HEDP) or an amino-phosphonate
  • the percarbonate can be incorporated into detergent compositions without additional protection, but preferred executions of such compositions utilise a coated form of the material.
  • the preferred coating is a mixed salt of an alkali metal sulphate and carbonate.
  • the weight ratio of the mixed salt coating material to percarbonate lies in the range from 1:200 to 1:4, more preferably from 1:99 to 1:9, and most preferably from 1:49 to 1:19.
  • the mixed salt is of sodium sulphate and sodium carbonate which has the general formula Na2SO4.n.Na2CO3 wherein n is from 0.1 to 3, preferably n is from 0.3 to 1.0 and most preferably n is from 0.2 to 0.5.
  • Another preferred coating material is citrate, or mixtures of citrate with sulphate or carbonate. Water soluble surfactants may also be used as coating materials.
  • silicate of SiO2:Na2O ratio from 1.6:1 to 3.4:1, preferably 2.8:1, applied as an aqueous solution to give a level of from 2% to 10%, (normally from 3% to 5%) of silicate solids by weight of the percarbonate.
  • Magnesium silicate can also be included in the coating. However silicate should not be the major coating agent in order to maintain good dispensing properties. If present, the silicate level in the coating should be less than 3% by weight of the percarbonate.
  • the particle size range of the crystalline percarbonate is from 150 micrometers to 1500 micrometers, preferably from 250 micrometers to 1000 micrometers with a mean particle size of from 500 micrometers to 700 micrometers.
  • the percarbonate Whilst heavy metals present in the sodium carbonate used to manufacture the percarbonate can be controlled by the inclusion of sequestrants in the reaction mixture, the percarbonate still requires protection from heavy metals present as impurities in other ingredients of the product.
  • Suitable silicates are those having an SiO2:Na2O ratio in the range from 1.6 to 3.4, the so-called amorphous silicates of SiO2 : Na2O ratios from 2.0 to 2.8 being preferred. These materials can be added at various points of the manufacturing process, such as in the form of an aqueous solution serving as an agglomerating agent for other solid components, or, where the silicates are themselves in particulate form, as solids to the other particulate components of the composition.
  • crystalline layered sodium silicates of general formula NaMSi x O 2x+1 .yH2O wherein M is sodium or hydrogen, x is a number from 1.9 to 4 and y is a number from 0 to 20.
  • Crystalline layered sodium silicates of this type are disclosed in EP-A-0164514 and methods for their preparation are disclosed in DE-A-3417649 and DE-A-3742043.
  • x in the general formula above has a value of 2, 3 or 4 and is preferably 2. More preferably M is sodium and y is 0 and preferred examples of this formula comprise the ⁇ , ⁇ , ⁇ and ⁇ forms of Na2Si2O5.
  • Crystalline layered silicates are incorporated either as dry mixed solids, or as solid components of agglomerates with other components.
  • ingredients which may be dry added into the composition in their granular form include carbonate, bicarbonate, sesquicarbonate, sulphate, citrate or mixtures of these all of which have been described above.
  • some components may be added in the granular form of the acid, for example citric acid. It will be understood that such granulates may consist solely of one component, or may be co-granulates of two of more components.
  • Granular components which also comprise substantial amounts of surfactants may also be dry added into the finished composition.
  • surfactant particles of the present invention may take the form of flakes, prills, marumes, noodles, ribbons, but preferably take the form of granules.
  • a preferred way to process the particles is by agglomerating powders (such as those described hereinabove e.g. aluminosilicate, carbonate) with high active surfactant pastes and to control the particle size of the resultant agglomerates within specified limits.
  • Such a process involves mixing an effective amount of powder with a high active surfactant paste in one or more agglomerators such as a pan agglomerator, a Z-blade mixer or more preferably an in-line mixer such as those manufactured by Schugi (Holland) BV, 29 Chroomstraat 8211 AS, Lelystad, Netherlands, and Gebruder Lodige Maschinenbau GmbH, D-4790 Paderborn 1, Elsenerstrasse 7-9, Postfach 2050, Germany. Most preferably a high shear mixer is used , such as a Lodige CB (Trade Name).
  • a high active surfactant paste comprising from 50% by weight to 100% by weight, preferably 70% by weight to 85% by weight of surfactant is used.
  • the surfactant sustem may comprise any of the groups of anionic, nonionic, cationic, amphoteric, and zwitterionic surfactants, or mixtures of these.
  • the paste may be pumped into the agglomerator at a temperature high enough to maintain a pumpable viscosity, but low enough to avoid degradation of the anionic surfactants used.
  • An operating temperature of the paste of 50°C to 80°C is typical.
  • a particularly suitable process of making surfactant particles from high active surfactant pastes is more fully described in EP 510 746, published on 28th October, 1992.
  • mean particle size as defined herein is calculated by sieving a sample of the composition into a number of fractions (typically 5 fractions) on a series of Tyler sieves. The weight fractions thereby obtained are plotted against the aperture size of the sieves. The mean particle size is taken to be the aperture size through which 50% by weight of the sample would pass.
  • the surfactant containing granules should have a mean partle size of less than 480 micrometers, preferably less than 400 micrometers, and most preferably less than 350 micrometers.
  • Detergent compositions of the present invention may, optionally, include anti-redeposition and soil suspension agents, bleach activators, optical brighteners, soil release agents, suds suppressors, enzymes, fabric softening agents, perfumes and colours, as well as other ingredients known to be useful in laundry detergents.
  • Anti-redeposition and soil-suspension agents suitable herein include cellulose derivatives such as methylcellulose, carboxymethylcellulose and hydroxyethycellulose, and homo-or co-polymeric polycarboxylic acids or their salts.
  • Polymers of this type include copolymers of maleic anhydride with ethylene, methylvinyl ether or methacrylic acid, the maleic anhydride constituting at least 20 mole percent of the copolymer. These materials are normally used at levels of from 0.5% to 10% by weight, more preferably from 0.75% to 8%, most preferably from 1% to 6% by weight of the composition.
  • polyethylene glycols particularly those of molecular weight 1000-10000, more particularly 2000 to 8000 and most preferably about 4000. These are used at levels of from 0.20% to 5% more preferably from 0.25% to 2.5% by weight. These polymers and the previously mentioned homo- or co-polymeric polycarboxylate salts are valuable for improving whiteness maintenance, fabric ash deposition, and cleaning performance on clay, proteinaceous and oxidizable soils in the presence of transition metal impurities.
  • the composition comprises peroxyacid bleach precursor.
  • the solid peroxyacid bleach precursors of the present invention comprise precursors containing one or more N- or O- acyl groups, which precursors can be selected from a wide range of classes.
  • Suitable classes include anhydrides, esters, imides and acylated derivatives of imidazoles and oximes, and examples of useful materials within these classes are disclosed in GB-A-1586789.
  • the most preferred classes are esters such as are disclosed in GB-A-836988, 864,798, 1147871 and 2143231 and imides such as are disclosed in GB-A-855735 & 1246338.
  • Particularly preferred precursor compounds are the N-,N,N1N1 tetra acetylated compounds of formula wherein x can be 0 or an integer between 1 & 6.
  • TAMD tetra acetyl methylene diamine
  • TAED tetra acetyl ethylene diamine
  • TAHD tetraacetyl hexylene diamine
  • activators are perbenzoic acid precursors such as benzoyloxybenzene sulphonate (BOBS) and benzoyl caprolactam.
  • BOBS benzoyloxybenzene sulphonate
  • benzoyl caprolactam benzoyl caprolactam
  • a peroxyacid bleach precursor is present at a level of at least 0.5% by weight of the composition.
  • the particles of peroxyacid bleach precursor preferably have a particle size of from 100 micrometers to 1500 micrometers.
  • peroxyacid bleach precursors can be partially replaced by preformed peracids such as N,N phthaloylaminoperoxy acid (PAP), nonyl amide of peroxyadipic acid (NAPAA), 1,2 diperoxydodecanedioic acid (DPDA) and trimethyl ammonium propenyl imidoperoxy mellitic acid (TAPIMA).
  • PAP N,N phthaloylaminoperoxy acid
  • NAPAA nonyl amide of peroxyadipic acid
  • DPDA 1,2 diperoxydodecanedioic acid
  • TAPIMA trimethyl ammonium propenyl imidoperoxy mellitic acid
  • Other bleach precursors include glycolate esters (described in EP 507475); 4h-3,1 - benzoxazin - 4 ones; cationic precursors (described in EP 458396 and EP 464880); ester carbonate activators (described in EP 475511), NOBS, iso-NO
  • Preferred optical brighteners are anionic in character, examples of which are disodium 4,41-bis-(2-diethanolamino-4-anilino -s- triazin-6- ylamino)stilbene-2:21 disulphonate, disodium 4,41-bis-(2-morpholino -4-anilino-2-triazin-6-ylaminostilbene-2:21-disulphonate,disodium 4, 41-bis-(2,4-dianilino-s-triazin-6-ylamino)stilbene-2:21 - disulphonate, monosodium 41,411-bis-(2,4-dianilino-s-triazin-6 ylamino)stilbene-2- sulphonate, disodium 4,41-bis-(2-anilino-4-(N-methyl-N-2-hydroxyethylamino)-2-triazin-6-ylamino)stilbene-2,21 - disulphonate, disodium 4,41-bis-
  • Soil-release agents useful in compositions of the present invention are conventionally copolymers or terpolymers of terephthalic acid with ethylene glycol and/or propylene glycol units in various arrangements. Examples of such polymers are disclosed in the commonly assigned US Patent Nos. 4116885 and 4711730 and European Published Patent Application No. 0272033.
  • a particular preferred polymer in accordance with EP-A-0272033 has the formula (CH3(PEG)43) 0.75 (POH) 0.25 (T-PO) 2.8 (T-PEG) 0.4 ]T(PO- H) 0.25 ((PEG)43CH3) 0.75 where PEG is -(OC2H4)O-, PO is (OC3H6O) and T is (pCOC6H4CO).
  • Certain polymeric materials such as polyvinyl pyrrolidones typically of MWt 5000-20000, preferably 10000-15000, also form useful agents in preventing the transfer of labile dyestuffs between fabrics during the washing process.
  • Another optional detergent composition ingredient is a suds suppressor, exemplified by silicones, and silica-silicone mixtures.
  • Silicones can be generally represented by alkylated polysiloxane materials while silica is normally used in finely divided forms, exemplified by silica aerogels and xerogels and hydrophobic silicas of various types. These materials can be incorporated as particulates in which the suds suppressor is advantageously releasably incorporated in a water-soluble or water-dispersible, substantially non-surface-active detergent-impermeable carrier.
  • the suds suppressor can be dissolved or dispersed in a liquid carrier and applied by spraying on to one or more of the other components.
  • useful silicone suds controlling agents can comprise a mixture of an alkylated siloxane, of the type referred to hereinbefore, and solid silica. Such mixtures are prepared by affixing the silicone to the surface of the solid silica.
  • a preferred silicone suds controlling agent is represented by a hydrophobic silanated (most preferably trimethyl-silanated) silica having a particle size in the range from 10 nanometers to 20 nanometers and a specific surface area above 50 m2/g, intimately admixed with dimethyl silicone fluid having a molecular weight in the range from about 500 to about 200,000 at a weight ratio of silicone to silanated silica of from about 1:1 to about 1:2.
  • a preferred silicone suds controlling agent is disclosed in Bartollota et al. US Patent 3,933,672.
  • Other particularly useful suds suppressors are the self-emulsifying silicone suds suppressors, described in German Patent Application DTOS 2,646,126 published April 28, 1977.
  • An example of such a compound is DC0544, commercially available from Dow Corning, which is a siloxane/glycol copolymer.
  • the suds suppressors described above are normally employed at levels of from 0.001% to 0.5% by weight of the composition, preferably from 0.01% to 0.1% by weight.
  • the preferred methods of incorporation comprise either application of the suds suppressors in liquid form by spray-on to one or more of the major components of the composition or alternatively the formation of the suds suppressors into separate particulates that can then be mixed with the other solid components of the composition.
  • the incorporation of the suds modifiers as separate particulates also permits the inclusion therein of other suds controlling materials such as C20-C24 fatty acids, microcrystalline waxes and high MWt copolymers of ethylene oxide and propylene oxide which would otherwise adversely affect the dispersibility of the matrix. Techniques for forming such suds modifying particulates are disclosed in the previously mentioned Bartolotta et al US Patent No. 3,933,672.
  • Another optional ingredient useful in the present invention is one or more enzymes.
  • Preferred enzymatic materials include the commercially available amylases, neutral and alkaline proteases, lipases, esterases and cellulases conventionally incorporated into detergent compositions. Suitable enzymes are discussed in US Patents 3,519,570 and 3,533,139.
  • Fabric softening agents can also be incorporated into detergent compositions in accordance with the present invention. These agents may be inorganic or organic in type. Inorganic softening agents are examplified by the smectite clays disclosed in GB-A-1,400,898. Organic fabric softening agents include the water insoluble tertiary amines as disclosed in GB-A-1514276 and EP-B-0011340.
  • Levels of smectite clay are normally in the range from 5% to 15%, more preferably from 8% to 12% by weight, with the material being added as a dry mixed component to the remainder of the formulation.
  • Organic fabric softening agents such as the water-insoluble tertiary amines or dilong chain amide materials are incorporated at levels of from 0.5% to 5% by weight, normally from 1% to 3% by weight, whilst the high molecular weight polyethylene oxide materials and the water soluble cationic materials are added at levels of from 0.1% to 2%, normally from 0.15% to 1.5% by weight.
  • these materials can be added to the aqueous slurry fed to the spray drying tower, although in some instances it may be more convenient to add them as a dry mixed particulate, or spray them as a molten liquid on to other solid components of the composition.
  • Example 3 Example 4 Example 5 Spray dried powder (from Example 1) 25.9 - 26.3 Spray dried powder (from Example 2) - 30.9 - Sodium Percarbonate * 17.5 13.0 16.3 Enzyme Granulate * 1.9 0.7 1.0 Layered Silicate (SKS-6® ex Hoechst) * 12.4 8.0 8.8 Bleach Activator (TAED) Granulate 6.0 2.7 2.8 Sodium Bicarbonate * 4.5 5.8 4.0 Anionic Surfactant Granulate 1 25.0 20.7 2
  • the granular components marked with an asterisk (*) in examples 3 to 5 have a bulk density of greater than 800 g/l.
  • the anionic surfactant granulate (indicated as 1) in examples 3 to 5 comprises 35% by weight anionic surfactant, 26% by weight zeolite A, 28% sodium carbonate, 5% carboxymethyl cellulose, the balance being water.

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EP93309042A 1993-11-11 1993-11-11 Composition de détergent granulaire Withdrawn EP0653481A1 (fr)

Priority Applications (8)

Application Number Priority Date Filing Date Title
EP93309042A EP0653481A1 (fr) 1993-11-11 1993-11-11 Composition de détergent granulaire
US08/637,700 US5756445A (en) 1993-11-11 1994-10-11 Granular detergent composition comprising a low bulk density component
CN94194702A CN1047792C (zh) 1993-11-11 1994-10-11 一种颗粒洗涤剂组分和含此组分的颗粒洗涤剂组合物
BR9408033A BR9408033A (pt) 1993-11-11 1994-10-11 Composição de detergente granular compreendendo um componente de baixa densidade aparente
PCT/US1994/011511 WO1995013344A1 (fr) 1993-11-11 1994-10-11 Composition detergente granulaire comprenant un composant a faible masse volumique en vrac
CA002174721A CA2174721C (fr) 1993-11-11 1994-10-11 Composition detergente granulaire comprenant un composant a faible masse volumique en vrac
AU10393/95A AU1039395A (en) 1993-11-11 1994-10-11 Granular detergent composition comprising a low bulk density component
JP7513824A JPH09505097A (ja) 1993-11-11 1994-10-11 低嵩密度成分を含む粒状洗剤組成物

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
EP93309042A EP0653481A1 (fr) 1993-11-11 1993-11-11 Composition de détergent granulaire

Publications (1)

Publication Number Publication Date
EP0653481A1 true EP0653481A1 (fr) 1995-05-17

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EP (1) EP0653481A1 (fr)
JP (1) JPH09505097A (fr)
CN (1) CN1047792C (fr)
AU (1) AU1039395A (fr)
BR (1) BR9408033A (fr)
CA (1) CA2174721C (fr)
WO (1) WO1995013344A1 (fr)

Cited By (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1996001887A1 (fr) * 1994-07-07 1996-01-25 Henkel Kommanditgesellschaft Auf Aktien Agent de lavage et de blanchiment en poudre
WO1997012955A1 (fr) * 1995-10-04 1997-04-10 The Procter & Gamble Company Procede d'elaboration d'une composition detergente a faible densite par agglomeration avec un sel double inorganique
WO1997012956A1 (fr) * 1995-10-04 1997-04-10 The Procter & Gamble Company Procede d'elaboration d'une composition detergente a faible densite par agglomeration d'un sel hydrate
WO1997043399A1 (fr) * 1996-05-14 1997-11-20 The Procter & Gamble Company Procede de preparation de compositions de detergence faible densite par agglomeration suivie d'un chauffage dielectrique
EP0863973A1 (fr) * 1995-09-26 1998-09-16 The Procter & Gamble Company Composition detergente comprenant un melange d'adjuvant bicarbonate-zeolite
WO1998054286A1 (fr) * 1997-05-30 1998-12-03 Unilever Plc Compositions detergentes particulaires
US5958871A (en) * 1995-09-26 1999-09-28 The Procter & Gamble Company Detergent composition based on zeolite-bicarbonate builder mixture
US6069124A (en) * 1997-05-30 2000-05-30 Lever Brothers Company Division Of Conopco, Inc. Granular detergent compositions and their production
US6221831B1 (en) 1997-05-30 2001-04-24 Lever Brothers Company, Division Of Conopco, Inc. Free flowing detergent composition containing high levels of surfactant
GB2356201A (en) * 1999-11-13 2001-05-16 Procter & Gamble Detergent compositions
US6303558B1 (en) 1997-05-30 2001-10-16 Lever Brothers Co., Division Of Conopco Detergent composition containing at least two granular components
WO2008047302A2 (fr) * 2006-10-16 2008-04-24 The Procter & Gamble Company Composition détergente solide pour lessive, de faible densité, hautement soluble dans l'eau, avec peu d'adjuvant

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP4509741B2 (ja) * 2004-11-02 2010-07-21 花王株式会社 繊維製品の花粉付着防止剤

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Publication number Priority date Publication date Assignee Title
US4478735A (en) * 1981-05-20 1984-10-23 Lion Corporation Process for producing granular detergent composition
EP0139523A2 (fr) * 1983-10-19 1985-05-02 Unilever Plc Poudres détergentes et procédés pour leur production
DE3534888A1 (de) * 1984-10-02 1986-04-10 Toyo Soda Manufacturing Co., Ltd., Shinnanyo, Yamaguchi Koernige zeolith-zusammensetzung als builder und sie enthaltendes waschmittel
EP0270240A2 (fr) * 1986-10-31 1988-06-08 Unilever Plc Poudres détergentes et leur procédé de préparation
EP0344629A1 (fr) * 1988-06-03 1989-12-06 Henkel Kommanditgesellschaft auf Aktien Composition adsorbente granulaire avec une capacité de dégagement ameliorée

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GB1538607A (en) * 1976-11-26 1979-01-24 Unilever Ltd Process for manufacture of detergent powders
DE3424987A1 (de) * 1984-07-06 1986-02-06 Unilever N.V., Rotterdam Verfahren zur herstellung eines pulverfoermigen waschmittels mit erhoehtem schuettgewicht
GB8609044D0 (en) * 1986-04-14 1986-05-21 Unilever Plc Detergent powders

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4478735A (en) * 1981-05-20 1984-10-23 Lion Corporation Process for producing granular detergent composition
EP0139523A2 (fr) * 1983-10-19 1985-05-02 Unilever Plc Poudres détergentes et procédés pour leur production
DE3534888A1 (de) * 1984-10-02 1986-04-10 Toyo Soda Manufacturing Co., Ltd., Shinnanyo, Yamaguchi Koernige zeolith-zusammensetzung als builder und sie enthaltendes waschmittel
EP0270240A2 (fr) * 1986-10-31 1988-06-08 Unilever Plc Poudres détergentes et leur procédé de préparation
EP0344629A1 (fr) * 1988-06-03 1989-12-06 Henkel Kommanditgesellschaft auf Aktien Composition adsorbente granulaire avec une capacité de dégagement ameliorée

Cited By (19)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1996001887A1 (fr) * 1994-07-07 1996-01-25 Henkel Kommanditgesellschaft Auf Aktien Agent de lavage et de blanchiment en poudre
EP0863973A1 (fr) * 1995-09-26 1998-09-16 The Procter & Gamble Company Composition detergente comprenant un melange d'adjuvant bicarbonate-zeolite
EP0863973A4 (fr) * 1995-09-26 1999-02-10 Procter & Gamble Composition detergente comprenant un melange d'adjuvant bicarbonate-zeolite
US5958871A (en) * 1995-09-26 1999-09-28 The Procter & Gamble Company Detergent composition based on zeolite-bicarbonate builder mixture
WO1997012955A1 (fr) * 1995-10-04 1997-04-10 The Procter & Gamble Company Procede d'elaboration d'une composition detergente a faible densite par agglomeration avec un sel double inorganique
WO1997012956A1 (fr) * 1995-10-04 1997-04-10 The Procter & Gamble Company Procede d'elaboration d'une composition detergente a faible densite par agglomeration d'un sel hydrate
CN1111595C (zh) * 1995-10-04 2003-06-18 普罗格特-甘布尔公司 使用无机复盐通过附聚制备低密度洗涤剂组合物的方法
CN1110543C (zh) * 1995-10-04 2003-06-04 普罗格特-甘布尔公司 通过与水合盐附聚制造低密度洗涤剂组合物的方法
US6063751A (en) * 1996-05-14 2000-05-16 The Procter & Gamble Company Process for making a low density detergent composition by agglomeration followed by dielectric heating
WO1997043399A1 (fr) * 1996-05-14 1997-11-20 The Procter & Gamble Company Procede de preparation de compositions de detergence faible densite par agglomeration suivie d'un chauffage dielectrique
US6069124A (en) * 1997-05-30 2000-05-30 Lever Brothers Company Division Of Conopco, Inc. Granular detergent compositions and their production
US6191095B1 (en) 1997-05-30 2001-02-20 Lever Brothers Company, A Division Of Conopco, Inc. Detergent compositions
US6221831B1 (en) 1997-05-30 2001-04-24 Lever Brothers Company, Division Of Conopco, Inc. Free flowing detergent composition containing high levels of surfactant
US6303558B1 (en) 1997-05-30 2001-10-16 Lever Brothers Co., Division Of Conopco Detergent composition containing at least two granular components
WO1998054286A1 (fr) * 1997-05-30 1998-12-03 Unilever Plc Compositions detergentes particulaires
GB2356201A (en) * 1999-11-13 2001-05-16 Procter & Gamble Detergent compositions
WO2008047302A2 (fr) * 2006-10-16 2008-04-24 The Procter & Gamble Company Composition détergente solide pour lessive, de faible densité, hautement soluble dans l'eau, avec peu d'adjuvant
EP1918362A1 (fr) * 2006-10-16 2008-05-07 The Procter & Gamble Company Composition de lessive détergente solide de faible densité, hautement hydrosoluble et à faible teneur en adjuvant
WO2008047302A3 (fr) * 2006-10-16 2008-06-12 Procter & Gamble Composition détergente solide pour lessive, de faible densité, hautement soluble dans l'eau, avec peu d'adjuvant

Also Published As

Publication number Publication date
CN1047792C (zh) 1999-12-29
CA2174721A1 (fr) 1995-05-18
WO1995013344A1 (fr) 1995-05-18
CA2174721C (fr) 1999-12-14
AU1039395A (en) 1995-05-29
CN1139451A (zh) 1997-01-01
JPH09505097A (ja) 1997-05-20
BR9408033A (pt) 1996-12-17

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