WO1996003485A1 - Agents de blanchiment contenant une huile ou cire de paraffine dans des particules separees - Google Patents

Agents de blanchiment contenant une huile ou cire de paraffine dans des particules separees Download PDF

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Publication number
WO1996003485A1
WO1996003485A1 PCT/US1995/008724 US9508724W WO9603485A1 WO 1996003485 A1 WO1996003485 A1 WO 1996003485A1 US 9508724 W US9508724 W US 9508724W WO 9603485 A1 WO9603485 A1 WO 9603485A1
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WIPO (PCT)
Prior art keywords
wax
paraffin oil
granular
detergent composition
weight
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PCT/US1995/008724
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English (en)
Inventor
Kay Emma Fitzgibbon
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The Procter & Gamble Company
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Application filed by The Procter & Gamble Company filed Critical The Procter & Gamble Company
Priority to EP95926255A priority Critical patent/EP0772670A4/fr
Publication of WO1996003485A1 publication Critical patent/WO1996003485A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D11/00—Special methods for preparing compositions containing mixtures of detergents
    • C11D11/0082—Special methods for preparing compositions containing mixtures of detergents one or more of the detergent ingredients being in a liquefied state, e.g. slurry, paste or melt, and the process resulting in solid detergent particles such as granules, powders or beads
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D11/00—Special methods for preparing compositions containing mixtures of detergents
    • C11D11/0082—Special methods for preparing compositions containing mixtures of detergents one or more of the detergent ingredients being in a liquefied state, e.g. slurry, paste or melt, and the process resulting in solid detergent particles such as granules, powders or beads
    • C11D11/0088—Special methods for preparing compositions containing mixtures of detergents one or more of the detergent ingredients being in a liquefied state, e.g. slurry, paste or melt, and the process resulting in solid detergent particles such as granules, powders or beads the liquefied ingredients being sprayed or adsorbed onto solid particles
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/02—Inorganic compounds ; Elemental compounds
    • C11D3/12—Water-insoluble compounds
    • C11D3/124—Silicon containing, e.g. silica, silex, quartz or glass beads
    • C11D3/1246—Silicates, e.g. diatomaceous earth
    • C11D3/1253—Layer silicates, e.g. talcum, kaolin, clay, bentonite, smectite, montmorillonite, hectorite or attapulgite
    • C11D3/126—Layer silicates, e.g. talcum, kaolin, clay, bentonite, smectite, montmorillonite, hectorite or attapulgite 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
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/18—Hydrocarbons
    • 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
    • C11D3/39—Organic or inorganic per-compounds
    • C11D3/3902—Organic or inorganic per-compounds combined with specific additives
    • C11D3/3905—Bleach activators or bleach catalysts
    • C11D3/3907—Organic compounds
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/39—Organic or inorganic per-compounds
    • C11D3/3942—Inorganic per-compounds
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/39—Organic or inorganic per-compounds
    • C11D3/3945—Organic per-compounds

Definitions

  • the present invention concerns the improved stability of certain bleaching agents in detergent compositions.
  • it relates to the improved stability of percarbonate bleach particles.
  • Percarbonate bleach is currently being proposed as an alternative to perborate bleach which has commonly been used in detergent compositions in the past.
  • Sodium percarbonate is an attractive perhydrate for use in detergent compositions because it dissolves readily in water, is weight efficient and, after giving up its available oxygen, provides a useful source of carbonate ions for detergency purposes.
  • Inorganic perhydrate bleaches are invariably incorporated into detergent compositions by dry addition of the crystalline bleach to the remainder of the particulate components towards the end of the detergent manufacturing process.
  • the bulk of these components are in the form of spray-dried granules.
  • W092/6163 published on 16th April, 1992, discloses detergent compositions in which percarbonate stability is improved by controlling levels of both moisture and heavy metal ions in the composition. This is considered as the closest known prior art.
  • a densified, spray-dried component is admixed with a surfactant agglomerate, as well as citrate, silicate, percarbonate and bleach activator.
  • Perfume and suds suppressor (incorporating low levels of paraffin oil and wax) are then sprayed on to the whole composition.
  • At least one granular component comprising paraffin oil and/or wax.
  • the paraffin oil and/or wax which is water- insoluble and hydrophobic, reduces the tendency of the component to absorb water.
  • the invention relates to a granular detergent composition
  • a granular detergent composition comprising at least two particulate components: a) a first particulate component comprising a bleaching agent chosen from the group comprising alkalimetal percarbonate, peroxyacid, perimidic acid or combinations of these, said first particulate component being substantially free of wax; b) a second particulate component comprising from 0.05% to 20% by weight of a water-insoluble paraffin oil and/or wax.
  • the second particulate comprises 1 to 5% by weight of paraffin oil and/or wax; and more preferably the paraffin oil has a pour point of from about -40 to 5°C.
  • the wax has a melting point between about 35 and about 110 °C; most preferably it is a microcrystalline wax having a melting point from 60 to 93°C.
  • the second particulate component comprises at least 2%, and preferably at least 5% by weight of anionic surfactant.
  • the second particulate component may be advantageously prepared by spray drying.
  • the finished product may comprise at least 40% by weight of the second particulate component.
  • the second particulate component further comprises a fabric softening clay.
  • the first particulate component which is substantially free of paraffin oil and wax, comprises less than 0.5% by weight of paraffin oil and wax.
  • the invention also relates to process for making a granular detergent composition
  • process for making a granular detergent composition comprising the steps of: (a) preparing an aqueous solution or slurry of detergent ingredients, said solution or slurry further comprising paraffin oil and/or wax; (b) spray drying said solution or slurry to form a powder; and
  • the invention also relates to a process for making a granular detergent composition comprising the steps of:
  • parffin oil and/or wax and percarbonate bleach Suitable paraffin oils, waxes, percarbonates and other bleach precursors will now be described in more detail.
  • Paraffin oils are hydrocarbons which may be any aliphatic, alicyclic, aromatic or heterocyclic saturated or unsaturated hydrocarbons having generally from about 12 to about 70 carbon atoms. Paraffins are generally obtained from petroleum by various methods inclusive of fractionation distillation, solvent extraction, cracking, reforming or polymerization of lower olefines or diolefines. Paraffin can also be synthesized from coal thereby using the Fischer-Tropsch process, or by hydrogenation of unsaturated hydrocarbons. Paraffins are-preferably obtained by distillation or solvent extracting the solid residus of petroleum distillation.
  • the liquid, at room temperature and atmospheric pressure, hydrocarbon herein has normally a pour point in the range of -40°C to 5°C and usually contains from 12 to 40 carbon atoms.
  • the liquid hydrocarbon should normally have a minimum boiling point of not less than 8
  • Liquid paraffins preferably of the naphthenic or paraffinic type, also known as mineral white oil are preffered.
  • Waxes are hydrocarbons which are typically derived from petroleum. Three types of wax may be distinguished (see Kirk-Othmer, Encyclopedia of Chemical Technology, 3rd Edition, Wiley,Vol. 24, pages 473 and 474): paraffin wax, microcrystalline wax and semicrystalline wax.
  • Paraffin wax consists principally of normal alkanes. It is composed of 40-90% normal paraffins and the remainder is C18-C36 isoalkanes and cycloalkanes. The melting point of the wax determines the actual grade and it varies between about 46°C and 71°C. Average molecular weight is between about 350 and 420.
  • a suitable paraffin wax for use in the present invention is BDH Pastillated Paraffin Wax, having a melting point of 51-55 °C
  • Microcrystalline and microcrystalline waxes contain substantial proportions of hydrocarbons other than normal alkanes.
  • Microcrystalline waxes typically have a melting point between 60°C and 93°C. Average molecular weight is between about 600 and 800.
  • a particularly preferred microcrystalline wax for use in the present invention is MMP ® , supplied by Shell.
  • Other waxes suitable for use in the present invention are :
  • Vegetable Wax including Candelilla; Carnauba;
  • Mineral Wax including Montan Wax and Peat Waxes
  • Synthetic Wax including Polyethylene Waxes
  • Fischer-Tropsch Waxes polymethylene (45-106 °C) ;
  • the amount of paraffin oil and wax used in the second particulate component should be from 0.005% to 20% by weight, preferably from 0.5% to 10% by weight and most preferably from 1% to 5% by weight of the second particulate component.
  • the granular compositions of the present invention further comprise a granular component comprising a bleaching agent chosen from the group comprising alkalimetal percarbonate, peroxyacid, perimidic acid or combinations of these. (This component is described herein as the "first particulate component")
  • Percarbonate will generally be solid and granular in nature. It may be added to granular detergent compositions without additional protection. However, such granular compositions may utilise a coated form of the material which provides better storage stability for the percarbonate in the granular product.
  • the sodium salt of percarbonate is preferred for use in the present invention.
  • Sodium percarbonate is an addition compound having a formula corresponding to 2Na2C03.3H202, 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 a ino-phosphonate, that is incorporated during the manufacturing process.
  • the percarbonate may be incorporated into detergent compositions without additional protection, but preferred embodiments of the invention utilise a coated form of the material. Suitable coating materials include the alkali and alkaline earth metal carbonates and sulphates or chlorides.
  • the most preferred coating material comprises a mixed salt of alkali metal sulphate and carbonate.
  • a mixed salt of alkali metal sulphate and carbonate Such coatings together with coating processes have previously been described in GB 1 466 799, granted to Interox on 9th March, 1977.
  • the weight ratio of the mixed salt coating material to percarbonate lies in the range from 1:200 to 1:4, more preferably from 1:100 to 1:10, and most preferably from 1:50 to 1:20.
  • the mixed salt is of sodium sulphate and sodium carbonate which has the general formula Na2S04.n.Na2C03 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 suitable coating material is sodium silicate of Si02:Na20 ratio from 1.6:1 to 3.4:1, preferably 2.8:1, applied as an aqueous solution to give a level of less than 2% of silicate solids by weight of percarbonate.
  • Magnesium silicate can also be included in the coating.
  • This percarbonate when present, is normally incorporated at a level of from 3% to 35% by weight, more preferably from 5% to 30% by weight and most preferably from 8% to 25% by weight of the total composition.
  • compositions of the invention may contain bleaching agents more suited to low temperature bleaching.
  • bleaching agents more suited to low temperature bleaching.
  • These will include, for example, preformed organic peracids and perimidic acids.
  • preformed peroxy acids or perimidic acids which are useful in the present invention:
  • C-PAP 2-carboxy-phthaloylaminoperoxy caproic acid
  • NAPAA Nonyl amide of peroxy adipic acid
  • Diperoxybrassylic acid Other detergent ingredients may optionally be incorporated into the compositions of the present invention. Various suitable ingredients will now be described in more detail.
  • the composition comprises peroxyacid bleach precursor.
  • the solid peroxyacid bleach precursors of the present invention comprise precursors containing one or more N- or 0- 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 1 N 1 tetra acetylated compounds of formula
  • x can be 0 or an integer between 1 & 6.
  • TAMD tetra acetyl methylene diamine
  • TAED tetra acetyl ethylene diamine
  • TAHD tetraacetyl hexylene diamine
  • bleach precursors are the perbenzoic acid precursors such as benzoyloxybenzene sulphonate (BOBS), benzoylcaprolactam, acyloxybenzene sulphonates (NOBS, iso-NOBS) , sugar derivatives (PAG, TAG, and those described in EP 257039) , malonate derivatives (described in EP 517482), cationic precursors (described in EP 512533, EP 508623 and EP 405152), glycolate esters (described in EP507475) and 2-phenyl 4h-3 1-benzoxazin- 4-one, a ino derived bleach activators, benzoxazin-type activators and acyl lactam activators.
  • perbenzoic acid precursors such as benzoyloxybenzene sulphonate (BOBS), benzoylcaprolactam, acyloxybenzene sulphonates (NOBS, iso-NOBS) , sugar derivatives (PAG, TAG,
  • amido derived bleach activators which can be employed in the present invention are amide substituted compounds of the general formulas:
  • R is an alkyl, aryl, or alkaryl group containing from about 1 to about 14
  • R is an alkylene, arylene or alkarylene group containing from about 1 to about 14 carbon atoms
  • R is H or an alkyl, aryl, or alkaryl group containing from about 1 to about 10 carbon atoms
  • L is essentially any suitable leaving group.
  • a leaving group is any group that is displaced from the bleaching activator as a consequence of the nucleophilic attack on the bleach activator by the perhydroxide anion. This, the perhydrolysis reaction, results in the formation of the peroxycarboxylic acid.
  • a group to be a suitable leaving group it must exert an electron attracting effect. It should also form a stable entity so that the rate of the back reaction is negligible.
  • the L group must be sufficiently reactive for the reaction to occur within the optimum time frame (e.g., a wash cycle) . However, if L is too reactive, this activator will be difficult to stabilize for use in a bleaching composition.
  • pKa of the conjugate acid of the leaving group although exceptions to this convention are known. Ordinarily, leaving groups that exhibit such behavior are those in which their conjugate acid has a pKa in the range of from about 4 to about 13, preferably from about 6 to about 11 and most preferably from about 8 to about 11.
  • Preferred bleach activators are those of the above general formula wherein L is selected from the group consisting of:
  • R is as defined above and Y is -S0 3 M or -CO-, M wherein M is an alkali metal, ammonium or substituted ammonium cation, with sodium and potassium being most preferred
  • bleach activators of the above formulae include (6-octanamido- caproyl)oxybenzenesulfonate, (6- nonanamidocaproyl)oxybenzenesulfonate, (6-decanamido- caproyl) oxybenzenesulfonate, and mixtures thereof as described in U.S. Patent 4,634,551, incorporated herein by reference.
  • R ⁇ is H, an alkyl, aryl, alkoxyaryl, or alkaryl group containing from 1 to about 12 carbon atoms, or a substituted phenyl group containing from about 6 to about 18 carbons. See copending U.S. applications 08/064,562 and 08/082,270, which disclose substituted benzoyl lactams.
  • lactam activators include benzoyl caprolactam, octanoyl caprolactam, 3, 5, 5-trimethylhexanoyl caprolactam, nonanoyl caprolactam, decanoyl caprolactam, undecenoyl caprolactam, benzoyl valerolactam, octanoyl valerolactam, decanoyl valerolactam, undecenoyl valerolactam, nonanoyl valerolactam, 3,5,5- trimethylhexanoyl valerolactam and mixtures thereof. See also U.S. Patent 4,545,784, issued to Sanderson, October 8, 1985, incorporated herein by reference, which discloses acyl caprolactams, including benzoyl caprolactam, adsorbed into sodium perborate.
  • Bleach precursors will normally be in fine powder or crystalline form in which at least 90% by weight of the powder has a particle size of less than 150 micrometers.
  • solid bleach precursors are generally reagglomerated, granulated, encapsulated or spray dried with other components.
  • Such peroxyacid bleach precursor granules are dry blended in the detergent composition and generally have a particle size range of from 300 micrometers to 1500 micrometers.
  • Some bleach precursors are pasty or liquid at room temperature and have to be granulated with porous substrates such as zeolite or silica.
  • a peroxyacid bleach precursor is present at a level of at least 0.5% by weight of the composition.
  • These 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
  • Photosensitive bleaching agents such as zinc phthalocyanine trisulphonate may also be incorporated into the compositions of the present invention.
  • a wide range of surfactants can be used in the detergent compositions.
  • a list of suitable cationic surfactants is given in U.S.P. 4,259,217 issued to Murphy on March 31, 1981.
  • the finished compositions of the present invention will preferably contain from 2% by weight to 30% by weight, and preferably from 5% to 25% by weight of anionic surfactant.
  • 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.
  • Mixtures of anionic surfactants are suitable herein, particularly blends of sulphate, sulphonate and/or carboxylate surfactants.
  • Mixtures of sulphonate and sulphate surfactants are normally employed in a sulphonate to sulphate weight ratio of from 5:1 to 1:2, preferably from 3:1 to 2:3, more preferably from 3:1 to 1:1.
  • Preferred sulphonates include alkyl benzene sulphonates having from 9 to 15, most preferably from 11 to 13 carbon atoms in the alkyl radical, and alpha- sulphonated methyl fatty acid esters in which the fatty acid is derived from a Ci2 -C 18 fatty source, preferably from a C ⁇ g-C ⁇ g fatty source.
  • the cation is an alkali metal, preferably sodium.
  • Preferred sulphate surfactants in such sulphonate sulphate mixtures are alkyl sulphates having from 12 to 22, preferably 16 to 18 carbon atoms in the alkyl radical.
  • Another useful surfactant system comprises a mixture of two alkyl sulphate materials whose respective mean chain lengths differ from each other.
  • One such system comprises a mixture of C14-C15 alkyl sulphate and C_ ⁇ - C ] _g alkyl sulphate in a weight ratio of C14-C1 . 5: C ⁇ g-C]_g of from 3:1 to 1:1.
  • the alkyl sulphates may also be combined with alkyl ethoxy sulphates having from 10 to 20, preferably 10 to 16 carbon atoms in the alkyl radical and an average degree of ethoxylation of 1 to 6.
  • the cation in each instance is again an alkali metal, preferably sodium.
  • anionic surfactants suitable for the purposes of the invention are the alkali metal sarcosinates of formula
  • R-CON (R) CH 2 COOM wherein R is a C9-C17 linear or branched alkyl or alkenyl group, R' is a C1-C alkyl group and M is an alkali metal ion.
  • R is a C9-C17 linear or branched alkyl or alkenyl group
  • R' is a C1-C alkyl group
  • M is an alkali metal ion.
  • Preferred examples are the lauroyl, Cocoyl (C12-C14), myristyl and oleyl methyl sarcosinates in the form of their sodium salts.
  • sulphonation products of fatty acid methyl esters containing a alkyl group with from 10 to 20 carbon atoms Preferred are the C16-18 methyl ester sulphonates (MES), or mixtures of C16-18 and C12-14 methyl ester sulphonates.
  • MES C16-18 methyl ester sulphonates
  • 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 C]_ 3 -C_5 primary alcohols containing 6-9 moles of ethylene oxide per mole of alcohol and the C ⁇ _ ⁇ _- C15 primary alcohols containing 3-5 moles of ethylene oxide per mole of alcohol.
  • Another class of nonionic surfactants comprises alkyl polyglucoside compounds of general formula
  • RO C n H 2n O
  • t Z
  • x 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.
  • the preferred amine for use in the present invention is N- (Rl) -CH2 (CH20H) -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.
  • a further class of surfactants are the semi-polar surfactants such as amine oxides.
  • Suitable amine oxides are selected from mono C _C2 0 preferably C ⁇ o ⁇ i4 N- alkyl or alkenyl amine oxides and propylene-1, 3-diamine dioxides wherein the remaining N positions are substituted by methyl, hydroxyethyl or hydroxpropyl groups.
  • Cationic surfactants can also be used in the detergent compositions herein and suitable quaternary ammonium surfactants are selected from mono Cg-C ] _ , preferably c 10 ⁇ c 14 N-alkyl or alkenyl ammonium surfactants wherein remaining N positions are substituted by methyl, hydroxyethyl or hydroxypropyl groups.
  • the surfactant containing particles will further comprise components selected from a wide range of possible ingredients which are commonly used in laundry detergents.
  • the particles will contain some detergent builder:
  • the builder system is present in an amount of from 25% to 60% by weight of the composition, more preferably from 30% to 60% by weight.
  • Preferred builder systems are free of boron compounds and any polymeric organic materials are preferably biodegradable. Whilst a range of aluminosilicate ion exchange materials can be used, preferred sodium aluminosilicate zeolites have the unit cell formula
  • aluminosilicate materials are in hydrated form and are preferably crystalline, containing from 10% to 28%, more preferably from 18% to 22% water in bound form.
  • 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 CaC0 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 characterised by their calcium ion exchange rate which is at least 130 mg equivalent of CaC0 /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 CaC0 3 /litre/minute/ (gram/litre) [2 grains/gallon/minute/ (gram/gallon) ] to 390 mg equivalent of CaC0 /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 CaC0 3 /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 [ (A10 2 ) 12 (Si0 2 ) 12 ]. xH 2 0 wherein x is from 20 to 30, especially 27.
  • Zeolite X of formula Na 8 6 t (A10 2 ) gg (Si0 2 ) 106 ] • 276 H 2° is also suitable, as well as Zeolite HS of formula Nag [ (AL0 2 ) 6 (Si0 2 ) 6 ] 7.5 H 2 0) .
  • 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 or citric acid, 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-l, 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 maleie 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.
  • 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.
  • Water-soluble silicates which are suitable for use in compositions of the present invention may be amorphous or layered.
  • Such silicates may be characterised by the ratio of Si0 2 to Na 0 in their structure.
  • this ratio may typically lie in the range of from 3.3:1 to 2.0:1, preferably 3.3:1 to 2.4:1, more preferably 3.3:1 to 2.8:1, most preferably 3.3:1 to 3.0:1.
  • Crystalline layered sodium silicates have the general formula
  • 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 ) and preferred examples of this formula comprise the ⁇ -, ⁇ -, ⁇ -, ⁇ - forms of Na 2 Si 2 ⁇ 5- These materials are available from Hoechst AG, Germany, as, respectively, NaSKS-5, NaSkS-7, NaSKS-11 and NaSKS-6. The most preferred material is ⁇ - Na 2 Si 2 ⁇ 5, NaSKS-6.
  • the particulate component or components which contain the surfactant and builder may be made by any convenient process.
  • useful processing routes include spray drying, agglomeration, extrusion, prilling etc.
  • One particularly preferred processing route is to spray dry some or all of the surfactant and builder with the paraffin oil and/or wax.
  • spray dried powders typically have a porosity of greater than 25% and consequently a high tendency to absorb water. The presence of the paraffin oil or wax helps to reduce this.
  • Another processing route is to spray paraffin oil or molten wax onto a base particle so that it is adsorbed and/or coats the surface of the base particle.
  • Paraffin oil or wax may be sprayed on as a single component, or premixed with other liquid components such as nonionic surfactant.
  • Still another processing route, suitable for making high bulk density, high detergent active particles is by agglomerating detergent powders and highly viscous surfactant pastes in a high shear mixer. Paraffin oil or wax may also be incorporated into this type of agglomerated component. A more detailed description of such a process is given in the Applicants' co-pending application EP510746, published on 28th October, 1992.
  • Detergent compositions of the present invention may, optionally, include anti-redeposition and soil suspension agents, bleach activators, optical brighfeeners, 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.
  • Preferred optical brighteners are anionic in character, examples of which are disodium 4, 4 1 -bis- (2- diethanolamino-4-anilino -s- triazin-6- ylamino) stilbene-2:2 1 disulphonate, disodium 4,4 1 -bis- (2-morpholino -4-anilino-2-triazin-6-ylaminostilbene- 2:2 1 -disulphonate,disodium 4, 4 1 -bis- (2, -dianilino-s- triazin-6-ylamino) stilbene-2:2 ⁇ - disulphonate, monosodium 4 1 ' U-bis- (2, 4-dianilino-s-triazin-6 ylamino) stilbene-2- sulphonate, disodium 4,4 1 -bis-(2- anilino-4- (N-methyl-N-2-hydroxyethylamino) -2-triazin-6- ylamino) stilbene-2,2 1
  • 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
  • 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 m ⁇ /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 applieation 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 C 2Q -C 2 4 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.
  • microcrystalline waxes are used in the second particulate component of the present invention, it may be possible to reduce or even eliminate other suds suppressors due to the suds suppressing effect of the microcrystalline wax itself.
  • 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, upases, 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 exemplified 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 25%, more preferably from 8% to 20% 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° 0 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.
  • the wax is incorporated into the same particulate component as the fabric sofening clay.
  • a suitable process for such a composition is described in the Applicants co-pending application number EP634479 published on 18th January, 1995. In that application the benefits of co-agglomerating insoluble silicates such as clays with soluble silicates are described.
  • the present invention encompasses particulate components wherein wax is used as an agglomerating agent either instead of, or in addition to, the soluble silicate (or other binders) . Additionally or alternatively the molten wax may be sprayed onto a base particle which comprises the clay.
  • LAS C11-C13 linear alkyl benzene sulphonate
  • TAS C16-C18 alkyl sulphate
  • Nonionic C45E7 C14-C15 alcohol ethoxylated with an average of 7 ethoxy groups per molecule
  • Polymer Co-polymer of acrylic and maleic acid, supplied by BASF as Sokolan CP5 m .
  • Wax BDH Pastillated Paraffin Wax
  • TAED N,N,N,N-tetraacetylethylene diamine
  • Percarbonate Sodium percarbonate having 13 Av02, coated 2.5% Carbonate/Sulphate All levels are % by weight of a finished detergent composition.
  • Example 2 Comp .
  • the spray dried powder of comparative example A was further coated with 2 parts (i.e. 2% by weight of finished product composition) of wax. This was done by spraying wax directly onto a falling mass of the spray dried powder in a drum mixer.
  • the spray dried powder of comparative example A was further coated with 7 parts (i.e. 7% by weight of finished product composition) of a mixture of wax (2 parts) and nonionic C45E7 (5 parts) .
  • the mixture was sprayed onto the spray dried powder using the same process as example 3.
  • the blown powder of example 1 was further coated with 2 parts (i.e. 2% by weight of finished product composition) ' of wax. This was done by spraying wax directly onto a falling mass of the spray dried powder in a drum mixer. The resulting percarbonate stability was even further improved over that of example 1.
  • the clay agglomerate of Example 6 was made by agglomerating the bentonite clay together with glycerol wax and an excess of water. The resulting agglomerates were then dried in a fluidised bed to a moisture level of 5% by weight of the clay agglomerate.
  • Example 7 the clay agglomerate similar to that in Example 6 was formed in the absence of the wax. Molten wax was then sprayed on to the surfaces of the agglomerate in the fluid bed dryer which was maitained at a temperature below the melting point of the wax.
  • a finished product was made up using the clay agglomerates of Examples 6 and 7, together with 40% active anionic surfactant agglomerates (at 21 % by weight of the finished detergent product) , and the dry-mixed powders of Example 1 (total 50.2% by weight of the finished product) , and balanced to 100% with additional sodium sulphate.

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Abstract

L'invention concerne une composition de détergent granulaire comprenant au moins deux éléments en particules: a) un premier élément en particules contenant un agent de blanchiment choisi dans le groupe comprenant un percarbonate d'un métal alcalin, un peroxyacide, un acide périmidique ou leurs combinaisons, ce premier élément étant pratiquement dépourvu d'huile et de cire de paraffine; b) un deuxième élément en particules comprenant 0,05 à 20 % en poids d'une huile et/ou cire de paraffine non hydrosoluble. On décrit aussi des procédés permettant d'obtenir cette composition de détergent granulaire.
PCT/US1995/008724 1994-07-21 1995-07-12 Agents de blanchiment contenant une huile ou cire de paraffine dans des particules separees WO1996003485A1 (fr)

Priority Applications (1)

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EP94305377.7 1994-07-21
EP94305377 1994-07-21
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EP94308959.9 1994-12-02

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2781235A1 (fr) * 1998-07-16 2000-01-21 Favre Clairbois Particules nettoyantes, sable auto-nettoyant a base desdites particules, procede de fabrication
US6056905A (en) * 1997-06-16 2000-05-02 Lever Brothers Company Division Of Conopco, Inc. Production of detergent granulates
US6133223A (en) * 1997-06-27 2000-10-17 Lever Brothers Company, Division Of Conopco, Inc. Production of detergent granulates
US6274544B1 (en) 1997-06-16 2001-08-14 Lever Brothers Company, Division Of Conopco, Inc. Production of detergent granulates

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US4265779A (en) * 1978-09-09 1981-05-05 The Procter & Gamble Company Suds suppressing compositions and detergents containing them
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US4192761A (en) * 1977-06-23 1980-03-11 The Procter & Gamble Company Detergent compositions containing a suds regulating system
US4265779A (en) * 1978-09-09 1981-05-05 The Procter & Gamble Company Suds suppressing compositions and detergents containing them
US4363740A (en) * 1980-07-29 1982-12-14 Lever Brothers Company Process for making controlled sudsing detergent powder
US4430243A (en) * 1981-08-08 1984-02-07 The Procter & Gamble Company Bleach catalyst compositions and use thereof in laundry bleaching and detergent compositions
US4451387A (en) * 1982-08-19 1984-05-29 Lever Brothers Company Suds control agents and detergent compositions containing them
US4615814A (en) * 1984-04-02 1986-10-07 Purex Corporation Porous substrate with absorbed antistat or softener, used with detergent

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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6056905A (en) * 1997-06-16 2000-05-02 Lever Brothers Company Division Of Conopco, Inc. Production of detergent granulates
US6274544B1 (en) 1997-06-16 2001-08-14 Lever Brothers Company, Division Of Conopco, Inc. Production of detergent granulates
US6429184B1 (en) 1997-06-16 2002-08-06 Lever & Brothers Company, Division Of Conopco, Inc. Production of detergent granulates
US6133223A (en) * 1997-06-27 2000-10-17 Lever Brothers Company, Division Of Conopco, Inc. Production of detergent granulates
FR2781235A1 (fr) * 1998-07-16 2000-01-21 Favre Clairbois Particules nettoyantes, sable auto-nettoyant a base desdites particules, procede de fabrication

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