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WO2001046366A1 - Compositions detergentes contenant un sel polyphosphate - Google Patents

Compositions detergentes contenant un sel polyphosphate Download PDF

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Publication number
WO2001046366A1
WO2001046366A1 PCT/US1999/030633 US9930633W WO0146366A1 WO 2001046366 A1 WO2001046366 A1 WO 2001046366A1 US 9930633 W US9930633 W US 9930633W WO 0146366 A1 WO0146366 A1 WO 0146366A1
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WO
WIPO (PCT)
Prior art keywords
detergent composition
sodium
magnesium
polyphosphate salt
alkali metal
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Application number
PCT/US1999/030633
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English (en)
Inventor
Alvin Jun Deng
Robert Ya-Lin Pan
Original Assignee
The Procter & Gamble Company
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by The Procter & Gamble Company filed Critical The Procter & Gamble Company
Priority to PCT/US1999/030633 priority Critical patent/WO2001046366A1/fr
Priority to AU22073/00A priority patent/AU2207300A/en
Publication of WO2001046366A1 publication Critical patent/WO2001046366A1/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
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/02—Inorganic compounds ; Elemental compounds
    • C11D3/04—Water-soluble compounds
    • C11D3/06—Phosphates, including polyphosphates

Definitions

  • the present invention relates to detergent compositions having a polyphosphate salt.
  • Polyphosphates are known as chelating agents, chemical polishes for stainless steel, and catalysts or dehydrating agents in chemical reactions.
  • a typical sodium polyphosphate is sodium tripolyphosphate.
  • STPP Sodium tripolyphosphate
  • STPP is a builder commonly used in detergent compositions.
  • STPP may revert or hydrolyze to form part pyrophosphate and part orthophosphate, the latter being a less-efficient builder and having among other disadvantages a detrimental effect on the softness of the fabrics being washed.
  • the hydrolysis of some of the STPP is compensated for, by raising the level of STPP in the product.
  • a significant drawback in the elimination or reduction of tripolyphosphate builders from detergent products is a corresponding decrease in the whiteness maintenance of fabrics.
  • the present invention relates to detergent compositions having a polyphosphate salt. More particularly, it relates to detergent compositions having a mixed polyphosphate salt which includes an alkali metal ion and a magnesium counter ion, and has the formula:
  • MxMg((n-x+2)/2)P n O3n + i wherein n is an integer from 3 to 25, x is an integer from 1 to n, and M is an alkali metal.
  • the present invention also relates to a process for making a mixed polyphosphate salt including the steps of mixing an alkali metal phosphate with a magnesium counter ion to form a mixture, and heating the mixture at about 700- 800 °C to form a mixed polyphosphate salt.
  • detergent composition or “detergent” is intended to designate any of the agents conventionally used for removing soil, such as general household detergents or laundry detergents of the synthetic or soap type.
  • the present invention relates to a detergent composition containing a mixed polyphosphate salt which includes an alkali metal ion and a magnesium counter ion, and which has the formula: MxMg((n-x+2)/2)P n O 3n+ ⁇ , wherein n is an integer from 3 to 25, x is an integer from 1 to n, and M is an alkali metal.
  • the detergent composition of the present invention shows less hydrolysis and retains more performance after treatment by a simulated tower process, as compared to a conventional polyphosphate.
  • conventional polyphosphates such as Glass H, reverts or hydrolyzes during the crutching and/or spray-drying processing steps for making detergent products.
  • the conventional polyphosphates form lower chain length polyphosphates including pyrophosphate and orthophosphate, which are less efficient builders and which may having, among other disadvantages, a detrimental effect on the softness and whiteness of the fabrics being washed.
  • the mixed polyphosphate salt of the present invention show less hydrolysis and improved whiteness maintenance of fabrics than conventional polyphosphate.
  • the detergent composition in the present invention provides a much better structurant which improves the hardness and wear rate when included into a laundry bar or a tablet.
  • the mixed polyphosphate salt of the present invention has the formula: MxMg((n-x+2)/2)P n O 3n+ i ) wherein n is an integer from 3 to 25, x is an integer from 1 to n, and M is an alkali metal.
  • x is from n-2 to n.
  • M is preferably a sodium ion, or a potassium ion. More preferably, M is sodium and n is from 10 to 25.
  • the mixed polyphosphate salt may be formed by combining an alkali metal phosphate and a magnesium counter ion.
  • a preferred magnesium counter ion is derived from a magnesium compound selected from the group consisting of magnesium chloride, magnesium sulfate, magnesium phosphate, magnesium hydroxide, and a mixture thereof. Magnesium chloride and magnesium hydroxide are more preferred.
  • a preferred alkali metal phosphate is selected from the group consisting of sodium phosphate, potassium phosphate, sodium pyrophosphate, potassium pyrophosphate, and a mixture thereof. Sodium phosphate is more preferred.
  • the mixed polyphosphate salt is preferably formed by mixing the alkali metal phosphate with a magnesium counter ion to form a mixture, and heating the mixture at about 700-800 °C.
  • the mixture may be maintained at this temperature for about 1-2 hours, and then quenched to form the mixed polyphosphate salt.
  • the detergent composition herein typically contains, by weight of the detergent composition, from about 0.5% to about 15% of the mixed polyphosphate salt, preferably from about 2% to 8% of the mixed polyphosphate salt.
  • the detergent composition herein is formed by mixing the mixed polyphosphate salt and other detersive ingredients to make a slurry, and further processed according to methods known in the art, or by admixing the pre-formed mixed polyphosphate salt with the other detersive ingredients after, for example, a tower process.
  • This mixed polyphosphate salt may replace all or part of a conventional builder, preferably all or part of a conventional phosphate builder.
  • Other Detersive Ingredients may replace all or part of a conventional builder, preferably all or part of a conventional phosphate builder.
  • the detergent composition of the present invention can optionally include one or more detersive ingredients or other materials for assisting or enhancing cleaning performance, treatment of the substrate to be cleaned, or to modify the aesthetics of the detergent composition (e.g., perfumes, colorants, dyes, etc.).
  • detersive ingredients or other materials for assisting or enhancing cleaning performance, treatment of the substrate to be cleaned, or to modify the aesthetics of the detergent composition (e.g., perfumes, colorants, dyes, etc.).
  • the following are illustrative examples of such optional detergent materials.
  • the list of components is non-limiting. JL Detersive Surfactant
  • the detergent composition optionally comprises a detersive surfactant.
  • the detersive surfactant is selected from the group consisting of an anionic surfactant, a cationic surfactant, an amphoteric surfactant, a nonionic surfactant, and a mixture thereof.
  • the detergent composition comprises at least about 0.01 % of a detersive surfactant; more preferably at least about 0.1 %; more preferably at least about 1 %; more preferably still, from about 5% to about 60%.
  • the fine surfactant containing particles have been removed from the composition.
  • fine particles below 75 microns, more preferably below 150 microns, even more preferably below 250 microns have been removed from the composition.
  • anionic surfactants useful herein, typically at levels from about 0.1 % to about 50%, by weight, include the conventional C ⁇
  • LAS C ⁇
  • the C-12-C18 betaines and sulfobetaines can also be included in the overall compositions.
  • C 0-C20 conventional soaps may also be used. If high sudsing is desired, the branched-chain C-10-C16 soaps may be used.
  • Other conventional useful anionic surfactants are listed in standard texts.
  • Other suitable anionic surfactants that can be used are alkyl ester sulfonate surfactants including linear esters of C8-C20 carboxylic acids (i.e., fatty acids) which are sulfonated with gaseous SO3 according to "The Journal of the American Oil Chemists Society", 52 (1975), pp. 323-329.
  • Suitable starting materials would include natural fatty substances as derived from tallow, palm oil, etc.
  • Other anionic surfactants useful for detersive purposes can also be included in the laundry detergent compositions. These can include salts (including, for example, sodium, potassium, ammonium, and substituted ammonium salts such as mono-, di- and triethanolamine salts) of soap, C8-C-22 primary of secondary alkanesulfonates, C8-C24 olefinsulfonates, sulfonated polycarboxylic acids prepared by sulfonation of the pyrolyzed product of alkaline earth metal citrates, e.g., as described in British patent specification No.
  • alkylpolyglycolethersulfates (containing up to 10 moles of ethylene oxide); alkyl glycerol sulfonates, fatty acyl glycerol sulfonates, fatty oleoyl glycerol sulfates, alkyl phenol ethylene oxide ether sulfates, paraffin sulfonates, alkyl phosphates, isethionates such as the acyl isethionates, N-acyl taurates, alkyl succinamates and sulfosuccinates, monoesters of sulfosuccinates (especially saturated and unsaturated C12-C18 monoesters) and diesters of sulfosuccinates (especially saturated and unsaturated C6-C12 diesters), sulfates of alkylpolysacchandes such as the sulfates of alkylpolyglu
  • Resin acids and hydrogenated resin acids are also suitable, such as rosin, hydrogenated rosin, and resin acids and hydrogenated resin acids present in or derived from tallow oil. Further examples are described in "Surface Active Agents and Detergents" (Vol. I and II by Schwartz, Perry and Berch). A variety of such surfactants are also generally disclosed in U.S. Patent 3,929,678, issued December 30, 1975 to Laughlin, et al. at Column 23, line 58 through Column 29, line 23 (herein incorporated by reference). A preferred disulfate surfactant has the formula
  • R is an alkyl, substituted alkyl, alkenyl, aryl, alkaryl, ether, ester, amine or amide group of chain length C ⁇
  • a and B are independently selected from alkyl, substituted alkyl, and alkenyl groups of chain length C-i to C28.
  • a and B in total contain at least 2 atoms;
  • A, B, and R in total contain from 4 to about 31 carbon atoms;
  • X and Y are anionic groups selected from the group consisting of sulfate and sulfonate, provided that at least one of X or Y is a sulfate group; and
  • M is a cationic moiety, preferably a substituted or unsubstituted ammonium ion, or an alkali or alkaline earth metal ion.
  • the disulfate surfactant is typically present at levels of incorporation of from about 0.1 % to about 50%, preferably from about 0.1 % to about 35%, most preferably from about 0.5% to about 15% by weight of the detergent composition.
  • the laundry detergent compositions typically comprise from about 0.1 % to about 50%, preferably from about 1 % to about 40% by weight of an anionic surfactant.
  • AE alkoxylated alcohol
  • PFAA's polyhydroxy fatty acid amides
  • APG's alkyl polyglycosides
  • C-10-C 8 glycerol ethers C-10-C 8 glycerol ethers
  • condensation products of primary and secondary aliphatic alcohols with from about 1 to about 25 moles of ethylene oxide (AE) are suitable for use as the nonionic surfactant in the detergent composition.
  • AE ethylene oxide
  • the alkyl chain of the aliphatic alcohol can either be straight or branched, primary or secondary, and generally contains from about 8 to about 22 carbon atoms.
  • nonionic surfactants of this type include: TergitolTM 15-S-9 (the condensation product of Cn-C-15 linear alcohol with 9 moles ethylene oxide) and TergitolTM 24-L-6 NMW (the condensation product of C12- 4 primary alcohol with 6 moles ethylene oxide with a narrow molecular weight distribution), both marketed by Union Carbide Corporation; NeodolTM 45-9 (the condensation product of C-14-C15 linear alcohol with 9 moles of ethylene oxide), NeodolTM 23-3 (the condensation product of C-12-C 3 linear alcohol with 3 moles of ethylene oxide), NeodolTM 45-7 (the condensation product of C14-C15 linear alcohol with 7 moles of ethylene oxide) and NeodolTM 45-5 (the condensation product of C14-C15 linear alcohol with 5 moles of ethylene oxide) marketed by Shell Chemical Company; KyroTM EOB (the condensation product of C13-C15 alcohol with 9 moles ethylene oxide), marketed by The Procter & Gamble Company; and Gena
  • Rl is H, or C-1.4 hydrocarbyl, 2-hydroxy ethyl, 2-hydroxy propyl or a mixture thereof
  • R2 is C5.31 hydrocarbyl
  • Z is a polyhydroxyhydrocarbyl having a linear hydrocarbyl chain with at least 3 hydroxyls directly connected to the chain, or an alkoxylated derivative thereof.
  • Typical examples include the C-12-C-18 and C12-C14 N-methylglucamides. See U.S. 5,194,639 and 5,298,636. N-alkoxy polyhydroxy fatty acid amides can also be used; see U.S. 5,489,393.
  • alkylpolysaccharides such as those disclosed in U.S. Patent 4,565,647, Llenado, issued January 21 , 1986, having a hydrophobic group containing from about 6 to about 30 carbon atoms, preferably from about 10 to about 16 carbon atoms, and a polysaccharide, e.g. a polyglycoside, hydrophilic group containing from about 1.3 to about 10, preferably from about 1.3 to about 3, most preferably from about 1.3 to about 2.7 saccharide units.
  • alkylpolysaccharides such as those disclosed in U.S. Patent 4,565,647, Llenado, issued January 21 , 1986, having a hydrophobic group containing from about 6 to about 30 carbon atoms, preferably from about 10 to about 16 carbon atoms, and a polysaccharide, e.g. a polyglycoside, hydrophilic group containing from about 1.3 to about 10, preferably from about 1.3 to about 3, most preferably from about 1.3 to
  • Polyethylene, polypropylene, and polybutylene oxide condensates of alkyl phenols are also suitable for use as the nonionic surfactant of the surfactant systems of the detergent composition, with the polyethylene oxide condensates being preferred.
  • These compounds include the condensation products of alkyl phenols having an alkyl group containing from about 6 to about 14 carbon atoms, preferably from about 8 to about 14 carbon atoms, in either a straight-chain or branched-chain configuration with the alkylene oxide.
  • nonionic surfactants of this type include IgepalTM CO-630, marketed by the GAF Corporation; and TritonTM X-45, X-114, X-100 and X-102, all marketed by the Rohm & Haas Company. These surfactants are commonly referred to as alkylphenol alkoxylates (e.g., alkyl phenol ethoxylates).
  • condensation products of ethylene oxide with a hydrophobic base formed by the condensation of propylene oxide with propylene glycol are also suitable for use as the additional nonionic surfactant in the detergent composition.
  • the hydrophobic portion of these compounds will preferably have a molecular weight of from about 1500 to about 1800 and will exhibit water insolubility. Examples of compounds of this type include certain of the commercially-available PluronicTM surfactants, marketed by BASF.
  • nonionic surfactant are the condensation products of ethylene oxide with the product resulting from the reaction of propylene oxide and ethylenediamine.
  • the hydrophobic moiety of these products consists of the reaction product of ethylenediamine and excess propylene oxide, and generally has a molecular weight of from about 2500 to about 3000.
  • This hydrophobic moiety is condensed with ethylene oxide to the extent that the condensation product contains from about 40% to about 80% by weight of polyoxyethylene and has a molecular weight of from about 5,000 to about 11 ,000.
  • this type of nonionic surfactant include certain of the commercially available TetronicTM compounds, marketed by BASF.
  • amine oxide surfactants are also preferred nonionics.
  • the detergent compositions may comprise amine oxide in accordance with the general formula I:
  • the structure (I) provides one long-chain moiety R (EO) x (PO) y (BO) z and two short chain moieties, CH2R'.
  • R' is preferably selected from hydrogen, methyl and -CH2OH.
  • R1 is a primary or branched hydrocarbyl moiety which can be saturated or unsaturated, preferably, R 1 is a primary alkyl moiety.
  • R1 is a hydrocarbyl moiety having chainlength of from about 8 to about 18.
  • Rl may be somewhat longer, having a chainlength in the range C12-C24.
  • AQA alkoxylated quaternary ammonium
  • Cationic surfactants useful as a component of the surfactant system is a cationic choline ester-type quat surfactant which are preferably water dispersible compounds having surfactant properties and comprise at least one ester (i.e. -COO-) linkage and at least one catatonically charged group.
  • Suitable cationic ester surfactants, including choline ester surfactants have for example been disclosed in U.S. Patents Nos. 4,228,042, 4,239,660 and 4,260,529. 2_ Conventional Builders
  • a conventional detergent builder can optionally be included in the detergent compositions herein to assist in controlling mineral hardness.
  • the conventional builder is selected from the group consisting of a pyrophosphate, an orthophosphate, a tripolyphosphate, a higher phosphate, an alkali metal carbonate or a bicarbonate, an alkali silicate, an aluminosilicate, a polycarboxylate, and a mixture thereof
  • Inorganic as well as organic builders can be used. Builders are typically used in fabric laundering compositions to assist in the removal of particulate soils.
  • the level of conventional builder can vary widely depending upon the end use of the composition and its desired physical form.
  • the compositions will typically comprise at least about 1% conventional builder, and preferably from about 5% to about 60% of a conventional builder.
  • Granular formulations typically comprise from about 10% to about 80%, more typically from about 15% to about 50% by weight, of the conventional builder. Lower or higher levels of conventional builder, however, are not meant to be excluded.
  • Conventional inorganic detergent builders include, but are not limited to, the alkali metal, ammonium and alkanolammonium salts of polyphosphates (exemplified by the tripolyphosphates, pyrophosphates, and glassy polymeric meta-phosphates), phosphonates, phytic acid, silicates, carbonates (including bicarbonates and sesquicarbonates), sulphates, and aluminosilicates.
  • polyphosphates exemplified by the tripolyphosphates, pyrophosphates, and glassy polymeric meta-phosphates
  • phosphonates phosphonates
  • phytic acid e.g., silicates
  • carbonates including bicarbonates and sesquicarbonates
  • sulphates sulphates
  • aluminosilicates aluminosilicates.
  • non-phosphate builders are required in some locales.
  • compositions herein function surprisingly well even in the presence of the so-called “weak” builders (as compared with phosphates) such as citrate, or in the so-called “underbuilt” situation that may occur with zeolite or layered silicate builders.
  • silicate builders examples include the alkali metal silicates, particularly those having a SiO2:Na2O ratio in the range 1.6:1 to 3.2:1 and layered silicates, such as the layered sodium silicates described in U.S. Patent 4,664,839, issued May 12, 1987 to H. P. Rieck.
  • NaSKS-6 is the trademark for a crystalline layered silicate marketed by Hoechst (commonly abbreviated herein as "SKS-6").
  • Hoechst commonly abbreviated herein as "SKS-6”
  • the Na SKS-6 silicate builder does not contain aluminum.
  • NaSKS-6 has the delta-Na2SiO5 morphology form of layered silicate.
  • SKS-6 is a highly preferred layered silicate for use herein, but other such layered silicates, such as those having the general formula NaMSi x ⁇ 2 ⁇ + -y ⁇ O wherein M is sodium or hydrogen, x is a number from 1.9 to 4, preferably 2, and y is a number from 0 to 20, preferably 0 can be used herein.
  • Other silicates may also be useful such as for example magnesium silicate, which can serve as a crispening agent in granular formulations, as a stabilizing agent for oxygen bleaches, and as a component of suds control systems.
  • Aluminosilicate builders are useful in the detergent composition. Aluminosilicate builders are of great importance in most currently marketed heavy duty granular detergent compositions. Aluminosilicate builders include those having the empirical formula: M z (zAl ⁇ 2) y ] xH 2 O wherein z and y are integers of at least 6, the molar ratio of z to y is in the range from 1.0 to about 0.5, and x is an integer from about 15 to about 264.
  • polycarboxylate refers to compounds having a plurality of carboxylate groups, preferably at least 3 carboxylates.
  • Conventional polycarboxylate builder can generally be added to the composition in acid form, but can also be added in the form of a neutralized salt. When utilized in salt form, alkali metals, such as sodium, potassium, and lithium, or alkanolammonium salts are preferred.
  • citrate builders e.g., citric acid and soluble salts thereof (particularly sodium salt) are polycarboxylate builders of particular importance due to their availability from renewable resources and their biodegradability.
  • Citrates can also be used in granular compositions, especially in combination with zeolite and/or layered silicate builders. Oxydisuccinates are also especially useful in such compositions and combinations.
  • Useful conventional succinic acid builders include the C5-C20 alkyl and alkenyl succinic acids and salts thereof.
  • a particularly preferred compound of this type is dodecenylsuccinic acid.
  • Specific examples of conventional succinate builders include: laurylsuccinate, myristylsuccinate, palmitylsuccinate, 2-dodecenylsuccinate (preferred), 2- pentadecenylsuccinate, and the like.
  • Fatty acids e.g., C12-C18 monocarboxylic acids
  • Such use of fatty acids will generally result in a diminution of sudsing, which should be taken into account by the formulator.
  • the various conventional alkali metal phosphates such as the well-known sodium tripolyphosphates, sodium pyrophosphate and sodium orthophosphate can be used, especially in the formulation of solids used for hand-laundering operations.
  • Conventional phosphonate builders such as ethane-1-hydroxy-1 ,1- diphosphonate and other known phosphonates (see, for example, U.S. Patents 3,159,581 to Diehl, issued December 1 , 1964; 3,213,030 to Diehl, issued October 19, 1965; 3,400,148 to Quimby, issued September 3, 1968; 3,422,021 to Roy, issued January 14, 1969; and 3,422,137 to Quimby, issued January 14, 1969) can also be used.
  • Alkoxylated polycarboxylates such as those prepared from polyacrylates are useful herein to provide additional grease removal performance. Such materials are described in WO 91/08281 and PCT 90/01815 at p. 4 et seq.. Chemically, these materials comprise polyacrylates having one ethoxy side-chain per every 7-8 acrylate units.
  • the side-chains are of the formula -(CH2CH2 ⁇ ) m (CH2) n CH3 wherein m is 2-3 and n is 6-12.
  • the side-chains are ester-linked to the polyacrylate "backbone" to provide a "comb" polymer type structure.
  • the molecular weight can vary, but is typically in the range of about 2000 to about 50,000.
  • Such alkoxylated polycarboxylates can comprise from about 0.05% to about 10% of the compositions herein. 4_ Bleaching Compounds - Bleaching Agents and Bleach Activators
  • the detergent compositions herein may optionally contain bleaching agents or bleaching compositions containing a bleaching agent and one or more bleach activators.
  • bleaching agents will typically be at levels of from about 1 % to about 30%, more typically from about 5% to about 20%, of the detergent composition, especially for fabric laundering.
  • the amount of bleach activators will typically be from about 0.1 % to about 60%, more typically from about 0.5% to about 40% of the bleaching composition comprising the bleaching agent-plus-bleach activator.
  • Oxygen Bleaching Agents Preferred detergent compositions comprise, as part or all of the laundry or cleaning adjunct materials, an oxygen bleaching agent.
  • Oxygen bleaching agents useful in the detergent composition can be any of the oxidizing agents known for laundry, hard surface cleaning, automatic dishwashing or denture cleaning purposes. Oxygen bleaches or mixtures thereof are preferred, though other oxidant bleaches, such as oxygen, an enzymatic hydrogen peroxide producing system, or hypohalites such as chlorine bleaches like hypochlorite, may also be used.
  • Oxygen bleaches or mixtures thereof are preferred, though other oxidant bleaches, such as oxygen, an enzymatic hydrogen peroxide producing system, or hypohalites such as chlorine bleaches like hypochlorite, may also be used.
  • Oxygen bleaches deliver "available oxygen” (AvO) or "active oxygen” which is typically measurable by standard methods such as iodide/thiosulfate and/or eerie sulfate titration. See the well-known work by Swern, or Kirk Othmer's Encyclopedia of Chemical Technology under "Bleaching Agents".
  • AvO content of such an oxygen bleach compound usually expressed as a percent, is equal to 100 * the number of active oxygen atoms * (16 / molecular weight of the oxygen bleach compound).
  • an oxygen bleach will be used herein, since this benefits directly from combination with the transition-metal bleach catalyst.
  • the oxygen bleach herein can have any physical form compatible with the intended application; more particulariy, solid-form oxygen bleaches as well as adjuncts, promoters or activators are included.
  • Common oxygen bleaches of the peroxygen type include hydrogen peroxide, inorganic peroxohydrates, organic peroxohydrates and the organic peroxyacids, including hydrophilic and hydrophobic mono- or di- peroxyacids.
  • These can be peroxycarboxylic acids, peroxyimidic acids, amidoperoxycarboxylic acids, or their salts including the calcium, magnesium, or mixed-cation salts.
  • Peracids of various kinds can be used both in free form and as precursors known as “bleach activators” or “bleach promoters" which, when combined with a source of hydrogen peroxide, perhydrolyze to release the corresponding peracid.
  • oxygen bleaches are the inorganic peroxides such as Na2 ⁇ 2, superoxides such as KO2, organic hydroperoxides such as cumene hydroperoxide and t-butyl hydroperoxide, and the inorganic peroxoacids and their salts such as the peroxosulfuric acid salts, especially the potassium salts of peroxodisulfuric acid and, more preferably, of peroxomonosulfuric acid including the commercial triple-salt form sold as OXONE by DuPont and also any equivalent commercially available forms such as CUROX from Akzo or CAROAT from Degussa. Certain organic peroxides, such as dibenzoyl peroxide, may be useful, especially as additives rather than as primary oxygen bleach.
  • Mixed oxygen bleach systems are generally useful, as are mixtures of any oxygen bleaches with the known bleach activators, organic catalysts, enzymatic catalysts and mixtures thereof; moreover such mixtures may further include brighteners, photobleaches and dye transfer inhibitors of types well-known in the art.
  • Preferred oxygen bleaches include the peroxohydrates, sometimes known as peroxyhydrates or peroxohydrates. These are organic or, more commonly, inorganic salts capable of releasing hydrogen peroxide readily. They include types in which hydrogen peroxide is present as a true crystal hydrate, and types in which hydrogen peroxide is incorporated covalently and is released chemically, for example by hydrolysis. Typically, peroxohydrates deliver hydrogen peroxide readily enough that it can be extracted in measurable amounts into the ether phase of an ether/water mixture. Peroxohydrates are characterized in that they fail to give the Riesenfeld reaction, in contrast to certain other oxygen bleach types described hereinafter.
  • Peroxohydrates are the most common examples of "hydrogen peroxide source” materials and include the perborates, percarbonates, perphosphates, and persilicates. Other materials which serve to produce or release hydrogen peroxide are, of course, useful. Mixtures of two or more peroxohydrates can be used, for example when it is desired to exploit differential solubility. Suitable peroxohydrates include sodium carbonate peroxyhydrate and equivalent commercial "percarbonate” bleaches, and any of the so-called sodium perborate hydrates, the "tetrahydrate” and “monohydrate” being preferred; though sodium pyrophosphate peroxyhydrate can be used.
  • Percarbonate bleach includes, for example, dry particles having an mean particle size in the range from about 500 micrometers to about 1 ,000 micrometers, not more than about 10% by weight of said particles being smaller than about 200 micrometers and not more than about 10% by weight of said particles being larger than about 1 ,250 micrometers.
  • Percarbonates and perborates are widely available in commerce, for example from FMC, Solvay and Tokai Denka.
  • Bleaching agents other than oxygen bleaching agents are also known in the art and can be utilized herein.
  • One type of non-oxygen bleaching agent of particular interest includes photoactivated bleaching agents such as the sulfonated zinc and/or aluminum phthalocyanines. See U.S. Patent 4,033,718, issued July 5, 1977 to Holcombe et al. If used, detergent compositions will typically contain from about 0.025% to about 1.25%, by weight, of such bleaches, especially sulfonate zinc phthalocyanine.
  • Bleach activators useful herein include amides, imides, esters and anhydrides. Commonly at least one substituted or unsubstituted acyl moiety is present, covalently connected to a leaving group as in the structure R-C(O)-L.
  • bleach activators are combined with a source of hydrogen peroxide, such as the perborates or percarbonates, in a single product. Conveniently, the single product leads to in situ production in aqueous solution (i.e., during the washing process) of the percarboxylic acid corresponding to the bleach activator.
  • the product itself can be hydrous, for example a powder, provided that water is controlled in amount and mobility such that storage stability is acceptable.
  • the product can be anhydrous.
  • the atom in the leaving group connecting to the peracid-forming acyl moiety R(C)O- is most typically O or N.
  • Bleach activators can have non-charged, positively or negatively charged peracid-forming moieties and/or noncharged, positively or negatively charged leaving groups.
  • One or more peracid-forming moieties or leaving-groups can be present. See, for example, U.S. 5,595,967, U.S. 5,561 ,235, U.S. 5,560,862 or the bis-(peroxy-carbonic) system of U.S. 5,534,179.
  • Bleach activators can be substituted with electron-donating or electron-releasing moieties either in the leaving-group or in the peracid-forming moiety or moieties, changing their reactivity and making them more or less suited to particular pH or wash conditions.
  • electron-withdrawing groups such as NO2 improve the efficacy of bleach activators intended for use in mild-pH (e.g., from about 7.5- to about 9.5) wash conditions.
  • Cationic bleach activators include quaternary carbamate-, quaternary carbonate-, quaternary ester- and quaternary amide- types, delivering a range of cationic peroxyimidic, peroxycarbonic or peroxycarboxylic acids to the wash.
  • An analogous but non-cationic palette of bleach activators is available when quaternary derivatives are not desired.
  • cationic activators include quaternary ammonium-substituted activators of WO 96-06915, U.S.
  • EP-A-284292, EP-A-331 ,229 and EP-A-03520 including 2- (N,N,N-trimethyl ammonium) ethyl-4-sulphophenyl carbonate-(SPCC); N- octyl,N,N-dimethyl-N 10-carbophenoxy decyl ammonium chloride-(ODC); 3- (N,N,N-trimethyl ammonium) propyl sodium-4-sulphophenyl carboxylate; and N,N,N-trimethyl ammonium toluyloxy benzene sulfonate.
  • SPCC 2- (N,N,N-trimethyl ammonium) ethyl-4-sulphophenyl carbonate-(SPCC); N- octyl,N,N-dimethyl-N 10-carbophenoxy decyl ammonium chloride-(ODC); 3- (N,N,N-trimethyl ammonium) propyl sodium-4-sulph
  • cationic nitriles as disclosed in EP-A-303,520 and in European Patent Specification 458,396 and 464,880.
  • Other nitrile types have electron-withdrawing substituents as described in U.S. 5,591 ,378; examples including 3,5-dimethoxybenzonitrile and 3,5-dinitrobenzonitrile.
  • bleach activator disclosures include GB 836,988; 864,798; 907,356; 1 ,003,310 and 1 ,519,351 ; German Patent 3,337,921 ; EP-A-0185522; EP-A- 0174132; EP-A-0120591 ; U.S. Pat. Nos. 1 ,246,339; 3,332,882; 4,128,494; 4,412,934 and 4,675,393, and the phenol sulfonate ester of alkanoyl aminoacids disclosed in U.S. 5,523,434.
  • Suitable bleach activators include any acetylated diamine types, whether hydrophilic or hydrophobic in character.
  • Preferred bleach activators include N,N,N'N'-tetraacetyl ethylene diamine (TAED) or any of its close relatives including the triacetyl or other unsymmetrical derivatives.
  • TAED and the acetylated carbohydrates such as glucose pentaacetate and tetraacetyl xylose are preferred hydrophilic bleach activators.
  • acetyl triethyl citrate a liquid, also has some utility, as does phenyl benzoate.
  • Preferred hydrophobic bleach activators include decyl oxybenzoic acid, sodium lauroyl oxybenzene sulfonate, sodium nonanoyloxybenzene sulfonate (NOBS or SNOBS), substituted amide types and activators related to certain imidoperacid bleaches, for example as described in U.S. Patent 5,061 ,807, issued October 29, 1991 and assigned to Hoechst Aktiengesellschaft of Frankfurt, Germany.
  • Japanese Laid-Open Patent Application (Kokai) No. 4- 28799 for example describes a bleaching agent and a bleaching detergent composition comprising an organic peracid precursor described by a general formula and illustrated by compounds which may be summarized more particularly as conforming to the formula:
  • L is sodium p-phenolsulfonate
  • R ⁇ is CH3 or C12H25 and R2 is H.
  • peracids and bleach activators herein are those derivable from acyclic imidoperoxycarboxylic acids and salts thereof of the formula:
  • the structure of the corresponding bleach activators is obtained by deleting the peroxy moiety and the metal and replacing it with a leaving-group L, which can be any of the leaving-group moieties defined elsewhere herein, in preferred embodiments, there are encompassed detergent compositions wherein, in any of said compounds, X is linear C3-C8 alkyl; A is selected from:
  • n is from 0 to about 4
  • R1 and E are said terminal hydrocarbyl groups
  • R2, R3 and R4 are independently selected from H, C1-C3 saturated alkyl, and C1-C3 unsaturated alkyl
  • said terminal hydrocarbyl groups are alkyl groups comprising at least six carbon atoms, more typically linear or branched alkyl having from about 8 to about 16 carbon atoms.
  • bleach activators include sodium-4-benzoyloxy benzene sulfonate (SBOBS); sodium-1-methyl-2-benzoyloxy benzene-4-sulphonate; sodium-4-methyl-3-benzoyloxy benzoate (SPCC); trimethyl ammonium toluyloxy-benzene sulfonate; or sodium 3,5,5-trimethyl hexanoyloxybenzene sulfonate (STHOBS).
  • SBOBS sodium-4-benzoyloxy benzene sulfonate
  • SPCC sodium-4-methyl-3-benzoyloxy benzoate
  • STHOBS sodium 3,5,5-trimethyl hexanoyloxybenzene sulfonate
  • Bleach activators may be used in an amount of up to 20%, preferably from 0.1-10% by weight, of the composition, though higher levels, 40% or more, are acceptable, for example in highly concentrated bleach additive product forms or forms intended for appliance automated dosing.
  • R5 R5 or mixtures thereof, wherein R is alkyl, aryl, or alkaryl containing from about 1 to about 14 carbon atoms including both hydrophilic types (short Rl ) and hydrophobic types (R1 is especially from about 8 to about 12), R is alkylene,
  • R is H, or an alkyl, aryl, or alkaryl containing from about 1 to about 10 carbon atoms, and
  • L is a leaving group
  • a leaving group as defined herein is any group that is displaced from the bleach activator as a consequence of attack by perhydroxide or equivalent reagent capable of liberating a more potent bleach from the reaction.
  • Perhydrolysis is a term used to describe such reaction.
  • bleach activators perhydrolyze to liberate peracid.
  • Leaving groups of bleach activators for relatively low-pH washing are suitably electron-withdrawing.
  • Preferred leaving groups have slow rates of reassociation with the moiety from which they have been displaced.
  • Leaving groups of bleach activators are preferably selected such that their removal and peracid formation are at rates consistent with the desired application, e.g., a wash cycle.
  • the pK of the conjugate acid of the leaving group is a measure of suitability, and is typically from about 4 to about 16, or higher, preferably from about 6 to about 12, more preferably from about 8 to about 11.
  • Preferred bleach activators include those of the formulae, for example the
  • R is a linear or branched alkyl, aryl, or alkaryl
  • R is an alkyl chain
  • R is H or R
  • Y is H or a solubilizing group.
  • Preferred solubilizing groups include -SO3 " M + , -CO2 " M + , -SO4 " M + , -N + (R)
  • any of the above bleach activators are preferably solids having crystalline character and melting-point above about 50 deg. C; in these cases, branched alkyl groups are preferably not included in the oxygen bleach or bleach activator. Melting-point reduction can be favored by incorporating branched, rather than linear alkyl moieties into the oxygen bleach or precursor.
  • the activator can have good water-solubility or dispersability while still being capable of delivering a relatively hydrophobic peracid.
  • M is alkali metal, ammonium or substituted ammonium, more preferably Na or K
  • X is halide, hydroxide, methylsulfate or acetate.
  • Solubilizing groups can, more generally, be used in any bleach activator herein. Bleach activators of lower solubility, for example those with leaving group not having a solubilizing group, may need to be finely divided or dispersed in bleaching solutions for acceptable results.
  • Preferred bleach activators also include those of the above general formula wherein L is selected from the group consisting of:
  • bleach activators of the above formulae include:
  • bleaching results can be obtained from bleaching systems having with in-use pH of from about 6 to about 13, preferably from about 9.0 to about 10.5.
  • activators with electron-withdrawing moieties are used for near-neutral or sub- neutral pH ranges.
  • Alkalis and buffering agents can be used to secure such pH.
  • Acyl lactam activators are very useful herein, especially the acyl caprolactams (see for example WO 94-28102 A) and acyl valerolactams (see U.S. 5,503,639) of the formulae:
  • R6 is H, alkyl, aryl, alkoxyaryl, an alkaryl group containing from 1 to about 12 carbon atoms, or substituted phenyl containing from about 6 to about 18 carbons.
  • acyl caprolactams including benzoyl caprolactam adsorbed into sodium perborate.
  • NOBS, lactam activators, imide activators or amide-functional activators, especially the more hydrophobic derivatives are desirably combined with hydrophilic activators such as TAED, typically at weight ratios of hydrophobic activator:TAED in the range of 1 :5 to 5:1 , preferably about 1 :1.
  • lactam activators are alpha-modified, see WO 96-22350 A1 , July 25, 1996. Lactam activators, especially the more hydrophobic types, are desirably used in combination with TAED, typically at weight ratios of amido-derived or caprolactam activators:TAED in the range of 1 :5 to 5:1 , preferably about 1 :1. See also the bleach activators having cyclic amidine leaving-group disclosed in U.S. 5,552,556.
  • Nonlimiting examples of additional activators useful herein are to be found in U.S. 4,915,854, U.S. 4,412,934 and 4,634,551.
  • the hydrophobic activator nonanoyloxybenzene sulfonate (NOBS) and the hydrophilic tetraacetyl ethylene diamine (TAED) activator are typical, and mixtures thereof can also be used.
  • the superior bleaching/cleaning action of the detergent compositions is also preferably achieved with safety to natural rubber machine parts, for example of certain European washing appliances (see WO 94-28104) and other natural rubber articles, including fabrics containing natural rubber and natural rubber elastic materials. Complexities of bleaching mechanisms are legion and are not completely understood.
  • the bleaching compounds can be catalyzed by means of a manganese compound.
  • a manganese compound Such compounds are well known in the art and include, for example, the manganese-based catalysts disclosed in U.S. Pat. 5,246,621 , U.S. Pat. 5,244,594; U.S. Pat. 5,194,416; U.S. Pat. 5,1 14,606; and European Pat. App. Pub. Nos.
  • Preferred examples of these catalysts include Mn'V2(u-O)3(1 ,4,7-trimethyl-1 ,4,7- triazacyclononane)2(PFg)2, Mn"'2(u-O) ⁇ (u-OAc)2(1 ,4,7-trimethyl-1 ,4,7- triazacyclononane)2-(CIO4)2, Mnl V 4(u-O)6(1 ,4,7-triazacyclononane)4(CIO4)4, Mn!Mnl 4(u-O) ⁇ (u-OAc)2-(1 ,4 ,7-tri methyl- 1 ,4,7-triazacyclononane)2(CIO4)3, Mnl v (1 ,4,7-trimethyl-1 ,4,7-triazacyclononane)- (OCH3)3(PF6), and mixtures thereof.
  • metal-based bleach catalysts include those disclosed in U.S. Pat. 4,430,243 and U.S. Pat. 5,1 14,61 1.
  • the use of manganese with various complex ligands to enhance bleaching is also reported in the following United States Patents: 4,728,455; 5,284,944; 5,246,612; 5,256,779; 5,280,1 17; 5,274,147; 5,153,161 ; and 5,227,084.
  • compositions and processes herein can be adjusted to provide on the order of at least one part per ten million of the active bleach catalyst species in the aqueous washing liquor, and will preferably provide from about 0.1 ppm to about 700 ppm, more preferably from about 1 ppm to about 500 ppm, of the catalyst species in the laundry liquor.
  • optical brighteners or other brightening or whitening agents known in the art can be incorporated at levels typically from about 0.05% to about 1.2%, by weight, into the detergent compositions herein.
  • Commercial optical brighteners which may be useful in the detergent composition can be classified into subgroups, which include, but are not necessarily limited to, derivatives of stilbene, pyrazoline, coumarin, carboxyhc acid, methinecyanines, dibenzothiphene-5,5-dioxide, azoles, 5- and 6-membered-ring heterocycles, and other miscellaneous agents. Examples of such brighteners are disclosed in "The
  • the detergent compositions herein may also optionally contain one or more iron and/or manganese chelating agents.
  • chelating agents can be selected from the group consisting of amino carboxylates, amino phosphonates, polyfunctionally-substituted aromatic chelating agents and mixtures therein, all as hereinafter defined.
  • EDDS ethylenediamine disuccinate
  • these chelating agents will generally comprise from about 0.1 % to about 15% by weight of the detergent compositions herein.
  • Enzymes can be included in the detergent compositions for a variety of purposes, including removal of protein-based, carbohydrate-based, or triglyceride-based stains from substrates, for the prevention of refugee dye transfer in fabric laundering, and for fabric restoration.
  • Suitable enzymes include proteases, amylases, lipases, cellulases, peroxidases, and mixtures thereof of any suitable origin, such as vegetable, animal, bacterial, fungal and yeast origin.
  • Preferred selections are influenced by factors such as pH-activity and/or stability optima, thermostability, and stability to active detergents, builders and the like.
  • bacterial or fungal enzymes are preferred, such as bacterial amylases and proteases, and fungal cellulases.
  • Detersive enzyme means any enzyme having a cleaning, stain removing or otherwise beneficial effect in a laundry, hard surface cleaning or personal care detergent composition.
  • Preferred detersive enzymes are hydrolases such as proteases, amylases and lipases.
  • Preferred enzymes for laundry purposes include, but are not limited to, proteases, cellulases, lipases and peroxidases.
  • Highly preferred for automatic dishwashing are amylases and/or proteases, including both current commercially available types and improved types which, though more and more bleach compatible though successive improvements, have a remaining degree of bleach deactivation susceptibility.
  • Enzymes are normally incorporated into detergent or detergent additive compositions at levels sufficient to provide a "cleaning-effective amount".
  • cleaning effective amount refers to any amount capable of producing a cleaning, stain removal, soil removal, whitening, deodorizing, or freshness improving effect on substrates such as fabrics, dishware and the like. In practical terms for current commercial preparations, typical amounts are up to about 5 mg by weight, more typically 0.01 mg to 3 mg, of active enzyme per gram of the detergent composition. Stated otherwise, the compositions herein will typically comprise from 0.001 % to 5%, preferably 0.01 %-1 % by weight of a commercial enzyme preparation.
  • Protease enzymes are usually present in such commercial preparations at levels sufficient to provide from 0.005 to 0.1 Anson units (AU) of activity per gram of composition.
  • AU Anson units
  • E Suds Suppressors Compounds for reducing or suppressing the formation of suds can be incorporated into the detergent compositions. Suds suppression can be of particular importance in the so-called "high concentration cleaning process" as described in U.S. 4,489,455 and 4,489,574 and in front-loading European-style washing machines.
  • the compositions herein will generally comprise from 0% to about 5% of suds suppressor.
  • compositions herein A wide variety of other ingredients useful in detergent compositions can be included in the compositions herein, including other active ingredients, carriers, hydrotropes, processing aids, dyes or pigments, fillers for solid compositions, etc.
  • suds boosters such as the C-
  • the CI Q- C-14 monoethanol and diethanol amides illustrate a typical class of such suds boosters.
  • Use of such suds boosters with high sudsing adjunct surfactants such as the amine oxides, betaines and sultaines noted above is also advantageous.
  • soluble magnesium salts such as MgCl2, MgSO4, and the like, can be added at levels of, typically, 0.1 %-2%, to provide additional suds and to enhance grease removal performance.
  • the detergent compositions herein will preferably be formulated such that, during use in aqueous cleaning operations, the wash water will have a pH of between about 6.5 and about 1 1 , preferably between about 7.5 and 10.5.
  • Laundry product formulations preferably have a pH between about 9 and about 11. Techniques for controlling pH at recommended usage levels include the use of buffers, alkalis, acids, etc., and are well known to those skilled in the art.
  • the granular detergent compositions of the present invention preferably have a bulk density of at least about 250 g/liter, more preferably from about 400 g/liter to 1200 g/liter.
  • the detergent composition is made into a solid form, such as a bar, a tablet, or other solid form.
  • 2(A102Si ⁇ 2)i2- 27H2O having a primary particle size in the range from 0.1 to 10 micrometers size in the range from 0.1 to 10 micrometers
  • Anhydrous sodium carbonate (mean size of the particle size distribution is between 200 ⁇ m and 900 ⁇ m)
  • KCarbonate Anhydrous potassium carbonate (mean size of the particle size distribution is between 200 ⁇ m and 900 ⁇ m)
  • NaBicarbonate Anhydrous sodium bicarbonate (mean size of the particle size distribution is between 400 ⁇ m and 1200 ⁇ m)
  • NaSilicate Amorphous Sodium Silicate (SiO2:Na2O; 2.0 ratio)
  • MA/AA Copolymer of 1 :4 maleic/acrylic acid average molecular weight about 70,000.
  • TAED Tetraacetylethylenediamine HEDP 1 ,1-hydroxyethane diphosphonic acid Silicone antifoam Polydimethylsiloxane foam controller with siloxane- oxyalkylene copolymer as dispersing agent with a ratio of said foam controller to said dispersing agent of 10:1 to 100:1.
  • laundry detergent compositions A to F are prepared in accordance with the invention:

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Abstract

La présente invention concerne des compositions détergentes contenant un sel polyphosphate. Plus particulièrement, cette invention concerne une composition détergente contenant un sel polyphosphate mélangé qui renferme un métal alcalin et un contre-ion de magnésium, représentée par la formule: MxMg((n-x+2)/2)PnO3n+1, dans laquelle n est un nombre entier compris entre 3 et 25, x est un nombre entier compris entre 1 et n, et M représente un métal alcalin. En outre, cette invention concerne un procédé de formation de sel polyphosphate mélangé.
PCT/US1999/030633 1999-12-22 1999-12-22 Compositions detergentes contenant un sel polyphosphate WO2001046366A1 (fr)

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AU22073/00A AU2207300A (en) 1999-12-22 1999-12-22 Detergent compositions having a polyphosphate salt

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Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5302363A (en) * 1993-05-03 1994-04-12 Monsanto Company Process for preparing anhydrous polyphosphate mixed alkali metal salts
WO1999036494A1 (fr) * 1998-01-13 1999-07-22 The Procter & Gamble Company Compositions granulees presentant une aptitude amelioree a la dissolution

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5302363A (en) * 1993-05-03 1994-04-12 Monsanto Company Process for preparing anhydrous polyphosphate mixed alkali metal salts
WO1999036494A1 (fr) * 1998-01-13 1999-07-22 The Procter & Gamble Company Compositions granulees presentant une aptitude amelioree a la dissolution

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