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EP1754774B1 - Compositions détergentes comportant des hydrotropes - Google Patents

Compositions détergentes comportant des hydrotropes Download PDF

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Publication number
EP1754774B1
EP1754774B1 EP06122351A EP06122351A EP1754774B1 EP 1754774 B1 EP1754774 B1 EP 1754774B1 EP 06122351 A EP06122351 A EP 06122351A EP 06122351 A EP06122351 A EP 06122351A EP 1754774 B1 EP1754774 B1 EP 1754774B1
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EP
European Patent Office
Prior art keywords
compositions
detergent
liquid
composition
aqueous
Prior art date
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EP06122351A
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German (de)
English (en)
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EP1754774A3 (fr
EP1754774A2 (fr
Inventor
Jean-Pol Boutique
Walter Broeckx
Steven Coosemans
Lorenzo Gualco
David Ingram
James Johnston
Eric Tcheou
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Procter and Gamble Co
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Procter and Gamble Co
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Priority claimed from EP00952615A external-priority patent/EP1203066B1/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
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/86—Mixtures of anionic, cationic, and non-ionic 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
    • C11D3/0005—Other compounding ingredients characterised by their effect
    • C11D3/0021—Dye-stain or dye-transfer inhibiting 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
    • C11D3/20—Organic compounds containing oxygen
    • C11D3/2003—Alcohols; Phenols
    • C11D3/2041—Dihydric alcohols
    • C11D3/2044—Dihydric alcohols linear
    • 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
    • C11D3/20—Organic compounds containing oxygen
    • C11D3/2003—Alcohols; Phenols
    • C11D3/2041—Dihydric alcohols
    • C11D3/2051—Dihydric alcohols cyclic; polycyclic

Definitions

  • the present invention relates to detergent compositions, especially liquid, granular and tablet forms of laundry detergent compositions, that comprise improved hydrotropes, wherein the hydrotropes are organic molecules in which two polar groups are separated from each other by at least 5 aliphatic carbon atoms; liquid compositions that contain such hydrotropes have a viscosity, dilution profile and dissolution behavior that render the product effective and convenient for use as a liquid laundry detergent composition.
  • Liquid laundry detergent products offer a number of advantages over dry, powdered or particulate laundry detergent products.
  • Liquid laundry detergent products are readily measurable, speedily dissolved in wash water, non-dusting, are capable of being easily applied in concentrated solutions or dispersions to soiled areas on garments to be laundered and usually occupy less storage space than granular products.
  • liquid laundry detergents may have incorporated into their formulations materials which would deteriorate in the drying operations employed in the manufacture of particulate or granular laundry detergent products. Because liquid laundry detergents are usually considered to be more convenient to use than granular laundry detergents, they have found substantial favor with consumers.
  • detergent compositions in tablet form by compacting a granular detergent composition.
  • Such tablets offer the convenience to consumers of a pre-measured detergent dosage without the inconvenience and untidiness of measuring a sufficient amount of a granular detergent composition for each wash.
  • Such products also offer considerable convenience to those consumers who launder the clothes outside or away from their residence (e.g. at a laundromat) because the consumer is required to transport only precisely as much laundry detergent as she or he needs for clothes laundering.
  • Detergent compositions may be made in tablet form by compacting detergent particulates.
  • Laundry detergent components which may be compatible with each other in granular and/or tablet products, may tend to interact or react with each other in a liquid, especially in an aqueous liquid environment.
  • a disadvantage with conventional granular/powder detergent compositions has been relatively poor dissolution, dispersion and solubility performance.
  • a disadvantage with conventional tablet detergent compositions has been the conflict between making the tablets sufficiently strong and durable to avoid breaking apart during manufacture, transportation and/or storage, while at the same time making the tablets in a manner such that the tablets rapidly disintegrate upon contact with wash water.
  • WO96/33800 relates top stable monophasic liquid compositions comprising a surfactant agent and a coupling agent which is a C4-C12 alkane substituted with two hydroxyl groups or alkoxylates.
  • EP 136 844 relates to glycoside containing detergents.
  • WO 96/30483 relates to aqueous alkaline isotropic liquid detergents comprising a mixture of anionic and nonionic surfactant, together with a hydrotrope and dissolved hydrogen peroxide.
  • aqueous or liquid laundry detergent compositions provide a liquid detergent product that has a viscosity, dilution profile and dissolution behavior that render the product useful and convenient as a liquid laundry detergent composition.
  • liquid detergent products containing these hydrotropes demonstrate excellent cleaning performance, excellent compositional and physical stability and favorable product rheological behavior.
  • These certain hydrotropes may be most generally classified as organic molecules in which two polar groups are separated from each other by at least 5 aliphatic carbon atoms.
  • the liquid detergent products are aqueous.
  • a nonaqueous liquid detergent may comprise a hydrotrope having two polar groups separated from each other by at least 5 aliphatic carbon atoms as well as from about 49% to about 99.95% by weight of the composition of a surfactant-containing non-aqueous liquid phase and from about 1% to about 50% by weight of the composition of particulate material which is substantially insoluble in said liquid phase and which is selected from peroxygen bleaching agents, bleach activators, organic detergent builders, inorganic alkalinity sources and combinations thereof, is provided.
  • Hydrootrope generally means a compound with the ability to increase the solubilities, preferably aqueous solubilities, of certain slightly soluble organic compounds, more preferably “hydrotrope” is defined as follows (see S.E. Friberg and M. Chiu, J. Dispersion Science and Technology, 9(5&6), pages 443 to 457, (1988-1989 )):
  • Non-Aqueous or “Anhydrous” - As used herein, “non-aqueous” or “anhydrous” are used synonymously and both describe a fluid in which the free water content is less than about 1 %.
  • Polar groups refers to functional groups which have a permanent electric dipole moment that arises from the partial charges on atoms linked by polar bonds.
  • the polar group itself may be anionic or uncharged.
  • Dissolution refers to the rate at which the detergent product mixes with water and releases the active ingredients in the wash
  • particles means the entire size range of a detergent final product or component or the entire size range of discrete particles, agglomerates, or granules in a final detergent product or component admixture. It specifically does not refer to a size fraction (i.e., representing less than 100% of the entire size range) of any of these types of particles unless the size fraction represents 100% of a discrete particle in an admixture of particles.
  • the entire size range of discrete particles of that type have the same or substantially similar composition regardless of whether the particles are in contact with other particles.
  • the agglomerates themselves are considered as discrete particles and each discrete particle may be comprised of a composite of smaller primary particles and binder compositions.
  • Geometric Mean Particle Diameter As used herein, the phrase “geometric mean particle diameter” means the geometric mass median diameter of a set of discrete particles as measured by any standard mass-based particle size measurement technique, preferably by dry sieving.
  • hydrotropes described in this section are an essential component of the present detergent compositions.
  • hydrotrope in which two polar groups are separated from each other by at least 5, preferably 6, aliphatic carbon atoms.
  • Suitable polar groups for inclusion in the hydrotrope include are hydroxyl ions.
  • Particularly preferred hydrotropes are selected from the group consisting of:
  • 1,4 Cyclo Hexane Di Methanol may be present in either its cis configuration, its trans configuration or a mixture of both configurations.
  • the present invention comprises liquid laundry detergent compositions which are aqueous and which are suitable for use in an automatic washing machine or for pretreating stains and spots on textile or fabric articles prior to washing.
  • the present liquid laundry detergent compositions may comprise solely a surfactant-rich liquid-phase or they may contain both a surfactant-rich liquid-phase and solid particulate phase which is suspended in the liquid phase.
  • the surfactant-rich liquid-phase comprises the hydrotropes, and optionally organic diluents.
  • hydrotropes of the present invention when incorporated into liquid products of the present invention, provide the key ingredient to prevent gelling and/or thickening of the liquid detergent compositions taught herein.
  • the detergent compositions are non-aqueous, having a surfactant-rich non-aqueous liquid phase and having a solid particulate phase suspended in said liquid phase.
  • the surfactant-containing, non-aqueous liquid phase will generally comprise from about 49% to 99.95% by weight of the detergent compositions herein. More preferably, this liquid phase is surfactant-structured and will comprise from about 52% to 98.9% by weight of the compositions. Most preferably, this comparative non-aqueous liquid phase will comprise from about 55% to 70% by weight of the compositions herein.
  • Such a surfactant-containing liquid phase will frequently have a density of from about 0.6 to 1.4 g/cc, more preferably from about 0.9 to 1.3 g/cc.
  • hydrotropes described above prevent the formation of the viscous surfactant phases formed upon dilution, because the hydrotrope can effectively interact with the ordered, structured layers of surfactant molecules, disrupt them and promote the formation of isotropic low - viscosity surfactant phases.
  • hydrotropes also provide other benefits for improving the rheology of liquid detergent compositions.
  • Ethoxylated quatemized amine materials are described in greater detail below.
  • the liquid phase of the liquid detergent compositions herein is preferably formed from hydrotropes, nonionic and anionic surfactants, and one or more organic diluents.
  • Organic Diluents The major component of the liquid phase of the detergent compositions herein comprises one or more aqueous or non-aqueous organic diluents.
  • the organic diluents used in this invention may be either surface active liquids, i.e., surfactants, or non-surfactant liquids referred to herein as solvents.
  • solvents may be either surface active liquids, i.e., surfactants, or non-surfactant liquids referred to herein as solvents.
  • solvent is used herein to connote the non-surfactant liquid portion of the compositions herein. While some of the essential and/or optional components of the compositions herein may actually dissolve in the "solvent"-containing liquid phase, other components will be present as particulate material dispersed within the "solvent"-containing liquid phase. Thus the term “solvent” is not meant to require that the solvent material be capable of actually dissolving all of the detergent composition components added thereto.
  • the liquid diluent component will generally comprise from about 50% to 90%, more preferably from about 50% to 80%, most preferably from about 55% to 75%, of a structured, surfactant-containing liquid phase.
  • the liquid phase of the compositions herein will comprise both liquid surfactants and non-surfactant solvents.
  • the liquid detergent compositions herein also preferably comprise from about 1% to 50% by weight, more preferably from about 29% to 44% by weight, of additional solid phase particulate material which is dispersed and suspended within the liquid phase.
  • additional solid phase particulate material will range in size from about 0.1 to 1500 microns, more preferably from about 0.1 to 900 microns. Most preferably, such material will range in size from about 5 to 200 microns.
  • the additional particulate material utilized herein can comprise one or more types of detergent composition components which in particulate form are substantially insoluble in the liquid phase of the composition.
  • Such materials include peroxygen bleaching agents, bleach activators, organic detergent builders, inorganic alkalinity sources and combinations thereof.
  • the types of particulate materials which can be utilized are described in detail, below, as follows, however, some materials can either be included in the particulate component or in the surfactant-containing liquid phase.
  • the particulate material comprises the dye transfer inhibitor PVNO (see above for detailed description), an aluminosilicate detergent builder as well as other particulate minor components.
  • the detergent compositions herein can, and preferably will, contain various other optional components.
  • the preferred particulate foam control agent used herein contains a silicone antifoam compound, an organic material and a carrier material onto which the silicone antifoam compound and the organic material are deposited.
  • the carrier material is preferably a native starch or zeolite.
  • the silicone antifoam compound is selected from the group consisting of polydiorganosiloxane, solid silica and mixtures thereof.
  • the organic material is selected from:
  • the dispersing polymer is selected from the group consisting of copolymers of acrylic acid and maleic acid, polyacrylates and mixtures thereof.
  • Silicone suds suppressors known in the art which can be used are, for example, disclosed in U.S. Pat. No. 4,265,779, issued May 5, 1981 to Gandolfo et al and European Patent Application No. 89307851.9, published Feb. 7, 1990, by Starch, M. S. Silicone defoamers and suds controlling agents in granular detergent compositions are disclosed in U.S. Pat. No. 3,933,672, Bartolotta et al , and in U.S. Pat. No. 4,652,392, Baginski et al, issued Mar. 24, 1987 .
  • An exemplary silicone based suds suppressor for use herein is a suds suppressing amount of a particulate foam control agent consisting essentially of:
  • dye transfer inhibiting agents include polyvinyl pyrrolidone polymers, polyamine N-oxide polymers, copolymers of N-vinylpyrrolidone and N-vinylimidazole, manganese phthalocyanine, peroxidases, and mixtures thereof. These agents typically comprise from about 0.0 1 % to about 10% by weight of the composition, preferably from about 0.01 % to about 5%, and more preferably from about 0.05% to about 2%.
  • Preferred polyamine N-oxides are those wherein R is a heterocyclic group such as pyridine, pyrrole, imidazole, pyrrolidine, piperidine and derivatives thereof.
  • the N-O group can be represented by the following general structures: wherein R 1 , R 2 , R 3 are aliphatic, aromatic, heterocyclic or alicyclic groups or combinations thereof; x, y and z are 0 or 1; and the nitrogen of the N-O group can be attached or form part of any of the aforementioned groups.
  • the amine oxide unit of the polyamine N-oxides has a pKa ⁇ 10, preferably pKa ⁇ 7, more preferred pKa ⁇ 6.
  • Any polymer backbone can be used as long as the amine oxide polymer formed is water-soluble and has dye transfer inhibiting properties.
  • suitable polymeric backbones are polyvinyls, polyalkylenes, polyesters, polyethers, polyamide, polyimides, polyacrylates and mixtures thereof. These polymers include random or block copolymers where one monomer type is an amine N-oxide and the other monomer type is an N-oxide.
  • the amine N-oxide polymers typically have a ratio of amine to the amine N-oxide of 10:1 to 1:1,000,000.
  • the number of amine oxide groups present in the polyamine oxide polymer can be varied by appropriate copolymerization or by an appropriate degree of N-oxidation.
  • the polyamine oxides can be obtained in almost any degree of polymerization. Typically, the average molecular weight is within the range of 500 to 1,000,000; more preferred 1,000 to 500,000; most preferred 5,000 to 100,000.
  • poly(4-vinylpyridine-N-oxide) which as an average molecular weight of about 50,000 and an amine to amine N-oxide ratio of about 1:4.
  • PVNO poly(4-vinylpyridine-N-oxide)
  • amine to amine N-oxide ratio of about 1:4.
  • PVNO poly(4-vinylpyridine-N-oxide)
  • Further suitable dye transfer inhibitors can be found in U. S. Pat. No. 5,466,802, issued Nov. 14, 1995 to Panandiker et al. , which is hereby incorporated by reference.
  • the present invention further comprises additional agents to provide fabric care benefits. As described above, these additional agents may be necessary because the high concentrations of detergent concentration in the aqueous laundering solutions used in the present invention may damaged the garments and fabrics contact by the aqueous laundering solutions.
  • the present invention may also include materials which could be added to laundry products that would associate themselves with the fibers of the fabrics and textiles laundered using such products and thereby reduce or minimize the tendency of the laundered fabric/textiles to deteriorate in appearance.
  • Any such detergent product additive material should, of course, be able to benefit fabric appearance and integrity without unduly interfering with the ability of the laundry product to perform its intended function.
  • fabric appearance benefits can include, for example, improved overall appearance of the laundered fabrics, reduction of the formation of pills and fuzz, protection against color fading, improved abrasion resistance, etc.
  • PEI 600 E20 having the general formula: wherein B is a continuation by branching of the polyethyleneimine backbone.
  • E is an ethyleneoxy unit having the formula: -(CH 2 CH 2 O)mH wherein m has an average value of about 20.
  • an average value of 20 is that sufficient ethylene oxide or other suitable reagent is reacted with the polyethyleneimine starting material to fully ethoxylate each N-H unit to a degree of 20 ethoxylations.
  • some N-H unit hydrogen atoms will be replaced by less than 20 ethoxy units and some will be replaced by more than 20 ethoxy units, therefore, the average of the number of ethoxylations is 20.
  • the units which make up the polyalkyleneimine backbones are primary amine units having the formula: H 2 N-CH 2 CH 2 ]- and -NH 2 which terminate the main backbone and any branching chains, secondary amine units having the formula: and which, after modification, have their hydrogen atom substituted by an average of 20 ethyleneoxy units, and tertiary amine units having the formula: which are the branching points of the main and secondary backbone chains, B representing a continuation of the chain structure by branching.
  • the tertiary units have no replaceable hydrogen atom and are therefore not modified by substitution with ethyleneoxy units.
  • cyclic polyamine can be present in the parent polyalkyleneimine backbone mixture.
  • Each primary and secondary amine unit of the cyclic alkyleneimines undergoes modification by the addition of alkyleneoxy units in the same manner as linear and branched polyalkyleneimines.
  • the indices w, x, and y have values such that the average molecular weight of the polyethyleneimine backbone prior to modification is about 600 daltons.
  • each branch chain must terminate in a primary amine unit, therefore the value of the index w is y + 1 in the case where no cyclic amine backbones are present.
  • the average molecular weight for each ethylene backbone unit, -NCH 2 CH 2 -, is approximately 43 daltons.
  • the polyamines of the present invention can be prepared, for example, by polymerizing ethyleneimine in the presence of a catalyst such as carbon dioxide, sodium bisulfite, sulfuric acid, hydrogen peroxide, hydrochloric acid, acetic acid, etc.
  • a catalyst such as carbon dioxide, sodium bisulfite, sulfuric acid, hydrogen peroxide, hydrochloric acid, acetic acid, etc.
  • Specific methods for preparing these polyamine backbones are disclosed in U.S. Patent 2,182,306, Ulrich et al., issued December 5, 1939 ; U.S. Patent 3,033,746, Mayle et al., issued May 8,1962 ; U.S. Patent 2,208,095, Esselmann et al., issued July 16,1940 ; U.S. Patent 2,806,839, Crowther, issued September 17,1957 ; and U.S.
  • Polymeric polycarboxylate materials can be prepared by polymerizing or copolymerizing suitable unsaturated monomers, preferably in their acid form.
  • Unsaturated monomeric acids that can be polymerized to form suitable polymeric polycarboxylates include acrylic acid, maleic acid (or maleic anhydride), fumaric acid, itaconic acid, aconitic acid, mesaconic acid, citraconic acid and methylenemalonic acid.
  • the presence in the polymeric polycarboxylates herein of monomeric segments, containing no carboxylate radicals such as vinylmethyl ether, styrene, ethylene, etc. is suitable provided that such segments do not constitute more than about 40% by weight of the polymer.
  • Particularly suitable polymeric polycarboxylates can be derived from acrylic acid.
  • acrylic acid-based polymers which are useful herein are the water-soluble salts of polymerized acrylic acid.
  • the average molecular weight of such polymers in the acid form preferably ranges from about 2,000 to 100,000, more preferably from about 2,000 to 10,000, even more preferably from about 4,000 to 7,000, and most preferably from about 4,000 to 5,000.
  • Water-soluble salts of such acrylic acid polymers can include, for example, the alkali metal, salts.
  • Soluble polymers of this type are known materials. Use of polyacrylates of this type in detergent compositions has been disclosed, for example, Diehl, U.S. Patent 3,308,067, issued March 7, 1967 . Such materials may also perform a builder function.
  • polymeric materials suitable for use as thickening, viscosity control and/or dispersing agents include polymers of: castor oil derivatives; polyurethane derivatives, and polyethylene glycol.
  • the optional thickening, viscosity control and/or dispersing agents should be present in the compositions herein to the extent of from about 0.1% to 4% by weight. More preferably, such materials can comprise from about 0.1 % to 2% by weight of the detergents compositions herein.
  • Clay Soil Removal/Anti-redeposition Agents The compositions of the present invention can also optionally contain water-soluble ethoxylated amines having clay soil removal and anti-redeposition properties. If used, soil materials can contain from about 0.01% to about 5% by weight of the compositions herein.
  • the most preferred soil release and anti-redeposition agent is ethoxylated tetraethylenepentamine.
  • Exemplary ethoxylated amines are further described in U.S. Patent 4,597,898, VanderMeer, issued July 1, 1986 .
  • Another group of preferred clay soil removal-anti-redeposition agents are the cationic compounds disclosed in European Patent Application 111,965 , Oh and Gosselink, published June 27, 1984.
  • clay soil removal/anti-redeposition agents which can be used include the ethoxylated amine polymers disclosed in European Patent Application 111,984, Gosselink, published June 27, 1984 ; the zwitterionic polymers disclosed in European Patent Application 112,592, Gosselink, published July 4, 1984 ; and the amine oxides disclosed in U.S. Patent 4,548,744, Connor, issued October 22, 1985 .
  • Preferred clay-removing compounds include ethoxylated quatemized amines.
  • Preferred ethoxylated quaternized amine materials are selected from the group consisting of compounds having the general formula: wherein each x is independently less than about 16, preferably from about 6 to about 13, more preferably from about 6 to about 8, or wherein each x is independently greater than about 35.
  • Materials suitable for use in the present invention can be purchased from the BASF Corporation in Germany, and the Witco Chemical Company.
  • the degree of ethoxylation is important to the viscosity of the final detergent compositions described herein. Specifically, for the general structure: when x is less than about 13 the ethoxylated quatemized amine clay materials can be added to the present liquid heavy duty detergent compositions as liquids without causing undesired thickening at low temperatures. Likewise, when the degree of ethoxylation for the same structure is greater than about 35, that is when x is greater than about 35, these higher ethoxalated materials can be added to the formulations as stable solid without melting at high temperatures and without causing low temperature product thickening.
  • CMC carboxy methyl cellulose
  • An effervescent may be added to the tablet mix in addition to the detergent ingredients.
  • the addition of this effervescent to the detergent tablet improves the disintegration time of the tablet.
  • the amount will preferably be between 5 and 20 % and most preferably between 10 and 20% by weight of the tablet.
  • the effervescent should be added as an agglomerate of the different particles or as a compact, and not as separated particles.
  • the tablet Due to the gas created by the effervescency in the tablet, the tablet can have a higher D.F.S. and still have the same disintegration time as a tablet without effervescency.
  • the D.F.S. of the tablet with effervescency is kept the same as a tablet without, the disintegration of the tablet with effervescency will be faster.
  • dispersion aid could be provided by using compounds such as sodium acetate or urea.
  • suitable dispersion aid may also be found in Pharmaceutical Dosage Forms: Tablets, Volume 1, Second edition, Edited by H.A. Lieberman et all, ISBN 0-8247-8044-2 .
  • the effervescent system may comprise and acid and a base, such as citric acid and sodium bicarbonate, and/or the effervescent system may comprise an enzyme, such as catalase and/or peroxidase and a source of peroxide, such as hydrogen peroxide.
  • Binders - Non gelling binders can be integrated to the particles forming the tablet in order to further facilitate dispersion.
  • suitable non-gelling binders include synthetic organic polymers such as polyethylene glycols, polyvinylpyrrolidones, polyacrylates and water-soluble acrylate copolymers.
  • the handbook of Pharmaceutical Excipients second editi on, has the following binders classification: Acacia, Alginic Acid, Carbomer, Carboxymethylcellulose sodium, Dextrin, Ethylcellulose, Gelatin, Guar gum, Hydrogenated vegetable oil type I, Hydroxyethyl cellulose, Hydroxypropyl methylcellulose, Liquid glucose, Magnesium aluminum silicate, Maltodextrin, Methylcellulose, polymethacrylates, povidone, sodium alginate, starch and zein.
  • binders also have an active cleaning function in the laundry wash such as cationic polymers, i.e. ethoxylated hexamethylene diamine quaternary compounds, bishexamethylene triamines, or others such as pentaamines, ethoxylated polyethylene amines, maleic acrylic polymers.
  • cationic polymers i.e. ethoxylated hexamethylene diamine quaternary compounds, bishexamethylene triamines, or others such as pentaamines, ethoxylated polyethylene amines, maleic acrylic polymers.
  • Non-gelling binder materials are preferably sprayed on and hence have an appropriate melting point temperature below 90°C, preferably below 70°C and even more preferably below 50°C so as not to damage or degrade the other active ingredients in the matrix.
  • non-aqueous liquid binders i.e. not in aqueous solution
  • they may also be solid binders incorporated into the matrix by dry addition but which have binding properties within the tablet.
  • Non-gelling binder materials are preferably used in an amount within the range from 0.1 to 15% of the composition, more preferably below 5% and especially if it is a non laundry active material below 2% by weight of the tablet.
  • gelling binders such as nonionic surfactants are avoided in their liquid or molten form.
  • Nonionic surfactants and other gelling binders are not excluded from the compositions, but it is preferred that they be processed into the detergent tablets as components of particulate materials, and not as liquids.
  • smectite-type clays There are two distinct classes of smectite-type clays; in the first, aluminum oxide is present in the silicate crystal lattice; in the second class of smectites, magnesium oxide is present in the silicate crystal lattice.
  • the general formulas of these smectites are Al 2 (Si 2 O 5 ) 2 (OH) 2 and Mg 3 (Si 2 O 5 ) (OH) 2 for the aluminum and magnesium oxide type clay, respectively. It is to be recognised that the range of the water of hydration in the above formulas can vary with the processing to which the clay has been subjected.
  • the three-layer, expandable alumino-silicates useful herein are further characterised by a dioctahedral crystal lattice, while the expandable three-layer magnesium silicates have a trioctahedral crystal lattice.
  • the clays employed in the compositions of the instant invention contain cationic counterions such as protons, sodium ions, potassium ions, calcium ion, magnesium ion, and the like. It is customary to distinguish between clays on the basis of one cation predominantly or exclusively absorbed.
  • a sodium clay is one in which the absorbed cation is predominantly sodium.
  • Such absorbed cations can become involved in exchange reactions with cations present in aqueous solutions.
  • a typical exchange reaction involving a smectite-type clay is expressed by the following equation: smectite clay (Na) + NH 4 OH_ smectite clay (NH 4 ) + NaOH.
  • cation exchange capacity (sometimes termed “base exchange capacity") in terms of milliequivalents per 100 g. of clay (meq./100 g.).
  • base exchange capacity cation exchange capacity
  • the cation exchange capacity of clays can be measured in several ways, including by electrodialysis, by exchange with ammonium ion followed by titration or by a methylene blue procedure, all as fully set forth in Grimshaw, "The Chemistry and Physics of Clays", pp. 264-265, Interscience (1971 ).
  • the cation exchange capacity of a clay mineral relates to such factors as the expandable properties of the clay, the charge of the clay, which, in turn, is determined at least in part by the lattice structure, and the like.
  • the ion exchange capacity of clays varies widely in the range from about 2 meq/100 g. for kaolinites to about 150 meq/100 g., and greater, for certain clays of the montmorillonite variety.
  • Illite clays have an ion exchange capacity somewhere in the lower portion of the range, i.e., around 26 meq/100 g. for an average illite clay.
  • Illite and kaolinite clays are preferably not used as the clay in the instant compositions. Indeed, such illite and kaolinite clays constitute a major component of clay soils and, as noted above, are removed from fabric surfaces by means of the instant compositions.
  • smectites such as nontonite, having an ion exchange capacity of around 70 meq/100 g.
  • montmorillonite which has an ion exchange capacity greater than 70 meq/100 g.
  • clay minerals useful herein can be characterised as expandable, three-layer smectite-type clays having an ion exchange capacity of at least about 50 meq/100 g.
  • the smectite clays used in the compositions herein are all commercially available. Such clays include, for example, montmorillonite, volchonskoite, nontronite, hectorite, saponite, sauconite, and vermiculite.
  • the clays herein are available under various tradenames, for example, Thixogel #1 and Gelwhite GP from Georgia Kaolin Co., Elizabeth, New Jersey; Volclay BC and Volclay #325, from American Colloid Co., Skokie, Illinois; Black Hills Bentonite BH450, from International Minerals and Chemicals; and Veegum Pro and Veegum F, from R.T. Vanderbilt. It is to be recognised that such smectite-type minerals obtained under the foregoing tradenames can comprise mixtures of the various discrete mineral entities. Such mixtures of the smectite minerals are suitable for use herein.
  • smectite-type clays having a cation exchange capacity of at least about 50 meq/100 g. are useful herein, certain clays are preferred.
  • Gelwhite GP is an extremely white form of smectite clay and is therefore preferred when formulating white granular detergent compositions.
  • Volclay BC which is a smectite-type clay mineral containing at least 3% of iron (expressed as Fe 2 O 3 ) in the crystal lattice, and which has a very high ion exchange capacity, is one of the most efficient and effective clays for use in laundry compositions and is preferred from the standpoint of product performance.
  • Appropriate clay minerals for use herein can be selected by virtue of the fact that smectites exhibit a true 14 ⁇ x-ray diffraction pattern. This characteristic pattern, taken in combination with exchange capacity measurements performed in the manner noted above, provides a basis for selecting particular smectite-type minerals for use in the granular detergent compositions disclosed herein.
  • the clay is preferably mainly in the form of granules, with at least 50% (and preferably at least 75% or at least 90%) being in the form of granules having a size of at least 100mm up to 1800mm, preferably up to 1180mm, preferably 150-850mm.
  • the amount of clay in the granules is at least 50%, usually at least 70% or 90%, of the weight of the granules.
  • polymers of ethylene oxide, acrylamide or acrylic acid are preferred. These polymers dramatically enhance the deposition of a fabric softening clay if their molecular weights are in the range of from 100 000 to 10 million. Preferred are such polymers having a weight average molecular weight of from 150000 to 5 million.
  • the most preferred polymer is poly (ethylene oxide).
  • Molecular weight distributions can be readily determined using gel permeation chromatography, against standards of poly (ethylene oxide) of narrow molecular weight distributions.
  • the amount of flocculant is preferably 0.5-10% by weight of the tablet, most preferably about 2 to 6%.
  • the flocculant is preferably mainly in the form of granules, with at least 50% by weighty (and preferably at least 75% and most preferably at least 90%) being in the form of granules having a size of at least 100mm up to 1800mm, preferably up to 1180mm and most preferably 150-850mm
  • the amount of flocculant in the granules is at least 50%, generally at least 70% or 90%, of the weight of the granules.
  • compositions which are commonly used in detergent compositions and which may be incorporated into the detergent tablets of the present invention include chelating agents, soil release agents, soil antiredeposition agents, dispersing agents, brighteners, suds suppressors, fabric softeners, dye transfer inhibition agents and perfumes.
  • a clay material when compressed prior to incorporation into a tablet or in a cleaning composition, improved disintegration or dispensing is achieved.
  • tablets comprising clay which is compressed prior to incorporation into a tablet disintegrate more rapidly than tablets comprising the same clay material which has not been compressed prior to incorporation into a tablet.
  • the amount of pressure used for the compression of the clay is of importance to obtain clay particles which aid disintegration or dispensing.
  • the clay component is obtained by compression of a clay material.
  • a preferred process comprises the steps of submitting the clay material to a pressure of at least 10MPa, or even at least 20MPa or even 40MPa. This can for example be done by tabletting or roller compaction of a clay material, optionally together with one or more other ingredients, to form a clay tablet or sheet, preferably followed by size reduction, such as grinding, of the compressed clay sheet or tablet, to form compressed clay particles. The particles can then be incorporated in a tablet or cleaning composition.
  • Tabletting methods and roller compaction methods are known in the art.
  • the compression of the clay can be done in a Lloyd 50k tablet press or with a Chilsonator roller compaction equipment, available form Fitzpatrick Company.
  • Nonaqueous liquid detergent compositions comprising a surfactant-rich liquid phase and a solid phase were prepared as follows: %, By weight Composition A Composition B Nonionic Surfactant 21.27 20.14 BPP Solvent 18.30 17.33 LAS Surfactant 15.83 14.99 Ethoxylated quaternized amine clay material 1.29 1.22 Hydrotrope 4.80 0.00 Na-Citrate dehydrate 6.73 6.37 Na-Carbonate 9.89 9.37 Bleach Activator 5.94 5.62 Sodium Perborate 11.87 11.24 EDDS 1.17 1.11 Duramyl Enzyme 0.79 0.87 Carezyme Enzyme 0.03 0.03 Protease Enzyme 0.79 0.75 Antifoaming Agents 0.61 0.85 Plastic Microspheres 0.51 0.49 Titanium dioxide 0.50 0.47 Brightener 0.20 0.19 PEG 8000 0.40 0.38 Perfume 1.72 1.63 Miscellaneous 2.16 2.15
  • Liquid detergent composition A is prepared according to the present invention and thus contains the preferred hydrotrope 1,4 Cyclo Hexane Di Methanol.
  • liquid detergent composition B is nearly identical to composition A, except that composition B contains none of the hydrotrope and its other components have been slightly rebalanced.
  • compositions were tested using the "Rate of Liquid Detergent Product Dissolution in Water Test" described in great detail above.
  • the conductivity was measured by electrode immersed in the water at the beginning of the test-detergent composition solution and the % of dissolution by and converted into The following results were obtained: Composition A Composition B Time Conductivity % Dissolution Conductivity % Dissolution 0 s (T 0 ) 0 0 0 0 30 s 28 19 12 7 60 s 40 27 17 10 120 s 54 37 23 14 180 s 62 42 31 18 240 s 68 47 39 23 360 s 78 53 44 26 600 s 81 55 49 29 660 s 91 62 51 30
  • the dissolution values were obtained by dividing the measured conductivity at each individual time by the measured conductivity at full dissolution and multiplying by 100.
  • An aqueous liquid detergent composition according to the present invention is prepared as follows:
  • Nonaqueous liquid detergent compositions comprising a surfactant-rich liquid phase and a solid phase were prepared as follows: %, By weight Composition nA Composition nB Composition C Composition D Composition nE NaLAS 14.6 14.9 13.9 13.0 14.9 HLAS 0.0 0.0 1.0 1.9 0.0 Nonionic Surfactant 20.6 20.7 20.7 20.7 20.7 NaCitrate dihydrate 3.3 3.3 3.3 3.3 3.3 Copolymer of Acrylic Acid and Maleic Acid 2.9 2.9 2.9 2.9 2.9 2.9 2.9 2.9 2.9 EDDS 1.2 1.2 1.2 1.2 1.2 Ethoxylated Quaternized amine clay material 1.3 1.3 1.2 1.3 1.3 Sodium Perborate 11.5 11.5 11.5 11.5 11.5 Bleach Activator 2.9 5.8 2.9 2.9 2.9 Triacetin 12.5 0.0 12.5 12.5 8.7 NaCarbonate 9.6 9.6 9.6 9.6 9.6 BPP Solvent 9.1 17.8 9.1 9.1 12.0 Hydrotrope 3.8
  • compositions are in accordance with the invention.
  • a B C D E F G H I Spray-dried Granules LAS 10.0 10.0 15.0 5.0 5.0 10.0 - - - QA S 1.0 1.0 - - - - DTPA, HEDP and/or EDDS 0.3 0.3 0.5 0.3 - - - - MgSO4 0.5 0.5 0.1 - - - - - - Sodium citrate - - - 3.0 5.0 - - - - Sodium carbonate 10.0 10 15 10 7 10 - - - Sodium sulphate 5.0 5.0 - - 5.0 3.0 - - - Sodium silicate 1.6R - - - - 2.0 - - - Zeolite A 16.0 18.0 20.0 20.0 20.0 20.0 - - - - SKS-6 - - - 3.0 5.0 - - - - MA/AA or AA 1.0 2.0
  • compositions exemplified above have at least 90% by weight of particles having a geometric mean particle diameter of from about 850 microns with a geometric standard deviation of from about 1.2. Unexpectedly, the compositions have improved aesthetics, flowability and solubility.
  • Examples 2a-3b were prepared in an analogous fashion to the process described above and according to the formulation compositions detailed below.
  • Table 1 Composition nA Composition B
  • Composition C (%) (%) (%)
  • Anionic agglomerates 1 34
  • Nonionic agglomerates 2 9.57 9.57 9.57
  • Layered silicate 3 2.7 1.5 1.5 Sodium percarbonate 12.43 12.43 12.43
  • 2:Nonionic agglomerates comprise of 24% nonionic surfactant, 6% ethoxylated hexamethylene diaminequat, 40% acetate/zeolite mix, 20% carbonate and 10% zeolite.
  • 3:Layered silicate comprises of 95% SKS 6 and 5% silicate.
  • 4:Bleach activator agglomerates comprise of 81% TAED, 17% acrylic/maleic copolymer (acid form) and 2% water.
  • 5:Ethylene diamine N,N-disuccinic acid sodium salt/Sulphate particle comprise of 58% of Ethylene diamine N,N-disuccinic acid sodium salt, 23% of sulphate and 19% water.
  • 6:Zinc phthalocyanine sulphonate encapsulates are 10% active.
  • 7:Suds suppressor comprises of 11.5% silicone oil (ex Dow Coming); 59% of zeolite and 29.5% of water.
  • 8:Sodium salt of Linear Alkyl Benzene Sulphonate / DiIsoPropylBenzeneSulphonate comprises of 67% Linear Alkyl Benzene Sulphonate and 33% DilsoPropylBenzeneSulphonate.
  • a tablet binder composition was sprayed onto the above detergent base powders according to the following compositions: Table 2 Example 1a Example 1b Example 2a Exampl 2b Example 3a Example 3b Powder A 99% 99% Powder B 98.5% 98.5% Powder C 98.5% 98.5% Polyethyleneglycol 1% 0.9% 1.50% 1.35% 1.5% 1.3% 1,4 cyc / ohexanedimethan ol 0.1% 0.15% 0.2%
  • the tensile strength of the tablet samples which contained CHDM were greater than the CHD tablet samples of virtually identical composition, but which contained no CHDM.
  • Example 3a Example 3b Density at a tablet hardness of 5.5kP 1035 1010 Density at a tablet dispensing of15% 1052 1035
  • the amount of dispensing of a detergent tablet as tabulated above in table 4 can be determined through an experimental test which measures the amount of detergent product dispensed during an automatic wash process in the following way:
  • the level of residues is determined by repeating the procedure 10 times and an average residue level is calculated based on the ten individual measurements.

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Claims (6)

  1. Composition détergente aqueuse pour le lavage du linge comprenant un hydrotrope, dans laquelle l'hydrotrope est constitué d'un premier groupe polaire et d'un deuxième groupe polaire, séparés l'un de l'autre par au moins 5 atomes de carbone aliphatiques, dans laquelle le premier groupe polaire et le deuxième groupe polaire sont l'un et l'autre des groupes hydroxyle, et où ladite composition comprend en outre un agent tensioactif détersif.
  2. Composition détergente aqueuse pour le lavage du linge selon la revendication 1, dans laquelle les groupes polaires sont séparés par 6 atomes de carbone aliphatiques, de préférence les groupes polaires sont séparés par au plus 8 atomes de carbone aliphatiques, plus préférablement les groupes polaires sont séparés par au plus 10 atomes de carbone aliphatiques.
  3. Composition détergente aqueuse pour le lavage du linge selon l'une quelconque des revendications 1 ou 2, dans laquelle l'hydrotrope est choisi dans le groupe constitué de :
    (a) 1,4 cyclohexane diméthanol :
    Figure imgb0020
    (b) 1,6-hexanediol:
    Figure imgb0021
    (c) 1,7 heptanediol :
    Figure imgb0022
     et
    (d) leurs mélanges.
  4. Composition détergente aqueuse pour le lavage du linge selon l'une quelconque des revendications 1 à 3, où la composition détergente est caractérisée en outre par un ingrédient choisi dans le groupe constitué de : additifs organiques d'agents tensioactifs non ioniques choisis dans le groupe constitué de triacétate de glycérol, citrate d'acétyl-triéthyle ou leurs mélanges, enzymes, matériaux de type amine quaternaire éthoxylée et leurs mélanges.
  5. Composition détergente liquide aqueuse selon l'une quelconque des revendications 1 à 4, où la composition détergente inclut de 0,01 % à 10 % d'un agent pour le soin des tissus, choisi parmi le groupe des agents inhibant la décoloration et des polymères de maintien des teintures.
  6. Procédé de lavage de tissus salis, caractérisé par les étapes consistant à mettre en contact ledit tissu dans une solution aqueuse de lavage du linge avec une composition détergente liquide selon l'une quelconque des revendications 1 à 5.
EP06122351A 1999-08-10 2000-08-08 Compositions détergentes comportant des hydrotropes Expired - Lifetime EP1754774B1 (fr)

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US15634099P 1999-09-27 1999-09-27
US18812300P 2000-03-09 2000-03-09
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US15023306P 2006-08-23 2006-08-23
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ES2323353B1 (es) * 2008-01-11 2010-04-21 Juan Perez Montalt Producto semisolido para la limpieza y rehabilitacion superficial de multi-materiales y su uso.
JP6220652B2 (ja) * 2013-11-26 2017-10-25 日華化学株式会社 医療器具用洗浄剤組成物
EP3101100B1 (fr) 2015-06-05 2018-02-07 The Procter and Gamble Company Composition détergente liquide concentrée pour le lavage du linge

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