Classifications

• • C—CHEMISTRY; METALLURGY
  • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
  • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
  • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
  • C11D3/16—Organic compounds
  • C11D3/37—Polymers
  • C11D3/3703—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
  • C11D3/3715—Polyesters or polycarbonates
• • C—CHEMISTRY; METALLURGY
  • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
  • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
  • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
  • C11D3/02—Inorganic compounds ; Elemental compounds
  • C11D3/12—Water-insoluble compounds
  • C11D3/124—Silicon containing, e.g. silica, silex, quartz or glass beads
  • C11D3/1246—Silicates, e.g. diatomaceous earth
  • C11D3/1253—Layer silicates, e.g. talcum, kaolin, clay, bentonite, smectite, montmorillonite, hectorite or attapulgite
  • C11D3/1266—Layer silicates, e.g. talcum, kaolin, clay, bentonite, smectite, montmorillonite, hectorite or attapulgite in liquid compositions

Definitions

• the present invention relates to stable concentrated liquid detergent compositions containing a clay softening system. More in particular, the present invention relates to softening through the wash liquid detergent compositions comprising a clay softening system and specific modified soil release polymers.
• Liquid detergent compositions providing fabric softening throughout the wash cycle have been described in art.
• clays are well known as fabric softening agents through the wash.
• the relative ability of the softening clays to meet various performance criteria is very much depending on the presence and concentration of adjunct detergent ingredients.
• adjunct detergent ingredient is the presence of soil release polymers.
• Said soil release polymers when used even at low concentrations, interact strongly with the clay, resulting in loss in performance of the soil-release polymer, flocculation of the clay and problems with physical stability of the liquid detergent.
• Concentrated liquids contain a lower amount of water compared to conventional liquid detergents. This results in an increase in electrolyte and solids levels in these liquid detergent formulas.
• Another change is the dependence on non-aqueous solvents to aid in the solubilization of detergent components.
• liquid softening-through-the-wash detergent composition comprising a clay softening system in combination with specific modified polyesters. It has now been surprisingly found that the specific modified polyesters according to the present invention are fully compatible with the clay-softening system. This finding allows us to formulate liquid detergent compositions which have both excellent softening and cleaning performance.
• the present invention relates to concentrated liquid detergents comprising a clay-softening system and specific modified polyesters. All percentages, ratios herein are by weight, unless otherwise specified.
• the present invention relates to concentrated liquid detergents, in such case, the liquid detergent compositions according to the present invention will contain a lower amount of water, compared to conventional liquid detergents.
• the level of water in the concentrated liquid detergents of the present invention is less than 50%, preferably less than 40% by weight of the total detergent composition.
• the clay softening system hereof will comprise a fabric softening clay present in an amount of at least 0.5%, preferable from 4% to 30% by weight of the detergent composition.
• the preferred clays are of the smectite type. Smectite type clays are widely used as fabric softening ingredients in detergent compositions. Most of these clays have a cation exchange capacity of at least 50 meq./100g.
• Smectite clays can be described as three-layer expandable materials, consisting of alumino-silicates or magnesium silicates.
• smectite-type clays There are two distinct classes of smectite-type clays; in the first, aluminium 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 A1 2 (Si 2 0 5 ) 2 (OH) 2 and Mg 3 (Si 2 O 5 ) (OH) 2 , for the aluminium and magnesium oxide type clay, respectively.
• the range of the water of hydration can vary with the processing to which the clay has been subjected.
• atom substitution by iron and magnesium can occur within the crystal lattice of the smectites, while metal cations such as Na + , Ca 2+ , as well as H + can be co-present in the water of hydration to provide electrical neutrality.
• 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 equilibrium exchange reactions with cations present in aqueous solutions.
• one equivalent weight of solution cation replaces an equivalent of sodium, for example, and it is customary to measure clay cation exchange capacity in terms of milliequivalents per 100g. of clay (meq/100g.).
• the cation exchange capacity of clays can be measured in several ways, including electrodialysis, by exchange with ammonium ion followed by titration, or by a methylene blue procedure, all as set forth in Grimshaw, The Chemistry and Physics of Clays, Interscience Publishers, Inc. pp. 264-265(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 determinated 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.
• Illite clays have an ionexchange capacity somewhere in the lower portion of the range, ca. 26 meq/100 g. for an average illite clay.
• illite and kaolinite clays are not useful in the instant compositions. Indeed such illite and kaolinite clays constitute a major component of clay soils.
• smectites such as nontronite having an ionexchange capacity of approximately 50 meq/100 g.
• saponite which has an ion exchange capacity greater than 70 meq/100g.
• the smectite clays commonly used for this purpose herein are all commercially available. Such clays include, for example, montmorillonite, volchonskoite, nontronite, hectorite, saponite, sauconite, and vermiculite.
• the clays herein are available under commercial names such as "fooler clay” (clay found in a relatively thin vein above the main bentonite or montmorillonite veins in the Black Hills) and various tradenames such as Thixogel #1 (also, “Thixo-Jell”) and Gelwhite GP from Georgia Kaolin Co.
• smectite-type minerals obtained under the foregoing commercial and tradenames can comprise mixtures of the various discrete mineral entitites. Such mixtures of the smectite minerals are suitable for use herein.
• Preferred for use herein are the montmorrillonite clays.
• the value of (x+y) is the layer charge of the hectorite clay.
• hectorite clays are preferably selected on the basis of their layer charge properties, i.e. at least 50% is in the range of from 0.23 to 0.31.
• hectorite clays of natural origin having a layer charge distribution such that at least 65% is in the range of from 0.23 to 0.31.
• the hectorite clays suitable in the present composition should preferably be sodium clays, for better softening activity.
• Sodium clays are either naturally occuring, or are naturally-occuring calcium-clays which have been treated so as to convert them to sodium-clays. If calcium-clays are used in the present compositions, a salt of sodium can be added to the compositions in order to convert the calcium clay to a sodium clay. Preferably, such a salt is sodium carbonate, typically added at levels of up to 5% of the total amount of clay.
• hectorite clays suitable for the present compositions include Bentone EW and Macaloid, from NL Chemicals, N.J., U.S.A., and hectorites from Industrial Mineral Ventures.
• the clay softening system herein can comprise clay-flocculating agents.
• the compositions herein may comprise, from 0.05% to 20% by weight of the clay, of flocculating agent, if its molecular weight is 100.000-800.000.
• Preferred molecular weight of the flocculating agent is 150.000-300.000.
• Most of these materials are fairly long chain polymers and copolymers derived from such monomers as ethylene oxide, acrylamide, acrylic acid, dimethylamino ethyl methacrylate, vinyl alcohol, vinyl pyrrolidone, ethylene imine. Gums, like guar gum, are suitable as well.
• polymers of ethylene oxide, acryl amide, or acrylic acid are preferred.
• the polymers should be fairly long chain, i.e., have a weight average molecular weight of at least 100,000.
• weight average molecular weight of the polymers should not exceed 10 million.
• the detergent compositions herein also essentially contain from 0.01 to 2%, preferably from 0.05 to 0.5 by weight of a modified polyester.
• Modified polyesters herein are substantially linear end-capped esters having molecular weight ranging from 500 to 5000, preferably from 1000 to 3500; said ester consisting essentially of, on a molar basis :
• polyesters are described in the Applicants copending application USSN 08/088705.
• Preferred polyesters herein are random copolymers of dimethyl terephtalate, dimethyl sulfoisophtalate, ethylene glycol and 1-2 propane diol, the end groups consisting primarily of sulphobenzoate and secondarily of mono esters of ethylene glycol and/or propane-diol.
• the target being to obtain is a polymer capped at both end by sulphobenzoate groups, "primarily", in the present context most of said copolymers herein will be end-capped by sulphobenzoate groups.
• some copolymers will be less than fully capped, and therefore their end groups may consist of monoester of ethylene glycol and/or propane 1-2 diol, thereof consist “secondarily” of such species.
• polyesters herein contain about 46% by weight of dimethyl terephtalic acid, about 16% by weight of propane -1.2 diol, about 10% by weight ethylene glycol, about 13% by weight of dimethyl sulfobenzoid acid and about 15% by weight of sulfoisophtalic acid, and have a molecular weight of about 3500.
• the polyesters and their method of preparation are described in detail in EPA 311 342.
• the liquid detergent composition may comprise one or more of a surfactant selected from a wide range of surfactants.
• alkyl sulfate surfactants hereof are water soluble salts or acids of the formula ROSO 3 M wherein R preferably is a C 10 -C 24 hydrocarbyl, preferably an alkyl or hydroxyalkyl having a C 10 -C 18 alkyl component, more preferably a C 12 -C 15 alkyl or hydroxyalkyl, and M is H or a cation, e.g., an alkali metal cation (e.g. sodium, potassium, lithium), or ammonium or substituted ammonium (e.g.
• R preferably is a C 10 -C 24 hydrocarbyl, preferably an alkyl or hydroxyalkyl having a C 10 -C 18 alkyl component, more preferably a C 12 -C 15 alkyl or hydroxyalkyl
• M is H or a cation, e.g., an alkali metal cation (e.g. sodium, potassium, lithium), or ammonium or substituted
• alkylamines such as ethylamine, diethylamine, triethylamine, and mixtures thereof, and the like.
• Branched alkylsulfates are especially preferred.
• Preferred anionic surfactants include alkyl alkoxylated sulfate surfactants hereof are water soluble salts or acids of the formula RO(A) m SO3M wherein R is an unsubstituted C 10 -C 24 alkyl or hydroxyalkyl group having a C 10 -C 24 alkyl component, preferably a C 12 -C 18 alkyl or hydroxyalkyl, more preferably C 12 -C 15 alkyl or hydroxyalkyl, A is an ethoxy or propoxy unit, m is greater than zero, typically between about 0.5 and about 6, more preferably between about 0.5 and about 3, and M is H or a cation which can be, for example, a metal cation (e.g., sodium, potassium, lithium, calcium, magnesium, etc.), ammonium or substituted-ammonium cation (e.g.
• R is an unsubstituted C 10 -C 24 alkyl or hydroxyalkyl group having a C
• alkylamines such as ethylamine, diethylamine, triethylamine, and mixtures thereof, and the like.
• alkyl ethoxylated sulfates as well as alkyl propoxylated sulfates are contemplated herein.
• substituted ammonium cations include methyl-, dimethyl, trimethyl-ammonium cations and quaternary ammonium cations such as tetramethyl-ammonium and dimethyl piperdinium cations and those derived from alkylamines such as ethylamine, diethylamine, triethylamine, mixtures thereof, and the like.
• Exemplary surfactants are C 12 -C 15 alkyl polyethoxylate (1.0) sulfate (C 12 -C 15 E(1.0)M), C 12 -C 15 alkyl polyethoxylate (2.25) sulfate (C 12 -C 15 E(2.25)M), C 12 -C 15 alkyl polyethoxylate (3.0) sulfate (C 12 -C 15 E(3.0)M), and C 12 -C 15 alkyl polyethoxylate (4.0) sulfate (C 12 -C 15 E(4.0)M), wherein M is conveniently selected from sodium and potassium.
• alkyl ester sulfonate surfactants including linear esters of C 8 -C 20 carboxylic acids (i.e., fatty acids) which are sulfonated with gaseous SO 3 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.
• the preferred alkyl ester sulfonate surfactant especially for laundry applications, comprise alkyl ester sulfonate surfactants of the structural formula : wherein R 3 is a C 8 -C 20 hydrocarbyl, preferably an alkyl, or combination thereof, R 4 is a C 1 -C 6 hydrocarbyl, preferably an alkyl, or combination thereof, and M is a cation which forms a water soluble salt with the alkyl ester sulfonate.
• Suitable salt-forming cations include metals such as sodium, potassium, and lithium, and substituted or unsubstituted ammonium cations, such as monoethanolamine, triethanolamine.
• R 3 is C 10 -C 16 alkyl
• R 4 is methyl, ethyl or isopropyl.
• methyl ester sulfonates wherein R 3 is C 10 -C 16 alkyl.
• anionic surfactants useful for detersive purposes can also be included in the laundry detergent compositions of the present invention.
• These can include salts (including, for example, sodium, potassium, ammonium, and substituted ammonium salts such as mono-, di- and triethanolamine salts) of soap, C 9 -C 20 linear alkylbenzenesulfonates, C 8 -C 22 primary of secondary alkanesulfonates, C 8 -C 24 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 oleyl 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 C 12 -C 18 monoesters) and diesters of sulfosuccinates (especially saturated and unsaturated C 6 -C 12 diesters), sulfates of alkylpolysaccharides such as the sulfates of alkylpolyglucoside
• 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 tall 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).
• the laundry detergent compositions of the present invention typically comprise from about 1% to about 40%, preferably from about 5% to about 25% by weight of such anionic surfactants.
• Highly preferred nonionic surfactants are poly hydroxy fatty acid amide surfactants of the formula wherein R 1 is H, or R 1 is C 1-4 hydrocarbyl, 2-hydroxy ethyl, 2-hydroxy propyl or a mixture thereof, R 2 is C 5-31 hydrocarbyl, and Z is a polyhydroxyhydrocarbyl having a linear hydrocarbyl chain with at least 3 hydroxyls directly connected to the chain, or an alkoxylated derivative thereof.
• R 1 is methyl
• R 2 is a straight C 11-15 alkyl or alkenyl chain such as coconut alkyl or mixtures thereof
• Z is derived from a reducing sugar such as glucose, fructose, maltose, lactose, in a reductive amination reaction.
• compositions of the present invention may comprise amine oxide in accordance with the general formula I: R 1 (EO) x (PO) y (BO) z N(O)(CH 2 R') 2 .qH 2 O (I)
• the structure (I) provides one long-chain moiety R 1 (EO) x (PO) y (BO) z and two short chain moieties, CH 2 R'.
• R' is preferably selected from hydrogen, methyl and -CH 2 OH.
• R 1 is a primary or branched hydrocarbyl moiety which can be saturated or unsaturated, preferably, R 1 is a primary alkyl moiety.
• R 1 is a hydrocarbyl moiety having chainlength of from about 8 to about 18.
• R 1 may be somewhat longer, having a chainlength in the range C 12 -C 24 .
• amine oxides are illustrated by C12-14 alkyldimethyl amine oxide,hexadecyl dimethylamine oxide, octadecylamine oxide and their hydrates, especially the dihydrates as disclosed in U.S. Patents 5,075,501 and 5,071,594, incorporated herein by reference.
• the invention also encompasses amine oxides wherein x+y+z is different from zero, specifically x+y+z is from about 1 to about 10, R 1 is a primary alkyl group containing 8 to about 24 carbons, preferably from about 12 to about 16 carbon atoms; in these embodiments y + z is preferably 0 and x is preferably from about 1 to about 6, more preferably from about 2 to about 4; EO represents ethyleneoxy; PO represents propyleneoxy; and BO represents butyleneoxy.
• amine oxides can be prepared by conventional synthetic methods, e.g., by the reaction of alkylethoxysulfates with dimethylamine followed by oxidation of the ethoxylated amine with hydrogen peroxide.
• Preferred embodiments include dodecyldimethylamine, tetradecyldimethylamineoxidedihydrate,hexadecyldimethylamin eoxidedihydrate and octadecyldimethylamine oxide dihydrate.
• R' H
• R' CH 2 OH
• hexadecylbis(2- hydroxyethyl)amine oxide such as hexadecylbis(2- hydroxyethyl)amine oxide, tallowbis(2-hydroxyethyl)amine oxide, stearylbis(2-hydroxyethyl)amine oxide and oleylbis(2- hydroxyethyl)amine oxide, dodecyldimethyl(2- hydroxyethyl)amine oxide dihydrate.
• Suitable nonionic surfactants comprises alkyl polyglucoside compounds of general formula RO (C n H 2n O) t Z x wherein Z is a moiety derived from glucose; R is a saturated hydrophobic alkyl group that contains from 12 to 18 carbon atoms; t is from 0 to 10 and n is 2 or 3; x is from 1.3 to 4, the compounds including less than 10% unreacted fatty alcohol and less than 50% short chain alkyl polyglucosides.
• Compounds of this type and their use in detergent are disclosed in EP-B 0 070 077, 0 075 996 and 0 094 118.
• the laundry detergent compositions of the present invention typically comprise nonionic surfactants in the weight ratio of anionic surfactant to nonionic surfactant from 6:1 to 1:3, preferably from 5:1 to 2:1.
• Cationic detersive surfactants suitable for use in the laundry detergent compositions of the present invention are those having one long-chain hydrocarbyl group.
• cationic surfactants include the ammonium surfactants such as alkyldimethylammonium halogenides, and those surfactants having the formula : [R 2 (OR 3 ) y ][R 4 (OR 3 ) y ] 2 R 5 N+X- wherein R 2 is an alkyl or alkyl benzyl group having from about 8 to about 18 carbon atoms in the alkyl chain, each R 3 is selected from the group consisting of -CH 2 CH 2 -, - CH 2 CH(CH 3 )-, -CH 2 CH(CH 2 OH)-, -CH 2 CH 2 CH 2 -, and mixtures thereof; each R 4 is selected from the group consisting of C 1 -C 4 alkyl, C 1 -C 4 hydroxyalkyl, benzyl ring structures formed by joining the two R 4 groups,
• Preferred cationic surfactants are the water-soluble quaternary ammonium compounds useful in the present composition having the formula : R 1 R 2 R 3 R 4 N + X - (i) wherein R 1 is C 8 -C 16 alkyl, each of R 2 , R 3 and R 4 is independently C 1 -C 4 alkyl, C 1 -C 4 hydroxy alkyl, benzyl, and -(C 2 H 4 0) x H where x has a value from 1 to 5, and X is an anion. Not more than one of R 2 , R 3 or R 4 should be benzyl.
• the preferred alkyl chain length for R 1 is C 12 -C 15 particularly where the alkyl group is a mixture of chain lengths derived from coconut or palm kernel fat or is derived synthetically by olefin build up or OXO alcohols synthesis.
• Preferred groups for R 2 R 3 and R 4 are methyl and hydroxyethyl groups and the anion X may be selected from halide, methosulphate, acetate and phosphate ions.
• the laundry detergent compositions of the present invention typically comprise from 0.5% to about 5%, preferably from about 1% to about 3% by weight of such cationic surfactants.
• compositions according to the present invention may further comprise a builder system.
• a builder system Any conventional builder system is suitable for use herein including aluminosilicate materials, silicates, polycarboxylates and fatty acids, materials such as ethylenediamine tetraacetate, metal ion sequestrants such as aminopolyphosphonates, particularly ethylenediamine tetramethylene phosphonic acid and diethylene triamine pentamethylenephosphonic acid.
• phosphate builders can also be used herein.
• Suitable polycarboxylates builders for use herein include citric acid, preferably in the form of a water-soluble salt, derivatives of succinic acid of the formula R-CH(COOH)CH2(COOH) wherein R is C10-20 alkyl or alkenyl, preferably C12-16, or wherein R can be substituted with hydroxyl, sulfo sulfoxyl or sulfone substituents.
• Specific examples include lauryl succinate , myristyl succinate, palmityl succinate2-dodecenylsuccinate, 2-tetradecenyl succinate.
• Succinate builders are preferably used in the form of their water-soluble salts, including sodium, potassium, ammonium and alkanolammonium salts.
• Other suitable polycarboxylates are oxodisuccinates and mixtures of tartrate monosuccinic and tartrate disuccinic acid such as described in US 4,663,071.
• Suitable fatty acid builders for use herein are saturated or unsaturated C10-18 fatty acids, as well as the corresponding soaps. Preferred saturated species have from 12 to 16 carbon atoms in the alkyl chain.
• the preferred unsaturated fatty acid is oleic acid.
• Another preferred builder system for liquid compositions is based on dodecenyl succinic acid and citric acid.
• Detergency builder salts are normally included in amounts of from 10% to 80% by weight of the composition preferably from 20% to 70% and most usually from 30% to 60% by weight.
• detergent compositions may be employed, such as enzymes and stabilizers or activators therefore, soil-suspending agents, abrasives, bactericides, tarnish inhibitors, coloring agents, foam control agents, corrosion inhibitors and perfumes.
• the perfumes either hydrophobic or hydrophillic can be incorporated in a porous material such as silica.
• a protected system is described in EP 583 512.
• enzyme technologies which also provide a type of color care benefit. Examples are cellulase for color maintenance/ rejuvenation.
• Other examples are the polymers disclosed in EP 92870017.8 filed January 31,1992 and enzyme oxidation scavengers disclosed in EP 92870018.6 filed January 31, 1992.
• a stable liquid detergent composition according to the present invention is prepared, having the following compositions : % by weight of the total detergent composition A B C D Linear alkylbenzene sulfonate 10 15 23 - Polyhydroxy fatty acid amide - 5 - 4 Alkyl alkoxylated sulfate - - - 3 Alkyl sulphate 2 2 4 13 C12-C14 dimethyl ammonium chloride 2 2 2 2 2 Fatty acid 8 8 10 17 Oleic acid 2 2 2 - Citric acid 2 1 1 1 1 Diethylenetriamine pentamethylene 1.5 1.5 1.5 1.5 Phosphonic acid NaOH 5 7 8 7 Propanediol 4 4 4 7 Ethanol 7 7 10 3 Ethoxylated tetraethylene pentamine 0.7 0.7 0.7 0.7 0.7 Thermamyl R 300 KNU/g 0.1 0.1 0.1 0.1 Carezyme R 5000 CEVU/g 0.02 0.02 0.02 0.02 0.02 Protease 40 mg/g 0.6 0.6
• compositions were very good at displaying excellent softening and cleaning performance.

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• 1995
  • 1995-07-14 EP EP95201942A patent/EP0753569A1/de not_active Withdrawn
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  • 1996-07-11 JP JP9506740A patent/JPH11509258A/ja active Pending
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