MXPA99004185A - Hand wash laundry detergent compositions containing a combination of surfactants and soil release polymer - Google Patents

Abstract

The subject invention involves laundry detergent compositions, preferably in granular form, particularly useful for machine laundry operations. The compositions comprise:a) from about 6%to about 18%surfactant comprising 1) from about 5%to about 10%anionic surfactant selected from alkylbenzene sulfonate surfactant, alkyl sulfate surfactant and alkyl ethoxy ether sulfate surfactant;2) from about 0.2%to about 4%hydroxyalkyl quaternary ammonium cationic surfactant;and 3) from 0.4%to about 8%nonionic surfactant selected from alkyl ethoxy alcohol surfactant, amine oxide surfactant, and polyhydroxy fatty acid amide surfactant;b) from about 0.05 to about 4%polymeric soil release agent comprising:1) from about 10%to about 99.5%esters comprising, per mole of said ester:i) from about 1 to about 2 moles of sulfonated polyethoxy/propoxy end-capping units;ii) from about 0.5 to about 66 moles of units selected from the group consisting of a) oxyethyleneoxy units;b) a mixture of oxyethyleneoxy and oxy-1,2-propyleneoxy units;and c) a mixture of a) or b) with poly(oxyethylene)oxy units;iii) from about 1.5 to about 40 moles of terephthaloyl units;and iv) from 0 to about 26 moles of 5-sulfoisophthaloyl units;2) from about 0. 5%to about 20%crystallization-reducing stabilizer selected from sulfonate-type hydrotrope, alkylbenzene sulfonate, paraffin sulfonate, and mixtures thereof;and c) from about 80%to about 94%other components.

Description

COMPOSITIONS DETERGENTS FOR OPA AVA WHICH CONTAIN A COMBINATION OF TENSITIVE AGENTS AND LIBERADOR DE SUCIEDAD POLYMER TECHNICAL FIELD The invention relates to laundry detergent compositions by hand containing a certain mixture of surfactants and soil release polymer.

BACKGROUND OF THE INVENTION Around the world, many people can clean fabrics with washing machines with compositions containing soap and / or detergent. Products that provide improved cleaning of fabrics are continually being sought after. It is an object of this invention to provide washing detergent compositions that provide superior cleaning performance in machine washing operations.

BRIEF DESCRIPTION OF THE INVENTION The invention involves washing detergent compositions, preferably in granular form, comprising: a) from 6% to 18% of surfactant comprising. 1) from 5% to 10% of anionic surfactant selected from alkylbenzene sulphonate surfactant, alkyl sulfate surfactant and azoethoxy ester sulfate surfactant having an average of 0.5 to 9 moles ethoxy per mole of surfactant; 2) from 0.2% to 2% of cationic hydroxyalkyl quaternary ammonium surfactant having the structure: R R '"R" mN + r where R is long chain alkyl, R 'is short chain alkyl, R "is H (OCH2CHB) p-, B is H or CH3, n is 0 to 3, m is 0 to 3, n + m is 3, p is 0.5 to 4, p times m is 0.5 to 4, and z is a water soluble anion, and 3) from 0.4% to 8% nonionic surfactant selected from alkylethoxy alcohol surfactant having an average of 0. 5 to 25 moles ethoxy per mole of surfactant, amine oxide surfactant, and fatty acid polyhydroxy amide surfactant; b) from 0.5 to 4% of polymeric soil release agent comprising: ) from 10% to 99.5% of esters comprising, by ester mole: i) from 1 to 2 moles of polyethoxy / propoxy end-chelating units of the formula (M? 3S) (CH2) m (CH2CH2?) (RO) ) n- wherein it is a salt-forming cation such as sodium or tetraalkylammonium, m is 0 or 1, R is ethylene, propylene or a mixture thereof, and n is from 0 to 2; and mixtures thereof; ii) from 0.5 to 66 moles of units selected from the group consisting of: a) oxyethyleneoxy units; b) a mixture of oxyethyleneoxy and oxy-1,2-propyleneoxy units having a molar ratio of oxytyleneneoxy to oxy-1,2-propiieneoxi from 0.5: 1 to 10: 1; and c) a mixture of a) or b) with poly (oxyethylene) oxy units wherein the poly (oxyethylene) oxy units have a degree of polymerization of 2 to 4; with the proviso that when said poly (oxyethylene) oxy units have a degree of polymerization of 2, the molar ratio of poly (oxyethylene) oxy units to the total units of group ii) is on the scale of 0: 1. at 0.33: 1; and when said poly (oxyethylene) oxy units have a degree of polymerization of 3, the molar ratio of the poly (oxyethylene) oxy units to the total units of group ii) is on a scale of 0: 1 a 0. 22:; and when said poly (oxyethylene) oxy units have a degree of polymerization of 4, the molar ratio of the poly (oxyethylene) oxy units to the total units of group ii) is on the scale from 0: 1 to 0.14: 1; iii) from 1.5 to 40 moles of tereptaloyl units, and iv) from 0 to 26 moles of 5-sulfoisophthaloyl units of the formula - (0) C (C6H) (S03) C (0) - wherein M is salt forming cation as an alkali metal or tetraalkylammonium ion; 2) from 0.5% to 20% > of crystallization reducing stabilizer selected from sulfonate-type hydrotrope, alkylbenzenesulfonate, paraffin sulphonate, and mixtures thereof; and c) 80% > to 94% of other components.

DETAILED DESCRIPTION OF THE INVENTION All percentages used herein are in percent by weight unless otherwise specified. As used herein, the term "alkyl" means a hydrocarbyl portion that is straight (linear) or branched, saturated or unsaturated; unless otherwise specified, the alkyl is preferably saturated ("alkanyl") or unsaturated with double bonds ("alkenyl"), preferably with one or two double bonds. As used in this "long chain alkyl" means alkyl having 8 or more carbon atoms, and "short chain alkyl" means alkyl having 3 or fewer carbon atoms. The term "bait" is used herein in relation to materials having alkyl mixtures derived from mixtures of fatty acid from bait that are typically linear and having an approximate distribution of carbon chain length of 2% Cu, 29% Cie, 23% C18, 2% palmitoleic, 41% oleic, and 3% iinoleic (the first three enlisted being saturated). Other mixtures with similar alkyl distribution, such as those from palm oil are those derived from various animal baits and lard and are also included within the term bait. The bait, as used herein, may also be hardened (i.e., hydrogenated) to convert some or all of the unsaturated alkyl portions to saturated alkyl moieties. The term "coco" is used herein in relation to materials having alkyl mixtures derived from fatty acid mixtures of coconut oil which are typically linear and have an approximate carbon chain length distribution of 8% Cs, 7% Cio, 48% C12, 17% Cu, 9% C1ß, 2% C18, 7% oleic, and 2% linoleic (the first six enlisted being saturated). Other mixtures with alkyl distribution Similar, such as palm kernel oil, and babassu oil, are included within the term coconut. The compositions of the present invention are preferably in solid, granular form, although other forms of washing detergents are also included.

Surfactants The compositions of the invention contain from 6% to 18% surfactant, preferably from 8% to 15% surfactant, more preferably from 10% to 14% surfactant, and more preferably from 11% to 13% of surfactant. As used herein, "alkylbenzene sulfonate" surfactant means a salt of aiquilbepcensulfonic acid with an alkyl portion that is linear or branched, preferably having an average chain length of 9 to 16 carbon atoms, more preferably 11 to 14 carbon atoms. The alkyl is preferably saturated. Branched and linear branched or branched alkylbenzene sulfonate is known as ABS. Linear alkylbenzene sulfonate, known as LAS, is more biodegradable than ABS, and is preferred for the subject compositions of the invention. The acid forms of ABS and LAS are referred to herein as HBS and HLAS, respectively. The alkylbenzene sulfonates and methods for making them are described in U.S. Patent Nos. 2,220,099 and 2,477,383, incorporated herein by reference. The alkylbenzenesulfonic acid salts are preferably the alkali metal salts, such as sodium and potassium, especially sodium. Alkylbenzenesulfopic acid salts also include magnesium and ammonium. A particularly preferred surfactant LAS has a saturated direct alkyl with an average of 11.5 to 12.5 carbon atoms, and is a sodium salt (Cn.5-C12.5 L.AS Na). As used herein, "the alkyl sulfate surfactant" or "AS" includes the salts of alkylsulfuric acid, with a straight, branched or linear, long chain alkyl, preferably having an average chain length of 10 to 18 carbon atoms, more preferably 12 to 15 carbon atoms. Especially preferred is the alkyl sulfate made by sulfating primary alcohol derived from coconut or tallow and mixtures thereof. Alkyl sulfate salts include sodium, potassium, lithium, ammonium, and alkylammonium salts. Preferred salts of alkyl sulfate are sodium and potassium salts, especially sodium. As used herein, "alkyl ether-sulfate ether surfactant" or "AES" has the following structure R "O (C2H0)? S? 3R." R "is long chain alkyl preferably having an average from 10 to 18, more preferably from 12 to 15, carbon atoms. R "is preferably saturated, R" 'is preferably linear. The "degree of ethoxylation" (the number of moles of ethoxy per mole of surfactant) is represents x, and is, on average, from 0.5 to 9, preferably from 1 to 7, more preferably from 2 to 5, especially 3. M is a water soluble cation, for example, an alkali metal cation (sodium, potassium, lithium), an alkaline earth metal cation (eg, calcium, magnesium), an ammonium or substituted ammonium cation. it is preferably sodium or potassium, especially sodium.

The compositions of the invention comprise from 5% to 10% of anionic surfactant selected from alkylbenzenesulfonate surfactant, alkyl sulfate surfactant, and alkyl ethoxy ether surfactant; The compositions herein preferably comprise from 6% to 9%, more preferably from 6.5% to 8.5%, more preferably still from 7% to 8% of such anionic surfactant. The anionic surfactant preferably comprises mepos50%, more preferably at least 80%, more preferably 100%, of alkylbenzene sulfonate surfactant. As used herein, "cationic hydroxyalkyl quaternary ammonium surfactant" or "HAQA" means a surfactant having the following structure R R 'nR "mN * Z". R is a long chain alkyl, linear or branched, preferably having a degree of 9 to 16, more preferably 12 to 14 carbon atoms. R is preferably saturated. R is preferably linear. R 'is a short chain alkyl having from 1 to 3 carbon atoms; R 'is preferably methyl or ethyl, especially methyl. R "is H (OCH2CHB) p"; wherein B is H or CH 3, preferably H; and p is about an average of 0.5 to 4, preferably 0.8 to 2, more preferably of. n is 0 to 3, preferably 1 or 2, more preferably 2. m is 0 to 3, preferably 1 or 2, more preferably 1. n + m is 3. p times m is 0.5 to 4 preferably 0.8 to 2, preferably 1. 27 is an anion soluble in water, such as halide, sulfate, methylsulfate, etiisulfate, phosphate, hydroxide, fatty acid, (laurate, myristate, palmitate, oleate, or estareate), or nitrate anion. Preferably to Z "is chloride, bromide, or iodide, especially chloride The compositions herein comprise from 0.2% to 2% of cationic HAQA surfactant preferably from 0.3% to 1.2% more preferably less than 1%, even more preferably 0.4% at 0.8%, more preferably still at 0.5% and 0.7% As used herein, "alkyl ethoxy alcohol nonionic surfactant" or "AE" means an ethoxylated fatty alcohol surfactant Such a surfactant preferably has an alkyl long chain, preferably has an average of 9 to 18, more preferably 12 to 15 carbon atoms.The alkyl is preferably saturated.The alkyl is preferably linear.For the surfactant AE, the "degree of ethoxylation" (number of moles of ethoxy per mole of surfactant) is, on average, from 0.5 to 25, preferably from 5 to 12, more preferably from 6 to 10, especially 7-9.

As used herein, "amine oxide surfactant" has the structure O R 1 (OR 2) x N (R 3) 2 wherein R is a long chain alkyl, preferably having an average of 10 to 18, more preferably from 12 to 16 carbon atoms; R2 is an alkylene or hydroxyalkylene containing 2 to 3 carbon atoms; x is from 0 to 3, preferably 0 or 1, more preferably 0; and each R3 is alkyl or hydroxyalkyl, preferably alkyl, having 1 to 3, preferably 1, carbon atoms. The preferred amine oxide surfactants are the aminyldimethylamine oxides. As used herein, "polyhydroxy fatty acid amine surfactant" has the formula OR R3-C-N- wherein R4 is long-chain alkyl, preferably has an average of 10 to 18, more preferably 12 to 16, carbon atoms; R 5 is C 1 -C β -hydroxyalkyl alkyl, or alkyloxyalkyo, preferably methyl; And V is a polyhydroxyhydrocarbyl portion preferably derived from reducing sugar. Suitable reducing sugars include glucose, fructose, maltose, lactose, galactose, mannose, and xylose. As materials Crudes for making such a surfactant, high dextrose corn syrup, high fructose corn syrup, and high maltose corn syrup can be used as well as the individual sugars listed above. These corn syrups can produce a mixture of sugar components for V. R -CO-N < it can be, for example, cocamide, stearamide, oleamide, lauramide, myristamide, capricamide, palmitamide, ceboamide, etc. The synthesis methods for producing polyhydroxy fatty acid amides are found in U.S. Patent 5,194,639 of March 18, 1993 to Conpor, Scheibel and / or Severson incorporated herein by reference. The compositions herein comprise from 0.4% to 8% nonionic surfactant selected from alkyl ethoxy alcohol surfactant, amine oxide surfactant, and polyhydroxy fatty acid amide surfactant; The compositions herein preferably comprise from 2% to 7%, more preferably from 3% to 6%, more preferably from 3.5% to 5%, of nonionic surfactant. Such a nonionic surfactant preferably comprises at least 50% more preferably at least 80%, more preferably still 100%, of alkyl ethoxy ether surfactant. Preferably, the weight ratio of the nonionic surfactant to the cationic surfactant HAQA is greater than 2, preferably greater than 4, and even more preferably greater than 5, and more preferably greater than 6.

The compositions herein preferably include only, or substantially only, the surfactants described herein above, as the surfactant system of the present compositions preferably consist essentially of, or consist essentially of, anionic surfactant selected from the group consisting of alkylbenzene sulfonate, alkylsulfate and surfactant of AES (more preferably alkylbenzenesulfonate surfactant); HAQA surfactant; and nonionic surfactant selected from the group consisting of surfactant AE, amine oxide surfactant, and polyhydroxy fatty acid amide surfactant (more preferably surfactant AE).

Polymeric dirt release agent The polymeric soil release agent, hereinafter "SRA" is included in the detergent compositions present comprising from 0.05% to 4%, preferably from 0.06% to 1.5%, more preferably from 0.08% to 0.7%, also preferably 0.16% at 0. 4%, also preferably from 0.07% to 0.14%, of SRA. The SRA typically has hydrophilic segments to hydrophilize the surface of hydrophobic fibers such as polyester and nylon, and hydrophobic segments to deposit on the hydrophobic fibers and remain adhered to them through the completion of the washing and rinsing cycles, thus serving as an anchor for the segments hydrophilic This may allow stains that occur subsequent to the treatment of fabrics with SRA to be more easily cleaned in the subsequent washing of the fabric. The SRA useful in the compositions of the present invention is described in U.S. Patent No. 5,415,807 to Gosseiink, Kellett and / or Hall of May 16, 1995, incorporated herein by reference. The SRA encompasses composition mixtures comprising oligomeric, substantially linear, polyethoxy / propoxy sulphonated esters, endblockers and crystallization reducing stabilizers. The esters used comprise oxytyleneneoxy units and terephthaloyl units. Further preferred esters comprise oxy-1, 2-propyleneoxy, sufoisophthalate and, optionally, poly (exyethylene) oxy units with polymerization degree from 2 to 4. The SRA useful herein is a mixture of such esters with reaction by-products. , crystallization reducing stabilizers, and the like, wherein the SRA contains from 10% to 99.5% of linear esters of blocked ends, preferably from 25% to 97%, more preferably from 50% to 94%, of such esters. The esters are of relatively low molecular weight (ie, generally below the scale of fiber-forming polyesters) typically ranging from 500 to 8,000. The excellent SRA compositions are those in which at least 50% by weight of said ester has a molecular weight in the range of 500 to 5,000 and the SRA comprises at least 3% of said crystallization reducing stabilizer.

Taken in its broadest aspect, the SRA encompasses an oligomeric ester "of base structure" which is blocked on one, or preferably both, ends of the base structure by the essential end blocking units. The essential end blocking units are anionic hydrophilic derivatives of polyethoxy / propoxysulfonated groups and connected to the esters by an ester linkage. Certain uncharged arylcarbonyl hydrophobic units are essential in the base structure unit of the oligoester. Preferably, these are exclusively terephthaloyl units. Other hydrophobic, uncharged dicarbonyl units, such as isophthaloyl, adipoyl or the like, may also be present if desired, provided that the dirt release properties of the esters (especially the substantivity of the polyester) are not significantly reduced. It is also possible to optionally incorporate additional hydrophilic units within the main structure units of said esters. For example, hydrophilic anion units capable of forming two ester bonds can be used. Suitable anionic hydrophilic units of this typical specific are well illustrated by sulfonated dicarbonyl units, such as sulfoisophthaloyl, ie - (0) C (CßH3) S03M) C (0) - wherein M is a salt-forming cation as an ion of alkali metal or tetraalkhamium.

Generally, if one wishes to modify the units of the esters, the use of additional hydrophilic units is preferable to the use of additional non-charged hydrophobic units. The preferred esters of the SRA comprise, per mole of said ester: i) from 1 to 2 moles of sulphonated end-poiy-ethoxy / propoxy blockers of the formula (M03S) (CH2) m (CH2CH2?) (RO) n- wherein M is a salt-forming cation such as sodium or tetraalkylammo p, m is 0 or 1, R is ethylene, propylene or a mixture thereof, and n is from 0 to 2; and mixtures thereof; ii) from 0.5 to 66 moles of units selected from the group consisting of: a) oxyethyleneoxy units; b) a mixture of oxyethyleneoxy and oxy-1,2-propyleneoxy units wherein said oxyethyleneoxy units are present in a molar ratio of oxyethyleneoxy to oxy-1,2-propyleneoxy in the range of 0.5: 1 to 10: 1; and c) a rocking of a) or b) with poly (oxyethylene) oxy units where said poly (oxyethylene) oxy units have a degree of polymerization of 2 to 4; with the proviso that when said poly (oxyethylene) oxy units have a degree of polymerization of 2, the molar ratio of poly (oxyethylene) oxy units to the total units of group ii) is on a scale of 0: 1 to 0.33: 1; and when said poly (oxyethylene) oxy units have a degree of polymerization of 3, the molar ratio of poly (oxyethylene) oxy units to the total units of the group ii) is on a scale of 0: 1 to 0.22: 1; and when said poly (oxyethylene) oxy units have a degree of polymerization of 4, the molar ratio of poly (oxyethylene) oxy units to the total units of group ii) is in the range from 0: 1 to 0.14: 1; i¡¡) from 1.5 to 40 moles of terephthaloyl units; and iv) from 0 to 26 moles of 5-sulfoisophthaloyl units of the formula - (0) C (C 6 H) (S 0 3 M) C (0) - wherein M is a salt forming cation such as alkali metal ion or tetraalkylammonium ion. Preferred endblocking units of the esters are of the formula (M03S) (CH2) m (CH2CH20) (RO) n- where M is a salt-forming cation such as sodium or tetraalquiamopium, m is 0 or 1, R is ethylene, propylene, or a mixture thereof, and n is from 0 to 2; and mixtures thereof. The end blocking units are more preferably 2- (2-hydroxyethoxy) ethanesulfonate, sodium. Preferred end blocking esters are essentially in the form of double end blockers, comprising two moles of said end blocking units per mole of ester. The "base structure" of the ester of the soil release agent, by definition, comprises all units except those of the end blocking units; all the units incorporated within the ester being interconnected by means of ester bonds. Preferably, in embodiments wherein the ester base structure comprises only terephthaloyl units and oxyethyleneoxy units, the units terephthaloyl iii) are on the scale of one to 10 moles per ester. In preferred embodiments incorporating oxy-, 2-propyleneoxy units, the base structure of the ester comprises terephthaloyl, oxyethyleneoxy, and oxy-1,2-propyleneoxy units; The molar ratio of the last two types of units is on a scale of 0.5: 1 to 10: 1. In yet another highly preferred embodiment, hydrophilic units such as 5-sulfoisophthaloyl are present in the base structure and generally comprise from 0.05 to 26 moles per mole of said ester. The poly (oxyethylene) oxy units, which aid in the dissolution rate of the ester, typically constitute from 0 to 25 mole percent of the total oxyalkylenoxy units per ester depending on the degree of polymerization of the poly (oxyethylene) oxy units and the length of the base structure of the ester. The SRA of the subject is well illustrated by one comprising at least 25% ester having the empirical formula: (CAP) x (EG / PG) and (T) z wherein (CAP) represents the sodium salt form of the end blocking units i); (EG / PG) represents oxyethyleneoxy units, oxy-1, 2-propiIenoxi units, and poly (oxyethylene) oxy units ii); (T) represents the terephthaloiion units iii); x is from 1 to 2; and it is from 0.5 to 7; z is from 1.5 to 7; wherein x, y, and z represent the average number of moles of the corresponding units per mole of said ester. More preferably in esters of this type, the mole ratio of oxyethyleneoxy: oxy-1,2-propyleneoxy is on a scale of 1: 1 to 10: 1; x is 2, and is from 1 to 6, and z is from 2 to 6. The base structure of the esters herein is preferably modified by the incorporation of hydrophilic as 5-sulfoisophthalate. A preferred SRA comprises at least 25% ester having the empirical formula: (CAP) x (EG / PG) and (T) z (SIP) q where (CAP), (EG / PG), and (T) are as defined above and (SIP) represents the sodium sai form of 5-sulfoisophthaloyl units iv); x is from 1 to 2; and it is from 0.5 to 66; z is from 1.5 to 40; what is 0. 5 to 26; the mole ratio of oxyethyleneoxy: oxy-1,2-propyleneoxy is on a scale of 0.5: 1 to 10: 1; wherein x, y, z and q represent the average number of moles of the corresponding units per mole of said ester. More preferably in esters of this type, EG: PG is from 1: 1 to 5: 1, x is 2, and is from 3 to 18, z is from 3 to 15, and q is from 0.5 to 4; more preferably still x is 2, and is 5, z is 5, and q is 1. The SRA also comprises certain crystallization reducing stabilizers selected from the group consisting of: 1) sulphonate type hydrotrope selected from the group consisting of: a) (R1) nAr-S03M; b) (R2) Ar (S03M) -0- (R2) Ar (S03M); and c) mixtures thereof; wherein Ar is an aromatic hydrocarbon group, preferably phenyl, each R1 is hydrogen or a C1-C4 alkyl group, each R2 is a C1-C13 alkyl group, n is 0 to 3, and M is a alkali metal or tetraalkylammonium ion; 2) Alkali metal and tetraalkylammonium salt of linear and branched alkyl benzene sulfonate wherein the alkyl group is C5 to Cie, preferably from C10 to C1; 3) Alkyl chain sulfonate including paraffin sulfonate and other variations of thermally stable alkyl sulfonate such as olefin sulfonate and beta alkoxysulfonate, with 4 to 20 carbon atoms, with the proviso that the alkylsulfonate is substantially free of substituents capable of enter esterification / transesterification reactions under the conditions used to form the soil release agent; and 4) mixtures thereof The stabilizers can be integrated into the soil release agent to reduce the substantial difficulties attributable to undesirable crystallization of the oligomer during the preparation and / or after the introduction into the washing liquid. Oligomers with higher ratios of oxytelenoxy units to oxy-1,2-propyleneoxy (EG / PG) in the structure of the base structure are especially susceptible to crystallization.

The SRA preferably comprises, in addition to the ester, from 0.5% to 20% of crystallization reducing stabilizer selected from sulphonate type hydrotope, alkylbenzene sulfonate, paraffin sulphonate, and mixtures thereof. The preferred SRA comprises from 3% to 18%, more preferably from 6% to 15% or, more preferably still from 9% to 13% of said stabilizers. A preferred SRA that has an oiigomer with the empirical formula (CAP) 2 (EG / PG) 5 (T) 5 (SIP)? with 12% linear sodium dodecylbenzenesulfonate as a stabilizer, designated as SRA-1 herein, is made as described in Example V of U.S. 5.415.807, columns 19-20. In it, an ester composition is made from sodium 2- (2-hydroxyethoxy-Jetanesulfonate, dimethyl terephthalate, salt of sodium dimethyl 5-sulfoisophthalate, ethylene glycol and propylene, with the integration of 12% of sodium dodecylbenzenesulfonate. linear as a stabilizer The ratio of ethylene glycol to propylene glycol incorporated in the oligomer is 2.1: 1. To a 250 ml, three-necked, round-bottomed vessel equipped with a magnetic stirring bar, modified Claisen head, condenser ( set for distillation), thermometer and temperature controller (THERM-0-WATCH®, 2R) is added sodium 2- (2-hydroxyethoxy) ethanesulfonate (18.4 g, 0.096 mol) (prepared as in US Patent Example 1 4,415,8077), dimethyl terephthalate (Aldrich, 46.5 g, 0.240 moles), salt of dimethyl 5-sulfoisophthalate sodium (Aldrich, 14.2 g, 0.048 moles), ethylene glycol (Baker, 89.2 g, 1.44 moles), propylene glycol (Baker , 109.4 g, 1.44 moles) monobutyl hydrated tin oxide (M &T; T Chemicals, 0.47 g. 2% of the total prisoner of the reaction), sodium acetate (MCB, 0.98 g, 2 mol% salt of dimethyl 5-sulfoisophthalate, sodium). SIPONATE LDS-10® (Alcolac, linear sodium dodecylbenzenesulfonate, 10.0g, vacuum drying, 12% of the final weight of the oligomer), and silicone oil (DOW-710®, 0.08 g, 0.1% of the final weight of the ollgomero) . This mixture is heated to 180 ° C and maintained at that temperature overnight under argon as the methanol and water are distilled from the reaction vessel. The material is transferred to a 100 ml, single-neck, round-bottomed container and heated gradually for 20 minutes at 240 ° C in a Kugeirohr (Aldrich) apparatus at 0.5 mm Hg and held there for 5 hours. The reaction vessel is then allowed to cool by air quite rapidly at room temperature under vacuum (approximately 30 minutes). The reaction affords 56 g of the desired oligomer as an opaque green solid.

Other components The compositions of the present invention comprise from 81% to 94%, preferably from 84% to 92%, more preferably from 86% to 90%, of other components commonly used in laundry detergent products. A typical list of the types and species of other surfactants, detergency builders and other ingredients that may be included in the compositions of this subject appear in the U.S. Patent. No. 3,664,961, to Norris of May 23, 1972, incorporated herein by reference and EP 550, 652, of April 16, 1992. The following are representative of such materials, inmate are not designed to be limiting.

Detergency Meters The compositions of the present invention optionally but preferably comprise builders that help control mineral hardness. Inorganic as well as organic builders can be used. Builders are typically used in fabric washing compositions to aid in the removal of particulate soils. The level of builder can vary widely depending on the final use of the composition and its desired physical form. Inorganic builders include, but are not limited to, alkali metal, ammonium and alkanolammonium salts of polyphosphates (illustrated by tripolyphosphates, pyrophospates and polymeric vitreous meta-phosphates), phosphonates, silicates, carbonates, (including bicarbonates and sesquicarbonates) ) and aluminosilicates. Non-phosphate builders are required in some locations. In situations where phosphorus-based detergency builders can be used, different alkali metal phosphates such as well-known sodium tripolyphosphates (STPP), sodium pyrophosphates (TSPP) and sodium orthophosphates can be used.; STPP and TSPP are preferred, especially STPP. The builders of detergency phosphonate such as ethane-1-hydroxy-1, 1-disphosphonate and other known phosphonates (See, for example U.S. Patents, 3,159,581, 3,213,030, 3,422,021, 3,400,148 and 3,422,137) can also be used. Examples of silicate detergency builders are alkali metal silicates, particularly those having a SI02: Na20 in the scale 1.6: 1 to 3.2: 1, preferably 1.6: 1; and stratified silicates, such as the sodium layered silicates described in U.S.

Patent 4,664,839 of May 12, 1987 to Rieck. Other silicates may also be useful, such as, for example, magnesium silicate, which may serve as a tightening agent in granular formulations, as a stabilizing agent for oxygen bleaches, and as a component of foam control systems. Examples of carbonate builders are alkali metal carbonates and bicarbonates. The preferred one is sodium carbonate. The aluminosilicate builders are useful in the subject compositions. Aluminum aluminosilicate builders are of great importance in many granular detergent compositions currently sold. The aluminiosilicate builders include those that have the empirical formula Mz (2Al? 2) and. vH? Or where z and y are integers of at least 6, the molar relation of z to y is on the scale from 1.0 to 0.5, and v is an integer from 15 to 264.

Useful aluminosilicate ion exchange materials are commercially available. These alumiposilicates can be crystalline or amorphous in structure and can be aluminosilicates that occur naturally or synthetically derived. A method for producing aluminosilicate ion exchange materials is described in U.S. Patent 3,985,669, Krummel et al., October 12, 1976. The preferred synthetic crystalline aluminosilicate ion exchange materials useful herein are available under the designations Zeolite A. Zeolite P (B), Zeolite MAP and Zeoite X. In an especially preferred embodiment, the crystalline aluminosilicate ion exchange material has the formula Nai2 ((AI02) i2 (S02) 12) -vH20 where v is from 20 to 30, especially 27 This material is known as Zeolite A. Dehydrated zeolites (v = 0-10) can also be used. Preferably, the aluminosilicate has a particle size of 0.1-10 microns in diameter. Organic builders suitable for the subject compositions include, but are not restricted to, a wide variety of polycarboxylate compounds. As used herein, "polycarboxylate" refers to compounds having a plurality of carboxylate groups, preferably at least three carboxylates. Preferred polycarboxylate builders include citrates, succinates and oxydisuccinate. The polycarboxylate builders can generally be added to the compositions in acid form, but can also be added in the form of neutralized salts, such as sodium.

The compositions of the present invention comprise from 0% to 80% builder, preferably from 10% to 70%, more preferably from 20% to 60%, and more preferably still from 30% to 50%.

The subject compositions preferably comprise from 5% to 40%, more preferably from 10% to 30%, more preferably from 15% to 25%, of STPP. The subject compositions preferably comprise 2% a % sodium carbonate, more preferably 5% to 25%, more preferably still 10% to 20%. The compositions herein preferably comprise from 0% to 1% silicate, more preferably from 3% to 10%, and more preferably still from 5% to 8%.

Amaltants The detergent compositions herein may also optionally contain one or more iron and / or manganese chelating agents. Such a chelating agent may be selected from the group consisting of aminocarboxylates, amiphosphonates, polyfunctionally substituted aromatic chelating agents and mixtures thereof. Without attempting to be attached to the theory, it is believed that the benefit of these materials is due in part to their exceptional ability to remove iron and manganese ions from the wash solutions by the formation of soluble chelators. This agent is also useful in bleaching stabilizing components of the present compositions.

Amipocarboxylates useful as optional chelating agents include ethylenediamine tetraacetates, N-hydroxyethylethylenediamine triacetates, nitrile triacetates, ethynediamine tetrapropionates, triethylenenetetramine hexaacetates, diethylenetriamine pentaacetates, and ethanol diglycins; the alkali metal, ammonium, and substituted ammonium salts thereof; and mixtures thereof. Amino phosphates are also suitable for use as chelating agents in the present compositions, when at least low levels of total phosphorus are allowed in detergent compositions. Preferably, these aminophosphonates do not contain alkanyl or alkenyl groups with more than 6 carbon atoms. Preferred aminophosphonates are diethylenetriamine penta (methylenephosphonic acid), ethylenediaminetetra (methylene phosphonic) acid, and mixtures and salts and complexes thereof. Particularly preferred are the sodium, zinc, magnesium, and aluminum salts and complexes thereof, and mixtures thereof. Preferably such salts or complexes have a molar ratio of metal ion to chelating molecule of at least 1: 1, preferably at least 2: 1.

Such a chelating agent can be included in the subject compositions at a level of 0% to 5%, preferably from 0.1% to 2%, more preferably from 0.2% to 1%, more preferably still from 0.3% to 0.5%. Magnesium sulfate can optionally be included in the compositions present as a stabilizer for the agents previous chelators. This is included at a level of 0% to 4%, preferably from 0.5% to 2%.

Polymeric dispersing agent The subject compositions preferably comprise a polymeric dispersing agent. The suitable polymeric dispersing agent includes polymeric polycarboxylates and polythylene glycols, although others known in the art may also be used. It is believed, although it is not desired to be limited by theory, that the dispersing polymeric agent improves the overall performance of the builder, when used in combination with other builders (including lower molecular weight polycarboxylate) by growth inhibition. of crystal, peptization of particle dirt release, and antiredeposition.

The polymeric polycarboxylate material can be prepared by polymerizing or copolymerizing suitable unsaturated monomers, preferably in their acid form. The unsaturated monomeric acids can be polymerized to form suitable polymeric polycarboxylates including 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 polycarboxylate of monomeric segments, which do not contain carboxylate radicals such as vinyl methyl ether, styrene, ethylene, etc., is adequate provided that such segments do not constitute more than 40% by weight.

Particularly suitable polymeric polycarboxylates can be derived from acrylic acid. Such acrillic acid-based polymers which are useful are the water-soluble salts of polymerized acrylic acid. The average molecular weight of such polymer in acid form is preferably in the range of 2,000 to 10,000, more preferably 4,000 to 7,000, and more preferably 4,000 to 5,000. The water-soluble salts of such an acrylic acid polymer may include, for example, the alkali metal, ammonium and substituted ammonium salts. Suitable polymers of this type are known materials. The use of polyacrylate of this type in detergent compositions has been described, for example, in Diehi, U.S. Patent 3,308,067 of March 7, 1987. The acrylic / maleic acid-based copolymer can also be used as a preferred component of the dispersing agent. Such a material includes the water-soluble salts of copolymer of acrylic acid and maleic acid (or maleic anhydride). The average molecular weight of such copolymer in acid form is preferably in the scale of 2., 000 to 100,000, more preferably from 4,000 to 80,000, more preferably from 7,000 to 65,000. The ratio of acrylate to maleate segments in such copolymer will generally be in the range of 30: 1 to 1: 1, more preferably 10: 1 to 2: 1. The water-soluble salts of such a co-polymer of acrylic acid / maieic acid may include, for example, the alkali metal, ammonium and substituted ammonium salts. The suitable acrylate / maleate copolymer of this type is known material which is described in European patent application 068 915 of December 15, 1982, as well as in EP 193 360 of September 3, 1986 which also describes such a polymer comprising hydroxypropylacrylate. Still other useful agents include the maleic / acrylic / vinyl alcohol terpolymers. Such a material is described in EP 193,360, including, for example, acrylic / maleic / vinyl alcohol terpolymer 45/45/10. Another polymeric material that can be included is polyethylene glycol (PEG). PEG can exhibit dispersing agent performance as well as act as a clay-antiredeposition soil removal agent. The typical molecular weight scale for this object is in the range of 500 to 100,000, preferably 1, 000 to 50,000, more preferably 1, 500 to 10,000. The dispersing agents of polyaspartate and polyglutamate can also be used, especially in conjunction with zeolite builders. Dispersing agents such as polyaspartate preferably have an average molecular weight of 10,000. Another type of preferred dispersing agent includes carboxymethylcellulose (CMC) material. Such material is well known in the art. The above dispersing polymeric agent, if included, is typically at a level of from 0% to 7%, preferably from 0.5% to 3%, more preferably from 1% to 2.5%. The polyacrylate and acrylic / maleic copolymer dispersing agent is preferably included in the compositions present at a level of 0.5% to 3%, more preferably 1% to 2%. A CMC type dispersing agent is preferably included in the compositions present at a level of 0.1% to 1%, more preferably of 0. 2% to 0.5%. Another optional ingredient in the subject composition is a soil dispersing agent which is a water soluble or dispersible material of alkoxylated polyalkyleneamine. Such material may be included in the compositions present at a level of 0% or 1%, preferably of 0. 1% to 0.8%, more preferably from 0.3% to 0.5%. The alkoxylated polyalkyleneamine material has a polyalkyleneamine base structure of amine units having the general formula: (H2N-R1-) q + 1 (-NH-R1-) r (> N-R1-) q (-NH2) wherein: (i) each unit (H2N-R1-) is linked to (-NH-R1-) or (> N-R1-); (ii) each unit (-NH-R1-) is linked to either of the two units, with the proviso that each unit is linked to no more than one (H2N-R1-) and (-NH2); (iii) each unit (> N-R1") is linked to any of the three units, with the proviso that each unit is linked to no more than two (H2N-R1-) and (-NH2); (vii) the (-NH2) is linked to (-NH-R1-) or (> N-R1_); with the proviso that each link described in i), ii), iii), and iv) is between N of one unit and R1 of another unit. In the general formula described above, q is on an average of 0 to 250, preferably 1 to 100, more preferably 3 to 40, more preferably still from 5 to 25, and more preferably still from 7 to 15. In the above general formula, r is on the average of 3 to 700, preferably from 4 to 200, more preferably from 6 to 80, more preferably from 8 to 50, and more preferably from 15 to 30. In the general formula above, the ratio q: r is preferably from 0 to 1: 4, more preferably from 1: 1.5 to 1: 2.5, more preferably still from 1: 2 In the above general formula, R1 is a linear alkanylene having from 2 to 12 carbon atoms, preferably from 2 to 4 carbon atoms. For preferred polyalkyleneamine base structures, less than 50% of the portions R1 have more than 3 carbon atoms, more preferably less than 25% of portions R1 have more than 3 carbon atoms, and more preferably even less than 10% of portions R1 have more than 3 carbon atoms. More preferably R1 is selected from ethylene, 1,2-propylene, 1,3-propylene, and mixtures thereof. For more preferred base structures, substantially all units R1 are the same. The most preferred R1 is ethylene.

The polyakyleneteamine base structure described above has a molecular weight of at least 180 daitons, preferably has a molecular weight of 600 to 5000 daltons, and more preferably has a molecular weight of 1000 to 2500 daltops. On the previous polyalkyleneamine base structure, 50% to 100% of the hydrogens bound to the nitrogens are replaced; preferably from 90% to 100% of the hydrogens bonded to the nitrogens are replaced; more preferably substantially all the hydrogens bonded to the nitrogens are substituted. The substituents of the hydrogens bonded to the nitrogens are poly (alkyleneoxy) units having the formula: - (R30) pR2 in the above formula, R3 is a alkanien having 2 to 6 carbon atoms, preferably 2 to 4 carbon atoms. carbon. R3 is preferably selected from ethylene, 1,2-propyiene, and mixtures thereof. More preferably R3 is ethylene. In the above formula, R2 is selected from hydrogen, aikaryl having from 1 to 4 carbon atoms, and mixtures thereof.

Preferably R2 is hydrogen. In the above formula, p is on average from 1 to 50, preferably from 3 to 10. In general, p is preferably increased by increasing the molecular weight of the polyalkyleneamine base structure.

Those skilled in the art of alkoxylation of poiyalkyleneamines recognize that the "degree of ethoxylation" is defined as the average number of alkoxylations by nitrogen atom substitution sites and can be expressed as a fractional number.A polyalkyleneamine can have an equal degree of ethoxylation at 1 or greater and still have less than 100% of the substituted nitrogen-substituted polyalkyleneamine base structure sites The relative proportion of primary, secondary, and tertiary amine units in the polyalkyleneamine base structure will vary, depending on the mode PREPARATION OF THE BASE STRUCTURE Preferred "polyalkyleneamine base structures" herein include both polyalkyleneamine (PAA) and polyalkyleneimine (PAI); The preferred base structures are polyethylepamine (PEA) and polyethyleneimines (PEI). is obtained by a reaction involving ammonia and ethylene dichloride, followed by distillation n fractionated. The common PEAs include triethylenetetramine (TETA), tetraethylenepentamine (TEPA), and tetrabutilenpentamina. Above pentamine, ie hexamine, heptamine, octamine and possibly nonamine, the congenically derived mixture is not easily separated by distillation and may include other materials such as cyclic amines and piperazines. Cyclic amines may also be present with side chains in which nitrogen atoms appear. See U.S. Patent 2,792,372, Dickinson, issued May 14, 1957, incorporated herein by reference, which describes the preparation of PEA. The PEI includes the preferred polyalkyleneamine base structures, useful herein. The PEI can be prepared, for example, by polymerizing ethyleneimine in the presence of a catalyst such as carbon dioxide, sodium bisulfate, sulfuric acid, hydrogen peroxide, hydrochloric acid, acetic acid, etc. The specific methods for preparing PEIs are described in U.S. Patent 2,182,306, Ulrich et al., Issued on 5 December 1939; U.S. Patent 3,033,746, Mayle et al., May 8, 1962; U.S. Patent 2,208,095, Esselmapn et al., July 16, 1940; U.S. Patent 2,806,839, Crowther, September 17, 1957; and U.S. Patent 2,553,696, Wilson, May 21, 1951 (all incorporated herein by reference). In addition to the linear and branched compounds of PEIs, compounds useful herein also include cyclic amines that are typically labeled as synthetic artifacts. The presence of these materials can be increased or decreased depending on the conditions chosen by the formulator. The following is a non-limiting example of the synthesis of a preferred soil dispersion agent. Preparation of PEÍ 1800 E7: The "PEÍ 1800 E7" has a base structure of polyethyleneimine having an average molecular weight of approximately 1800, a ratio of q: r of about 1: 2, and an average degree of ethoxylation of about 7. The ethoxylation is carried out in a stirred stainless steel autoclave of 7.56 liters equipped for temperature measurement and control, pressure measurement, purging of vacuum and inert gas, sampling, and introduction of ethylene oxide as a liquid. A cylinder of -9.08 kg. Net weight of ethylene oxide is prepared to supply the ethylene oxide as a liquid by pumping the autoclave with the cylinder placed on a scale, so that the weight change of the cylinder can be monitored. A 750 g portion of PEI (Nippon Shokubai, EPOMIN SP-018® having an average molecular weight listed of 1800 and a q: r ratio of approximately 1: 2), equaling approximately 0.417 moles of the polymer and 17.4 moles of sites of nitrogen substitution, is added to the autoclave. The autoclave is then sealed and purged of air (by applying the vacuum to minus 12.702 kg of Hg, followed by pressurization with nitrogen at 17.575 kg / cm2, then ventilating it at atmospheric pressure). The contents of the autoclave are heated to 130 ° C while applying vacuum. After about one hour, the autoclave is charged with nitrogen at about 17.575 kg / cm2, while cooling in the autoclave at about 105 ° C. The ethylene oxide is then added to the autoclave incrementally over time while closely monitoring the pressure, temperature and flow rate of ethylene oxide in the autoclave. The ethylene oxide pump is turned off and applied e! cooling to limit any temperature increase that results from any exothermic reaction. The temperature is maintained between 100 and 110 ° C while the total pressure can be gradually increased during the course of the reaction to a maximum of about 24605 kg / cm2. After a total of 750 grams of ethylene oxide has been charged to the autoclave (barely equivalent to an ethylene oxide mold per PEI nitrogen substitution site), the temperature is increased to 110 ° C and the autoclave can be stirred for an additional hour. At this point, the vacuum is applied to remove any ethylene oxide without residual reaction. (If a degree of ethoxylation of 1 is desired, the procedure will proceed directly to the next deodorization step). The vacuum is then continuously applied while the autoclave is cooled to approximately 50 ° C while introducing 376 g of 25% sodium methoxide in a metapol solution (1.74 moles) to achieve 10% catalyst loading based on the nitrogen substitution sites PEÍ). The methoxide solution is sucked into the vacuum autoclave and then the temperature control point of the autoclave is increased to 130 ° C. A device is used to monitor the energy consumed by the agitator. The energy of the agitator is monitored together with the temperature and pressure. The energy and temperature values of the agitator increase gradually as the methane is removed from the autoclave and the viscosity of the mixture increases and stabilizes at approximately 1 hour, indicating that most of the methanol has been removed. The mixture is heated and further stirred under vacuum for an additional 30 minutes. The vacuum is removed and the autoclave is cooled to 105 ° C while it is charged with nitrogen at 17,575 kg / cm2 and then it is ventilated at atmospheric pressure. The autoclave is charged at 14.06 kg / cm2 with nitrogen. The ethylene oxide is added back to the autoclave in an increased manner as above while closely monitoring the pressure, temperature and flow velocity of the ethylene oxide in the autoclave while maintaining the temperature between 100 and 110 ° C and is limited any increase in temperature due to the exothermic reaction. After the addition of 4500 g of ethylene oxide (resulting in a total of 7 moles of ethylene oxide per mole of the PEI nitrogen substitution site) it is achieved in several hours, the temperature is increased to 110 ° C and the mixture is stirred for an additional hour. The reaction mixture is then collected in purged nitrogen containers and then transferred into a 22-L 3-neck round-bottomed flask equipped with heating and stirring. The strong alkaline catalyst is neutralized by adding 167 g of methanesulfonic acid (1.74 moles). The reaction mixture is then deodorized by spraying with inert gas (argon or nitrogen) by gas dispersion fritting and by the reaction mixture for about 1 V4 while stirring and heating the mixture to about 100-130 ° C.

Enzymes Enzymes can be included in the subject compositions for a wide variety of purposes for fabric laundry, including the removal of protein-based, carbohydrate-based or triglyceride-based stains, for example, and for the prevention of the transfer of shelter dye and for the restoration of the fabric. Enzymes that can be incorporated include proteases, amylases, lipases, cellulases, and peroxidases, as well as mixtures of two or more thereof. Other types of enzymes can also be included. Said enzymes may be of any suitable origin, such as vegetable, animal, bacterial, fungal and yeast origin. However, their selection is governed by several factors such as the activity of pH and / or optimum stability, thermostability, stability in the presence of active detergents, detergency builders and the like. In this regard, bacterial or fungal enzymes, such as bacterial amylases and proteases, and fungal cellulases are preferred. The subject compositions typically comprise from 0% to about 5%, preferably from about 0.1% to about 2%, most preferably from about 0.5% to about 1.5% of commercial enzyme preparations. Suitable examples of proteases are the subtilisins that are obtained from the particular strains of B. subtills and B. licheniforms. Another suitable protease is obtained from a Bacillus strain, having a maximum activity on the pH scale of 8-12, developed and sold by Novo Industries A / S under the registered trade name ESPERASE®. The preparation of said enzyme and analogous enzymes is described in British patent specification no. 1, 243,784 from Novo. Suitable proteolytic enzymes for removing protein-based stains that are commercially available include those sold under the trade names ALCALASE® and SAVINASE® by Novo Industries A / S (Denmark) and MAXATASE® by International Bio-Synthetics, Inc. (Netherlands). The protease enzymes are included in the commercial preparations in the subject compositions at levels sufficient to provide from about 0.004 to about 2 Anson units (AU) of activity per gram of the compositions, preferably from about 0.006 to about 0.1 AU, also from about 0.005 to approximately 0.02 AU. Amylases include, for example, α-amylases described in British patent specification no. 1, 296,839 (Novo), RAPIDASE®, International Bio-Synthetics, Inc. and TERMAMYL®, Novo Industries. The amylase is preferably included in the subject compositions so that the activity of the amylase is from about 0.02 KNU to about 5 KNU per gram of the composition, most preferably from about 0.1 KNU to about 2 KNU, most preferably still from about 0.3. KNU to approximately 1 KNU (KNU is a unit of activity used commercially by Novo Ind.). Useful cellulases in the subject compositions include bacterial and fungal cellulases. Preferably, they will have an optimum pH between 5 and 9.5. The cellulases described in the PCT patent application No. WO 91/17243, such as CAREZYME® (Novo), are especially useful cellulases. The cellulase is preferably included in the subject compositions, so that the activity of the cellulase is approximately 0.1.

CEVU at about 20 CEVU per gram of the composition, most preferably from about 1 CEVU to about 10 CEVU, most preferably from about 2 CEVU to about 5 CEVU. (The activity of a cellulase material (CEVU) is determined from the reduced viscosity of a standard CMC solution of the following way. A substrate solution containing 35 g / l of CMC (Hercules 7 LFD) is prepared in a tris pH regulator of 0.1 M at a pH equal to 9.0. The cellulase sample to be analyzed is dissolved in the same pH regulator. 10 ml of substrate solution and 0.5 ml of enzyme solution are mixed and transferred to a viscometer (ie, Haake VT 181, NV sensor, 181 fm), thermofixed at 40 ° C. Viscosity readings are taken as soon as possible after mixing and again 30 minutes later. The activity of a ceiulase solution that reduces the viscosity of the substrate solution by half under these conditions is defined as 1 CEVU / liter).

Lipase enzymes suitable for detergent use include those produced by microorganisms of the pseudomonas group, such as a Pseudomonas stutzeri ATCC 19,154, as described in British Patent 1, 372,034. The LIPOLASE® enzyme derived from Humicola lanuginosa and commercially available from Novo (see also EP 341 947) is a preferred lipase. The lipase is preferably included in the subject compositions, so that the activity of the lipase is from about 0.001 KLU to about 1 KLU per one gram of the composition, most preferably from about 0.01 KLU to about 0.5 KLU, most preferably still from approximately 0.02 KLU to approximately 0.1 KLU. (KLU is a unit of activity used commercially by Novo Ipd.). Peroxidase enzymes are used in combination with oxygen sources, ie, percarbonate, perborate, persuiphate, hydrogen peroxide, etc. These are used for "solution bleaching", that is, to prevent the transfer of dyes or pigments removed from the substrates during washing operations to other substrates in the wash solution. A large scale of enzyme materials and means for their incubation in synthetic detergent compositions are also described in the US patent. 3,553,139, issued on January 5, 1971 to McCarty et al. The enzymes are also described in the patent of E.U.A. 4,101, 457, Place et al., Issued July 18, 1978, and in the patent of E.U.A.4,507,219, Hughes, issued March 28, 1985. Enzymes for use in detergents can be stabilized by various techniques. Enzyme stabilization techniques are described and exemplified in the U.S. patent. 3,600,319, issued August 17, 1971 to Gedge et al., And European patent application no. 199 405, published on October 29, 1986, Venegas. Enzyme stabilization systems are also described, for example, in E.U.A. 3,519,570.

Bleaching compounds-bleaching agents in bleach activators The subject detergent compositions may optionally contain bleaching agents or a bleaching composition containing a bleaching agent and one or more bleach activators. The bleaching agent is typically at a level of from 0% to about 25%, preferably from about 5% to about 20% of the subject compositions. The amount of the bleach activator is typically from 0% to about 10%, preferably from about 0.5% to about 5% of the subject compositions. The bleaching agent can be any of the bleaching agents useful for detergent compositions in textile cleaning, 4 hard surface cleaning, or other cleaning purposes that are now known or are about to be known. The above include oxygen bleaches as well as other bleaching agents. Perborate bleaches, ie, sodium perborate (ie, mono-tetrahydrate) can be used. A preferred level of perborate bleach in the subject composition is from about 5% to about 20%, most preferably from about 10% to about 16%. Another category of bleaching agent that can be used comprises percarboxylic acid bleaching agents and salts thereof. Suitable examples of such a class of agents include magnesium monoperoxyterephthalate hexahydrate, the magnesium salt of metachloroperbenzoic acid, 4-nonylamino-4-oxoperoxybutyric acid, diperoxidedecanodiolco acid and 6-nonylamino-6-oxoperoxycaproic acid. Other peroxygen bleaching agents can also be used. Suitable peroxygen bleach compounds include sodium carbonate peroxidate and equivalent "percarbonate" bleaches, sodium pyrophosphate peroxydrate, urea peroxydrate, and sodium peroxide. Persulfate bleach (ie, OXONE®, commercially manufactured by DuPont) can also be used. Mixtures of bleaching agents can also be used. The peroxygen bleaching agent (perborate, percarbonate, etc.) is preferably combined with a bleach activator, which it leads to the production in situ in the aqueous solution (ie, during the washing process) of the peroxyacid corresponding to the bleach activator. Several non-limiting examples of activators are described in the U.S. patent. 4,915,854 issued April 10, 1990, to Mao et al., And patent of E.U.A. 4,412,934. The activators of nananoiloxibenzensulfonato (NOBS) and tetracetylethylenediamine (TAED) are typical and mixtures thereof can also be used as well. A preferred level of bleach activator of NOBS or TAED in the subject compositions is from about 0.5% to about 5%, most preferably from about 0.8 to about 3%, most preferably still from about 1.2% to about 2.5%.

Fabric Softening Clay A preferred fabric softening clay is a smectite-like clay. Smectite-type clays can be described as expandable, three-layered clays, ie, aluminosilicates and magnesium silicates, having an ion exchange capacity of at least about 50 meq / 100 g of clay. Preferably the clay particles have a size that can not be perceived tactilely, so that they do not have a gritty feel in the treated fabric of the garments. Fabric softening clay, if desired, may be included in the compositions of the subject invention at levels of approximately 0.1% to approximately %, preferably from about 0.2% to about 15%, most preferably from about 0.3% to about 10%. Although any of the smectite-type clays is useful in the compositions of the subject invention, certain clays are preferred. For example, Gelwhite GP is an extremely white form of smectite-like clay and is therefore preferred to formulate white detergent compositions. Volclay BC, which is a smectite-type clay mineral containing at least 3% iron (expressed as Fe203) in the glass mesh, and which has a very high ion exchange capacity, is one of the more efficient and effective clays to be used in instant compositions from the point of view of product development. On the other hand, certain smectite clays are sufficiently contaminated by other silicate minerals that their ion exchange capacities are within the scale of requirement; said clays are not preferred in the subject compositions.

Clay flocculating agent It has been found that the use of a clay flocculating agent in a softening clay containing composition provides an improved softening clay distribution in the garments, which results in a better fabric softening development, compared to the compositions that they comprise only softening clay. The polymer clay flocculating agent is selected to provide the improved distribution of the clay fabric softener. Typically such materials have a high molecular weight, greater than about 100,000. Examples of such materials may include long-chain polymers and copolymers derived from the monomers such as ethylene oxide, acrylamide, acrylic acid, dimethylaminoethyl methacrylate, vinylalcohol, vinylpyrrolidopa and ethylenimine. Gums, like guar gums, are also suitable. The preferred clay flocculating agent is a poly (ethylene oxide) polymer. The amount of clay flocculating agent included in the subject compositions, if any, is about 0.2% -2%, preferably about 0.5% -1%.

Dye transfer inhibiting ingredient Another optional component in the subject compositions is a dye transfer inhibiting ingredient (DTI) to prevent the decrease in color fidelity and intensity in the fabrics. A preferred polymeric DTI material is capable of binding fugitive dyes to prevent them from depositing on the fabrics. Non-limiting examples of the polymeric DTI materials include polyvinyl pyridine N-oxide, polyvinyl pyrrolidone (PVP), PVP-polyvinylimidazole copolymer, and mixtures thereof. Copolymers of N-vinylpyrrolidone and N-vinyiimidazole polymers (called "PVPI") are also preferred. The amount of DTI included in the subject compositions, if any, is about 0.05% -5%, preferably about 0.2% -2%.

Photoblank A preferred optional component of the composition of the The subject invention is a photobiocidal material, particularly phthalocyanine photobleaching agents which are described in the U.S. patent. 4,033,718, issued July 5, 1977, hereby incorporated by reference. The preferred photoblast is a metal compound of phthalocyamine, the metal preferably having a balance of +2 or +3; zinc and aluminum are the preferred metals. Said photobleach is available, for example, under the trade name TI OLUS. Zinc phthalocynia sulfonate is commercially available under the trade name QUANTUM® from Ciba Geigy. The photobleaching component, if included, is typically found in the subject compositions at a level of from 0% to about 0.02%, preferably from about 0.001% to about 0.01%.

Filler Sodium sulfate and calcium carbonate are well known and are often used as filler components of the subject compositions. The filler also includes minerals, such as talc and minerals that contain hydrous magnesium silicate, where the silicate is mixed with other minerals, for example, old mother rocks such as ia dolimite. Sodium sulfate is a preferred filler material. The filler material is typically at a level of 0% to approximately 60%, preferably from about 15% to about 40%, most preferably from about 20% to about 35%.

Optical brightener Any optical brightener or other brightener or bleaching agent known in the art can be incoforated in the subject detergent compositions. Commercial optical brighteners that may be useful can be classified into subgroups, which include, but are not necessarily limited to, stilbene, pyrazoline, coumarin, carboxylic acid, metincyanine, 5,5-dibensotifen, azole, heterocycles 5 and 6 member ring, and other miscellaneous agents. Examples of such brighteners are deciphered in "The Product and Application of Fluorescent Brightening Agents," M. Zahradnik, published by John Wiley & Sons, New York (1982). Anionic brighteners are preferred. Specific examples of optical brighteners that are useful in the subject compositions are those identified in the US patent. 4,790,856, issued to Wixon on December 13, 1988. Such brighteners include the TINOPAL UNPA®, TINOPAL CBAS® and TINOPAL 5BM®, TINOPAL AMS-GX® series, available from Ciba Geigy; ARTIC WHITE CC® and ARTIC WHITE CWD®. available from Hiltop-Davis, located in Italy; 2- (4-Stryl-phenol) -2H-naphtho [1,2-d] trizloes; 4,4'-bis (1, 2,3-triazole-2- il) stilbenes; 4,4'-bis (steryl) bisphene; and the aminocoumarins. Specific examples of said brighteners include 4-methyl-7-diethylamino coumarin; 1,2-bis (-benzimidazol-2-yl) ethylene; 1,3-diphenyl-frazolines; 2,5-bis (benzoxazol-2-yl) thiophene; 2-estryl-naf- [1,2-d] oxazole; and 2- (stilbene-4-yl) -2H-naphtho- [1,2-djtriazole. See also patent of E.U.A. 3,646,015, issued on February 29, 1972 to Hamilton. Preferred brighteners also include disodium salt of 4,4'-bis ((4-anilino-6-bi (2-hydroxyethyl) -amino-1, 3,5-trizin-2-yl) amino) stilbe -no-2,2-disulfonic, 4-4'-bis (2-sufoetyryl) biphenium and disodium salt of 4,4'-bis ((4-anilino-6-morpholino-1, 3,5-triazin -2-yl) -amino) stilben-2,2-disuiphonic. Said optical brightener, and mixtures thereof, typically is at a level in the compositions from 0% to about 1%, preferably about 0.1% -3%.

Foam suppressant Compounds for reducing or suppressing the formation of foams can be incoforated in the compositions of the subject invention.

A wide variety of materials can be used as a foam suppressant. See, for example, Kirk Othmer Encyclopedia of Chemical Technology, third edition, Volume 7, pages 430-447 (John Wiley & Sons, Inc., 1979).

A preferred category of suds suppressor comprises silicone suds suppressors, said category includes polyorganosiloxane oils, such as polydimethylsiloxane, dispersions or emulsions of polyorganosiloxane oils or resins, and combinations of polyorganoxylan with silica particles wherein the polyorganosiloxane is chemoabsorbed or merges into the silica. Silicon foam suppressors are well known in the art and, for example, are described in the patent of E.U.A. 4,265,779 issued May 5, 1981 to Gandolfo and others; patent of E.U.A. 3,933,672, Bartolotta et al .; patent of E.U.A. 4,652,392, Baginski et al., Issued March 24, 1987; and European Patent Application No. 89307851.9, published on February 7, 1990. An exemplary silicone based on the foam suppressant, designated SS-1 herein is polydimethyl siloxane with trimethylsillole end blocking units available from Dow Croning . The subject compositions comprise 0% to about 1%, preferably about 0.05% to about 0.1% foam suppressant.

Auxiliary surfactant The compositions of the subject invention may contain optional surfactants commonly used in detergent products. Typical listings of the classes and species of said surfactants, for example, anionic, non-ionic surfactants, zwiteriónicos and amphoteric, appear in E.U.A. 3,664,961, E.U.A. 3,929,678, E.U.A. 4,844,821 and EP 550,652. Such auxiliary surfactants may include Oto-Cie alkylalkoxycarboxylate (especially ethoxy carboxylates 1-5) glycerol ethers of C? O-C? 8, alkyl polyglycosides of C10-C18 and its corresponding sulphated polyglycosides and esters of α-sulfonated fatty acid of C? -C? 8. Said auxiliary surfactants may include 1 or more of the C6-Ci2 alkylphenollalkoxylates (especially ethoxylates and ethoxylates / mixed propoxylates), and C ?2-C18 betaines and sulfobetaines (sultaipas). The additional C10-C20 fatty acid soaps Auxiliary surfactants are also possible. Said auxiliary surfactant is preferably not present, but may be included at a level of 0% to a total of about 5%, also approximately 0.5-2.

Water The granular compositions of the subject invention typically comprise from about 2% to about 15% in water, preferably from about 4% to about 12% in water, most preferably from about 5% to about 10% in water.

Diverse components Dyes, pigments, germicides, perfumes, glycerin, sodium hydroxide, alkylbenzene, fatty alcohol and other minor agents, some of which are impurities that are carried by the surfactant manufacturing processes, can also be incoforated in the compositions object. If included, said other material is typically at a level of from 0% to about 3%.

EXAMPLES The following exemplifies the compositions of the subject invention, but are not intended to limit the scope of the subject invention. Examples are granular detergents that can be made by well-known methods, such as spray-drying a slurry or slurry, and dry-binder or binder in the mixers. The following list of components is used in the examples. LAS: linear C11-C13 aiquilbenzene suifonate, sodium salt.

KDQA: linear C12-C14 dimethylhydroxyethyl quaternary ammonium chloride. AE: ethoxy (7) linear C14-C? 5 alcohol STYPP: sodium tripolyphosphate. Silicate: sodium silicate having a S ^ Na ?O ratio of 1.6. Carbonate: sodium carbonate. DTPA: diethylenetriamine pentaacetate, solium salt DTPMP: diethylenetriamine penta (methylene phosphonic acid). Copolymer A / M: copolymer of acrylic acids and slates, designated SOKALAN HP-22R by BASF. CMC: carboxymethylcellulose having an average molecular weight of 63,000.

SRA-1: polymeric soil release agent described below. Protease: protease enzyme product designated SAVINASE 13TR by Novo Industries. Amylase: amylase enzyme product designated 120T by Novo Industries. Cellulase: cellulase enzyme product designated CAREZIME 5TR from Novo Industries, having the activity of 5000 CEVU / g. Lipase: lipase enzyme product designated LIPOLASA 100TR by Novo Industries. Perborate: sodium perborate monohydrate or tetrahydrate. TAED: tetraacetylethylenediamine. ZPS: zinc phthaloyanine sulfonate, designated QUANTUMR by Ciba Geigy. MgSO4: magnesium sulfate. Brightener: stybenedisulfonate, designated BLANKOPHOR DMLR by Miles Laboratories. SS-1: polydimethisiloxane with trimethylsilyl end blocking units designated EAF from Dow Corning. Sulfate: sodium sulfate. The numbers in the following tables are percent by weight.

EXAMPLE EXAMPLE The present invention includes methods for laundry of fabrics using the compositions described above. Preferred methods are machine washing operations using said compositions. The subject methods include the isolation of the subject compositions in water, typically at concentrations from about 3000 ppm to about 8000 ppm, preferably from about 4000 ppm to about 7000 ppm, most preferably from about 5000 ppm to about 6000 ppm where the fabrics are washed. The washing operations preferably carried out are carried out at washing solution temperatures of about 10 ° C to about 90 ° C, most preferably of about 12 ° C to about 70 ° C, for a period of about 10 minutes to about 60 minutes, most preferably from about 15 minutes to about 40 minutes. The washing solutions of preference are found in the pH range of from about 9.5 to about 10.8, most preferably from about 10.0 to about 10.5. Although the particular embodiments of the subject invention have been described above, it will be apparent to those skilled in the art that various changes and modifications of the subject invention can be carried out without departing from the spirit and scope of the invention. It is intended to cover, in the appended claims, all modifications that are within the scope of said invention.

Claims (11)

NOVELTY OF THE INVENTION CLAIMS

1. - A detergent composition comprising: a) 6% a 18% surfactant, the composition comprising: 1) from 5% to 10% of anionic surfactant selected from alkylbenzenesulfonate, alkyl sulfate surfactant and sulfate alkyl ethoxy ester surfactant having an average of 0.5 to 9 moles ethoxy per mol of surfactant agent; 2) from 0.2% to 2% of the cationic hydroxyalkylammonium quaternary surfactant having the structure: R R'nR "mN + Z", wherein R is long chain alkyl, R 'is short chain alkyl, R "is H (OCH2CHB) p-, B is H or CH3, n is 0 or 3, m is 0 to 3, n + m is 3, p is 0.5 to 4, p times m is 0.5 to 4, and z is an anion water soluble; and 3) from 0.4% to 8% nonionic surfactant selected from alkylethylalcohol alcohol surfactant having an average of 0.5 to 25 moles ethoxy per mole of surfactant, amine oxide surfactant, and polydroxy amide fatty acid surfactant b) 0.5 to 4% polymeric soil release agent comprising: 1) from 10% to 99.5% of esters comprising, per mole of ester: i) from 1 to 2 moles of polyethoxy / propoxy blocking units of the formula (M03S) (CH2) m (CH2CH2?) (RO) n-where M is a salt-forming cation such as sodium or tetraalkylammonium, M is 0 or 1, R is ethylene, propylene or a mixture of them, and N is from 0 to 2; Y mixtures thereof; I) from 0.5 to 66 moles of units (EP / PG), comprising oxyethyleneoxy (EG) and optionally oxy-1,2-propyleneoxy (PG) selected from: a) oxyethyleneroxy units; b) a mixture of oxyethyleneoxy oxy-1, 2-propyleneoxy units having a molar ratio of oxyethyleneoxy to oxy-1,2-propyleneoxy of 0.5: 1 to 10: 1; and c) a mixture of a) or b) with poly (oxyethylene) oxy units wherein the poly (oxyethylene) oxy units have a degree of polymerization of 2 to 4; with the proviso that when said poly (oxyethylene) oxy units have a degree of polymerization of 2, the molar ratio of poly (oxyethylene) oxy units to the total units of the group of I) is on the scale of 0: 1 to 0.33: 1; and when said poly (oxyethylene) oxy units have a degree of polymerization of 3, the molar ratio of the poly (oxyethylene) oxy units to the total units of the group of ii) is on the scale of 0: 1 to 0.22: 1; and when said poly (oxethylene) oxy units have a degree of polymerization of 4, the molar ratio of the poll (oxyethylene) oxy units to the total units of the group of ii) is on the scale of 0: 1 to 0.14: 1; iii) from 1.5 to 40 moles of terephthalollo units, and iv) from 0 to 26 moles of 5-sulfuroptloyl units of the formula - (0) C (C6H3) (S03M) C (0) - wherein M is cation forming of salt as an alkali metal or tetraalkylammonium ion; 2) from 0.5% to 20% > of crystallization reducing stabilizer selected from sulfonate-type hydrotrope, alkylbenzenesulfonate, paraffin sulphonate, and mixtures thereof; and c) from 80% to 94% of other components.

2. - The composition according to claim 1, further characterized in that the weight ratio of the nonionic surfactant to the cationic surfactant is greater than 4.

3. A detergent composition containing: a) from 6% to 18% agent surfactant, the composition containing: 1) from 5% to 10% of the cationic surfactant selected from the alkybenzenesulfonate surfactant, alkyl sulfate surfactant and alkyl ethoxy ether sulfate surfactant having an average of 0.5 to 9 moles of ethoxy per mole of surfactant; 2) from 0.2% to 2% of hydroxyalkyl quaternary ammonium cationic surfactant having the structure: R R'nR "mN * Z", wherein R is a long chain aluyl, R 'is a short chain alkyl, R "is H (OCH2CHB) p-, B is H or CH3, n is 0 to 3, m is 0 to 3, n + m is 3, p is 0.5 to 4, p to m is 0.5 to 4, and Z "is a water-soluble anion; and 3) from 0.4% to 8% of a nonionic surfactant selected from the alkyethoxyacolic acid teyosioactive agent having an average of 0.5 to 25 moles ethoxy per mole of surfactant, amine oxide surfactant and acid amide surfactant. polyhydroxy fatty acid wherein the weight ratio of the nonionic surfactant to the hydroxyalkyl ammonium cationic surfactant is greater than 4.; b) from 0.05% to 4% polymeric soil release agent, the soil release agent containing: 1) from 10% to 99.5% of esters comprising, per mole of said ester: i) from 1 to 2 moles of polyethoxy / propoxy blocking units of the formula (M03S) (CH2) m (CH2CH2?) (RO) n- where M is a cation that forms salt as sodium or tetraalkylammonium, M is 0 or 1, R is ethylene, propylene or a mixture thereof, and N is from 0 to 2; and mixtures thereof; ii) from 0.5 to 66 moles of units (EP / PG), comprising oxyethyleneoxy (EG) and optionally oxy-1,2-propyleneoxy (PG) selected from: a) oxyethyleneoxy units; b) a mixture of oxyethyleneoxy oxy-1,2-propyleneoxy units having a molar ratio of oxyethyleneoxy to oxy-1,2-propyleneoxy from 0.5: 1 to 10: 1; and c) a mixture of a) or b) with poly (oxyethylene) oxy units wherein the poly (oxyethylene) oxy units have a degree of polymerization of 2 to 4; with the proviso that when said poly (oxyethylene) oxy units have a degree of polymerization of 2, the molar ratio of poly (oxyethylene) units oxia the total units of the group of ii), is on a scale of 0: 1 to 0.33: 1; and when said poly (oxyethylene) oxy units have a degree of polymerization of 3, the molar ratio of the poly (oxyethylene) oxy units to the total units of the group of i) is on the scale from 0: 1 to 0.22: 1.; and when said poly (oxyethylene) oxy units have a degree of polymerization of 4, the molar ratio of the poly (oxyethylene) oxy units to the total units of the group of ii) is on the scale of 0: 1 to 0.14: 1; Ii) from 1.5 to 40 moles of tereptaloyl units, and iv) from 0 to 26 moles of 5-sulfuroptloyl units of the formula - (0) C (C6H3) (S03M) C (0) - wherein M is cation salt former as an alkali metal or tetraalkylammonium ion; 2) from 0.5% to 20% of crystallization reduction stabilizer selected from the sulphonate type hydrotrope, alkylbenzene sulfonate, paraffin sulphonate and mixtures thereof; and c) from 80% to 94% of other components.

4. The composition according to any of claims 1-3, further characterized in that: 1) in the structures of the anionic surfactants, i) the alkylbenzenesulfonate surfactant has an alkyl with an average of 9 to 16 carbon atoms; ii) the alkylbenzene sulfonate surfactant has an alkyl with an average of 10 to 16 carbon atoms; iii) the alkyl ethoxy ether sulfate surfactant has an alkyl with an average of 10 to 16 carbon atoms, and has 1 to 7 moles ethoxy per mole of surfactant; 2) in the structure of the cationic surfactant, R is alkyl having an average of 9 to 16 carbon atoms, R 'is methyl or ethyl, m is 1 or 2, n is 1 or 2 and p is 1; and, 3) in the structures of the nonionic surfactants, i) the amine oxide surfactant has the structure: OR R1 (OR2) xN (R3) 2 wherein R1 is alkyl having an average of 10 to 18 carbon atoms, R2 is an alkylene group or hydroxyquiniene having 2 to 3 carbon atoms, x is 0 to 3, and each R3 is alkyl or hydroxyalkyl having from 1 to 3 carbon atoms; I) the polyhydroxy fatty acid amide surfactant has the structure O R5 R4- C- N- V wherein R 4 is alkyl having an average of 10 to 18 carbon atoms, R 5 is C 1 -C 6 alkyl, hydroxyalkyl or alkyloxyalkyl, and V is a polyhydroxyhydrocarbyl portion derived from a reducing sugar.

5. The composition according to any of claims 1-3, further characterized in that the polymeric dirt release agent comprises: (1) from 25% to 97%, preferably from 50% to 94% or, said esters have a molecular weight of 500 to 8,000, preferably 500 to 5,000, the esters having the formula: (CAP) x (EG / PG) and (T) z (SIP) q, where the EG: PG ratio is 1: 1 to 5: 1, preferably 2: 1, x is 2, and is 3 to 18, preferably 5, z is 3 to 15, preferably 5, and q is 0.5 to 4, preferably 1; and (2) from 3% to 18%, preferably from 6% to 15% of said stabilizer, the stabilizer being preferably alkylbenzene sulfonate of

6. - The composition according to claims 1-3, further characterized in that the anionic surfactant comprises at least 80% of said alkylbenzenesulfonate agent, and the nonionic surfactant comprises at least 80% of said alkylethoxyalkyl surfactant.

7. The composition according to any of claims 1-3, further characterized in that the composition comprises from 0.4% to 0.8% of the cationic surfactant and from 2% to 7% of the nonionic surfactant.

8. The composition according to any of claims 1-3, further characterized in that the composition comprises from 8% to 15% of said surfactant, from 0.08% to 1.5% of said polymeric soil release agent and from 84%. % to 92% of other components.

9. The composition according to any of claims 1-3, further characterized in that in the structure of the cationic surfactant, R is alkyl having an average of 12 to 14 carbon atoms, R 'is methyl, B is H , m is 1, and n is 2.

10. The composition according to any of claims 1-3, further characterized in that the anionic surfactant is 100% of said alkylbenzenesulfonate surfactant, the alkyl having an average of 11 to 14 atom is carbon; and the nonionic surfactant is 100%, said alkylethoxyalkyl surfactant having an average of 12 to 15 carbon atoms, and having from 7 to 9 moles of ethoxy per mole of surfactant.

11. The composition according to any of claims 1-3, further characterized in that the composition comprises from 10% to 14% of surfactant, the surfactant consisting essentially of (% by weight of the composition) from 6% to 9% of said alkylbenzenesulfonate surfactant, from 0.3% to 1.2%, said hydroxyalkyl quaternary amino cationic surfactant and from 3% to 6% of said agent acrylethylalcohol surfactant; from 0.16% to 0.4% of said polymeric soil release agent and from 86% to 90% of other components. SUMMARY OF THE INVENTION The present subject invention includes laundry detergent compositions, preferably in granular form, particularly useful for machine washing operations; the compositions comprise; a) from about 6% to about 18% surfactant comprising, 1) from about 5% to about 10% surfactant selected from the aiquilbenzenesulfonate surfactant, alkyl sulfate surfactant and alkyl ethoxy ether sulfate surfactant; 2) from about 0.2% to about 4% of hydroxyalkyl quaternary ammonium cationic surfactant and 3) from 0.4% to about 8% nonionic surfactant selected from the alkylethylethoxy alcohol surfactant, amine oxide surfactant and agent polyhydroxy fatty acid amide surfactant; b) from about 0.05 to about 4% polymeric soil release agent comprising: 1) from about 10% to about 99.5% of esters comprising formaldehyde of said ester, i) from about 1 about 2 moles of end blocking units of polyethoxy / propoxy sulphonated; ii) from about 0.5 to about 66 moles of units selected from the group consisting of a) hoxyethyleneoxy units, b) a mixture of oxyethyleneoxy and oxy-1,2-propionidoxy units; and c) a mixture of a) or b) with poll (oxyethylene) oxy units; iii) of approximately 1.5 a about 40 moles of terephthaloyl units; and iv) from 0 to about 26 moles of 5-sulfoisophthaloyl units; 2) from about 0.5% to about 20% crystallization, reducing the selected stabilizer of the sulfonate hydrotope, alkylbenzene sulfonate, paraffin sulphonate and mixtures thereof; and c) from about 805 to about 94% of other components. SR / VM * sll * sff * jtc * cgm * xma * mvh P99 / 619F