PT100605A - DETERGENT COMPOSITIONS - Google Patents

Abstract

The present invention provides laundry detergent compositions comprising one or more water soluble anionic, cationic, ampholytic or zwitterionic detersive surfactants or mixtures thereof and a combination of (a) at least 1 % by weight of the composition of a polyhydroxy fatty acid amide having formula (I), wherein R1 is H, a C1-C4 hydrocarbyl, 2-hydroxy ethyl, 2 hydroxy propyl, or mixtures thereof, R<2> is a C5-C31 hydrocarbyl, and Z is a polyhydroxyhydrocarbyl having a linear hydrocarbyl chain with at least 3 hydroxyl groups directly connected to the chain, or an alkoxylated derivative thereof; and (b) at least 1 % by weight of the composition of a substantially water-insoluble ethoxylated C11-C15 primary aliphatic alcohol containing an average of no more than five ethylene oxide groups per mole and having an ethylene oxide content of less than 50 % by weight. Preferred water soluble surfactants are anionic surfactants and more preferred compositions are free of alkyl benzene sulfonate surfactants.

Description

5 10 15

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2S 30

The present invention relates to nonionic surfactant detergent compositions comprising nonionic surfactant systems comprising one or more pharmaceutically acceptable acid addition salts. The present invention relates to nonionic surfactant compositions comprising one or more nonionic surfactant fatty acid amides, fabric cleaning compositions and, more particularly, to fabric cleaning compositions capable of providing the removal of grease and oil stains. The surfactant systems of commercially available fabric cleaning compositions are designed so as to remove a wide variety of types of soil from the surface of the fabrics. Most of these systems are based on one or more anionic surfactants, with lower levels of other types of surfactants, such as nonionic, ampholytic and cationic surfactants. In particular, a combination of a greater proportion of anionic surfactants and a minor proportion of nonionic surfactants are often used to provide one. acceptable balance of particulate debris and dirt removal characteristics of fats and oils. Detergent compositions incorporating triphosphonic systems in which the most important component is nonionic are known in the art, for example, ; -EF-A-0006268L and? GE 2206601T but any commercial application, tends to be of a specialized nature. because the compositions that are based: in. anionic surfactants provide a detergency; acceptable over a broader spectrum of soil types, are more compatible with adjuvants such as optical brighteners and softening additives. and are less aggressive with respect to fabric dyes and washing machine components. Accordingly, there remains a need to provide detergent compositions which have a better removal of greasy and oily soils without any sacrificial effects.

elimination of other types of dirt and no impact on the performance of other detergent ingredients. The present invention provides washing detergent compositions which contain nonionic ionic systems which comprise one or more polyhydroxylated fatty acid amides and one or more additional nonionic trisynthetic active agents. When included in such laundry detergent compositions, these nonionic toner systems unexpectedly improve the effectiveness of the greasy / oily stain compositions over a wide spectrum of washing conditions. U.S. Patent Application Serial Number 07/578760 (attorney's dossier number 4265), copending and transferred in conjunction with it, filed September 2, 1990, refers to non-nucleosurfactant systems. ionic surfactants which comprise combinations of certain polyhydroxylated fatty acid amides or other additional nonionic activating agents. Polyhydroxylated fatty acid amides of the formula R *

in which is H, a hydrocarbyl group in C? -C? 2-hydroxymethyl, 2-hydroxy-prop-11-one or. the siias mixtures; it

Re is a hydrocarbyl radical in which Z is a hydroxylated hydrocarbyl group which has a linear hydrocarbyl chain with at least three hydrayl groups directly attached to the chain or an alloxylated derivative thereof. The weight ratio of the polyhydroxylated fatty acid amide to the additional nonionic surface active agent may be in the range of 4/1 Pg ** - **.

Mod. 7 | -20,000 · χ.-901θα 20 25. 30

about 1: 5 to about 5: 1. As optional components, other types of surface active agents, such as anionic, cationic, ampholytic, hybrid and semi-polar surface active agents, may be included, and detergent compositions incorporating these active systems are also included. Unexpectedly the Applicant has discovered that detergent compositions incorporating nonionic thionioactive actives of this general type comprise certain combinations of polyhydroxylated fatty acid amides and water insoluble ethoxylated nonionic agents which together with other agents water soluble protons provide unexpected benefits of removal of oily and greasy soil without lowering the detergency performance relative to other types of soil. GENERAL BACKGROUND OF THE INVENTION

In the prior art, a wide variety of polyhydroxylated fatty acid amides is described. For example, the N-acyl glucamides and the N-methyl glucamides are described by J. Boodby, A., Marcus, E. Chin and P. Finn in &quot; The Thermotropic Liquid-Crystalline Properttes oF Some Straight Chain- Carbohydrate Amphiphiles, r Liquid Crystalsr. 1988, Vol. 3, NS. 11, pages 1569-1581 and by A. Muller-Fahrnow, V. Zábel, M. Stei-Fa and R. Hilgenfeld in &quot; Molecular and Crystal Structure of Nonionic Detergent &quot;, Nananaly-N-methylglucamide &quot;; J. Chem. Soc. Chem. Commun., 1986, pages 1573-1574. The use of N-alkyl polyhydroxyamides has recently been of substantial interest for use in biochemistry, for example in the dissociation of biological membranes. See, for example, the article in N-D-Gluco-N-methyl-alkanamide Compounds, New Class o-f Non-Ionic Detergent for 5 35 1 1 10 15

Mod. 71 -20,000 Âμ. 25 ° C.

Membrane Biochemistry ", Biochem. J. (1982), Vol. 207, pp. 363-366, by J. E. K. Hildreth. The use of N-alkyl-glueamides in detergent compositions has also been reported. U.S. Patent 2,965,576, issued December 20, 1960 to E. R. Wilson and U.S. Patent 809,060, issued February 18, 1959, issued to Thomas Heley &amp; Ca., Ltd. relates to detergent compositions containing anionic safeners and certain amide-activating agents, which may include N-methylglucamide, added as low boiling foaming agents These compounds include a N-acyl radical of a higher straight chain fatty acid having ten to fourteen carbon atoms. These compositions may also contain auxiliary materials such as alkali metal phosphates, alkali metal silicates, sulfates and carbonates, it is also generally indicated that additional constituent compositions may be included in the compositions to impart desirable qualities to the composition, such as fluorescent dyes, whitening, perfume, etc. U.S. Patent Application Serial No. 703,798 issued March 8, 1955 to A-M-,

Stehwartz, refers to. aqueous detergent compositions containing the condensation reaction product of N-alkyl glucamine and an aliphatic ester of a fatty acid. The product of this reaction is indicated as being usable in aqueous detergent compositions without further purification. and also how to prepare an acylated glucamine sulfuric ester as described in U.S. Patent Number Z 717,894, issued September 13, 1955 to AM Schwartz. PCT International Application WO 83/04412, published December 22, 1983, filed by J. Hildreth, relates to amphiphilic compounds containing pali-hydroxylated aliphatic groups which are disclosed in US Pat. said to be useful for a variety of purposes, including the use as active agents in cosmetics, pharmaceuticals, shampoos, lotions and ointments " as emulsifying and dispersing agents for medicinal and biochemical products to solubilize membranes, whole cells or other tissue samples and for the preparation of liposomes. Included in this specification are the compounds of one of the formulas R'CON (R) CI-kR &quot; and R 'CON (R) R', in which R is hydrogen or an organic grouping, R 'is an aliphatic hydrocarbon group with at least three carbon atoms and R &quot; is the residue of an aldose. European Patent Application Serial No. 768, published October 12, 1988, filed by H. Kelkenberg et al., Relates to the use of N-polyhydroxy-alkylated fatty acid amides as thickening agents In aqueous detergent systems. Included are amides of the general formula wherein R1 is a C1 -C6 alkyl radical (preferably at C5 -C17), R1 is hydrogen, a C1 -C6 alkyl group (preferably C1 -C4) or an alkylene oxide and X is a polyhydroxy alkyl radical having from four to seven carbon atoms, for example N-methyl glucan, of coconut fatty acid. The thickening properties of the amides are indicated as of particular use in liquid petroleum systems containing paraffinic sulphonates, although aqueous surfactant systems may contain other anionic surfactants, such as alkylaryl sulfates, sulfo- salts of sulfosuccinic acid semi-esters and fatty alcohol esters and nonionic thioactive agents such as polyglycol ethers of fatty alcohols, polyglycol alkyl phenol ethers , polyglycol ester of fatty acids polypropylene / polyoxyethylene mixed polymers, etc. As examples, reference is made to sulfate shampoos of 735 - 715

1B

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paraffin / N-methyl-glucamide of coconut fatty acid / nonionic surfactant. In addition to the thickening properties, the pali-hydroxylated fatty acid amides are said to have superior skin tolerance properties. U.S. Patent Number 2,982,737 issued to Borttner et al. on May 2, 1961, relates to detergent bars containing urea, anionic surfactant anionic sodium tauryl sulfate and a N-alkyl glucagon nonionic surfactant which is selected from N-methyl-N -sorbiethyl-lauramide and N-methyl-N-sorbityl-amide. Other glucogenic surfactants are mentioned, for example, in DT 2 226 872, published on December 20, 1973, filed in the name of HW Eckert et al., Which relates to washing compositions comprising one or more fluorogenic agents active agents and binder salts selected from polymeric phosphates, sequestering agents and alkaline washing compounds, improved by the addition of an N-acyl polyhydroxy alkylamine of the general formula R 1 CH 2 CH 3 CH 2 CHOH CH 3 CHOH, in which R 1 is an alkyl radical in C1-3 alkyl, R8 is a C1 -C4 alkyl radical. and n is 3 or 4. The N-acyl-polyhydroxy alkylamine is added as a soil suspending agent. ... • The American Dividend Númere Patent. 3 654 * 166 ". issued April 4, 1972 a. H-W.Eckert et al. Refers to. composition; detergents, comprising at least one active-activating agent selected from the group consisting of thio-actives? anionic, non-ionic, hybrid and nonionic, and as textile softening agent a compound of · M-acyl-N-alkyl-polyhydrazine-alkyl of general formula R 1 NCZ) (1) wherein Rt is R 1 is a C 1 -C 4 alkyl radical and R 2 is a total of twenty-three to thirty-nine carbon atoms and Z is a polyhydroxy group which may be -CH, (CHO) d H H OH, wherein m is 3 or 4. U.S. Patent Application Serial No. 835 pp., (C) on May 3, 1977 to H. Moller et al., relates to cosmetic skin care compositions containing N-polyhydroxy alkylamines which include compounds of formula R 1 N (R) CH <CHOH) which is H, lower alkyl, hydroxy-alkyl or amino-alkyl, as well as amine-heterocyclic alkyl, R is equal to Rx mass can not be H and R3 is CH3 OH or COOH. granted on April 26, 1963, assigned to Commerc ial Solvents Corporation, relates to stabilized formaldehyde solutions against polymerization with addition of amides of the general formula RC (O) N (R) 8, wherein R is a carboxylic acid function group having at least seven atoms of carbon, R4 is hydrogen, or a lower alkyl group and 6 is a glypicol radical having at least five carbon atoms.

Mod. 7 | - 20,000 χ. German Patent Publication No. 1 261 861 of February 20, 1968, issued to A. Heins, relates to glucamine derivatives useful as wetting and dispersing agents of formula N ( R (Rx) (1) in which R is a sugar residue of glucamine, R 2 is a C 1 -C 4 alkyl radical and R 2 is a C 1 -C 10 acyl radical (U.S. Patent No. 745 036, published on 15 February 1956, assigned to Atlas Powder Company, refers to heterocyclic amides and their carboxylic esters which may be useful as chemical intermediates, wetting agents, dispersants, detergents, textile softeners, etc. The compounds are represented by the general formula in which R 1 is the residue of an anhydrized hexanopentol or a carboxylic acid ester thereof, R 2 is a monovalent hydrocarbonate monoester and a monovalent hydrocarbon monocarboxylate is the acyl radical of a carboxylic acid having two to twenty carbon atoms the carbon atoms of the present invention. i

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2 303 312 627, issued April 4, 1967 to DT Haoker, relates to solid toilet bars which are substantially free of anionic detergents and alkaline-based materials and which contain lithium soap of certain fatty acids, a nonionic counter ion activator selected from certain condensates of propylene oxide / ethylenediamine / ethylene oxide, condensates of propylene oxide / propylene glycol / ethylene oxide and palletized ethylene glycol and which also contain a component (I), wherein RC (O) contains from about 10 to about 14 carbon atoms and R 1 and R 2 are each H or groups C alquilo-C alquilo alkyl, said alkyl groups containing a total number of carbon atoms comprised between two to about seven and a total number of substituent hydroxyl groups comprised between two to about six. A substantially similar disclosure is found in U.S. Patent 3,312,626. also granted on April 4, 1967, to Hooverer TV. The use of nonionic activating agents in detergent compositions is known in the art. U.S. Pat. No. 3,654,166, issued on 4 April 1974. The? Eckerfc et al., Refers to compositions. detergents comprising a thioactive agent: - scaling of hybrids and nonionic anionic acetic actives, and a compound of N-alkyl-N-aryl-N-polyhydroxy-alkyl

Another disclosure of the use of nonionic surfactants in detergent compositions is provided by British Invention Patent GB 1 241 754, which discloses that ethylene oxide adducts of substantially unbranched C 1 -C 4 monocarboxylic alcohols, m and a mean ethylene oxide content of from 10% to 51% by weight, may serve as agents

These detergency builder agents are used in a weight ratio of the active agent to the reinforcing agent, and the amount of the active agent in the form of anionic or nonionic organic solubilizers. However, the reference does not provide for the combinations according to the present invention, which employ water-insoluble polyhydroxylated fatty acid amide-activating agents also defined as triphenyl active agents in water insoluble etioxylates.

Mod. 71 · 20,000 «X. - 90/08

According to the present invention, there is provided a laundry detergent composition useful for washing fabrics in automatic washing machines, said composition comprising one or more anionic, cationic, ampholytic or soluble hygroscopic detergent agents in water or mixtures thereof and optionally detergent builders, said composition being characterized in that it comprises a) at least 17% by weight of the composition of a polyhydroxylated fatty acid amide having the formula general 25 r · · ':: - ·· ΐν. (I.e. 30

in which R4 is H, a hydrocarbyl group in C1 -C4 alkyl. 2-hydroxy-propyl, 2-hydroxy-propyl or a mixture thereof; R * is hydrocarbyl in C--· · and Σ is a polyhydroxycarbonyl radical having a linear hydrocarbon chain with at least three hydroxy groups directly attached to said chain or an alkylated derivative thereof; and 35 11 10 15

B) at least 1% by weight of the composition of an ethoxylated primary aliphatic alcohol substantially insoluble in water containing a mean of no more than five oxide groups of ethylene per mole and having an ethylene oxide content of less than 50% by weight. Preferably, the composition is granular and comprises from 3% to 155% by weight of anionic surfactant, from 10% to 10% component a) and from 1% to 10% component b>, the weight ratio of anionic active agent for the combined weights of a) and b) in the range of from 1: 3 to 3: 1, preferably the anionic neutralizing agent comprises a mixture of a proportion greater than one water soluble C C alquilo sulf alkyl sulfate and a minor proportion of an alkyl ethoxy sulfate per mole of alkyl ethoxy sulfate. The detergent composition according to the present invention comprises three essential components, namely a palyhydroxylated fatty acid amide, a water insoluble adduct of ethylene oxide of a C 1 -C 8 aliphatic alcohol a water soluble surface active agent which may be anionic, cationic, ampholytic or hybrid. amide of polyhydroxy fatty acid amide according to the present invention comprises compounds of the general formula (I): wherein R1, R2, R3, R4, in which R 1 is H, C 1 -C 4 hydrocarbyl, 2-hydroxyethyl, 2-hydroxypropyl or a mixture thereof, preferably alkyl;

Preferably, C 1 or C 2 8 alkyl, even more preferably C 1 -C 8 alkyl (i.e., methyl); and R 2 is a C 1 -C 8 hydrocarbyl group, preferably C 1-4 straight chain alkyl or alkenyl, more preferably straight chain C 1-6 alkyl or alkenyl, and still more preferably C 1-6 straight or branched chain alkyl or alkenyl, linear or mixtures thereof and Z is a polyhydroxy hydrocarbyl group having a linear hydrocarbyl d chain with at least three hydrazyl groups directly attached to the chain or an alkoxylated (preferably ethoxylated (preferably ethoxylated or propoxylated) derivative thereof; Preferably, Z is derived from a reducing sugar in a reductive amination reaction, more preferably Z is a glycyl group. high dextrose cereal syrup, high fructose cereal syrup and high maltose cereal syrup may be used, as well as individual sugars These cereal syrups may give rise to a mixture of sugar components for Z. It should be understood that in no way is it intended to exclude other suitable starting materials, Z is preferably selected from the group consisting of -ΟΗ ,  € ƒâ € ƒâ € ƒâ € ƒâ € ƒâ € ƒâ € ƒâ € ƒwherein n is one. number, integer ranging from 3 to 5V inclusive and R4 is K or a cyclic or all-Tactical mannosaccharide and the alkoxy derivatives thereof. Most preferred are glycylene groups wherein n is 4, in particular, -CH * - (CHOH) 4-CHxOH. In the general Formula CD, R * can, for. N-ethyl, N-propyl, N-isopropyl, N-butyl and N-2-hydroxy-ethyl or N-2-hydroxy-propyl. R * -CO-N &lt; may be, for example, coconut acid amide, stearamide, oleamide, lauramide, myristamine,

Mod. 71-20,000 · κ. 90/08 20 25 30

%, capricamide, palmitamide, tallow acid amide, etc. 2-deoxy-1-decyl maltityl, 1-deoxy-lactyl, 1-deoxy-galactyl, 1-deoxy-mannyl, 1-deoxy-maltotrioethyl, and the like. . The most preferred polyhydroxylated fatty acid amides have the following general formula R *

Wherein R 2 is a straight chain alkyl or alkenyl group. Methods for the preparation of polyhydroxylated fatty acid amides are known in the art. Generally, they may be prepared by reacting an alkylamine with a reducing sugar in an amination reaction under reducing conditions to form a corresponding N-alkyl polyhydroxy amine and then reacting the N-alkyl polyhydroxyamine with a fatty aliphatic acid ester and / or a triglyceride in a condensation / the N-alkyl, N-polyhydroxy amide product was obtained. Process for the preparation of compositions containing polyhydroxy fatty acid amides are described for example in British Patent Specification 80, 060, published February 18, 1955, filed by Thomas Hedley &amp; Co., Ltd, in U.S. Patent No. Z 965 576, issued December 20, 1960, issued to. E, R Wilson, U.S. Patent Number Z 705,798, issued March 8, 1955 to Anthony M. Schwartr and U.S. Patent Number 1,985,414, issued December 25, 1934 to Piggott, all incorporated herein by reference. .

1 I

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According to a preferred process for the preparation of N-alkyl or N-hydroxy-alkyl, N-deoxyglycyl-amides of fatty acids in which the glycyl component is derived from glucose and the N-alkyl or N-hydroxyl group N-alkyl, N-propyl, N-butyl, N-hydroxyethyl or N-hydroxy-propyl, the product is prepared by reacting N-alkyl glucamine or N-hydroxy- glucamine with a fatty acid ester selected from the fatty acid methyl esters, fatty acid ethyl esters and fatty triglycerides in the presence of a catalyst selected from the group consisting of trilithium phosphate, trisodium phosphate, tripotassium phosphate, teleassay. pentapotassium tripolyphosphate, lithium hydroxide, sodium hydroxide, potassium hydroxide, calcium hydroxide, lithium carbonate, sodium carbonate, potassium carbonate, disodium tartrate, dipo- tassium tartrate, double sodium and potassium tartrate, citrate trisodium citrate, tripotassium citrate, basic potassium silicates, basic sodium aluminosilicates and basic potassium aluminosilicates and mixtures thereof. The amount of catalyst used is preferably from about 0.5 mole% to about 50 mole%, more preferably from about 2.0% to about 10 mole%, relative to N -Alkyl-glucamine, or N-hydroxyalkyl glucamine based on the number of moles of the reaction is preferably a. temperatures ranging from about 20 ° C to about 150 ° C, typically from about twenty to about ninety minutes. triglycerides are used in the reaction mixture as the fatty ester source, the reaction is also preferably carried out using from about 1 to about 10% by weight of a phase transfer agent, calculated on a percentage by weight basis of the total reaction mixture , selected from polyethoxylated saturated fatty alcohols, alkylpolyglycerols, linear diamine actives of glucamide and their derivatives.

Mod. 71 -20,000 · χ. - 90/08 20 25 30

Preferably, this process is carried out as follows: a) preheating the fatty ester at about 1382Â ° C to about 170Â ° C; b) adding N-alkyl glucan or N-hydroxy alkyl glucan to the heated fatty acid ester and mixing to the extent necessary to form a biphasic liquid / liquid mixture; c) mixing the catalyst with the reaction mixture; and d) stirring during the specified reaction time interval. Also preferably, from about 2% to about 20% by weight of a linear N-alkyl / N-hydroxy-alkyl, N-glucosyl linear fatty acid amide product previously formed in as the phase transfer agent, if the fatty acid ester is a triglyceride. This compound serves as the seed for the reaction mixture, thereby increasing the rate of the reaction. In the Experimental part of the present specification, a more detailed description is given below in the experimental procedure. The &quot; fatty acid &quot; polyhydroxylated polymers used in accordance with the present invention also provide detergent formulators with the advantages of being readily or partially prepared from renewable, non-petrochemical and degradable natural raw materials. They also exhibit toxicity low to aquatic life. . In a particularly preferred embodiment of the present invention, the polyhydroxylated fatty acid amide materials are derived from tallow grease in such a way that R 2 is a C 16 -C 16 alkyl chain group

Mod. 7? -20,000 ex. 90/08 20 25 30

BF / linear. It should be recognized that, together with the polyhydroxylated fatty acid amides of general formula (I), the process used to produce them also typically gives amounts of non-volatile by-products such as polyhydroxy fatty acid cyclic esteramides. The level of these by-products varies depending on the particular reagents and the conditions of the process. Preferably, the polyhydroxylated fatty acid amide incorporated in the detergent compositions is provided in a total form that the compositions containing amides of palyhydroxylated fatty acids added to the detergent contain less than about 10%, preferably less than about 4% polyhydroxy cyclic fatty acid amide. Preferred processes described above are advantageous in that they give relatively low levels of by-products, including the cyclic amide product. The polyhydroxy fatty acid amide component is present at a level of at least 1% by weight of the composition, more preferably 1% to 10% by weight, and more preferably at a level comprised between 2% and 10% by weight. * / ♦ and 6% by weight.

Non-ionic active agents. The detergent detergent compositions according to the present invention comprise, in addition to the polyhydroxylated fatty acid amide component, one or more nonionic defoaming agents described herein. nonionic compounds described herein are referred to as &quot; additional nonionic activating agents &quot; Nonionic compounds other than the additional nonionic activating agents may optionally be included in the nonionic activating system of the present invention . These other optional nonionic compounds include the following: 10 15

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will be referred to hereinafter as &quot; optional nonionic &quot;. Without wishing to be bound by theoretical considerations, it is believed that when such optional non-ionic active agents are included in the nonionic tensio-active system of the present invention, they do not provide the unexpected benefits of stain removal already described hereinbefore.

Additional Nonionic Tonsyn-Ion Agents

Additional nonionic active agents useful in the compositions according to the present invention comprise condensed primary aliphatic alcohols condensed with an average of no more than five clumps of ethylene oxide per mole of alcohol. Such alcohol etioxylates must have an ethylene oxide content of less than 50% by weight and must be insoluble in water. A preferred aliphatic alcohol ethoxylate is a linear or substantially linear aliphatic alcohol containing a mean of twelve to fifteen carbon atoms in the alkyl chain, ethoxylated with an average of three ethoxy groups per mole of alcohol. The additional nonionic active agent is present at a viscosity of at least about 1% to about 1% to more preferably about 15% to about 6%. The third essential component of detergent washing compositions; according to the present invention &quot; is one or more water-soluble active agents, selected from anionic, cationic, ampholytic and hybrid anionic surfactants. 18 · &gt; Γ · r W '1

i /

Anionic Agents

The detergent detergent compositions according to the present invention may contain, in addition to the nonionic surfactant system according to the invention, one or more anionic surfactants as described below.

Alkyl Sulfonate ester TSnsio-active agents

Mod. 71-20,000 · χ. · 90/06

The alkyl sulphonate ester surfactants include linear esters of carboxylic acids at 0.01 (i.e., fatty acids), which are sulfonated with 5% gaseous according to &quot; The Journal of the American Oil Chemists Society &quot; 52 (1975), pp. 323-329. Suitable starting materials include natural fats such as those derived from tallow, palm oil, etc. The preferred alkyl ester sulphonate sulfonate agent, especially for laundry applications, comprises alkyl ester sulfonate functional agents of the structural formula.

O 25

Wherein R * is a hydrocarbon radical in QC, preferably a: alkyl radical, or a combination thereof; R4 is a C1-6 hydrocarbyl group, preferably an alkyl or their combination; and M is a cation which forms a water-soluble salt with the alkyl ester sulfonate. Carboxylates which form suitable salts include metal cations such as sodium, potassium and lithium and substituted or unsubstituted ammonium cations such as monoethanolamine, diethanolamine and triethanolamine. Preferably R 3 is a C 1 -C 4 alkyl group and R 4 is methyl, ethyl or isopropyl. Particularly preferred are sulfonates of methyl esters wherein R 3 is an alkyl radical in CHO-CLA.

Active Agent of Alkyl Sulfate 10 15 20

The alkyl sulfate thiogenic agents according to the present specification are water soluble salts or acids of the general formula ROSOsM, in which R is preferably a hydrocarbyl group, preferably an alkyl group or a hydroxy alkyl group having a C 1 -C 8 -alkyl component, more preferably an alkyl or hydroxyalkyl group in C 1 -C 4 -alkyl or a cation, for example an alkali metal (e.g., sodium, potassium, lithium) or ammonium or substituted ammonium salts (for example, methylammonium, dimethylammonium and triethylammonium) and quaternary ammonium cations, such as tetramethylammonium, dimethyl piperidinium and dimethylaminophenylaminates, and alkylamines derived from alkylamines such as ethylamine, diethylamine, triethylamine and the like. mixtures thereof and the like). 25

Preferred are alkyl groups. of chain with twelve to sixteen carbon atoms. more preferably with fourteen to fifteen carbon atoms.

The alkoxylated alkyl sulfates useful agents according to the present invention are salts or water soluble acids having the general formula R0 (A) wherein S is an unsubstituted alkyl or hydroxy-alkyl group having a

6-Ly-v = -i - // v? C? -C? alkyl; preferably a C1 -C4 alkyl or hydroxy alkyl group, and more preferably an alkyl group having twelve to eighteen carbon atoms, and especially twelve to fifteen carbon atoms; A is a unit of ethoxy or propoxy; m is greater than 0 * typically a number of from about 0.5 to about 6, and more preferably from about 0.5 to about 3; and Li is H or a cation such as, for example, a metal cation (eg sodium, potassium, lithium, calcium, magnesium, etc.), ammonium or substituted ammonium cation. To this end, ethoxylated alkyl sulfates, as well as propoxylated alkyl sulfates, are provided. Specific examples of substituted ammonium cations include methylammonium, dimethylammonium, trimethylammonium and quaternary ammonium cations, such as tetramethylammonium and dimethyl piperidinium ketals, and those derived from alkylamines, such as ethylamine, diethylamine, tristilamine, mixtures thereof and the like. Preferred examples of ethoxylated sulfate and alkylsulfonate agents are C2 -C10 alkyl ethoxysulfates which contain up to three ethoxy groups per mole of alkyl ethoxy sulfate. A particularly preferred triphosphate agent is C12-C12 alkyl; polyethoxylate (3.0) sulfate - (C -C-CΧΧ amp amp ampΨ) M). Other exemplary excipient agents include t-2-C,-CL-CL-Ethoxyethoxy-C)-C)-C alquilo-alkyl, C,-C,-C,-alkyl) (2â € ²-Oâ € ²-Oâ € ƒâ € ƒâ € ƒâ € ƒâ € ƒâ € ƒâ € ƒâ € ƒâ € ƒâ € ƒâ € ƒâ € ƒâ € ƒâ € ƒâ € ƒâ € ƒâ € ƒâ € ƒ (2.25) (C12 -C4 -C4) 0) M), where M is suitably chosen from sodium and potassium.

Other Agents Anionic TSnsio-actives

Other anionic surfactants 21 35 1 5 10 15

Mod. 7 | 20,000 ex. - 90/08 20 25

useful as detersives may also be included in the laundry detergent compositions according to the present invention. They may include salts (including, for example, sodium, potassium, ammonium and substituted ammonium salts, such as monoethanolamine, diethanolamine and triethanolamine salts) of soap, linear alkyl benzene sulphonates, Primary or secondary C3 -C4 olefin sulphonates, sulphonated polycarbophilic acids prepared by sulphonation of the pyrolysis products of alkaline earth metal citrates, for example, as described in the patent specification of British Invention Number 1,082,179, alkyl in Ce-β-polyglycol ether sulfates (containing up to ten moles of ethylene oxide); alkyl glycerol sulfonates, glyceryl acyl glycol sulfonates, oleyl glycerol fatty sulfates, alkyl phenol ethylene oxide ether sulfates, paraffin sulfonates, alkyl phosphates, isethionates such as acyl isethion N-acyl taurates, alkyl succinamates and sulfo succinates, mono-esters of sulfo-succinates (especially saturated and unsaturated C 1 -C 12 monoesters) and diesters of sulpho-succinates (especially C-esters Saturated and unsaturated alkyl acyl sarcosinates, alkyl polysaccharide sulphates, such as alkyl polyfluoroside sulfates, sulfated nonionic compounds which are described below, primary, branched and substituted alkylsuccinates. alkyl-β-ethoxy-carbaxylatosols such as those of the general formula wherein R² is a C--C alquil alkyl radical, k is an integer from 0 to 10 and M is a cation forming soluble salts. Also suitable are acid resins and alkyl esters. in hydrogenated materials such as pine resin, hydrogenated pine resin and resin acids and hydroganic resin acids present in the oak (tall oil) derivatives. Other examples are described in "Surface Active Agents and Detergent &quot; (Vol. I and II, by Sehwartz, Perry and Berch). A big

22 35 10 15

Mod. 71 20,000 Âμ. · 20 25 30

variety of these surfactants is also referred to in U.S. Patent 3,929,678 issued to Laughlin et al. on December 30, 1975, at column 23, line 58 to column 29, line 23 incorporated herein by reference). Preferred anionic surfactant systems employed in the laundry detergent compositions according to the present invention are free of alkyl benzene sulfonate salts. An especially preferred system comprises a mixture of a higher proportion of a water soluble C C-C alquilo -s alkyl sulfate and a minor proportion of a C--C--C e-alkyl sulphate containing an average of three ethoxy groups per mole of alkyl ethoxy sulfate. The laundry detergent compositions according to the present invention typically comprise from about 1% to about 20%, preferably from about 3% to about 15%, and most preferably from about 5% to about 10%. % by weight of anionic surfactants. Other Tensioactive Agents The laundry detergent compositions according to the present invention may also contain cationic, ampholytic, hybrid and semi-polar surfactants. Cationic surfactants suitable for use in the laundry detergent compositions according to the present invention are those having a long chain hydrocarbyl group. Examples of such cationic surfactants include the surfactants of ammonium halides, such as alkyl dimethyl ammonium halides and the surfactants having the formula ## STR5 ## wherein R 1, R 2, R 3,

Mod. 71-20,000 cc. Wherein R 2 is an alkyl benzyl group having from about eight to about eighteen carbon atoms in the alkyl radical; each R * is selected from the group consisting of -CH 2 CH 2 CH 2 CH (CH 4 -, -CH 2 Η (O, OH) -, -CH (CH 2) h Cl and each of R 'is selected from the group consisting of C 1 -C 4 -alkyl, benzyl ring structures formed by joining the two R 3 groups, wherein R 2 is any hexose or hexose polymer having a molecular weight less than which is about 1,000 and hydrogen when y is not 0, R 'is the same as R4 or is an alkyl radical in which chain the total number of carbon atoms of R2 plus NR10 SO4 is more than about eighteen, each y is a number from 0 to about 10 and the sum of the values of y ranges from 0 to about 15; and X is any compatible anion. Other cationic taining agents useful according to the present invention are also described in U.S. Pat. U.S. Patent 4,228,044, issued to Cambre on October 14, 1980, incorporated herein by reference. laundry detergent compositions according to the present invention comprise: typically 0%. to about 25% - preferably about 35 to about 15% by weight of such cationic surfactants. Ampholytic active agents are also useful for use in laundry detergent compositions according to the present invention. These surfactants may be described in their. aliphatic derivatives of secondary or tertiary amines or aliphatic derivatives of heterocyclic secondary or tertiary amines wherein the aliphatic radical may be straight chain or branched. One of the substituents 24 1 5 10 15

Mod. 71-20,000 χ. - 90/08 25 30 * η γγτ iC.Ôi.í ·! ✓

aliphatic radicals contains at least about eight carbon atoms, typically between about eight and about eighteen carbon atoms, and at least one contains an anionic group which promotes solubilization in water, for example, earboxy, sulfonate, sulfate . See U.S. Patent 3,929,678, issued December 30, 1975 to Laughlin et al., Column 19, lines 18-5 (incorporated herein by reference) as examples of amphiphilic surfactants. When included herein laundry detergent compositions according to the present invention typically comprise from 0% to about 15%, preferably from about 1% to about 10% by weight, of such ampholytic surfactants. Hybrid surfactants are also suitable for use in laundry detergent compositions. These tensioactive agents can be broadly described as derivatives of secondary or tertiary amines derived from secondary and tertiary amines heterocycles or derivatives of quaternary ammonia, quaternary phosphonium or tertiary sulfonium compounds. See U.S. Patent Number 3,929,678, issued to Laughlin et al. in 30t of Dexembrane of 1973, column 19, line 38, to column 22, line 48 (here incorporated by reference), for examples of hygienic active-activating agents. When included herein, detergent laundry detergent compositions of according to the present invention: typically comprise from 0% to about 15%, preferably from about 1%. to about 10% by weight of these hygienic active agents. Non-ionic semi-polar active agents are a special category of nonionic surfactants which include water-soluble amine oxides which contain an alkyl group having about 10 25 35

to about eighteen carbon atoms are two groups selected from the group consisting of alkyl groups and hydroxy alkyl groups containing from one to about three carbon atoms; water-soluble phosphine oxides which contain an alkyl group having from about ten to about eighteen carbon atoms and two groupings selected from the group consisting of alkyl groups and hydroxy alkyl groups containing from about one to about three atoms of carbon; and water soluble sulfoxides containing an alkyl grouping of from about 10 to about 18 carbon atoms and a grouping selected from the group consisting of alkyl and hydroxy alkyl groups having from about one to about three carbon atoms.

Mod. 7 | -20,000 â † '90.80

Semi-polar nonionic detergent surfactants include amine oxide surfactants having the following general formula (II): wherein R * is an alkyl, hydroxy-alkyl or alkyl-phenyl group or mixtures thereof, about eight to about twenty-two carbon atoms;  € ƒâ € ƒâ € ƒâ € ƒâ € ƒâ € ƒâ € ƒâ € ƒâ € ƒâ € ƒâ € ƒâ € ƒâ € ƒR1 is a leaving group or hydroxyalkylene containing from about â € ƒâ € ƒâ € ƒto two to about three carbon atoms; x is a number from 0 to about 3; and each R ° is an alkyl or hydroxyalkyl group containing from about one to about three carbon atoms or a group of ethylene polyoxide containing from about one to about three ethylene oxide groups R * groups may be attached to one another, for example via an oxygen or nitrogen atom, to form a ring structure.

These amine oxide tenside agents include, in particular, the alkyl oxides in

Mod. 71-20,000 οχ. 70/08 20 25 30 35

When the detergent compositions according to the present invention are included herein, the compositions of the present invention comprise typically from 0% to 1% to about 15%, preferably from about 1% to about 10% by weight of these semi-polar nonionic surfactants.

Baking Agents

Detergent laundry compositions according to the present invention may comprise inorganic or organic detergent builders to assist in controlling mineral hardness. The level of doping agent may vary within wide limits depending on the end use of the composition and its intended physical form. Liquid formulations typically comprise at least about 1%, more typically from about 5% to about 50%, preferably from about 5% to about 30%, by weight detergent builder. The granular formulations typically comprise at least about 1%, more typically, from about 10% to about 80%. preferably from about 15% to about 50% by weight of the detergent builder. The detergent builder is not intended to exclude &quot; &quot; lower &quot; or higher levels of bulking agent. Inorganic detergent builders include, but are not limited to, alkali metal, ammonium and alkanolammonium salts of polyphosphates, exemplified by tripolyphosphates, pyrophosphates and vitreous polymeric metaphosphates), phosphonates, -. silicates ,. carbonates (including bicarbonates and sesquicarbonates), sulfates and aluminosilicates. Borate-based builders may also be used, as well as builders containing borate forming substances which

2T

may produce borate in the detergent storage conditions or washing conditions, but are not preferred in the wash conditions at temperatures below about 50 ° C, especially below about 40 ° C. Preferred builder systems are also free of phosphates. Exemplary of silicate builders are alkali metal silicates, particularly those having a SiO2: NafJ ratio in the range of 1.6: 1 and 3.2: 1 and the layered silicates are as layered sodium silicates.

Preferred crystalline layer sodium silicates have the following general formula: 15

Mod. 71-20,000 · κ. -> / 08 20 2 &amp; 30

NaMSi "wherein M is sodium or hydrogen; x is a number from 1.9 to 4; and y is a number comprised between 0 and 20. Crystalline layered sodium silicates of this type are disclosed in European Patent Application No. 1,645,144 and the processes for their preparation are described in German Patents DE-A -3417649 and DE-A-3742043, incorporated herein by reference. For the purposes of the present invention and the above-mentioned general formula. x · tem. a value equal to 27 ° 3 &quot; or 4 and e is preferably 2. More preferably sodium M e and y is: O and preferred examples of this, formula include the alpha, beta, gamma and delta forms of NaxsyjB These products are available in the form HOECHST AGR Republic Federal of Germany, respectively, NaSKS-5, NaSKS-7, NaSKS-tt and NaSKS-6. The most preferred product is de-Na 2 Si 2 QB NaSKS-6. Other silicates, such as, for example, magnesium silicate, which serve as creping agents in granular formulations, may also be useful as stabilizing agents for bleaching agents

28 35 1 1 10

Mod. 71-20,000 e *. Containing oxygen and as component of foam control systems. Examples of carbonaceous bulking agents are alkaline earth and alkali metal carbonates, including sodium carbonate and sodium sesquicarbonata and theirs. mixtures with ultra-fine calcium carbonate, as referred to in German Patent Application 2 321 001, published November 15, 1973, the disclosure of which is hereby incorporated by reference.

The alumino-silicate builders are especially useful in the present invention. The alumino-silicate builders are of great importance in most of the granular detergent compositions of wide use corresponding to the sale on the market and can also be a significant builder ingredient in liquid detergent formulations. The alumino-silicate builders include those having the empirical formula M, CzAl &lt; V? 10) in which Li is sodium, potassium, ammonium or substituted ammonium; 2 is a number from about 0.5 to about 2; and y is the number 1; this material having a magnesium ion exchange capacity of at least about 50 milligram-equivalents of hardness, of CCOCO por per gram of. alumina-silica anhydride. Preferred alumino-sicates are the zeolite builders having the formula

Na, C (Al Q), <SiC £, ϊ., ΧΗ ^ Ο in which z and y are integers at least equal to 6, the molar ratio of z to y being in the range of 1.0 to about 0 , Ex is an integer of from about 15 to about 264.

The ion exchange products of aluminum-29 35 ιε, ζιιρρ

Mod. 7) - 20,000 · χ. · 90/08 20

2E 30 silicates are commercially available. These alumino-silicates may have crystalline or amorphous structure or may be naturally occurring alumino-silicates or synthetically prepared. A process for the production of alumino-silicate ion exchange materials is described in U.S. Patent 3,985,669, issued to Krummel et al. on October 12, 1976, hereby incorporated by reference. Preferred synthetic crystalline aluminosilicate ion exchange materials useful in accordance with the present invention are available under the following conditions. the designations of Zeolite A, Zeolite F (B) and Zeolite X. According to an especially preferred embodiment, the crystalline aluminosilicate ion exchange material has the following general formula

Na (A102) 12 (SiO2): wherein: x is a number from about 20 to about 30, especially about 27. This material is. known as Zeolite A. Preferably, the aluminosilicate has a particle size of between about 0.1 and 10 micrometers in diameter.

Specific examples of polyphosphates are the alkali metal tripaliphosphates, potassium sol-pyrazoles and sodium α-pyrophosphate. patássia and amoniay cr. orta-phosphate · of sodium · and patássia · the · sodium polymetaphosphate in which grade. of polymerization is between about 6 to about 21 and the salts of the optical acid.

Examples of phosphonate builder salts are the water-soluble salts of ethane-1-hydroxy-1,1-diphosphonate, particularly sodium and potassium salts, the water-soluble salts of methylene diphosphonic acid, for example , trisodium and tripotassium salts and the water-soluble salts of substituted methylene diphosphonic acids.

Mod. 71-20,000 · χ. - »0/08 20 30

Such as ethylidene phosphonates, isaprapylidene-phosphonates, benzyl methylene phosphonates and trisodium and tripotassium halogeno-methylidene phosphonates. The phosphonate salts of the aforementioned types are described in U.S. Patent Nos. 3,157,581 and 3,213,030, issued December 1, 1964 and in U.S. Pat. October 1965 to Diehl; U.S. Patent 3,232,021, issued January 14, 1969 to Roy; and U.S. Patents Nos. 3,400,148 and 3,232,137 issued to Quimby on September 3, 196B and January 14, 1969, respectively, and their disclosures are incorporated herein by reference. The polycarboxylate builders may generally be added to the compositions in acid form, but may also be added as neutralized salt. When used in the form of salts, alkali metal salts such as sodium, potassium and lithium salts, especially sodium, or ammonium or substituted ammonium salts (for example, alkanolammon) are preferred. Included among the polycarboxylate builders are a variety of useful material categories. A number of ether polycarboxylates have been mentioned in the literature which may be used as detergent builders. Examples of useful polycarboxylate ether include polyether carboxylates, - succinate ,. as described in U.S. Patent 3,128,287, issued April 7, 1964 to Berg and U.S. Patent Number 3,635,830 issued January 18, 1972 to Lamberti et al. , both incorporated herein by reference. A specific type of ether polycarboxylates useful as a bulking agent in the compositions according to the invention.

Mod. 71-20,000 ax. - $ 0/08 20 l I ►! ! The present invention also includes those having the general formula CH (A) (COOX) -CH (CDOX) -0-CH < CODX) -CH (COOX) (B) wherein A is H or OH; B is H or -O-CH (COOX) -O (COOX); and X is H or a salt forming cation. For example, if in the above-mentioned general formula A and B- are an H, then the compound is oxy-disuccinic acid and its salts are soluble in water. If A is OH and B is H, then the compound is tartrate monosuccinic acid (TMS) and its water soluble salts. If A is H and B is -Q-CH (COOX) -CHa (COOX), then the compound is tartrate disuccinic acid (TOS) and its water-soluble salts. For use in the compositions according to the present invention, mixtures of these bulking agents are especially preferred. Particularly preferred are mixtures of TMS with TDS in a TMS weight ratio of about 97-3 to about 20:50. These bulking agents are disclosed in U.S. Patent 4,663,636; 071, issued to Bush et al. on May 5, 1987. Suitable ether polycarboxylates also include cyclic compounds, particularly alicyclic compounds, as described in U.S. Patents Nos. X 92X 679r X 835 16X, 4 15 635.4 120 874 and 4 102, 903, all incorporated herein by reference. Other useful detergent builders include the ether hydroxy polycarboxylates represented by the general structure formula

In which M is hydrogen or a cation such that the resulting salt is soluble in water, preferably a cation 32 1 5 10 (a) 15

Mod. 7 | - 20,000 · χ. · »/ 08 20 25 30 35 zsrz ο!? Θ? S * of alkali metal, ammonium or substituted ammonium; n is a number of from about 2 to about 1 (preferably n is from about 2 to about 10, more preferably the average value of n is from about 2 to about 4); and each R is the same or different and is selected from hydrogen, C1-4 alkyl or C1-4 alkyl. (most preferably, R is hydrogen). Still other ether polycarboxylates include copolymers of maleic anhydride with ethylene or vinylmethyl ether of 1,3,5-trihydroxy-benzene-2,4,6-trisulphonic acid and carboxy-methyloxy-succinic acid. Organic polycarboxylate builders also include the various alkali metal, ammonium and substituted ammonium salts of polyacetic acids. Examples of polyacetic acid builders are sodium, potassium, lithia, ammonium and substituted ammonium salts of ethylenediaminetetraacetic acid and nitrile-triacetic acid. Also included are carboxylates such as melitic acid, succinic acid , polymaleic acid, benzene-1,3,5-tricarboxylic acid, benzenecarboxylic acid and carboxymethyloxy succinic acid and the soluble salts thereof. Citrus bulking agents, for example, cyclic acid, are soluble salts thereof, polycarboxylate builders, of particular importance for high-performance liquid detergent formulations, but may also be used in granular compositions. Suitable salts include the metal salts of sodium, lithium and potassium as well as salts. ammonium and substituted ammonium '. Other carboxylate-bulking agents include the carboxylated carbohydrates referred to in U.S. Patent Number 3 &quot; 723 322, granted to

33 1 5 10 15

Mod. 7 | 20,000 x. - 90/08 20 25 30, 18 S? To 5 5

Diehl on March 28, 1973, incorporated herein by reference. Also suitable in the laundry detergent compositions according to the present invention are 3,3-dicarboxy-4-oxa-1,6-hexanedioates and the related compounds referred to in U.S. Patent No. 4,566,984, . issued to Bush on January 28, 1986, hereby incorporated by reference. Useful succinic acid-based bulking agents include C 1 -C 8 -alkyl succinic acids and their salts. A particularly preferred compound of this type is dodecenyl succinic acid. Alkyl succinic acids are typically acids of the general formula R-CH (GOOH) CH (COOH), i.e. succinic acid derivatives in which R is a hydrocarbon derivative, for example, alkyl or alkenyl, preferably in C1-4 alkyl or in R may be substituted by substituents selected from hydroxy, sulfa, sulfoxy or. sulfanates, all as described in the above-mentioned patents. Succinate builders are preferably used in the form of their water-soluble salts, including sodium, potassium, ammonia and alkanolammonium salts. Specific examples of succinate builders include lauryl succinator myristyl succinator. naphthylate and the like. The lauryl succinates are the preferred builders of this group and are described in European Patent Application 86200690.5 / G 200 263, published on November 5, 1986. Examples of useful bulking agents also include carboxymethyloxymolonate, carboxymethyloxysuccinate, cis-cyclohexane-hexacarboxylate, sodium and potassium cise-cyclopentane-tetracarboxylate, polyacrylates soluble in water (these polyacrylates having molecular weights

Mod. 7] · 20,000 · χ.- 90/08 20 25 30

// homes with values up to about 2,000 can be effectively used as dispersing agents) and copolymers of maleic anhydride with vinyl methyl ether or ethylene. Other suitable polycarboxylates are the polyacetal carboxylates disclosed in U.S. Patent 4,144,226. issued to Crutchfield et al. on March 13, 1979, hereby incorporated by reference. These polyacetal carboxylates may be prepared by contacting, under palletizing conditions, a glyoxylic acid ester with a polymerization initiator. The resulting polyacetal carboxylate ester is then attached to chemically stable end groups to stabilize the polyacetal carboxylate against rapid depolymerization in alkaline solution, transformed into the corresponding salt and added to a surfactant. Polycarboxylate builders are also referred to in U.S. Patent 3,308,067, issued to Diehl in T, March 1967 &quot; incorporated herein by reference. Such materials include the water-soluble salts of homopolymers and copolymers of aliphatic carboxylic acids, such as maleic acid, itaconic acid, mesaconic acid, fumaric acid, acanítico acid, citraconic acid and methylene malonic acid. They can too. other organic builders known in the art may be used. For example, monocarboxylic acids and their solor-vexers salts having long chain hydrocarbyl groups may be used. These compounds include materials commonly referred to as &quot; sabtres. &Quot; hydrocarbyl radicals may be saturated or unsaturated.

Enzymes

In the detergent wash compositions of 35

Mod. 71-20,000 · χ. 90/08 20 25 30 35. In accordance with the present invention, detersive enzymes may be included for a variety of reasons including removal of triglyceride based, carbohydrate or protein based stains, for example, and prevention of dye transfer . Embodiments to be included include proteases, amylases, lipases. cellulases and peroxidases, as well as mixtures thereof. They may be of any suitable origin, such as plant, animal, bacterial, fungal and yeast origin. However, their choice depends on a number of factors, such as pH-activity and / or optimum stability, thermostability, stability versus active detergents, bulking agents, etc. In this regard, enzymes of bacterial or fungal origin, such as amylases and bacterial proteases and cellulases derived from fungi, are preferred. Suitable examples of proteases are subtilisins, which are obtained from particular strains of B. subtilis and B. licheniformis. Another suitable protease is that obtained from a strain of Bacillus having maximal activity over a pH range of 8 to 12, developed and sold by Novo Industries A / S under the tradename trade name Esperase &quot;. The preparation of this enzyme and analogous enzymes is described in the specification of British Invention No. 243,784. Navcr. Suitable proteolytic enzymes for the removal of stains derived from proteins that are commercially available include those sold under the registered trademarks of ALCALASE and SAVINASi. by -Firma Novo Industries A / A (Denmark) and under MAXATASE * by International Bio-Synthetics, Inc., (The Netherlands). Tam. in the category of proteolytic enzymes, the enzymes designated herein by Protease A and Protease B are preferred. Protease A and the processes for their preparation are described in U.S. Patent Application Ser. .

Mod. 71 -20,000 · χ. - 20/03 20 2 £ 30-35; -n

European Invention Number 130 756, published January 9, 1985, incorporated herein by reference. Protease B is a proteolytic enzyme which is distinguished from Protease A in that it has a leucine group substituted by thirasin at position 217 of its amino acid sequence. Protease B is described in European Patent Application No. No. 97303761.8, filed April 28, 1987 and incorporated herein by reference. In European Patent Application 130 756, filed by Bott-et-Garon, published January 9, 1985, there are also processes for preparation of Protease B, which is incorporated herein by reference. Amylases include, for example, alpha-amylases, obtained from a special strain of N. licheniformis, described in more detail in British Invention Patent Number 1 296 839 (New), incorporated herein by reference. Amylolytic proteins include, for example, RAPIDASE * from International Bio-Synthetics, Inc. and TERMAMYL &quot; from Novo Industries. Cellulases usable in the compositions according to the present invention include both bacterial and fungus origin cellulases. Preferably, they have an optimum pH of from about 5 to 9.5. Suitable cellulases are referred to in the. United States Invention. No. 4,435,307, issued to Barbesga- - - - - - - - - - - - - - - - - - - - - - - - - - - - : caldera cal "on March 6, 1984 and incorporated herein by reference * which relates to cellulases originating from fungi produced by Humicola insolens. Also suitable cells are referenced in British Patent Patents Nos. GB-A-2 075 025 - and GB-A-2 095 '275 and in the specification for the public inspection of German Patent DE-OS-247 Examples of such cellulases are cellulases produced by a strain of Humicola insolens (H. grays).

. im? t 6 / var. thermoidea), particularly the Humicola DSM 1800 strain, and cellulases produced by a Bacil-lus N fungus or a fungus which produces the cellulase 212 belonging to the genus Aeromonas and the cellulase extracted from hetatopancreas of a marine mollusk (Dolabella AUricula Solander) . Lipase enzymes suitable for use in detergent compositions include those produced by microorganisms of the Pseudomonas group, such as Pseudomonas stutzeri ATCC 19,154, as referred to in British Invention Patent No. 1,372,034, incorporated herein by reference. Suitable lipases include those having an immunologically positive cross-reaction with the lipase antibody produced by the microorganism Pseudomonas fluorescens IAM 1057. This lipase is a process for its purification are described in Japanese Patent Application Laid-Open No. 53-20487, published for on February 24, 1978. This lipase is available from Amano Pharmaceutical Co., Ltd., Nagoya, Japan, under the tradename Lipase P &quot; Amano &quot;, hereinafter referred to as &quot; Amano- These lipases according to the present invention should possess a positive immunological cross-reaction with the Amano-P antibody using the standard and well-known immunodiffusion procedure according to Qutherland et al. Med. Scan., 133, pages 76-79 CI950X These; lipases: is; a method for its immunological cross-reactivity with Amano-P are described in U.S. Pat. 4- issued to Thom et al. on November 17, 1987, hereby incorporated by reference. Typical examples thereof are amine-F, lipase. Pseudomonas fragm FERM 'P1339 lipase (available under the trade name of Ameno-B) to lipase from. Pseudomonas nitroredusens var. lipolyticum FERM P 1338 (available under the tradename Amano-CES), lipases from Chromobacter viscosum, for example, C. viscosum var. lipolyticum NRRLB 3673, 38 3 1 5 10 15 20 25 30 35

commercially available from the Toyo JoZo Co., Tagata, Japan; and the Chromobacter viscosum lipases of U.S. Biochsmical Corp., United States of America and Disoynth Co., The Netherlands, and the lipases from Pseudomonas gladioli. An especially preferred lipase enzyme is that manufactured and sold by Novo Industries A / S, Denmark, as the registered trademark of Lipolase (Biotechnology Newswatch, March 7, 1988, page 6) and mentioned together with other appropriate lipases in U.S. Pat. EP-A-2808 (Novo) and incorporated herein by reference. Peroxidase anzymes are used in combination with oxygen sources, for example percarbonate, perborate, persulfates, hydrogen peroxide, etc. They are used for &quot; solution bleaching &quot;, i.e. to avoid the transfer of dyes or pigments removed from the substrates during the washing apertures to other substrates present in the wash solution. Peroxidase enzymes are known in the art and include horseradish peroxidase, ligninase and haloperoxidase such as chloroperoxidase and bromoperoxidase. Detergent compositions containing peroxidase are referred to, for example, in International Patent Application WO 89/099813, published October 19, 1989. deposited by O. Kirk and assigned to. A wide range of enzyme materials and the means for their incorporation into synthetic detergent granules is referred to in U.S. Patent Application No. 3 553 139, issued January 3, 1971 to MacCarty et al. (Incorporated herein by reference.) Enzymes are further referred to in U.S. Patent 4,101,451, issued to Place et al. On July 18, 1978 and in U.S. Patent Number 4,507,219, issued to Hughes on March 26, 1995.

Mod. 7J-20,000 ex. · 90/08 20 25 30 35 ff and 1985, both incorporated herein by reference. The enzyme materials useful in the liquid detergent formulations and their incorporation into such formulations are described in U.S. Patent 4,261,886, issued to Hora et al. on April 14, 1981, also incorporated herein by reference. Enzymes are usually incorporated at levels sufficient to provide up to about 5 mg by weight, more typically from about 0.05 mg to about 3 mg of active enzyme per gram of the composition. For granular detergents, the enzymes are preferably coated or pre-filled with inert additives relative to the enzymes to minimize the formation of powder and improve stability during storage. The techniques for accomplishing this are well known to those skilled in the art. In liquid formulations, an enzyme stabilization system is preferably used. Techniques for stabilizing enzymes in aqueous detergent compositions are well known to those skilled in the art. For example, a technique for stabilizing enzymes in aqueous solutions comprises the use of free calcium ions from sources such as calcium acetate, calcium formate and calcium propionate. The calcium itfes &quot; may be used in combination with salts of carboxy acids. preferably? formeatas See, for example, U.S. Pat. No. 4, 318, 818, issued to Letton et al., March 9, 1982, incorporated herein by reference. It has also been proposed the use of palletizers, such as glycerol and disulfide, alkoxy alcohols, dialkyl glycol ethers, mixtures of polyfunctional alcohols with polyfunctional aliphatic amines (for example, alkanol amines, such as diethanolamine, triethanolamine, diisopropanolamine, etc. .) and boric acid or alkali metal borate. Enzyme stabilization techniques are further described and exemplified in US Pat.

gt; and

Mod. 71-20,000 βχ. - 90/08 20 25 30 35

U.S. Patent Number 4,261,886 issued to Horn et al. on April 14, 1981, in U.S. Patent Number 3,600,319 issued to Gedge et al. on August 17, 1971, both incorporated herein by reference and in European Patent Application Publication No. 0 199 405 and European Patent Application Number 86200586.5, published October 29, 1986 and filed by Venegas. Stabilizers which are not boric acid and cheap are preferred. Antibody stabilization systems are described in, for example, U.S. Patent Nos. 4,261,868, 3,660,319 and 3,551,570.

Bleaching Agents - Bleaching Agents and Bleach Activating Agents

The laundry detergent compositions according to the present invention may contain bleaching agents or bleaching compositions which contain a bleaching agent and one or more bleach activators. When included, the present bleach compounds typically comprise from about 1% to about 20%, more typically from about 1% to about 10% of that laundry detergent composition. In general, the bleaching compounds are optional components of the non-liquid formulations, for example granular detergents. If present, the amount of bleach activating agent is typically comprised: about 0.1%; and about 60%, more typically, from about 0.5% to about 40% of the bleaching composition.

The bleaching agents used herein may be any bleaching agents useful in detergent cleaning compositions for cleaning textile products, cleaning hard surfaces or other purposes of cleaning.

which are now known or have become known. A category of bleaching agent which may be used comprises percarboxylic acid bleaches and their salts. Suitable examples of this class of agents include magnesium monoperoxy phthalate hexahydrate, magnesium salt of methacrylic acid, chloro-perbenzoic acid, 4-nonylamino-4-oxo-peroxy-butyric acid and diperoxy-dodecanedioic acid. These bleaching agents are disclosed in U.S. Patent 4,483,781 issued to Hartman on November 20, 1984; in U.S. Patent Application Serial No. 740,446, filed by Burns et al. on June 3, 1985; in European Patent Application 0 133 354, as deposited by Banks et al. and published on February 20, 1985; and in U.S. Patent 4,412,934 issued to Chung et al. on November 1, 1983, all incorporated herein by reference. Very particularly preferred bleaching agents also include 6-nonylamino-6-oxo-peroxy-rocolic acid, as described in U.S. Patent No. 4,634,551, issued to Burns et al. on January 6, 1987, hereby incorporated by reference. The laundry detergent compositions according to the present invention; generally include a bleaching agent e.g. peroxigenic, in gerair; one. bleaching agent perhydrate, usually in the form of a salt. of sodium. Suitable perhydrate bleach agents may be any organic salts such as perborate, percarbonate. perphosphate and persilicate salts but is conventionally an alkali metal perborate or percarbonate, usually sodium. The sodium perborate may be in the form of the monohydrate of nominal formula NaB02Hpa or tetrahydrate, NaBO3, 3Hp. 42 1 5 10 15

Mod. 71 · 20,000 · χ. Sodium percarbonate, which is the preferred perhydrate, is an addition compound of the formula corresponding to 2Na, C, 3HH₂O commercially available as a crystalline solid . Most commercially available materials include a low level of a heavy metal sequestering agent, such as EDTA, 1-hydroxyethylidene-1,1-diphosphonic acid (HEDP)) or an aminophosphonate, which is incorporated in the detergent compositions during the manufacturing process. Although percarbonate can be incorporated into the detergent compositions without further protection, preferred embodiments of these compositions use a coated form of material. A wide variety of coatings may be used but the most economical is sodium silicate with the ratio of SiO2: Naphd between 1.6: 1 and 3.4: 1, preferably 2.8: 1, applied under the form of an aqueous solution, to obtain a level of between 2% and 10% (usually between 3% and 5%) and solid silicates by weight with respect to the percarbonate. In the coating, magnesium silicate may also be included. Peroxygen bleaching agents are preferably combined with bleach activators, which cause the production &quot; in &quot; in aqueous solution (i.e., during the washing process) of the acid weight corresponding to the bleach activator. A wide range of bleach activators, to which examples may refer, are disclosed in U.S. Patent No. 4,189,390 issued to Spadix. Preferred bleach activators include tetraethyl-alkylene diamines, p-thylmethane and tetracayl-ethylene diamine (TAED1 and tatraceti-glycoluryl (TAGU) of the general formula

1 R-C-L 18. SET .. 1992 10 15

Mod. 7 | 20,000 x. Wherein R is an alkyl group containing from about one to about eighteen carbon atoms wherein the longer linear alkyl chain extends from and includes the carbonyl carbon atom and contains from about six to about ten carbon atoms; and L is a leaving group whose conjugate acid has a pKa value in the range of from about 4 to about 13. These bleach activators are disclosed in U.S. Patent 4,913,854, issued to Mao and lime. on April 10, 1990, hereby incorporated by reference, and in U.S. Patent 4,412,934, which has previously been incorporated herein by reference. Bleaching agents other than those containing oxygen are also known in the art and can be used in the compositions according to the present invention. One type of bleaching agent which does not contain oxygen of particular interest includes zinc and / or aluminum sulfonated phthalocyanines. These materials may be deposited on the substrate during the washing process. Upon irradiation with light, in the presence of oxygen, as for example, in the tissues extended to light the zinc phthalocyanine is activated and, therefore, the substrate is bleached. Preferred zinc phthalocyanine and a photo-activated bleaching process are described in U.S. Patent No. 4,033,718, issued to Holcombe et al. on June 5, 1977, hereby incorporated by reference. Typically, the detergent compositions contain about 0.025% to about 1.25% by weight of sulfonated zinc phthalocyanine. (I.e.

44 35 1 5 10

Pollutant Release Agent

Mod. 7) - 20,000 Âμ. - 90/08 20 30

In the laundry detergent compositions according to the present invention, any polymeric soil release agent known to those skilled in the art may be employed. Polymeric soil release agents are characterized in that they have hydrophilic segments to hydrophilize the surface of the hydrophobic fibers, such as polyester and nylon fibers, as well as hydrophobic segments to deposit hydrophobic fibers and remain adhered thereto during the completion of the rinsing and rinsing cycles and thus serving as an anchor for hydrophilic segments. This may enable stains to form following treatment with the soil release agent to be more easily cleaned in the subsequent washing procedures. Polymeric soil release agents include cellulosic derivatives such as hydrazoether cellulosic polymers, block copolymers of ethylene terephthalate or propylene terephthalate with polyoxyethylene terephthalate or polyoxypropyl terephthalate or the like. Cellulosic derivatives which function as soil release agents are commercially available and include, cellulose hydroxy ethers as Methocel &lt; I, K (Daw X. Cellulosic soil release agents also include cellulosic agents selected from the group consisting of such as methylcellulose, ethylcellulose, hydroxypropylmethylcellulose and hydroxybutyl-methylcellulose A variety of cellulose derivatives useful as polymers of release is described in U.S. Patent Number 4, 000 093, 45351

10

Mod. 71 · 20,000 ex. - 90/00 20 30 issued to Nicol et al. December 28, 1976, incorporated herein by reference.

The soil release agents characterized by having hydrophobic segments of poly (vinyl ester) include poly (vinyl ester) graft copolymer, for example, vinyl esters of C1-4, preferably poly (vinyl esters) vinyl acetate) grafted onto alkylene polyoxide chains, such as ethylene polyoxide chains. These materials are known in the art and are described in European Patent Application 0 219 048, published April 22, 1987 and filed by Hud et al. Suitable commercially available soil release agents of this type include Sokalan &quot; type material, e.g., Sokalarf HP-22, available from BASF (West Germany).

One preferred type of soil release agent is a copolymer having random blends of ethylene terephthalate and ethylene polyoxyethylene terephthalate (PEO). More specifically, these polymers are comprised of repeating units of ethylene terephthalate and PEO terphahalate in a molar ratio of ethylene terephthalate units to PEO terphahalate units of from about 25:75 to about 35:65, containing said polyethylene oxide PEO tere-phthalate units. which has molecular weights of from about 300 to about 2,000. The molecular weight of this polymeric soil release agent is in the range of about 25,000 to about 55,000. See U.S. Patent 3,959,230 issued to Hays on May 25, 1976 which is incorporated herein by reference. See also U.S. Patent 3,903,929, issued to Basadur on July 8, 1975 (incorporated by reference) which discloses similar copolymers.

Another polymeric release agent of 46-35.

Mod. 71-20,000 βκ. - 90/06 25 30

The preferred soil is a palletizer having repeating units of ethylene terephthalate containing 10 to 15% by weight of ethylene terephthalate units together with 90 to 80% by weight of ethylene polyoxyethylene terephthalate units derived from a polyoxyethylene glycol with a weight average molecular weight of 300 to 5,000 and the molar ratio of ethylene terephthalate units to polyethylene terephthalate units of the polymeric compound is in the range of 2: 1 to 6: 1. Examples of this polymer include commercially available material Zelcon11 5126 (from Dupont) and Milease &quot; T (ICI &gt;). These polymers and processes for their preparation are more fully described in U.S. Patent No. 4,702 B57, Gosselink, issued October 27, 1987, which is hereby incorporated by reference. polymer is a sulphonated product of a substantially linear ester oligomer consisting of an alligator ester of terephthaloyl ester and repeating oxyalkyleneoxy units and terminal groupings covalently attached to the chain, said leaving agent being dirt derived from ethoxylated allylic alcohol, dimethyl terephthalate and 1,2-propylene diol, wherein the end groupings of each oligomer are on average a total of from about one to about four sulfonate groups These soil release agents are well described in U.S. Patent No. 4,968,451 issued to JJ Sch. eibel on November 6, 1990 and in U.S. Patent Application Serial No. 077474709, filed by E.P. Bosselink on January 29, 1990, which is hereby incorporated by reference. Other suitable polymeric soil release agents include polyoxyethylene 1,2-propylene terephthalate terephthalate-capped polyesters with polyoxyethylene terephthalate polyesters.

Mod. 71-20,000 ex. • 5 * 0) 06 20 25 30

ethyl or methyl esters described in U.S. Patent Number 4,711,730, issued December 8, 1987 to Bosselink et al .; the anionic end-capped oligomeric esters of U.S. Patent No. 4,721,580 issued to Gosselink on January 26, 1988, wherein the anionic end caps comprise polyethylene glycol (PEG) derived sulfo-polyethoxy groups, ; the block polyester oligomeric compounds of U.S. Patent Number 4,702,857, issued October 27, 1987 to Gosselink, having capped polyethoxy ends of formula X- (OCH3 CH3) n -, wherein n is a number comprised between 12 and about 45 and X is a C1 -C4 alkyl or preferably methyl radical, all of which are incorporated herein by reference. Additional soil release polymers include the soil release polymers described in U.S. Patent 4,877,896, issued October 31, 1989 to Maldonado et al., Which relates to anionic esters of terephthalate with capped ends , especially sulfo-aroyl, the said patent being incorporated herein by reference. The terephthalate esters contain asymmetrically substituted oxy-1,2-alkylenoxy units. If used, the soil release agents generally comprise from about 0.017. to about 10%, preferably from about 0.1% to about 5%, more preferably from about 0.2% to about 3% by weight of the laundry detergent compositions according to the present invention. invention. Gelling Agents

The laundry, according to the detergent compositions of the present invention, may also

and / or optionally containing one or more manganese and chelating agents as auxiliary materials. These chelating agents may be selected from the group consisting of aminocarboxylates, aminophosphonates, polyfunctionally substituted aromatic chelating agents and mixtures thereof, all as defined hereinbelow. Without wishing to be bound by any theory, it is believed that the benefit of these materials is in part due to their exceptional ability to remove the iron and manganese esters from the washing solutions by the formation of soluble chelates.

The aminocarboxylates useful as optional chelating agents of the compositions according to the present invention may have one or more, preferably at least two units of the -CH

In which M is hydrogen, alkali metal, ammonium or substituted ammonium (for example, ethanolamine) and x is a n + number of from about 1 to about 3, preferably 1.

Preferably, these aminocarboxylates do not contain alkyl or alkenyl groups having more than six carbon atoms. Usable aminocarboxylates include ethylenediaminetetraacetates, N-hydroxyethyl ethylene diamine triacetates, nitrilo-triacetates, ethylenediaminetetrapropionates, triethylene tetramitrite- hexenetates, diethyldiamine-pentacetates and ethanol-diglycins, their alkali metal, ammonium and substituted ammonium salts and mixtures thereof.

The aminophosphonates are also suitable for use as chelating agents in the compositions.

laundry detergent compositions according to the present invention when at least low levels of total phosphorus are allowed in the detergent compositions. The compounds having one or more, preferably at least two, units of the sub-structure -CH2 N - (CH2) k-P05Ma10

Mod. 7 | - 20,000 ex. - 90/08 20 25 in. wherein M is hydrogen, alkali metal, ammonium or substituted ammonium ex is a number from 1 to about 3, preferably 1, are useful and include ethylenediamine tetrakis (methylenephosphonates), nitrilo-tris (methylenephosphonates) and diethylene triamino- penzaquis-methylenephosphonates). Preferably, these aminophosphonates do not contain alkyl groups or alkenyl groups having more than about six carbon atoms. The alkylene groups can be shared by the sub-structures.

In the compositions according to the present invention, palatably substituted aromatic chelating agents are also useful. Such materials may comprise compounds having the general formula

OH

50 35, &quot; r 7-¾, &quot; r 7-¾ Mod. 71 · 20,000 · χ. Wherein at least one of R 2 is -SO 2 H or -CEGH or their soluble salts or mixtures thereof. U.S. Patent 3,812,054, issued to Connor et al. on May 21, 1974, incorporated herein by reference, discloses polyfunctionally substituted aromatic chelating agents and sequestrants. Preferred compounds of this type in the form of the acid are dihydroxy-disulfobenzenes such as 1,2-dihydroxy-3,5-disulfobenzene. The alkaline detergent builders may contain these materials in the form of alkali metal, ammonium or substituted ammonium salts (for example, monoethanolamine or triethanolamine).

If used, these chelating agents generally comprise from about 0.1% to about 10% by weight of the laundry detergent compositions according to the present invention. More preferably, the chelating agents comprise from about 0.1% to about 3.0% by weight of these compositions.

Argi Soil Removal Agents 1 a / Anti-redeposition

The clay / anti-redeposition agents useful in the laundry detergent compositions according to the present invention include water-soluble polyethylene glycols and ethoxylated amines. which have clay and anti-redeposition soil removal properties.

The polyethylene glycol compounds useful in the laundry detergent compositions according to the present invention are typically a molecular weight comprised within the range of about 400 to about 100,000, preferably between about 1,000 and about of 20,000, more preferably between about 2,000 and about 12,000, and most preferably between about 4,000 to about 8,000. These compounds are

10 15

Mod. 7 \ · 20,000 * x. - 90/08 20 25 30 available and sold as CarbowaxiH &gt;, which can be purchased from Union Carbide, Danbury, Conn. , USA.

The water-soluble ethoxylated amines are preferably selected from the group consisting of 1) ethoxylated monoamines having the general formula (XL -) - N- (R2) 2) ethoxylated diamines having one of the general formulas or R 2 - (R2) a) 3-ethoxylated polyamines which have the general formula R2 (R3) 4) ethoxylated amino polymers having the general formula (5) their mixtures; in which &amp; is 35 52 10 16

Mod. 71-20,000 Âμ. - 90/08 20 25 30

R? Or? 007 iUOi.t. IrHJL4? 0 II 0 | Or -CH 2 -NO-, -NO-, -NO-, -NO-, -NO-, -NO-, -NO-, -NO-, -NO-, -NO-,

R is -O-; R is H or alkyl or hydroxy-C1 -C4 alkyl is C1 -C2 alkylene, hydroxy-alkylene, alkenylene, arylene or alkynylene or a C1 -C3 oxy-alkylene moiety having between two and about twenty oxy-alkylene units provided that no N-bonding is formed: each R 'is C--C alquilo alkyl or hydroxy-C ou-alkyl or a -LX-group, or two R *-forms together form the (- Wherein R 2 is -O- or -CH 2 -, R is 1 or 2, s is 1 or 2 and R 2 is 3 or 4 X is a nonionic group, a anionic group or a mixture thereof, R * is an alkyl group, substituted hydroxyalkyl, alkenyl, aryl or alkaryl having substitution ions; R * is alkylene in hydrazinoalkylene, alkenylene, erylene or allylene or a halogenated alkylene grouping of from 2 to about 20 moieties of oxyalkylene, provided that 0- 0 and NO bonds are not formed; L is a hydrophilic chain containing the group of polyoxyalkylene - ((R * O V &lt; CH, wherein R3 is C1-4 alkylene or hydroxyalkylene and m and n are numbers such that the grouping &lt; CH 2 &quot; "Comprises at least about 50% by weight of said polyoxyalkylene group; for the said monoamines, m is comprised of:

Mod. 71-20,000 · χ. - 90/08 5 10 15 20 25 30

of from 0 to about 4 and π is at least equal to about 12; for said diamines, m is a number from 0 to about 3 &quot; n is at least equal to about 6 when R 1 is C 1 -C 3 alkylene, hydroxy alkylene and alkenylene, and at least about 3 when R 1 is other than C 1 -C 8 alkylene, hydroxy alkylene or alkenylene ; for said polyamines and amine polymers, m is a number from 0 to about 10 and n is at least about 3; a number from 3 to 8; q is 1 or 0; t is 1 or 0, with the proviso that t is 1 when q is 1; w is 1 or 0; x + y + z is at least 2; and y + z is at least equal to 2. The most preferred soil release and anti-redeposition agent is ethoxylated tetraethylene pentamine. Ethoxylated amines used as examples are described in U.S. Patent No. 4,597,898, issued to Van der Meer on July 1, 1986, incorporated herein by reference. Another group of preferred clay-removal / anti-redeposition agents is comprised of the cationic compounds referred to in European Patent Application No. 111,965, filed by Oh and Gosselink on June 27, 1984 and hereby incorporated by reference. Other clay-removal / anti-redeposition agents which may be used include the ethoxylated amine polymers described in European Patent Application No. 111 984r filed by Gosselink and published June 27; of i984; the hybrid polymers referred to in European Patent Application No. 112,592, filed by Gosselink and published on July 4, 1984; and the amine oxides described in U.S. Patent No. 4,548,744, issued to Condor on October 22, 1985; all incorporated herein by reference. Most preferred soil release and anti-redeposition agents are ethoxylated tetraethylene-pentamethylene and polyethylene glycols having a soft weight.

Mod. 7-20,000 x. - 90 (08 20 25 30

M ογτ inno iu · i iu; Jf. comprising from about 4,000 to about 8,000. The granular detergent compositions containing these compounds typically contain from about 0.0154 to about 1054 wt. Of clay removing agents; the liquid detergent compositions typically range from about 0.0154 to about 554 by weight. Polymeric Dispersing Agents Polycarboxylate polymer dispersing agents may be advantageously used in the laundry detergent compositions according to the present invention. These materials can help control calcium and magnesium hardness. In addition to acting as auxiliaries of builders in a manner analogous to the polycarbazilates described in the description of the anchoring agents, it is believed that, although not intended to be limited by theory, these high molecular weight dispersing agents can further enhance the length of global detergent builder agents inhibiting the growth of crystals of inorganic compounds by peptidicating the soil particles and by anti-redeposition when used in combination with other builders including low molecular weight polycarboxylates. The polycarboxylate materials which may be employed as palmeric polycarboxylate dispersing agents are polymers or copolymers containing at least about 60% by weight of segments of the general formula

• C-C

COOM n 55 35 1 10 15

Mod. 71 · 20,000 · χ. In which X, Y and Z are each selected from the group consisting of hydrogen, methyl, carboxy, carboxymethyl, hydroxy and hydroxymethyl; M is a salt-forming cation in a number ranging from about 30 to about 400. Preferably, X is hydrogen or hydroxy, Y is hydrogen or carboxy, X is hydrogen, and ΙΊ is hydrogen, alkali metal, ammonium or ammonium substituted. Polymeric polycarboxylate materials of this type can be prepared by polymerizing or copolymerizing appropriate unsaturated monomers, preferably in their acid form, unsaturated monomeric acids which can be polymerized to form suitable polymeric polycarboxylates include acrylic acid, maleic acid (or maleic anhydride), fumaric acid, itaconic acid, acronitic acid, mesaconic acid, citraconic acid and methylene malonic acid. The presence of monomeric segments in the polymeric polycarboxylates according to the present invention which are non-carboxylate radicals such as vinyl methyl ether, styrene, ethylene, etc., are suitable so long as these segments do not constitute more than about 40% by weight. Particularly suitable polymeric polycarboxylates may be derived from acrylic acid. Such acrylic acid based polymers useful in accordance with the present invention are the water soluble salts of polymerized acrylic acid. The average molecular weight of these polymers in the form of an acid is between about 4,000 and 7,000 and more preferably between about 4,000 and 5,000. The water-soluble salts of such homopolymers of acrylic acid may include, for example, the alkali metal, ammonium and substituted ammonium salts. Soluble polymers of this type are known materials. The use of polyacrylates of this type in the detergent compositions has been described, for example, in U.S. Patent 3,308,067,

56 4P n- {n o 1 10 15

Mod. 71 · 20,000 · χ. 90J08 20 30 35 1 / Ύ / / granted to Dishl on March 7, 1967; this patent is hereby incorporated by reference. The copolymers based on acrylic acid / maleic acid may also be used as the preferred component of the dispersing agent. These materials include the water-soluble salts of acrylic acid and maleic acid copolymers. The average molecular weight of such copolymers in the form of an acid is between about 5,000 and 100,000, preferably between about 6,000 and 60,000, more preferably between about 7,000 and 60,000. The ratio of acrylate segments to maleic segments of such copolymers is generally from about 30: 1 to about 1: 1, more preferably from about 10: 1 to 2: 1. The water-soluble salts of such acrylic acid / maleic acid copolymers may include, for example, alkali metal, ammonium and substituted ammonium salts. Acrylate / maleate copolymers of this type are known materials and are described in European Patent Application No. 66 915, published December 15, 1982, which publication is hereby incorporated by reference. When used, the polymeric dispersing agents are generally from about 0.2% to about 10%. preferably from about 1% to about 5% by weight of laundry detergent washers

Clarinets

Optical brighteners or other bleaching or bleaching agents known to those skilled in the art may be incorporated into the laundry detergent compositions according to the present invention. However, the choice of the enhancer depends on a number of factors, such as the type of detergent.

Mod. 71-20,000 · χ. - $ 0/08 25 30

the nature of the other components present in the detergent composition, the temperatures of the wash water, the degree of agitation and the proportion of the material to be washed for the size of the washing drum. The choice of the clarifier also depends on the material to be washed, for example, cotton material, synthetic material, etc. As most laundry detergent products are used to wash a wide variety of fabrics, the detergent compositions should contain a mixture of bleaching agents that is effective for a variety of fabrics. Of course, it is necessary that the individual components of such a clarifying mixture are compatible. Commercial optical shooters can be classified into subgroups which include, but are not necessarily limited to, stilbene, pyrazoline, cumarin, carboxylic acid, methocyanins, dibenzothiophene-5,5-dioxide derivatives, azoles, pentagonal heterocycles and hexagons and various other agents. Examples of such shooters are given in &quot; The Production and Application of Fluorescent Brightening Agents &quot;, li. Zahradnik, published by John Wiley &amp; Sons, New York (1982), the disclosures of which are hereby incorporated by reference. Stilbene derivatives include but are not necessarily limited to, derived from bis-CtriaziniD-amino-stilbene ;. derived from stilbene bis-acylamino; stilbene triazole derivatives; stilbene oxadiazal derivatives; stilbene oxazole derivatives; stilbene styryl derivatives. Certain bis- (thiazolyl) -amino-stilbene derivatives may be prepared from 4,4 "-diamino-styeno-2, 2'-disulfonic acid. The coumarin derivatives include, but are not necessarily limited to, derivatives substituted at the 3-position, 7-positions and at positions 3 and 7. Carboxylic acid derivatives include, but are not limited to, are necessarily limited to, fumaric acid derivatives; benzoic acid derivatives; p-phenylene-bis-acrylic acid derivatives; nephthalene derivatives; dicarboxylic acid; heterocyclic acid derivatives; and derived from kinetic acid. The cinnamic acid derivatives may further be subclassed in groups which include, but are not necessarily limited to, cinnamic acid derivatives, styryl-10-azoles, styryl-benzofurans, styryl-axadiazoles, styryl-triazoles, and styryl -poliphenyls, as reported on page 77 of the Zahradnik reference. The styryl azoles can be further sub-esterified in styryl-benzoxazoles, styryl-imidazoles and styryl-thiazoles, as referred to on page 78 of the Zahradnik reference. It is understood that these three subclasses identified may not necessarily reflect the exhaustive list of the subgroups in which the styryl azoles may be sublimated.Other optical brighteners are the dibenzothiophen-5,5-dioxide 120 derivatives referred to on pages 741-749 of The Kirk-Othmer Encyclopedia 3, pages 737-750 (John Wiley &amp; Sons, Tnc., 1962), which are incorporated herein by reference and include 3,5- Other optical brighteners are azole which are derived from pentagonal ring heterocycles, and may further be subdivided into mono-azoles and bis (2-azabicyclo [3.3.1] Examples of mono-azoles and bis-azoles are referred to in the aforementioned Kirk-Othmer reference. Yet other optical brighteners are those derived from hexagonal ring heterocycles, referred to in the aforementioned Kirk-Othmer reference. Examples of these compounds include pyrazine derivatives

Mod. 71-20,000 · χ. - 90/08 1 10 15

Mod. 71 · 20.001) 'X. · 90/08 20 25

,

Silyl 9? and 4-amino-naphthalamide-derived lighteners. In addition to the aforementioned clarifiers, a number of other agents may also be useful as lighteners. Exemplary of such agents are the lightening agents listed on pages 93-95 of the Zahradnik reference and include 1-hydroxy-3,6, S-pyrene-trisulfonic acid; 2,4-dimethoxy-1,3,5-triazol-6-yl-pyrene; 4,5-diphenyl-imidazolone disulfonic acid; and pyrazoline-quinoline derivatives. Other specific examples of optical brighteners are identified in U.S. Patent No. 4,790,856, issued to Wilon on December 13, 1948, the disclosure of which is hereby incorporated by reference. These brighteners include the Phorwhite series? of Verona enlighteners. Other lighteners described in this reference include Tinopal UNPA, Tinopal CBS and Tinopal 5BM; which can be obtained from Ciba-Geigy; Arctic White CC and Arctic White CDW, available from Hilton-Davis, located in Italy; 2- (4-styrylsulfonyl) -2H-naphthol-1,2,3-triazolones; 4,4'-bi s- <1,2,3-trienes ol-2-yl) -stenedenes; 4,4'-bis (styryl) -bis-phenyls; and gamma-amino-coumarins. Specific examples of such lighteners include 4-methyl-7-diaethylamino-coumarin; 1,2-bis- (bensimidazol-2-yl) ethylene; 1,3-diphenyl-prasolines; Z, 5-bis- <benzoxazol-Z-yl) -thiophene-2-styryl-1-naphth-1,2-dione; and 2- (stilben-4-yl) -2H-naphtho-1,2,3-triolol. Still other optical brighteners include those disclosed in U.S. Patent No. 3,646,015, issued February 29, 1972 to Hamilton , which is hereby incorporated by reference. If used, optical brighteners generally comprise from about 0.05% to about 2%, preferably from about 0.1% to about 1% by weight, of the laundry detergent compositions. 60 35 1 10 15

Mod. 71-20,000 ex. - $ 0/03 20 25

Foam Suppressors

Compounds known or which have become known to reduce or suppress foaming may be incorporated into the laundry detergent compositions according to the present invention. The incorporation of such materials, hereinafter referred to as &quot; foam suppressors &quot;, may be desirable because the optically active agents consisting of polyhydroxylated fatty acid amides can increase the stability of the foams of the detergent compositions. The suppression of the foam may be of particular importance when the detergent compositions include a triphosphating agent which gives a relatively large amount of foam in combination with the polyhydroxylated fatty acid ammonium counteractant. The suppression of the foam is particularly desirable in compositions intended for automatic front-loading washing machines. These machines are typically characterized in that they have drums for holding the laundry to be washed and the wash water having a horizontal and rotational action about that axis. This type of agitation may result in a high foaming and, consequently, a reduced cleanup. The use of suds suppressors may also be of particular importance in hot water wash conditions and high concentration of estrogenic agents. As foam suppressing agents, a wide variety of materials can be used. Foam suppressors are well known to those skilled in the art. They are generally described, for example, in Kirk-Othmer Encyclopedia of Chemical Technology, 3rd Edition, Volume 7r; pages 430-447 (John Wiley & Sons, Inc., 1979). One category of foam suppressing agents of particular interest comprises monocarboxylic fatty acids and the like.

Mod. 7 | -20,000 · χ. · »/ 08 20 25 30

soluble salts thereof. These materials are referred to in U.S. Patent No. 2,954,347 issued September 27, 1960 to Wayne St. John, the aforementioned patent being incorporated by reference. Monocarboxylic fatty acids and their salts used as suds suppressing agents typically have hydrazocarbyl chains having from ten to about twenty-four carbon atoms, preferably twelve to eighteen carbon atoms. Suitable salts include alkali metal salts, such as sodium, potassium and lithium salts, and ammonium and alkanolammonium salts. These materials are a preferred category of foam suppressing agents for detergent compositions. The laundry detergent compositions according to the present invention may also contain non-saphenous suds suppressing agents. These include, for example, high molecular weight hydrocarbons, such as paraffin, esters of fatty acids (for example, fatty acid triglycerides), fatty acids esters of monovalent alcohols, aliphatic ketones in chTC4 (eg stearone), etc. Other foam inhibiting agents include N-alkylated amino triazines such as tri-fluoro-amines, tetra-alkyl-melamines, penta-alkyl-methine and hexa-alkylmelamines or dialkyl-diamino-chlorotriazines, trialkyl-diamino-chlorines -triazines or tetra-alkyl-diamino-chloro-triazines formed as reaction products of cyanuric chloride with two or three moles of a primary or secondary amine containing from one to twenty-four carbon atoms, propylene oxide and mono- stearyl phosphate esters such as mono-stearyl phosphate esters and alcohols are esters of alkali monostearyl dimethal esters (eg, sodium, potassium, lithium), phosphates and phosphate esters. Hydrocarbons, such as paraffins and halogen-paraffin, may be used in liquid form. Liquid hydrocarbons are liquid at the temperature

Mod. 7i · 2θ.οαα «x. - eye 20 25 30 35

atmosphere and at atmospheric pressure and have a flow point in the range of about -40Â ° C to about + 52Â ° C and a mini boiling point of not less than about 110Â ° C (atmospheric pressure). It is also known that wax-like hydrocarbons may be used, preferably having a melting point of less than 100Â ° C. Hydrocarbons are a preferred category of foam suppressing agents for detergent compositions. Foaming suppressants consisting of hydrazones are described, for example, in U.S. Patent 4,265,779, issued to Gandolfo et al. on May 5, 1981 and hereby incorporated by reference. The hydrocarbons in this case include aliphatic, alicyclic, aromatic and heterocyclic saturated or unsaturated hydrocarbons having from about twelve to about seventy carbon atoms. The term &quot; paraffin &quot; as used in the discussion above on foam suppressors is intended to include mixtures of true paraffins and cyclic hydrocarbons. Another preferred category of non-tensioactive foam suppressing agents comprises suds suppressors by silicones. This category includes the use of polyorganosiloxane oils, such as polydimethylsiloxane, dispersions or emulsions of polyorganosiloxane oils or polyorganosiloxane resins and combinations of polyorganosiloxane with silica particles, wherein the polyorganosiloxane is chemisorbed-fused to silica. Silicone suds suppressors are well known in the art and are described, for example, in U.S. Patent 4,265,779 issued to Sandolfo et al. on May 5, 1981 and in European Patent Application No. 89307851.9, published February 7, 1990 and required by M. S, Starch, both incorporated herein by reference. Other foam suppressing agents of 63 1 5 10 H

Mod. 71-20,000 Âμ. Suitable liquids are described in U.S. Patent No. 3,455,839, which relates to compositions and processes for the destruction of the foam of aqueous solutions by the incorporation of small amounts of polydi-methyl fluids -siloxane. Mixtures of silicone and silanated silica are described, for example, in German Published Application for Public Inspection DOS 2 124 526. Simulent antifoaming agents and foam control agents in granular detergent compositions are described in U.S. Patent Number 3,933,672, issued to Bartolotta et al. and in U.S. Patent Number 4,652,392, issued to Baginski et al. on March 24, 1987. An example of a silicone based suds suppressing agent for use in accordance with the present invention is an amount of a suds suppressing agent of a suds controlling agent, consisting essentially of: (i) of polydimethylsiloxane having a viscosity of from about 20 cs. and about 1,500 cs at 25Â ° C; (ii) from about 5 to about 50 parts by weight of &lt; g &gt; The siloxane resin is composed of units of SiO 2 units in the ratio of units (CHS &gt; 1101 / a for units of SiO2 of from about 0.6 to about 1.2: 1 (Ii) from about 1 to about 20 parts per 100 parts by weight of (i) a solid silica gel. Foam suppressing agents, when used, are present in a &quot; foam suppressing amount &quot; By the expression &quot; suppressive amount of 64 1 5 15

Mod. 71-20,000 Âμ. - 90J0S 20 25 30

foam &quot;, it is intended that the formulator of the composition may choose an amount of this controlling agent and foam which controls the amount of the foam in the desired ratio. The amount of foam control varies with the chosen detergent-active agent. For example, with high foaming active agents, a relatively higher amount of the foam control agent is used to achieve the control of the foam required than in the case of thioester-active agents which give rise to a small amount of foams. The laundry detergent compositions according to the present invention generally comprise from about 0% to about 5% suds suppressing agent. When used as suds suppressors, the monocarboxylic fatty acids and their salts are typically present in amounts up to about 5% by weight of the detergent composition. Preferably, from about 0.5% to about 3% of foam suppressing agent and fatty monocarboxylate is used. Silicone foam suppressors are typically used in amounts up to about 2.0% by weight of the detergent composition, although larger amounts may be used. This upper limit is practical in nature, due mainly to the presumption of keeping the costs minimized and the effectiveness of smaller quantities to effectively control a. amount of foam. Preferably, about 0.01% to about 1% silicone foaming agent is used, more preferably from about 0.25% to about 0.5%. As used herein, the indicated weight percentages include any silica which may be used in combination with the polyorganosiloxanes, as well as any auxiliary materials that may be used. Monostearyl phosphates are generally used in amounts of from about 0.1% to about 2% by weight of the monostearyl phosphates.

Mod. 71-20,000 · χ. - 90 (08 20 25 30

compositions. Hydrocarbon foam suppressing agents are typically used in amounts of about 0.01% to about 5%, although higher levels may be used. Other Ingredients

A wide variety of other ingredients that may be included in the laundry detergent compositions according to the present invention include other active ingredients, carrier substances, hydrotropic substances, processing aids, colorants or pigments, solvents for liquid formulations, etc. . The liquid detergent compositions may contain water and other solvents as carrier substances. Suitable low molecular weight primary or secondary alcohols, exemplified by methanol, ethanol, propanol and isopropanol, are suitable. Monofunctional alcohols are preferred for the solubilization of the tanso-active agents but polyols such as those containing from about two to about six carbon atoms and from about two to about six hydroxy groups may also be used. The laundry detergent compositions according to the present invention will preferably be formulated in such a way that during use in the washing operations with water , the wash water has a pH of from about 6, ET to about 11, preferably from about 7.5 to about 10.5. The formulations of the liquid product preferably have a pH of from about 7.5 to about 9.5, more preferably from about 7.5 to about 9.0. Techniques for èò 35 1

fxi

controlling the pH so as to have the recommended levels in use include the use of buffers, alkaline bases, acids, etc. and are well known to those skilled in the art.

Mod. 71-20,000 ex. The present invention further provides a process for cleaning substrates such as fibers, fabrics, hard surfaces, skins, etc., contacting said substrate with a detergent composition containing the nonionic surfactant system according to present invention wherein the weight ratio of polyhydricated fatty acid amide to the additional surfactant agent present in the nonionic surfactant system is comprised within the range of from about 1: 5 to about 5: 1, in the presence of a solvent such as water or a water miscible solvent (for example, primary and secondary alcohols). For cleaning enhancement, stirring is preferably provided. Suitable means for providing agitation include scrubbing by hand, preferably with the aid of a brush or other cleaning device, automatic washing machines, automatic dishwashers, etc.

Experimental Procedure 25 30

This one . refers to an example of the process for preparing a N-methyl-1-deoxy-glucityl-lauramide tensioactive agent for use according to the present invention. Although an experimental chemist can vary the configuration of the An apparatus suitable for use in this house comprises a four-necked three-liter capacity, equipped with a motor-driven blade agitator and a thermometer of sufficient length to contact the reaction medium. The other two necks of the balloon are provided with a nitrogen distribution inlet and a lateral branch of wide diameter (note: the existence of the lateral branch of

Mod. 71-20,000 · χ. · 90/03 20 25 30 (> 1-γ Ur., .P99

1/'/

and wide diameter is important in the case of very rapid methanol release), to which is connected an efficient collection capacitor and a vacuum outlet. The latter is connected to a nitrogen distributor and a vacuum manometer and then to a vacuum cleaner and a trap. A 500 watt heating mantle with a variable temperature control ("Variac") transformer used to heat the reaction mixture is placed in a laboratory apparatus in such a way that it can be easily raised or lowered to better control the temperature of the reaction mixture . In the flask, N-methylglucamide (195 grams, 1 mole, Aldrich N4700-0) and methyl-1aurate (Procter & Gamble CE 1270, 220.9 grams 1 mole) were added. The solid / liquid mixture is heated with stirring under a stream of nitrogen until a melt (approximately twenty-five minutes) is formed. When the melt temperature reaches 145 DEG C., catalyst (pulverized anhydrous sodium carbonate, 10.5 grams, 0.1 mol, J.T. Baker) is added. The passage of the nitrogen is stopped and the aspirator is removed and the nitrogen is removed to give a vacuum of 5 inches of mercury (5/31 atmospheres). From this point forward, the temperature of the reaction mixture is maintained at 150 ° C by adjusting the Variac and / or by raising or lowering the heating mantle. At the end of seven minutes, the formation of the first methanol bubbles in the meniscus of the reaction mixture. A vigorous reaction follows immediately. The methanol is allowed to distill until its rate of formation decreases. Vacuum is adjusted to about 25.4 centimeters CIO inches) of mercury (10/31 atmospheres). The vacuum is increased approximately. (in inches Hg in minutes): 10 to 7T 10 to T, 25 to 10. After eleven minutes after the start of methanol release, heating and stirring are stopped, which coincides with formation of some foam. O8 is cooled

product and allowed to solidify.

The following examples are intended to exemplify compositions according to the present invention but are not necessarily limiting or otherwise defining the scope of the present invention, said scope being determined only by the appended claims. The invention is illustrated by means of the following Examples, wherein all indicated amounts are by weight, unless otherwise specified.

In the examples, the abbreviated identifications of the components have the following meanings:

Mod. 7 | 20,000 ax. · »0/08 25 30

C.I.AS TGA TAS tae; 4SE7 25E3: linear C1 -C4 alkylsulfanate, sodium tallow fatty acid glucityl amide, tallow alcohol sulfate sodium salt, C14 -C14 alkyl, sodium sulfate, in sodium α-ether sulfate containing an average of 7 moles of ethylene oxide per mole of alkyl sulfate, tallow alcohol ethoxylated with n moles of ethylene oxide per mole of alcohol, a predominantly linear C 10 -C 10 primary alcohol condensed with a mean T moles of ethylene oxide, a C 1 -C 4 primary alcohol condensed with a mean of 3 moles of ethylene oxide, 69 35 1/1 h TAED Silicate

Mod. 71-20,000 βχ. - $ 0/08 10 15 20 25 as

Carbonate: CMC: Zeolite A: Citrate: MA / AA: Psrborate monahydrate: Enzyme: Clarified DETPMP: Foam Suppressor: tetraacetyl-ethylenediamine, amorphous sodium silicate (normally the ratio of anhydrous sodium carbonate, sodium carboxymethylcellulose salt, sodium aluminosilicate hydrate of the formula Naj-A₂O₂SiO₂ 12271 0,, having a primary particle size comprised within of the range of 1 to 10 micrometers, dihydrate trisodium citrate, 1: 4 maleic anhydride / acrylic acid copolymer, average molecular weight of about 80,000, anhydrous sodium bleach parboiled of the empirical formula NaB02.Hp8 , mixed proteolytic and amylolytic enzyme sold by Novo Industries ASr-4,4'-bis- (2-chlorophenyl) -4-anisin-triazin-6-ylamino) - Disodium styeno-2,2'-disulfonate, diethylene triamine-methyl- (methylene phosphonic) acid, sold by Monsant under the trade mark of Dequest 2060, 25% paraffin wax of 50 DEG C., 17% paraffin, 20% hydrophobic silica and 5% paraffin oil. 5

Examples 10 15

Example 1: The following particulates are prepared:

Mod. 7 | - 20,000 · χ. - 90/08 20 25 30 TAS A 2.43 ^ 14/10 ^ 5.4 C 12.10 ^ 1 S 1.5 TBA 3.5 25E 3 3.0 Zeolite A 15.0 Citrate 6.5 Silicate ( 2.0 ratio) 3.5 Carbonate 13.6 MA / AA 4.25 DETPMP 0.38 CMC? 0.48 TAED 5.0 Perborata 16.0 Enzyme i.A Clarifier 0.19 &quot; Suds Supressor 3.0

B C 6.5 6.5 The performance of the three compositions was compared in tests with Tergotometsr and tests of washing machines on a natural scale. 35 71 SET. 1Cl 3 /! n.

Mod. 71-20,000 * x. - 20/08 20 25

THE

Tergotometer Assays

Six metal 2-liter containers were filled with 12-degree water of Clark hardness (Ca: Mg = 4: 1) and heated to 60 ° C. To each vessel was added 14 grams of product and dissolved / dispersed to give a product concentration by weight of 0.7%. 7.5 κ 7.5 cm stained smears of cotton and poly-cotton fabric were applied by applying separate strips of artificial shoe-polish and artificial oil of tallow (DM0) uniformly to each sample of fabric. A wipe of each type of fabric was then attached to the blade of each vessel and the blades were agitated within the vessel for forty-five minutes. The total number of replicates of each product was six. The mops were then rinsed with cold water, dried overnight and then graded by a panel of experts using a five-point Scheffé scale.

Tests on Washing Machines

For the similar comparison of the products, AEB Lavamat 980 automatic washing machines were used. A main wash cycle of 45 minutes at 60 ° C was chosen and a concentration was used. of product equal to 0.7% in water with 1Z degrees of Clark hardness (Ca and Plg-4) - For each product, six replicates were carried out. Each wash load comprised &quot; 5 kg woven fabric realistically dirty ballast consisting of cotton sheets and towels together with poly-cotton articles with a proportion of cotton polycotton cotton approximately equal to 5: 1 together with sets of stained cloths

The two sets of stains included: - 2 greasy cotton stains (lipstick, 72 30

DMQ) - 2 greasy polyester stains (make-up, shoe polish).

After rinsing with cold water, each cloth was dried and then graded by a panel of experts using a five-point Scheffé scale. The results of both assay techniques are pooled lower. Column LH shows the advantage of Composition A over Composition B, whereas the RH column shows the advantage of Composition A over Composition C. Tergotometer A / BA / C Cotton -sebo -0.3 -0.3 -polishing +0.6 +0.2 -DMO +1.1 (s) +0.8 Palialgodão sebum +0,2 +0 +0,4 polishing +0,8 +0,5 -DMO +1,5 (s) + 0.5 Washing machine lipstick / cotton + l, 5 (s) +0.2 DMO / cotton +1,2 +0,5 Make-up / polyester o I * + +0,5 Portion / polyester + l, 4 (s) +1.1 (s) s = statistically significant with a confidence level of 95%. The product C represents a composition of 73%

prior art and the A / C composition shows that Composition A according to the present invention provides stain removal benefits over Composition C over broad spectrum of soil and tissue types. Comparison between Compositions A and B shows the surprising benefit provided by the use of a combination according to the present invention over that provided by the use of a high level of polyhydroxylated fatty acid amide alone. 10

Example II

Mod. 71 · 20,000 c. - 90/08

Composition A of Example I was compared to the commercially available detergent composition (D), which differed only from Composition A in that the components 45AS, 25AE5S, TGA and 25E3 were replaced by 7.6% of 22LAS, 3% of 45E7 and 1.1% of APR, *. The comparison was carried out in AEG Lavamat 980 washing machines using the washing conditions and the procedure of Example Γ and a variety of stains on pieces of cotton, poly-cotton and poly-ester fabric. fabric washed by a panel of experts using a five-point Scheffé scale showed that Composition A provided improved stain removal over Composition D of &gt; Z psu relative to the polyester polish &gt; 1 psu in DMCT in poly-cotton &gt; 1.3 psu in cotton make-up.

Example III

Compound A of Example I was compared to that of two detergent compositions O and E which differed from A only in that the component 25E3 was replaced by 68E3 and 68E5, respectively, which was 30.

68E3 and 68E5 are predominantly linear C14-C1B primary alcohols condensed with an average of 3 and 5 moles of ethylene oxide, respectively. Performance comparisons were made using the conditions and procedure of the tergotomer test of Example I. Classification of the washed pieces of tissue by a panel of experts using the Scheffé 5-point scale showed that Composition A according to the present invention provided significant stain removal benefits over either Compositions D or E, none of which is a composition in accordance with the present invention.

The results of the comparisons are shown in the Table below. The LH column shows the advantages of Composi-15

Mod. 7) 20,000. 20 (08) in relation to Composition 0, whereas the RH column shows the advantage of Composition A over Composition Es 20

Palialgodão -sebo -paLi, mint -DMO

A / D A / E +0.3 -0.6 + 2T0s + 0.8s -0.3 + lr.8s

Polyester -sebo-polishing -DMO + 2.6s + 1.6s + 0.8s + 2.7s +0.3 + 1.5s s = statistically significant with a 95% confidence level. 75 35 1

Lisbon, 18.SEÍ992

By THE PROCTER &amp; GAMBLE COMPANY 5 10 15

from Prcpriedcoe Industrial Ssk &amp; Censeifõo * §jooú = 138§ Ιϋϋ ^

Mod. 71 -20,000 «x.-70/08 20 25 35 76

Claims (1)

1 <r r; 15 Mod. 71-20,000 x. - - - - - - - - - - - - - - A laundry detergent composition for cleaning fabrics in automatic washing machines, comprising one or more anionic, cationic, ampholytic or water soluble hybrids or mixtures thereof and optionally detergent builders, characterized in that it comprises , in combination, a) at least 1% by weight of the composition of a polyhydroxylated fatty acid amide having the formula in which R1 is H, C1 -C4 hydrocarbyl, 2-hisroxyethyl, 2-hydroxy-propyl or a mixture thereof, R4 is C1-3 hydrocarbyl and Z is a polyhydroxy hydrocarbyl radical having a linear hydrocarbon chain with at least 3 hydroxy groups directly attached to said chain or an alkoxylated derivative thereof: s - b> at least, weighs the composition of a substantially water-insoluble CX1-C12 IB aliphatic primary alcohol containing an average of not more than five ethylene oxide groups per mole and has an ethylene oxide content of less than 50 % by weight. 2§. Detergent laundry composition according to claim 1, characterized in that component (a) is a polyhydroxylated fatty acid amide of Formula (R). C (CHOH) 4CHPH Mod. 71-20,000 · χ. Wherein R2 is a straight chain alkyl or alkenyl group in 3i. Detergent laundry composition according to any one of claims 1 or 2, characterized in that R 2 is a C 1 -C 8 straight chain alkyl or alkenyl group or a mixture thereof and is methyl. 4ã. Detergent laundry composition according to any one of claims 1 to 3, characterized in that R 2 is a C 18 -C 17 straight chain alkyl group. derived from tallow grease. 5â. Detergent laundry composition according to any one of claims 1 to 4, characterized in that component b) comprises a linear or substantially linear aliphatic alcohol containing an average of 12-13 carbon atoms in the alkyl chain ethoxylated with a average of three ethoxy groups per mole of alcohol. A granular laundry detergent composition according to any one of claims 1 to 5, characterized in that it comprises between 3X and 15TS by weight of anionic surfactant, between 17% and 10% by weight of anionic surfactant. of component a) and between VA and 10% of component b>, the ratio of weight of anionic surfactant to the combined weights of components a) and b> comprised within the range of 1: 3 and 3: 1. 7ã. 5. A granular laundry detergent composition according to claim 6, characterized in that the anionic surfactant comprises sulfa. Mod.? | - 20,000 · χ. C 2--C alquil e alkyl ethoxysulfates containing an average of up to three-pair ethoxy groups of alkyl ethoxy sulfate and the like, their mixtures. Sã. A granular laundry detergent composition according to claim 7, characterized in that the anionic surfactant is free of alkyl benzene sulphate salts. ?The. Detergent laundry detergent composition according to any one of Claims 6 to 8, characterized in that the anionic surfactant comprises a mixture of a higher proportion by weight of the mixture of a sulphate and a lower proportion by weight of the mixture of a C12-C12 alkyl ethoxysulfate containing a mean of three ethoxy groups per mole of alkyl ethoxy sulfate. 10%. A granular laundry detergent composition according to any one of claims 6 to 9, characterized in that it incorporates a non-phosphated detergent builder system. III. A granular laundry detergent composition according to claim 10, characterized. in that the detergent builder is selected from aluminosilicates of synthetic or amorphous crystalline zeolites, alkali metal carbonates, alkali metal bicarbonates and organic alkali metal polycarboxylates, alkali metal silicates, crystalline layered sodium silicates, water soluble salts of acrylic acid homopolymer or copolymers of acrylic acid with maleic anhydride, amino polycarboxylates and mixtures of any of the foregoing. 79 35 1Lisboa, &amp; SE11992 By THE PROCTER &amp; BAMBLE COMPANY 5 10 15 VASC® MARQUES Itíf * Ageriie G !; &lt; ja &gt; 3, 1-H0G MfCStía Mod. 71 · 20,000 · χ. · 90/06 20 25 30 35 &lt; 80