WO1995033030A1

WO1995033030A1 - Liquid detergent composition containing oleoyl sarcosinates and anionic surfactants

Info

Publication number: WO1995033030A1
Application number: PCT/US1995/006294
Authority: WO
Inventors: Serge Gabriel Pierre Cauwberghs; Jean-Pol Boutique; Dimitris Lappas; Joseph Paul Morelli
Original assignee: The Procter & Gamble Company
Priority date: 1994-06-01
Filing date: 1995-05-18
Publication date: 1995-12-07
Also published as: AU2554095A; PE7896A1; CA2191563A1; MA23561A1; BR9507826A; JPH10508043A; EP0763088A1

Abstract

A liquid laundry detergent composition comprising a surfactant system said surfactant system comprising an oleoyl sarcosinate and one or more of an anionic surfactant selected from the group of alkyl alkoxylated sulfates and/or alkyl sulfates.

Description

LIQUID DETERGENT COMPOSITION CONTAINING OLEOYL SARCOSINATES AND ANIONIC SURFACTANTS

Field of the invention The present invention relates to a detergent composition having improved cleaning performance. More particularly, the invention is directed to a liquid detergent composition containing oleoyl sarcosinate and one or more anionic surfactants selected from the group consisting of alkyl alkoxylated sulfates and/or alkyl sulfates.

Background of the invention Detergent compositions useful for cleaning purposes, such as laundering of fabrics, have commonly utilized a variety of surfactants.

The ability of surfactants to clean a large variety of soils and stains from fabrics present in the typical load of laundry is of high importance in the evaluation of detergent performance. Unfortunately, the relative ability of each surfactant to meet various performance criteria is among others depending on the different usage conditions across geographies.

As a consequence, detergent formulators need to rebalance formulations with different surfactants in order to obtain optimum detergency performance. For example, in the United States, alkyl ethoxy sulfates are preferred surfactants over alkyl sulfates due to the high ratio of free hardness present under US wash conditions. In Europe, alkyl sulfates are preferred surfactants in medium to high built detergents because of their inherently better greasy cleaning performance under those conditions.

There is thus a standing desire for performance and flexibility reasons to make available a robust surfactant system capable of providing superior performance over a whole range of different use conditions across different geographies. The above objective has been met by a surfactant system comprising oleoyl sarcosinate and one or more anionic surfactants selected from the group consisting of alkyl alkoxylated sulfates and/or alkyl sulfates.

It has been surprisingly found that said surfactant system exhibits excellent detergency performance under various usage conditions inclusive different washing temperatures and different water hardness.

In addition, it has been found that the liquid detergent composition formulated with said surfactant system are very useful when the liquid detergent compositions are in direct contact with the fabrics such as during pretreatment. These compositions also provide excellent color care for dyed fabrics and excellent skin mildness for hand-wash operations.

Oleoyl sarcosinates have been described in the following patents and publications : U.S. 2,542,385; U.S. 3,402,990; U.S. 3,639,568; U.S. 4,772,424; U.S. 5,186,855; European Patent Publication 505,129; British Patent Publication 1,211,545; Japanese Patent Publication 59/232194; Japanese Patent Publication 62/295997; Japanese Patent Publication 02/180811; and Chemical Abstracts Service abstracts Nos. 61:3244q, 70:58865x and 83:181020p. Detailed description of the invention

The present invention relates to liquid detergent compositions containing a surfactant system, said surfactant system comprising oleoyl sarcosinate and one or more anionic surfactants selected from the group of alkyl alkoxy sulfates and/or alkyl sulfates.

The liquid detergent compositions preferably comprise at least 5%, more preferably from 10% to 65% and most preferably from 25% to 40% by weight of the surfactant system as described herein.

Preferably, the weight ratio of oleoyl sarcosinate to the alkyl alkoxylated sulfates and/or alkyl sulfates is from 1:10 to 10:1, more preferably from 1:6 to 2:1 and most preferably from 1:3 to 1:1. Oleoyl Sarcosinate

The present invention compositions comprise oleoyl sarcosinate, in its acid and/or salt form selected as desired for the compositions and uses herein, having the following formula:

wherein M is hydrogen or a cationic moiety. Preferred M are hydrogen and alkali metal salts, especially sodium and potassium. Oleoyl sarcosinate is commercially available, for example as Hamposyl O supplied by W. R. Grace & Co. Preferably the oleoyl sarcosinate will comprise from about 0.1% to about 80%, more preferably from about 1% to about 40%, and most preferably about 2% to about 30% by weight of the compositions.

In addition to the commercially-available oleoyl sarcosinate, oleoyl sarcosinate useful herein can also preferably be prepared from the ester (preferably the methyl ester) of oleic acid and a sarcosine salt (preferably the sodium salt) under anhydrous reaction conditions in the presence of a base catalyst with a basicity equal to or greater than alkoxide catalyst (preferably sodium methoxide). For example, the reaction may be illustrated by the scheme:

NaOCH₃ (cat)

This salt may optionally be neutralized to form the oleoyl sarcosinate in its acid form.

The preferred method for preparing oleoyl sarcosinate is conducted at a temperature from about 80°C to about 200°C, especially from about 120°C to about 200°C. It is preferred to conduct the reaction without solvent although alcohol solvents which have a boiling point of at least 100°C and are stable to the reaction conditions (ie. glycerol is not acceptable) can be used. The reaction may proceed in about 85% yield with a molar ratio of methyl ester reactant to sarcosine salt reactant to basic catalyst of about 1:1:0.05-0.2.

Methyl ester mixtures derived from high oleic content natural oils (preferably having at least about 60%, more preferably at least about 75%, and most preferably at least about 90% oleic content) are especially preferred as starting materials. Examples include high- oleic sunflower and rapeseed/canola oil. In addition, a high-oleic methyl ester fraction derived from either palm kernel oil or tallow is acceptable. It is to be understood that such oils typically will contain some levels of impurities, including some fatty acid impurities that may be converted to sarcosinate compounds by this synthesis method. For example, commodity canola/rapeseed oil may comprise a majority of oleic acid, and a mixture of fatty acid impurities such as palmitic, stearic, linoleic, linolenic and/or eicosenoic acid, some or all of which are converted to the sarcosinate by this reaction method. If desired for formulation purposes, some or all of such impurity materials may be excluded from the starting oil before preparing the oleoyl sarcosinate to be used in the present compositions.

Finally, sarcosine remaining in the reaction mixture can be converted to an amide by addition of maleic or acetic anhydride to the mixture, thereby minimizing the sarcosine content and any potential for formation of undesired nitrogen-containing impurities.

The synthesis of oleoyl sarcosinate may be carried out as follows to prepare the sodium oleoyl sarcosinate.

Synthesis of Oleoyl Amide of Sarcosine Sodium Salt - A 2 L, 3 -neck, round bottom flask.is fitted with thermometer, Dean-Stark trap with condenser, mechanical stirring, and a gas inlet adapter through which nitrogen is passed over the reaction mixture. The reaction vessel is charged with sarcosine (43.3 g, 0.476 mol), sodium methoxide 25% in methanol (97.7 g, 0.452 mol), and methanol (400 mL). The reaction is refluxed 15 min to neutralize the sarcosine and then methyl ester derived from Cargill regular high-oleyl sunflower oil (148.25 g, 0.5 mol) is added. After the methanol is removed with the Dean- Stark trap, reaction mixture is heated to 170°C for 1 hr to drive off any water. The reaction is initiated by the addition of sodium methoxide 25% in methanol (15.4 g, 0.0714 mol). Reaction is kept at 170°C for 2.5 hr during which methanol is collected in the Dean-Stark trap. The reaction is allowed to cool slightly and then methanol (200 g) is added. Maleic anhydride (9.43 g, 0.095 mol) is added to the methanol solution and the reaction is stirred at 60°C for 0.5 hr. Then most of the methanol is removed by rotary evaporation and acetone (2 L) is added to precipitate the product. The product is collected by suction filtration and allowed to air dry to give an off-white solid. Analysis of the reaction mixture by GC indicates the majority of the product is oleoyl sarcosinate, with minor amounts of the following impurities: sarcosine, oleic acid, and the sarcosinates derived from palmitic acid, stearic acid, and linoleic acid. A kyl alkoxylated sulfates and/or alkyl sulfates

The alkyl alkoxylated sulfate surfactants hereof are water soluble salts or acids of the formula RO(A)_mSO3M wherein R is an unsubstituted C10-C24 alkyl or hydroxyalkyl group having a C10-C24 alkyl component, preferably a Ci2-Cιg alkyl or hydroxyalkyl, more preferably C12-C15 alkyl or hydroxyalkyl, A is an ethoxy or propoxy unit, m is greater than zero, typically between about 0.5 and about 6, more preferably between about 0.5 and about 3, and M is H or a cation which can be, for example, a metal cation (e.g., sodium, potassium, lithium, calcium, magnesium, etc.), ammonium or substituted- ammonium cation. Alkyl ethoxylated sulfates as well as alkyl propoxylated sulfates are contemplated herein. Specific examples of substituted ammonium cations include methyl-, dimethyl, trimethyl-ammonium cations and quaternary ammonium cations such as tetramethyl-ammonium and dimethyl piperdinium cations and those derived from alkylamines such as ethylamine, diethylamine, triethylamine, mixtures thereof, and the like. Exemplary surfactants are C12-C15 alkyl polyethoxylate (1.0) sulfate (Ci2- i5E(1.0)M), C12-C15 alkyl polyethoxylate (2.25) sulfate (Ci2-Ci5E(2.25)M), C₁₂-C₁₅ alkyl polyethoxylate (3.0) sulfate (Ci2-Ci5E(3.0)M), and C12-C15 alkyl polyethoxylate (4.0) sulfate (Ci2-Ci5E(4.0)M), wherein M is conveniently selected from sodium and potassium.

The alkyl sulfate surfactants hereof are water soluble salts or acids of the formula ROSO3M wherein R preferably is a C}o-C24 hydrocarbyl, preferably an alkyl or hydroxyalkyl having a Cio-Cjg alkyl component, more preferably a C12-C15 alkyl or hydroxyalkyl, and M is H or a cation, e.g., an alkali metal cation (e.g. sodium, potassium, lithium), or ammonium or substituted ammonium (e.g. methyl-, dimethyl-, and trimethyl ammonium cations and quaternary ammonium cations such as tetramethyl-amrnonium and dimethyl piperdinium cations and quaternary ammonium cations derived from alkylamines such as ethylamine, diethylamine, triethylamine, and mixtures thereof, and the like). Detergent ingredients

In another embodiment of the present invention, a liquid detergent composition is provided comprising the surfactant system of the present invention mixed with detergent ingredients. A wide range of surfactants can be used in the detergent composition of the present invention. A typical listing of anionic, nonionic, ampholytic and zwitterionic classes, and species of these surfactants, is given in US Patent 3,664,961 issued to Norris on May 23, 1972.

Other suitable anionic surfactants that can be used are alkyl ester sulfonate surfactants including linear esters of Cg-C20 carboxylic acids (i.e., fatty acids) which are sulfonated with gaseous SO3 according to "The Journal of the American Oil Chemists Society", 52 (1975), pp. 323-329. Suitable starting materials would include natural fatty substances as derived from tallow, palm oil, etc.

The preferred alkyl ester sulfonate surfactant, especially for laundry applications, comprise alkyl ester sulfonate surfactants of the structural formula :

R³ - CH(SO₃M) - C(O) - OR⁴

wherein R³ is a Cg-C20 hydrocarbyl, preferably an alkyl, or combination thereof, R⁴ is a Cj-Cβ hydrocarbyl, preferably an alkyl, or combination thereof, and M is a cation which forms a water soluble salt with the alkyl ester sulfonate. Suitable salt-forming cations include metals such as sodium, potassium, and lithium, and substituted or unsubstituted ammonium cations, such as monoethanolamine, diethanolamine, and triethanolamine. Preferably, R³ is C10- 16 alkyl, and R⁴ is methyl, ethyl or isopropyl. Especially preferred are the methyl ester sulfonates wherein R³ is CJO-CIO alkyl.

Other anionic surfactants useful for detersive purposes can also be included in the laundry detergent compositions of the present invention. These can include salts (including, for example, sodium, potassium, ammonium, and substituted ammonium salts such as mono-, di- and triethanolamine salts) of soap, C9-C20 linear alkylbenzenesulfonates, Cg-C22 primary of secondary alkanesulfonates, C -C24 olefinsulfonates, sulfonated polycarboxylic acids prepared by sulfonation of the pyrolyzed product of alkaline earth metal citrates, e.g., as described in British patent specification No. 1,082,179, C -C24 alkylpolyglycolethersulfates (containing up to 10 moles of ethylene oxide); alkyl glycerol sulfonates, fatty acyl glycerol sulfonates, fatty oleoyl glycerol sulfates, alkyl phenol ethylene oxide ether sulfates, paraffin sulfonates, alkyl phosphates, isethionates such as the acyl isethionates, N-acyl taurates, alkyl succinamates and sulfosuccinates, monoesters of sulfosuccinates (especially saturated and unsaturated Ci2^_Cι monoesters) and diesters of sulfosuccinates (especially saturated and unsaturated Cg-C^ diesters), sulfates of alkylpolysaccharides such as the sulfates of alkylpolyglucoside (the nonionic nonsulfated compounds being described below), and alkyl polyethoxy carboxylates such as those of the formula RO CJ^CI^O^-C-^COO- M+ wherein R is a C -C22 alkyl, k is an integer from 0 to 10, and M is a soluble salt- forming cation. Resin acids and hydrogenated resin acids are also suitable, such as rosin, hydrogenated rosin, and resin acids and hydrogenated resin acids present in or derived from tall oil. Further examples are described in "Surface Active Agents and Detergents" (Vol. I and II by Schwartz, Perry and Berch). A variety of such surfactants are also generally disclosed in U.S. Patent 3,929,678, issued December 30, 1975 to Laughlin, et al. at Column 23, line 58 through Column 29, line 23 (herein incorporated by reference). When included therein, the laundry detergent compositions of the present invention typically comprise from about 1% to about 40%, preferably from about 5% to about 25% by weight of such anionic surfactants.

One class of nonionic surfactants useful in the present invention are condensates of ethylene oxide with a hydrophobic moiety to provide a surfactant having an average hydrophilic-lipophilic balance (HLB) in the range from 8 to 17, preferably from 9.5 to 14, more preferably from 12 to 14. The hydrophobic (lipophilic) moiety may be aliphatic or aromatic in nature and the length of the polyoxyethylene group which is condensed with any particular hydrophobic group can be readily adjusted to yield a water-soluble compound having the desired degree of balance between hydrophilic and hydrophobic elements. Especially preferred nonionic surfactants of this type are the C9-C15 primary alcohol ethoxylates containing 3-12 moles of ethylene oxide per mole of alcohol, particularly the C12-C15 primary alcohols containing 5-8 moles of ethylene oxide per mole of alcohol.

Another class of nonionic surfactants comprises alkyl polyglucoside compounds of general formula

RO (C_nH_2nO)_tZ_x

wherein Z is a moiety derived from glucose; R is a saturated hydrophobic alkyl group that contains from 12 to 18 carbon atoms; t is from 0 to 10 and n is 2 or 3; x is from 1.3 to 4, the compounds including less than 10% unreacted fatty alcohol and less than 50% short chain alkyl polyglucosides. Compounds of this type and their use in detergent are disclosed in EP-B 0 070 077, 0 075 996 and 0 094 118.

Very suitable as nonionic surfactants are poly hydroxy fatty acid amide surfactants of the formula

R² - C(O) - N(R!) - Z,

wherein R¹ is H, or R* is Cι_4 hydrocarbyl, 2-hydroxy ethyl, 2-hydroxy propyl or a mixture thereof, R² is C5.31 hydrocarbyl, and Z is a polyhydroxyhydrocarbyl having a linear hydrocarbyl chain with at least 3 hydroxyls directly connected to the chain, or an alkoxylated derivative thereof. Preferably, R¹ is methyl, R² is a straight Cj ι_i5 alkyl or alkenyl chain such as coconut alkyl or mixtures thereof, and Z is derived from a reducing sugar such as glucose, fructose, maltose, lactose, in a reductive amination reaction. When included therein, the laundry detergent compositions of the present invention typically comprise nonionic surfactants in the weight ratio of anionic surfactant to nonionic surfactant from 3:1 to 1:3, preferably from 2.5:1 to 1.5 to 1.

Cationic detersive surfactants suitable for use in the laundry detergent compositions of the present invention are those having one long-chain hydrocarbyl group. Examples of such cationic surfactants include the ammonium surfactants such as alkyldimethylammonium halogenides, and those surfactants having the formula :

[R²(OR³)_y][R⁴(OR³)_y]₂R⁵N+X-

wherein R² is an alkyl or alkyl benzyl group having from about 8 to about 18 carbon atoms in the alkyl chain, each R³ is selected from the group consisting of -CH2CH2-, -

CH₂CH(CH₃)-, -CH₂CH(CH2OH)-, -CH₂CH₂CH₂-, and mixtures thereof; each R⁴ is selected from the group consisting of C1-C4 alkyl, C1-C4 hydroxyalkyl, benzyl ring structures formed by joining the two R⁴ groups, -CH2CHOH- CHOHCOR⁶CHOHCH2OH wherein R⁶ is any hexose or hexose polymer having a molecular weight less than about 1000, and hydrogen when y is not 0; R^ is the same as R⁴ or is an alkyl chain wherein the total number of carbon atoms of R² plus R⁵ is not more than about 18; each y is from 0 to about 10 andthe sum of the y values is from 0 to about 15; and X is any compatible anion.

Preferred cationic surfactants are the water-soluble quaternary ammonium compounds useful in the present composition having the formula :

R₁R R3R4N⁺X- (i)

wherein R\ is Cg-Cj6 alkyl, each of R2, R3 and R4 is independently C1-C4 alkyl, C1-C4 hydroxy alkyl, benzyl, and -(C2H4θ)_xH where x has a value from 1 to 5, and X is an anion. Not more than one of R2, R3 or R4 should be benzyl.

The preferred alkyl chain length for R_j is C12-C15 particularly where the alkyl group is a mixture of chain lengths derived from coconut or palm kernel fat or is derived synthetically by olefin build up or OXO alcohols synthesis. Preferred groups for R2R3 and

R4 are methyl and hydroxyethyl groups and the anion X may be selected from halide, methosulphate, acetate and phosphate ions.

Examples of suitable quaternary ammonium compounds of formulae (i) for use herein are : coconut trimethyl ammonium chloride or bromide; coconut methyl dihydroxyethyl ammonium chloride or bromide; decyl triethyl ammonium chloride; decyl dimethyl hydroxyethyl ammonium chloride or bromide; C 12- 15 dimethyl hydroxyethyl ammonium chloride or bromide; coconut dimethyl hydroxyethyl ammonium chloride or bromide; myristyl trimethyl ammonium methyl sulphate; lauryl dimethyl benzyl ammonium chloride or bromide; lauryl dimethyl (ethenoxy)4 ammonium chloride or bromide; choline esters (compounds of formula (i) wherein R\ is -CI_2-O-C(O)-Ci2-l4 lkyl and R2R3R4 are methyl).

Other cationic surfactants useful herein are also described in U.S. Patent 4,228,044, Cambre, issued October 14, 1980.

When included therein, the laundry detergent compositions of the present invention typically comprise from 0.5% to about 5%, preferably from about 1% to about 3% by weight of such cationic surfactants. The compositions according to the present invention may further comprise a builder system. Any conventional builder system is suitable for use herein including aluminosilicate materials, silicates, polycarboxylates and fatty acids, materials such as ethylenediamine tetraacetate, metal ion sequestrants such as aminopolyphosphonates, particularly ethylenediamine tetramethylene phosphonic acid and diethylene triamine pentamethylenephosphonic acid. Though less preferred for obvious environmental reasons, phosphate builders can also be used herein.

Suitable polycarboxylates builders for use herein include citric acid, preferably in the form of a water-soluble salt, derivatives of succinic acid of the formula R- CH(COOH)CH2(COOH) wherein R is C 10-20 alkyl or alkenyl, preferably C12-16, or wherein R can be substituted with hydroxyl, sulfo sulfoxyl or sulfone substituents. Specific examples include lauryl succinate , myristyl succinate, palmityl succinate2- dodecenylsuccinate, 2-tetradecenyl succinate. Succinate builders are preferably used in the form of their water-soluble salts, including sodium, potassium, ammonium and alkanolammonium salts.

Other suitable polycarboxylates are oxodisuccinates and mixtures of tartrate monosuccinic and tartrate disuccinic acid such as described in US 4,663,071. Especially for the liquid execution herein, suitable fatty acid builders for use herein are saturated or unsaturated CIO- 18 fatty acids, as well as the corresponding soaps. Preferred saturated species have from 12 to 16 carbon atoms in the alkyl chain. The preferred unsaturated fatty acid is oleic acid. Other preferred builder system for liquid compositions is based on dodecenyl succinic acid and citric acid.

Detergency builder salts are normally included in amounts of from 3% to 50% by weight of the composition preferably from 5% to 30% and most usually from 5% to 25% by weight.

The detergent composition according to the present invention may optionally contain bleaching agents or bleaching compositions containing a bleaching agent and one or more bleach activators. When present, bleaching agents will typically be at levels of from about 1% to about 30%, more typically from about 5% to about 20%, of the detergent composition, especially for fabric laundering. If present, the amount of bleach activators will typically be from about 0.1% to about 60%, more typically from about 0.5% to about 40% of the bleaching composition comprising the bleaching agent-plus- bleach activator.

The bleaching agents used herein can be any of the bleaching agents useful for detergent compositions in textile cleaning or other cleaning purposes that are now known or become known. The bleaches suitable for the present invention can be activated or non-activated bleaches.

Bleaches suitable for the present invention include peroxygen bleaches. Examples of suitable water-soluble solid peroxygen bleaches include hydrogen peroxide releasing agents such as hydrogen peroxide, perborates, e.g. perborate monohydrate, perborate tetrahydrate, persulfates, percarbonates, peroxydisulfates, perphosphates and peroxyhydrates. Preferred bleaches are percarbonates and perborates.

The hydrogen peroxide may also be present by adding an enzymatic system (i.e. an enzyme and a substrate therefore) which is capable of generating hydrogen peroxide at the beginning or during the washing and/or rinsing process. Such enzymatic systems are disclosed in EP Patent Application 91202655.6 filed October 9, 1991.

Other peroxygen bleaches suitable for the present invention include organic peroxyacids such as percarboxylic acids.

Suitable examples of this class of agents include magnesium monoperoxyphthalate hexahydrate, the magnesium salt of metachloro perbenzoic acid, 4-nonylamino-4- oxoperoxybutyric acid and diperoxydodecanedioic acid. Such bleaching agents are disclosed in U.S. Patent 4,483,781, Hartman, issued November 20, 1984, U.S. Patent Application 740,446, Burns et al, filed June 3, 1985, European Patent Application 0,133,354, Banks et al, published February 20, 1985, and U.S. Patent 4,412,934, Chung et al, issued November 1, 1983. Highly preferred bleaching agents also include 6- nonylamino-6-oxoperoxycaproic acid as described in U.S. Patent 4,634,551, issued January 6, 1987 to Burns et al.

A preferred percarbonate bleach comprises dry particles having an average particle size in the range from about 500 micrometers to about 1,000 micrometers, not more than about 10% by weight of said particles being smaller than about 200 micrometers and not more than about 10% by weight of said particles being larger than about 1,250 micrometers. Optionally, the percarbonate can be coated with silicate, borate or water- soluble surfactants. Percarbonate is available from various commercial sources such as FMC, Solvay and Tokai Denka. Mixtures of bleaching agents can also be used.

Peroxygen bleaching agents, the perborates, the percarbonates, etc., are preferably combined with bleach activators, which lead to the in situ production in aqueous solution (i.e., during the washing process) of the peroxy acid corresponding to the bleach activator. Various nonlimiting examples of activators are disclosed in U.S. Patent 4,915,854, issued April 10, 1990 to Mao et al, and U.S. Patent 4,412,934. The nonanoyloxybenzene sulfonate (NOBS) and tetraacetyl ethylene diamine (TAED) activators are typical, and mixtures thereof can also be used. See also U.S. 4,634,551 for other typical bleaches and activators useful herein.

Highly preferred amido-derived bleach activators are those of the formulae:

R¹N(R5)C(O)R²C(O)L or R¹C(O)N(R5)R C(O)L

wherein R¹ is an alkyl group containing from about 6 to about 12 carbon atoms, R² is an alkylene containing from 1 to about 6 carbon atoms, R^ is H or alkyl, aryl, or alkaryl containing from about 1 to about 10 carbon atoms, and L is any suitable leaving group. A leaving group is any group that is displaced from the bleach activator as a consequence of the nucleophilic attack on the bleach activator by the perhydrolysis anion. A preferred leaving group is phenyl sulfonate.

Preferred examples of bleach activators of the above formulae include (6- octanamido-caproyl)oxybenzenesulfonate, (6-nonanamidocaproyl)oxybenzenesulfonate, (6-decanamido-caproyl)oxybenzenesulfonate, and mixtures thereof as described in U.S. Patent 4,634,551, incorporated herein by reference.

Another class of bleach activators comprises the benzoxazin-type activators disclosed by Hodge et al in U.S. Patent 4,966,723, issued October 30, 1990, incoφorated herein by reference. A highly preferred activator of the benzoxazin-type is :

Still another class of preferred bleach activators includes the acyl lactam activators, especially acyl caprolactams and acyl valerolactams of the formulae:

» wherein R^ is H or an alkyl, aryl, alkoxyaryl, or alkaryl group containing from 1 to about 12 carbon atoms. Highly preferred lactam activators include benzoyl caprolactam, octanoyl caprolactam, 3,5,5-trimethylhexanoyl caprolactam, nonanoyl caprolactam, decanoyl caprolactam, undecenoyl caprolactam, benzoyl valerolactam, octanoyl valerolactam, decanoyl valerolactam, undecenoyl valerolactam, nonanoyl valerolactam, 3,5,5-trimethylhexanoyl valerolactam and mixtures thereof. See also U.S. Patent 4,545,784, issued to Sanderson, October 8, 1985, incoφorated herein by reference, which discloses acyl caprolactams, including benzoyl caprolactam, adsorbed into sodium perborate.

Bleaching agents other than oxygen bleaching agents are also known in the art and can be utilized herein. One type of non-oxygen bleaching agent of particular interest includes photo activated bleaching agents such as the sulfonated zinc and/or aluminum phthalocyanines. See U.S. Patent 4,033,718, issued July 5, 1977 to Holcombe et al. If used, detergent compositions will typically contain from about 0.025% to about 1.25%, by weight, of such bleaches, especially sulfonate zinc phthalocyanine.

If desired, the bleaching compounds can be catalyzed by means of a manganese compound. Such compounds are well known in the art and include, for example, the manganese-based catalysts disclosed in U.S. Pat. 5,246,621, U.S. Pat. 5,244,594; U.S. Pat. 5,194,416; U.S. Pat. 5,114,606; and European Pat. App. Pub. Nos. 549,271 Al, 549,272A1, 544.440A2, and 544,490A1; Preferred examples of these catalysts include Mn^IV2(^u"⁰)3( ! ,4,7-trimethyl- 1 ,4,7-triazacyclononane)2(PF6)2, Mn^ιπ2(u-O) \ (u- OAc)2( 1 ,4,7-trimethyl- 1 ,4,7-triazacyclononane)2_(Clθ4)2, Mn^IV4(u-O)6( 1 ,4,7- triazacyclononane)4(Clθ4)4, Mn^Mn^{1 V}4(u-O) \ (u-O Ac)2_( 1 ,4, 7-trimethyl- 1 ,4,7- triazacyclononane)2(Clθ4)3, Mn^ -trimethyl- J-triazacyclononane)-

(OCH3)3(PF<5), and mixtures thereof. Other metal-based bleach catalysts include those disclosed in U.S. Pat. 4,430,243 and U.S. Pat. 5,114,611. The use of manganese with various complex ligands to enhance bleaching is also reported in the following United States Patents: 4,728,455; 5,284,944; 5,246,612; 5,256,779; 5,280,117; 5,274,147; 5,153,161; and 5,227,084.

As a practical matter, and not by way of limitation, the compositions and processes herein can be adjusted to provide on the order of at least one part per ten million of the active bleach catalyst species in the aqueous washing liquor, and will preferably provide from about 0.1 ppm to about 700 ppm, more preferably from about 1 ppm to about 500 ppm, of the catalyst species in the laundry liquor.

The detergent composition according to the present invention may comprise amines. Such amines will generally correspond to the formula :

wherein R\ is Cg-C22 alkyl. alkenyl, cycloaliphatic or polycyclic group which may be substituted with up to three hydroxyl or phenyl groups and which may optionally be interrupted with up to 12 ethylene oxide moieties; wherein R2 and R3 are each H or Cj-Cj straight or branched chain alkyl or alkenyl groups which may be substituted with up to 12 ethylene oxide moieties; and wherein Ri and R2 may be taken together to form an imidazoline group of the structure:

wherein R4 is Cg - Cj alkyl.

Preferably in the above formulas, R\ is Cg-Cjg alkyl; R2 and R3 are each C1-C4 alkyl, optionally interrupted with 1 or 2 ethylene oxide moieties; and R4 is Cjo - j6 alkyl. Amines of the above formulas, as indicated, are generally known as surfactant amines. Such materials are described in greater detail in Kirk-Othmer; Encyclopedia of Chemical Technology, Fourth Edition, Volume 2, "Fatty Amines," Pages 405-425 (1992). This article is incoφorated herein by reference.

Suitable primary amines, i.e., those wherein, in the above formulas, R2 and R3 are both hydrogen, include 1-hexylamine, l-octylamine, laurylamine, palmitylamine, stearoylamine, oleoylamine, coconutalkylamine, tallowalkylamine, 6-amino-l-hexanol; 3- isopropoxypropylamine, 3 -(2-methoxyethoxy)-propylamine, 2-(2-aminoethoxy)-ethanol and cyclohexylamine.

Suitable secondary amines, i.e., those wherein, in the above formulas, only one of R2 and R3 is hydrogen, include dicoconutalkylamine, di-n-dodecylamine, di-n- hexadecylamine, di-n-octadecylamine, and ditallowalkylamine.

Suitable tertiary amines, i.e., those wherein, in the above formulas, neither R2 nor

R3 is hydrogen, include coconutalkyldimethylamine, dimethyloleylamine, di-n- decylmethylamine, dicoconutalkylmethylamine, tri-n-octylamine, tri-n-dodecylamine, hexadecyltris(ethyleneoxy)dimethylamine, tallowalkylbis(2-hydroxyethyl)amine, stearoylbis(2-hydroxyethyl)amine, and oleoylbis(2-hydroxyethyl)amine.

Suitable imidazolines useful herein are those of the formula:

wherein R4 is C9 - C13 alkyl. Such materials are commercially marketed under the trade name VARINE.

Suitable polycyclic amines include those based on rosin acids. Examples of such amines are those of the formula:

wherein x and y range from 1 to 3. Amines of this type are marketed under the trade name POLYRAD. Of all of the foregoing amines the preferred materials are the trialkyl amines marketed under the tradename ADOGEN, the long chain alkyldimethyl amines marketed under the tradename ARMEEN and the ethoxylated amines marketed under the tradename ETHOMEEN. The most preferred amines for use in the compositions herein are 1-hexylamine, l-octylamine, n-dodecyldimethylamine (ARMEEN DM12D) and bis- hydroxyethylcoconutalkylamine (ETHOMEEN C/12).

Without being bound by theory, it is believed that amines of the foregoing type are protonated under the pH conditions of use for the detergent compositions herein. The resulting cationic protonated amine species then interacts with the oleoyl sarcosinate, and perhaps other anionic surfactants, to form a lipophilic surfactant pair. This in turn leads to greater surface absoφtivity and superior detergency for greasy/oily soils. The alkylamines useful herein, which generally have pKa's 9-11, can also provide buffering capacity for the detergent compositions in which they are used.

Preferably, the liquid compositions according to the present invention are in "concentrated form"; in such case, the liquid detergent compositions according to the present invention will contain a lower amound of water, compared to conventional liquid detergents. The level of water is less than 50%, preferably less than 30%, more preferably less than 20% of water by weight of the detergent compositons.

Said concentrated products provide advantages to the consumer, who has a product which can be used in lower amounts and to the producer, who has lower shipping costs.

Other components used in detergent compositions may be employed, such as enzymes and stabilizers therefore, soil-suspending agents, soil-release polymers, abrasives, bactericides, tarnish inhibitors, coloring agents, foam control agents, corrosion inhibitors and perfumes.

The following examples are meant to exemplify compositions of the present inventions, but are not necessarily meant to limit the scope of the invention.

EXAMPLE I

The following wash tests are done to demonstrate the robustness of the OS/AS or OS/AES surfactant system compared to AS or AES surfactant systems.

Test conditions :

- Test in washing machine - 1 cycle

- Temperature 40°C

- Composition of the ballast load : 2.5kg terry towels - City water (2.5 mmole 1 hardness)

- Product usage 100 mis

Test procedure :

The design of the test is such as to evaluate the greasy soil release performance of the textile items between the compositions to be tested and the reference composition. The test is carried out on a range of greasy stains which are applied on white cotton. The stains are split in halves to have a direct comparison with the reference. In total 4 cycles are run after each other whilst swapping machines to account for machine variability. Each cycle contains 1 replicate per comparison.

Grading is done under controlled light conditions by expert graders.

Differences are recorded in panel score units (psu), positive being performancewise better than the reference product.

Grading scale (PSU grading) 0 = Equal 1 = 1 think this one is better 2 = 1 know this one is a little better

3 = This one is a lot better

4 = This one is a whole lot better

The PSU grading data are statistical recount, an average of the 4 replicates is made.

A liquid detergent composition is prepared containing the following ingredients :

% by weight of the detergent composition

Cj2-Ci4 N-methyl glucamide 6.5

Cj2-Ci4 fatty alcohol ethoxylate 6.5

C12-C16 fatty acid 7

Citric acid anhydrous 6.0

Diethylene triamine penta methylene phosphonic acid 1.0

Monoethanolamine 13.2

Propanediol 12.7

Ethanol 1.8

Amylase (300KNU/g) 0.1

Lipolase (lOOKNU/g) 0.15

Protease (34g l) 0.5

Endo-A (5000 CEVU/G) 0.05

Carezyme (5000 CEVU/g) 0.09

Terephthalate-based polymer 0.5

Boric acid 2.4

Minors and water

TABLE I (Reference)

The liquid detergent compositions of Table I is supplemented as indicated below

(compositions AI AH) :

Composition Al - without oleoyl sarcosinate with 22% AS (C 12-C j 5 alkyl sulfate)/4%AES (C 12-C 15 alkyl ethoxylated sulfate)

Composition All - without oleoyl sarcosinate with 0%AS/26%AES. Results

STAIN REFERENCE Al AΠ

Hydrophobic greasy stain 0 +0.1 -1.7* (make-up/motor oil

Hydrophillic greasy stain 0 -0.2 -1.7* (beeffbutter)

* significant difference, at 95% confidence Interval (LSD)

Conclusion :

AES surfactants are deficient versus AS systems in the absence of oleoyl sarcosinate.

The liquid detergent compositions of Table I is supplemented as indicated below (compositions BI/BII) :

Composition BI - with oleoyl sarcosinate (9%OS) with 9%AS

Composition BII

- with oleoyl sarcosinate (9%OS) with 9%AES.

Results

STAIN REFERENCE Al AΠ

Hydrophobic greasy stain 0 0.9* 1.1* (make-up/motor oil

Hydrophillic greasy stain 0 1* 0.7* (beef/butter)

* significant difference, at 95% confidence Interval (LSD)

Conclusion AES surfactants provide equal detergency performance compared with AS when formulated with oleoyl sarcosinate. EXAMPLE π

The following liquid detergent compositions are made :

% by weight of the detergent compositions

B D

Cj2-Ci5 Alkyl ethoxylated sulfate - 11.0 6.0 16.0

Oleoyl Sarcosinate 6 3 12 9

Linear alkylbenzene sulfonate 14 - 6 - ^c12"^c15 A ^sulfate 4 16.0 - -

C12-C14 N-methyl glucamide - 7.0 9.0 6

C12-C14 fatty alcohol ethoxylate 12.0 5.0 3.0 4

C12-C16 Fatty acid 7 7 7 7 citric acid anhydrous 6.0 4.5 3.5 3.5

Diethylene triamine penta methylene phosphonic acid 1.0 1.0 2.0 2.0

Monoethanolamine 13.2 12.7 12.8 11.0

Propanediol 12.7 14.5 13.1 10.0

Ethanol 1.8 1.8 4.7 5.4

Amylase (300KNU/g) 0.1 0.1 0.1 0.1

Lipolase(100KNU/g) 0.15 0.15 0.15 0.15

Protease (34g/l) 0.5 0.5 0.5 0.5

Endo-A (5000 CEVU/g) 0.05 0.05 0.05 0.05

Carezyme (5000 CEVU/g) 0.09 0.09 0.09 0.09

Terephthalate-based polymer 0.5 0.5 0.5 0.5

Boric acid 2.4 2.4 2.8 2.8

DC 3225C 0.03 0.04 0.03 0.04

Aerosil 200 0.03 0.04 0.04 0.03

Branched silicone 0.3 0.3 0.3 0.3

Water & Minors up 1 to 100% The above liquid detergent compositions (A-D) are found to be very efficient in the removal of greasy/oily soils under various usage conditions.

Claims

CLAIMS 20

1. A liquid laundry detergent composition comprising a surfactant system, said surfactant system comprising an oleoyl sarcosinate and one or more of an anionic surfactant selected from the group of alkyl alkoxylated sulfates and/or alkyl sulfates.

2. A liquid laundry detergent composition according to Claim 1 in concentrated form comprising less than about 30% water.

3. A liquid laundry detergent composition according to either Claim 1 or 2 wherein the anionic surfactant is selected from the group of alkyl alkoxy sulfates.

4. A liquid laundry detergent composition according to any of Claims 1-3 wherein the anionic surfactant is selected from an alkyl ethoxylated sulfate.

5. A liquid laundry detergent composition according to any of Claims 1-4 wherein the anionic surfactant is C12-C15 alkyl ethoxylated sulfate.

6. A liquid detergent composition according to either Claim 1 or 2 wherein the anionic surfactant is C12-C15 alkyl sulfate.

7. A liquid laundry detergent composition according to any of Claims 1-6 further comprising a nonionic surfactant selected from the polyhydroxy fatty acid amides.

8. A liquid laundry detergent composition according to Claim 7 wherein the nonionic surfactant is C12-C14 N-methyl glucamide.

9. A liquid laundry detergent composition according to any of Claims 1-8 further comprising surfactants, builders, enzymes and other conventional detergent ingredients.

10. Use of a liquid laundry detergent composition according to any of Claims 1-9 for pretreatment of fabrics.