SK21593A3 - Polyhydroxy fatty acid amides in zeolite/layered silicate built detergent - Google Patents

Abstract

Disclosed is a built detergent composition, comprising one or more anionic, nonionic or cationic detersive surfactants, or mixtures thereof, optional detersive adjuncts, and optional auxiliary builders, wherein the composition contains at least about 1 % by weight of a zeolite or layered silicate builder, or mixture thereof; and at least about 1 % by weight of a polyhydroxy fatty acid amide material of formula (I) wherein: R<1> is H, C1-C4 hydrocarbyl, 2-hydroxy ethyl, 2-hydroxy propyl, or a mixture thereof; R<2> is a C5-C31 hydrocarbyl; and Z is a polyhydroxyhydrocarbyl having a linear hydrocarbyl with at least 3 hydroxyls directly connected to the chain, or an alkoxylated derivative (preferably ethoxylated or propoxylated) thereof.

Description

Technical field

The invention relates to detergent compositions in which detergent builders are combined with a zeolite or layered silicate base or mixtures thereof with polyhydroxy fatty acid amides.

Current state

Various builders have been proposed for use in detergent compositions. Such materials serve a variety of functions, including hardness suppression, peptization, pH control, and the like. Tripolyphosphate has been a selected activator for many years, but recent developments in the art have brought about activating materials such as gelatin, various polycarboxylates, and the like. Currently, a number of fully formulated detergent compositions comprise a zeolite builder or a carboxylate builder or a mixture thereof i.

Developing high performance laundry detergent compositions

phosphate was a major challenge for industry. In terms of effect, even the best zeolite activators often result in an underactivated situation in hard water. In addition, commercially available zeolite activating agents can cope with calcium hardness, but are not particularly effective against magnesium hardness.

Recently, the possibility of using layered silicates as detergent builders has been discovered. Layered silicates, however, cope with magnesium hardness, but are somewhat less effective in controlling calcium hardness.

Currently, almost all phosphate-free, high-performance granular detergents contain a zeolite builder. Although zeolite-activated laundry detergents are widely marketed, their drawbacks are well known by the formulator. In order to increase the detergency performance of zeolite and layered silicate compositions, experienced formulators typically add a variety of detergent adjuvants to the detergent compositions. Thus materials such as cleaning enzymes, soil release polymers are used to increase the efficiency of the activated detergent compositions. bleaches and bleach activators.

In addition, it should also be taken into account that, although for several years new detergent formulators have sought to replace phosphate-activated detergents with equally effective phosphate-free detergents, there has recently been an interest to build detergents with reduced reliance on oil-derived surfactants and other non-renewable sources.

A number of polyhydroxy fatty acid amides are further described in the art. For example, N-acyl. N-methyl glucamides are described by JV Goodby, M. ft. Marcus, E. Chin and PL Finn in The Thermotropic Liquid-Crystal Properties of Some Straight Chain Carbohydrate ftmphiphiles in Liquid Crystals, 1988, vol. 3, no. 11, p. 1569-1581 and A. Muller-Fahrn, V. Zabel, M. Steif and R. Hilgenfeld in Molecular and Crystal Structure of a Nonionic Detergent ^: Nonanoyl-N-methylglucamide in J. Chem. Soc. Chem. Commun., 1986, p. The use of N-alkyl polyhydroxyamide surfactants has recently been of particular interest for use in biochemistry, for example in the dissociation of biological membranes (see also, e.g., the ND-Gluco-N-methyl-alkanamide Compounds magazine and New Class chem. J., 1982, vol. 207, pp. 363-366, by JEK Hildreth.

The use of N-alkyl glucamides in detergent compositions has also been discussed in the literature. U.S. Pat. No. 2,965,576, issued December 20, 1960; No. 809,060, published Feb. 18, 1959, discloses detergent compositions comprising anionic surfactants and certain amide surfactants, which may include N-methylglucamide added as a low temperature suds booster. These compounds include the straight chain N-acyl radical of a higher chain fatty acid having 10 to 14 carbon atoms. These compounds may also contain auxiliary materials such as alkali metal phosphates, alkali metal silicates, sulfates and carbonates. It is also generally disclosed that additional ingredients may be included in the compositions for imparting desirable properties to the composition, such as fluorescent dyes, bleaching agents, fragrances, and the like.

U.S. Pat. No. 2,703,798, issued March 8, 1955, refers to aqueous detergent compositions comprising the condensation reaction product of N-alkylglucamine and an aliphatic fatty acid ester. The product of this reaction is reported to be useful in aqueous detergent compositions without further purification. It is also known to prepare a sulfur ester of an acyl glucukamine as described in U.S. Pat. No. 2,717,894, issued September 13, 1955.

PCT International Patent Application WO 83/04412, published

22-12, 1983 discloses amphiphilic compounds containing polyhydroxylaliphatic groups, designated as being useful for a variety of purposes, including use as a surfactant in cosmetics, pharmaceuticals, shampoos, lotions.

eye ointments such as emulsifiers and dosing agents in medicine and biochemistry for solubilizing membranes, whole cells and other tissue samples, and for preparing liposomes. Included herein are compounds of formula R 'CONCR 1 CH ₂ R''andR' * CONCR 1 R ', wherein R is hydrogen or an organic group. R 'is an aliphatic hydrocarbon group of at least three carbon atoms and R''is an aldose residue.

European patent specification no. 0 285 768, published Oct 12

1988, refers to the use of N-polyhydroxy fatty acid amides as thickeners in aqueous detergent systems. Included are amides of the formula R ₁ O ₍ NC X) R ₂ , wherein R 1 is C 1 -C 8 C 8 preferably C 7 -C 17 alkyl, R 2 is hydrogen, C 1 -C 6 C 8 preferably C 1 -C 6 alkyl, or alkene oxide and X is polyhydroxyalkyl having four to seven carbon atoms, e.g. Fatty N-methylglucamide. The amide thickening properties are suitable for use in liquid paraffin sulphonate-containing surfactants, although aqueous systems may contain other anionic agents such as alkylarylsulfonates, sulfosuccinic acid salts and fatty alcohol ether sulfonates, and nonionic surfactants such as fatty alcohol polyglycol ether, especially coconut fatty acid glycerate active surfactant systems, active active acid esters, polypropylene-polyethylene oxide blended polymers, etc. Examples are paraffin paraffin sulphonate / coconut fatty acid N-methylglucamide formulations / nonionic shampoo surfactant. In addition to the densifying abilities it is mentioned. that amides

N-polyhydroxy fatty acids have better skin tolerance properties.

U.S. Pat. No. 2,982,737, issued May 2, 1961, discloses detergent bars comprising urea, anionic sodium lauryl sulfate surfactant, and an N-alkylglucamide nonionic surfactant selected from N-methyl, N-sorbityl-lauramide and N methyl, N-sorbity1 myristamide.

Other glucamide surfactants are described, for example, in German Pat. No. 2,226,872, published Dec. 20, 1972, which relates to a laundry composition comprising one or more surfactants and activating salts selected from polymeric phosphates, scavengers and scouring alkali, improved by the addition of N-acylpolyhydroxyalkyl-amine of the formula

R 1 C (O) NCR ₂ ) CH ₂ (CHOH) n CH ₂ OH where R 1 is C 1 -C 3 alkyl, R ₂ is

C 10 -C ₂₂ alkyl and n are 3 or 4. N-acylpolyhydroxyalkyl-amine is added as an impurity suspending agent.

U.S. Patent No. 3,654,166, issued Apr. 4, 1972, discloses detergent compositions comprising at least one surfactant selected from the group of anionic zwitterionic surfactants and nonionic surfactants and textile softener, N-acyl, N- alkyl 1-polyhydroxyalkyl compounds of the formula R ₁ (C ₂ ) C (O) R ₂ , wherein R 1 is C 10 -C ₂₂ alkyl, R ₂ is C ₇ -C ₂ alkyl, R 1 and R ₂ have a total of 23 to 39 carbon atoms, and Z is polyhydroxylalkyl; which may be -CH ₂ (CHOH) _m CH ₂ OH where m is 3 or 4.

U.S. Pat. No. 4,021,539, issued May 3, 1977, discloses skin care cosmetic compositions containing N-polyhydroxyalkyl-amines which include compounds of the formula R 1 NRCR) CH (CH 2 H> mR 2 wherein R 1 is H, lower alkyl, hydroxy-lower alkyl or aminoalkyl, as well as heterocyclic aminoalkyl, R is the same as R 1, but both cannot be H and R ₂ is CH ₂ OH or COOH.

French patent no. No. 1,360,018, issued April 26, 1963, relates to formaldehyde solutions stabilized against polymerization by the addition of amides of the formula RC (O) N (R 1) G. wherein R is a carboxyl functional group having at least seven carbon atoms, R 1 is hydrogen or a lower alkyl group and G is a glycitol radical of at least 5 carbon atoms.

German patent specification no. No. 1,261,851 of February 29, 1968 relates to glucamine derivatives useful as wetting and dispersing agents of formula N (R) (R 1) (R 2). wherein R is a sugar residue of glucamine, R 1 is a C 10 -C 20 alkyl radical and R 2 is a C 1 -C 5 acyl radical.

British patent no. No. 745,036, published February 15, 1956, relates to heterocyclic amides and their carboxylic esters, which are said to be useful as chemical mediators, emulsifiers, wetting and dispersing agents, fabric softeners, etc. The compounds are represented by the formula N (R) CR 1) C (O) R 2, wherein R is a residue of hexapentol or a carboxylic acid ester thereof, dehydrated, R 1 is a monovalent hydrocarbon radical, and -C (O) R 2 is a carboxylic acid acyl radical having 2 to 25 carbon atoms.

U.S. Pat. No. 3,312,627, issued April 4, 1967, discloses solid toilet blocks that are substantially free of anionic detergents and alkaline activating agents and which contain lithium soap of certain fatty acids, a surfactant selected from certain propolylene oxide-ethylenediamine ethylene oxide condensates, propylene oxide-propylene glycol-ethylene oxide condensates and polymerized ethylene glycol, and also contain a nonionic foaming component which may include a polyhydroxyamide of formula RCXCONR ¹ (R ² ) wherein RCCO) contains from about 10 to about 14 carbon atoms, and R ¹ and R ² each have H or C 1 -C 6 alkyl groups, these alkyl groups having a total carbon number of from 2 to about 7 and a total number of hydroxyl substituent groups of from 2 to about 6. A substantially similar solution is disclosed in U.S. Pat. No. 3,312,626, also issued Apr. 4, 1967.

SUMMARY OF THE INVENTION

The present invention is based on the discovery that some polyhydroxy fatty acid amide-containing detergent compositions can provide excellent overall cleaning performance with complete or partial replacement of commonly used petroleum-derived surfactants such as linear alkyl 1-benzene sulfonates. These polyhydroxy fatty acid amides may be obtained predominantly or wholly from natural renewable raw materials and, moreover, are degradable and exhibit less aquatic toxicity. These polyhydroxy fatty acid amides can increase the solubility and dissolution of the surfactant and auxiliary activating salts during use of the detergent compositions. In addition, these polyhydroxy fatty acid amides can surprisingly increase the effectiveness of zeolite-based and layered silicate activating ingredients under underactivated washing conditions.

The present invention provides a zeolite-activated detergent composition comprising one or more anionic, non-ionic or cationic detersive surfactants, or mixtures thereof, optionally detersive ingredients, and optionally auxiliary builders. which, according to the invention, is characterized in that it contains at least 1 mass. % of a detergent activator of zeolite or layered silicate or mixtures thereof and at least 1 wt.

% amide material in the form of a polyhydroxy fatty acid amide of formula 0 I | R ¹ I R ² - 1 1 C 1 - N - FROM.

wherein R ¹ is H, C 1 -C 4 hydrocarbyl, 2-hydroxyethyl, 2-hydroxypropyl or a mixture thereof, R ² is C 5 -C 31 hydrocarbyl and Z is a polyhydroxyhydrocarbyl having a linear hydrocarbyl chain with at least 3 hydroxyl groups directly attached to said chain, or an alkoxy derivative thereof, preferably ethoxylated or propoxylated.

In the granular detergent composition of the invention, the zeolite activator is preferably Zeolite A.

According to one embodiment of the invention, Z in the polyhydroxy fatty acid amide is derived from a reducing sugar. R ¹ is methyl and R ² is C 9 -C 17 alkyl or alkenyl. For example, it contains -CH ₂ (CHOH) ₄ CH ₂ OH.

Part Z in said polyhydroxy fatty acid amide may be derived from maltose. According to a preferred embodiment, the Z moiety in said polyhydroxy fatty acid amide is derived from a mixture of monosaccharides, disaccharides and optionally higher carbohydrates, the mixture containing at least 1% of at least one disaccharide, preferably maltose.

The zeolite ^: polyhydroxy fatty acid amide ratio in the detergent composition of the invention is from 1 to 20: 1, preferably 1: 5 to 15: 1, most preferably 13 to 10: 1.

The detergent composition of the invention may further comprise one or more anionic surfactants selected from the group consisting of alkyl sulfates. alkylethoxylated sulfates. alkyl ester sulfonates, preferably methyl ester sulfonates. alkylbenzenesulfonates. It may further comprise an alkyl ethoxylate or alkyl polyglycoside nonionic surfactant or a mixture thereof.

The detergent composition of the invention may also additionally comprise a polycarboxylate builder.

The invention further relates to a method of improving the ability to clean a fabric of a detergent composition comprising one or more anionic. a nonionic or cationic detersive surfactant, or mixtures thereof, a zeolite-based or layered silicate activator. or a mixture thereof, optionally cleaning adjunct ingredients, and optionally auxiliary activating agents, said composition comprising at least 1% by weight of said detergent composition. % of the amide material in the form of a polyhydroxy fatty acid amide of the formula

0 I I R ¹ | R ² - 1 1 C 1 - N - Z.

wherein R ¹ is H, C 1 -C 4 hydrocarbyl. 2-hydroxyethyl, 2-hydroxypropyl or a mixture thereof,

^R2 is C5-C31 hydrocarbyl and Z is polyhydroxyhydrocarbyl having the hydrokarby1ový-linear chain with at least 3 hydroxyl groups, preferably

C11-C17

N-methylglucamide, C11-C17

Or a mixture of said glucamide and maltamide or an alkoxylated derivative thereof, wherein the ratio of zeolite to polyhydroxy fatty acid amide is from 1:10 to 20% and the fabrics are laundered by this composition in a conventional manner.

Said method may advantageously be further characterized in that said detergent composition comprises one or more anionic surfactants.

In the process according to the invention, part Z in said polyhydroxy fatty acid amide may be derived from mixed monosaccharides, disaccharides and polysaccharides obtainable from plant sources.

The R ² moiety in said polyhydroxy fatty acid amide may, according to another feature of the process, be C 15 -C 17 alkyl, alkenyl, or mixtures thereof.

Finally, the process of the invention may be characterized in that said anionic surfactant is not an alkylbenzenesulfonate surfactant.

Thus, the invention provides an improved cleaning surfactant system comprising zeolite and / or layered silicate based builders. According to the invention, polyhydroxy fatty acid amides are used in zeolite and / or layered silicate activated detergents to provide enhanced detergency.

The individual components of the detergent compositions of the present invention will now be described. First, polyhydroxy fatty acid amide surfactant amide surfactants will be described in more detail.

The compositions of the invention will contain at least about 1% and typically from about 3% to about 50 and preferably from about 3% to about 30% of the polyhydroxy fatty acid amide surfactant described below.

The amide surfactant component of the invention, based on polyhydroxy fatty acid amide, has the structural formula:

OR ¹

II

^R2 - C - N - Z, is H, C 1 -C 4 hydrocarbyl, 2-hydroxyety1, 2-hydroxy-propy1 or a mixture thereof, preferably C1 -C4 alkyl, more preferably Ci or C2 alkyl, most preferably Ci alkyl (i.e., methyl) and R ² is C 5 -C 31 hydrocarbyl, preferably straight chain C 7 -C 19 alkyl or alkenyl, more preferably straight chain C 9 -C 17 alkyl or alkenyl, and most preferably straight chain C 11 -C 17 alkyl or alkenyl or a mixture thereof; and Z is a polyhydroxyhydrocarbyl having a linear hydrocarbyl chain of at least 3 hydroxyl groups, directly attached to the chain, or an alkoxylated (I) thereof wherein R ¹ (preferably ethoxylated or propoxylated) derivative. Part Z will preferably be derived from a reducing sugar in a reductive amination reaction; more preferably Z is glycityl. Suitable reducing sugars include glucose, fructose, maltose, galactose, mannose, and xylose. As raw materials, high dextrose cereal syrup, high maltose cereal syrup, as well as the individual sugars mentioned above can be used. These cereal syrups may provide a mixture of sugar components for Z. However, it should be noted that in no case is the exclusion of other suitable raw materials monitored. Preferably, Z will be selected from the group consisting of

CH ₂ - (CHOH) _n -CH ₂ OH, -CH (CH ₂ OH) - (CHOH) n -CH ₂ OH,

-CH ₂ - (CH0H) ₂ CCHOR ') CHOH) _-CH2 OH, and alkoxylated derivatives thereof, where n is an integer from 3 to 5, inclusive. R 1 is H or a cyclic or aliphatic monosaccharide. Most preferred are glycityls wherein n is 4, especially -CH ₂ - (CHOH) 4 -CH ₂ OH.

In formula (I), R ¹ may be, for example, N-methyl, N-ethyl, N-propyl, N-isopropyl, N-butyl, Ν-2-hydroxyethyl or

Ν-2-hydroxypropy1.

R ² -CO-N? Can be, for example, coconut fatty acid amide, stearamide. oleamide, lauramide. caprinamide, palmitamide, tallow amide, etc.

Z may be 1-deoxyglucity1, 2-deoxyfructity1,

1-deoxymaltity1, 1-deoxylactity1, N-1-deoxygalactity1,

N-1-deoxymannity1, 1-deoxymaltotriotity1, etc.

Methods for making polyhydroxy fatty acid amides are known in the art. In general, they can be produced by reacting an alkylamine with a reducing sugar and a reducing amination reaction to form the corresponding N-alkyl-1-polyhydroxyamine and then reacting the N-alkyl-polyhydroxyamine with a fatty aliphatic ester or triglyceride in the condensation / amination process to form the amide , N-polyhydroxy fatty acid. Processes for making compositions containing polyhydroxy fatty acid amides are described, for example, in United Kingdom patent no. No. 809,060, published Feb. 18, 1959, U.S. Pat. No. 2,965,576, issued Dec. 20, 1960, U.S. Pat. No. 2,703,798, issued Aug. 8, 1955, and U.S. Pat. No. 4,198,424, issued Dec. 25, 1934, the disclosure of which is incorporated herein by reference.

In one method of making N-alkyl or N-hydroxyalkyl, N-deoxyglycityl fatty acid amides, wherein the glycityl component is derived from glucose and the N-alkyl or N-hydroxyalkyl functionality is N-methyl, N-ethyl, N-propyl, N -butyl, N-hydroxyethyl or N-hydroxypropyl, the product is obtained by reacting an N-alkyl or N-hydroxyalkyl-glucamine with a fatty ester selected from fatty methyl esters, fatty ethyl esters and fatty triglycerides in the presence of a catalyst selected from the group consisting of trilinate phosphate. trisodium phosphate, trisodium phosphate, tetrasodium pyrophosphate, pentadrasinium tripolyphosphate.

lithium hydroxide, sodium hydroxide, potassium hydroxide, calcium hydroxide, lithium carbonate.

sodium carbonate, potassium carbonate, disodium tartrate, dipotassium tartrate, sodium potassium tartrate. trisodium citrate, trisodium citrate, basic sodium silicates, basic potassium silicates, basic aluminum aluminosates and basic catalysts, and potassium aluminosates and mixtures thereof. The amount is preferably from 0.5 mol% to about 50 mol%.

more preferably from about 2.0 mol% to about 10 mol%, based on

N-alkyl- or N-hydroxyalkyl-gleamine molar base. The reaction is preferably carried out at a temperature of from about 138 ° C to about 170 ° C for typically from about 20 to about 90 minutes. When carbohydrates are used as a fatty ester source in the reaction mixture, the reaction is also preferably carried out using from about 1 to about 10 masses. % of a phase transfer agent calculated on the basis of the weight percent of the total reaction mixture selected from fatty alcohol polyethoxylates, alkyl polyglycosides, a linear glycamide surfactant and mixtures thereof.

Preferably, the process is carried out as follows. First, the fatty ester is preheated to a temperature of from about 138 ° C to about 170 ° C. N-alkyl or N-hydroxyalkyl-glucamine is then added to the heated fatty acid ester and mixed to the extent necessary to form a biphasic liquid / liquid mixture. The catalyst is then mixed into the reaction mixture and stirred for the indicated reaction time.

Also preferably, from about 2% to about 20% of the preformed apid product is added to the reaction mixture

N-alky1 / N hydroxyalky1. N-linear glucose of a 1-fatty acid, based on the weight of the reactants, as a phase transfer agent when the fatty ester is a triglyceride. This also vaccinates the reaction, thereby increasing the reaction rate. A detailed experimental procedure is given below.

The amide materials in the form of the polyhydroxy fatty acid amides used herein also provide advantages for the detergent formulator in that they can be prepared wholly or primarily from natural, renewable feedstocks and that they are degradable. They are also characterized by low aquatic life toxicity.

It will be appreciated that, together with the polyhydroxy fatty acid amides of formula (I), the processes for their production also typically produce a number of nonvolatile by-products such as esteramides and cyclic polyhydroxy fatty acid amide. The level of these by-products will vary depending on the particular reagents and process conditions. Preferably, the polyhydroxy fatty acid amide included in the detergent compositions of the invention will be used in such a form that the composition containing the polyhydroxy fatty acid amide added to the detergent comprises less than 10% and preferably less than 4% cyclic polyhydroxy fatty acid amide. acid. The preferred processes described above are advantageous in that they yield relatively low yields of by-products, including such cyclic amide-by-products.

Activating additives based on zeolite and layered silicate will now be described. The compositions may comprise an activator of zeolite or layered silicate or a mixture thereof.

The level of activating additive of zeolite and / or layered silicate may vary widely depending upon the end use of the composition and its desired physical form. The detergent compositions will contain at least about 1% of such an activating additive. Liquid formulations typically comprise from about 5% to about 50%. typically; from about 5% to about 30% by weight of the activating additive. Granular formulations typically comprise from about 10% to about 80%, more typically from about 15% to about 50%, by weight of the activating additive. However, lower or higher levels of activating ingredients are not excluded. Preferably, the weight ratio of the activating additive of zeolite or layered silicate, or a mixture thereof, to the polyhydroxy fatty acid amide is from about 1-10 to about 20-1, more preferably from about 15 to about 15 L, most preferably from about 1- 2 to about 10-1.

Zeolite builders are categories of aluminosilicate builders which have gained importance in the composition of current high performance detergents, particularly granular formulations. The zeolite builders of the composition of the invention may have a crystalline or amorphous structure and may occur naturally or may be derived synthetically. the production of zeolite materials is well known in the art. e.g. U.S. Pat. No. 4,985,669, issued Oct. 12, 1976, which is incorporated herein by reference. Preferred synthetic ion exchange zeolite materials useful in the present case are available under the designation Zeolite A, Zeolite P CB) and Zeolite X. In general, zeolite builders of the composition of the invention include those having the formula ^:

Na _z [CA102> z (S1O2 ₎ y1-xH ₂ O, wherein z and y are integers of at least 6, wherein the molar ratio of z is from 1 to about 0.5 and x is an integer from about 15 to about 264, and has a magnesium ion exchange capacity of at least 50 milligrams equivalents of CaCl2 hardness per gram of anhydrous aluminosilicate. In a particularly preferred embodiment, the crystalline aluminum ion exchange material has the formula ^:

Nai ₂ t (C 10 O 12) C 12 O ₁₂ ) x H ₂ O, wherein x is from about 20 to about 30, especially about 27. This material is known as Zeolite A.

Layer silicate based activating agents are also known in the art. See, for example, sodium silicate layered activating agents described in U.S. Pat. No. 4,664,839, issued May 12, 1987, which is incorporated herein by reference.

Preferably, the detergents for use below these temperatures are below about 50 ° C, especially below about 40 ° C, are substantially free of borate-containing activators and borate-forming activators.

borate-containing activating agents and borate-forming activating agents, compositions. % of the activating agent that the composition comprises no additives containing borates of more than about 2 or activating borates, and preferably no additives of more than about 0.5% and most preferably substantially 0%.

In addition to the polyhydroxy fatty acid amides and zeolite builder, the compositions of the invention contain one or more other surfactants, which may be anionic, cationic or nonionic. Typically, the surfactant system will include one or more anionic and / or nonionic surfactants optionally used to the polyhydroxy fatty acid amide. It is particularly preferred to include an anionic surfactant for effective overall cleaning under a wide variety of washing conditions. The advantages of the invention are particularly apparent when its compositions contain hardness-sensitive surfactants such as alkylsulfonates, alkylsulfonates (e.g., methylsulfonate.), Alkylalkoxylated sulfonates (e.g., alkyl ethoxylated sulfonates), and alkylbenzenesulfonates (e.g., linear alkylbenzenesulfonate). It is further desirable to further incorporate a conventional nonionic surfactant, such as an alkyl ethoxylate or alkyl glycoside, as described below. Typically, the amount of additional detersive surfactant present is from about 1% to about 50% by weight of the detergent composition, preferably from about 3% to about 40%, more preferably from about 5% to about 30%. Suitable surfactants will be described below.

The first group are alkyl ester sulfonate surfactants. These surfactants include linear C8-C20 carboxylic acid esters (i.e., fatty acids) that are sulfonated with SO3 gas according to The Journal of the ('

American Oil Chemists Society, 52 (1975), p. Suitable starting materials include natural fatty substances, such as those derived from tallow, palm oil, coconut oil, and the like.

Preferred alkyl ester sulfonate surfactants, especially for laundry purposes, include alkyl ester sulfonate surfactants of the structural formula ^:

R ³

CH

I

OR ⁴

SO 3 M wherein R ³ is C 8 -C 20 hydrocarbyl, preferably alkyl, or a combination thereof, R ⁴ is C 1 -C 6 hydrocarbyl, preferably alkyl, or a combination thereof, and M is a cation that forms a water-soluble salt with an alkyl ester sulfonate. Suitable sodium, potassium and lithium unsubstituted ammonium salts, and quaternary ammonium ions, and dimethylpiperidinium and cations of monoethanolamine, dietamolamine and salts include metal salts as salts and substituted or as methyl-, dimethyl-, trimethyl-, for example, tetramethyl ammonium-derived. from alkanoamines, e.g.

triethanolamine. Preferably R ^{3 is}

C 14 -C 16 alkyl and R ⁴ is methyl, ethyl or isopropyl. Particularly preferred are methyl ester sulfonates wherein R ³ is C 14 -C 16 alkyl.

The alkylsulfonate surfactants used in the compositions of the invention are water-soluble salts or acids of formula ROSO3M, wherein R is preferably a C 10 -C 24 hydrocarbyl, preferably an alkyl or hydroxyalkyl having a C 10 -C 20 alkyl component, more preferably a C 12 -C 18 alkyl or hydroxyalkyl and M is H or a cation, e.g. alkali metal cation (e.g. sodium, potassium and lithium), substituted or unsubstituted ammonium

d.

i í l í

cations such as methyl, dimethyl and trimethylammonium and dimethylpiperidinium; and cations derived from alkanolamines such as ethanolamine, diethanolamine, triethanolamine and mixtures thereof. Typically, an alkyl lower wash temperature is preferred (e.g. below 50 chain is preferred above about 50 ° C).

chain with C12-C16 for ° C) and C16-C18 and alkyl wash temperatures (e.g.

The surfactants in the form of the alkylalkoxylated t-sulfates used in the compositions of the invention are water-soluble salts or acids of the formula R0 (A) n SO3M. wherein R is an unsubstituted C 10 -C 24 alkyl or hydroxyalkyl group having a C 10 -C 24 alkyl component, preferably a C 12 -C 20 alkyl or hydroxyalkyl, more preferably a C 12 -C 16 alkyl or hydroxyalkyl, f is an ethoxy or propoxy group, m is greater than zero, typically between about 0.5 and about 6 "more preferably between about 0.5 and 3 and M is H or a cation which may 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 sulfonates are contemplated herein. Particular examples of substituted ammonium cations include methyl. dimethyl-, trimethylammonium cations and quaternary ammonium ions such as tetramethylammonium and dimethylpiperidinium and cations derived from alkanolamines, e.g. monoethanolamine, diethanolamine and triethanolamine and mixtures thereof. Exemplary surfactants are C12-C18 alkylpolyethoxylate (1,0) sulfate, C12-C18 alkylpolyethoxylate (2,25) sulfate, C12-C18 alkylpolyethoxylate (3,0) sulfate, and C12-C18 alkylpolyethoxylate (4,0) sulfate, where M is usually selected from sodium and potassium.

Other anionic surfactants useful for cleaning purposes may also be included in the detergent compositions of the invention. These may include salts (including, for example, sodium, potassium, ammonium, and substituted ammonium salts, such as iuono-, di-, and tri-ethanol amine salts), soaps, C9-C20 linear alkylbenzene sulfonates,

C 6 -C 22 primary secondary alkanesulfonates,

C8-C24 olefin sulfonates, sulfonated polycarboxylic acids of the metal citrate product prepared by sulfonating pyrolized alkaline earths, e.g. 1 082 179, alkyl glycerol sulphonates, fatty acyl glycerol sulphonates, oleyl glycerol sulphates, paraffin sulphates, alkyl phosphates, acyl taurates, fatty acid amides containing sulfonates, (e.g. acyl isethionates, acids or methylaurides, monoesters of sulfosuccinate (C12-C18 monoesters), diesteps of C12-C18 monoesters), destaters and unsaturated C6-C14 diesters)

N-acyl sarcosinates, alkylpolysaccharide sulfates such as alkylpolyglucoside sulfides (nonionic unsulfated compounds are described below), branched primary branched alkyl sulfates and alkylpolyethoxycarboxylates as compounds of Formula 16

RO (CH ₂ CH ₂ O) k CH ₂ COO-M-, wherein R is C 8 -C 22 alkyl, k is an integer from 0 to 10 and M is a cation forming the soluble salt and fatty acids esterified with isethionic acid and neutralized with sodium hydroxide.

Resin acids and hydrogenated resin acids are also suitable, such as rosin, hydrogenated colony 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 Schvartz, Perry and Berch). A number of such surfactants are also generally described in U.S. Pat. No. 3,929,678, issued Dec. 30, 1975, et al. 23, r. 58 to stí. 29, r. 23, which is incorporated herein by reference.

Suitable nonionic surfactants are generally described in U.S. Pat

1975. stí. 13, r. 14 to stí. 16

no. No. 3,929,678, issued Dec. 30.

r. 6, which is incorporated herein by reference. Exemplary but not limiting classes of suitable nonionic surfactants are listed below.

Polyethylene, polypropylene and polybutylene oxide condensates of alkylphenols. In general, polyethylene oxide condensates are preferred. These compounds include the condensation products of alkylphenols having an alkyl group containing from about 6 to carbon atoms in either a straight chain or branched configuration with an alkylene oxide. In a preferred embodiment, the ethylene oxide is present in an amount equal to from 5 to about 25 moles of ethylene oxide per mole of alkyl phenol. Commercially available nonionic surfactants of this type include Igepal ™ C0-630, supplied by GAF Corporation and Triton ™ all supplied by Rohm

X-45, X-114 X-100 and X-102 and Haas Company. These surfactants are commonly referred to as alkylphenolalkoxylate, e.g. alkyl phenol ethoxylates.

2. The condensation products of aliphatic alcohols with from about 1 to about 25 moles of ethylene oxide. The alkyl chain of the aliphatic alcohol may be either straight or branched, primary or secondary, and typically contains from about 10 to about 20 carbon atoms. Particularly preferred are the condensation products of alcohols having an alkyl group containing from about 10 to about 20 carbon atoms with from about to about 18 moles of ethylene oxide per mole of alcohol.

Examples of commercially available nonionic surfactants (a condensation product of this type include Tergitol ™ 15-S-9

C11-C15 linear secondary alcohol with 9 moles of ethylene oxide), Tergitol ™ 24-L-6 NMV (condensation product of C12-C14 primary alcohol with 6 moles of ethylene oxide with narrow molecular weight distribution), supplied by both Union Carbide Corporatin, Neodol ™ 45-9 C-condensation product of C14-C15) linear alcohol with 9 moles of ethylene oxide), Neodol ™ 23-6.5 (condensation product of C12-C13 linear alcohol with 6.5 moles of ethylene oxide), Neodol ™ 45-7 (condensation product of C14-C15) linear alcohol with 7 moles Neodol ™ 45-4 (condensation product of C14-C15 linear alcohol with 4 moles of ethylene oxide), supplied by Company and Kyro ™ EOB (condensation C13-C15 alcohol with 9 moles of ethylene oxide), supplied by Procter and Gambia Co. These surfactants are commonly referred to as alkyl ethoxylate.

3. The condensation products of ethylene oxide with a hydrophobic base, formed by the condensation of propolyene oxide with propylene glycol. The hydrophobic portion of these compounds preferably has a relative molecular weight of from about 1500 to about 1800 and exhibits water insolubility. The addition of polyoxyethylene moieties to this hydrophobic moiety tends to increase the solubility of the molecule as a whole in water and the liquid nature of the article is maintained until the polyoxyethylene content is about 50% of the total weight of the condensation product, corresponding to condensation with up to about 40 moles of ethylene oxide. Examples of compounds of this type include certain of the commercially available Pluronic ™ surfactants available from BÄSF.

4. The condensation products of ethylene oxide with the product resulting from the reaction of propylene oxide and ethylenediamine. The hydrophobic portion of these products consists of a reaction product of ethylenediamine and excess propylene oxide and generally has a relative molecular weight of from about 2500 to about 3000. This hydrophobic portion is condensed with ethylene oxide to the extent that the condensation product contains from about 40% to about 80% by weight of polyoxyethylene and has a relative molecular weight of from about 5,000 to about 11,000. Examples of this type of nonionic surfactant include certain. from commercially available Tetronic ™ compounds.

supplied by BASF-

5. Semi-polar nonionic surfactants are special categories. which include water-soluble amine oxides containing one alkyl moiety of from about 10 to about 18 carbon atoms and 2 moieties selected from the group consisting of alkyl groups and hydroxyalkyl groups of 1 to 3 carbon atoms; furthermore, water-soluble phosphine oxides containing one alkyl alkyl moiety of from about 10 to about 18 carbon atoms and 2 moieties selected from the group consisting of alkyl groups and hydroxyalkyl groups of from 1 to about 3 carbon atoms: and water-soluble sulfoxides containing one alkyl moiety having from about 10 to about 18 carbon atoms and a moiety selected from the group consisting of alkyl and hydroxyalkyl moieties with from about 1 to about 3 carbon atoms.

Semi-polar nonionic detergent surfactants include amine oxide surfactants of the formula:

I

R ³ (OR ⁴ ) x N (R ⁵ ) ₂ .

wherein R ³ is an alkyl, hydroxyalkyl or alkylphenyl group or mixtures thereof containing from about 8 to about 22 carbon atoms; R ⁴ is an alkylene or hydroxyalkylene group containing from about 2 to about 3 carbon atoms or mixtures thereof, x is from 0 to 31 and each R ⁵ is an alkyl or hydroxyalkyl group containing from about 1 to about 3 carbon atoms or a polyethylene oxide group containing from about 1 to about 3 ethylene oxide groups. The R ⁵ moieties may be attached to each other, for example via an oxygen or nitrogen atom, to form a ring structure. These amine oxide surfactants particularly include C 10 -C 16 alkyldimethylamine oxides and C 8 -C 12 alkoxyethyldihydroxyethylaminoxides.

6. The alkyl polysaccharides disclosed in U.S. Pat. No. 4,565,647, issued January 21, 1986, having a hydrophobic group containing from about 6 to about 30 carbon atoms, preferably from about 10 to about 16 carbon atoms, and a polysaccharide, e.g. polyglycoside. a hydrophilic group comprising from about 1.3 to about 10, preferably from about 1.3 to about 3, most preferably from about

1.3 to about 2.7 carbohydrate units. Any reducing saccharide containing 5 or 66 carbon atoms may be used, for example glucose, galactose, and galactosyl moieties may be substituted for the glucosyl moieties (optionally, the hydrophobic moiety is attached at 2-, 3-, 4-, etc. positions to yield glucose or galactose unlike glucoside or galactoside). For example, the intersaccharide linkages may be between one position of additional carbohydrate units and 2-,

3-, 4- and / or 6- preceding saccharide units.

Alternatively, but less desirable, there may be a polyalkylene oxide chain linking the hydrophobic moiety and the polysaccharide moiety. A preferred alkylene oxide is ethylene oxide. Typical hydrophobic groups include alkyl groups, either saturated or unsaturated, branched or unbranched, containing from about 8 to about 18, preferably from about 10 to about 16, carbon atoms. Preferably, the alkyl group is a straight chain saturated alkyl group. The alkyl group may contain up to about 3 hydroxyl groups and / or the polyalkylene oxide chain may contain up to about 10, preferably less than 5, alkylene oxide moieties. Suitable alkylpolysaccharides are octyl, nonydecyl, undecyldodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl and octadecyl, di-. tri-, tetra-, penta- and hexaglucosides, galactosides, lactosides, glucose, fructosides, fructose and / or galactose. Suitable mixtures include coconut alkyl, di-, tri-, tetra- and pentaglucosides and tallow alkyl-tetra-, penta- and hexaglucosides.

Preferred alkylpropylglycosides have the formula:

R ² O (C 11 H 2 nO) t (glycosyl) _x , wherein R ² is selected from the group consisting of alkyl, alkylphenyl, hydroxyalkyl, hydroxyalkylphenyl, and mixtures thereof, wherein the alkyl groups contain from about 10 to about 18, preferably from about 12 to about 14 carbon atoms, n is 2 or 3, preferably 2, t is from 0 to about • t '

10, preferably 0 and x is from about 1.3 to about 10, preferably from about 1.3 to about 3, and most preferably from about 1.3 to about 2.7. The glycosyl is preferably derived from glucose. To prepare these compounds, an alcohol or an alkylpolyethoxyalcohol is first formed and then reacted with glucose or a glucose source to form a glucoside (attachment at the 1- position). The additional glycosyl units can then be attached between their 1-position and their previous 2-, 3-, 4- and / or 6-glycosyl unit position, preferably the 2- position.

7. Fatty acid amide surfactants having the formula

R ⁶ --- C --- N ^(R7) ₂ wherein ^R6 is an alkyl group containing from about 7 to about 21 (preferably from about 9 to about 17) carbon atoms and each R ⁷ is selected from the group consisting of from hydrogen, C 1 -C 4 alkyl, C 1 -C ₄ hydroxyalkyl, and -CC ₂ H ₄₀ O x H, wherein x varies from about 1 to about 3. Preferred amides are C 8 -C 20 ammonium amides, monoethanolamides, diethanolamides and isopropanolamides.

Cationic surfactants may also be included in the detergent compositions of the invention. Cationic surfactants include ammonium surfactants such as alkyldimethylammonium halides, and these surfactants have the formula;

[R? (0R ³⁾ L d R ⁴ (OR ³⁾ x) ₂ R ⁵ N ⁺ X- wherein R ² is a1kýlová or alkyl benzyl group having from about to about 18 carbon atoms in the alkyl chain, each ^R3 is selected from the group consisting of -CH 2 CH 2 -. -CH2CHCCH3) -,

-CH ₂ CH (CH ₂ OH) -, -CH ₂ CH ₂ CH 2 and mixtures thereof.

wherein each R ⁴ is selected from the group consisting of benzyl, ring structures -CH 2 CHOH-CHOHCOR ⁶ CHOHCH ² OH, C 1 -C ₄ alkyl, C 1 -C 4 hydroxyalkyl, formed by linking two R ⁴ groups wherein R ⁶ is any hexose or hexose polymer having a relative molecular weight of less than about 1000 and hydrogen when y is not 0; R ⁵ is the same as R ⁵ or is an alkyl chain wherein the total number of carbon atoms R ² plus R ⁵ is not more than 18; wherein each y is from 0 to about 10 and the sum of the y values is from 0 to about 151 and X is any compatible anion.

Other cationic surfactants. useful herein are also described in U.S. Pat. No. 4,228,044, issued Oct. 14, 1980, which is incorporated herein by reference.

In addition to the above, other include ampholytic surfactants may be included in the detergent compositions herein. Active agents for these. These broader terms are described as aliphatic derivatives of secondary or tertiary amines, or aliphatic derivatives of heterocyclic and tertiary amines, in which the aliphatic radical may have a straight or branched chain. One of the aliphatic substituents contains at least 8 carbon atoms, typically from about 8 to about 18 carbon atoms, and at least one contains an anionic solubilizing group for dissolution in water, for example, a carboxyl, sulfonate or sulfate group. Examples of ampholytic surfactants are disclosed in U.S. Pat. No. 3,929,678, issued Dec. 30, 1975, pp. 19, r. 18-35, which is incorporated herein by reference.

Zwitterionic surfactants may also be included in the detergent compositions of the invention. These surfactants can be broadly described as derivatives of secondary and tertiary amines, or derivatives of quaternary ammonium, quaternary phosphonium or tertiary sulfonium compounds. Examples of zwitterionic surfactants are disclosed in U.S. Pat. No. 3,929,678, issued Dec. 30, 1975, et al. 19, r. 38 to stl. 22, r. 48, which is incorporated herein by reference.

Ampholithic surfactants and surfactant ions are generally used in combination with one or more anionic and / or nonionic surfactants.

The detergent compositions of the invention may also contain auxiliary builders, including both inorganic and organic detergent builders to assist in controlling mineral hardness. Typical amounts of the activator auxiliary are from about 5 to about 200% by weight of the zeolite / layered silicate activator.

Inorganic builders include, but are not limited to, alkali metal mixtures, ammonium salts, and alkanolammonium salts of polyphosphates (e.g., tripolyphosphates, pyrophosphates, and glassy polymeric metaphosphates), phosphonates, phytic acid, silicates, carbonates (including bicarbonates and sesquicarbonates), sulfonates and aluminosicates. Borate activating agents as well as activating agents containing borate-forming materials that can form borate under detergent storage or washing conditions (collectively referred to as borate activating agents) may also be used. Preferably, non-borate builders are used in the compositions of the invention for use at washing temperatures below about 50 ° C, in particular below about 40 ° C.

Examples of silicate builders are alkali metal silicates, especially those having a SiO 2 ^: Na 2 O ratio in the range of 1.6: 1 to 3.2 ^: 1. However, other silicates, such as magnesium silicate, may also be used as pearlescent agents. an agent in granular formulations, as a stabilizing agent for oxygen bleaches, and as a component in a foam control system.

Aluminosicates other than zeolites may also be used. In general, the aluminosicates will have the empirical formula M _of C 2 H 10 -SiC (2), where M is sodium. potassium, ammonium or substituted ammonium, z is from about 0.5 to about 2a, and y is 1, although not necessarily within the scope of the formulas set forth above in the description of zeolites.

Examples of carbonate builders are alkali metal carbonates, including sodium carbonate and sodium sesquicarbonate, and mixtures thereof, and ultrafine calcium carbonate. as described in German Pat. No. 2,321,001, published

November 15, 1973, which is incorporated herein by reference.

Phosphate and phosphonate builders may be added, although it is generally desirable to replace these builders with zeolite / layered silicate builders and optionally other builders and detergent builders. If so, they are preferably present only at low levels. Preferably, the phosphate builder comprises less than about 10%, more preferably less than about 5%, and most preferably substantially 0 percent by weight of the total builder in the composition.

Specific examples of polyphosphates are alkali metal, sodium, potassium and ammonium pyrophosphate, sodium and potassium and ammonium pyrophosphate, sodium and potassium orthophosphate, sodium polymetaphosphate, wherein the degree of polymerization ranges from about 6 to about 21 and the phytic acid salt.

Examples of phosphonate salt activating agents are the water-soluble salts of ethane-1-hydroxy-1,1-diphosphonate, especially sodium and potassium salts. water-soluble salts of methylenedisulfonic acid, for example tri-sodium and tri-potassium salts; and water-soluble salts of substituted methylenediphosphonic acids, such as ethylidene-, isopropylidene-, benzylidene-phosphonate tri-sodium or tri-potassium, and halomethylidene-phosphonates. Activating additives based on phosphonate salts of the above type are described in U.S. Pat. Nos. 3,159,581, issued Dec. 1, 1964, and 3,213,030, issued on Oct. 19, 1965, U.S. Pat. No. 3,422,021, issued Jan. 14, 1969, U.S. Pat. No. 3,400,148, issued September 3, 1968, and U.S. Pat. 14 January 1969, which is incorporated herein by reference.

Organic detergent builders suitable for the purposes of the invention include, but are not limited to, a wide variety of polycarboxylate compounds. The term polycarboxylate herein refers to compounds having multiple carboxyl groups, preferably at least 3 carboxylates.

As a rule, the polycarboxylate builder can be added to the composition in acid form, but can also be added in the form of a neutralized soluble salt. When used in the form of salts, alkali metal salts (such as sodium, potassium and lithium or alkanolammonium salts) are preferred.

A variety of useful materials are included among the polycarboxylate builders. One important category of polycarboxylate builders includes ether polycarboxylates. A number of ether polycarboxylates have been described for use as detergent builders. Examples of useful ether polycarboxylates include oxydisuccinate. as described in U.S. Pat. No. 3,128,287, issued April 6, 1964, and U.S. Pat. No. 3,635,830, issued Jan. 18, 1972, which is incorporated herein by reference.

A particular type of ether polycarboxylates useful as activating additive in the compositions of the invention also includes those having the general formula:

CH (A) (COOX) - CH (COOX) - O - CH (COOX) - CH (COOX) B wherein A is H or OH; B is H or -O-CH (COOX) -CH 2 (COOX); and X is

H or a cation forming salt. For example, if in the above formula, parts A and B are equal to H, then the compound is succinic acid and its water-soluble salts. If Part A is OH and Part B is H, then the compound is tartrate monosuccinic acid (TMS) and its water-soluble salts. If part A is Ha part

B-O-CH (COOX) -CH 2 (COOX). then the compound is tartrate-disuccinic acid (TDS) and its water-soluble salts. The compositions of these activating ingredients are particularly suitable for use in the detergent composition of the invention. Particularly suitable are mixtures of TMS and TDS in a weight ratio of TMS to TDS of from about 97 ^: 3 to about 20 = 80. These activating ingredients are described in U.S. Pat. No. 4,663,071, issued May 5, 1987.

Suitable ether polycarboxylates also include cyclic compounds, especially alicyclic compounds.

as described herein

679, 3,835 in U.S. Pat. 3 923

120 874 and 4 102 903, all of which are here

163, 4,158,635, 4 are incorporated herein by reference.

Other useful detergent builders include ether hydroxy polycarboxylates represented by the structure:

HO- [C (R) (COOM) -C (R) (COOM) -01n-H, wherein M is hydrogen or a cation forming the resulting salt in a water-soluble form, preferably a substituted ammonium cation, n (preferably n from about 2 n on average from about 2 to about different and selected from hydrogen substituted alkyl (with the exception of yet other maleic acid polycarboxylates with ethylene 5-trihydroxybenzene-2,4, and carboxymethyloxysuccinic acid Organic polycarboxylate miscellaneous alkali metals, ammonium

alkali metal, ammonium or ammonium is a from about 2 to about 15 to around 10. more convenient is a 4) and each R is identical or

C 1 -C 4 alkyl or C 1 -C 4 R is hydrogen).

include copolymers of anhydride or vinylethyl ether, 1,3,

5-trisulfonic acid.

feed additives also include and substituted ammonium salts of polyacetic acids. Examples include sodium. potassium, lithium. ammonium and substituted ammonium salts of ethylenediaminetetraacetic acid and nitriotriacetic acid.

Polycarboxylates such as mellitic acid are also suitable.

succinic acid, polymaleic acid, benzene-1,3,5-tricarboxylic acid. carboxymethyloxysuccinic acid and soluble salts thereof.

Citrates, e.g. citric acid and its soluble salts (especially sodium) are polycarboxylate builders of particular importance for high performance liquid detergent formulations, but can also be used in granular compositions.

Other carboxylate builders include the carboxylate sugars described in U.S. Pat.

3, 1973, which is incorporated herein by reference.

Also suitable in the detergent compositions of the invention are

3,3-dicarboxy-4-oxa-1,6-hexanodioates and related compounds disclosed in U.S. Pat. No. 4,566,984, issued Jan. 29, 1986, incorporated herein by reference. Suitable succinic acid activating agents include C5T-C20 alkyl succinic acids and salts thereof. A particularly preferred compound of this type is dodecenylsuccinic acid. Alkylsuccinic acids typically have the general formula

R-CH (COOH) CH2COOH), i. succinic acid derivatives wherein R is a hydrocarbon, e.g. C 10 -C 20 alkyl or alkenyl, preferably C 12 -C 16, or wherein R may be substituted with hydroxyl or sulfo-, sulfoxy- or sulfone substituents, all of which are described in the aforementioned patents.

Succinate builders are preferably used in the form of their water-soluble salts, including sodium, potassium, ammonium and alkanolammonium salts.

Specific examples of succinate builders include lauryl succinate, myristyl succinate. palmitylsuccinate.

2-dodecylsuccinate (most preferred), 2-pentadecenylsuccinate and the like. Lauryl succinates are preferred activating ingredients in this group and are described in European Patent Application 86200690.5 / 0.200.236, published Nov. 5, 1986.

Examples of useful activating ingredients also include sodium and potassium carboxymethyloxymalonate, carboxymethylsuccinate, or s-cyclohexane hexacarboxylate, or s-cyclopentane tetracarboxylate, water-soluble polyacrylates (these polyacrylates, having relative molecular weights up to about 2000, may also be used) substances) and copolymers of maleic anhydride with vinyl methyl ether or ethylene.

Other suitable polycarboxylates are the polyacetal carboxylates described in U.S. Pat. No. 4,144,226, issued Mar. 13, 1979, incorporated herein by reference. These polyacetal carboxylates can be prepared by contacting one another under the polymerization conditions of glyoxylic acid ester and

Polyacetal carboxylate ester is a stable end group for polymerization.

then connected

Resulting to chemically stabilize the polyacetal carboxylate against rapid depolymerization in an alkaline solution.

convert to the corresponding salt and add to the surfactant.

Polycarboxylate activating agents are described in U.S. Pat. No. 3,308,067, issued March 7, 1967, the disclosure of which is incorporated herein by reference. Such materials include the water-soluble salts of homo- and copolymers of aliphatic carboxylic acids such as maleic, itaconic, mesaconic, fumaric, aconitic, citraconic and methylenemalonic acids.

Other activating ingredients known in the art may also be used, for example monocarboxylic acids and soluble salts thereof having long chain hydrocarbyls. These also include referred to as soaps. Typically, the materials generally used are the chain lengths of C10-C20Hydrocarbyls may be saturated or unsaturated.

Enzymes for a variety of purposes, including protein, sugar or triglyceride based stain removal, and e.g. to prevent leakage of dye. The enzymes used may include proteases, amylases, lipases, cellulases and peroxidases, as well as mixtures thereof. They may be of any suitable origin, of plant, animal, bacterial, fungal or yeast origin. However, their choice is governed by a number of factors such as pH activity and / or optimum stability, thermal stability, stability with respect to the active detergents. activating additives, etc. In this regard, enzymes of bacterial and fungal origin, such as bacterial amylase and protease and fungal origin cellulase, are preferred.

Suitable examples of proteases are subtilisins which are obtained from particular strains of B. subtilis and B.icheniforms. Other suitable

2. The protease is obtained from a Bacilus strain having a maximum activity in the pH range of 8-12, developed and marketed by Novo Industries A / S pd. prot. no. Esperase. The preparation of this enzyme and analogous enzymes is described in British Pat. Proteolytic enzymes suitable for removing protein-based stains available on the market include those sold under the trade names ALCALASE ™ and SAVINASE ™ by Novo Industries Ä / S (Denmark) and MAXATÄSE ™ by Bio-synthetics, Inc. . (Netherlands) Of interest in the category of proteolytic enzymes especially for liquid detergent compositions, the enzymes referred to herein are Protease A and Protease B. Protease A and methods for its preparation are described in European Patent Application 130,756, published January 9, 1985, which is hereby incorporated herein by reference. we refer to this as part of the description. Protease B is a proteolytic enzyme that differs from Protease A in that it has a tyrosine-substituted leucine at position 217 in its amino acid sequence. The enzyme Protease B is described in European Patent Application no. No. 130,756, published Jan. 9, 1985, which is incorporated herein by reference.

Amylases include, for example, alpha-amylases obtained from a particular strain of B.1icheniforms, described in more detail in British Patent Specification No. 5,940,519. No. 1,296,839, to which we have already referred as part of the description. Amylolytic proteins include, for example, RAPIDASE ™ from International Bio-Synthetics, Incs. and TERMAMYL ™ from Novo Industries.

Cellulases useful in the present invention include cellulases of both bacterial and fungal origin. They preferably have an optimum pH between 5 and 9.5. Suitable cellulases are described in U.S. Pat. No. 4,435,307, issued Mar. 6, 1984, which is incorporated herein by reference, which discloses a cellulase of fungal origin made from Humicola insolens. Suitable cellulases are also disclosed in GB-A-2 075 028 and GB-A-2 095 275 and DE-OS-2 247 832.

Examples of such cellulases are cellulases produced from Humicola Insolens (Humicola grisea var. Thermoidea), in particular Humicola DSM 1800, and celluloses produced by Bacilus N or a cellulase producing fungus 212 belonging to the genus Aeromonas and cellulases extracted from hepatopancreas sea buckthorn ).

Suitable lipase enzymes for use in detergents include lipases produced by microorganisms of the Pseudomonas family, such as Pseudomonas stutzeri ATCC 19.154, described in British Pat. 1 327 034, to which reference is made here. Suitable lipases include lipases having a positive immunological reaction with a lipase antibody produced by Pseudomonas fluorescens IAM 1057. This lipase and the method for its production are described in Japanese Patent Application no. 53-20487, published 24.

This lipase is available from Amano Pharmaceutical Co.Ltd., Japan under the designation Lipase P Amano, hereinafter referred to as Amano-P. Such lipases of the invention should exhibit a positive immunologic interaction with

With an Amano-P antibody, using the standard and well known immunodiffusion procedure of

Ouc hter1ony (Acta. Med. Scan.,

133, p. 76

1950).

These lipases and a method for their immunological interaction with Amano-P are also described in U.S. Pat.

no. No. 4,707,291, issued

November 17, 1987, which is incorporated herein by reference. Typical examples of this lipase are Amano-P lipase, lipase ex Pseudomonas fragu FERM P 1339 (available under the designation Amano-B), lipase ex Pseudomonas nitroreducens var. lipolyticum FERM P 1338 (available under the designation Amano-CES), lipases ex Chromobacter viscosum, e.g.

Chromobacter viscosum var.1ipolyticum NRRLB 3673, commercially available from Toyo Jozo Co., Japan 1 and Chromobacter viscosum lipases from U. S. Biochemical Corp., USA and Disoynth Co., The Netherlands and lipases ex Pseudomonas gladiol i.

Peroxidase enzymes are used in conjunction with oxygen sources, e.g. percarbonate, perborate, persulfate, hydrogen peroxide, etc. They are used for bleaching a solution, i. to prevent transfer of dyes or pigments taken from substrates during washing operations to other substrates in the wash solution. Peroxidase enzymes are known in the art and include, for example, horseradish peroxidase, ligninase and haloperoxidase such as chloro-, and bromo-peroxidase. Peroxidase-containing detergent compositions are described, for example, in PCT International Application WO / 099813. published Oct. 19, 1989, to which we refer.

A wide variety of enzyme materials and compositions for incorporating them into synthetic detergent granules are also described in U.S. Pat. No. 3,553,139, issued Jan. 5, 1971, the disclosure of which is incorporated herein by reference. Enzymes are further described in U.S. Pat. No. 4,101,457, issued Jul. 18, 1978, and U.S. Pat. No. 4,507,219, issued Mar. 26, 1985, which is incorporated herein by reference. Enzyme materials useful for liquid detergent formulations and their incorporation into such formulations are described in U.S. Pat. No. 4,261,868, issued Apr. 14, 1981, incorporated herein by reference.

Enzymes are normally incorporated in amounts 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 composition.

For granular detergents, the enzymes are preferably coated or formulated into beads by means of additives inert to the enzymes to minimize dust formation and improve storage stability. Procedures for achieving this goal are well known in the art. Stabilization procedures for enzymes are preferably used in liquid formulations. One method of stabilizing the enzyme in aqueous solutions, for example, involves using free calcium ions from a source such as calcium acetate, the ions may be calcium formate and calcium proprionate. Calcium can be used in combination with salts of short-chain carboxylic acids, for example, formates, see e.g. U.S. Pat. No. 4,318,818, issued March 9, 1982, which is incorporated herein by reference. It has also been suggested to use polyols such as glycerol and sorbitol, alkoxy alcohols, dialkyl glycoethers, mixtures of polyhydric alcohols with polyfunctional aliphatic amines (e.g. alkanolamines such as diethanolamine, triethanolamine, di-isopropanolamine, etc.) and boronic acid or alkali metal borate. Enzyme stabilization procedures are further described and explained by way of example in the patent specification

US # No. 4,261,868, issued Apr. 14, 1981, and U.S. Pat.

No. 600,319, issued Aug. 17, 1971, both of which are incorporated herein by reference and published on Oct. 29, 1986. Preference is given to stabilizers without boric acid and borates. Enzyme stabilization systems are also exemplified by e.g. U.S. Pat. 4 261 868, no. 3 60Q and no. 3 519

The detergent compositions of the invention may contain bleaches

570th

and bleaching compositions comprising a bleach and one or more bleach activators. If present, the bleaching compounds will typically be comprised at levels of from about 1% to about%, more typically from about 1% to about 10% of the detergent composition. Generally, bleaching compounds are in non-liquid formulations, e.g. granular formulations, optional ingredients. If present, the bleach activator content will typically be from about 0.1% to about 60%. more typically from about 0.5% to about 40% of the bleaching composition.

The bleaches used in the compositions of the invention may be any bleaches suitable for detergent compositions in textile cleaning. cleaning hard surfaces or any other cleaning purposes that are now known. These include oxygen bleaches as well as other bleaches. For washing conditions below about 50 ° C, in particular below about 40 ° C, it is preferred that the compositions of the invention do not contain borates or a material that can form borate on site under detergent storage and washing conditions. Under these conditions, it is therefore preferred whether a borate-free bleach or a borate-free bleach is used. Preferably, the detergents for use at these temperatures are substantially free of borates or borate-forming materials. In this context, substantially free of borates or borate-forming materials is meant that the composition comprises no more than about 2 wt. % of any type of borate containing or forming material and preferably no more than 1%, more preferably 0%.

One category of bleach that can be used includes peroxycarboxylic acid bleaches and salts thereof. Suitable examples of this class of bleach include monoperoxyphthalate hexahydrate, magnesium salt of meta-chloroperbenzic acid, 4-nonylamino-4-oxoperoxybutyric acid and diperoxydodecadioic acid. Such bleaches are described in U.S. Pat. No. 4,483,781, issued Nov. 20, 1984; 740,446, filed Jun. 3, 1985, European Patent Application 0 133 354, published Feb. 20, 1985, and in U.S. Pat.

US # No. 4,412,934, issued Nov. 1, 1983, all of which are incorporated herein by reference. Preferred bleaches also include acid

6-nonylamino-6-oxoperoxycaproic acid as described in the patent

No. 3, U.S. Pat. No. 4,634,551, issued Jan. 6, 1987, which is incorporated herein by reference.

Another category of bleach. which may be used includes halogen bleaches. Examples of hypohalite bleaches include, for example, trichloroisocyanuric acid and sodium and potassium dichloroisocyanurates, and N-chloro- and N-bromoalkanesulfonamides. Such materials are normally added in an amount of 0.5-10 wt.

% of the finished product, preferably 1-5 wt. %.

Peroxide bleaches may also be used. Suitable peroxygen bleach compounds include sodium carbonate peroxyhydrate, sodium pyrophosphate peroxyhydrate, urea peroxyhydrate, and sodium peroxide.

The peroxygen bleaches are preferably combined with bleach activators which result in the formation of the peracid corresponding to the bleach activator directly in an aqueous solution of Ct. during the wash process).

Preferred bleach activators incorporated into the compositions of the invention have the general formula:

II

R - C - L wherein R is an alkyl group containing from about 1 to about 18 carbon atoms, the longest linear alkyl chain extending from the carbonyl carbon and comprising from about 6 to about 10 carbon atoms and L is a leaving group whose conjugated acid it has a pKa ranging from about 4 to about

These activators are described in U.S. Pat

no. 4 915

854, issued 10.

No. 4, 1990, which is incorporated herein by reference, as well as in U.S. Pat.

412 934, to which we have already referred above.

Bleaches other than oxygen bleaches are also known in the art and can be used in the present case.

T

Which is particularly interesting.

bleach.

One type of non-oxygen includes photoactivated bleaches such as sulfonated zinc and aluminum phthalocyanines. These materials can be deposited on the substrate during the wash process. Upon irradiation with light, in the presence of oxygen, such as after daylight drying, the sulfonated zinc phthalocyanine is activated and as a result the substrate is whitened. A preferred zinc phthalocyanine and photoactivated bleaching process is described in U.S. Pat. No. 4,033,718, issued Jul. 5.

1977, which is incorporated herein by reference. Typically, detergent compositions will contain from about 0.025% to about 1.25% by weight of sulfonated zinc phthalocyanine.

Any soil release agent known to those skilled in the art may be used to practice the invention. Polymeric soil release agents are characterized by having hydrophobic Other hydrophilic surface segments of hydrophobic fibers, such as polyester and nylon, and hydrophobic segments for depositing on hydrophobic fibers and to remain adhered during completion of wash or rinse cycles, so as to serve as anchorage for hydrofi Other segments. This makes it possible for stains appearing after treatment with the soil release agent to be easier to clean in later washing processes.

While it may be beneficial to use polymeric soil release agents in any of the detergent compositions discussed herein, particularly those compositions.

which are used for laundry and other applications where grease and oils need to be removed from hydrophobic surfaces, the presence of polyhydroxy fatty acid amide in detergent compositions can enhance the effectiveness of many of the more commonly used types of soil release agents. The anionic surfactants interfere with the ability of certain soil release agents to deposit on and remain on hydrophobic surfaces. These polymeric soil release agents have nonionic hydrophilic or hydrophobic segments Other segments which ⁷ are interactive with anionic surfactants.

Compositions in which it is possible to obtain enhanced efficacy of a polymeric soil release agent using a polyhydroxy fatty acid amide are those. comprising an anionic surfactant system, a soil release agent that is interacting with the anionic surfactant, and an amount of a polyhydroxy fatty acid amide (CPFA) supporting the soil release agent, wherein (I) the interaction between the soil release agent and the anion system The surfactant of the detergent composition can be illustrated by comparing the deposition level of the soil release agent (SRA) on hyphrophobic fibers (e.g., polyester) in aqueous solution between the (A) control test, which measures the deposition of SRC of the detergent composition in aqueous solution in in the absence of additional detergent ingredients, and (B) by assay

An SRA / anionic surfactant, wherein the same type and amount of anionic surfactant system used in the detergent composition is combined in aqueous solution with SRA, at the same weight ratio of SRA to the anionic surfactant system of the detergent composition, with reduced deposition in ( B) shows (A) the interaction of an anionic surfactant; and (II) whether the detergent composition contains an amount of a polyhydroxy fatty acid amide promoting soil release agent can be determined by comparing the SRA deposition of the SRA / anionic surfactant of (B) with the deposition of the soil release agent in (C) in SRA / anionic a surfactant / PFA assay wherein the same level of polyhydroxy fatty acid amide detergent composition is combined with the soil release agent and the anionic surfactant system corresponding to said SRA / anionic surfactant, wherein improved deposition of the soil release agent in the assay ( C) with respect to Test (B), indicates that an amount of polyhydroxy fatty acid amide supporting the soil release agent is present. For this purpose, the tests should be performed at anionic surfactant concentrations in aqueous solution that are above the critical micelle concentration (CMC) of the anionic surfactant and preferably above 100 parts per million. The concentration of the polymeric soil release agent should be at least 15 parts per million. A sample of polyester fabric should be used as the source of hydrophobic fibers. The same samples are immersed and mixed in aqueous solutions at 35 ° C for the respective tests for 12 minutes, then removed and analyzed. The level of deposition of the polymeric soil release agent can be determined by labeling the agent prior to treating the sample with radiation and then conducting radiochemical analysis by methods known in the art.

As an alternative to the radiochemical analytical methodology described above, the deposition of the release /

impurities determined alternatively in the above assays (i.e., A, B. and C) by determining the absorbency of the solutions with respect to CUV ultraviolet light) according to methods well known in the art. The reduced UV absorption in the test solution after removal of the hydrophobic fibrous material corresponds to the increased SRA delay. As will be appreciated by those skilled in the art, UV analysis should not be used for test solutions containing material types and levels that cause excessive UV absorption interference, such as high levels of surfactants with aromatic groups (e.g. alkylbenzene sulfonates, etc.)

Thus, the amount of soil release agent of the polyhydroxy fatty acid amide is understood to mean the amount of a surfactant that will promote the deposition of the soil release agent on the hydrophobic fibers as described above, or an amount that can improve performance. for cleaning the grease / oil for fabrics washed in a given detergent composition in a subsequent cleaning operationThe amount of polyhydroxy fatty acid amide required to promote deposition will vary with the selected anionic surfactant, the amount of anionic surfactant, the particular selected soil release agent, as well as a particular polyhydroxy fatty acid amide. Generally, the compositions will contain from about 0.01% to about 10% by weight of the polymeric soil release agent, more typically from about 0.1% to about 5% and from about 4% to about 50%, more typically from about 5% to about 30%. % anionic surfactant. Such a composition should generally comprise at least about 1%. preferably at least about 3% by weight of the polyhydroxy fatty acid amide, although the solution is limited to such a case.

Polymeric soil release agents in which the efficacy is enhanced by polyhydroxy fatty acid amide in the presence of an anionic surfactant include soil release agents having (Ca) one or more nonionic hydrophiles Other components consisting essentially of (1) degree polyoxyethylene segments polymerization at least

Or (2) oxypropylene or polyoxypropylene segments having a degree of polymerization of from 2 to 110. wherein said hydrophilic segment does not include any oxypropylene unit unless it is attached to adjacent portions at each end by ether linkages; or (3) a mixture of oxyalkylene units containing oxyethylene; 1 to about 30 oxypropyl units. said mixture comprising sufficient oxyethylene units such that the hydrophilic component has a hydrophilicity sufficiently large to increase the hydrophilicity of conventional polyester synthetic fiber surfaces when depositing a soil release agent on such a surface, said hydrophile Other segments preferably comprising at least 25% oxyethylene units and more preferably, in particular, for such components having about 20 to 30 oxypropyl units, at least about 50% oxyethyl ion units; or (b) one or more hydrophilic components comprising (1) C3 oxyalkylene terephthalate segments, where present. wherein said hydrophobic components also contain oxyethylene terephthalate, the ratio of oxyethylene terephthalate: C3 oxyalkylene terephthalate units is 2 - 1 or less. (2) C4-C6 alkylene or C4-C6 oxyalkylene segments or mixtures thereof. (3) poly (vinyl ester) segments. preferably poly (vinyl acetate) segments having a degree of polymerization of at least 2 or (4) C 1 -C 4 alkyl ether or C 4 hydroxyalkyl substituents or mixtures thereof. wherein said substituents are present in the form of C 1 -C 4 alkyl ether or C 4 hydroxyalkyl ether cellulose derivatives or mixtures thereof, and such cellulose derivatives are amphiphilic such that they have a sufficient level of C 1 -C 4 alkyl ether and / or C 4 hydroxyalkyl units to deposit on conventional polyester synthetic fiber surfaces a sufficient level of hydroxyl content once they have adhered to such a surface of conventional synthetic fibers. to increase the surface hydrophilicity of the fibers or combinations (a) and (b).

Typically, polyoxyethylene segments (a) (1) will have a degree of polymerization of from 2 to about 200. although higher levels, preferably from 3 to about 150, more preferably from 6 to about 100, can be used. Suitable C4-C6 oxyalkylene hydrophobic segments include, but are not limited to. terminating polymeric soil release agents such as M03S (CH2> nOCH2CH2O-) wherein M is sodium and n is an integer from 4 to 6 as described in U.S. Patent No. 4,721,580, incorporated herein by reference description.

Polymeric soil release agents useful in the present invention include cellulose derivatives such as hydroxyether cellulose polymers, copolymer blocks of ethylene terephthalate or propylene terephthalate with polyethylene oxide or polyethylene oxide terephthalate, and the like.

Cellulose derivatives. which are functional as soil release agents are commercially available and include cellulose hydroxyethers such as Methocel ¹¹ (Dow).

Cellulosic soil release agents for use in the invention consisting of also include those selected from the group consisting of:

C 1 -C 4 alkyl and C ⁴ hydroxyalkyl cellulose such as methylcellulose, ety1ce1u1óza, hydroxypropy1mety1ce1u1óza and hydroxybutyl methylcellulose. A number of cellulose derivatives useful as soil release agents are described in U.S. Pat. No. 4,000,093, issued Dec. 28, 1976, which is incorporated herein by reference.

The soil release agents marked with poly (vinyl ester) hydrophobic segments include graft copolymers of poly (vinyl ester), for example C 1 -C 6 vinyl esters, preferably poly (vinyl acetate) grafted on polyalkylene oxide backbones, such as polyethylene oxide backbones. Such materials are known in the art and are described in European Patent Application 0 219 048, published Apr. 22, 1987. Suitable commercially available soil release agents of this kind include Sokalan ™ type materials, e.g. Sokalan ™ HP-22, available from BASF (Germany).

One type of preferred soil release agent is a copolymer having random blocks of ethylene terephthalate and ethylene oxide (PEO) terephthalate. More specifically, the polymers are comprised of repeating units of ethylene terephthalate and PEO terephthalate in a molar ratio of ethylene terephthalate units to PEO terephthalate units of from about 2575 to about 35:65, said PEO terephthalate units comprising polyethylene oxide having relative molecular weights of from about 300 to about 2000. the molecular weight of the soil release agent is in the range of about 25,000 to about 55

000, see also U.S. Pat.

959 230 Excluded 25. 5.

1976, which is incorporated herein by reference. Similar copolymers are also described in U.S. Pat. No. 3,893,929, issued Jul. 8, 1975, which is also incorporated herein by reference.

Another preferred polymeric soil release agent is polyester repeating units having 10 to wt ethylene terephthalate units.

ethylene terephthalate units together with up to mass.

polyoxyethylene terephthalate units derived from polyoxyethylene glycol of average relative molecular weight

300

5000 and the molar ratio of ethylene terephthalate units to polyoxyethylene terephthalate units in the polymer compound is between 2: 1 and 6: 1. Examples of this polymer include commercially available Zelcon ® 5126 from Dupont and Milease ⁸ from ICI. These polymers and methods for their preparation are described in more detail in U.S. Pat. No. 4,702,857, issued Oct. 27, 1987, which is incorporated herein by reference.

Another preferred polymeric soil release agent is a sulfone product of a suitably linear ester oligomer consisting of an oligomeric ester backbone of terephthaloyl and oxyalkyleoxy repeating units and end moieties covalently attached to the backbone, said soil release agent being derived from alkyl, ethyl alcohol, ethoxylate, 2 propylenediol, wherein after sulfonation the terminal portions of each oligomer have an average of from about 1 to about 4 sulfonated groups in total. These soil release agents are described in more detail in U.S. Pat. No. 4,986,451, issued Nov. 6, 1990, which is incorporated herein by reference.

Other suitable polymeric soil release agents include 1,2-propylene terephthalate-polyoxyethylene terephthalate polyesters terminated with ethyl or methyl groups, according to U.S. Pat. No. 4,711,730, issued Dec. 8, 1987, anionically terminated oligomeric esters of U.S. Pat. No. 4,721,580, issued Jan. 26, 1988, wherein the anionic ends are sulfo-polyethoxy groups derived from polyethylene glycol (PEG) block polyester oligomer compounds of U.S. Pat. No. 4,702,857, issued Oct. 27, 1987, having a polyethoxy terminus of X-COCH2 CH2 n - wherein n is from about 12 to about 43 and X is C1-C8 alkyl or preferably methyl, all of which are incorporated herein by reference. as part of the description.

Other polymeric soil release agents include the soil release agents of U.S. Pat. No. 4,877,896, issued Oct. 31, 1989, which discloses anionically terminated terephthalate esters, especially sulfoaroyl esters, the disclosure of which is incorporated herein by reference. Terephthalate esters contain unsymmetrically substituted oxy-1,2-alkyleneoxy units. Among the soil release agents of U.S. Pat. No. 4,877,896 includes materials with polyoxyethylene hydrophilic components or C3 oxyalkylene terephthalate (propylene terephthalate) repeating units in the range of hydrophobic components of (b) (1) above. They are soil release agents characterized by either or both of the above criteria, which particularly benefit from the addition of polyhydroxy fatty acid amides in the presence of anionic surfactants to the compositions of the invention.

If used, soil release agents will generally comprise from about 0.01% to about 10.0% by weight of the detergent compositions, typically from about 0.1% to about 5%. about 3.0%.

The detergent compositions of the invention may also optionally contain one or more ferrous or manganese chelating agents as a supplement to the activating additive. Such chelating agents may be selected from the group consisting of aminocarboxylates, aminophosphonates, polyfunctionally substituted aromatic chelating agents, and mixtures thereof, as all defined below. Without wishing to be bound by theory, it is believed that the utility of these materials derives in part from their extraordinary ability to remove iron and manganese ions from washing solutions by forming soluble hehelates.

Aminocarboxylates suitable as optional chelating agents in the compositions of the invention may have one or more, preferably at least two, substructure units

CH ₂ (CH ₂ ) x -COOM, wherein M is hydrogen, an alkali metal, ammonium or substituted ammonium (e.g., ethanolamine) and x is from about 3, preferably 1.

Preferably, these amino carboxylates do not contain alkyl or alkenyl groups having more than about carbon atoms. Useful amino carboxylates include ethylenediaminetetraacetates,

N-hydroxyethylethylenediamine triacetates, nitrile triacetates, ethylenediamine aminotetrapropionates, diethylenetriaminepentaacetates triethylenetetraamine hexaacetates, ethanodiglycines, their alkali metal salts, ammonium salts and substituted ammonium salts thereof.

Aminophosphates are also suitable for use as chelating agents in the compositions of the invention when at least low levels of total phosphorus are allowed in the detergent compositions. Compounds with one or more, preferably at least two, units of the substrate are suitable.

CH ₂

N - (CH ₂ ) _X - PO ₃ M ₂ , wherein M is hydrogen, alkali metal, ammonium or substituted ammonium and x is from 1 to about 3, preferably 1, including ethylenediaminetetrakis (methylene phosphonates), nitrilotris (methylenephosphonates) and diethylenetri triisamine (methylenephosphonates). Preferably, these aminophosphonates do not contain alkyl or alkenyl groups having more than about 6 carbon atoms. Alkylene groups can be shared by substructures.

Polyfunctionally substituted aromatic chelating agents are also useful in the compositions of the invention. These materials may include compounds having the general formula

OH

R wherein at least one R is -SO 3 H or -COOH or soluble salts and mixtures thereof. U.S. Pat. No. 3,812,044, issued May 21, 1974, which is incorporated herein by reference, discloses polyfunctionally substituted aromatic chelating agents and shading agents. Preferred compounds of this type in acid form are dihydroxysulfobenzenes such as 1,2-dihydroxy-3,5-disulfobenzene. The alkaline detergent compositions may comprise these materials in the form of an alkali metal salt, ammonium or substituted ammonium (e.g., mono- or triethanolamine salts).

If used, the chelating agents will generally comprise from about 0.1% to about 10% by weight. % of detergent compositions.

More preferably, the chelating agents will contain from about 0.1% to about 3.0% by weight of such compounds.

Compositions of the invention may also optionally contain water-soluble ethoxylated amines having clay removal properties and anti-deposition properties. Granular detergent compositions containing these compounds typically contain from about 0.01% to about 10.0% by weight in water. soluble, ethoxylated amines. Liquid detergent compositions will typically contain from about 0.01% to about 5%. These compounds are selected from the group consisting of:

(1) ethoxylated monoamines having the formula:

(XL) -N- (R ² ) ₂ (2) ethoxylated diamines having the formula:

R ² N-R 1 NR ² (R ²⁾ 2 NR ¹ N (R ²⁾ ₂

I

L L L

II XXX or (XL-) 2-NR ¹ -N- (R ² ) 2 (3) ethoxylated polyamines having the formula:

R ³ - [( ^{2 2} ) g- (R ⁴ ) tNL.XJ _P (4) ethoxylated amine polymers having the general formula:

R ² [(R ² ) 2 -N] n (R ¹ -N) x (R ¹ -NjyCR ¹ -NLX) _z

I

L

I x

and

(5) mixtures thereof, wherein A ¹ is 0 I 0 I 0 I 0 I 0 I • 1 -NC-. I 1 -NC0-. I 1 -NCN-. I | 1 -CN-, | 1 -OCN-. I • 1 R 1 R 1 1 R R 1 R 1 R

0 I 0 I 0 I 1 -WHAT- 1 -OCO- 1 -OC

-CNC or -O-;

R is H or C 1 -C 4 alkyl or hydroxyalkyl; R ¹ is

A C 2 -C 12 alkylene, hydroxyalkylene, alkenylene, arylene or alkarylene or a C 2 -C 12 oxyalkylene moiety having from 2 to about 20 oxyalkylene units, provided that no O-N bonds are formed; each R ² is C 1 -C 4 or hydroxyalkyl, -LX, or two R ² together with the -CCH 2 R ¹ group. -A ^2- (CH 2) s wherein A ² is -O- or -CH 2 -, r is 1 or 2, s is 1 or 2, and r + s is 3 or 4; X is a nonionic group, an anionic group or mixtures thereof R ³ is a substituted C 3 -C 12 alkyl, hydroxyalkyl, alkenyl, aryl or alkaryl group having substitution positions; R ⁴ is a C 1 -C 12 alkylene, hydroxyalkylene, alkenyl, rylene or alkarylene or a C 2 -C 3 oxyalkylenyl moiety having from 2 to 20 oxyalkylene units, provided that no O-O or O-N bonds are formed; L is a hydrophilic chain which contains the polyoxyalkylene moiety - ^[(R5 0) m (CH2CH20) nJ -, wherein R ⁵ is C 3 -C 4 alkylene or hydroxyalkylene Aman are numbers such that the part -CCH2CH20) n- comprises at least about 50 wt . % of said polyoxyalkylene moiety; for said monoamines, m is from 0 to about 4, n is at least about 12; for said diamines, m is from 0 to about 3 and n is at least about 6 when R ¹ is hydroxyalkylene or alkenylene and at least about 3,

C ₂ -C ₂ alkylene when R ¹ is other than C ₂ -C 3 alkylene. hydroxyalkylene or alkenylene; for said polyamine and amine polymers, m is from about to and n is at least 3; p is from 3 to 8, q is or 0, provided that t is 1. when q is 1; v is 1 or 0;

is at least 2;

and y + z is at least 2. The most preferred agent for releasing impurities and preventing their re-deposition is ethoxylated as described in tetraethylenepentamine. Exemplary amines are further disclosed in U.S. Pat. No. 4,579,898, issued Jul. 1.

1986, which is incorporated herein by reference. Another group of preferred agents for the removal of clay impurities and to prevent their re-deposition are the cationic compounds described in European Patent Application no. No. 111,965, published Jun. 27, 1984, which is incorporated herein by reference. Other agents for removing clay impurities and preventing re-deposition include the ethoxylated amine polymers described in European patent application no. 111 984, published Jun. 27, 1984, zwitterionic polymers, described in European Patent Application Ser. 112,592 published Jul. 4, 1984; and amine oxides disclosed in U.S. Pat. No. 4,548,744, issued Oct. 22, 1985, all of which are incorporated herein by reference.

Other agents may also be used in the compositions of the invention to remove clay impurities and prevent their re-deposition. Another type of preferred agent of this type includes carboxymethylcellulose (CMC) materials. These materials are well known in the art.

Polymeric dispersing agents may advantageously be used in the compositions of the invention. These materials can assist in controlling calcium and magnesium hardness. Suitable polymeric dispersing agents include polymeric polycarboxylates and polyethylene glycols, although other materials known in the art may also be used. Without wishing to be bound by the theory, it is believed that polymeric dispersants promote the overall performance of the detergent activator. when used in combination with other activating additives (including lower relative molecular weight polycarboxylates), inhibiting crystal growth, peptizing particulate impurities, and preventing re-deposition.

Polymeric dispersing agents are generally used in amounts of from about 0.5% to about 5% by weight of the detergent composition, more usually from about 1.0% to about 2.0%.

Polycarboxylate materials that can be used as the polymer dispersant in the compositions of the invention are those polymers or polymers that contain at least about 60 wt. % of general formula segments:

FROM

I

C --- I

COOM n

wherein X, Y and Z are each selected from the group consisting of hydrogen, methyl, carboxy, carboxymethyl, hydroxy and hydroxymethyl, a salt-forming cation and is from about 30 to about 400. Preferably X is hydrogen or hydroxy, Y is hydrogen or carboxyl, Z is hydrogen and M is hydrogen, alkali metal, ammonium or substituted ammonium.

Polymeric polycarboxylate materials of this type can be prepared by polymerizing or polymerizing suitable unsaturated monomers, preferably in their acid form. Unsaturated monomeric acids that can be polymerized to form suitable polymeric polycarboxylates include acrylic acid, malic acid (or maleic anhydride), fumaric acid, itaconic acid, aconitic acid, mesaconic acid, citraconic acid, and methylene ammonium acid.

The presence of polymeric segments containing no carboxyl radicals, such as vymethylether, sylene, ethylene, etc., in the polymeric polycarboxylates used herein is suitable provided that such segments do not constitute more than about 40 wt. %.

Particularly suitable polymeric polycarboxylates may be derived from acrylic acid. Such acrylic acid-based polymers useful in the compositions of the invention are the water-soluble salts of polymerized acrylic acid. The average relative molecular weight of such polymers in acid form is preferably in the range of from about 2000 to 10,000, more preferably from about 4000 to 7000, and most preferably from about 4000 to about 5000. Water-soluble salts of such acrylic acid polymers may include, for example, alkali metal salts. , ammonium and substituted ammonium salts. Soluble polymers of this type are known materials. The use of polycarboxylates of this type in detergent compositions is described, for example, in U.S. Pat. No. 3,308,067, issued March 7, 1967, the disclosure of which is incorporated herein by reference.

Copolymers based on acrylic acid and maleic acid may also be used as a preferred component of the dispersing agent and the anticorrosive agent. Such materials include the water-soluble salts of copolymers of acrylic acid and maleic acid. The average molecular weight of such copolymers in acid form is preferably from about 2000 to about 100,000, preferably from about 5000 to 75,000, most preferably from about 7,000 to about 65,000. The ratio of acrylate segments to maleic segments in the copolymers is up to about 1 will generally range from about 30

First

more preferably from about 10 to 10

Water-soluble salts of such acrylic and maleic copolymers may include, for example, alkali metal salts, ammonium substituted ammonium salts.

Soluble acrylate maleate copolymers of this type are known materials as described

European patent application no. 66915, published

115. 12.

1982, which is incorporated herein by reference.

Another polymeric material that may be included is polyethylene glycol (PEG). PEG may be characterized by the effective properties of a dispersing agent, as well as acting as an agent for removing clayey impurities and preventing re-deposition. Typical molecular weight ranges for these purposes range from about 500 to about 100,000, preferably from about 1000 to about 50,000, and most preferably from about 1,500 to about 10,000.

Furthermore, any brightener in the art can be incorporated into the detergent composition of the invention.

The choice of the brightener composition will depend on the detergent, the nature of the other compositions, the temperature of the water scrubbing components, or the bleaching agents known for use in a variety of detergent factors such as the type present in the detergent mixing stage and the ratio of scoured material to tank size.

The choice of brightener will also depend on the type of material to be cleaned, for example, whether it is cotton, synthetic fabrics, etc. Since most detergent products are used to clean a variety of fabrics, the detergent compositions should contain a blend of brighteners that will be effective for various fabrics. It is of course necessary that the individual components of such a brightener mixture be compatible with each other.

The commercially available optical brighteners which can be used according to the invention can be classified into two subgroups, including, but not limited to, stilbene derivatives, pyrozoline. coumarin, carboxylic acid, methinyanines, dibenzotifene-5,5-dioxide, azoles, 5- and 6-membered ring heterocycles and other miscellaneous reagents. Examples of such brighteners are described in M. Zahradnik's The Production and Application of Fluorescent Brightening Agents, published by Johl Viley &amp; Sons, New York, 1983, which is incorporated herein by reference.

Stilbene derivatives that can be used in the present invention include, but are not limited to, bis (triazinyl) amino-stilbene derivatives; bisacylamine derivatives of stilbene; stilbene triazole derivatives, stilbene oxadiazole derivatives; oxazole derivatives of stilbene; and styryl derivatives of stilbene.

Some bis (triazinyl1) aminostylbene derivatives that can be used in the present invention can be prepared from 4,4'-diamine-stilbene-2,2'-disulfonic acid.

Coumarin derivatives that may be used in the present invention include, but are not limited to, derivatives substituted in the third position, in the seventh position, and in the third position.

Carboxylic acid derivatives which may be used in the present invention include, but are not limited to, filmaric acid derivatives, benzoic acid derivatives, p-phenyl-bis-acrylic acid derivatives, naphthalenecarboxylic acid derivatives, heterocyclic acid derivatives and cinnamic acid derivatives.

Cinnamic acid derivatives which can be used in the present invention can be further classified into groups which include, but are not limited to, cinnamic acid derivatives, styrazoles, styrylbenzofurans, styryloxadiazoles, styryltriazoles and styryl polyphenyls, as described on p. . 77 of the cited publication by Zahradnik.

The styryzoles can be further classified into styrylbenzoxazoles, styrylimidazoles and styrylthiazoles as described on page 14. 78 cited publication by Zahradnik. It will be appreciated that the three subclasses do not necessarily provide an exhaustive list of subgroups to which the styrylazoles can be screened for a class of optical brighteners that may be useful in the present invention are the dibenzothiophene-5,5-disoxide derivatives described on p. 741-749 Encyclopedia The Kirk Othmer Encyclopedia of Chemical Technology, Vol. 3, p. 737-750, J. Viley and Son Inc., 1962, incorporated herein by reference, and include 3,7-diaminodibenzothiophene-2,8-disulfonic acid-5,5-dioxide.

Another class of optical brighteners that can be used in the present invention includes azoles that are derivatives

5-membered ring heterocycles. These may be further subdivided into monoazoles and bisazoles. Examples of monoazoles and bisazoles are given in the encyclopedia cited above.

Another class of brighteners that can be used in the present invention are derivatives of the 6-membered ring heterocycles described in the cited encyclopaedia. Examples of such compounds include brighteners derived from 4-aminonaphthalamide.

In addition to the disclosed brightening agents, various other agents may also be used as the brightening agents. Examples of such different agents are described on p. 93-95 of Zahradnik's cited publication and include 1-hydroxy-3,6,8-pyrenetri-sulfonic acid;

2,4-dimethoxy-11,3,5-triazin-6-yl-pyrene; acid

4,5-diphenylimidazolone disulfone and pyrazoline-quinoline derivatives.

Other specific examples of optical brighteners that can be used in the present invention are those disclosed in U.S. Pat. No. 4,790,856, issued Dec. 13, 1988, which is incorporated herein by reference. These brighteners include the Phorwite ™ brightener family of Verona. Other brighteners described in this literature include: Tinopal UNPA, Tinopal CBS and Tinopal 5BM, available from Ciba-Geigy; Artic Vhite CC and Artic Vhite CVD, available from Hi1ton-Davis, based in Italy; 2- (4-styry1-feny1) -2H- naphthol [1,2-d] triazoles; 4,4'-bis- (1,2,3-triazol-2-y1) -stil- benes;

4,4 bisCstyryljbisfenyly; and γ-aminocoumarins. Particular examples of such brighteners include 4-methyl-7-dimethylaminoamocoumarin;

1,2-bis (benzimidazol-2-y1) -ethylene; 1,3-diphenylphrazolines;

2,5-bis (benzoxazol-2-y1) -thiophene; 2-styry1-naphth [1,2-d] oxazole; and 2- (stilben-4-yl) -2H-naphtho- [1,2-d] triazole-

Other optical brighteners that can be used in the present invention include those disclosed in U.S. Pat. No. 3,664,015, issued Feb. 29, 1972, which is incorporated herein by reference.

Compounds of the invention may further include compounds known or which have become known for reducinginfinine and / or suppressing foam formation. First of all, hereinafter referred to as suds suppressors, surfactants may be desirable because they are based on an acid amide according to the detergent composition compositions.

importantly, when the detergent foaming surfactant of the polyhydroxy fatty acid invention may enhance foam stability The foam suppression may be particularly the composition comprising a relatively high agent in combination with a polyhydroxy fatty acid amide surfactant. Such suppression is particularly desirable for use in automatic washing machines with front compositions to be filled. These scrubbers are in typical and washing water, eventually characterized by having a horizontal by axis axis. This type of blending can have and consequently reduced cleaning foaming can also be particularly important to have a laundry drum and which revolves around this consequence of high foam formation effect. The use of suppressors in hot water conditions and at high surface concentrations

As suds suppressors in active agent compositions.

according to the invention, a wide variety of materials can be used as suds suppressors. Foam supersors are well known to those skilled in the art. They are generally described, for example, in the Kirk Othemer Encyclopedia (Kirk Othmer Encyclopedia of Chemical Technology, Third Edition, vol. 7, pp. 430-447, J. Viley and Dons Inc., 1979). One category of particularly interesting suds suppressor includes monocarboxylic fatty acids and soluble salts thereof. These materials are described in U.S. Pat. No. 2,954,347, issued Sep. 27, 1960 to Vayne. John, referred to herein as part of the description. The monocarboxylic fatty acids and their salts, for use as a suds suppressor, typically have hydrocarbyl chains of 10 to about 24 carbon atoms. Suitable salts include alkali metal salts such as sodium, potassium and lithium salts and ammonium and alkanolammonium salts. These materials are preferred categories of suds supersor for detergent compositions.

The detergent compositions may also contain suds suppressors which are not surfactants. These include, for example: high molecular weight hydrocarbons such as paraffin, fatty acid esters (e.g., triglycerides of fatty acids), fatty acid esters of monovalent alcohols, aliphatic C 1 -C 4 ketones (e.g., stearone), etc. Other suds inhibitors include N-alkylated aminotriazine such as tri- to hexa-alkylmellamines or di- to tetra-alkyldiamine-chlorotriazines formed as products of two or three moles of a primary or secondary amine containing 1 to 24 carbon atoms, propylene oxide and monostearyl phosphate is monostearyl alcohol phosphate ester and monostearyl diphosphates and alkali metal phosphate esters (e.g. sodium, potassium and lithium). Hydrocarbons such as paraffin and halogen paraffin can be used in liquid form. Liquid hydrocarbons will be liquid at room temperature and atmospheric pressure and will have a pour point in the range of about -40 ° C to about. 5 ° C and minimum boiling point not less than 110 ° C at atmospheric pressure. It is also known to use waxy hydrocarbons preferably having a melting point below about 100 ° C. Hydrocarbons constitute a preferred category of suds suppressors for detergent compositions. Hydrocarbon suds suppressors are described, for example, in U.S. Pat. 4,265,779, issued

5 May 1981, which is incorporated herein by reference. Thus, hydrocarbons include aliphatic, alicyclic, aromatic and heterocyclic saturated or unsaturated hydrocarbons having from about 12 to about 70 carbon atoms. The term paraffin used in this explanation of suds suppressors is meant to include mixtures of true paraffins and cyclic hydrocarbons.

Another preferred category of non-surfactant suds suppressors includes silicone suds suppressors. This category includes the use of polyorganosiloxane oils such as polydimethyldiloxane, a dispersion or emulsion of polyorganosiloxane oils or resins, and a combination of polyorganosiloxane with silica particles, wherein the polyorganosiloxane is chemisorbed or fused to silica. Icon suds suppressor strengths are well known in the art and are described, for example, in U.S. Pat. No. 4,265,779, issued May 5, 1981, and European Patent Application Ser. No. 89307851.9, published Feb. 7, 1990, which is incorporated herein by reference.

Other si iconic suppressors of foaming are described in U.S. Pat. No. 3,455,839, which relates to compositions and methods for defoaming aqueous solutions by adding small amounts of polydimethylsiloxane fluids.

Mixtures of silicon icon and silane silicon forces are described, for example, in German patent application DOS 2

124 526.

Si1 icon defoamers and suds control agents in granular detergent compositions are described in U.S. Pat. No. 3,933,672 and U.S. Pat. No. 4,652,392, issued Mar. 24, 1987.

An exemplary si icon-based suds suppressor for use in the compositions of the invention is an amount of suds suppressor, comprising a suds suppressor consisting essentially of:

(1) a polydimethylsiloxane fluid having a viscosity of from about 20 en. to about 1500 cs. at 25 ° C;

) 2) from about 5 to about 50 parts per 100 parts by weight of (1) a siloxane resin composed of (CH3) 3 Si0i / 2 units of S1O2 units of ratio (CH3) 3 Si0i / 2 to S1O2 units of from about 0.6: 1 to about 1.2: 1; and (3) from about 1 to about 20 parts per 100 parts by weight of (1) solid silica gel.

For any detergent compositions for use in automatic washing machines, the foam should not be formed to the extent that it will flow through the scrubber. The suds suppressors, when used, are preferably present in a suds suppressing amount. By "suds suppressor" is meant that the formulator of the composition can select the amount of this agent to control? The amount of suds control agent will vary according to the detergent surfactants selected. For example, with more suds surfactants, relatively more control agent is used; foaming to achieve the desired foaming control than less foaming surfactants. In general, sufficient suds suppressor should be incorporated into the low-foaming detergent compositions so that the foam formed during the washing cycle of the automatic washing machine (ie by mixing the detergent in aqueous solution at the intended wash temperature and concentration) does not exceed about 75% of the drum empty volume. determines the difference between the total volume of the drum and the water plus the laundry.

Typically, the compositions of the invention will contain from 0% d to about 5% suds suppressor, the monocarboxylic fatty acids and salts thereof will typically be present in amounts up to about 5% by weight of the detergent composition. Preferably, from about 0.5% to about 3% of a fatty carboxylate suds suppressor is used. The Si icon suds 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 of a practical nature since it is to keep costs as low as possible and the effectiveness of smaller amounts for effective foaming control. Preferably, from about 0.01% to about 1% of the 1 icon suds suppressor is used, more preferably from about 0, 25% to about 0.5%. In this context, the percentages given include all silica. which can be used in combination with polyorganosiloxanes as well as other additive materials. which can be used. Monostearyl phosphates are generally used at levels of from about 0.1% to about 2% by weight of the composition.

Hydrocarbon suds suppressors are typically used in amounts of from about 0.01% to about 5.0, although higher amounts may be used.

Finally, a number of other ingredients may be included in the compositions of the invention, including other active ingredients, carriers, hydrotopes, processing aids, dyes and pigments, solvents for liquid formulations, and the like.

Liquid detergent compositions may contain water and other solvents as carriers. Primary or secondary low molecular weight alcohols such as methanol, ethanol, propanol and isopropanol are suitable. Monohydroxy alcohols are preferred for solubilizing the surfactant, but polyols such as those containing from 2 to about 6 carbon atoms and from 2 to about 6 hydroxyl groups (e.g., propylene glycol, ethylene glycol, glycerin, and 1,2-propanediol) may also be used.

The detergent compositions of the invention will preferably be formulated such that during use in aqueous cleaning processes the wash water will have a pH between about 6.5 and about 11, preferably between about 7.5 and about 10.5. Liquid product formulations preferably have a pH between about 7.5 and about 9.5, more preferably between about 7.5 and about 9.0. Procedures for controlling pH at recommended levels of use include buffering agents, alkalis, acids, etc., which are well known to those skilled in the art.

The invention further relates to a process for improving the performance of detergents comprising anionic, nonionic and / or cationic surfactants and an activating additive of zeolite or layered silicate or a mixture thereof, by incorporating the above amide surfactant based on such a composition polyhydroxy fatty acid amide such that the weight ratio of zeolite and / or layered silicate to polyhydroxy fatty acid amide surfactant is from about 1-10 to about 20: 1.

r

The invention further relates to a method of cleaning substrates such as fibers, textiles, hard surfaces, leather, etc. by contacting said substrate with a detergent composition comprising one or more anionic, nonionic or cationic surfactants, an activator of zeolite or layered silicate, or a mixture thereof, and said polyhydroxy fatty acid amide, wherein the weight ratio of said activator to the activator; said polyhydroxy fatty acid amide surfactant is from about 1-10 to about 20: 1, in the presence of a solvent such as water or a water-miscible solvent (e.g., primary or secondary alcohols). Stirring is preferably carried out to facilitate cleaning. Suitable mixing means include mixing hands or cleaning agents such as brushes, fabrics, sponges. rags, etc., automatic dishwashers, automatic washing machines for cleaning textiles (eg clothing), etc.

In the above methods, the preferred weight ratio of the activating additive of zeolite and / or layered silicate to polyhydroxy fatty acid amide is from about 15 to about 15: 1, most preferably from about 1 = 3 to about 10 = 1.

DETAILED DESCRIPTION OF THE INVENTION

Examples 1-12

This experiment provides an example of a production method

N-methyl-1,1,1-deoxyglucityl-lauramide surfactant for use in the invention. Although a skilled chemist can vary the configuration of the device, one suitable device for the application comprises a three-liter four-necked flask equipped with a motor-driven paddle stirrer and an environment-long thermometer. The other two necks sufficient for contact with the reaction flasks are provided with a nitrogen inlet arm (note: a wide-pass and wide-sided side arm is important in the case of a very rapid nitrogen leak) to which an efficient collector condenser and vacuum outlet are connected. This is connected to the nitrogen and vacuum escape evacuation and then to the hood and trap.

The 500-watt heating jacket with a variable temperature control unit ('Variac') used to heat the reaction is placed on the laboratory vise so that it can be easily lifted to further control the reaction temperature.

N-methylglucamine (195 g, 1.0 mol, Aldrich,

M4700-0) methyl laurate (Procter & Gambia CE 1270, 220.9 g.

1.0 mol) was placed in a flask. The mixture of solid and liquid is heated under stirring under a stream of nitrogen to form a melt (approximately 25 minutes). When the melt temperature reaches 145 ° C, catalyst (anhydrous powdered sodium carbonate, 10.5 g, 0.1 mol, J. T. Baker) is added. The nitrogen inlet is closed and the aspirator and the nitrogen leakage are aligned to create a vacuum of 16.65 kPa. From this point, the reaction temperature is maintained at 150 ° C by aligning the Variac and / or raising or lowering the jacket.

Within 7 minutes, the first bubbles of methanol are visible on the meniscus of the reaction mixture. This is followed by an intense reaction. Methanol is distilled until its flow rate drops. The vacuum is adjusted to a vacuum of 33.33 kPa. This vacuum is increased approximately as follows Cv kPa in minutes) - 33.33 kPa in 3 min, 66.66 kPa in 7 min, 83.31 kPa in 10 min. ΖΆ 11 minutes from the start of the methanol evolution, heating and stirring are discontinued while some foaming occurs. The product is cooled and solidified.

The following examples are intended to illustrate exemplary compositions of the invention, but are not intended to limit or otherwise define the scope of the invention as defined by the claims.

These examples show high performance granular detergent compositions comprising polyhydroxy fatty acid amide and zeolite and / or layered silicate builders.

Basic granules 1 2 3 4 C 10 -C 18 alkyl sulfate 16.9 10.1 11.5 C14-C15 alkylethoxy (2, 25) sulfate 5.6 C12-C18 alkyl sulfate 16.9 Linear C12 alkylbenzenesulfonate 10.1 N-methyl, Ν-1-deoxyglucityl- coconut fat amide 5.6 2.4 5.6 5.6 Zeolite A 30.1 18.8 18.8 30.1 sodium citrate 6.3 6.3 sodium carbonate 16.9 21.9 21.9 16.9 sodium silicate 5.6 5.6 5.6 5.6 sodium sulfate 15.0 15.0 15.1 15.1 sodium polyacrylate C4500 mhm 1.1 1.1 1.1 1.1 polyethylene glycol (800 mhm) 1.1 1.1 1.1 1.1 tallow fatty acid 1.1 1.1 1.1 1.1

brightener 0.2 0.2 0.2 0.2 Admixture and spraying 1 2 3 4 protease ($ 1.4 enzyme activ.) 0,9 - 0.9 0.0 0.9 perfume 0.3 0.3 · 0.3 0.3 C12-C13 alkyl ethoxylate (6.5 mole) 1.1 1.1 1.1 1.1 Water 3.8 3.8 3.8 3.8 Pretty 100.0 100.0 100.0 100.0

Examples 1-4 are formulations for preferred use of about 1400 parts per million by weight of wash water for temperatures below about 50 ° C. The above examples are realized by combining the basic granular components as a suspension and spray-drying them to about 4-8% residual moisture. The remaining dry ingredients are mixed in granular or powder form with spray-dried granules in a rotary mixer and liquid additives (Cionic surfactant and spray).

Basic granules 5 6 7 Linear C12 alkylbenzenesulfonate 8.6 C14-C15 alkyl sulfate 12.6 C16-C18 fatty acid 2.2 2.2 zeolite 7.0 7.0 20.4 polyacrylate (4500 mhm) 3.3 3.3 3.5 polyethylene glycol (8000 mhm) 1.3 1.3 1.5 sodium carbonate 10.7 10.7 sodium sulfate 5.0 5.0 5.0 sodium silicate 5.0 5.0 3.0 Differently 7.1 • 7.1 7.9

admixture 5 6 7 zeolite 5.0 5.0 5.0 N-methyl, 1-Ν-deoxyglucityl- coconut fat amide 6.4 6.4 3.2 C16-C18 methyl ester sulfate 19.1 C12-C18 alkyl sulfate 19, 1 various (bleach, activ .. salts, filler salts, etc. '. ) 17.2 17.2 20.4 spray C12-C13 Alkyloxyethoxylate (6.5 mol) 2.0 2.0 2.0 perfume 0.5 0.5 0.5 water and various 8.2 8.3 6.4 Ce1kom 100.0 100.0 100.0

The compositions of Example 5-7 represent summarized formulations prepared by suspending the basic granular ingredients and spray-drying to about 5% moisture and admixing additional granular or powdered dry ingredients. The powder is de-dusted by spraying with liquid additives. The product is intended for use at a concentration of about 1050 parts per million at a washing temperature of less than about 50 ° C.

Basic qranules 8 9 10 11 Linear C12 alkylbenzene- sulfonate 6.8 C14-C15 alkyl sulfate 4.6 7.6 7.6 C12-C18 alkyl sulfate 2.4 2.4 2.4 2.2 C16-C18 alkyloxyethoxylate (11 moles) 1.1 1.1 1.1 zeolite 22.0 24.7 21.3 13.0 acrylate / maleate copolymer (60000 mhm) 4.3 5.6 4.3 polyacrylate (4500 mhm) 5.0 water faculties. ingredients 9.4 9.2 10.1 10.2 admixture N-methyl, 1-Ν-deoxyglucity1- coconut fat amide 7.0 4.0 N-methyl, 1-Ν-deoxyglucityl- tallow fatty acid amide 4.0 6.0 sodium citrate 8.0 sodium carbonate 17.5 3.17 17.5 17.0 sodium silicate 3.5 3.0 3.5 3.0 layered silicate 11.0 - bleaching agents salts, etc.) 27.3 24.1 19.4 24.8

spray

perfume 0.4 0.4 0.4 0.5 power icon liquid 0.5 0.5 0.5 0.5 Pretty 100.0 100.0 100.0 100.0 Example compositions 8 to 10 are p preferably used in

concentrations of about 6,000 parts per million by weight of wash water at temperatures from about 30 ° C to 95 ° C. These compositions are made by suspending the basic granular ingredients and spray drying to about 9 moisture. The remaining dry ingredients are added and mixed in a rotary mixing drum followed by spraying the addition of the final liquid ingredients.

Basic granules 12 13 14 Linear C12 alkylbenzene- 5.0 5.9 sulfonate N-methyl, 1-Ν-deoxyglucity1- lauramide 5.9 C14-C15 alkyl sulfate 5.9 C 12 -C 18 alkyl sulfate 2.5 2.5 2.5 zeolite 23.5 14.0 20.5 polyacrylate (4500 MV) 3.9 3.9 3.9 sodium citrate 6.0 sodium carbonate 12.7 16.0 12.7 water and various additives 8.1 8.2 8.7

39.9

Admixture and spraying

Coconut fat N-methyl, Ν-1-deoxyglucityl amide 5.9

Fatty acid N-methyl, N-1-deoxyglucitylamide various (bleach, activating salts, filler salts, etc.) 37,5

5.6

37.9

Total 100.0 100.0 100.0

Examples 12-14 show high performance granular detergent compositions of standard density and for wash temperatures between about 30-95 ° C, at concentrations of about 8,000 parts per million by weight of wash water basis. The compositions are prepared by spray drying the basic granular components to about 10-13% moisture, adding additional dry powder components such as bleach, activators and other supplements and spraying with liquid components such as perfume, nonionic agents or suds suppressors in liquid form.

Example 15

The following alternative process for preparing polyhydroxy fatty acid amides is used. Use a reaction mixture consisting of

84.87 g fatty acid methyl ester (source:

Procter & Gambia methyl ester CE1270), 75 g N-methyl-D-glucamine (source =

Aldrich

Chemical Company M4700-0), 1.94 g sodium methoxide (source:

Aldrich Chemical Company 16, 499-2) and 68.51 g of methyl alcohol.

The reaction vessel comprises a standard backflow arrangement equipped with a drying tube, a condenser and a stirring bar. In this procedure, N-methyl 1 g of luminosin is combined with methanol under stirring under argon and heating is started with good stirring (stirring bar; reflux). After 15-20 minutes when the solution reached the desired temperature, the ester and the catalyst were added as sodium methoxide. Samples are taken periodically to monitor the progress of the reaction, but it is noted that the solution is quite clear after 63.5 minutes. The reaction is almost complete at this point. The reaction mixture was refluxed for 4 hours. After removal of methanol, the product obtained weighs

156.15 grams. After vacuum drying and purification, an overall yield of purified product is obtained. However, the percentage is not calculated on this basis since regular sampling during the course of the reaction makes the overall percentage yield insignificant. The reaction can be carried out at 80% to 90% reagent concentrations for up to 6 hours to give products with extremely low by-product formation.

The following statements are not intended to limit the invention, but merely to further illustrate the additional technology that can be considered by the formulator in the production of a wide variety of polyhydroxy fatty acid detergent.

compositions of amides used

It will be readily appreciated that polyhydroxy fatty acid amides are subject to some instability under highly alkaline or highly acidic conditions due to their amide bond.

Although decomposition can be tolerated, I prefer it.

that these materials are not exposed

PH about 11, with values greater than excessively prolonged time. Values of preferably 10, even below about 3 after the pH of the final product (liquids) are typically 7.0-9.0.

During the production of polyhydroxy fatty acid amides, it will typically be necessary to at least partially neutralize the basic catalyst used to form the amide bond. While any acid can be used for this purpose, the detergent formulator knows that it is simple and expedient to use an acid that provides an anion that is otherwise useful and desirable in the finished detergent composition. For example, for neutralization purposes, citric acid and the resulting citrate ion (about 1 is left with a suspension of about 40% polyhydroxy fatty acid amides for pumping into the later subsequent phases of the overall detergent production. Similarly, acid forms of materials such as oxydisuccinate, nitrilotriacetate, ethylenediaminetetraacetate, tartarate / succinate and the like.

Polyhydroxy fatty acid ides derived from coconut alkyl fatty acids (predominantly C12-C14) are more soluble than their alkyl tallow counterparts (predominantly C16-C18) - As a result, C12-C14 materials are somewhat easier to formulate in liquid compositions and are more soluble in cold water-containing laundry solutions.

Materials

However, C16-C18 are also quite useful, especially in circumstances where hot to hot washing water is used. Indeed, C16-C18 materials may represent better detergent surfactants than their C12-C14 counterparts.

The formulator can thus proceed on the basis of the requirement to balance the ease of manufacturing verse.

potency in selecting a particular polyhydroxy fatty acid amide for use in a given formulation.

It will also be obvious.

that the solubility of polyhydroxy fatty acid amides can be increased by having points of saturation and / or branching of the chains in the fatty acid moiety. Thus, materials such as polyhydroxy fatty acid amides derived from oleic and isostearic acids may be more soluble than their n-alkylated counterparts.

Similarly, the solubility of polyhydroxy fatty acid amides prepared from disaccharides, trisaccharides, etc. usually greater than the solubility of their monosaccharide derived counterparts.

Higher solubility can be particularly useful in formulating liquid compositions. In addition, polyhydroxy fatty acid amides in which the polyhydroxylated group is derived from maltose also prove to be particularly well-functioning detergents when used in combination with conventional alkylbenzenesulfonate (LAS) surfactants. While not wishing to be bound by theory, it appears that combinations of LAS with polyhydroxy fatty acid amides derived from higher saccharides such as maltose cause a substantial and unexpected decrease in interfacial tension in the aqueous environment, thereby promoting detergency efficiency. (The production of maltose-derived polyhydroxy fatty acid amide is described below.

Polyhydroxy fatty acid amides can be produced not only from purified sugars, but also from hydroxylated starches, e.g. cereal starch, potato starch or any suitable starch derived from plant products containing mono-, di-, etc. a saccharide required by the formulator. This is particularly important from an economic point of view.

Thus, a high-glucose obsy syrup may be suitable and economically used.

high maltose cereal syrup, etc. The feedstock for the polyhydroxy fatty acid amide can also be provided by dehydrated hydrolyzed cellulose pulp.

As mentioned above, polyhydroxy fatty acid amides derived from higher carbohydrates such as maltose, lactose, etc. are more soluble than their glucose counterparts. In addition, it appears that more soluble polyhydroxy fatty acid amides may aid in solubilizing their more soluble counterparts to varying degrees. Thus, the formulator may choose a raw material containing, for example, a high glucose cereal syrup, or choose a syrup containing a small amount of maltose (e.g. 1%). or more).

The resulting mixture of polyhydroxy fatty acids will generally exhibit more favorable solubility properties over a wider temperature range and concentrations than would be achieved with pure polyhydroxy fatty acid amide derived from glucose. In addition to all the economic advantages of using sugar mixtures rather than pure sugar starting materials, polyhydroxy fatty acid amides prepared from mixed sugars can provide very substantial advantages in terms of efficacy and ease of formulation. However, in some cases, some loss of grease removal capacity (dishwashing) at maltamide fatty acid levels above about 25% and some foaming loss above about 33% may be noted (the percentages given are percentages of maltamide-derived polyhydroxy fatty acid amide, polyhydroxy fatty acid amide derived from glucose in the mixture). This may vary depending on the chain length of the fatty acid moiety. Typically, the formulator choosing the use of such mixtures may consider it preferable to select mixtures of polyhydroxy fatty acid amides that contain ratios of monosaccharides (e.g., glucose) and D1- and higher carbohydrates Inapr. maltoses from about 4 = 1 to about 99: 1.

The production of preferred non-cyclized polyhydroxy fatty acid amides from fatty esters and N-alkyl polyols can be carried out in alcoholic solvents at a temperature of about 30 ° C to 90 ° C, preferably about 50 ° C to 80 ° C. suitable for formulators of, for example, liquid detergents to carry out such processes in a 1,2-propylene glycol solvent, since the glycol solvent does not necessarily have to be removed from the reaction product prior to use in the final detergent formulation. Similarly, the formulator, for example, of solid, typically granular detergent compositions, may find it advantageous to carry out such processes at 30 ° C to ° C in solvents containing ethoxylated alcohols, such as ethoxylated (E 3-8) C 12 -C 14 alcohols such as e.g.

NEODOL

R06.5 (Shell).

When such ethoxylates are used, it is preferred not to contain substantial amounts of mono-ethoxylated alcohol (determination T).

Although the processes for making polyhydroxy fatty acid amides by themselves and others do not form part of the syntheses of the invention, the formulator may take the polyhydroxy fatty acids as described below.

Typically, the industrial scale reaction to prepare acyclic polyhydrose fatty acid amides will comprise two steps. In a first step, an N-alkyl polyhydroxyamine derivative will be prepared from the desired sugar or a mixture of sugars by forming an adduct of N-alkylamine and sugar, followed by reaction with hydrogen in the presence of a catalyst. In a second step, the reaction of said polyhydroxyamine, preferably with a fatty ester, is carried out to form an amide bond. Although a wide variety of N-alkyl polyhydroxyamines useful in Step 2 of the reaction sequence can be prepared by various procedures described in the prior art, the following process using an economically advantageous sugar syrup is preferred. It should be borne in mind that, for best results, the manufacturer should choose syrups which are fairly light in color or preferably totally colorless (water colors).

Example of preparation of N-alkyl polyhydroxyamines from sugar syrup derived from plant sources.

The first step is the formation of the adduct. The following procedure is a standard process in which about 420 g of an approximately 55% glucose solution (cereal syrup - about 231 g of glucose - about

1.28 mol), having a Gardner color of less than 1, is reacted with approximately 119 g of an approximately 50% aqueous solution of methylamine (59.5 g methylamine - 1.92 mol). The methylamine solution (MMA) is purified and protected with N 2 and cooled to about 10 ° C to 20 ° C.

The cereal syrup is added slowly to the MMA solution at the indicated reaction temperature as shown. The Gardner color is measured at the indicated approximate times in minutes.

Time in minutes: TAB. 1 120 180 240 10 30 60 Reaction temperature ° C Gardner color (approxim.)

0 1 1 1 1 1 1 20 1 1 1 1 1 1 30 1 1 2 2 4 5 50 4 6 10 - - - Than can be derived from above listed data, is a Gardner

the color for the adduct is much worse when the temperature rises around 30 ° C and about 50 ° C, while the time when the adduct has. The Gardener color below 7 is only about 30 minutes. For the next reaction and / or holding times, the temperature should not be less than about 20 ° C. The Gardner color should not be less than about 4 to obtain a good glucamine color.

When lower temperatures are used to form an adduct, the time to reach a substantial equilibrium concentration by using higher amine to sugar ratios is shortened. At a molar ratio of 1.5 = 1 amine to sugar, equilibrium is reached in about 2 hours at a reaction temperature of about 30 ° C. At a 1.2: 1 molar ratio, under the same conditions, the time is at least about 3 hours. For good color, the combination of amine sugar ratio, reaction temperature and reaction time is chosen to achieve a substantially equilibrium conversion, e.g. more than about 90%, preferably more than about 95%, and even more preferably more than about 99 based on sugar and inks having a value of less than about 7, preferably less than about 4 and most preferably less than about 1 for the adduct.

Using the above process at a reaction temperature of less than about 20 ° C and cereal syrups with different Gardner colors as mentioned, the color of the MMÄ adduct (after reaching essentially equilibrium in at least about 2 hours) as shown in Table 2.

ΤΑΒ. 2

Cereal syrup

GArdner Color (Approx.)

1 0 0 0 0 0

adduct

4/5 7/8 7/8 1 2 1

As can be seen from the table, the starting sugar material must be very close to colorless in order to obtain a continuously acceptable adduct. When the sugar has a Gardner color with an ambient value of 1, the adduct is sometimes acceptable and sometimes unacceptable. When the Gardner color is above 11, the resulting adduct is unacceptable. The better the initial color of the sugar, the better the color of the adduct.

The second step is a hydrogen reaction in which the above-mentioned adduct having Gardner color 1 or less is hydrogenated according to the following procedure.

About 539 g of adduct in water and about 23.1 g of Unidet Cytalytyst G49B Ni catalyst are added to a 1 liter autoclave and purified twice with 1.38 MPa H2 at a temperature of about 20 ° C. The hydrogen pressure is increased to about 100 psig and the temperature is raised to about 50 ° C. The pressure is then increased to about 11 MPa and the temperature is maintained at about 50-55 ° C for about 3 hours. The product at this point is approximately 95% hydrogenated. The temperature is then raised to about 85 ° C for about 30 minutes and the reaction mixture is decanted and the catalyst is filtered off. After removal of water and evaporation of MMA, the product is approximately 95% of N-methylglucamine as a white powder.

The above procedure was repeated with about 23.1 g of Raney nickel catalyst with the following changes. The catalyst is washed three times and the reactor, with the catalyst in the reactor, is purged twice with 1.38 MPa H2, the reactor is pressurized with hydrogen at 11 MPa for two hours, the pressure is released in one hour and the reactor is pressurized again at 11 MPa. The adduct is then pumped into a reactor at a pressure of 1.38 MPa and a temperature of 20 ° C and the reactor is purified with 1.38 MPa of H 2, etc., as above.

In any case, the resulting product is greater than about 95% N-methylglucamine, has less than about 10 parts Ni per million, based on glucamine, and has a coloring of &lt; of a solution having a lower Gardner color than about 2.

Crude N-methylglucamine is color stable at about 140 ° C for a short time exposure.

It is important to have a good adduct having a low sugar content (less than about 50, preferably less than about 1%) and a good color (less than about 7, preferably about 4 Gardnera, and most preferably less than about 1).

In another reaction, the adduct is prepared by mixing with about 159 g of about 50% methylamine in water, which is purified and protected with N 2 at a temperature of about 10-20 ° C. Approximately 330 g of approximately 70% cereal syrup (near white water color) is degassed with N 2 at a temperature of about 50 ° C and added slowly to the methylene solution at a temperature less than about 20 ° C. The solution is stirred for about 30 minutes to give approximately 95% adduct as a very light yellow solution.

About 190 g of adduct in water and about 9 g of United Catalytyst G49B Ni catalyst are added to a 200 mL 1 L autoclave and purified three times with H 2 at a temperature of about 50 ° C. The pressure is raised to 1.72 MPa and the temperature is maintained at about 50 ° C to 55 ° C for about 3 hours. The product, which is approximately 95% hydrogenated at this point, is then brought to an elevated temperature of about 85 ° C for about 30 minutes and the resulting product is approximately 95% -x-N-methylglucamine as a white solid after removal of water and evaporation. powder.

It is also important to minimize contact between the adduct and the catalyst when the H2 pressure is less than about 6.88 MPa to minimize the nickel content of the glucamine. The nickel content of N-methyl glucamine in this reaction is about 100 parts per million compared to less than 110 parts per million in the previous reaction i.

The following reactions with hydrogen are performed to directly compare the effects of reaction temperatures.

A 20 milliliter autoclave reactor is used, following a procedure similar to that described above, to obtain the adduct and to carry out the reaction with hydrogen at different temperatures.

The product for use in the manufacture of a globulin is prepared by combining approximately 420 g of an approximately 55% solution (231 g of glucose, 1.28 moles) of glucose (cereal syrup) using a 99DE cereal syrup supplied by CarGill, with less color. than 1 Gardner) and about 119 g of 50% methylamine (59.5 g MMA; 1.92 moles) (from Air Products). The reaction procedure is as follows:

1) Add about 119 g of a 50% methylamine solution to the nitrogen purged reactor. nitrogen protected. and cooled to less than about 10 ° C.

2) Degass and purify a 55% cereal syrup solution at 10 ° C - 20 ° C with nitrogen to remove oxygen from the solution.

3) Add the cereal syrup solution slowly to the methylamine solution and maintain the temperature at less than about 20 ° C.

4) Once all the cereal syrup solution is added, stir for about 1 to 2 hours.

The adduct is used for the hydrogenation reaction immediately after formation or stored at a low temperature to prevent further degradation.

The reactions of the glucamine adduct with hydrogen are as follows:

1) Add about 134 g adduct (color less than about 1 Gardner) and about 5.8 g G49B Ni to a 200 mL autoclave.

2) Purify the reaction mixture with about 1.38 IMPa H2 twice at about 20 ° C - 30 ° C.

3) Pressurize H 2 at about 400 psig and raise the temperature to about 50 ° C.

4) Increase the pressure to about 3.45 MPa, allow to react for about 3 hours. The temperature is maintained at about 50 ° C-55 ° C. Sample 1.

5) Raise the temperature to about 85 ° C for about 30 minutes.

6) Decant and filter the nickel catalyst. A sample of 2 shall be taken.

The conditions for constant temperature reactions are as follows:

1) Add about 134 g adduct and about 5.8 g G49B Ni to a 200 mL autoclave.

(2) Purify the reaction mixture with approximately 1.38 MPa H2 twice at low temperature.

3) Pressurize H 2 at about 400 psig and raise the temperature to about 50 ° C.

4) Increase the pressure to about 3.45 MPa, allow to react for about 3.5 hours. The temperature is maintained at the temperature indicated.

5) Decant and filter the nickel catalyst. Sample 3 is taken for a temperature of about 50 ° C-55 ° C, sample 4 for a temperature of about 75 ° C, and sample 5 for a temperature of about 85 ° C (reaction time for about 85 ° C is about 45 minutes).

All experiments have a similar purity of N-methylglucamine (about $ 95). whereas the Gardner colors in the experiments are similar immediately after the reaction, but only a two-stage heat treatment provides good color fastness. The 85 ° C experiment gives a marginal color immediately after the reaction.

Example 16

The preparation of tallow fatty acid amide (solidified) from N-methylmalate amine for use in the detergent compositions of the invention is carried out as follows.

In the first step, maltose monohydrate (ftldrich. 01318KV) is used as the reactant. methylamine (40 wt.% in water) (,1dich, 03325 ™) and Raney nickel as a 50% slurry. / UAS 52-73B. Aldrich, 12921LV).

The reactants are added to the glass insert (250 maltose.

428 methylamine solution, 100 g catalyst slurry - 50 g Raney nickel) and placed in a 3 L swinging autoclave, which is purged with nitrogen (3x2, 78 MPa) and hydrogen (2x2.78 MPa), and vibration is vibrated under H2 at temperature rooms over the weekend in the temperature range from 28 ° C to 50 ° C. The crude reaction mixture was vacuum filtered 2X through a microfiber filter with a silica gel plug. The filtrate is concentrated to a viscous material. The final traces of water are removed azetropically by dissolving the material in methanol and then removing the methanol and water on the rotary launcher. Final drying is carried out under high vacuum. The crude product is dissolved in reflective methanol. filtered, cooled for recrystallization, filtered and the filtered cake dried under vacuum at 35 ° C. This is Fraction # 1. The filtrate was concentrated until a precipitate began to form and stored in a refrigerator overnight. The solid was filtered and dried under vacuum. This is Fraction # 2. The filtrate is again concentrated to half its volume and recrystallization is performed. Very little precipitate is formed. A small amount of ethanol is added and the solution is left in the freezer over the weekend. The solid was filtered and dried under vacuum. The combined solids form N-methyl maltamine which is used in step 2 of the overall synthesis.

In the second step it is used as reactants

N-methylmaltamine from step 1. solidified tallow fatty acid methyl esters, sodium methoxide (25% methanol), anhydrous methanol (solvent), wherein the molar ratio of amine to ester is 1-1, the initial catalyst level is 10 molar% (w / w) maltamine) and is increased to 20 mol% and the solvent content is 50 wt.

In a sealed bottle, 20.36 g of tallow methyl ester is heated to its melting point (in a water bath) and filled into a 250 ml three-necked round-bottomed reaction flask with mechanical stirring. The flask is heated to approximately 70 ° C to prevent the ester from solidifying. Separately, 25.0 g of N-methyl maltamine is combined with 45.36 g of methanol and the resulting suspension is added to the tallow ester with good stirring. 1.51 g of 25% sodium methoxide in methanol is added. After four hours, the reaction mixture did not become clear, so an additional 10 mol% catalyst (to a total of 20 mol%) was added and the reaction was allowed to continue overnight at about 68 ° C, after which time the mixture became clear. The flask is then adjusted for distillation. The temperature was raised to 110 ° C. Distillation at atmospheric pressure is continued for 60 minutes. The distillation under high vacuum is then started and continued for 114 minutes. The product is left in the reaction flask at 110 ° C (outside temperature) for 60 minutes. The product is taken from the flask and triturated in ethyl ether over the weekend. The ether was removed on a rotary evaporator and the product was stored overnight in an oven and ground to a powder. Any residual N-methyl maltamine is removed from the product using silica gel. The silica gel suspension in 100 µl methanol is filled into a funnel and washed several times with 100% methanol. A concentrated sample of the product (20 g in 100 mL of 100% methanol) was poured onto silica gel and eluted several times under vacuum and several methanol washes. Collected eluent to dryness in a rotary launcher. Any residual ester was removed by trituration in ethyl acetate overnight, evaporated

This is followed by filtration. The product is

N-methylmaltamine alkylated

1 fatty acid.

In an alternative process, step 1 of the previous reaction process may be carried out using a commercially available cereal syrup containing glucose or glucose mixtures and typically 5% or more maltose. The resulting polyhydroxy fatty acid amides and mixtures thereof can be used in the detergent compositions of the invention.

In yet another process, step 2 of the previous reaction process may be carried out in 1,2-propylene glycol or NEODOL. At the discretion of the formulator, propylene glycol or NEODOL need not be removed from the reaction product prior to its use in formulating detergent compositions. Again, at the desire of the formulator, the methoxide catalyst may be neutralized with citric acid to yield sodium citrate, which may remain in the polyhydroxy fatty acid amide.

Depending on the desire of the formulator, the compositions discussed herein may comprise more or less different suds control agents. Typically, high sudsing is desirable for dishwashing, so that no suds control agent is needed, with top loading can be and with front loading machines

For washing fabrics in washing machines, some suds control may be desirable to a large extent to suds control. A wide variety of suds control agents are known in the art and can be routinely selected here as desired. Indeed, the choice of suds control agents or suds control agents for any particular detergent composition will depend not only on the presence and amount of the polyhydroxy fatty acid amide used therein, but also on the other surfactants present in the formulation. However, it appears that silicone-based suds control agents of different types (i.e. can be used in smaller amounts) are more effective for use with polyhydroxy fatty acid amides than different other types of suds control agents. The Si 1 foam control agents available as X2-3419 and 02-3302 (Dow Corning) are particularly useful herein.

The fabric wash composition formulation, which may advantageously contain a soil release agent, has a choice of a variety of known materials (see, for example, U.S. Patent Nos. 3,952,152, 4,116,885, 4,238,531, 4,702,857). and 4,877,896). Other soil release materials that can be used include the nonionic oligomeric esterification product of the reaction mixture comprising a source of C 1 -C 4 alkoxy-terminated polyethoxy units (e.g. CH 3 [OCH 2 CH 2] ββ 9), a source of terephthaloyl units (e.g. dimethyl terephthalate); a source of poly (oxyethylene) oxy units (e.g., polyethylene glycol 1500); a source of oxyisopropyleneoxy units (e.g., 1,2-propylene glycol); and a source of oxyethyleneoxy units (e.g., ethylene glycol), especially wherein the molar ratio of oxyethyleneoxy units to oxyisopropyleneoxy units is at least about 0.5

1. such anionic soil release agents have the general formula;

wherein R ¹ is lower (e.g. C 1 -C 4) alkyl, especially methyl; x and y are integers from 6 to about 100; m is an integer from about 0.75 to about 30; n is an integer from about 0.25 to about 20 and R ² is a mixture of both H and CH 3 to provide a molar ratio of oxyethylene oxyisopropyleneoxy of at least about 0.5 = 1.

Another suitable type of soil release agent useful in the compositions of the invention is of the generally anionic type described in U.S. Pat. No. 4,877,896, but provided such agents are substantially free of HOROH-type monomers wherein R is propylene or higher alkyl. The soil release agents of U.S. Pat. No. 4,877,896 may thus contain, for example, the reaction product of dimethyl terephthalate, ethylene glycol, 1,2-propylene glycol and 3-sodium sulfobenzoic acid, while these additional soil release agents may contain, for example, the reaction product of dimethyl ether terephthalate, ethylene glycol, 5-sodium sulfobisophthalate and 3-sodium sulfobisophthalate. Such agents are preferred for use in granular laundry detergents.

The formulator may also determine that it is preferable to include a non-borate bleach, especially in high performance granular laundry detergents. There is a variety of peroxide bleaches available on the market and usable here, but among them is suitable and economical percarbonate. Thus, the compositions of the invention may comprise a solid percarbonate bleach, normally in the form of the sodium salt, included in an amount of from 3% to 20% by weight, more preferably from 5% to 18% by weight, and most preferably from 9% to 15% by weight of the composition.

Sodium percarbonate is an addition compound having the formula corresponding to 2Na 2 CO 3 - 3H 2 O 2 and is commercially available as a crystalline solid. Most commercially available materials include a small amount of a heavy metal scavenger such as EDTA, 1-hydroxyethylidene-1,1-diphosphonic acid (HEDP) or an aminophosphonate incorporated during the manufacturing process. For use in the invention, the percarbonate can be incorporated into the detergent compositions without additional protection, but preferred embodiments of the invention use a stable form of material (FMC). Although a variety of coatings may be used, the most economical is sodium silicate with a SiO 2 ^: Na 2 O ratio of 1.6 = 1 to 2.8 ^: 1, preferably 2.0 = 1, applied as an aqueous solution and dried to provide a level of content from 2% to 10% (normally from 3% to 5 solid silicate particles based on percarbonate weight. Magnesium silicate and a chelating agent may also be used so that one of these may also be included in the coating.

The particle size range of crystalline percarbonate is from 350 microns to 450 microns with a center of approximately 400 microns. When coated, these particles have a size in the range of 400 to 600 microns.

Although the heavy metals present in the sodium carbonate used for the production of percarbonate can be controlled by the inclusion of scavengers in the reaction mixture, the percarbonate nevertheless requires protection from the heavy metals present as impurities in the other components of the product. It has been found that the total content of iron, copper and manganese ions in the product should not exceed 25 parts per million and preferably should be less than 20 parts per million in order to avoid an unacceptably negative effect on the stability of the persimmon.

The modern thickened laundry granules have the following composition.

Example 17

___________________________________________________ component materials. %

C14-C15 alkyl alcohol-sulfonic acid, 1113.01.3

C14-C15 alkylpolyethoxy (2.25) sulfonic acid 5.6

C12-C13 alkylpolyethoxylate (6.5) 1.45

C12-C114 fatty acid N-methyl glucamide 2.5 aluminosic sodium sodium (as hydrated Zeolite®) 25.2 crystalline layered silicate ¹ activator 23.2 citric acid10.0 sodium carbonate for yield. Washing pH9.90 Sodium polyacrylate (mol% 2000 - 4500) 3.2 Diethylenetriamine pentaacetic acid 0.45

Savinase ² 5,60,70 6-Nonanoylamino-6-oxo-peroxycaproic acid 7.40 Sodium perborate monohydrate 2,10 Nonanoylbenzenesulfonic acid 5.00 Brightening agent 0.10 ^L layered silicate activators are known in the art. Most preferred are layered sodium silicates. See e.g. layer silicate activators according to U.S. Pat. No. 4,664,895, issued May 12, 1987, which is incorporated herein by reference.

² Available from Novo Nordisk A / S, Copenhagen.

Significantly most preferred granules of the above types are those containing from about 0.0001% to about 2% by weight of said polyhydroxy fatty acid amide, and most preferably wherein the anionic surfactant is not an alkylbenzenesulfonate surfactant.

Example 18

The following example illustrates a detergent composition of the invention with a perborate bleach and a bleach activator, which is prepared by mixing the ingredients listed below in a mixing drum.

In the example, Zeolite A refers to a hydrated crystalline Zeolite A containing about 20% water and having an average particle size of 1 to 10, preferably 3 to 5 microns; LAS means C12.3 linear sodium alkyl benzenesulfonate; AS is sodium C14-C15 alkyl sulfate; nonionic agent means coconut alcohol alcohol concentrated with about 6.5 moles of ethyleneoxyde per mole of alcohol and free of unethoxylated and monoethoxylated alcohol, also abbreviated as CnAE6.5T; and DTPA means diethylenetriamine pentacetate.

Weight parts

final composition % granules Basic granule ¹ 51.97 100.00 AS 9.44 18.16 LAS 2.92 5.62 humidity 4:47 8.60 sodium silicate (1.6 ratio) 1:35 2.60 sodium sulfate 6.47 12.45 sodium polyacrylate (4500 mol. hm. ) 2.61 5.02 PEG 8000 1.18 2.27 nonionic agent 00:46 0.89 sodium carbonate 13.29 25.57 brightener 0.20 0.38 sodium aluminosilicate 9.11 17.53 DTPA 0.27 00:52 perfume 0.20 0.38 NAPAA Granules ² 6.09 100.00 NAPM 2.86 46,96 LAS 0.30 4.93 sulfate and various 2.93 48.11 Granules NOBS ³ 3.88 100.00 NOBS 3.15 81.19 LAS 0.12 3.09 PEG 8000 00:19 4.90 Differently 0.42 10.82 Zeolite granules ⁴ 12,00 100.00 sodium aluminosilicate 7.39 61.58 PEF 8000 1:50 12.58 nonionic agent 1.16 9.70 humidity 1.66 13.83 Differently 00:29 2:42

Additive layered sodium silicate

SKS-6 15.84

protease

(activity 0.078 mg / g) perborate monohydrate 0.52 sodium 1:33 citric acid 6.79 C12-C114 N-methylglucamide 1.58 Total final composition 100.00

^The base granules are produced by spray drying from an aqueous mixture of the above ingredients by mixing with a crutcher.

² is obtained freshly prepared sample of NAPAA in the form of a wet cake, which typically consists of about 60% water, about 2% peroxyacid available oxygen (AvO) (corresponding to about 36% NAPAA), and the rest (about 4%) unreacted starting material. This wet cake is a crude reaction product of NAAA (adipic acid monononylamide), sulfuric acid and hydrogen peroxide, which is subsequently quenched by addition to water followed by filtration, washed with distilled water, washed with phosphate buffer and finally subjected to suction filtration to obtain a wet cake. . A portion of the wet cake is air dried at room temperature to obtain a dry sample, which typically consists of about 5% AvO (corresponding to about 90% NAPAA) and about 110% unreacted starting material. When dry, the pH of the sample is about 4.5. The granules are prepared by mixing

51.7 parts dry NAPAA wet cake (containing about 10% unreacted ingredients), about 11.1 parts paste (45% active) sodium C12.3 linear alkylbenzene sulfonate (LAS). about 43.3 parts of sodium sulfate and about 30 parts of water in the mixer

Cuisinart. After drying, the granules (which contain about 47% NAPAA) are sized by passing through a No. 1 sieve. 14 Tyler mesh and retain any particles that do not pass through sieve no. 65 Tyler Mesh The average peracid amide particle is about 5 to 40 microns and the mean particle size is about 10-20 microns, as determined by Malvern particle size analysis.

³ Granules NOBS (nonanoyl oxybenzenesulfonate) was prepared in accordance with U.S. Patent Wh- 4,997,596 issued 5. 3. 1991, incorporated herein by reference as part of the description.

⁴ Zeolite granules having the following composition are made by mixing Zeolite A with PEG 8000 and CnAE6.5T in an Eirich energy intensive mixer R08.

Mass parts

Before drying ______ After drying

Zeolite Ä (includes bind, water)

PEG 8000

CnAE6.5T

Free water

70.00

10.80

8.40

10.80

76,99

12:49

9.72

0.80

PEG 8000 is in aqueous form containing 50% water and is at a temperature of about 12.8 ° C. CnAE6.5T is in a liquid state and is maintained at a temperature of approximately 32.2 ° C. Both liquids are combined by pumping through a 12-element static mixer. The resulting binder material has an exit temperature of about 23.9 ° C and a viscosity of about 5000 c / s. The ratio of PEG 8000 and CnAE6.5T passing through the static mixer is 72: 28.

The Eirich Energy Intensive Mixer R08 is operated in batch type mode. First, weigh 34.1 kg of Zeolite A powder into the pan of the mixer. The mixer is started by first allowing the pan to rotate counter-clockwise at approximately 75 rpm and then allowing the rotor blade to rotate clockwise at 1800 rpm. The binder material is then pumped directly from the static mixer into the Eirich energy mixer R08, which contains Zeolite Ä. The binder feed rate is about 2 minutes. The mixer continues stirring for an additional one minute for a total batch time of approximately 3 minutes. The batch is then discharged and collected in a fiber drum.

The batch step is repeated until approximately 225 kg of wet product has accumulated · The discharged product is then dried in a fluid bed at 1-16 ° C - 132 ° C. The drying process removes most of the free water and changes the composition as described above. All the energy input to the product is at a batch mode of about 1362 Nm / kg at a rate of about 2.26 N / kg-s.

Example 19

The granular laundry detergent composition suitable for use at the relatively high concentrations customary for front load automatic washing machines, particularly in Europe and over a wide temperature range, is as follows.

__________________________________________________ component materials. %

SOKALAN CP5 (100% active as Na salt) ¹ 3,52

DEQUEST 2066 (100% as acid) ² 0.45

TINOPAL DMS ³ 0.28

40.49 MgSO

Zeolite A (anhydrous 2 - 5 / u) 17.92

CMC (100 active) ⁴ 0.47

Na2C039.44 Citric acid3,5 layered silicate SKS-612,9 tallow alkyl sulphate (100% active; per salt) 2.82

C14-C15 alkyl sulfate (100% active; Na salt) 3.5

C12-C15 alkyl E0 (3) sulfate 1,76

C16-C18 N-methylglucamide 4,1

DOBANOL C12-C15 EQ (3) 3.54

LIPOLASE (100,000 LU / g) ⁵ 0.42

SAVINASE (4.0 KNPU) ⁶ 1.65 perfume0.53

X2-3419 ⁷ 0.22 starch1.08 stearyl alcohol 0.35 sodium percarbonate (coated) 22.3 tetraacetylenediamine (TAED) 5.9 zinc phthalocyanate0.02 water (except zeolite) residue ¹ SOCALAN is sodium polyacrylate / sodium maleate available from Co. Hoechst ² Pentaphosphonomethyl diethylenetriamine type manufactured by Monsanto.

^A typical brightener available from Ciba Geigy.

⁴ Available from Metasaliton under Circulation. name. Finnfix.

⁵ LIP0LASE is a lipolytic enzyme from NOVO.

⁶ SAVINASE is a protease enzyme from NOVO ⁷ X2-3419 is a 1 iconic suds suppressor available from Dow Corning.

The granule preparation process comprises various tower drying processes (A), agglomeration (B), addition of dry additives (CC), etc., as described below. The percentages are based on the finished composition.

First, using the standard procedures the following

the ingredients are mixed with a crutcher and dried 3.52% 0.45% 0.28% 0.49% 7.10% in drying tower (A). SOKALAN CP5 DEQUEST 2066 TINOPAL DMS boron sulphate ZEOLITE A in clear CMC . f orme 0.47 % It is then carried out agglomeration surface active substances (B). It will first be executed agglomeration (BI) sodium salt tallow

alkyl sulfate and sodium salt of a C12-C15 (E0C3) sulfate paste. 50% active tallow alkyl sulfate paste and 70% C12-C15 E0C3 paste)

sulfate are agglomerated with Zeolite A a carbonate sodium according to following recipe (contribution to detergent formulation after drying the agglomerate). tallow alkyl sulfate 2.82% C12-C15 E0 (3) sulphate 1,18 t Zeolite A 5.3% sodium carbonate 4.5% It is then agglomerated (B2) C14-C15 alkyl sulfate, C12-C15 alkyl ethoxy sulfate, DOBANOL C12-C15 E0 (3) and C16-C18 N-methyl. C16-C18 glucamine material is merging

with DOBANOL (C12-C15 ECO3) present during the reaction of the methyl ester and N-methylglucamine. C12-C15 (OC3) acts as a melting point reducing agent, allowing the reaction to proceed without the formation of cyclic glucamides, which are undesirable. A mixture is obtained; surfactants of 20% DOBANOL (C12-C15 ECO3) and 80% C16-C18 N-methylglucamide and agglomerate together with 19% sodium carbonate.

The above particle is then agglomerated with an active paste (70%) of the sodium salt of C14-C15 alkyl sulfate and of C12-C15 ECO3 sulfate and ZEOLITE A and the added sodium carbonate. These particles are characterized by good dispersibility of C16-C18 N-methylglucamide and in cold water.

The overall composition of these □ of particles (post to formulate detergent after drying the agglomerate) is ^: Cie-Cie N-methylglucamide 4.1 % DOBANOL C12-C15 E0 0.94 % Sodium carbonate 4.94% Zeolite A 5.3 % Na C14-C115 alkyl sulfate 3.5 % Na C12-C15 EOC3) sulphate 00:59 i% The next process is dry formulation additives (C). Adding the following components: peruh1 or tan 22.3 % TAED (tetraacetylenediamides) n) 5.9 % layered silicate SKS 6 from Hoechst 12.90 % citric acid 3.5% 1ipoláza 0.42 % 100,000 LU / g SAVINASE 4.0 KNPU 1.65 % zinc phthalocyanide (Fotobielidlo) 0.02 % They are then applied by spraying following CD ingredients) DOBANOL C12-C115 E0 2.60 % perfume 0.53 % As suds suppressors common agglomerated (E) force icon foam suppressor Z2-3419 (95% - 97% linear get 1 icon high relative mass 3 5% hydrophobic oxide from Dov Corning with Zeolite A (size 2 - 5 / u), starch and a stearyl alcohol binder. This particle has the following composition = Zeolite A 0.22 % starch 1.08 % X2-3419 0.22 % stearyl 0.35 %

The detergency of the preparation is characterized by excellent solubility, higher and excellent foaming control. when used in a European washing machine, e.g. when using 85 g of detergent in an AEG-type washing machine for washing cycles at 30 ° C, 40 ° C, 60 ° C and 90 ° C.

Example 20

In any of the preceding examples, the fatty acid glucamide surfactant may be replaced by an equivalent amount of maltamide surfactant, or mixtures of glucamide and maltamide surfactants derived from plant sources.

The compositions have shown that the use of ethanolamides helps the stability of the finished formulations at lower temperatures. In addition, the use of amino-oxide and / or sulphobetaine (aka sultain) surfactants provides better foaming.

When particularly high foaming compositions are desired, it is preferred that less than about 5, preferably less than about 2%, and most preferably substantially no C 14 or higher fatty acids are present, as these may suppress foaming. Thus, the high suds composition formulator avoids the use of a plurality of such suds suppressing fatty acids in compositions with polyhydroxy fatty acid amides and / or prevents the formation of C 14 higher fatty acids when storing the finished compositions. One simple means is to use C12 ester reactants to prepare polyhydroxy fatty acid amides for the compositions of the invention. Fortunately, however, the use of amino-oxide or sulfobetaine surfactants can overcome some of the negative effects on fatty acid induced foaming.

A formulator wishing to add anionic optical brighteners to liquid detergents containing relatively high concentrations (e.g., 10% or more) of anionic or polyanionic substituents such as polycarboxylate builders may find it useful to premix the brightener with water and polyhydroxy fatty acid amide. and then adding the premix to the final composition.

Dispersants in the form of polyglutamic acid and polyaspartic acid can advantageously be used with zeolite-activated detergents. Other examples of useful suds control ingredients are AE fluid or flakes and DC-544 (Dow Corning).

It will be appreciated by those skilled in the art of chemistry that the preparation of polyhydroxy fatty acid amides for compositions of the invention using di- and higher carbohydrates such as maltose will result in the formation of polyhydroxy fatty acid amides wherein the linear substituent Z is terminated with polyhydroxyl. circular structure. Such materials are considered to be fully applicable and do not depart from the scope and spirit of the invention described and explained in the description and defined in the claims.

pole

SPARE PARTY

Claims (15)

PATENT CLAIMS A detergent-activated composition comprising one or more anionic, non-ionic or cationic detersive surfactant, or mixtures thereof, optionally detersive ingredients and optionally auxiliary activating agents, characterized in that it contains at least 1 mass. % of a detergent builder of zeolite or layered silicate or a mixture thereof and at least 1 mass. % of the amide material in the form of a polyhydroxy fatty acid amide of the formula ABOUT II R ² z, wherein R ¹ is H, C 1 -C 6 or a mixture thereof. hydrocarbyl, 2-hydroxyethyl, 2-hydroxypropyl R ² is C5-C31 hydrocarbyl and Z is a polyhydroxyhydrocarbyl having a linear hydrocarbyl chain with at least 3 hydroxyl groups directly attached to said chain, or an alkoxylated derivative thereof. The granular detergent composition of claim 1 wherein the zeolite builder is Zeolite ft. The composition of claim 11, wherein the Z moiety in the amide material in the form of a polyhydroxy fatty acid amide is derived from a reducing sugar, R ¹ is methyl, and R ² is C 9 -C 17 alkyl or alkenyl. The composition of claim 3, wherein Z comprises -CH ₂ (CH ₂ OH) 4 CH ₂ OH. The composition of claim 1, wherein the Z moiety in said polyhydroxy fatty acid amide is derived from maltose. The composition of claim 1, wherein the portion From said polyhydroxy fatty acid amide it is derived from a mixture of monosaccharides, disaccharides and possibly higher carbohydrates, the mixture containing at least 1% of at least one disaccharide, preferably maltose. The detergent composition according to claim 1, characterized in that the ratio of polyhydroxy fatty acid amide zeolite is from 1 'to 10: 20: 1, preferably from 15 to 15: 1, most preferably from 1 to 3 to 10: 1. The detergent composition according to claim 1, characterized in that it comprises one or more anionic surfactants selected from the group consisting of alkyl sulfates, alkylethoxylated sulfates, alkyl ester sulfonates, preferably methyl ester sulfonates and alkylbenzene sulfonates. The detergent composition of claim 8, further comprising an alkyl ethoxylate or alkyl polyglycoside nonionic surfactant or a mixture thereof. 10. The detergent composition of claim 1 additionally comprising a polycarboxylate builder. 11. A method of improving the fabric cleansing performance of a detergent composition comprising one or more anionic, nonionic or cationic detersive surfactant, or a mixture thereof, a zeolite or layered silicate activator, or a mixture thereof, optionally a detersive ingredient, and optionally an auxiliary activator; characterized by. wherein at least 1 wt.% is incorporated into said detergent composition. % of the amide material in the form of a polyhydroxy fatty acid amide of the formula wherein R ¹ is H. C 1 -C 4 hydrocarbyl, 2-hydroxyethyl, 2-hydroxypropyl or a mixture thereof. R ² is C5-C31 hydrocarbyl a Z is a polyhydroxyhydrocarbyl having a linear hydrocarbyl chain with at least 3 hydroxyl groups preferably C11-C17 N-methyl maltamide or a mixture of said glucamide and maltamide or an alkoxylated derivative thereof, wherein the ratio of zeolite to polyhydroxy amide. the fatty acid is from 1: 10 to 20: 1 and fabrics are laundered with the composition in a conventional manner. Method according to claim 11, characterized in that. wherein said detergent composition comprises one or more anionic surfactants. Method according to claim 11, characterized in that. that part c Z in said polyhydroxy fatty acid amide is derived from mixed monosaccharides, disaccharides and polysaccharides, In obtainable from plant sources. The method according to claim 11, characterized in that. wherein the R ² moiety in said polyhydroxy fatty acid amide is C 15 -C 17 alkyl, alkenyl, or mixtures thereof. The method according to claim 11, characterized in that. wherein said anionic surfactant is not an alkylbenzenesulfonate surfactant.