SK24593A3 - Detergent compositions containing polyhydroxy fatty acid amide alkyl alkoxylated sulfate - Google Patents

Description

Technical field -. ·. ··

The invention relates to detergent compositions comprising alkyl alkoxylated sulfates and polyhydroxy fatty acid amides as surfactants.

BACKGROUND OF THE INVENTION

The ability of detergent compositions to clean soils and stains from various types of fabrics in large quantities during washing as well as cleaning other surfaces (e.g.

hard surfaces, hair, etc.) is very important in evaluating detergents. One type of surfactant which is valuable in terms of its overall cleaning performance, particularly in terms of excellent stain cleaning performance, are surfactants based on and alkylated alkoxides.

While these surfactant systems have excellent efficacy, it is desirable to find surfactant systems for various cleaning purposes that have increased cleaning efficiency of fats and oils. One of the most common types of surfactants associated with alkylalkoxylated surfactants to improve fat / oil cleaning properties is the group known as alkylbenzenesulfonates, especially linear alkylbenzenesulfonates.

These surfactant fat / oil, in wide alkyl] benzenesulfonates are substances can provide excellent cleaning of temperature and temperature ranges. However, typically derived predominantly from the raw materials at the present time, there is an increase in oil consumption. Therefore, it would be desirable to produce detergent compositions based on alkylalkoxylated sulphates that provide comparable overall cleaning performance values with a reduced or even eliminated amount of alkyl benzene sulfonate and its replacement with a surfactant that is largely or entirely derived from renewable non-petroleum sources.

Conventional nonionic surfactants in combination with alkylalkoxylated sulfates, such as alkyl ethoxylates, may provide acceptable cleaning, but typically require relatively long wash times, high wash temperatures, and high surfactant concentrations to achieve fat / oil cleaning.

The present invention provides detergent surfactant systems having an excellent ability to clean fat and oil over a wide range of water temperatures and wash concentrations by combining alkylalkoxylated sulfates and certain polyhydroxy fatty acid amide surfactants. In addition, polyhydroxy fatty acid amides may be obtained for the most part or entirely from natural, renewable raw materials of non-petroleum origin.

Various polyhydroxy fatty acid amides have been described in the art. For example, N-acyl, N-methylglucamides are described in J.V. Goodby, M. A. Marcus, E. Chin and P.L. Finn in The Thermotropic Liquid-Crystal1ine Properties of Some Straight Chain Carbohydrate Amphiphiles, Liquid Crystals, 1988. vol.3, no.11, p. 1569-1581, and A. Müller-Fehrnov, V. Zabel, M. Steifa and R.Hilgenfeld in Molecular and Crystal Structure of a Nonionic Detergent: Nonanoy1-N-Detergent; Nonanoyl-N-methylglucamide, J. Chem.Soc.Chem.Commun., 1986, pp. 1573-1574. The use of N-alkyl 1-polyhydroxyamide surfactants is of particular concern for use in biochemistry, for example, dissociation of biological membranes. See e.g. article N-D-Gluco-N-methyl-alkanamide Compounds, and the Nev Class of Non-Ionic Detergents For Membrane Biochemistry, Biochem J. (1982), Vol.207, pp.363-366, by J.E.K.

The use of N-alkyl glucamides in detergent compositions has also been described. U.S. Pat. No. 296576, issued December 20, 1960 to E.R. Wilson and BG Patent No. 809060. published February 18, 1959, by Thomas Hedley and Co., Ltd. relates to detergent compositions containing anionic surfactants, which may include N-methylglucamide. added as a low temperature sudsing agent. These compounds include the straight chain N-acyl radical of a higher chain fatty acid having from 10 to 14 carbon atoms. These compositions may also contain auxiliary materials such as alkali metal phosphates, alkali metal silicates, sulfates and carbonates. It is also generally stated that other ingredients may be included in the compositions to improve the desired properties of the composition, such as fluorescent dyes, bleaching agents, etc ...

U.S. Pat. No. 2703798, issued March 8, 1955 to A. M. Schartz, relates to aqueous detergent compositions comprising the condensation reaction product of N-alkylglucamine and an aliphatic fatty acid ester. The product of this reaction is useful in aqueous detergent compositions without further purification. It is also known to prepare a sulfuric acid ester and an acylated glucamine as described in U.S. Pat. No. 2717894, issued September 13, 1955

A.M.Schwartzov i.

PCT International Application WO 83/04412, published 22.

December 1983, J. Children et al.

containing polyhydroxyl aliphatic groups, designated as being useful for a variety of purposes, including use as surfactants in cosmetic compositions.

drugs, shampoos, lotions and eye ointments as emulsifiers and dispersants for medical use and in biochemistry for solubilizing membranes, whole cells or other tissue samples, and for preparing liposomes. Included in the disclosure are compounds of the formula R'CNN (R) CH2R and R'CON (R) R ', where R is hydrogen or an organic group. R 'is an aliphatic hydrocarbon group of at least three carbon atoms and R' is the remainder of the aldose.

European patent no. 0285768, published October 12, 1988, by H. Kelkenberg et al., Relates to the use of N-polyhydroxyalkyl fatty acid amides as thickeners in aqueous detergent systems. Included are amides of the formula R1OCOINCXJR2 wherein R1 is C1-C17 (preferably Cy-C1-6 alkyl, R2 is hydrogen, C1-C18 (preferably C1-C6) alkyl, or alkylene oxide and X is polyhydroxyalkyl having four to seven carbon atoms, e.g.

Coconut fatty acid N-methylglucamide. The amide thickening properties are indicated to be particularly suitable for use in liquid paraffin sulfonate-containing surfactant systems, although the aqueous surfactant systems may contain other anionic surfactants such as alkylarylsulfonates, olefin sulfonates, sulfosuccinic acid (poly) sulfosuccinic acid ester polyether sulfonates, fatty alcohol ether glycerol ethers. alkylphenol, polyglycol ether of fatty alcohol, polyglycol ether of alkyl phenol, polyglycol ester of fatty acid, polypropylene oxide-polyethylene oxide blended polymers, etc.

An example is the coconut fat paraffin sulphonate / N-methylglucamide shampoo formulations (nonionic surfactant. In addition to the thickening properties, N-polyhydroxyalkyl fatty acid amides are said to be excellent in terms of skin tolerance.

U.S. Pat. No. 2982737, issued May 2, 1961 to Boettnet et al., Relates to urea-containing detergent bars, sodium lauryl sulfate surfactant, and an N-alkylglucamide nonionic surfactant selected from N-methyl, N-sorbityllauramide, and N- methyl, N-sorbityl myristamide.

i j and j

í i

Other glucamide surfactants are described, for example, in DT no. 2226872, published December 20, 1973, by HVEckert et al., For detergents containing one or more surfactants and builder salts selected from the group consisting of polymeric phosphates, scavengers and laundry alkali, improved by the addition of N - acylpolyhydroxyalkylamine of the formula R 1 (C) O (R 2 CH 2 (CHGH) n - CH 2 OH, where R 1 is C 1 -C 3 -alkyl, R 2 is C 10 -C 22 alkyl and is 3 or 4. N-Acylpolyhydroxyalkylamine is added as a suspending agent dirt.

U.S. Pat. No. 3654166, issued April 4, 1972 to H. V. Eckert et al., Relates to detergent compositions comprising at least one surfactant selected from the group of anionic agents and zwitterionic surfactant ions.

and a nonionic surfactant and a fabric softener, an N-acyl, N-alkyl-1-polyhydroxyalkyl compound of the formula R1NC2) COR2, wherein R1 is C10-C22alkyl. 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 polyhydroxyalkyl, which may have the formula -CH 2 (CHOH) mCH 2 OH where m is 3 or 4.

U.S. Pat. 4021539, issued May 3, 1877, to H. Moller et al., Relates to skin care cosmetic compositions containing N-polyhydroxyalkylamines which include compounds of the formula R 1 (R) CH (CHOH) _m R 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.

1360018, April 26, 1963, Commercial

Solvents

Corporation, relates to formaldehyde solutions stabilized to polymerization by the addition of amides of the formula

RC (O) N (R 1) G, where

R is a 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 no.

1261861, 29.

February 1968,

A. Heins, relates to glucamine derivatives useful as a wetting sugar residue of glucamine, R 1 is a C 10 -C 20 alkyl radical, and R 2 is

C1-C5 acyl radical.

GB patent published February 15, 1956, Atlas Povder Company, relates to heterocyclic amides and their carboxylic esters, which are said to be useful as chemical intermediates, emulsifiers, wetting and dispersing agents, detergents, fabric softeners, etc. The compounds are represented by the formula N (R) (R 1) C (O) R 2. wherein R is a residue of hexanpentol or a carboxylic acid ester thereof, dehydrated, R 1 is a monovalent hydrocarbon radical, and -C (O) R 2 is an acyl radical of a carboxylic acid having 2 to 25 carbon atoms.

U.S. Patent 3,312,627, issued April 4, 1967 to DTHooker, discloses solid toilet bars that are substantially free of anionic detergents and alkaline activating materials and which contain certain fatty acids, nonionic surfactants selected from certain propylene oxide, ethylene amine and n-ethylene oxide. condensates.

propylene oxide propylene glycol-ethylene oxide condensates and polymerized ethylene glycol and also contain a nonionic filler component which may contain a polyhydroxide amide of formula ROCOINR ¹ (R ² ) wherein DRCO) contains from about 10 to about 14 carbon atoms and R ¹ and R ² are each H or R ² These alkyl groups contain a total number of carbon atoms of from 2 to about 7 and a total number of substituent-hydroxyl groups of from 2 to about 6. A substantially similar solution is disclosed in U.S. Pat. No. 3312626, also issued April 4, 1967 to DTHooker.

SUMMARY OF THE INVENTION

The present invention provides a low foaming detergent

preparation containing. generally, surface active compound am i d polyhydroxy fatty j kys elines of formula 0 R ¹ 1 1 1 1 1 1 R ^2- C ~ N ' FROM where R ¹ is H, C -Oihydrokarby1. 2-hydroxyethy1 and 1 ebo 2-hydroxypropy1, R ² is C5-C31 hydrocarbyl and Z is polyhydroxyhydrokarby1. having linear hydrocarbyl chain

with at least 3 hydroxyls directly attached to this chain, or alkoxylated derivatives thereof; an alkylalkoxylated sulfate surfactant; and in a suds suppressing amount, a suds suppressing agent, preferably selected from the group consisting of monocarboxylic fatty acids and salts thereof, are iconic agents. suppressing the formation of foam and alkali metal di-salt of monostearyl phosphates or phosphate esters

Ί and high molecular weight hydrocarbon suds suppressors and mixtures thereof; wherein the composition is preferably characterized by a weight ratio of alkylalkoxylated sulfate polyhydroxy fatty acid amide of about 10 = 1 to about 1:10, preferably about 5 = 1 to about 1 = 5, most preferably from about 4 ^: 1 to about 1: first

Preferred alkylalkoxylated sulfate surfactants are alkyl ethoxylated sulfates having a degree of ethoxylation ranging from about 0.5 to about 6.

In another aspect, the present invention provides detergent compositions comprising alkyl ethoxylated sulfate surfactants and polyhydroxy fatty acid amides as described above wherein R ¹ is methyl, R ² is C 1 -C 17 alkyl or alkenyl, Z is glycityl derived from a reducing sugar, or an alkoxylated derivative thereof, and the polyhydroxy fatty acid alkylethoxylated phosphate-amide phosphate ratio is from about 1 = 1 to about 4 = 1, preferably about 3 ^: 1.

In a further aspect of the invention, there are provided detergent formulations of amine polyhydroxy fatty acids with alkylalkoxylated (preferably ethoxylated) sulfate surfactants as described above. further comprising a co-surfactant selected from alkyl sulfates, alkyl sulfonate esters, alkyl phenolalkoxylates, alkylbenzenesulfonates, alkyl ethoxylates, mixtures. Preferably, up to about 25% of paraffin sulfonates and alkyl polyglycosides and their surfactant are from about 1% by weight of the detergent composition. Additional surfactant adjuvants may be present in addition to the detergent composition, as well as optional detergent ingredients and other ingredients known in the art or otherwise desirable for inclusion in detergent compositions.

As mentioned above, the present invention provides a reduced sudsing detergent composition comprising a polyhydroxy fatty acid amide surfactant.

of the general formula □ I I R ¹ | 1 1 R ² -C ~ 1 N ~ Z

C1-Cahydrocarbyl, is C5-C31 having directly derivatives;

and wherein R ¹ is H, 2-hydroxypropyl, R ² polyhydroxyhydrocarbyl, with at least 3 hydroxyls, or an alkoxylated surfactant thereof;

suds suppressors. comprising monocarboxylic silicone suds suppressors and monostearyl phosphates, or preferably a weight ratio of polyhydroxy fatty acid, preferably from about 1 = 5 to about 1-1. Preferably also an alkylethoxylated sulfate ethoxylation greater than 0.5, from about 0.5 to about 3.

2-hydroxyethyl or hydrocarbyl and Z is a linear hydrocarbyl chain attached to this chain, an alkylalkoxylated sulfate foam suppressant preferably selected from the group of fatty acids and their salts, foaming and hydrocarbon substances, alkali metal di-salts with phosphate esters and mixtures thereof, sulfates to amides up to about 1:10, from about 4 ^: 1 to sulfate comprises having step 6. preferably a

or and the alkylated alkoxylated is from about 10: 1 to about 5: 1, even more preferably the alkylated alkoxylated surfactant, typically from about 0.5 to about 5: 1.

In a particularly preferred embodiment, R ^{1 is} methyl. R ² is C 1 -C 17 alkyl or alkenyl and Z is glycityl derived from a reducing sugar or an alkoxylated derivative thereof and the ratio of the alkyl 1-ethoxylated sulfate surfactant to the polyhydroxy fatty acid amide is from about 4 = 1 to about 1 = 1.

The individual components are described in more detail below.

Polyhydroxy fatty acid amide surfactants

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

The polyhydroxy fatty acid amide surfactant component of the present invention includes compounds of Formula I

R ¹

I

R ² -C CN 2 Z (I) wherein R ¹ is H, C 1 -C 4 hydrocarbyl. 2-hydroxyethyl, 2-hydroxypropyl, or a mixture thereof, preferably C 1 -C 1 alkyl, more preferably C 1 or C 2 alkyl, most preferably C 1-6 alkyl (ie methyl), and R ² is C 5 -C 31 hydrocarbyl, preferably straight chain alkyl or alkenyl of 7 to 19 atoms and Z is a polyhydroxyhydrocarbyl having a linear hydrocarbyl chain with at least 3 hydroxyls directly attached thereto, or an alkoxylated (preferably ethoxylated or propoxylated) derivative thereof. . Z preferably will be derived from a reducing sugar in a reductive amination reaction; preferably Z is glycityl. Suitable reducing sugars include glucose, fructose, maltose, lactose, galactose, mannose, and xylose. As raw materials, high dextrose cereal syrup, high fructose cereal syrup and high maltose cereal syrup, as well as the individual sugars mentioned above, may be used. These cereal syrups may provide a mixture of Z sugar components. However, it should be noted that the use of other suitable raw materials is not excluded at all. Z preferably will be selected from the group consisting of _-CH2 - (CHOH) n -CH ₂ OH, -CH _(CH2 OH) - (CHOH) CH ₂ add-OH, -CH2- (CH0H) 2 (CH0R ') ( CH 2 H -CH 2 OH, wherein n is an integer from 3 to 5 inclusive and R 1 is H or a cyclic or aliphatic monosaccharide and its alkoxylated derivatives. Most preferred are glycityls wherein n is 4, especially -CH ₂ (CHOH) 4-CH ₂ OH.

In formula I, R ¹ can be, for example, N-methyl, N-ethyl, N-propyl, N-isopropyl, N-butyl. Ν-2-hydroxyethyl or Ν-2-hydroxypropyl.

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

Z can be

1-deoxyglucyl 1,

2-deoxyfruktity1,

1-deoxyma11 and ty1,

1-deoxygalactites 1,

1-deoxymannity1,

1-deoxymethyl tert-butyl, etc.

Methods for making polyhydroxy fatty acid amides are known in the art. In general, they can be made by reacting an alkylamine with a reducing sugar in a reductive amination reaction to form the corresponding N-alkyl polyhydroxyamines, and then reacting the N-alkyl polyhydroxyamine with a (aliphatic) fatty acid ester or triglyceride in the condensation / amidation step. to form an N-alkyl, N-polyhydroxy fatty acid amide. Methods for making compositions containing polyhydroxy fatty acid amides are described, for example, in GB patent specification.

no. 809060, published

18th

February 1959, Thomas Hedley and Co.,

Ltd., U.S. Pat.

2965576, issued December 20, 1960,

E.R. Wilson and U.S. Pat

2,703,798th

Anthony M. Schvartz, issued March 8, 1955 and US patent

1985424, issued December 25, 1934,

Piggott, which are incorporated herein by reference.

In a preferred process for preparing amides of N-hydroxyalkyl.

N-deoxyglycityl fatty acids, wherein the glycityl component is derived from glucose and

The N-alkyl or N-hydroxyalkyl function is N-methyl,

N-ethyl, N-propyl, N-butyl, N-hydroxyethyl or N-hydroxypropyl, the product is produced by the reaction of N-alkyl- or

N-hydroxyalkyl glucamine with a fatty acid ester selected from the group consisting of fatty acid methyl ester, fatty acid ethyl ester and fatty acid triglycerides in the presence of a catalyst selected from the group consisting of lithium phosphate, sodium phosphate, potassium phosphate, sodium pyrophosphate, pentasodium tripolyphosphate, lithium hydroxide, sodium hydroxide, potassium hydroxide, calcium hydroxide, lithium carbonate. sodium carbonate, potassium carbonate, potassium tartrate, sodium potassium tartrate, trisodium citrate, basic sodium silicates, basic potassium silicates, basic sodium aluminosilicates and basic potassium aluminosilicates, and mixtures thereof. The amount of catalyst is preferably from about 0.5 mol% to about 50 mol%, preferably from about 2.0 mol. % to about 10 mol. % based on mol of N-alkyl or N-hydroxyalkyl-glucamine. The reaction is preferably carried out at a temperature of from about 138 ° C to about 170 ° C, typically from about 20 to about 90 minutes. When triglycerides are used as the source of a fatty acid ester in the reaction mixture, the reaction is also preferably carried out using about 1 to 10 wt. % of a phase transfer agent based on the total reaction mixture and expressed as a percentage by weight selected from the group consisting of saturated fatty alcohol polyethoxylates, alkyl polyglycosides, linear glycamide surfactants and mixtures thereof.

Preferably, this process is carried out as follows;

(a) preheating the fatty acid ester to about 138 ° C to about 170 ° C;

b) N-alkyl or N-hydroxylglucamine is added to the preheated fatty acid ester and mixed to the extent necessary to form a biphasic liquid / liquid mixture;

c) mixing the catalyst into the reaction mixture; and

d) the mixture is stirred for the necessary time.

Preferably, from about 2% to about 20% of the preformed linear N-alkyl / N-hydroxyalkyl, N-linear glucosyl fatty acid amide is also added to the reaction mixture, based on the weight of the reactants, as a phase transfer agent when the fatty acid ester is triglycerld. In this way, the reaction mixture is seeded and the reaction rate is clearly increased. Specific experimental embodiments are set forth in the Examples below.

The polyhydroxy fatty acid amides used herein provide advantages for detergent formers in that they can be prepared wholly or primarily from natural renewable raw materials and that they are degradable. They also show low aquatic life toxicity.

It should be noted that together with the polyhydroxy fatty acid amides of formula I, non-volatile by-products such as ester amides and cyclic polyhydroxy fatty acid amide are also typically formed in their production processes. The level of these by-products will vary depending on the reagents used and the process conditions. Preferably, the polyhydroxy fatty acid amide incorporated into the detergent compositions of the invention will be used in such a form that the composition comprising the polyhydroxy fatty acid amide added to the detergent comprises less than 10% and preferably less than 4% cyclic polyhydroxy fatty acid amide. . The preferred processes described above are advantageous in that they yield low by-product yields, including such cyclic amide by-products.

about

Alkylalkoxylated sulphates.

The alkylalkoxylated sulfate surfactants used herein are the water-soluble acid salts of the formula

R0 (A) _m SO 3 M, where

R is an unsubstituted C 10 -C ₂₄ alkyl or hydroxyalkyl group having a C 10 -C 24 alkyl component, preferably C 12 -C 20 alkyl or hydroxyalkyl, more preferably C 14 -C 18 alkyl or hydroxyalkyl, A is an ethoxy or propoxy unit, m is greater than zero, typically between about 0.5 and about 6 more preferably between

0.5 and about 3 and M is or a cation, which may be, for example, a metal cation (e.g.

sodium, potassium.

lithium, calcium, magnesium 4, etc.), ammonium or substituted ammonium cation

There are alkylpropoxylated contemplated alkyl ethoxylated sulfates i

Specific examples of substituted ammonium cations include methyl, dimethyl, trimethylammonium and quaternary ammonium cations such as tetramethylammonium, dimethylpiperidinium, and alkanolamine-derived cations, e.g. monoethanolamine, diethanolamine and triethanolamine and mixtures thereof. Examples of surfactants are C12-C 1-6 alkylpolyethoxylate (10) sulfate, C12-C10 alkyl polyethoxylate (2.25) sulfate, C12-C 1-6 alkylpolyethoxylate (3.0) sulfate, and C12-C 1-6 alkylpolyethoxylate (4.O) sulfate, where M is usually selected from the group of sodium and potassium.

Foaming suppressors

The compounds known or suppressed the formation of foam according to the invention. The inclusion of suds suppressors, will be amide-based active substances or will be known, for reduction, may be included in formulations of such materials - agents desirable here, since surface polyhydroxy fatty acids may increase foam stability of the detergent composition. a relatively high sudsing surfactant in combination with a polyhydroxy fatty acid amide surfactant. Foam suppression is particularly useful in automatic washing machines.

desirable for preparations for

These washing machines are typically characterized by having laundry and washing water drums having a horizontal axis and rotating about it. This type of mixing can lead to high foam formation and, as a result, to reduced cleaning performance.

The use of suds suppressors may also be particularly important in hot water wash conditions and high surfactant concentration conditions.

As reagents.

foam suppressors, various materials can be used: those skilled in the art are suds suppressors well known. For example, they are described in Kirk

Othmer

Encyclopedia of

Chemical Technology Third Edition.

7, p.

430-447 (John

Viley and Sons

IRIC., 1979). One category of suds suppressors.

is particularly interesting and includes monocarboxylic fatty acids and soluble salts thereof. These materials are discussed in the US patent

2954347 vydanom

27th

September which iterary

1960, Vayne John, legacy. Monocarboxylic fatty acids and is included herein as use as suds suppressors.

salts thereof, typically have hydrocarbyl chains of 10 to about 24 carbon atoms, preferably 12 to 18 carbon atoms. Suitable salts include alkali metal salts such as sodium, potassium or lithium salts and ammonium and alkanolammonium salts. These materials represent a preferred category of suds suppressors for detergent compositions.

The detergent compositions may also contain agents.

suds suppressors, which are not surfactants.

These include, for example:

high molecular weight hydrocarbons such as paraffins, fatty acid esters (e.g. triglycerides of fatty acids), fatty acid esters of monohydric alcohols, aliphatic C18-C40 ketones (e.g.

triglycerides of fatty acids), stearate, etc. Other aminotriazine inhibitors, such as tri- to tetra-alkyldiaminochlorotriazines, cyanuric chloride with two or aliphatic C18-C40 ketones (e.g. foaming include N-alkylated hexa-alkylmelamines or di-to formed as products of three moles of a primary or secondary amine containing i to 24 to 24). carbon atoms, propylene oxide monostearyl phosphates such as monostearyl alcohol phosphate ester and monostearyl di-alkali metal (e.g.

Na, K, Li) phosphates and phosphate esters.

In liquid form, hydrocarbons such as paraffins and halogen paraffins can be used. Liquid hydrocarbons will be liquid at room temperature and atmospheric pressure, and will have a freezing point of between about -40 ° C and about

5 ° C and a minimum boiling point of not less than about 110 ° C (atmospheric pressure). It is also known to use waxy hydrocarbons, preferably those 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. Patent No. 4,265,770, issued May 5, 1985 to Gandolfo et al., Which is incorporated herein by reference. Hydrocarbons include aliphatic, alicyclic.

aromatic and heterocyclic saturated or unsaturated hydrocarbons having from about 12 to 70 carbon atoms. The term "paraffin" as used herein includes mixtures of genuine paraffins and cyclic hydrocarbons.

Another preferred category of suds suppressors includes silicone suds suppressors. This category includes the use of polyorganosiloxane oils.

such as polydimethylsiloxane, dispersions or emulsions of polyorganosiloxane oils or resins, and combinations of polyorganosiloxanes with silica particles, wherein the polyorganisiloxane is chemisorbed or fused to silica. Silicone-based suds suppressors are well known in the art, and are described, for example, in U.S. Patent 4,265,779, issued May 5, 1981 to Gandolfo et al., And European Patent Application Ser. 89307851.9, published Feb. 7

1990, Starch M.S., both of which are incorporated herein by reference.

Other silicone-based suds suppressors are disclosed in U.S. Pat. No. 3,455,839, which relates to compositions and methods for defoaming aqueous solutions by incorporating small amounts of polydimethylsulfoxide fluids.

Mixtures of silicones and silanated silica are described e.g. in German Patent Application DOS 2124526. Si icon antifoams and foam control agents in granular detergent compositions are described in U.S. Patent 3,933,672 to Bartolotta et al. and U.S. Patent 4,652,392 to Baginski et al. issued March 24, 1987.

An example of an anti-suds suppressor based on an icon of the amount of a suds suppressor that is essentially formed &quot;

(a) a polydimethylsiloxane liquid having a viscosity of from about cs to about 1500 cs at 25 ° C;

b) from about 5 to about 50 parts per 100 parts by weight of (i) a siloxane resin consisting of <CH 3> 3 SiO 2/2 units, wherein SiO 2 units relative to (CH 3) 3 SiO 2/2 units and S 1 O 2 from about 0. 6 = 1 to about 1.2 = 1 and

c) from about 1 to about 20 parts per 100 parts by weight of (xi) solid silica gel.

For any detergent composition that is used in automatic washing machines, the foam should not be formed in excess and thus flow from the washing machine. The suds suppressors, when used, are preferably present in a suds suppressing amount. “A foam-suppressing amount. it is intended that in the formulation it is possible to select an amount of this foam control agent so that the detergent composition will control sufficiently the foam formation and result in low foaming for use and automatic washing machines.

The amount of suds control agent will vary according to the detergent surfactant selected. For example, for high sudsing surfactants, relatively more suds control agent is used to achieve the desired suds control. than a less foaming surfactant. Generally, such an amount of suds suppressor should be incorporated into the suds suppressor detergent compositions that the foam that is formed during the wash cycle in an automatic washing machine (i.e., as the detergent is stirred in an aqueous solution at a certain temperature and concentration) does not exceed about 75 % of the void volume of the washing drum, preferably the foam will not exceed about 50% of said void volume, wherein the void volume is determined as the difference between the total volume of the drum and the volume of water plus laundry.

When monocarboxylic fatty acids and salts thereof are used as a suds suppressor, they will typically be present in amounts up to about 5% by weight of the detergent composition. From about 0.5% to about 3% of fatty monocarboxylate antifoams are generally used. Anti-foaming iconic agents are typically used in amounts up to about 2.0% by weight of the detergent composition, although higher amounts may be used. This upper limit is virtually natural, as it is obvious to minimize costs and use effective small amounts for effective suds suppression. Preferably, from about 0.01% to about 1% of a silicone-based suds suppressor is used, more preferably from about 0.25% to about 0.5%. These percentages include any silicas which may be used in combination with polyorganosiloxanes, other materials may be used. Hydrocarbon suds suppressors are typically used in amounts ranging from about 0.01% to about 5%, although higher levels can also be used. Monostearyl phosphate antifoams are typically used in amounts of from about 0.1 to about 2% by weight of the compositions.

In another aspect of the present invention, there is provided a detergent composition comprising the polyoxyethylated sulfate surfactants as described above and polyhydroxy fatty acid amides such as

R ² is C 9 -C 17 alkyl or wherein R ¹ is methyl, alkenyl, preferably

C 11 -C 17 alkyl or alkenyl, Z is a glycityl derived from a reducing sugar, or an alkoxylated derivative thereof, and the ratio of alkylethoxylated sulfate to polyhydroxy fatty acid amide is from about 1.25 ^: 1 to about 1 ^: 4, preferably from about 1.25: 1 to 1 1,25.

The most preferred polyhydroxy fatty acid amides are described above.

In another aspect of the present invention, detergent compositions of polyhydroxy fatty acid amides and alkylalkoxylated (preferably ethoxylated sulfates) surfactants as described above are further provided, further comprising an auxiliary surfactant selected from other nonionic surfactants selected from the group consisting of: including alkyl ethoxylates, alkylphenolalkoxylates (preferably ethoxylates) and alkyl polyglycosides (preferably alkyl polyglycosides). The ratio of polyhydroxy fatty acid amides to the other nonionic surfactant is from about 1 = 10 to about 10 = 1 / preferably about 1 = 5 to about 5 = 1. Other surfactants may also be added. The most commonly used include, but are not limited to, alkyl sulfates, alkyl ester sulfonates, alkylbenzenesulfonates. paraffin sulphonates and mixtures thereof. Preferably, the auxiliary surfactant comprises from about 1% to about 25% by weight of the detergent composition. Further, adjuvants may be present in the detergent compositions as well as optionally detergent ingredients and other ingredients known in the art or otherwise desirable for incorporation into detergent compositions. Preferred polyhydroxy fatty acid amides, alkylalkoxylated sulfates, and surfactants in the proportions described above are preferred in each aspect of the invention.

Anionic auxiliary surfactants

Anionic auxiliary surfactants suitable for cleaning purposes may also be incorporated into said compositions. these

substances can also include salts (including, for example, sodium. potassium, ammonium and substituted ammonium salts such as nono-, di- and triethanolamine salts of soaps, C9-C20 linear

alkylbenzenesulfonates, primary or secondary alkanesulfonates,

Cs-C24-olefin sulfonates.

sulfonated polycarboxylic acids prepared by sulfonating the pyrolysis product of alkaline earth metal citrates, e.g. as described in British Pat. 1082179, alkylglycerol sulfonates, fatty alkylglycerol sulfonates, oleyl glycerol sulfonates, alkylphenolethylene oxide ether sulfates, paraffin sulfonates. alkylphosphates, isothionates such as acylisethionate. N-acy1tauráty. methyltauride fatty acid amides, alkyl succinates and sulfosuccinates, sulfosuccinate monoesters (especially saturated and unsaturated C12-Cieraonoesters), sulfosuccinate diesters (especially saturated and unsaturated C 6 -C 14 diesters), alkyl sulfates such as sulfosuccinates, sulfonates such as sulfosuccinates; (described below).

branched primary alkyl sulfates, alkyl polyethoxycarboxylates such as those. that have the formula

RO (CH 2 CH 2 O) k CH 2 COO-M ⁺ , where

R is C 8 -C 22 alkyl, k is an integer from 0 to 10, and M is a cation forming a soluble salt and fatty acids esterified with isethionic acid and neutralized with sodium hydroxide. Resin acids and hydrogenated resin acids are also suitable, for example, rosin. hydrogenated rosin and bituminous acids present in or derived from body oil. Further examples are described in "Surface Active Agents and Detergents" (Volume I and II, Schvartz, Perry and Berch). Various such surfactants are also generally described in U.S. Pat. 3929678, issued i

On December 30, 1975 to Laughlin et al., Column 23, line 58 through column 29, line 23 (cited herein as a reference).

The alkylsulfate surfactants are water-soluble salts or acids of formula ROSO3M, wherein R is preferably C10-C24 hydrocarbyl, preferably alkyl or hydroxyalkyl, having a C10-C20 alkyl component, preferably a C12-C18 alkyl or hydroxyalkyl component, and M is H or a cation, e.g. an alkali metal cation (e.g., sodium, potassium, lithium), substituted or unsubstituted ammonium cations such as methyl, dimethyl, trimethylammonium, and quaternary ammonium cations e.g. tetramethylammonium and dimethylpiperidinium; and cations derived from alkanolamines such as ethanolamine, diethanolamine, triethanolamine and mixtures thereof, and the like. Typically, C12-C16 alkyl chains are preferred for lower wash temperatures (e.g., below about 50 ° C and C 1 -C 6 alkyl chains are preferred for higher wash temperatures (e.g., above about 50 ° C).

Alkylbenzenesulfonic surfactants are well known in the art. These surfactants have C9 and higher alkyl groups, preferably linear alkyl groups, to provide a class of linear alkylbenzene sulfonates (LAS) of commercially available surfactants. These surfactants can be used either in the form of an acid or a soluble salt, preferably a soluble salt form. Suitable salts include metal salts (e.g., sodium, potassium, and lithium) as well as substituted and unsubstituted ammonium salts such as those which have been as previously described for alkyl sulfate salts.

Alkyl ester sulfonate surfactants include linear esters of C8-C20 carboxylic acids (i.e. fatty acids) which are sulfonated with SO3 gas according to The Journal of the American Oil Chemists Society, 52 (1975), p. 323-329. Suitable starting materials include natural fatty substances derived from tallow, palm and coconut oil, etc.

Preferred alkyl ester sulfonate surfactants.

in particular for washing machine applications, alkyl ester sulfonate surfactants of the general formula zahŕňajú

R ³ -CH-C-OR ⁴

I

SO ₃ M wherein R ³ is C 6 -C 20 hydrocarbyl, preferably alkyl or combinations 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 salt-forming cations include metal cations such as sodium, potassium and lithium, and substituted or unsubstituted ammonium cations such as methyl, dimethyl, trimethyl and quaternary ammonium cations, e.g. tetramethylammonium and dimethylpiperidinium; and cations derived from alkanolamines, e.g. monoethanolamine, diethanolamine and triethanolamine. Preferably R ^{3 is C} 10 -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.

In addition, other nonionic surfactants can be added to the anionic surfactants and incorporated into the compositions.

Nonionic auxiliary surfactant detergents

Suitable nonionic detergent surfactants are generally disclosed in U.S. Pat. No. 3,929,668, Laughlin et al., Issued December 30, 1975, at column 13, line 6, which is incorporated herein by reference. Examples of classes of useful nonionic surfactants are given below, but are not limited to these examples.

Polyethylene, polypropylene and polybutylene oxide condensates of alkylphenols. Generally, polyethylene oxide condensates are preferred. These compounds include the condensation products of alkylphenols having an alkyl group of about 6 to 12 carbon atoms or in a straight or branched chain with alkylene oxide. In a preferred embodiment, the ethylene oxide is present in an amount of from about 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 CAF Corporation, and Triton ™ X-45. X-114, X-100 and X-102, all supplied by the Rohm and Haas Company. These surfactants are commonly referred to as alkylphenolalkoxylates, e.g. alkylphenoxyethoxy.

2. The condensation products of aliphatic alcohols with about 1 to 25 moles of ethylene oxide. The alkyl chain of the aliphatic alcohol may be straight or branched, primary or secondary, and typically contains about 8 to about 20 carbon atoms. Particularly preferred are the condensation products of alcohols having an alkyl group containing about 10 to about 20 carbon atoms with about 2 to about 18 moles of ethylene oxide per mole of alcohol. Examples of commercially available nonionic surfactants of this type include Tergitol ™ 15-S-9 (Cn-C 18 linear secondary alcohol condensation product and 9 moles of ethylene oxide), Targitol ™ 24-L-6

NMV (condensation product of C12-C14 primary alcohol with 6 moles of narrow molecular weight ethylene oxide), both manufactured by Union Carbide Corporation, Neodol ™ 45-9 (condensation product of C14-C15 linear alcohol with 9 moles of ethylene oxide), Neodol ™ 23- 6.5 (condensation product of C12-C31 linear alcohol with 6.5 moles of ethylene oxide), Neodol ™ 45-7 (condensation product of C14-C151 linear alcohol with 7 moles of ethylene oxide), Neodol ™ 45-4

4 mol C14-C151 linear alcohol supplied by Shell Chemical (condensation product of C13-Cisalcohol (condensation product of ethylene oxide), marketed

Company, and Kyro ™ E0B and 9 moles of ethylene oxide).

supplied by The Procter and Gemble Company. These nonionic surfactant forms are commonly referred to as

3. The condensation products of ethylene oxide with a hydrophobic base formed by condensation of propylene oxide with propylene glycol. The hydrophobic portion of these compounds preferably has a molecular weight of from about 1500 to about 1800 and is insoluble in water. The addition of polyoxyethylene groups to this hydrophobic moiety increases the aqueous solubility of the molecule as a whole and maintains the liquid nature of the product to a point where the polyoxyethylene content is about 50% of the total weight of the condensation product, corresponding to the condensation of up to about 40 moles ethylene oxide. Examples of compounds of this type include certain commercially available Pluronic ™ surfactants available from BASF.

4. Condensation products by reaction of propylene oxide ethylene oxide with the product formed and ethylenediamine. The hydrophobic group of these products consists of reaction and excess propylene oxide and generally has an ethylenediamine product having a molecular weight of from about 2500 to about 3000.

This hydrophobic group is condensed with ethylene oxide so.

wherein the condensation product comprises from about% to about 80 wt. polyoxyethylene and has a molecular weight of from about 5000 to about 11000. Examples of this type of nonionic surfactant include certain commercially available Tetronic ™ compounds available from BASF.

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

Semi-polar nonionic detergent surfactants include amino oxide surfactants of the formula

R ³ (OR ⁴ ) _X N (R ⁵ > 2 wherein R ³ is alkyl, hydroxyalkyl or phenyl or a mixture thereof containing from about 8 to about 22 carbon atoms. R ⁴ is an alkylene or hydroxyalkylene group containing from about 2 to and having 3 oxygen atoms or mixtures thereof, x has a value of up to about

3, and each R ⁵ is an alkyl or hydroxyl 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.

R 1 groups can be linked to each other e.g.

via an oxygen or nitrogen atom to form a ring structure.

These amine oxide surfactants preferably include

Clo-C18 alkylamine and nooxides

C8-C12 alkoxyethyldihydroxyethyl amine oxides.

6. Alkylpolysaccharides described

US Patent 456567

Llenado issued on 21.

January 1986, having a hydrophobic group containing from about 6 to about carbon atoms, preferably from about to about carbon atoms, and a polysaccharide such as polyglycoside, a group that is hydrophobic, contains from about

1.3 to about

2.7 carbohydrate units

Any reducing carbohydrate may be used.

containing or 6 carbon atoms, for example glucose, galactose and galactose groups, may replace glucose groups.

(Alternatively, the hydrophobic group is attached at 2-,

3-, 4-, etc. to yield glucose or galactose as opposed to glucoside or galactoside). The intersaccharide linkages may be e.g. between one position of the other saccharide units and the 2-, 3-, 4a / or 6-positions of the preceding saccharide units.

Alternatively, but less desirable, there may be a polyalkylene oxide chain linking the hydrophobic group and the polysaccharide group. The preferred alkenyl oxide is ethylene oxide. Typical hydrophobic groups include alkyl groups, either saturated or unsaturated, branched or unbranched, containing about 8 to 18, preferably 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 hydroxy groups and / or the polyalkylene oxide chain may contain up to about 10, preferably less than 5, alkylene oxide groups. Suitable alkylpolysaccharides are octyl, nonyldecyl, undecyldodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl and octadecyl, di-, tri-.

tetra-, penty-.

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 alkyl polyglycosides have the formula

R ² 0 (CnH2n0) t (glycosyl) x wherein ^R2 is selected from the group consisting of alkyl, alkylphenyl, hydroxyalky1, hydroxyalkylfeny1 and mixtures thereof in which alkyl groups contain from about 10 to about 18, preferably about 12 to about 14 carbon n is 2 or 3, preferably 2, t is from 0 to 10, preferably 0 and x is from about 1.3 to about 10, preferably from about 1.3 to about 3, most preferably from about 1, 3 to 2.7. The glycosyl is preferably derived from glucose. To prepare these compounds, an alcohol or an alkylpolyethoxy alcohol is first formed and then reacted with glucose, or a source of glucose, to form a glucoside (attachment at position 1). Further glycosyl units may then be attached between their 1-position and the 2-, 3-, 4-, and / or 6-, preferably 2-, position of the preceding glucose units.

7. Fatty acid amide surfactants have the formula

Ο

R 6 "C" N (R ⁷ > 2) wherein R ⁶ 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 hydrogen, alkyl,

C 1-4 -hydroxyalkyl and - (C 2 H 4 O) x H, wherein x varies from about 1 to about 3.

Preferred amides are C 5-20 ammonium amides, monoethanolamides, diethanolamides and isopropanolamides.

Cationic surfactants

Cationic surfactants can also be included as auxiliary surfactants in the detergent compositions of the invention.

Cationic surfactants include ammonium surfactants such as alkyldimethylammonium halides and surfactants having the formula (R ² (OR ³ ) (R ³ ) y ₎ R ² N ⁺ X - wherein R ² is alkyl or alkylbenzyl a group having from about 8 to about 18 carbon atoms in the alkyl chain, each R ³ is selected from the group consisting of -CH 2 CH 2 -, -CH 2 CH (CH 3) -, -CH 2 CH (CH 2 OH) -, -CH 2 CH 2 CH 2 - and mixtures thereof , each R ⁴ is selected from the group consisting of C 1 -C 4 alkyl, C 1 -C 6 hydroxyalkyl, benzyl, a ring structure formed by joining two R ⁴ groups, -CH 2 CHOH-CHOHCOR ⁶ CHOHCH ² OH. where R ⁶ is any hexose or hexose polymer having a molecular weight of less than about 1000. and hydrogen when v is not R, R ⁵ is the same as R ⁴ or is an alkyl chain where the total number of carbon atoms R ² plus R ⁵ is not is greater than about 18, each y is from 0 to about 10 and the sum of the y values is from 0 to about 15 and X is any compatible cation.

Other cationic surfactants are also described in U.S. Pat. No. 4228044, Cambre, issued October 14, 1980, which is incorporated herein by reference.

substances of preparations may be incorporated substances. These surfactants are described as aliphatic derivatives of amines or aliphatic derivatives of tertiary amines in which it is branched. One of the aliphatic about 8 carbon atoms, typically from at least one, contains anionic carboxy, sulfonate, sulfate. Laughlin et al., Issued May 30, 18-35 (incorporated herein as a literary ampholytic surfactant).

Other auxiliary surfactants

The detergent ampholytic surfactants are, in a broad sense, secondary or tertiary heterocyclic secondary, and the aliphatic radical or substituents contains at least about 8 to about 18 carbon atoms and a water-soluble group, e.g. See U.S. Pat. No. 3929678, December 1975, column 19, line reference) for examples of substances.

Zwitterionic surfactants can be incorporated into the detergent compositions of the invention. These surfactants are broadly described as derivatives of secondary tertiary secondary tertiary amines, derivatives of heterocyclic derivatives of quaternary amines or ammonium, quaternary phosphonium or tertiary sulfonium compounds. See U.S. Patent et al., Issued December 30, 1975. Column 19,

no. 3929678, Laughlin row 38 through column

22, line 48 (incorporated herein by reference) for examples of zwitterionic surfactants.

Ampholytic surfactants and zwitterionic surfactants are typically used in combination with one or more anionic and / or nonionic surfactants.

Activating agents

Detergents The compositions of the present invention may contain inorganic or organic detergent builders to assist in controlling mineral hardness. The level of the builders varies widely depending upon the end use of the formulation and its desired form. Liquid formulations typically contain at least about 1%, more typically from about 5% to about 50%, preferably about 5% to about 30%, by weight of the detergent activator. Granular compositions typically comprise at least about 1%, more typically from about% to about 80%, preferably from about 15% to about 50% by weight of the detergent activator. However, this does not exclude lower or higher levels of the activating agent.

Inorganic activating agents include, but are not limited to, alkali metal salts, ammonium and alkaloammonium salts of polyphosphates and glassy polymeric metaphosphates), phytic acids, silicates, carbonates, bicarbonates, and sesquiches carbonates).

and aluminum phosphates.

Examples of alkali metal silicate activators, especially those having a ratio in the range of 1.6 = 1 to 3.2 = 1, and layered silicates such as sodium silicates, described in U.S. Pat. 4664839, issued May 12, 1987 to H.P. Réck, cited herein as a literary reference for completeness. However, other silicates may also be used, such as magnesium silicate, which may serve as a beading agent in granular formulations, as a stabilizing agent for oxygen bleaches, and as a component of the foam control system.

phosphonates (including sulphates and silicates with SiO 2 = Na 2 O are layered

Examples of carbonate activators are metal and alkaline earth and alkali metal carbonates, including sodium carbonate and sodium sesquicarbonate, and mixtures thereof with ultrafine calcium carbonate, as described in DE-patent application no. No. 231001, published Nov. 15, 1973, cited herein for the sake of completeness as a 1 and tertiary reference.

Alumina activate additives are particularly useful in the present invention. Aluminosic activating agents are very important in the most commonly available granular detergent formulations and may also be an essential activating component in liquid detergent formulations. Aluminosic activating agents include those having the empirical formula ^:

M _z (from AlO 2 -ySiO 2>

where M is sodium, potassium, ammonium or substituted ammonium substituent z is from about 0.5 to about 2 and Y is 1; it has such a material ion-exchange a magnesium capacity of at least about 50 milligrams eq CaCO 3 hardness per gram of anhydrous aluminosilicate.

Preferred aluminosilicates are zeolite activators having the formula

For _z / (A102) _of SiO2 / - XH2O where after Y are integers of at least 6, the molar ratio of z to y ranges from 1.0 to about 0.5 and x is an integer from about 15 to about 24.

Suitable aluminosilicate ion exchange materials are commercially available. These aluminosilicates may be crystalline or have an amorphous structure and may be aluminosilicates from natural sources or synthetic. A method for preparing aluminosilicate ion exchange materials is described in U.S. Patent 3,956,569, Krummel et al., Issued October 12, 1976, which is incorporated herein by reference in its entirety. Preferred synthetic crystalline aluminosilicate ion exchange resins useful in the present invention are available under the designation Zeolite A, Zeolite P (B) and Zeolite X. In a particularly preferred embodiment. have crystalline aluminosilicate ion exchange materials of the formula ^:

Where x has a value of from about 20 to about 30, in particular about 27. This material is known as Zeolite A. Preferably, the particles and the luminosity have a particle size of from about 0.1 to about 30 to about 30 to about 30. 10 micrometers in diameter.

Specific examples of polyphosphates are alkali metal tripolyphosphates, sodium, potassium and ammonium pyrophosphate, sodium and potassium orthophosphate, sodium polymetaphosphate having a degree of polymerization ranging from about 1 to about 21, and phytic acid salts.

Examples of phosphonate activating salts are the water-soluble salts of ethane-1-hydroxy-1,1-diphosphonate, especially the sodium and potassium salts, the water-soluble salts of methylenedisphonic acid, e.g. trisodium and trisodium salts and water-soluble salts of substituted methylenediphosphonic acids, such as trisodium and trisodium salts of ethylidene, isopropylidene, benzylmethylidene and halomethylidene phosphonates. Phosphonate activating salts of the aforementioned types are described in U.S. Patent Nos. 3159581 and 321030, issued December 1, 1964 and October 19, 1965, to Diehl, U.S. Pat. No. 3422021, issued Jan. 14, 1969. Roy and U.S. Pat. Nos. 3400148 and 3422137, issued September 3, 1968 and January 14, 1969, Quimby, the disclosures of which are herein incorporated by reference. Organic detergent builders suitable for the purposes of the present invention include, but are not limited to, a large number of polycarboxylate compounds. As used herein, polycarboxylates are compounds having multiple carboxylate groups, preferably at least 3 carboxylates.

Polycarboxylate activators may generally be added to the formulation in acid form, but may also be added in the form of a neutralized salt. When used in the form of a salt, alkali metal salts, such as sodium, potassium, and lithium salts, especially sodium salts, or ammonium and substituted ammonium salts (e.g. alkanolammonium) are preferred.

Various categories of suitable materials are included among the polycarboxylate builders. One important category of polycarboxylate activators is ether polycarboxylates. A considerable number of ether polycarboxylates have already been described for use as detergent builders. Examples of suitable ether polycarboxylates include oxydisuccinates as described by Berg in U.S. Patent 3128287, issued April 7, 1964, and Lamberti et al., U.S. Patent 3635830, issued January 18, 1972, both of which are incorporated herein by reference.

A specific type of ether polycarboxylates useful as activating agents of the present invention also includes those having the general formula:

CH (A) (C00x) -CH (C00x) -0-CH (C00x) -CH (C00x) (B).

wherein A is H or OH, B is H or -O-CH (COOX) -CH ₂ (COOX) and XH or a salt-forming cation. For example, if in the above formula A and B are both H, then the compound is oxydisuccinic acid and its water-soluble salts. When A is OH and B is H, the compound is monosuccinic acid tartrate (TMS) and its water-soluble salts. If A is H and B is -O-CH (COOX) -CH 2 (COOX), then the compound is disuccinic acid tartrate (TDS) and its water-soluble salts. Mixtures of these activating agents are particularly preferred for use in the present invention. Particularly preferred are mixtures of TMS and TDS in a weight ratio of TMS to TDS of from about 97 = 3 to about 20? 80. These activators are described in U.S. Patent 4,663,971, issued to Bush et al. May 5, 1987.

Suitable ether polycarboxylates also include cyclic compounds, particularly alicyclic compounds, as described in US Patent Nos. 3923679, 3835163, 4158635, 4120874 and 4102903, all of which are incorporated herein by reference for completeness.

Other suitable detergent builders include the ether hydroxy polycarboxylates of the formula

HO- / C (R) (COOM) -C (R) (COOM) -O / _n -H wherein M is hydrogen or a cation whose resulting salt is water-soluble, preferably an alkali metal, ammonium or substituted ammonium cation , n is about 2 to about 15 (preferably n is about 2 to about 10, preferably about 2 to about 4) and each R is the same or different and is selected from the group consisting of hydrogen, C1-4 alkyl or C1-4 substituted alkyl (preferably R is hydrogen).

Still other ether polycarboxylates include maleic anhydride copolymers with ethylene or vinyl methyl ether, 1.3,

5-trihydroxybenzene-2,4,6-trisulfonic acid and carboxymethylsuccinic acid.

Organic polycarboxylate builders also include various alkali metal salts, ammonium and substituted ammonium salts of polyacetic acids.

Examples of polyacetic acid activating salts are sodium, potassium.

lithium, ammonium and substituted ammonium salts of ethylenediamine amino tetraacetic acid and nitroacetic acid.

Also included are polycarboxylates such as mellitic acid, succinic acid, polymaleic acid, benzene-1,3,5-tricarboxylic acid, benzene pentacarboxylic acid, and carboxymethyloxysuccinic acid, and soluble salts thereof.

Citrate activating agents, e.g. citric acid and soluble salts thereof are polycarboxylate builders especially important for high performance liquid detergent compositions, but can also be used in granular compositions. Suitable salts include metal salts such as sodium, lithium and potassium salts as well as ammonium and substituted ammonium salts.

Other carboxylate activators include the carboxylated sugars described in US Patent 3723322 to Diehl. issued March 28, 1972, which is incorporated herein by reference.

Also suitable in the detergent compositions of the invention are 3,

3-Dicarboxy-4-oxa-1,6-hexadienoates and the compounds derived therefrom are described in U.S. Patent 4,566,984, Bush, issued Jan. 28, 1986. Suitable succinic acid activators include C5-20 alkyl succinic acids and salts thereof . A particularly preferred compound of this type is dodecylsuccinic acid. Alkyl succinic acids have the typical formula R-CH (COOH) CH2 (COOH), i. succinic acid derivatives wherein R is a hydrocarbon, e.g. C 10-20 alkyl or alkenyl, preferably C 12-16, or wherein R may be substituted with hydroxyl, sulfo, sulfoxy or sulfone substituents are all described in the aforementioned patents.

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

Specific examples of succinate activators include: lauryl succinate. myristyl succinate, palmityl succinate,

2-dodecenyl succinate (preferably), 2-pentadecenyl succinate and the like. Lauryl succinates are preferred activators of this class and are described in European Patent Application 86200690.5 / 0200263, published November 5, 1986.

Examples of suitable activating agents also include sodium and potassium carboxymethyloxymalonate, carboxymethyloxysuccinate, cis-cyclohexane hexacarboxylate, cis-cyclopentyl-tetracarboxylate, water-soluble polyacrylates (these polyacrylates having a molecular weight greater than about 2000 may also be effectively used) and a maleic anhydride copolymer with vinyl methyl ether or ethylene.

Other suitable polycarboxylates are the polyacetyl carboxylates described in U.S. Patent 4,144,226, Crutchfield et al.

1979, which is cited herein as a reference for completeness. These polyacetyl carboxylates may be prepared as such.

by contacting, under polymerization conditions, a glyoxylic ester of polymerization initiator. The resulting polyacetal carboxylate ester is then attached to chemically stable end groups to stabilize the polyacetal carboxylate to rapid depolymerization in an alkaline solution, converted to the corresponding salt, and added to the surfactant.

Polycarboxylate activating agents are also described in U.S. Patent 330867, Diehl, issued March 7, 1967, which is incorporated herein by reference.

Such materials include homoa copolymers of aliphatic carboxylic acids such as maleic itaconic acid.

mesacone fumar, aconitine.

citracone and methylene and ion.

Other organic activating agents known in the art can also be used. For example, monocarboxylic acids and soluble salts thereof having a long hydrocarbyl chain may be used. These also include materials commonly referred to as soaps. Chain lengths of C10-C20 are common. The hydrocarbyls may be saturated or unsaturated.

enzymes

Enzymes for a variety of purposes may also be included in detergent compositions, including stain removal based on proteins, sugars, or triglycerides, for example, to prevent the transfer of released dye. Enzymes that are incorporated into the compositions include proteases, mylases, lipases, celluloses, and peroxidases, as well as mixtures thereof. They may be of any suitable origin, such as from plant, animal, fungal and yeast sources. However, their choice is governed by various factors such as pH activity and / or stability optimum, thermostability, stability to active detergents, activating agents and the like. In this regard, bacterial or fungal enzymes such as bacterial amylases and proteases and fungal celluloses are preferred.

Suitable examples of proteases are subtilisins that can be obtained from particular strains and B. subtilis and B.icheniformis. Another suitable protease is obtained from a Bacillus strain having a maximum activity in the range of ph 8-12, developed and sold by Novo Indutries A / S under the registered trademark Esperase ¹¹ . The preparation of this enzyme and analogous enzymes is described in British patent no. 1243784 from Novo. Proteolytic enzymes suitable for the removal of protein-based stains are commercially available and include ALC AL ASE ™ and S AVIN ASE ™ from Novo Industries A / S (Denmark) and M AX AT ASE ™ from Internation 1 Bio-Synthetics, Inc. . (Netherlands).

Of interest in the category of proteolytic enzymes, especially for liquid detergent compositions, are enzymes referred to as Protease A and ProteaseB. Protease A and methods for its preparation are described in European Patent Application 130756, published January 9, 1985, which is incorporated herein by reference. Protease B is a proteolytic enzyme that differs from Protease A in that it has the leucine replaced by tyrosine at position 217 in its amino acid sequence. Protease B is described in European patent application no. No. 87303761.8, published Apr. 28, 1987, which is incorporated herein by reference. Methods for preparing Protease B are also described in European Patent Application 130756, Bott et al., Published Jan. 9, 1985, which is incorporated herein by reference.

Amylases include, for example, H-amylases obtained from a special strain of B-licheniformis, described in more detail in the description of British patent no. 1296839 (Novo), incorporated herein by reference. Amylotic proteins include, for example, RAPIDASE ™, International Bio-Synthetic, Inc. and TERMAMYL ™. Novo Industries.

Cellulases useful in the present invention include bacterial and fungal celluloses. Preferably these will have a pH optimum between 5 and 9.5. Suitable cellulases are described in U.S. Patent 4,435,307, Berbesgoard et al., Issued March 6, 1984, which is incorporated herein by reference, which discloses fungal cellulose produced by Humicola insolens. Suitable cellulases are also disclosed in GB-A-2075028. GB-A-2095275 and DE-OS 2247832.

Examples of such cellulases are cellulases produced by Humicola insolens (Humicola grisses var. Thermoidea, in particular humicola by DSM 1800, and cellulases produced by Bacillus N or cellulase 212 produced by a fungus belonging to the genus Acremonas and cellulase extracted from hepatopancreata Aurula molluscans).

Suitable lipase enzymes for detergent use include those produced by microorganisms of the Pseudomonas family, such as Pseudomonas stutzerl ATCC 19.19154, as described in British patent no. 1372034, which is incorporated herein by reference. Suitable lipases include those that exhibit a positive immunological cross-reaction with the lipase antibody produced by Pseudomonas fluorescences IAM 1057. This lipase and its method of purification have been described in Japanese Patent Application no. 53-20487. This lipase is available from Amano Pharmaceutical Co., Ltd., Nagoya, Japan under the trademark Lipase P Amano, hereinafter referred to as Amano-P. Such lipases of the present invention should exhibit a positive immunological cross-reaction with the Amano-P antibody, using the standard and well known Ouchterlony immunodiffusion procedure (Acta. Med. Scan., 133, 76-79, 1950). These lipases and their method of immunological response and Amano-P are also described in U.S. Patent 4707291, Thom et al., Issued November 17, 1987, which is cited herein by reference. Typical examples are Amano-P lipase, a Pseudomonas lipase. fragi FERM 1339 (available under the trade name Amano-CES), Chromobacter multiosum lipases, e.g. Chromobacter viscosum var. lypolyticum NRRLB, commercially available from Toyo Jozo Co., Tagata, Japan and other Chromobacter viscosum lipases from U.S. Pat. Biochamical Corp., USA and Biosynth. Co., The Netherlands and lipases from Pseudomonas glad ioli.

Peroxidase enzymes are used in combination with oxygen sources. e.g. percarbonate. perborates. persulphates, hydrogen peroxide, etc. These are used for bleaching the solution, i. j. to prevent the transfer of dyes or pigments removed from the substrate 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 chlorine and bromine peroxidase.

Peroxidase-containing detergent formulations are described, for example, in PCT International Application WO 89/099813, published October 19,

1989, Kirk 0, assigned to Novo Industries A / S, which is incorporated herein by reference.

A wide variety of enzyme materials and methods for incorporating them into synthetic detergent granules are also described in U.S. Pat. No. 3553139, issued Jan. 5, 1971 to Mc Carty et al., (Incorporated herein by reference). Enzymes are further described in U.S. Pat. 4101457, Plače a spol. issued July 18, 1978 and U.S. Pat. 4507219, Hughes, issued March 25, 1985 (both incorporated herein by reference). Enzyme materials suitable for thermal detergent compositions and their incorporation into such compositions are described in U.S. Patent 4,262,868, Hora et al., Issued April 14, 1981, which is incorporated herein by reference.

Enzymes are usually incorporated in amounts sufficient to provide up to about 5 mg, more typically about 0.05 mg to about 3 mg, of active enzyme per gram of formulation.

For granular detergents, the enzymes are preferably coated or formulated into beads using enzyme-inert additives to minimize dust formation and improve storage stability. Embodiments techniques are well known in the art. In liquid formulations, it is preferred to use an enzyme stabilization system. Enzyme stabilization techniques for aqueous detergent compositions are well known in the art. For example, one technique of stabilizing enzymes in aqueous solutions involves the use of free calcium ions from sources such as calcium acetate, calcium formate and calcium propionate. Calcium ions may be used in combination with short chain carboxylic acid salts, preferably formates. See e.g. U.S. Patent 4,318,818 to Letton et al

On March 9, 1982, which is incorporated herein by reference. It has also been proposed to use polyols such as glycerol and sorbitol, alkoxy alcohols, dialkyl glycol ethers, mixtures of polyvalent alcohols with polyfunctional aliphatic amines (e.g., alkanolamines such as diethanolamine, triethanolamine, diisopropanolamine, etc., boric acid or alkali metal borate. described and examples thereof in US Patent 4261868, issued April 14, 1981 to Horn et al., US Patent 3600319, issued August 17, 1971 to Gedgeov, et al., incorporated herein by reference, and European Patent Application Publication No. 0199405, Application No. 86200486.5, published October 29, 1986, Venegas, Preferred are stabilizers that do not contain boric acid and borates. Enzyme stabilization systems are also described, for example, in U.S. Patent Nos. 4261868, 3600319 and 3519570.

Bleaching compounds - bleaching agents and bleach activators

The detergent compositions of the invention may contain bleaching agents or bleaching compositions containing a bleaching agent and one or more non-bleach activators. When a bleaching compound is present, the buide is typically present in an amount of from about 1% to about 20%. more typically from about 1% to about 10% of a detergent composition. Generally, bleaching compounds are optional ingredients in non-liquid formulations, e.g. granular detergents. If present, the amount of bleach activator is typically from about 0.1% to about 60%, more typically from about 0.5% to about 40% of the bleaching composition.

The bleaching agents used herein may be any bleaching agent suitable for detergent compositions for cleaning textiles, solid surfaces, or for other cleaning purposes that are known or become known. These include oxygen bleaches as well as other bleaching agents. For washing under conditions below about 50 ° C, especially below about 40 ° C, it is preferred that the compositions do not contain borates or a material that can form borates in situ (i.e., borate forming material) under detergent storage or washing conditions. Under these conditions, it is also advantageous to use a bleaching agent which does not contain or form borates. Preferably, the detergents used at these temperatures are substantially free of borates and borate-forming material.

Substantially free of porates and borate-forming materials means that the formulation contains no more than about 1% by weight of borate-forming or borate-containing material of any type, preferably no more than 1¾. more preferably 0

One category of bleaching agents that may be used includes peroxycarboxylic acid bleaching agents and salts thereof. Suitable examples of this category of agents include magnesium monoperoxyphthalate hexahydrate, the magnesium salt of meta-chlorobenzoic acid. 4-nonylamino-4-oxoperoxybutyric acid and diperoxydodecanedioic acid. Such bleaching agents are described in U.S. Pat. No. 4,483,781, Hartman, issued Nov. 20, 1984, US Patent Application 740448, Burns et al., Filed Jun. 3, 1985, European Patent Application No. 0133354, Benks et al., Published Feb. 20, 1985; No. 4412943, Chung et al. issued Nov. 1, 1983, all of which are incorporated herein by reference. Highly preferred bleaching agents also include 6-nonylamino-6-oxoperoxycaproic acid as described in U.S. Pat. No. 4634551, issued Jan. 6, 1987 to Burns.

Another category of bleaching agents that can be used includes halogen bleaching agents. Examples of hypohalite bleaching agents include, for example, chloroisocyanuric acid and sodium and potassium dichloroisocyanurates, and N-chloro and N-bromoalkylsulfonamides. Such materials are normally added in an amount of 0.5-10% by weight of the final product, preferably 1-5% by weight.

Peroxygen bleaching agents may also be used. Suitable peroxide bleaching agents include sodium carbonate peroxyhydrate, sodium pyrophosphate peroxyhydrate, urea peroxyhydrate, and sodium peroxide.

The peroxygen bleaching agents are preferably combined with bleach activators, resulting in in situ production in an aqueous solution (i.e. during the wash process) of the peroxyacid corresponding to the bleach activator.

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

RCL wherein R is an alkyl group containing from about 1 to about 18 carbon atoms, wherein the longest linear alkyl chain extending from and adjacent to the carbonyl oxygen contains, including, about 6 to about 10 carbon atoms and L is a leaving group whose conjugated acid has pK a in the range of about 4 to about 13. Bleach activators are described in U.S. Pat. 4915854, issued

On April 10, 1990, Maovi et al., Incorporated herein by reference, and in U.S. Pat. No. 4412934, which was previously mentioned.

Bleaching agents other than those in the art and may be in a given non-oxygen bleaching agent include photoactivated zinc and aluminum bleaching phthalocyanine. These oxygen bleaching agents are known in the art. One type of particular interest, agents such as sulfonated materials, can be deposited in the substrate during the wash process. After irradiation with light, in the presence of oxygen, as well as after introduction of substances for drying in daylight. the sulfonated zinc phthalocyanine is activated and as a result the substrate is whitened. Preferred zinc phthalocyanines and photoactivated bleaching processes are described in U.S. Pat. No. 4,033,718, issued Jul. 5, 1977 to Holcombe et al., Incorporated herein by reference. Typically, detergent compositions will contain about 0.025% to about 1.25% by weight of sulfonated zinc phthalocyanine.

Polymeric soil release agents

Any polymeric soil release agents known to those skilled in the art may be used in the practice of the invention. Polymeric soil release agents are characterized by having both hydrophobic segments for hydrophilizing the surface of hydrophobic fibers, such as polyester and nylon, and hydrophobic segments, for depositing on the hydrophobic fibers and to adhere to them throughout the wash and rinse cycle. and thus served as anchorage for hydrophilic Other segments. This will allow stains that appear after treatment with the soil release agent to be easier to clean in other washing processes.

While it may be beneficial to use polymeric soil release agents in any of the detergent compositions herein, especially those intended for laundry and other applications where grease and oil are removed from hydrophobic surfaces, the presence of polyhydroxy fatty acid amide in detergent compositions also containing anionic surfactants. active substance can increase the effectiveness of many commonly used types of polymeric soil release agents. Anionic surfactants interfere with the ability of some soil release agents to deposit under and adhere to hydrophobic surfaces. These label releasing polymeric agents have non-ionic hydrophobic segments or hydrophobic segments that interact with anionic surfactants.

Compositions in which the effectiveness of polymeric soil release agents can be achieved using polyhydroxy fatty acid amides are those comprising an anionic surfactant, a soil release agent interacting with the anionic surfactant, and a polyhydroxy fatty acid amide release enhancing agent PFA), wherein: (I) the interaction of anionic active and the composition system, the release polyester may be) by experiment, in the composition in a detergent, and wherein the agents are anionic.

surface contamination in the aqueous solution by the solvent. releasing the active agent by comparing the level (SRA) on the hydrophobic solution between (A) measures the deposition of SRA in the absence of

SRA / anionic surface and amount of anionic in detergent

SRA, with the same surfactant system (CB) against (A) and (II) amide release of the reagent assay, actively the same amide level surfactantly combines the formulation ratio, surface contamination of detergent deposition agent, fibers (e.g. The composition of a mass detergent composition shows the interaction of whether the detergent polyhydroxy fatty impurities can SRA / an ionic release agent / PFA by aqueous (B) testing the same type of active agent in an aqueous solution of SRE k wherein the anionic composition used with the acid can be determined surfactant. impurities in the (C) assay wherein the anionic deposition of the surfactant is reduced, comprising an amount of a support agent for comparing the deposition of the SRA agent of (B) and deposition in the SRA / anionic surfactant polyhydroxy fatty acid detergent composition with the soil release agent; new system surfactant corresponding to said SRA / Anionic surfactant. wherein the improved deposition of the soil release agent in Test (C) relative to Test (B) indicates that an amount of polyhydroxy fatty acid amide is present.

the promoting agent should be soil release tests. For given purposes, it should be carried out at anionic concentrations.

of a surfactant in an aqueous solution that is above about 100ppm. The concentration of the polymeric soil release agent should be at least 15 ppm. 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 appropriate tests for 12 minutes, then removed and analyzed. The level of deposition of the polymeric soil release agent can be determined by radiolabelling the soil release agent prior to sample processing and then conducting radiochemical analysis by techniques known in the art.

As an alternative to the radiochemical assay method described above, deposition of the reagent in the above assays may be indicated by assays.

A, B,

C) determining the absorbance of the 1 st radiation (UV) of the test solutions, using techniques well known in the art.

The decrease in UV absorbance in the test solution after removal of the hydrophobic fibrous material corresponds to an increase in SRA deposition. As will be appreciated by those skilled in the art, UV analysis should not be used for test solutions containing types and concentrations of materials that cause excessive UV absorbance interference, such as high surfactant contents and aromatic groups (e.g., alkylbenzenesulfonates, etc.)

The amount of soil release agent of the polyhydroxy fatty acid amide is understood to be the amount of the surfactant which will promote the deposition of the soil release agent on the hydrophobic fibers as described above, or the amount for which improved grease cleaning performance can be achieved. / textile oils washed in said detergent composition in a subsequent cleaning operation i.

The amount of polyhydroxy fatty acid amide required to promote deposition will vary depending on the anionic surfactant selected, the amount of anionic surfactant, the particular soil release agent selected, and the polyhydroxy fatty acid amide choice. Generally, the compositions will contain from about 0.01% to about 10% by weight of the soil release polymeric agent, typically from about 0.1% to about 5% and from about 5% to about 50%, more typically from about 5% to about 30%. % anionic surfactant. Such compositions will generally contain at least about 1, preferably at least about 3% by weight of polyhydroxy fatty acid amide, although the solution is not limited to this range.

Polymeric soil release agents in which the polydydroxy fatty acid amide enhancement efficiency is in the presence of an anionic surfactant, including soil release agents, having: a) one or more nonionic hydrophilic components consisting essentially of 1 (grade polyoxyethylene segments) or (2) oxypropylene or polyoxypropylene segments having a degree of polymerization of from 2 to 10, wherein said hydrophilic segment comprises no oxypropylene unit unless attached to adjacent portions at each end by ether linkages; or 3) a mixture of oxyalkylene units containing oxyethylene and from 1 to about 30 oxypropylene units, said composition comprising sufficient oxyethylene units such that the hydrophilic component has a hydrophilicity sufficiently large to increase the hydrophilicity of conventional polyester syn surfaces. wherein said phydrof comprises at least about 25% oxyethylene components having about 20 to at least about 50% oxyethylene soil release on such other segments preferably comprise units, and more preferably, such 30, oxypropylene units, units; or b) one or more hydrophobic components comprising i)

C ₃ oxylene terephthalate segments, wherein, if the hydrophobic component is also an oxyethylene terephthalate-containing component, the dive unit of the oxyethylene terephthalate is: C ₃ oxyalkylene terephthalate about 2 - 1 or lower; iii) poly (vinyl ester) segments, preferably poly (vinyl acetate), having a degree of polymerization of at least 2, or iv) C 1 -C 4 alkyl ether or C 1-4 hydroxyalkyl ether substituents, or mixtures thereof, wherein said substituents are present in the form of

C 1 -C 6 -alkyl or C 1-4 hydroxyalkylether cellulose derivatives, or mixtures thereof. and these cellulose derivatives are emphiphilic, thereby having a sufficient level of C 1 -C 4 alkyl ether and / or

Cihydroxyalkyl ether units for deposition on conventional polyester synthetic fibers on their surface and maintain a sufficient level of hydroxyl content.

once adhered to the surface of these conventional synthetic fibers, to enhance hydrophilicity or combinations of a) and b).

Typically, polyoxyethylene segments a) will have a degree of polymerization of from about 2 to about 200, although higher levels, preferably from 3 to about 150, more preferably from 6 to about 100, can be used. Suitable oxy-C4-C6alkylene hydrophobic segments include, but are not thus limited by such endings of soil release polymeric agents such as M03S (CH2) nOCH2CH2O-, wherein M is sodium and n is an integer from 4 to 6, as described in U.S. Pat. No. 471580, issued Jan. 26, 1988 to Goselink, which is incorporated herein by reference in its entirety.

Polymeric agents.

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

Cellulose derivatives functional as soil release agents are commercially available and include cellulose hydroxyethers such as Metocel ^R (Dov-.

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

including C 1 -C 4 alkyl and C 5 hydroxyalkyl cellulose such as methylcellulose ethylcellulose, hydroxypropylcellulose and hydroxybutylmethylcellulose. Various cellulose derivatives useful as soil release polymers,

No. 4000093, issued Dec. 28, 1976, are described in U.S. Pat.

Nicol et al., Incorporated herein by reference.

The soil release agents characterized by the polyvinyl ester (hydrophobic segments) include graft (I) copolymers of polyivinyl ester), e.g. C C6vimylestery. preferably poly (vinyl acetate) grafted on polyalkylene oxide backbones such as polyethylene oxide chains.

Such materials are known in the art and are described in European Patent Application 0219048, published April 22, 1987.

Kud et al. Suitable commercially available soil release agents of this type 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 polyethylene oxide (PEO) terephthalate. More specifically, the polymers consist of repeating units of ethylene terephthalate and PEOterephthalate in a molar ratio of ethylene terephthalate units to PEO terephthalate units of from about 25 = 65, said PEO terephthalate units containing polyethylene oxide having molecular weights of from about 300 to about 2000 molecular weight. impurities, ranging from about 25,000 to about 55,000. See U.S. Pat. No. 3959230, Hays, issued May 25, 1976, which is incorporated herein by reference. See also U.S. Pat. No. 3893929, Basedur, issued July 8, 1975 (incorporated herein by reference), which discloses similar copolymers.

Another preferred soil release agent is an ethylene terephthalate recurring polyester containing 10-15% by weight of ethylene terephthalate units derived from polyoxyethylene glycol having an average molecular weight of 300-5000 and the molar ratio of ethylene terephthalate units to polyoxyethylene ether of polyoxyethylene ether is polyoxyethylene ether. 1 and 6 = 1. Examples of this polymer include the commercially available material Xelcon ^H 5126 (from Dupont) and Milease ^{8 T.} No. 4702857, issued Oct. 27, 1987 to Goselink, which is incorporated herein by reference.

Another preferred polymeric soil release agent.

is a sulfonated product of a substantially linear ester oligomer comprising an oligomeric ester backbone of terephthaloyl and oxyalkyleneoxy recurring units and terminal groups covalently attached to the chain, said soil release agent being derived from allyl alcohol ethoxylate, dimethyl terephthalate, and 1,2-propylene diol the terminal groups of each oligomer on average, in total from about 1 to 4 sulfone groups. These soil release agents are disclosed in U.S. Patent No. 4,968,451, issued November 6, 1990 to J. J. Scheibel and E-P.Gosselink, US Application No. 07/474709, filed January 29, 1990, cited herein for reference for completeness.

Other suitable polymeric soil release agents include ethyl or methyl 1-terminated

1

2-propylene terephthalate-polyoxyethylene terephthalate polyesters of U.S. Pat. No. 4711730, issued Dec. 8

1987, Gosselink et al., An ion-terminated oligomeric esters of

U.S. Pat. 4721580, issued

On Jan. 26, 1988, Gosselink, wherein the anionic terminus comprises sulfo-polyethoxy groups derived from polyethylene glycol (PEG), block polyester oligomeric compounds of U.S. Pat.

No. 4702857, issued Mar. 27.

Oct. 1987, Gosselink, having a polyethoxy terminus of the formula

X- (OCH 2 CH 2) -, wherein n has a value of from about to and X is C 1 -C 6 alkyl, or preferably methyl.

The cited patents are all listed herein for the sake of completeness.

Other polymeric soil release agents include agents.

soil release according to U.S. Pat.

4877896, issued

31 October

1989, Maldonado et al., Which describes anionic.

especially sulfoarcyl, terminated terephthalate esters.

This patent is incorporated herein by reference. Terephthalate esters contain unsymmetrically substituted oxy-, 2-

2-alkyleneoxy. Among the soil release polymers according to

U.S. Pat. 487796 includes materials with polyoxyethylene hydrophilic components or materials

C3oxyalkylene terephthalate (polypropylene terephthalate)

repeating units in the range of the music-phobic components b) i) above. These are polymeric soil release agents. which are characterized by either one or both. and by these criteria, which particularly benefit from the incorporation of polyhydroxy fatty acid amides in the presence of anionic surfactants in the compositions of the invention.

If soil release agents are used, these generally form from time to time

10.0% by weight of detergent compositions, typically from as i

0.1 to about 5%, preferably from about 0.2

Chelating agents

The detergent compositions of the invention may also optionally contain one or more iron and manganese chelating agents as auxiliary material activating ingredients. Such chelating agents may be selected from the group consisting of aminocarboxylates, aminophosphonates, polyfunctional-substituted aromatic chelating agents, and mixtures thereof, as still defined. Without wishing to be bound by theory, the utility of these materials is believed to be in part due to their ability to remove iron and manganese ions from washing solutions by forming soluble chelates.

Amino-carboxylates suitable as optional chelating agents in the compositions of the invention may have one or more.

preferably at least two, units of the structure

CH2 'N - (CH2> x - COOM, /

wherein M is hydrogen, an alkali metal, an ammonium or substituted ammonium group (e.g., ethanolamine) and x is 1 to about 3, preferably 1. Preferably, these aminocarboxylates do not contain alkyl or alkenyl groups having more than carbon atoms.

Useful aminocarboxylates include ethylenediaminetetraacetates,

N-hydroxyethylethylenediamine triacetates, nitrilotriacetates, ethylenediamine inotetrapropionates, triethyleneamine hexaacetates, diethylenetriaminopentaacetates and ethanodiphenyl acetates, their alkali metal salts, ammonium salts and substituted ammonium salts, and mixtures thereof.

Aminophosphonates are also suitable for use as chelating agents in the compositions of the invention as long as at least low concentrations of total phosphorus in detergent compositions are allowed. Compounds with one or more, preferably at least two, units of the formula

CH

N - (CU ₂ ) x - PO 3 M 2.

wherein M is hydrogen, an alkali metal. ammonium or substituted ammonium, and x is 1 to about 3, preferably 1, are suitable and include ethylenediamine amine (methylenephosphonates), nitrilotris (methylene phosphonates) and diethylenetriaminepentakis (methylenephosphonates). Preferably, these aminophosphonates do not contain alkyl or alkenyl groups having more than about 6 carbon atoms. Alkylene groups may be together with substrates.

Polyfunctional-substituted aromatic chelating agents are also useful in the compositions of the invention. These materials may contain compounds of the general formula

OH

OH wherein at least one R is -SO 3 H or -COOH, or soluble salts thereof, and mixtures thereof. U.S. Pat. No. 3812044, issued May 21, 1974, to Connor et al., Incorporated herein by reference in its entirety, discloses polyfunctional-substituted aromatic chelating and screening agents. Preferred compounds of this type in acid form are dihydroxydisulfobenzenes such as 1,2-dihydroxy-3,5-disulfobenzene. The alkaline detergent compositions may contain these materials in the form of alkali metal salts, ammonium or substituted ammonium salts (e.g., mono- or triethanolamine salts).

If used, these chelating agents will generally be from about 0.1% to about 10% by weight of the detergent composition of the invention. More preferably, the chelating agents will contain from about 0.1% to about 3.0% by weight of such compositions.

Agents to remove and prevent dirt

The compositions of the invention may also optionally contain water-soluble ethoxylated amines. having the ability to remove clay and counteract it. Granular detergent compositions containing these compounds typically contain from about 0.01% to about 10.0% by weight of water-soluble ethoxylated amines; liquid detergent compositions, typically from about 0.01% to about 5%. These compounds are preferably selected from the group consisting of

1) ethoxylated monoamines of formula (X-L) -N- (R ² ) 2

2) ethoxylated diamines of formulas

R ² - N - R ¹ I - N- R ² I <1 (R ²⁾ 2 - N - ^R1 - N - (R ²⁾ 2 1 1 L I 1 L I 1 L I 1 X 1 X 1 X

or (X - L) ₂ --N - R ¹ --N - (R ² ) 2

3) ethoxylated polyamines of the formula

R ²

I

R ³ - [Ä ¹ ) q - (R ⁴ ) t - N - L - X] p

4) ethoxylated amine polymers of general formula

R ² [(R 2) 2 - NJw - [R ¹ - N 1x] [R ¹ - Nly - (R ¹ - N - L - X) z

I

L

I

X

5) mixtures thereof, wherein A ¹ is

□ I I 0 I I 0 I I 0 1 1 0 I I 1 1 NC -, I 1 1 - NCO -, I 1 1 - NCN -. I j - CN - I • 1 1 - OCN I 1 R 1 R 1 1 R R 1 R 1 R

0 1 I 0 I I 0 I 1 1 1 WHAT - , 1 1 -oco-. 1 1 -OC

0

II II

-CNC51 or -0-

R is H or C 1-6 alkyl or hydroxyalkyl, R ¹ is C 2-12 and alkylene, hydroxyalkylene, alkenylene. arylene or a1 karylene, or a C 2-3 oxyalkylene group having from 2 to about 20 oxyalkylene units, with the proviso that no O-N bonds are formed, each R ² is C 1-4 or hydroxyalkyl, -LX, or two R 2 ² together form a -CCH2) r -A ² - (CH 2> s-. wherein a ² is -0- or -CH 2. r is 1 or 2, p is 1 or 2 and r + s is 3 or 4, X is a nonionic group, anionic group or a mixture thereof, R ³ is substituted C 3 -C 12 alkyl, hydroxyalkyl, alkenyl, aryl or alkaryl having substitution positions, R ⁴ is C 1 -C 12 alkylene, hydroxyalkylene, and 1-kenylene, arylene or alkarylene or C2 -C3oxyalkylénová group having 2 to 20 oxyalkylene units with the proviso that no bonds are formed 0-0 or 0-N, L is a hydrophilic chain which contains the polyoxyalkylene moiety - / ^(R5 0) _{m <CH2} CH20 ) n / -, where R ⁵ is C 3 -C 4 alkylene or hydroxyalkylene and m and n are numbers such that the -CCH 2 CH 2 O) _n - form at least about 50% by weight of said polyoxyalkylene group; for said monoamines, m is from 0 to about 4 and 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 C 2 -C 8 alkylene.

hydroxyalkylene or alkenylene, and at least about 3 when R is other than C 2 -C 3 alkylene, hydroxyalkylene or alkylene; for said polyamines and amine polymers, m is from 0 to about 10 and n is at least

about 3. p is from 3 to 8 q is 1 or 0, t is 1 or 0 with t condition. that t is 1 when q is 1, v ¹ is 1 or 0, x + y + z is at least 2 and x + y is a at least 2. The most preferred agent.

releasing clay impurities and counteracting deposition thereof is ethoxylated tetraethylenepentaamine. Examples of ethoxylated amines are further described in U.S. Pat. No. 4597898, VanderMeer, issued Jan. 1

On Jul. 1, 1986, which is incorporated herein by reference. A further group of preferred clay soil removal and deposition agents are the cationic compounds described in European Patent Application Ser. 111965, Oh and Gosselink, published Jun. 27, 1984, which is incorporated herein by reference. Other clay soil removal and deposition agents that may be used include the ethoxylated amine polymers described in European Patent Application 111984, Gosselink, published Jun. 27, 1984; The zwitterionic polymers described in European patent application 112592, Goselink, published July 4, 1984, and the amine oxides described in US Patent No. 5,201,519. No. 4,548,744, Connor, issued Oct. 22, 1985, all of which are incorporated herein by reference in their entirety.

Other clay soil removal and / or deposition agents can also be used in the compositions of the invention. Another type of preferred deposition agents include carboxymethylcellulose (CMC) materials. Such materials are well known in the art.

Polymeric dispersing agents

Polymeric polycarboxylate 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 agents known in the art may be used.

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

Polycarboxylate materials.

which can be used as polymeric carboxylate dispersants are such polymers or copolymers.

containing at least about% by weight of segments of the formula

XZ

Ii

C -C -

II

YC00M wherein X, Y and Z are each selected from the group consisting of hydrogen, methyl. and n is from about 30 to about 400. Preferably X is hydrogen or hydroxyl, Y is hydrogen or carboxy, 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 copolymerizing suitable unsaturated monomers, preferably in their acid form. Unsaturated monomeric acids that can be polymerized to suitable polymeric polycarboxylates include acrylic acid, maleic acid, (or maleic anhydride), fumaric acid.

and tonic acid.

aconitic acid, masaconic acid, citraconic acid, and methyl malonic acid. Presence of monomer segments in polymeric carboxylates containing no carboxylate radicals such as vinyl methyl ether, styrene, ethylene.

etc. it is suitable provided that such segments do not constitute more than about 40% by weight.

Particularly suitable polymeric polycarboxylates may be derived from acrylic acid. Such acrylic acid-based polymers useful in the compositions of the present invention are the water-soluble salts of polymerized acrylic acid. The average molecular weight of such polymers in acid form preferably ranges from about 2000 to 1000, more preferably from about 4000 to 7000 and most preferably from about 4000 to 5000. Water-soluble salts of such acrylic acid polymers may include, for example, alkali metal salts, ammonium and substituted ammonium salts. Suitable polymers of this type are known materials. The use of polyacrylates of this type in detergent compositions has been described, for example, by Diehl in U.S. Pat. No. 3308067, issued Mar. 7, 1967. This patent is incorporated herein by reference in its entirety.

Acrylic / maleic acid copolymers can also be used as a preferred dispersant / anti-deposition 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 100000, more preferably from about 5000 to 75000, most preferably from about 7000 to 65000. The ratio of acrylate segments to maleate in such a copolymer will generally range from about 30 = 1 to about 1. = 1, more preferably from about 10 = 1 to 2 = 1. Water-soluble salts of such acrylic acid / maleic acid copolymers may include, for example, alkali metal salts, ammonium and substituted ammonium salts. Soluble acrylate / maleate copolymers of this type are known materials as described in European Patent Application No. 6,669, published December 15, 1982

which is incorporated herein by reference.

Another polymeric material that can be used is polyethylene glycol (PEG). PEG has the property of a dispersing agent and also acts as a clay soil removal and deposition agent. A typical molecular weight range for these purposes is in the range of about 500 to about 10,000, preferably from about 1000 to about 50,000, more preferably from about 1,500 to about 10,000.

Brightening agents

Any optical brightener or other brightening or bleaching agents known in the art may be incorporated into the detergent composition of the invention.

The choice of brighteners for use in detergent compositions will depend on a number of factors such as the type of detergent, the nature of the other ingredients present in the detergent composition, the wash water temperature, the degree of mixing, and the ratio of wash material to tank size.

The choice of brighteners also depends on the type of material to be purified, e.g. for cotton, synthetic materials, etc.: Because most laundry detergent products are used for cleaning different textiles, detergent products should contain a blend of brightening agents that will be effective for different textiles. It goes without saying that the individual components of such mixtures must be compatible.

Commercially available brighteners that can be used in the present invention can be classified as a subgroup that includes, but is not limited to, stilbene derivatives.

pyrazolocoumarin, carboxylic acids, cyanogen, dibenzothiepine-5,5-dioxide, azoles.

5- and 6-membered cyclic heterocycles and other miscellaneous reagents.

Examples of such brighteners are described in The

Production and Application of

Fluorescent

Grightening Agents.

M. Zahradnik, publ. John Viley and Sons, New York (1982), incorporated herein by reference.

Stilbene derivatives that may be used in the present invention include, but are not limited to, bis (triazines) amino-stilbene, triazole derivatives of stilbene.

there are limited, bisacylamino derivatives of oxad and azole derivatives of stilbene.

stilbene, oxazole derivatives of stilbene, and styryl derivatives of stilbene.

Some bis-triazinyl) aminostilbene 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 at the 3-position, the 7-position, and the 3-and 7-positions.

Carboxylic acid derivatives that may be used in the present invention include, but are not limited to, fumaric acid derivatives, benzoic acid derivatives. benzoic acid derivatives, p-phenylene bis-acrylic acid derivatives, naphthalene dicarboxylic 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 including, but not limited to, cinnamic acid derivatives, arylazole, styrylbenzofuran, styryl oxadiazoles. styrylazoles, styrylbenzofurans, styryloxadiazoles, styryltriazoles and styrylpolyphenyls as described on p. 77 of the cited Gardener's publication.

The styrylazoles can be further classified into styrylbenzoxazoles, four 1-imidazoles, and styrylthiazoles as described on p. 78 of the Horticultural Work cited. Of course, these three subclasses do not necessarily include an exhaustive list of subgroups into which the styrylazoles can be sorted.

Another class of optical brighteners that can be used in the present invention are the dibenzothiepine-5, 5-dioxide derivatives described on p. 741-749 in The Kirk-Othmer Encyclopedia of Chemical Technology, Vol. 3, p. 737-750 (John Viley &amp; Son, Inc., 1962). the disclosure of which is incorporated herein by reference, and includes 3,7-diamino benzothiophene-2,8-disulfonic acid 5,5-dioxide.

Another class of optical brighteners that can be used in the present invention include azoles that are derivatives of 5-membered heterocycles. These may be further subdivided into monoazoles and bisazoles. Examples of monoazoles and bisazoles are described in Kirk-Ortmer.

Another class of brighteners that can be used in the present invention are the six-membered heterocyclic derivatives described in Kirk-Othmer cited above. Examples of such compounds include brighteners derived from pyrazine and brighteners derived from 4-aminophthalamide.

In addition to the brighteners mentioned, mixed agents can also be used as brighteners. Examples of such mixed reagents are described on p. 93-95 of Gardener's above work and include 1-hydroxy-3,6,8-pyrene-trisulfonic acid, 2,4-dimethoxy-1,3,5-triazine

6-y1 pyrene.

4,5-Diphenylimidazolone disulfonic acid pyrazoline quinoline derivatives.

Other specific examples of optical brighteners that can be used in accordance with the present invention.

are substances which are disclosed in U.S. Pat. Vixon, 470856, 13.

December

1988, which is incorporated herein by reference.

include the Phorwhite TM brightener range

These brighteners from Verona. Other brighteners described in this reference include; Tinopal UNPA,

Tinopal CBS and Tinopal 5BM, available from Ciba-Geigy; Arctic Vhite

CC and Arctic Vhite CVD, available from Hilton-Devis, based in Italy; 2- (4-styryl-phenyl) -2H-naphtho [1,2-d] triazoles, 4,4 &apos;

- bis' (styryl) bisphenols and γ-aminocoumarins. Specific examples of these brighteners include 4-methyl-7-diethylaminocoumarin, 1,2-bis (benzimidazol-2-yl) ethylene, 1,3-diphenylphrazolines, 2.

5-bis (benzoxazol-2-yl) -thiophene, 2-styryl-naphthyl (1,2-d) oxazole, and 2. (stilbenzen-4-yl) -2H-naphtho (-, -, 2- d) triazole.

Other optical brighteners that can be used in the present invention are those described in U.S. Pat. 364015, issued Feb. 29, 1972, to Hamilton, which is incorporated herein by reference.

Other ingredients

A wide variety of other ingredients useful in detergent compositions may be used in the compositions of the invention, including other active ingredients, carriers, hydrotropes, refining agents, colorants or pigments, solvents for liquid formulations.

Liquid detergent compositions may contain water and other solvents as carriers. Suitable are primary or secondary alcohols having a low molecular weight, examples of which are methanol, ethanol, propenol, and isopropropanol. Monofunctional alcohols are preferred for sulphising surfactants. however, polyols such as those containing 2 to about 6 carbon atoms and 2 to about 6 hydroxy groups (e.g., propylene glycol, ethylene glycol, glycerine and 1,3-propanediol) may also be used.

The detergent compositions of the invention will preferably be formulated so. Accordingly, the wash water will have a pH between 6.5 and about 11, preferably between 7.5 and 10.5 during use in aqueous cleaning operations. Liquid formulations preferably have a pH between about 7.7 and about 9.5, more preferably between about 7.5 and about 9.0. Techniques for controlling pH at recommended values using buffers, alkalis, acids, etc., and well known to those skilled in the art.

The present invention further provides a method of cleaning a substrate such as fibers, fabrics. solid surfaces, leather, etc. by contacting said substrate with the detergent compositions of the present invention in the presence of a solvent such as water or a solvent. water miscible (e.g., primary and secondary alcohols).

Stirring is usually performed to increase cleaning efficiency. Suitable mixing devices include rubbing with a hand or brush or other cleaning equipment, automatic washing machines, automatic dishwashers, etc.

DETAILED DESCRIPTION OF THE INVENTION.

This experiment provides a method of manufacture

N-methyl,

The 1-deoxyglucolidine surfactant used according to the invention. While many variations of the apparatus will be apparent to those skilled in the art, one suitable apparatus for use in the process includes a three liter four-necked flask equipped with a motorized stirrer and a thermometer of sufficient length to contact the reaction medium. a wide-pass side arm (note: a wide-pass side arm is important in the case of very rapid methanol evolution) to which an efficient collector cooler and vacuum outlet are connected. This is connected to the nitrogen and vacuum meter, then to the hood and trap. The 500-Watt heating mantle with a temperature control unit (Variac) used to heat the reaction is placed on a laboratory jack so that it can be easily lifted or lowered for further temperature control of the reaction.

N-ethylglucamine (195 g, 1.0 mol, Aldrich. M4700-0) and methylleurate (Procter and Gambia CE 1270, 220.9 g 1.0 mol) were placed in a flask. The mixture of solid and liquid is heated with stirring under a stream of nitrogen to form a melt (about 25 minutes). When the melt reached 245 ° C, a catalyst (anhydrous powdered sodium carbonate, 10.5 g, 0.1 mol, J.T.Baker) was added. The nitrogen inlet is closed and the nitrogen outflow is adjusted to produce a vacuum of 16.65 kPa. From this point, the temperature is maintained at 150 ° C using a Varuac A (or by raising or lowering the jacket position.)

The first methanol bubbles on the meniscus of the reaction mixture are evident within 7 minutes. Soon, an intense reaction follows. The methanol is distilled off until its flow rate drops. The vacuum is adjusted to about 33.33 kPa. This vacuum is increased approximately as follows (in kPa per minute): 33.33 kPa in 3 min, 66.66 kPa in 7 min, 83.31 kPa in 10 min. Heating and stirring were discontinued within 11 minutes of detecting methanol evolution, with some foaming. The product is cooled and solidified.

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

Examples 1-6

These examples show high performance granular detergent compositions comprising polyhydroxy fatty acid amides, alkylethoxylated sulfates and antifoams.

Basic granules 1 2 3 C14-C15 alkyl sulfate 11.3 C 1 -C 6 alkylethoxy (2.25) sulfate 11.2 16.9 5.6 N-Inyl 1-Ν-1-deoxyglucyl 1- coconut fat amide 11.2 5.6 5.6 Zeolite A 30.1 30.1 18.8 sodium citrate 11.3 sodium carbonate 22.0 22, .0 16.9 sodium silicate 3.0 3.0 5.6 sodium sulfate 8.0 8.0 11.1 sodium polyacrylate (4500 wt) 3.5 3.5 2, 1 polyethylene glycol (8000 mhm) 1.1 1.1 1.1

tallow fatty acid 2.1 1.1 1.1 brightener 0.2 0.2 0.2 Admixture and spraying anti-foaming agent flakes ^x 1.0 0.5 protease (1.4% of assets. enzyme) 0.9 1.0 0.5 perfume 0.3 0.3 0.3 C12 ^- C13 alkyloxyethoxylate (6.5 mol) 1.1 1.1 1.1 water and admixtures 5.2 5.1 5.8 100.0 100.0 100.0

^x The antifoaming agent flakes contain approximately% silica dispersion (si 1 icon oil.

encapsulated in flakes.

containing, in particular, PEG (8000mhm) in an amount of greater than 80% and a minor amount of optionally water-soluble components. Examples 1-3 are formulations for preferred use of about 1400 ppm, based on the weight of the wash water, at temperatures below about 50 ° C. The above examples are realized by combining the granular base ingredients as a suspension and spray drying to about 4-8% residual moisture. The remaining dry ingredients are mixed in granular or powder form to the spray-dried granules in a rotary mixer and sprayed with a liquid component (non-ionic surfactants and perfume).

Basic granules 4 5 6 C14-C15 alkyl sulfate 5.8 C16 Ci8alkyletoxy (2.25) sulfate 6.0 C 18 -C 18 fatty acid 2.2 2.2 Zeoli te 7.0 7.0 7.0 polyacrylate (4500 mhm) 3.3 3.3 3.3 polyethylene glycol (8000 mhm) 1.3 1.3 1.3

sodium carbonate 10.7 10.7 10.7 sodium sulfate 5.0 5.0 5.0 sodium silicate (SiO 2 / Na 2 O = 2 5.0 5.0 5.0 various ingredients 7.1 7.1 7.1 admixture Zeolite ft 5.0 5.0 5.0 N-methyl-N-1-deoxyglycyl amide of coconut fat 4.0 6.4 4.4 C14-C15 alkyl sulfate 11.8 C12-C18 alkyl sulfate 13.1 16.1 C12-C18 alkylethoxy (2) sulfate 5.0 C 1 -C 6 alkylethoxy (2.25) sulfate 4.0 anti-foaming agent flakes ^x 1.0 0.5 various (filler salts, brightener, enzyme, buffer, zeolite, or the like activator, etc.) 17.2 17.2 16.5 spray C12-13 alkyl ethoxylate (6.5 mol) 2.0 2.0 2.0 perfume 0.5 0.5 0.5 water and various 8.2 9.4 8.4 100.0 100.0 100.0 ^x Anti-foaming agent flakes contain pribiižne 5% dispersion silicon dioxide (with i 1 icon) oil, encapsulated in flake.

containing, in particular, PEG (8000 mhm) in an amount greater than 80% and a minor amount of optionally water-soluble components.

The compositions of Examples 4-6 are condensed granular formulations prepared by suspending and spray drying the granule base ingredients having a moisture content of about 5% and other dry powder or granular ingredients. The resulting mixture is dust-free by spraying with the liquid components.

The product is mixed for use at a concentration of about 1000 ppm.

at washing temperatures below about 30 ° C.

Examples 7-12

The following examples demonstrate high performance liquid formulations containing polyhydroxy fatty acid amides, alkyl ethoxylated sulfates and antifoam agents.

Ingredients 7 8 9 10

N-methyl-N-1-deoxyglycyl amide

of coconut fat 4.2 3.1 3,1 8,5 C14-C15 alkylethoxy (2, 25) sulfate 12.6 9.3 8 .5 C12-C18 alkylethoxy (2,5) sulfate 6.2 C12-14 alkyl sulfate 3.1 C12-14 alkyl ethoxylate 3.4 2 5 dodecy1trimetylamóniumchlorid 0.5 0 2 dodecylsuccinate 5.0 sodium citrate 3.4 15.0 5.0 TMS / TDS (80/20) ^x 3.4 C-C fatty acid 3.0 3.0 oxydisuccinate 20.0 ethoxylated tetramethylenepentamine 1.5 2.0 polyacrylate 4500 mhm) 1.5 1.5 1 Icon Oil Cprotipenivé 0.9 0.9 agent) various (enzymes, brighteners). releasing agents stabilizers, etc. 15.3 14.0 14.0 16.3 Water 52.7 51.2 51.2 54.0 100.0 100.0 100.0 100.0

^x TMS / TDS is tartrate monosuccinate / tartrate disuccinate

ingredients 11 12 N-methyl-N-1-deoxyglycyl amide of coconut fat 5.5 5.5 C12-13 alkyl ethoxylate (6.5 mol) 2.5 2.5 Ci4-15a1kyletoxylát (2.25) sulfate 17.0 17.0 oleic acid 3.0 3.0 dodecy1tr i methylammonium umchior i d 0.2 0.2 Thionic acid 1.0 1.0 monoetano1amín 2.5 2.5 ethoxylated tetramethylenepentamine 1.5 1.5 protease (3.1% active) 0.5 0.4 mylase (11.5% active) 0.2 Silicone oil 0.5 various and solvent to to 100.0 100.0 Examples 7-12 are preferably used at about 2000 ppm. relative to the washing water, at temperatures below about 50 ° C. prepare with a combination of non-aqueous solvents, water surface active pastes or solutions melted fatty acids,

aqueous solutions of polycarboxylate activators and other salts, aqueous ethoxylated tetraethylenepentanine, buffering agents, caustic substances and remaining water. The pH is adjusted to about pH 8.5 using either aqueous citric acid solution or sodium hydroxide solution. After adjusting the pH, final ingredients such as soil release agents, emulsions, dyes and perfumes are added and the mixture is mixed until a single phase is obtained.

Example 13

An alternative method of preparing polyhydroxy fatty acid amides is as follows. Reaction mixture containing 84.87 g of fatty acid methyl ester (source: Procter and Gambia methyl ester CE1270), 75 g of N-methyl-D-glucamine (source: Aldrich Chemical Company M4700-0), 1.04 g of sodium methoxide (source:

Aldrich Chemical Company 16, 499-2) and 68.51 g of methanol are used in this procedure. The reaction vessel contains standard reflux equipment equipped with a drying tube, a condenser and a stirring bar. In this procedure, N-methylglutamine is mixed with methanol under stirring under argon and heating is started well with stirring (stirring bar, reflux). After 15-20 minutes, when the solution has reached the desired temperature, ester and sodium methoxide are added as catalyst. Samples are taken periodically to monitor the progress of the reaction, but it should be noted that the solution is quite clear after 63.5 minutes. It is considered that the reaction is in fact almost complete at this point. The reaction mixture is maintained at reflux for 4 hours. Removal of the ethanol yielded a crude product weighing 156.6 grams of pure product. However, the percentage yields are not calculated on this basis because regular sampling distorts the overall percentage yield. The reaction is carried out at 80% and 90% reactant concentrations for up to 6 hours to produce products with very little by-product formation.

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

It will be noted that polyhydroxy fatty acid amides, due to their amide bond, are subject to some instability under highly basic or highly acidic conditions. While some decomposition can be tolerated, it is preferred that these materials are not exposed to a pH greater than about 11, preferably 10, or under about 3 for an excessively long time. The pH of the final product (liquid) is usually 7.0 to 9.0.

During the production of polyhydroxy fatty acid amides, it is typically important to neutralize, but at least partially, the basic catalyst used to form the amide bond. While an acid can be used for this purpose, it will be obvious to the formulator that it is simple and expedient to use an acid that provides an anion and which is otherwise suitable and desirable in the final detergent composition. For example, citric acid and the resulting citrate ion (about 1 is left with a suspension of about 40% polyhydroxy fatty acid amide can be used for neutralization and pumped to the subsequent processing steps of the detergent production process. Similarly, acid forms of materials such as oxydisuccinate, nitrilotriacetate, ethylenediaminotetraacetate, tartrate / succinate and the like.

Polyhydroxy fatty acid amides derived from coconut alkyl-1 fatty acids (predominantly C12-C14) are more soluble than their alkyl-tallow counterparts (predominantly C1-C18) - As a result, C12-C14 materials are predominantly easier to formulate into liquid compositions and are more soluble in cold water washing baths. The Cie-Cie materials are also quite useful, especially under conditions where warm to hot water is used. Cie-C 18 materials can be better detergents than surfactants

C12 -C14 counterparts.

The formulator can thus proceed to ease the production of verse.

efficacy in selecting a particular polyhydroxy fatty acid amide for use in said compositions.

It will also be apparent that the solubility of polyhydroxy fatty acid amides may be increased by having unsaturated sites and / or branching in the fatty acid group. Therefore, materials such as oleic and isostearic acid polyhydroxy fatty acid amides are more soluble than their n-alkyl counterparts.

Similarly, the solubility of polyhydroxy fatty acid amides prepared from disaccharides, trisaccharides, etc. will usually be greater than that of their monosaccharide derived counterpart. Higher solubility may also be useful in formulating liquid preparations. In addition, polyhydroxy fatty acid ides in which the polyhydroxy group is derived from maltose are shown to be particularly good detergents. when used in combination with conventional alkylbenzene sulfonate (LAS) surfactants

- 67 substances. While not wishing to be bound by any theory, it appears that the combination of LAS with polyhydroxy fatty acid amides derived from higher carbohydrates such as maltose causes a substantial and unexpected decrease in interfacial tension in the aqueous medium, thereby promoting detergency efficiency. (The production of maltose-derived polyhydroxy fatty acid amide is described below.)

Polyhydroxy fatty acid rides may be produced not only from purified sugars, but also from hydrolysed starches, e.g. corn starch, potato starch or any suitable starch derived from vegetable products containing mono-, di-, etc. carbohydrates required by the formulator. This is particularly important from an economic point of view. High glucose corn syrup, high maltose corn syrup, etc. can thus be advantageously and economically used. The feedstock for the polyhydroxybutyric acid amide may also be provided by a wood hydrolyzed cellulose pulp.

As mentioned above, polyhydroxy fatty acid amides derived from higher saccharides such as maltose, lactose, etc. are more soluble than their glucose counterparts. In addition, it appears that more soluble polyhydroxy fatty acid amides can aid in the solubilization of their more soluble counterparts in varying degrees. Thus, the formulator may choose raw materials containing, for example, high glucose cereal syrup, but may choose a syrup that contains a small amount of maltose (e.g., 1% or more). The resulting mixture of polyhydroxy fatty acids will generally exhibit more advantageous 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 of the economic advantages of using sugar mixtures preferentially to 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. In some cases, however, some loss of grease removal capacity (washing dishes) may be observed at maltamide fatty acid levels above about 25% and some foaming loss above about 33% (the percentages given are percentages of glucose-derived polyhydroxy fatty acid amide in the composition). This may vary depending on the chain length of the fatty acid moiety. Typically, the formulator, selecting the use of such mixtures, may look for a preferred choice of a mixture of polyhydroxy fatty acid amides that contain ratios of monosaccharides (e.g. glucose) and di- and higher carbohydrates (e.g. maltose) from about 4 = 1 to about 99:

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 temperatures of about 30 to 90 ° C. preferably about 50 to 80 ° C. It has now been determined that it may be convenient for a liquid detergent formulator to carry out such procedures in a 1,2-propylene glycol solvent, since the glycol solvent does not necessarily have to be completely removed from the reaction product before use in the final detergent formulation. Similarly, a formulator of, for example, solid, typically granular, detergent formulations may find it advantageous to carry out the process at 30 to 90 ° C in solvents that include ethoxylated alcohols such as ethoxylated (E 3-8) C 12 -C 14 alcohols such as NEODOL 23 E06.5 (Shell). When such ethoxylates are used, it is preferred that they do not contain a substantial amount of the unethoxylated alcohol, and most preferably they do not contain a substantial amount of the mono-ethoxylated alcohol. (Determination of T).

Although the processes for making polyhydroxy fatty acid amides per se form part of the invention, the formulator may consider other polyhydroxy fatty acid amide syntheses as described below.

Typically, the reaction for preparing preferred polyhydroxy fatty acid amides will comprise: step 1 - preparing an N-alkyl polyhydroxyamine derivative from the desired sugar or sugar mixture by forming an adduct of N-alkylamine and sugar, followed by reaction with hydrogen in the presence of a catalyst; followed by step 2- reacting said polyhydroxyamine with, preferably, a fatty ester to form an amine bond. Although advice can be prepared

In the prior art, N-alkyl polyhydroxyamines are preferred, using the economically advantageous sugar syrup as raw material. It should be appreciated that for best results when using such syrups, the manufacturer should choose syrups that are fairly light in color or preferred. quite colorless (water color).

Preparation of N-alkyl polyhydroxyamine from sugar syrup obtained from plants

I. Adduct Formation - The following procedure is a standard process in which about 420 g of about 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 about 119 g. g 50% aqueous methylamine solution (59.5 g methylamine - 1.92 mol). Methylamine solution

(MMA) is bubbling and protect N2 and cool to about 10 to 20 ° C. Cereal syrup is adds slowly to MMA solution at that reaction temperature. Gardner color with measured at the stated approximate times in minutes. Table 1 Time in minutes: 10 30 60 120 180 240 reaction. temperature ° Gardner color (Pribiižne)

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 - -

As can be seen from the above, Garaner's color for the adduct is much worse when the temperature rises above about 30 ° C and about 50 ° C, with a time when the adduct has a Gardner color below 7 is only about 30 minutes. For longer reactions and / or holding times, the temperature should not be less than about 20 ° C. The Gardner color should not be less than about 7 and preferably about 4 to obtain a good glucamine color.

If lower temperatures are used to form the adduct, the time to reach a substantially equilibrium adduct concentration using higher amine to sugar ratios will be shortened. With a molar ratio of 1.5 L of amine to sugar, equilibrium is reached in about two hours at a reaction temperature of about 30 ° C. At a molar ratio of 1.2 = 1, under the same conditions, this time is at least about three hours. For good color, the amine = sugar combination, the reaction temperature and the reaction time are selected to achieve a substantial equilibrium transformation, e.g., greater than about 90, preferably greater than about 95% and even more preferably greater than about 99% based on sugar; the color is less than about 4, more preferably less than about 1, for the adduct.

Using the above procedure at a reaction temperature of less than about 20 ° C and cereal syrups with different Gardner colors as indicated, the color of the MKA adduct (after reaching a substantial equilibrium that is reached in at least about two hours) as shown in the table second

Table 2

Gardner color (approx.)

corn syrup 1 1 1 1 + 0 0 0+ adduct 3 4/5 7/8 7/8 1 2 1 How is it table Obviously, must a flat starting sugar material very close colorless in to was obtained acceptable adduct. If sugar  has Gardner's color as i 1, is an adduct sometimes

acceptable and sometimes unacceptable. As the Gardner color is greater than 1, the resulting adduct is unacceptable. The better the initial color of the sugar, the better the color of the adduct.

II. Reaction with Hydrogen - The adduct mentioned above, having a Gardner color or less, is hydrogenated as described below.

About 539 g of the adduct in water and about 23.1 of the United Catalyst G49B Ni-catalyst were charged into a 1 liter autoclave and bubbled twice with 1.32 MPA of hydrogen at 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 three hours. The product is hydrogenated from about 95 at this stage. 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 MMA evaporation, the product is 95% N-methylglucamine as a white powder.

The above procedure was repeated with about 23.1 g of Raney-Ni catalyst with the following changes. The catalyst is washed three times and the reactor, with the catalyst in the reactor, is purged twice with hydrogen at 50 psi and pressurized with hydrogen at 100 psi for two hours, releasing the pressure for one hour and repressurizing the reactor to 100 psi. The adduct is then pumped into a reactor at pressures of 1.38 MPa and 20 ° C and the reactor is purged with hydrogen at 1.38 MPa, etc., as above.

In any case, the resulting product is greater than about 95% of N-methylglucamine, has less than about 10 ppm Ni relative to the globulin, and has a solution color of less than about 2 for the Gardner color.

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

It is important to have a good starting material having a low sugar content (less than about 5%, preferably less than about 1 and a good color (less than about 7, preferably less than about 4 Gardner, more preferably less than about 1)).

In another reaction, the adduct is prepared from about 159 g of about 50% methylamine in water, which is bubbled through and sparged with nitrogen at about 10 -20 ° C. Asdi 330 g of about 70% syrup (almost aqueous white) is degassed with nitrogen at about 50 ° C and slowly added to the methylene amine solution at a temperature of less than about 20 ° C. The solution is stirred for about 30 minutes to give about 95% adduct which is a very light yellow solution. About 190 g of adduct in water and about 9 g of United Catalyst C49B Ni-catalyst were placed in a 200 mL autoclave and purged three times with hydrogen at 20 ° C. The hydrogen pressure is increased to about 50 psig and the temperature is raised to about 50 ° C. The pressure is raised to 1.72 MPa and the temperature is maintained at about 50-55 ° C for about three hours. The product at which time the substance is hydrogenated from about 96 is then heated to about 85 ° C for about 30 minutes and the product is, after removal of water and evaporation, about 95% N-methylglucamine as a white powder.

It is also important to minimize contact between the adduct and the catalyst if the hydrogen pressure is less than about 6.88 MPa of N-methylglucamine to minimize the Ni content of the glucamine. The nickel content of N-methylglucamine in this reaction is about 100 ppm compared to less than 10 ppm in the previous reaction.

The following reactions with hydrogen were performed to directly compare the effect of reaction temperatures.

A 200 ml reactor is used in a typical design similar to that described above for the preparation of the adduct and for the hydrogen reaction at different reaction temperatures.

The adduct used in the production of glucamine is prepared by combining as 429g and 55 glucose (cereal syrup) as a solution (231 g glucose, 1.28 mol) (prepared using 99DE cereal syrup from Gardner) and about 119 g 50% methylamine 59.6 g MMA, 1.92 mol) (from Air Products).

The reaction procedures are as follows ^:

1. About 119 g of a 50% methylamine solution is charged to a nitrogen purged reactor, covered with nitrogen and cooled to below about 10 ° C.

2. Degass and / or purge with nitrogen at 10-20 ° C a 55% cereal syrup solution to remove oxygen in the solution.

3. Slowly add the corn syrup solution to the methylamine solution and keep it below about 20 ° C-

4. After all the corn syrup solution has been added, stir for about 1-2 hours.

The product is used immediately after preparation for the hydrogenation reaction or stored at a lower temperature to prevent further degradation.

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

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

2. The reaction mixture is purged with hydrogen at about 20 psig and about 20-30 ° C.

3. Pressurize with hydrogen to a pressure of about 2.7 MPa and raise the temperature to about 50 ° C.

4. The pressure is increased to about 3.45 MPa. Allow to react for about 3 hours. The temperature is maintained at about 50-55 ° C. Sample 1.

5. The temperature is raised to about 85 ° C for about 30 minutes.

6. Decant and filter the Ni-catalyst. Sample 2 is taken.

Conditions for reaction at constant temperature; 1. To be added about 134 g adduct a about 5.8 g G49B Ni to 200 ml autoclave. 2. He will inflate sa twice hydrogen at as i 1.38 MPa at low temperature. 3- Pressurizes with hydrogen to about 2.47 MPa and the temperature rises at about

50 ° C.

4. Maintain pressure at about 3.45 MPa, allow to react about 3.5 MPa, allow to react for about 3.5 hours. The temperature is maintained at that temperature.

5. Decant and filter the Ni-catalyst. Sample 3 is taken at about 50-55 ° C, sample 4 at about 75 ° C and sample 5 at about 75 ° C. (The reaction time is about 45 minutes at about 85 ° C.)

All experiments yield a similar purity of N-methylglucamine (about 94%), Gardner's colors are similar in the experiments immediately after the reaction, but only a two-stage heat treatment provides good color fastness and the experiment at 85 ° C gives a poor color immediately after the reaction.

Example 14

Preparation of a fatty acid amide (solidified) from N-matylamatamine for use in the detergent compositions of the invention.

Step 1-Reactants: maltose monohydrate (Aldrich, 01318KW), methylalamine (40% w / w in water) (Aldrich, 03325TM), Raney-Nickel, 50% suspension (UAD 52-73D, Aldrich. 12921V).

The reactants were placed in a glass cartridge (250 g of maltose, 428 g of methylamine solution, 100 g of catalyst slurry - 50 g of Raney-Ni) and placed in a 31 liter rocking autoclave which was purged with nitrogen (3 x 2 MPa) and hydrogen ( 2 x 2.78MPa), and rocked under a hydrogen atmosphere at room temperature over the weekend at a temperature range of 20 to 50 ° C. The crude reaction mixture was vacuum filtered 2X through a glass microfiber filter with a 1 µg stopper. The filtrate is concentrated to a viscous material. The final traces of water are removed azeotropically by dissolving the material in methanol and then removing the methanol / water mixture on a rotary evaporator. Final drying is carried out under high vacuum. The crude product was dissolved in refluxing methanol, filtered, cooled for recrystallization, filtered and the filter 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 section 2. The filtrate is again concentrated to half its volume and recrystallization is carried out. Very little precipitate is formed. A small amount of ethanol is added and the solution is stored in a refrigerator over the weekend. The solid was filtered off and dried under vacuum. The combined solids contain N-methyl maltamine which is used in step 2 of the overall synthesis.

Step 2 - Reactants ^: N-methylmaltamine (from step 1), hardened tallow methyl esters, sodium metoside (25% in methanol), absolute methane, (solvent), molar ratio 1 = 1 amine: ester, initial catalyst concentration 10 mol% (hmotn./p.

maltamine) and increased to 20 mol%, solvent content 50 wt%).

In a sealed bottle, 20.36 g of tallow methyl ester was heated to the melting point (water bath) and placed in a 250 ml 3-necked round bottom flask equipped with a mechanical stirrer. The flask is heated to about 75 ° C to prevent the ester from solidifying. Separately, 25.0 g of N-methylmaltamine was combined with 45.36 g of methanol, and the resulting suspension was 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 was not clear yet, so an additional 10 mol% catalyst (to a total of 20 mol%) was added and the reaction continued overnight (about 68 ° C), after which time the reaction mixture was clear. The reaction flask is then adjusted for distillation. The temperature is raised to about 110 ° C.

Distil at atmospheric pressure for 60 minutes. Distillation is then started at high vacuum and continued for 14 minutes, after which time the product is very sticky. The product is left in the reaction flask for 60 min at 110 ° C (external temperature). The product was then removed from the flask and triturated with ethyl ether over the weekend. The ether is removed on a rotary evaporator and the product is stored overnight in an oven and ground to a powder. Any residual N-methyl maltamine is removed from the product using silica gel. A slurry of silica gel in 100 methanol was placed in a funnel and washed several times with 100% methanol. A concentrated sample of the product (20 g in 100 mL of 100% methanol) was placed on silica gel and eluted several times under vacuum and several washes. The combined eluate was evaporated to dryness (rotary evaporator). Any residual tallow ester was removed by trituration with ethyl acetate overnight followed by filtration. The filter cake is dried overnight in an oven. The product is alkyl-lactic acid N-methyl maltamide.

In the following alternative process, step 1 of said reaction process may be carried out using a commercial corn syrup containing glucose or a mixture of glucose and typically 5% or more of maltose. The resulting polyhydroxy fatty acid amides and mixtures thereof can be used in any of the detergent compositions of the invention.

In yet another process, Step 2 of the previous reaction process can 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, as desired by 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 requirements of the formulator, the composition of the invention may optionally contain more or less suds control agents. Typically, high sudsing is desirable for dishwashing and therefore no suds control agent will be used. For the washing of fabrics in top-load washing machines, some foam control is desirable, and for front-load washing machines, foam control can be largely preferred. A wide variety of suds control agents are known in the art and may be routinely selected as desired. The choice of suds control agents or mixtures of such agents for any detergent composition will depend not only on the presence and amount of polyhydroxy fatty acid amide, but also on the other surfactants present in the composition. However, it is apparent that the use of polyhydroxy fatty acid amides, silicone suds control agents of different types (i.e., lower concentrations can be used) are more effective than various other types of suds control agents. Particularly suitable are the 1 icon suds control agents available as X2-3419 and Q2-3302 (Dov Corning).

The fabric wash formulator, which may advantageously contain a soil release agent, has a choice of a variety of known materials (see, for example, U.S. Patent Nos. 3962152, 4116885. 4238531, 4702857, 4721580 and 4877896). Other soil release materials that are suitable include the nonionic oligomeric esterification products of the reaction mixture containing a source of C 1 -C 4 alkoxy-terminated polyethoxy units (e.g.

CH3 (OCH2CH2) (OH), a source of terephthaloyl units (e.g.

di-methyl 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 where the molar ratio of oxyethyleneoxy units to oxyisopropyleneoxy units is at least about 0.5: 1. Such anionic agents they have the general formula for releasing impurities:

wherein R ¹ is lower (e.g., C 1 -C 4 alkyl, especially methyl, x and y are each an integer from about 6 to about 100, m is an integer from about 0, 75 to about 30, n is an integer from about 0, 25 to 20 and ^R2 is a mixture of H and CH 3 with the proviso that the mole ratio of oxyethyleneoxy - oxyizopropylénoxy is at least about 0.5 first

Another preferred type of soil release agents are those of the anionic type described in U.S. Patent 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 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 include, for example, the reaction product of dimethyl ether terephthalate, ethylene glycol, 5-sodium sulfosobenzoate and 3-sodium sulfobisophthalate. Such agents are preferred for use in granular laundry detergents.

The formulator may also determine that it is preferable to use a non-perborate bleaching agent, especially in high performance granular laundry detergents.

Various peroxide bleaches are commercially available, and can be used, but of these the most available and economical percarbonate is available. Thus, the compositions of the invention may contain a solid percarbonate bleaching agent, normally in the form of the sodium salt, incorporated at a concentration of from 3% to 20% by weight, more preferably from 5% to 18% by weight and most preferably from 8% to 15% by weight of the composition.

Sodium percarbonate is an addition compound having the formula corresponding to 2Na2CO3-3H2O2 and is commercially available as a crystalline solid. Most commercially available materials include a small amount of heavy metal separator, such as EDTA,

1-hydroxyethylidene-1,1-diphosphonic acid (HEDP) or aminophosphate, which are incorporated during the manufacturing process. For use in the compositions of the invention, the percarbonate may be included in the detergent compositions without further protection, but preferred embodiments of the invention use a stable form of material (FMC). Various coatings may be used.

the most economical is sodium silicate SiO2

Na 2 O in a ratio of 1.6 to 2.8 L, preferably 2.0 - 1 L applied as an aqueous solution and drying to give a concentration of from 2% to 10% (usually 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 of the crystalline percarbonate is from 350 microns to 450 microns with a diameter of approximately 400 microns. When coated, the crystals range in size from 400 to 600 microns.

The heavy metals present in the sodium carbonate used for the production of the percarbonate can be controlled by incorporating scavengers into the reaction mixture, yet the percarbonate still requires protection from the heavy metals present as impurities in other product components. It has been found that the total concentration of iron, copper and manganese ions in the product should not exceed 25 ppm and preferably should be less than 20 ppm to avoid an adverse effect on the percarbonate stability.

The modern thickened detergent granule has the following composition.

Example 15

Component _________________________________________________ mass. %

C 14 -C 15 alkylalcohol sulfonic acid, 113.00

C14-C15 alkylpolyethoxy (2.25) sulfonic acid 5.60

C12-C13 alkylpolyethoxylate (6.5) 1.45

C12-C114 fatty acid such as N-methylglucamide2,5 sodium aluminosilicate (as hydrated Zeolite A) 25,2 crystalline layered silicate-based activator ¹ 23,2 citric acid10,0 sodium carbonate for washing pH = 9,90 sodium polyacrylate ( (2000 - 4500) 3.2 diethylenetriaminepentaacetic acid 0.45

Savinase ² 0.70 6-Nonancy-1-6-oxo-peroxycaproic acid 7.40 Sodium perborate monohydrate2.10 Nonanoylbenzenesulfonic acid 5.00 Brightening agent 0.10 ¹ Layered silicate materials are known in the art. Layered sodium silicate is preferred. See e.g. sodium silicate based layered actives, U.S. Pat. No. 4,666,495, issued May 12, 1987 to HP Rieck, which is incorporated herein by reference. A suitable layered silicate activator is available as SKS-6 from Hoechst.

² Available from Novo Nordisk A / S, Copenhagen.

Significantly preferred granules of the mentioned types are those containing about 0.0001% to 2% by weight of the active enzyme and at least about 1% by weight. said polyhydroxy fatty acid amide; and most preferably wherein the anionic surfactant is not an alkylbenzenesulfonate surfactant.

Described herein are compositions which are liquid and are intended to be laundered as the compositions of the invention. It should be noted that the stability of enzymes in such detergents should be less than in granular detergents. By using typical enzyme stabilizers such as formates and boric acid, lipase and cellulase enzymes can be protected from degradation by protease enzymes. However, lipase stability is still relatively poor in the presence of alkylbenzene sulfonate surfactants. LAS partially denatures the lipase and further causes the denatured lipase to be less resistant to protease attack.

In view of the above requirements, which may have been somewhat problematic in liquid formulations, there is an incentive to provide liquid detergent formulations containing together enzymes lipase, protease and cellulase. It is particularly desirable to provide this tertiary enzyme system in stable liquid detergents together with an effective cleaning surfactant composition. In addition, it is difficult to incorporate stable peroxidase and / or amylase enzymes into such formulations.

It has now been found that it is possible to obtain various mixtures of lipases, proteases, cellulases, amylases and peroxidases which are adequately stable in the presence of some non-alkylbenzene sulfonate surfactant systems so that it is possible to formulate highly

II

R ² - C wherein R ¹ is H, C 1 -C 4, or a mixture thereof, effective solid and liquid detergents. Formulation of stable, liquid, enzyme-containing detergent compositions is a very advantageous embodiment achieved by the technology of the invention.

Liquid detergents of the prior art typically comprise LAS or mixtures of LAS with surfactants of the type RC (A) mSO 3 M (AES) described above, i. j. of the LAS / AES mixture. In contrast, the liquid detergents of the invention comprise binary mixtures of AES and polyhydroxy fatty acid amides of the type described herein. Although a minimum amount of LAS will be present, it should be understood that this will reduce the stability of the enzymes. Accordingly, it is preferred that the liquid formulations are substantially free of (i.e., contain less than about 10%, preferably less than about 5%, more preferably less than about 1%, and most preferably 0 LAS).

The present invention provides liquid detergent compositions comprising:

a) from about 1% to about 50%, preferably from about 4% to about 40%, of an anionic surfactant,

b) from about 0.0001% to about 2% of an active purification enzyme;

c) an enzyme activity increasing the amount (preferably from about 0.5 to about 12%) of the polyhydroxy fatty acid amide of the formula

R ¹

NZ hydrocarbyl, 2-hydroxyethyl, 2-hydroxypropyl R ² is C 5 -C 31 hydrocarbyl and Z is polyhydroxyhydrocarbyl having a linear hydrocarbyl chain with at least 3 hydroxyls directly attached to the side chain, or alkoxylated derivatives thereof, and said composition is substantially free of alkylbenzenesulfate.

The water-soluble anionic surfactant herein preferably represents (AES):

R 0 (A) _m SO ₃ M wherein R is an unsubstituted C 10 -C 24 alkyl or hydroxyalkyl (C 10 -C 24) group, A is an ethoxy or propoxy unit, m is an integer greater than 0 and M is hydrogen or a cation. Preferably, R is an unsubstituted C 12 -C 18 alkyl group. A is an ethoxy unit, m is from about 0.5 to about 6, and M is a cation. The cation is preferably a metal cation (e.g. preferably sodium or potassium, lithium, calcium, magnesium, etc.) or an ammonium or substituted ammonium cation.

It is preferred that the ratio of the above surfactant (AES) to the polyhydroxy fatty acid amide be from about 1

 2. to about 8 most preferably from 1, p about 1 advantage from  1 to as i 1 as i 4 = first 1 1 do äs i 5: 1 alternately they can preparations by invention to contain am i d polyhydroxy fatty acid, AES and from about 0.5 ¾ do about 5 ¾

a C8-C22 (preferably C10-C20) condensation product of a linear alcohol with from about 1 to about 25, preferably from about 2 to about 18 moles of ethylene oxide per mole of alcohol.

As described above, the liquid formulations of the invention have a pH in a 10% solution in water at 20 ° C of from about 6.5 to about 11.0, preferably from about 7.0 to about 8.5.

The instant compositions preferably further comprise from about 0.1% to about 50% of a detergent builder. These compositions preferably contain from about 0.1% to about 20% citric acid or its water-soluble salts and from about 0.1% to about 20% water-soluble succinate-tartrate, especially its sodium salt and mixtures thereof, or from about 0.1% to about 20% by weight. % of oxydisuccinate or mixtures thereof with the above-mentioned activating additives. It is also possible to use 0.1¾ - 50¾ alkenylsuccinate.

Preferred liquid formulations of the invention include from about 0.0001 ¾ to about 2, preferably from about 0.0001 ¾ to about 1, most preferably from about 0.001 ¾ to about 0.5, based on the active base of the purification enzyme. These enzymes are preferably selected from the group consisting of protease (preferably), lipase (preferably), amylase, cellulase, peroxidase, and mixtures thereof. Preference is given to formulations with two or more classes of enzymes, most preferably one of which is a protease.

Various purification proteases, cellulases, etc. are described in the literature, purification lipases having a slightly smaller extent. Optionally, the formulator may select Amano AKG lipases and Bacillis Sp lipase (e.g., Solvay enzymes). See, such lipases are described in EP-A-0399681, published November 28, 1990, EP-A-0218272, published on April 15, 1987, which are incorporated herein by reference.

Suitable fungal lipases include those produced by Humicola lanuginosa and Thermomyces lanuginosus. Most preferred is a lipase obtained by cloning a gene from Humicola lanuginosa and expressed in a gene in Aspergillus oryzae as described in European Patent Application 0258068, incorporated herein by reference, commercially available under the trade name

LIPOLASE.

From about 2 to about 20,000, preferably from about 10 to about 6,000 lipase units of lipase per gram (LU / g) of the product may be used in such formulations. Lipase unit is the amount of lipase that produces 1 µmol of titrated butyric acid per minute in a pH meter where pH is 7.0, 30 ° C and the substrate is an emulsion of tributyrin and gum arabic, in the presence of Ca ⁺⁺ and NaCl in phosphate buffer .

The following example illustrates a high performance liquid detergent composition comprising:

a) an enzyme selected from proteases, cellulases, and lipases, or preferably a mixture thereof, typically containing from about 0.0% to about 2% by weight of the total composition, although the amounts to be used may be adjusted according to the requirements of the formulator so as to has obtained an effective amount (ie, clay-removing impurities) of said enzyme or enzyme mixture.

b) a polyhydroxy fatty acid amide surfactant of the type described herein, typically in an amount of at least about 2% by weight of the composition, more typically from about 3% to about 15%, preferably from about 7% to about 14%.

c) surfactants of the type R0 (A) tnSO3M as described herein, preferably R0 (CH2CH2O) mSO3M, wherein R is C14-C15 (avg) and m is 2-3 (avg), wherein m is H or a water-soluble salt-forming cation, e.g. Na ⁺ , and said surfactant constitutes from about 5% to about 25% by weight of the composition,

d) optionally, surfactants of the ROSO3M type as described herein, preferably wherein R is C 14 -C 15 (avg) and said surfactant constitutes from about 1% to about 10% by weight of the composition,

(e) a liquid carrier, in particular water or a water-alcohol mixture;

f) optionally but preferably effective amounts of an enzyme stabilizer, typically from about 1% to about 10% by weight of the composition,

g) optionally, but preferably, water-soluble activating agents, in particular polycarboxylic activating agents, typically from about 4% to about 25% by weight of the composition,

(h) optionally, various cleaning ingredients, brighteners, etc., as described herein, typically (if used) in an amount of about 1% to about 10% by weight of the composition; and

(i) the preparation is substantially free of LAS.

Example 16

Ingredients _________________________________________________%

Sulfonic acid C14-C15 alkylpolyethoxylate (2.25) 21.00

N-methyl C 12 -C 14 fatty acid 7.0 ¹ mono tartrate disuccinate and sodium (mixture of ^80: 20) 4.00 Acid citrónová3,80

C12-C14 fatty acid3,00 tetraethylenepentamine ethoxylate (15-18) 1.50 ethoxylated copolymer of polyethylene and polypropylene terephthalate polysulfonic acid0,20

Protease B (34g / L) ² 0.68

Lipase (100 KLU / g) ³ 0.47

Cellulase (5000 cevu / g) ⁴ 0.14 Brightener 36 ⁵ 0.15 Ethanol5.20 Monoethanolamine 2.00 Sodium formate0.32

1,2 propanediol 8,00 sodium hydroxide 3,10 silicone suds suppressor 0,0375 boric acid 2,0 water / various up to 100,00 ¹ Prepared as described above.

² Protease B is a modified serine protease described in European patent application no. No. 87,303761, filed Aug. 28, 1987, particularly p. 17, 24 and 98.

^The lipase used herein is a lipase obtained by cloning a gene from Humicola lanuginosa and expressed in Aspergillus oryzae as described in European Patent Application 0258068, available under the trade name LIPOLASE (from Novo Nordisk A / S, Copenhagen, Denmark).

The cellulase used herein is available under the trademark Carezyme (Novo Nordisk, A / S, Copenhagen, Denmark).

⁵ Brightener 36 is commercially available as TINOPAL TAS 36.

The brightener is added to the formulation as a separately prepared brightener premix (4.5%> monoethanolamine (60%) and water (35.5%).

Examples 17 A-D

The following examples illustrate light hollow cleaning agents which are specially formulated for washing dishes and for cleaning other hard surfaces. According to Examples A to D, the surfactants contain various alkyl ethoxy sulfate surfactants which, using standard technology, are abbreviated to indicate their average degree of ethoxylation, C12-13 (E0 (8.8) sulfate means a sulfated C12-13 alcohol fraction These anionic ethoxy sulphates are preferably used in the form of their Na ⁺ or ΝΗΝΗ salts C12-13 amine oxide is a mixed C12-13 (average) dimethylamine oxide.

The C12-14AP betaine is

C 12 / 14H25 / 29 CONH (CH 2) 3 N ⁺ (CH ₃ ) ₂ CH ₂ CO ₂ H

C12-14AP sultaine is

C12 / 14H25 / 29C0NHCCH2) 3N '(CH3) 2CH2CH (0H) CH ₂ SO ₃ H C12-14DM betaine is

Cl 2 / 14H25 / 29N ⁺ (CH 3) 2 CH ₂ C0 ₂ H,

Ethoxylated nonionic surfactant (C9-11E0C8) denotes C8 -alcohols ethoxylated with an average of 8 moles of ethylene oxide. The cations Ca ⁺ · * · and Mg ^ * 'are generally introduced in the form of calcium or magnesium chloride. The equilibrium of the formulation is achieved by adding water up to 100% and a citrate / propylene glycol system in the glucamide surfactant (1-5%) and 1-3% cumene or xylene sulfonate hydrotropic agent. The pH is typically in the range of 6.8-7.4 (NH4 · ¹ · salts) or 7-8.2 CNa ⁺ salts).

Percentage (w / w)

A B C D C12-14N-methylglucamide d 11.0 8.0 12.7 9.0 C12-13 LCO, 8) sulphate - 16.0 10,0 9.0 (C12-14EOO) sulphate 11.0 - 2.7 14.0

C12-13ECK6,5) sulphate - - - 3.0 C12-14 AP betaine - - 2.0 - C12-14 AP sultain - - - 1.0 C12-13 amine oxide 2.5 - - 1.0 C12-14 DM betaine - 2.0 - - C9-11E0 0.5 8.0 7.0 - Ca ⁺⁺ - - 0.5 1.0 Mg ⁺⁺ 0.9 00:25 - - balance to to to to 100% Liquid detergent preparation for washing machines suitable for the use at high (relative) concentrations for automatic washing machines

front-filled, especially in Europe, for a wide temperature range.

Component wt.

N-methylglucamine acid (C12)

of coconut fat 14 C14-15 E0 (2,25) sulphate, Na salt 10,0 C14-15 E0 4.0

acid anhydride

C12-14 alkenylsuccinic ¹ 4.0 C12-14 fatty acid ^x 3.0 citric acid (anhydrous) 4.6 Protease (enzyme) ² 0.37 Termamyl (enzyme) ³ 0.12 L i po lase (enzyme) ⁴ 0.36 Carezyme (enzyme) ⁵ 0.12 Deguest 2060S ⁶ 1.0 NaOH (pH 7.6) 5.5 1,2-propanediol 4.7 ethanol 4.0 sodium metaborate 4.0 CaCl ₂ 0,014 ethoxylated tetraethylenepentam disulfide ⁷ 0.4 brightener ⁸ 0.13 Si lane ⁹ 0.04 soil release polymer ¹⁰ 0.2 Silicone (antifoam) ¹¹ 0.4 Siicone dispersing agent ¹² 0.2 water and various to 100

¹ As SYNPRAX 3 from ICI or DISA from Monsanto ² As Protease B as described in EPO 0342177, November 15, 1989, percent to 40 g / l.

³ Amylase, from Novo, percent to 300 KNU / g.

⁴ Lipase, from Novo, percent to 100 KLU / g.

⁵ Celulase from Novo, percent to 5000 CEVU / 1.

⁶ Available from Monsanto.

⁷ From BASF as LUTENSOL P6005.

⁸ SLANKOPHOR CPG766, Bayer.

⁹ Silane corrosion inhibitor, available as A1130 from Union Garbide or DYNASYLAN TRIAMINO from Huls.

¹⁰ Polyester, U.S. Pat. No. 4,711,730.

¹¹ Silicone antifoam agent available as Q2-3302 from Dow Corni ng.

¹² Dispersant for si 1 icon antifoam available as DC-3225C from Dow Corning.

¹³ The preferred fatty acid is a proportion of palm oil having% oleic, and 2% stearic acid and the same amount of linoleic acid.

Example 19

Granular detergent composition, suitable for use at relatively high concentrations in front-load automatic washing machines, especially in Europe, and over a wide temperature range.

component

weight

SOKALAN CPS (100% active as Na salt) ¹ 3.52

DEQUEST 2066 (100% active as acid) ² 0.45

TINOPAL DMS ³ 0.28

MgSCM0,49

Zeolite A (anhydrous 2-5 nm) 17.92

CMC (100% active) ⁴ 0.47

NaC039,44 citric acid 3.50 layered silicate SKS-612.90 tallow alkyl sulfate (100% active, Na salt) 2.82

C14-15 alkyl sulfate (100% active, Na salt) 3.50

C12-15 alkyl (E0 (3)) sulfate 1,76

C16-18 N-methylglucamide4,10

DOBANOL C12-15 E0 (3) 3.54

LIPOLASE (100.00 LU / g) ^δ 0.42

SAVINASE (4.0 KNPU) ⁶ 1.65 perfume 0.53

X2-3419 ⁹ 0,22 Starch

1.08 stearyl alcohol 0.35 sodium percarbonate (coated) 22.30 tetraethylenediamine (TAED) 5.90 zinc phthalocyanine 0.02 water (ex zeolite) to 100% ¹ SOKALAN is sodium polyacrylate / maleate available from Hoechst.

² Monsanto label for pentaphosphonomethyldiethylenetriamine.

³ Optical brightener available from Ciba Geigy.

⁴ Trademark FINNFIS by Metasaliton.

⁵ LIPOLASE lipolytic enzyme from NOVO.

⁶ SAVINASE protease enzyme from NOVO.

⁷ X2-3419 is 1 icon antifoam available from Dov

Corning.

The process for preparing granules involves various tower drying.

agglomeration, addition of dry ingredients, etc. as below The percentages are based on the final formulation.

A. Mixing and blowing towers

Using standard techniques, mix and tower the following components: SOKALAN CPS 3.52% DEQDEST 2066 0.45% TINOPAL DMS 0.28% magnesium sulfate 0.49% Zeolite A as anhydrous 7,10% CMC 0.47%

B. Surfactant agglomerates

BI. Agglomeration of sodium tallow alkyl sulfate and C 12-15E0 (3) sulfate sodium paste

50% active tallow alkyl sulfate paste and 70% paste

The C12-15EO (3) sulphate is agglomerated with Zeolite A and sodium carbonate in the following composition (fraction in the detergent composition after drying the agglomerate).

tallow alkyl sulfate

Cl2-i5E0 (3) sulfate

Zeolite A sodium carbonate

2.82%

1,18%

5,30%

4.50%

B2. Agglomerates of C14-15 alkylsulfate, C12-isalkylethoxysulfate, Dobanol C12-isE0 (3) and C18-N-methylglucosamide.

The C 16-18 glucosoamide nonionic material is synthesized with Dobanol (12-12EOO) present during the reaction of the methyl ester and N-methylglucamine. C12-isE0 (3) acts as a depressant of melting point due to which the reaction proceeds without formation of cyclic glucosamides which are undesirable.

A mixture of surfactants with 20% Dobanol is obtained

C12-15EO (3) and 80% C18-N-methylglucosamide and coagglomerated with 10% sodium carbonate.

Thereafter, the above particles are coagglomerated with a highly active paste (70 ') of C 15 -isalkyl sulfate C 12 -isE0 (3) sulfate sodium salt and Zeolite A, and in particular sodium carbonate. These particles have good cold water dispersibility for C16-1e N ^- methylglucosamide.

Throughout the formulation these particles They are represented (ratio in detergent after drying the agglomerate) as follow: C18-18 N-methylglucamide 4.10 ¾ DOBANOL C12-15 E0 0.94 ¾ sodium carbonate 4.94 % Zeollte A 5.30 ¾ Na C14-15 alkyl sulfate 3:50 ¾ For C12-15 E0 (3) sulphate 0.59 % C. Dry ingredients The following ingredients are added: percarbonate 22:30 ¾ TAED (tetraacetylethylenediamine) 5.90 ¾ SKS 6 layered Siat by Hoechst 12.90 % citric acid 3.50 ¾ Lipolase 0.42 ¾ 100000 LU / g SAVINASE 4.0 KNPU 1.65 Zinc phthalocyanine (photo brightener) 0.02 ¾ D- Spraying on DOBANOL C12-15 E0C3) 2.60 ¾ perfume 0.53 ¾

E. Suds suppressant

Si 1 iconic suds suppressor X2-3419 (95-97% high molecular weight silicone, 3-5¾ hydrophobic silica) from Dov Corning is coagglomerated with Zeolite A (2-5 µm size), starch and stearyl alcohol binder.

The particles have the following composition:

Zeolite And Starch

X2-3419 stearyla1koho1

0.22%

1.08%

0.22%

0.35%

The detergent composition exhibits excellent solubility and excellent foaming control when used in European washing machines, for example when using 85 g in an AEG washing machine at 30 ° C, 40 ° C, 60 ° C and 90 ° C for washing cycles.

Example 20

In all of the preceding examples, the fatty acid glucamide surfactant may be replaced by an equivalent amount of a maltamide surfactant or a glucamine / maltamide surfactant mixture obtained from natural sugar sources.

In the formulations, the use of ethanolamide appears to aid in maintaining the stability of the finished formulations in cold storage. In addition, the use of sulfobetaine (sultain) surfactants provides increased foaming.

The following examples illustrate other liquid formulations which are particularly suitable for Light Hollow Use as in dishwashers.

Example 21 A-D component percent weight. A B C D

Cis-i-Alkyl Ethyl Sulfate (E0) 16.0 9.0 12.0 - C12-14alkylethoxysulfate C3 E0) - 14.0 - 11.0 C10 alkyl ethoxylate (C8E0) 7.0 3.0 7.0 1.0 C12-14 N-methylglucamide 8.0 9.0 12.0 6.0 coconut oil diethanolamide - - - 5.0

dimethyldodecylamine - 1.0 - 2.0 cocoamine doproxyhydroxysilane - 1.0 3.0 - kokoam i dopropy1be tin n 2.0 - - - Mg '* - - 1, o 1.0 Ca ⁺ * 0.5 1.0 - - sodium toluenesulfonate 3.0 3.0 3.0 3.0 ethanol 4.0 4.0 4.0 4.0 Water to 100

For detergents where high sudsing is desired (e.g., in the case of dishwashing detergents), it is preferred that they contain no suds suppressing agents. Since fatty acids containing 14 or more carbon atoms may act as suds suppressing agents, it is preferred that dishwashing compositions contain less than 5% by weight, preferably less than about 2%, of C 14 and more fatty acids, and in particular to contain no C 14 or more fatty acids. Therefore, experts in the case of high suds cleaners avoid introducing a quantity of such suds suppressing fatty acids into high suds cleaners containing polyhydroxy fatty acid amides and / or avoid formation of fatty acids of 14 or more carbon atoms when storing the finished cleansing compositions of the invention . A simple solution is to use 12-carbon ester reagents to prepare polyhydroxy fatty acid amides. Fortunately, the use of amine oxide or sulfobetaine surfactants can prevent the negative effects on fatty acid foaming.

A person skilled in the art wishing to add anionic brightening agents to liquid cleaning compositions containing relatively high concentrations (e.g., 10¾ and above) of anionic or polyanionic substituents, such as polycarboxylate activators, may find it advantageous to prepare an optical masterbatch composition with a brightener. with polyhydroxy fatty acid amide, and then add this to the final formulation.

Polyglutamic acid or polyaspartic acid dispersants can suitably be used with detergents containing zeolite activating agents. AE liquid or flakes and DC-544 (Dou Corping) are further examples of antifoaming agents that can be used in the compositions of the invention.

It will be appreciated by those skilled in the art that the preparation of polyhydroxy fatty acid amides 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 by a polyhydroxy ring structure. Such materials are fully within the scope of the present invention and do not depart therefrom.

Claims (14)

PATENT CLAIMS CLAIMS 1. A detergent composition comprising at least 1% by weight of an alkylalkoxylated sulfate surfactant and optionally surfactants and adjuvants, characterized in that the improvement comprises incorporation into the surfactant. preparation at least polyhydroxy fatty 1 of % by weight amide of formula as a surfactant • where R ¹ is H, □ R ¹ II 1 R ² -C "N" Z C 1 -C 4 hydrocarbyl, 2-hydroxyethyl or 2-hydroxypropy1, R ² is C7-C31 hydrocarbyl a Z is polyhydroxyhydrocarbyl, which has a linear hydrocarbyl chain with at least 3 hydroxyls directly attached to said chain, or an alkoxylated derivative thereof, and said composition is characterized in optionally containing a suds suppressant amount of a suds suppressor, and having a polyhydroxy fatty acid amide ratio of alkylalkoxylated sulfate of from 1 to 2 = 10 to 10 ^: 1, preferably 1 = 1 to 1: 4. 2. A detergent composition according to claim 1 comprising at least 3% polyhydroxy fatty acid amide and at least 3% alkyl ethoxylated sulfate and said suds suppressor is selected from the group consisting of monocarboxylic fatty acids and salts thereof with 1 iconic agents. for suds suppressors, monostearyl phosphate suds suppressors and hydrocarbon suds suppressors and hydrocarbon suds suppressors. The detergent composition of claim 2, further comprising from 1% to 25% of a co-surfactant component. A detergent composition according to claim 3, wherein said surfactant auxiliary comprises an alkylbenzene sulfonate surfactant, an alkyl sulfate surfactant, an alkyl ester sulfonate surfactant, an alkyl ethoxylate, an alkylphenolalkoxylated surfactant, an alkylpolyglycoside, or a paraffin glycoside, or a paraffin glucoside thereof. 5. A detergent composition according to claim 4, wherein said suds suppressor comprises at least 0.5% monocarboxylic fatty acid or salt thereof. 6. The detergent composition according to claim 4, characterized in that R ¹ is methyl. R ² is C 9 -C 10 alkyl or alkenyl, Z is -CH 2 CCHOH, -CH 2 OH, -CH (CH 2 OH) - (CHOH) _n -1 -CH 2 OH, or -CH 2 - (CHOH) 2 (CHO ') (CHOH) -CH 2 OH, n is an integer from 3 to 5 inclusive and R 'is H or a cyclic or aliphatic monosaccharide. bb 7. The detergent composition according to claim 6, characterized in that Z is-CH2 (CH0H) 4 CH ₂ 0H. 8. The formulation of claim 1 wherein said polyhydroxy fatty acid amide is Z derived from maltose. Composition according to claim 1, characterized in that, with respect to the polyhydroxy fatty acid amide, Z is derived from a mixture of monosaccharides, disaccharides and optionally higher carbohydrates, the mixture comprising at least one disaccharide, preferably maltose. • 10. A detergent composition according to claim 1, further comprising at least 1% by weight of a detergent builder. The detergent composition according to claim 1, wherein said alkylalkoxylated sulfate based surfactant is a C 14 -C 18 -alkylethoxylated sulfate having an average degree of ethoxylation of from 0.5 to 6. 12- Method of washing textiles. characterized in that it comprises contacting said fabrics with an aqueous medium. comprising a detergent composition according to claim 1. The method of claim 12, wherein said Z group in the polyhydroxy fatty acid amide is derived from mixed monosaccharides, disaccharides and polysaccharides available from plant sources. A method according to claim 12, characterized in that. wherein said R ² group in the polyhydroxy fatty acid amide is C 15 -C 17 alkyl, alkenyl, or a mixture thereof.