CZ42493A3 - Detergent composition containing amides of polyhydroxy-fatty acids and alkylalkoxyl sulfates - Google Patents

Abstract

Detergent compositions are disclosed containing alkyl alkoxylated sulfate and certain polyhydroxy fatty acid amide surfactants in combination with suds suppressors or auxiliary surfactant component, or in select ratios of alkyl alkoxylated sulfate to polyhydroxy fatty acid amide, and combinations thereof.

Description

Conventional nonionic surfactants in combination with alkyl alkoxylated sulfates, such as alkyl ethoxylates, may provide acceptable cleaning, but typically require relatively long wash times, high wash temperatures, and high surfactant concentration 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 can be obtained for the most part or completely from natural, renewable, non-petroleum raw materials.

Various polyhydroxy fatty acid amides have been described in the art. N-Ajyl, N-methylglucamides are described, for example, in JWGoodby, A. toarcus, E.Chin and PkFinn in The Thermotropic LiquidGrystalline Properties of Some Straight Chain Carbohydrate Attphiphiles ¹ *, Liauid Cr.ystals, 1988, vol. 3, No.11, pp. 1569-1581, and A. Müller-Eahrnow, V. Zabel, Fo. Hilgenfeld in "Molecular and Crystal Gtructure of a NoAionic Detergent: Nonanoyl-N-methylglucamide ^M , J. Chem. Chem. Commun., 1986, pp. 1573-1574. The use of N-alkyl polyhydroxy amide surfactant materials is centered aktivníah ¹ Wear attention for use in biochemistry, for example in the dissociation of biological membranes. See, eg, ND-Gluco-N-methyl-alkanamide Compounds, and the New Class of Non-ionic Detergents For Hemembrane Biochemistry, Biochem, J. (1982), Vol.207, pp 363-366, by JEKHildreth.

The use of N-alkyl glucamides in detergent compositions has also been described. U.S. Patent No. 2965576, issued December 20, 1960 to E.R. Wilson and GB Patent No. 809060, published February 18, 1959, issued to Thomas Hedley and Co., Ltd. relates to detergent compositions comprising anionic surfactants and certain amide surfactants, which may include N-methylglucamide (s) added as a low temperature suds booster. These compounds include a 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 dye, bleach, etc.

US Patent No. 2703798, issued March 8, 1-55 by A.M. Schwartz 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. Patent No. 2,717,894, issued September 13, 1955 to A.M. Schwartz.

PCT International Application WO 83/04412, published December 22, 1983, by J. Childeth, relates to amphiphilic compounds containing polyhydroxyl aliphatic groups designated as being useful for various purposes including use as surfactants in cosmetics, pharmaceuticals, shampoos, lotions and eye ointments, as emulsifiers and dispersants, for medical use and in biochemistry, for the solubilization of membranes, whole cells or other tissue samples, and for the preparation of

-4liposomes. Included in this disclosure are compounds of formula R * CON (R) CH ₂ R ^M and RGON (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 an aldose residue .

European Patent No. 0285768, published Oct. 12, 1988 by H. Kelkenberg et al., Relates to the use of N-polyhydroxyalkyl fatty acid amides as thickening agents in aqueous detergent systems. Included are amides of the formula R G (O) N (X) _R2 wherein R ^ is C ^ -C ^ (preferably C ^ Cy-Jelkyl, R ₂ is hydrogen, ^C ^ - ^G 18 (preferably C ^ -C ^ J is an alkyl or alkylene oxide and X is a polyhydroxyalkyl having four to seven carbon atoms, e.g., N-methylglucamides of coconut fatty acid. The amide thickening properties are indicated to be particularly suitable for use in liquid surfactant systems containing paraffin sulfonates although aqueous surfactants. the active systems may include other anionic surfactants such as alkylarylsulfonates, olefin sulfonates, sulfosuccinic acid semi-ester salts and fatty alcohol ether sulfonates, and nonionic surfactants such as fatty alcohol polyglycol ether, polyphenol alkylphenol, polyglycol ester fatty acids, polypropylene oxide-polyethyl polyethylene oxide, etc. .. Examples are shampoo formulations of paraffinsulfonate (coconut fatty acid N-methylglucamide) In addition to the thickening properties, N-polyhydroxyalkyl fatty acid amides are said to be excellent in terms of skin tolerance.

U.S. Patent No. 2982737, issued May 2, 1961 to Boettner et al., Relates to urea-containing detergent bars, a sodium lauryl sulfate surfactant, and an N-alkyl amide nonionic surfactant selected from N-methyl, N-sorbityl lauramide; and N-methyl, N-sorbityl myristamide.

Other glucamide surfactants are described, for example, in DT δ. 226872, published December 20, 1973, by HWEckert et al., Which relates to detergents containing one or more surfactants and builder salts selected from the group consisting of polymeric phosphates ⁷ , scavengers and laundry alkalis, improved by the addition of N an acylpolyhydroxyalkyl amine of the formula R ₁ is C 1 H 6 R 8 (CH 3) CHOH 4 -C 1 OH, where R ₄ is C 1 -C 4 -alkyl, R ₂ is C 1 -C 4 -alkyl and n is 3 or 4.

N-Acyl polyhydroxyalkylamine is added as an impurity suspending agent.

U.S. Patent No. 3,654,166, issued April 4, 1972 to HW Eckert et al., Relates to detergent compositions comprising at least one surfactant selected from the group of anionic surfactants, zwitterionic agents ^7, and nonionic surfactants and a fabric softener, N-acyl, N-alkylpolyhydroxyalkyl compounds of formula R 1 N (Z) C (O) R ₂ , wherein R ₁ is C ₀ -C ₂₂ alkyl, R ₂ is C ₁ -C 4 alkyl, R ₁ and R ₂ have a total of from 23 to 39 carbon atoms and 2 is a polyhydroxyalkyl which can be -CH formula _of (GH0H) _of GH 0H where m is 3 or 4.

U.S. Patent 6,402,139, issued May 3, 1977 to H. Müller et al., Relates to skin care cosmetic compositions containing N-polyhydroxyalkylamines which include compounds of the formula R 4 N (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 Rp but both cannot be H, and R ₂ is CH ₂ OH or GOOH.

French Patent No. 1360018, April 26, 1963, to Commercial Solvents Corporation, relates to formaldehyde solutions stabilized against polymerization by the addition of amides of the formula R @ 1 R @ R @ R @ 2 G, wherein R is a carboxylic acid functional group having at least seven carbon atoms;

-6-hydrogen or a lower alkyl group; and G is _a glycitol radical of at least 5 carbon atoms.

German Patent No. 1261861, February 29, 1968, to A. Heins, relates to glucamine derivatives useful as wetting and dispersing agents having the formula N (r) (R ^) (R ^) wherein R is a sugar residue of glucamine, R ^ is a C 1 -C 2 ^G alkyl radical and is a C 1 -C 4 acyl radical;

GB patent published February 15, 1956, Atlas Powder 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 pc) R 1, wherein R is a dehydrated water residue of hexanpentol or a carboxylic acid ester thereof, 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-ethylenediamine-ethylene oxide condensates, propylene oxide propylene glycol. -ethylene oxide condensates and polymerized ethylene glycol and also contain a nonionic foaming component, which may include a polyhydroxyamide of formula RC (O) Nr (r), wherein RC (O) contains from about 10 to about 14 carbon atoms and R ¹ and R ² are each H or C ₁ -C 6 -alkyl groups, said alkyl groups having a total number of carbon atoms of from 2 to about 7 and a total number of substituents of hydroxyl groups of from 2 to about 6. No. 3312626, also issued April 4, 1967, to DT Hooker.

SUMMARY OF THE INVENTION

The present invention provides a low sudsing detergent composition comprising, in general, a polyhydroxy fatty acid amide surfactant of the formula

OR ¹

R ² _ C - II - a wherein R ¹ is H, C ^ -C ^ alkyl, 2-hydroxyethyl or 2-hydroxypropyl, R ² is a C ^ -C ^ alkyl, and Z is a linear 'hydrocarbon radical having at least three hydroxyl groups directly bonded to the hydrocarbon chain or alkoxylated derivatives thereof with an alkylalkoxylated sulfate surfactant; and in an amount of suds suppressor, a suds suppressor, preferably selected from the group consisting of monocarboxylic fatty acids and salts thereof, silicone suds suppressors and alkali metal di-salts of monostearyl phosphates or phosphate esters, and suds suppressors high molecular weight hydrocarbon foams and mixtures thereof; wherein the composition is preferably characterized by a weight ratio of alkyl-alkoxylated sulfate: polyhydroxy fatty acid amide of about 10: 1 to about 1:10, more preferably about 5: 1 to about 1: 5, most preferably from about 4: 1 to about 1: 1 .

Preferred alkyl alkoxylated sulfate surfactants are alkyl ethoxylated sulfates having an ethoxylation degree ranging from about 0.5 to about 6.

In another aspect, the present invention provides detergent compositions comprising alkylethoxylated sulfate surfactants and polyhydroxy fatty acid amides as described above, wherein R is methyl, R is

9 ~ ^{G G} I ^Y · lkyl or alkenyl, Z is gl.ycityl derived from a reducing sugar or a derivative thereof and alkoxyloveného ratio of alkyl ethoxylated sulfate: polyhydroxy masses TNE acid is from about 1: 1 to about 4: 1, preferably about 3: 1.

In another aspect of the invention, detergent compositions are provided with polyhydroxy fatty acid amides and alkylalkoxylated (preferably ethoxylated) sulfate surfactants as described above, further comprising a co-surfactant selected from alkyl sulfates, alkyl sulfonate esters, alkyl phenolalkoxylates, alkylbenzenesulfonates, alkylbenzenesulfonates, alkylbenzenesulfonates, alkylbenzenesulfonates , and alkyl polyglycosides and mixtures thereof. Preferably, the surfactant auxiliary comprises from about 1% to about 25% by weight of the detergent composition. Additional surfactant adjuvants may additionally be present in the detergent composition as well as optionally 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 detergent composition comprising as surfactant a polyhydroxy fatty acid amide of formula

OR ^{1 -} H 1 - O - N - Z wherein R ¹ is H, C 1 -C 4 hydrocarbyl, 2-hydroxyethyl, or 2-hydroxypropyl, R ² is C 1 -C 4 hydrocarbyl and Z is polyhydroxyhydrocarbyl having a linear hydrocarbyl chain with at least 3 hydroxyls directly attached to the chain, or alkoxylated derivatives thereof; an alkylalkoxylated sulphate surfactant; and foam forming an amount of a suds suppressor, preferably selected from the group consisting of monocarboxylic fatty acids and salts thereof,

-9 silicone suds suppressors and suds suppressor hydrocarbons, and alkali metal di-salts and monostearyl phosphates or phosphate esters, and mixtures thereof.

Preferably, the weight ratio of alkyl alkoxylated snipates to polyhydroxy fatty acid amide is from about 1:10 to about 10: 1, more preferably from about 1: 5 to about 5: 1 even more preferably from about 4: 1 to about 1: 1. Preferably also the alkylalkoxylated sulfate comprises a alkoxylated sulfate surfactant having an ethoxylation degree greater than 0.5, typically from about 0.5 to about 6, preferably from about 0.5 to about 3.

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

The individual components are described in more detail below.

Surfactants based on polyhydroxy fatty acid amides

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 comprises compounds of Formula I

-10ο Η ¹ ο '· ι

- c - Ιί - Ζ (I) wherein R 1 is Η, C 1 -C 2 hydrocarbyl, 2-hydroxyethyl, 2-hydroxypropyl, or a mixture thereof, preferably C 1 -C ₂ alkyl, more preferably C 1 or C ₂ alkyl, most preferably alkyl (i.e., methyl), and R ² is C ¹ -C 6 hydrocarbyl, preferably straight chain alkyl or alkenyl of 7 to 19 carbon atoms, more preferably straight chain alkyl or alkenyl of 11 and 17 carbon atoms, or a mixture thereof, and Z is a polyhydroxyhydrocarbyl having a linear hydrocarbyl chain with at least 3 hydroxyls directly attached to the chain, or an alkoxylated (preferably ethoxylated or propoxylated) derivative thereof. Z preferably will be derived from a reducing sugar in a reductive amination reaction; more preferably Z is glycityl. Suitable reducing sugars include glucose, fructose, maltose, lactose, galactose, mannose, and xylosis. As raw materials, high dextrosis 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. Z will preferably be selected from the group consisting of -CH ₂ - (CHOH) _n -CH ₂ OH, -CH (GH ₂ OH) - (GHOH) CH ₂ OH, -CH ₂ - (CHOH) ₂ (GHOR *) (CHOHJ) -C 1 OH, wherein n is an integer from 3 to 5 and k 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 -gh ₂ oh.

In Formula 1, for example, N-methyl, N-ethyl, N-propyl, N-isopropyl, N-butyl, N-2-hydroxyethyl or N-2-hydroxypropyl may be:

-1 12

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

Z. may be 1-deoxyglucityl, 2-deoxyfructityl,

1-deoxymaltityl, 1-deoxylactityl, 1-deoxygalactityl,

1-deoxymannityl, 1-deoxymaltotrotityl 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 polyhydroxy amine with an fatty acid ester (aliphatic) or triglyceride in the condensation / amidation stage to form N-alkyl, N-polyhydroxy fatty acid amide. Způsotyvýroby compositions containing polyhydroxy fatty acid amides are disclosed for example in GB patent no. 809060, published 18 _t February 1959, by Thomas Hedley & 0º., Ltd., U.S. Pat. No. 2,965,576, issued December 20, 1960, E.RrWilsonovi and US Patent 2703798, Aithony XSchwartz, issued March 8, 1955, and US Patent 1985424, issued December 25, 1934 to Piggott, which are incorporated herein by reference.

In a preferred process for the preparation of amides of N-hydroxyalkyl, the oxyglycetyl of 1-fatty acids, wherein the glycityl component is derived from glucose and the N-alkyl or N-hydroxyalkyl functionality is N-methyl, N-ethyl, N-propyl, N butyl, N-hydroxyethyl or N-hydroxypropyl, the product is prepared by reacting an N-alkyl or N-hydroxyalkyl glucamine with a fatty acid ester selected from the group consisting of a fatty acid methyl ester, an fatty acid ethyl ester, and a fatty acid triglyceride in the presence of a catalyst selected from the group consisting of lithium phosphate, sodium phosphate, potassium phosphate, sodium pyrophosphate, pentasodium tripolyphosphate, lithium hydroxide, 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. more preferably from about 2.0 mole% to about 10 mole% based on mol of N-alkyl or N-hydroxyalkyl-glucamine. The reaction is preferably carried out at a temperature of from about 13 ° C to about 170 ° C, typically from about 20 to about 90 minutes. When triglycerides are used as the fatty acid ester source in the reaction mixture, the reaction is also preferably carried out using about 1 to about 10 wt% of the phase transition agent based on the total reaction mixture and expressed as a weight percent selected from the group consisting of saturated polyethoxylates fatty alcohols, alkyl polyglycosides, linear glycamide surfactants and mixtures thereof.

Preferably, this process is carried out as follows

(a) preheating the fatty acid ester to about 1300 ° C to about 170 ° C;

b) adding N-alkyl or H-hydroxyalkylglucamine to the preheated fatty acid ester and mixing to the extent necessary to form a biphasic liquid / liquid mixture,

c) adding the catalyst to the reaction mixture; and

d) stirring the mixture for as long as necessary.

Preferably, from about 2% to about% 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 the phase transfer agent when the ester is triglyceride fatty acids.

In this way, the reaction mixture is seeded, thereby increasing the reaction rate

-13lost. Specific experimental embodiments are set forth in the Examples below.

The polyhydroxy fatty acid amides ** used herein provide benefits for detergent builders by

They can be prepared wholly or primarily from natural renewable feedstocks and are degradable ♦ They also show low aquatic 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 the 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 containing the polyhydroxy fatty acid amide added to the detergent comprises less than 10% and preferably less than 4% cyclic polyhydroxy fatty acid amide. fatty acids. The preferred processes described above are advantageous in that they yield low by-product yields, including such cyclic amide by-products.

Alkylalkoxylated sulphates.

Surfactants based alkylalkoxylovených sulfates, which are used herein are water soluble salts or acids of the formula RO (A) SO- Μ wherein R is an unsubstituted ^J ia 'Vanya alkyl or hydroxyalkyl group having ₁ QC G ^ alkyl component, preferably C ₁₂ -C ₂₀ alkyl or hydroxy alkyl, more preferably C ₁ -C ₆ alkyl or hydroxy alkyl, A is ethoxy or propoxy, m is greater than zero, typically between about 0.5 and about 6, more preferably between about 0, 5 and about 3 a

-14hi is Η or a cation | which may be, for example, a metal cation (eg, sodium, potassium, lithium, calcium, magnesium, etc.), ammonium or substituted ammonium cation.

Alkyl ethoxylated sulfates as well as alkyl propoxylated sulfates are contemplated herein. Specific examples of substituted ammonium cations include methyl, dimethyl, trimethylammonium and quaternary ammonium cations such as tetramethylammonium, dimethylpiperidinium and alkanolamine-derived cations, e.g., monoethanolamine, diethanolamine and triethanolamine, and mixtures thereof. Exemplary surfactants are g ^ l ^ ylpolyethoxyláty (LO) sulfét _g alkvlpolyethoxylót (2.25) sulfate, C galkylpolyethoxylát (3.0Jsulfát and i2 ^ ^_ ^ ^ ^and L8 "kylpolyethoxylát (4.0Jsulfát, wherein M is conveniently selected from sodium and potassium.

Alkyl alkoxylated sulfates will typically be included in the compositions in an amount of at least 1% by weight, typically from about 3% to about 30%, preferably from about 5% to about 20%.

Suds suppressors

Compounds known or will be known to reduce or suppress the formation of foam can be included in the compositions of the invention. The inclusion of such suds suppressor materials ** will be desirable here, since polyhydroxy fatty acid amide surfactants can enhance the foam stability of the detergent composition. Foam suppression can be particularly important when the detergent composition comprises a relatively high sudsing surfactant in combination with a polyhydroxy fatty acid amide surfactant. Foam suppression is particularly desirable for compositions for use in automatic washing machines. These washing machines are typically characterized by having laundry and washing water drums having a horizontal axis and rotating around it.

-15This type of mixing can lead to high foam formation and, as a result, to reduced cleaning ability. The use of suds suppressors may also be particularly important in hot water wash conditions and high surfactant concentrations.

Various materials can be used as suds suppressors. ⁱⁿ cuppers, suds suppressors are well known. For example, they are described in the Kirk Othmer Encyclopedia of Chemical Technology, Third Edition, Vol. 7, p. 430-447 (John Wiley &amp; Sons, Inc., 1979). One category of suds suppressors is of particular interest and includes monocarboxylic fatty acids and soluble salts thereof. These materials are discussed in U.S. Patent 2954347, issued Sep. 27, 1960, to V.

John, which is incorporated herein by reference, thionocarboxylic fatty acids and salts thereof, for use as suds suppressors, 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 suds suppressors which are not surfactants. These include, for example: hydrocarbons of high molecular weight such as paraffin, fatty esters (e.g. fatty acid triglycerides), fatty acid esters of monovalent alcohols, aliphatic ^G 18 ^-G 4Q ^ketones stearone), etc. Other suds inhibitors include N-alkylated aminotriazines such as triage hexa-alkylmelamines or di- to tetra-alkyldiaminochlorotriazines, formed as the products of two-cyanuric chloride

or with three moles of a primary or secondary amine containing 1 to 24 carbon atoms, propylene oxide and 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 halogenated 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 no less than about 110 ° C (atmospheric pressure). It is also known to use waxy hydrocarbons, preferably having a melting point below about 100 ° C. Hydrocarbons constitute a preferred category of suds suppressors for detergent compositions. Hydrocarbon suds suppressors are described, for example, in U.S. Patent No. 4,265,770, issued May 5, 1985 to Gandolfo et al., Incorporated herein by reference. Hydrocarbons include aliphatic, alicyclic, aromatic, and heterocyclic saturated or unsaturated hydrocarbons having about 12 to about 70 carbon atoms. The term paraffin as used herein includes mixtures of 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 polyorganosiloxane 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 No. 89307851.9, published Feb. 7, 1990, Starch 14. S., both of which are incorporated herein by reference.

Silicone-based suds suppressors. It is described in patent 3455639, which relates to preparations and methods for the foaming of aqueous solutions by incorporating small amounts of polyimethylsiloxysin liquids.

3 and 3 silica and alumina are described, for example, in German patent application DOS 2124526.

Silicone defoamers and suds controlling agents in granular detergent compositions are described in 88, U.S. Patent 3,963,672, to 3artolotta et al. and U3 patent 4652352, Sinskyski sol, issued March 24, 1987.

from (b) from (i)

For example, a silicone-based lung suppressant / agent comprising essentially:

a) polydimethylsiloxenovou fluids having viscosities of about 20 ² to about IQ IpOC.lo ² Bas ¹ 'about 5 to about 50 parts by weight of 100 parts non síloxsnová resin composed of ^^ 1/2 units wherein the ratio of SiC units to units and Sii ^ 9 ^ ^w, from about O: l S3I to 1.2: 1 and

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

For any detergent composition that is used in automatic buckles, the eyes should not look in excess, and overflow from the ors. The gentle suppressors, when used, are preferably present in an amount reducing the amount of antioxidant, and is meant that the amount of the suds controlling agent used in the formulation may be selected such that it will be sufficient to control the formation of the suds. the result will be a low sudsing detergent for use in automatic washing machines. The amount of suds controlling agent 3s will be based on the selected int-detecting intact surfactant. ,

JUDr. Otaí-sr ĎVORČÍX adlokajt

For example, for high sudsing surfactants, relatively more suds controlling agent is used to achieve the desired sudsing control than a less sudsing surfactant. In general, such an amount of suds suppressor should be incorporated into the foamed detergent compositions which are such that the foam that is collected during the washing cycle in an automatic washing machine (i.e., by mixing the detergent in aqueous solution at a certain temperature and concentration) , will not exceed about 75% of the empty drum volume, preferably the foam will not exceed about 50% of said drum volume, wherein the void volume is determined as the difference between the total drum volume and the water plus laundry volume »

If as suds suppressors, monocarboxylic fatty acids and salts thereof, will typically be ^r present in amounts up to about 5% by weight of the detergent composition · from about 0.5% to about 3% antifoaming agents based on fatty monocarboxylate usually using. Antifoam silicone 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, since it is of course an effort 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 by weight include any silicas which may be used in combination with polyorganosiloxanes, other filler materials may be used.

Hydrocarbon suds suppressors are typically used in amounts ranging from about 0.01% to about 5.0, although higher levels may be used. Monostea-19rylphosphate antifoam agents are typically used in amounts of from about 0.1% to about 2% by weight of the composition.

In another aspect of the invention there is provided a detergent composition comprising alkylethoxylated sulfate surfactants and polyhydroxy fatty acid amides as described above, wherein R ¹ is methyl, R ² is alkyl or alkenyl, preferably C 1 -C 4 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 about 1: 1 , 25. The most preferred polyhydroxy butyric acid amides are described above.

In another aspect of the invention, detergent compositions of polyhydroxy fatty acid amides and alkylalkoxylated (preferably ethoxy sulfate) surfactants are disclosed as described above, 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 polyglucosides). 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, alkyl benzene sulfonates, paraffin sulfonates, and mixtures thereof. Preferably, the co-surfactant component comprises from about 1% to about 25% by weight of the detergent composition. Further, adjuvants as well as optional detergent additives and others may be present in the detergent compositions

The components known in the art or otherwise desirable for incorporation into detergent compositions. Preferred polyhydroxy fatty acid amides, alkyl alkoxylated sulfates and surfactants in the proportions described above are preferably in each aspect of the invention.

Anionic auxiliary surfactants

Auxiliary anionic surfactants suitable for cleaning purposes may also be incorporated into said compositions, such as the salts (including, for example, sodium, potassium, ammonium and substituted ammonium salts such as mono-, di- and triethanolamine salts) of soaps, Cg. -C 1-4 linear alkylbenzenesulfonates, primary or secondary alkanesulfonates, γ-24-olefin sulfonates, sulfonated polycarboxylic acids prepared by sulfonating the pyrolysis product of alkaline earth citrate, e.g. as described in British Patent No. 1082179, alkyl glycerol sulfonates, fatty alkyl glycerol sulfonates, fatty alkyl glycerol sulfonates , alkalfenolethylenoxidethersulfáty, paraffin sulfonates, alkyl phosphates, isethionates such as the acyl isethionates, N-acyl taurates, fatty acid amides of methyl, alkyl succinamates and sulfosuccinates, monoesters of sulfosuccinates (especially saturated and unsaturated C ₂ ^ ^m ° g monoesters) diesters of sulfosuccinates (especially saturated and unsaturated diesters), N-acyl sarcosinates, alkylpolysaccharide sulfates such as alkylpolyglucoside sulfates (nonionic unsulfated compounds described below), branched primary alkyl sulfates, alkylpolyethoxycarboxylates such as those of the formula

RO (GH ₂ CH ₂ O) _to 0H ₂ GOCrM +, where

-21R 3® Gg-223 223 an integer of 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 resin acids and hydrogenated resin acids present in or derived from body oil. Other examples are described in Surface: Active Agents and P-itergGita (volumes X and II, Sohwartz, Perry and Berch). Various such surfactants are also generally described in US Patent No. 3929678, issued December 30, 1975 to Laughlin et al., Column 23, line 58 through column 29, line 23 (cited herein as a reference).

Surfactants are alkyl sulfates in the form of water soluble salts or acids of the formula ROSO-M wherein R preferably is a QC-hydrocarbyl, preferably an alkyl or hydroxyalkyl having a C ₁ alkyl component, more preferably C 2- ^C iθ alkyl or hydroxyalkyl, and M is H or a cation, e.g., a cationic metal (e.g., sodium, potassium, lithium), substituted or unsubstituted ammonium cations such as methyl, dimethyl, and trimethylammonium, and quaternary ammonium cations, e.g. tetramethylammonium adimethylpiperidinium and cations derived from alkanolamines such as ethanolamine, diethanolamine, triethanolamine and mixtures thereof and the like. Typically, alkyl chains of 2 ^{° C to} 16 ° C are preferred. ^Lower wash temperatures (eg, below about 50 ° C) and θ alkyl chains are preferred for higher wash temperatures (eg, above about 50 ° C).

Alkylbenzenesulfonate surfactants are well known in the art. These surfactants have C 8 and higher alkyl groups, preferably linear alkyl groups, to provide a class of linear alkyl benzene 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 previously described for alkyl sulfate salts.

Alkyl ester sulfonate surfactants include linear esters of C8-C18 carboxylic acids (i.e. fatty acids) that are sulfonated with SO2 gas according to The Journal of Anerican Oil Chemists Society, (1975), pp. 323-329. Suitable starting materials include natural fatty substances derived from tallow, palm and coconut oil, etc.

Preferred alkyl ester sulfonate surfactants, especially for washing machine applications, include alkyl ester sulfonate surfactants of the formula

4.

R ^J _ CH-C-0 «

AND

SO ₃ M wherein C ₀ -C -hydrocarbyl, preferably alkyl or their

The o d of the combination, R is C 1 -C 4 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., tetramethylamine and dimethylpiperidinium and alkanolamine derived cations such as monoethanolamine, diethanolamine and triethanolamine. Preferably, C 1 -C 6 is C 1-6 alkyl and R 1 is methyl, ethyl or isopropyl. Especially preferred are the methyl ester sulfonates wherein ^{R 3 C} 14 ^"C 1δ® ^{1 *-71.}

In addition, other nonionic surfactants may be added to the anionic surfactants and incorporated into the formulations.

Nonionic surfactant detergent adjuvants

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 thereto.

Polyethylene, polypropylene and polybutylene oxide condensates of alkylphenols. In general, polyethylene oxide condensates are preferred. These compounds include the condensation products of alkylphenols having an alkyl group of about 6 to about 12 carbon atoms either in the straight or branched chain with the 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 ™ CQ-630, supplied by ^G AF Corporation, and Triton ™ X-45, X-114, X-100 and X-102, all supplied by the Rohm and Haas Company. the active ingredients are generally referred to as alkylphenolalkoxylates, e.g., alkylphenol ethoxylates.

2. The condensation products of aliphatic alcohols with ca.

-241 to about 25 moles of ethylene oxide. The alkyl chain of the aliphatic alcohol may be either straight or branched, primary or secondary, and typically contains about 8 to about 2 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 (a condensation product of C ^ C, a c-linear secondary alcohol with 9 moles of ethylene oxide), ¹ → TM

^{M ±} Tergitol 24-L-6 NMW (the condensation product of C ^ -C ^ P ^ri "primary alcohol with 6 moles ethylene oxide with a narrow molecular weight distribution), both produced by Union Carbide

Corporation, Neodol 45-9 (condensation product of CC linear alcohol with 9 moles of ethylene oxide), Neodol

23-6.5 (the condensation product of C _1O -C ¹ linear alcoholic έ i ^ TM lu with 6.5 moles ethylene oxide), Neodol 45-7 (the condensation product of C, -C, j-linear alcohol with 7 moles of ethylene oxide) , TM>

Neodol 45-4 (the condensation product of linear alcohol with 4 moles of ethylene oxide), marketed by Shell Chemical Company, and Kyro EOB (the condensation product of C ₁ jC 5alkoholu with 9 moles ethylene oxide), marketed by The Procter & Gamble Company. These nonionic surfactants are commonly referred to as alkyl ethoxylates.

3. Hydrophobic base ethylene oxide condensation products 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 hydrophilic moiety increases the water 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 of ethylene oxide. Examples of compounds of this type

-25 include a number of commercially available Pluronic ™ surfactants supplied by BASF.

4. The condensation products of ethylene oxide with the product formed by the reaction of propylene oxide and ethylenediamine. The hydrophobic group of these products consists of a reaction product of ethylenediamine and an excess of propylene oxide and generally has a molecular weight of from about 2500 to about 3000. This hydrophobic group is condensed with ethylene oxide such that the condensation product contains from about 40% to about 80% polyoxyethylene and has a molecular weight of from about 5,000 to about 11,000. 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 which 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 amine oxide surfactants of the formula ^-

-260

R ³ (OR ⁴⁾ -N (R ⁵⁾

Wherein R is an alkyl, hydroxyalkyl or phenyl group or a mixture thereof containing from about 8 to about 22 carbon atoms,

R is an alkylene or hydroxyalkylene group containing from about 2 to about 3 carbon atoms or mixtures thereof; x has a value of 0 to about 3; each R6 is an alkyl or hydroxyalkyl group containing from about 1 to about 3 carbon atoms or a polyethylene oxide a group containing from about 1 to about 3 ethylene oxide groups. The R 6 groups can be linked to each other, e.g. through an oxygen or nitrogen atom, to form a ring structure.

These amine oxide surfactants preferably include C1-C6-C1-C4-alkyldimethylamine oxides and C1-C6-alkoxyethyldihydroxyethylamine oxides.

6. Alkylpolysaccharides disclosed in U.S. Patent 4,566,547, Uenado, issued January 21, 1986, having a hydrophobic group containing from about 6 to about 30 carbon atoms, preferably from about 10 to about 16 carbon atoms, and a polysaccharide, e.g., polyglycoside, it is hydrophilic, and contains from about 1.3 to about 10, preferably from about 1.3 to about 3, most preferably from about 1.3 to about 2.7 carbohydrate units. Any reducing saccharide containing 5 or 6 carbon atoms can be used, for example glucose, galactose and galactosyl groups can replace glucose groups. (Optionally, the hydrophobic group is attached at 2-,

3-, 4- etc. to obtain glucose or galactose as opposed to glucoside or galactoside) Inter-saccharide linkages may be, for example, between one position of additional saccharide units and the 2-, 3-, 4- and / or 6-positions of the preceding carbohydrate units.

Optionally, but less desirable, there may be a polyalkylene oxide chain linking the hydrophobic moiety to the polysaccharide moiety. The preferred alkylene oxide is ethylene oxide. typical hydrophobic groups include alkyl groups, either saturated or unsaturated, branched or unbranched, containing about 8 to about 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, fructosides, fructosides, fructosides, fructosides and fructosides. Suitable mixtures include coconut alkyl, di-, tri-, tetra- and pentaglucosides and tallow alkyl tetra-, penta, and hexaglucosides.

Preferred alkyl polyglycosides have the formula h ² O (On ^{H 2} n 0) _t (glycosyl) _χ wherein R ² is selected from the group consisting of alkyl, alkylphenyl, hydroxyalkyl, hydroxyalkylphenyl and mixtures thereof, wherein the alkyl groups contain about 10 to about 18, preferably about 12 to about 14 carbon atoms, n is 2 or 3, preferably 2, t is from 0 to about 10, preferably 0, and χ is from about 1.3 to about 10, preferably from about 1.3 to about 3, most preferably from about 1.3 to about 2.7. 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). ^ GALS glycosyl units can then be attached between their 1-position and _j 2_ 3, 4- and / or 6- positions. preferably 2-, previous glycosyl units

7. The fatty acid amide-based surfactants have the formula fi ·· 7

RC - N (R ') ₂ wherein R is an alkyl group containing from about 7 to about (preferably from about 9 to about 17) carbon atoms and each R is selected from the group consisting of hydrogen, ^G - [alkyl, C ^ hydroxyalkyl and wherein x varies from about 1 to about

3.

Preferred amides are Cg_ ₂ Qamoniumamidy, monoethanolamides, diethanolamides, and isopropanolamides.

Cationic surfactants

Cationic detersive surfactants may also be included as auxiliary surfactants in the detergent compositions of the present invention. The anionic surfactants include ammonium surfactants such as alkyldimethylammonium halides and surfactants having the formula (R ² (OR ³ ) y). Wherein R is an alkyl or alkylbenzyl group having from about 8 to about 18 carbon atoms in the alkyl chain, each R ^{4 is} OH ³ ) y / ₂ R ⁵ U ⁺ X ";

O

R is selected from the group consisting of -CH ₂ CH ₂ - (CH ₂ CH ₂ CH ₂ ) - 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 ^G pC 1 alkyl, C 1 -C 4 hydroxyalkyl, benzyl, a ring structure formed by linking two R ⁴ groups, -CH ² CHOH-CHOHCOR ⁶ CHOHCH ² OH, wherein R is any hexose or hexose polymer having a molecular moiety

A mass of less than about 1000, and hydrogen when y is not 0; AND

R is the same as R or is an alkyl chain wherein the total number of carbon atoms R plus R is not greater than es 18, each y is from 0 to about 10 and the sum of y is from 0 to about 15 and X is any compatible aaluate.

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

Other auxiliary surfactants

Ampholytic surfactants may be incorporated into said detergent compositions. These surfactants are broadly described as aliphatic derivatives of secondary or tertiary amines, or aliphatic derivatives of heterocyclic secondary and tertiary amines in which the aliphatic radical is straight or branched. One of the aliphatic substituents contains at least about 8 carbon atoms, typically from about 8 to about 18 carbon atoms, and at least one contains an anionic water-soluble group, e.g., carboxy, sulfonate, sulfate. See U.S. Patent No. 3,929,668, Daughlin et al., Issued Dec. 30, 1975, column 19, lines 18-35 (incorporated herein by reference) for examples of ampholytic surfactants.

Zwitterionic surfactants can be incorporated into the detergent compositions of the invention. These surfactants are broadly described as derivatives of secondary and tertiary amines, derivatives of heterocyclic secondary and tertiary amines, or derivatives of quaternary ammonium, quaternary phosphonium or tertiary sulfonium compounds. See U.S. Patent No. 3,929,668,

-30 Laughlin et al., Issued December 30, 1975, column 19, lines 38 to column 22, line 48 (incorporated herein by reference) for examples of zwitterionic surfactants.

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

Activating agents

The detergent compositions of the present invention may contain inorganic or organic detergent builders to assist in controlling mineral hardness.

The level of activating agents varies widely, depending on 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 10% 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 activating agent.

Inorganic activators include, but are not limited to, alkali metal salts, ammonium and alkali ammonium salts of polyphosphates (e.g., tripolyphosphates, pyrophosphates, and glassy polymeric metaphosphates), phosphonates, phytic acids, silicates, carbonates (including hydrogen carbonates and sesquicarbonates) ), sulfates and aluminosilicates.

Examples of silicate activators are alkali metal silicates, especially those having a SiO 2 / Na 2 O ratio in the range of 1.6: 1 to 3.2: 1 and layered silicates such as sodium layered silicates described in US Patent No. 4,666,839. issued May 12, 1987 to HPRieck, which is incorporated herein by reference in its entirety. However, other silicates may also be used, such as magnesium silicate, which may serve as a beading agent in granular formulations, as a stabilizer for oxygen bleaches, and as a component of a foam control system.

Examples of carbonate activators are alkaline earth and alkali metal carbonates, including sodium carbonate and sesquicarbonate, and mixtures thereof with ultrafine calcium carbonate, as disclosed in DSpatent Application No. 231001, published Nov. 15, 1973, cited herein for the sake of completeness. link.

Aluminosilicate builders are particularly useful in the present invention. ALuminosilicate builders are very important in the most commonly marketed granular detergent formulations and may also be an essential activator component in liquid detergent formulations. ALuminosilicate activators include those having the empirical formula:

M _z (zALO ₂ .ySiO ₂ ) wherein M is sodium, potassium, ammonium or substituted ammonium substituent, z is from about 0.5 to about 2 and Y is 1, and such material has an ion exchange capacity for magnesium of at least about 50 milligrams # equivalents CaCO 3 hardness per gram of anhydrous aluminosilicate. Preferred aluminosilicates are zeolite activators having the formula

-32Na / (A1O ") (SiO ₉ ) /.χΗ ₉ Ο of 4 zt 4 where after Y are integers 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 naturally occurring or synthetic synthetic aluminosilicates. A process for preparing aluminosilicate ion exchange materials is disclosed in U.S. Patent 3,956,569, Krummel et al., Issued Oct. 12, 195F6, 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 designations Zeolite A, Zeolite P (3) and Zeolite X. In a particularly preferred embodiment, the crystalline aluminosilicate ion exchange materials have the formula:

₁₂ / _{(AlO2) 12 (SiO2) 12} /.xH ₂ O wherein x is from about 20 to about 30, especially about 27. This material is that known as Zeolite A. Preferably, the aluminosilicate has a particle size from about 0 , 1 to 10 microns 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 6 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 methylenediphosphonic acids such as trisodium and trisodium salts, and the water-soluble salts of aubstituted methylene-diphosphonic acids. acids such as trisodium and tripotassium salts of ethylidene, isopropylidene, benzylmethylidene and halomethylidene phosphonates. Phosphonate activating salts of the above types are described in U.S. Patent Nos. 3159581 and 321030, issued December 1, 1964 and October 19, 1965 to Piehl, U.S. Pat.

US Patent No. 3422021, issued January 14, 1969 to Ro.y, and US Patent Nos. 3400148 and 3422137, issued September 3, 1968 and January 14, 1969 to Quimby, the disclosures of which are incorporated herein 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 salt form _f , 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. An additional number of ether polycarboxylates have already been described for use as detergent builders. Examples of suitable a-etherpolykarboxylétů 34hrnují oxydisuccinates as described _e B rgem in U.S. Patent 3,128,287, issued April 7, 1964 and Lamberti et al., U.S. Patent 3,635,830, 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) (COOX) -CH (COOX) -O-CH (COOX) -CH (COOX) 1B} wherein A is H or OH, B is H or -O-CH (COOX) -CH ₂ (COCX) 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. If A is OH and B is B, then the compound is monosuccinic acid tartrate (IMS) and its water-soluble salts. If A is H and B is -O-CH (COOX) -Cff ₂ (COOX), then the compound is disuccinic acid tartrate (TLS) 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, especially 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 formula

-35HO- (CH 2) (COOM) -C (R) (COQ & O-O / -H n 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, C 1-4 alkyl or C 1-4 substituted alkyl ( preferably R is hydrogen).

Still other ether polycarboxylates include copolymers of maleic anhydride with ethylene or vinyl methyl ether, 1,3,5-trihydroxybenzene-2,4,6-trisulfonic acid, and carboxymethyloxysuccinic acid.

Organic polycarboxylate builders also include various alkali metal salts of ammonium and substituted ammonium salts of polyacetic acids. Examples of polyacetic acid activating salts are sodium, potassium, lithium, ammonium and substituted ammonium salts of ethylenediaminetetraacetic acid and nitrilotriacetic acid.

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

The citrate activating agents, e.g. citric acid and its soluble salts, are polycarboxylate activating agents particularly important for high performance liquid detergent formulations, but can also be used in granular formulations. 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 U.S. Patent 3,723,322, Diehl, issued March 28, 1973, 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 described in U.S. Patent 4,566,984, Bush, issued Jan. 28, 1986. Suitable succinic activating agents include ^C 5-20 alkyl succinic acids and their salts. Particularly preferred compounds of this type are? dodecenylsuccinic acid. The alkyl anticarboxylic acids typically have the formula R-CH 2 CH 2 CH 3 CH 2 (COOH) ie succinic acid derivatives wherein R is a hydrocarbon, e.g., kyl or alkenyl, preferably 2 2-16 ^or ° may be substituted with hydroxyl, sulfo, sulfoxy or sulfone substituents , all of which are 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. Laurylsukoinates are preferred activators of this class and are described in European Patent Application 86200690.5 / 0200263, published Nov. 5, 1986.

Examples of suitable activating agents also include sodium and potassium carboxymethyloxymalonate, carboxymethyloxysuccinate, cis-cyclohexane hexacarboxylate, cis-cyclopentyl tetracarboxylate, water-soluble polyacrylates (these poly-37 acrylates having a molecular weight greater than about 2000 can also be effectively used as dispersants) and a copolymer of maleic anhydrides with vinyl methyl ether or ethylene.

Other suitable polycarboxylates are the polyacetal carboxylates described in U.S. Patent 4,144,226, Crutchfield et al., Issued March 13, 1979, which is incorporated herein by reference. These polyacetyl carboxylates can be prepared by contacting, under polymerization conditions, a glyoxylic acid ester and a polymerization initiator. The resulting polyacetal carboxylate ester is then attached to chemically stable end groups by stabilizing the polyacetal carboxylate against 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 3308067, Diehl, issued March 7, 1967, which is incorporated herein by reference. Such materials include homo- and copolymers of aliphatic carboxylic acids such as maleic, itaconic, mesaconic, fumaric, aconitic, citraconic and methylenemalonic acids.

Other organic activating agents known in the art may also be used. For example, monocarboxylic acids, and soluble salts of them having a hydrocarbyl chain length, may be used ^ hese also include materials generally referred to as soaps. * ¹ Typical chain lengths are C 1 -C 4 q. Hydrocarbyls can be saturated or unsaturated »

Enzymes

Enzymes for a variety of purposes, including removal, may also be included in detergent compositions

-38spots based on proteins, sugars or triglycerides, for example to prevent the transfer of released dye. Enzymes that are incorporated into preparations include proteases, amylases, lipases, cellulases and peroxidases, as well as mixtures thereof. They may be of any suitable origin, such as from plant, animal, bacterial, 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 are preferred. and fungal cellulases.

Suitable examples of proteases are subtilisins, which can be obtained from particular strains of B. subtilis and B, licheniformis. Another suitable protease is obtained from a Bacillus strain having a maximum activity in the pH range of 8-12, developed and sold by Novo Industries A / S under the registered trademark Egperase. The preparation of this enzyme and analogous enzymes is described in British Patent No. 1243784 to Novo. Proteolytic enzymes suitable for removing protein-based stains are commercially available

TM and include the substances under the trademarks ALCALASE and SAVINASE ™ from N _o Industries A / S (Denmark) and MAXATASE ™ from International Bio-Synthetics, Inc. (Netherlands).

Of interest in the category of proteolytic enzymes, especially for liquid detergent compositions, are enzymes referred to herein as Protease A and Protease B, 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 3 is _a proteolytic enzyme that differs from Protease A in that it has leucine replaced

-39tyrosine at position 21 in its amino acid sequence. Protease B is described in European Patent Application No. 87303761.8, published April 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.

Anylases include, for example, -amylases obtained from a special strain of B-licheniformis, described in more detail in the description of the British Patent No. 1296839 (Novo), incorporated herein by reference. Amylolytic proteins include, for example,

TM -r- TM

RAPIDASE ^X , International Bio-Synthetic, Inc. and TERMAISYL ¹ Novo Industries *

Cellulases useful in the present invention include bacterial and fungal cellulases. Preferably these will have a pH optimum between 5 and 9.5. Suitable cellulases are described in U.S. Patent 4,435,307, 3arbesgoard et al., Issued March 6, 1984, which is incorporated herein by reference, which discloses fungal cellulase 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 grisea 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 Aeromonas and cellulase extracted from hepatopancreas of sea bream (Dolabella Auricula Soland).

Suitable lipase enzymes for detergent use include those produced by the group microorganisms

Pseudomons, such as Pseudomonas stutzeri ATCC 1 9.1 91 54, is described in British Patent No. 1372034, which is incorporated herein by reference. Suitable lipases include those that exhibit a positive immunological cross-reaction with a lipase antibody produced by Pseudomonas fluorescens IAI 1057. This lipase and its method of purification have been described in Japanese Patent Application No. 53-20487, published February 24, 1978. This lipase is a lipase. available from Amano Pharmaceutical Co., Ltd., Nagoya, Japan under the trademark Lipase P (Amano, hereinafter referred to as Anano-P) Such lipases of the present invention should exhibit a positive immunological cross reaction with an Anano-P antibody, using a standard and the well-known immunodiffusion procedure of Ouchterlony (Acta. Med.Scan., 133, 76-79 1950). These lipases and a method for their immunological reaction with Amano-P are also described in U.S. Patent 4707291, Thom et al., Issued November 17, 1987, which is incorporated herein by reference. Typical examples thereof are Anano-P lipase, Pseudomonas fragi FESM P 1339 lipase (available under the trade name Amano-3), and Pseudomonas nitroreducens var. lipolyticum PERM P 133θ (available under the trade name Anano-CES), lipases from Chromobacter viscosum, e.g. Chromobscter viscosum var. lypol.yticum NRRLB 3673, commercially available from Toyo Jozo Co., Tagata, Japan and other Chromobacter viscosum lipases from U.S.Biochemieal Corp., USA and Diosynth Co. The Netherlands and lipases from Pseudomonas gladioli.

Peroxidase enzymes are used in combination with oxygen sources, e.g. percarbonates, perborates, persulphates, hydrogen peroxide, etc. These are used for bleaching the solution, ie to prevent the transfer of dyes or pigments removed from the substrate during washing operations,

-41on other substrates in the wash solution. Peroxidase enzymes are known in the art and include, for example, horseradish peroxidase, ligninase and haloperoxidase, as well as chlorine bromo-peroxidase. Peroxidase-containing detergent compositions are described, for example, in PCT International Application WO 89/099813, published Oct. 19, 1989, Kirk 0, granted to Novo Industries A / S, which is herein incorporated by reference.

A wide variety of enzyme materials and methods for incorporating them into synthetic detergent granules are also described in US Patent No. 3553139, issued Jan. 5, 1971 to Kartart et al. (cited herein as reference). The enzymes are further described in US Patent No. 4,101,457, Plače et al., Issued July 18, 1978, and in US Patent No. 4507219 to Hughes, issued Mar. 26, 1985 (both incorporated by reference). Enzyme materials suitable for liquid 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 are well known in the art. An enzyme stabilization system is preferably used in liquid formulations. Enzyme stabilization techniques for aqueous detergent compositions are well known in the art. For example, one technique of stabilizing enzymes in aqueous solutions involves using free calcium ions from sources such as calcium acetate, calcium formate, and calcium propionate. Calcium ions may be after

-42 in combination with short chain carboxylic acid salts, preferably formates. See, eg, US Patent 4,318,818, Letton et al., Issued Mar. 9, 1982, which is incorporated herein by reference. It has also been proposed to use polyols such as glycerol and sorbitol, alkoxyalcohols, dialkyl glycoethers, mixtures of polyvalent alcohols with polyfunctional aliphatic amines (e.g. alkanolamines such as diethanolamine, triethanolamine, di-isopropanolamine etc.), and boric acid or alkali metal borate. Enzyme stabilization techniques are further described and exemplified in US Patent 4261868, issued April 14, 1981 to Hoi novi et al., US Patent 3600319, issued August 17, 1971 to Gedgeoci et al., Which are incorporated herein by reference and in European patent application. No. 0199405, Application No. 86200566.5 published Oct. 29, 1986, Venegas. Stabilizers that do not contain boric acid and borates are preferred. Enzyme stabilization systems are also described, for example, in US 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 comprising a bleaching agent and one or more bleach activators. When a bleaching compound is present, it will typically be present in an amount of from about 1% to about 20%, more typically from about 1% to about 10, of the detergent composition. Generally, the bleaching compounds are optional ingredients in non-liquid formulations, e.g., granular detergents. When 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 of the bleaching agents 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 may form borates in situ. 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 borate-free and borate-forming material means that the composition contains no more than about 2% by weight of borate-forming material or containing borate of any type, preferably no more than 1%, more preferably 0%.

One category? The bleaching agents that can be used include peroxycarboxylic acid bleaching agents and salts thereof. Suitable examples of this category of ⁷ reagents include magnesium monoperoxyphthalate hexahydrate, magnesium salt of meta-chloroperbenzoic acid, 4-nonylamino-4-oxoperoxybutyric acid and diperoxydodecanedioic acid. Such bleaching agents are described in U.S. Patent 4,448,381, Bartman, issued Nov. 20, 1984, U.S. Patent Application 740448, Burns et al., Filed Jun. 3, 1985, European Patent Application 0133354, Banks et al., Published Feb. 20, 1984. 1985 and U.S. Patent No. 4,412,934, to 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 US Patent No. 4634551, issued January 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, trichloroisocyanuric acid and sodium and potassium dichloroisocyanurates, and N-chloro and β-bromo-alkalsulfonamides. Such materials are normally added in an amount of 0.5-10% by weight of the final product, preferably 1-5% by weight.

Peroxide bleaching agents can 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 washing process) of the peroxyacid corresponding to the bleach activator.

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

O tt

RGL 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 carbon comprises, including, about 6 to about 10 carbon atoms and L is a leaving group whose conjugated acid has pK ranging from about 4 to about 13 Bleach activators are described in U.S. Patent No. 4,915,854, issued April 10, 1990 to Mao et al., incorporated herein by reference, and in U.S. Patent No. 4,412,934, which has previously been incorporated herein by reference. listed.

Bleaching agents other than oxygen bleaching agents are known in the art and can be used in the present case. * One type of non-oxygen bleaching agent that is of particular interest includes photo activated bleaching agents such as jet sulfonated zinc and aluminum phthalocyanine. These materials can be deposited in the substrate during the washing process. After irradiation with light, in the presence of oxygen, such as by hanging the substances for daylight drying, the sulfonated zinc phthalocyanine is activated and, as a result, the substrate is bleached. Preferred zinc phthalocyanines and photoactivated bleaching processes are described in US Patent No. 4,033,718, issued to

Jul. 5, 1977, 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 hydrophilic segments for hydrophilizing the surface of hydrophobic fibers such as polyester and nylon, pulling hydrophobic segments, storing on hydrophobic fibers and adhering to them throughout the wash and rinse and so served as anchorage for hydrophilic segments.

This allows stains that appear after treatment with the soil release agent to be more easily cleaned in other washing processes.

While it may be beneficial to use polymeric soil release agents in any of the detergent compositions herein, particularly those intended for laundry and other applications where grease and oil are removed from hydrophobic surfaces, the presence of amide polyhydroxy fatty poles.

Acids in detergent compositions also containing anionic surfactants can enhance the effectiveness of many commonly used types of polymeric soil release agents. The ionic surfactants interfere with the ability of some soil release agents to deposit under and adhere to hydrophobic surfaces. These polymeric soil release agents have non-ionic hydrophilic segments or hydrophobic segments that are interactive with anionic surfactants.

Compositions that can improve the effectiveness of polymeric soil release agents using polyhydroxy fatty acid amides are those that include an anionic surfactant system, an anionic surfactant release agent, and a polyhydroxy fatty acid amide enhancing effect of the soil release agent. (PFA), wherein: (I) the anionic surfactant interaction between the soil release agent and the anionic surfactant system of the detergent composition can be illustrated by comparing the level of soil release agent (SRA) deposition on hydrophobic fibers (e.g., polyester) in aqueous solution between (A) and a control experiment in which the deposition of the SRA of the detergent composition in an aqueous solution is measured in the absence of other detergent additives, and (B) the SRA / anionic surface test. "active agent", wherein the same type and amount of anionic surfactant system used in the detergent composition is combined in aqueous solution with SRA, at the same weight ratio of SRA to the anionic surfactant system, with reduced deposition in (B) relative to (A) shows the interaction of an anionic surfactant; and (II) whether the detergent composition contains an amount of polyhydroxy fatty acid amide, the soil release promoting agent can be determined by comparing the SRA deposition of the SRA / anionic assay.

The surface active agent of (B) and depositing the reagent for v

impurity release in (C) in a Network A / sionic surfactant / PFA assay wherein the same level of polyhydroxy fatty acid amide detergent composition is combined with a soil release agent and an anionic surfactant system corresponding to said SRA / anionic surfactant assay and wherein the improved deposition of the soil release agent in Test (C) relative to Test (B) indicates that an amount and polyhydroxy fatty acid promoting soil release agent is present. For this purpose, the tests should be carried out at anionic surfactant concentrations in an aqueous solution that are above about 100 ppm. 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 performing radiochemical analysis by techniques known in the art.

^u as an alternative to the radiochemical analytical method popsahé above may be mentioned saving of soil release agent and the determination in the above tests ItJ. tests A, B and C) by determining the absorbance of the ultraviolet radiation (UV) of the test solutions, by 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, such as high

--48Contents of surfactants with aromatic groups (eg alkylbenzene sulfonates, etc.).

A polyhydroxy fatty acid amide soil release agent is an amount of the surfactant which will promote the deposition of a soil release agent on the hydrophobic fibers as described above, or an amount for which improved grease cleaning performance can be achieved. oils for the fabrics washed in the detergent composition in the next subsequent cleaning operation.

The amount of polyhydroxy fatty acid amide required to promote deposition will vary according to the anionic surfactant selected, the amount of anionic surfactant, the particular soil release agent selected, and the polyhydroxybutyric 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 wherein the activity is enhanced by a polyhydroxy fatty acid amide in the presence of an anionic surfactant include # 1 impurity release agents having: a) one or more nonionic hydrophilic components consisting essentially of 1 ( polyoxyethylene segments having a degree of polymerization of at least 2; or (2) oxypropylene or polyoxy propylene segments having a degree of polymer 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 10 oxypropylene units, said mixture containing sufficient amounts of oxyethylene units such that the hydrophilic component has a hydrophilicity sufficiently large to increase the hydrophilicity of conventional polyester synthetic fiber surfaces when depositing a soil release agent on such a surface, said hydrophilic segments preferably containing at least 25% oxyethylene units and more preferably such components having about 20 to 20 30, oxypropylene units, at least about 50% oxyethylene units; or b) one or more hydrophobic components comprising i) 9-6 oxyalkylene terephthalate segments, wherein, when the hydrophobic ingredient is also an oxyethylene terephthalate-containing ingredient, the ratio of oxyethylene terephthalate: C 1-6 oxyalkylene terephthalate units is about 2: 1 or less; 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 1-6 hydroxyalkyl ether substituents or mixtures thereof, wherein said substituents are present in the form of C 1 -C 4 -alkyl ether or C 1 -C 4 -alkyl alkyl cellulose derivatives, or mixtures thereof, and these cellulose derivatives are amphiphilic, thereby having a sufficient level of C 1 -C 4 alkyl ether and / or C 1-4 hydroxyalkyl ether units deposited on conventional polyester synthetic fibers on their surface and maintain a sufficient level of hydroxyl content once the poison they have adhered to the surface of these conventional synthetic fibers to enhance hydrophilicity, or combinations of a) and b).

-50—

Typically, the polyoxyethylene segments a) 1) will have a degree of polymerization of from about 2 to about £ 00 although higher levels can be used, preferably from about 3 to about 150, more preferably from about 6 to about 100. Suitable oxy-C 1 -C 8 alkylene hydroxy- The phobic segments include, but are not limited to, terminations of polymeric soil release agents such as MO 2 S 2 O 2 O 4 OC 2 CH 2 O-, wherein M is sodium and n is an integer from 4 to 6, as described in US Patent No. 5,201,549. No. 471580, issued Jan. 26, 1988 to Gosselink, which is incorporated herein by reference in its entirety.

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

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

Cellulosic soil release agents for use in the present invention also include those selected from the group consisting of C 1 -C 4 alkyl and C 1 hydroxyalkyl cellulose such as methylcellulose, ethylcellulose, hydroxypropylmethylcellulose and hydroxybutylmethylcellulose. Various cellulose derivatives useful as soil release polymers are described in U.S. Patent No. 4,400,003, issued Dec. 28, 1976 to Hicol et al., Incorporated herein by reference.

soil release agents characterized by polyesters (vinyl ester) with hydrophobic segments include graft copolymers of polyesters (vinyl ester), e.g., C 1 -C 4 vinyl esters, preferably poles (vinyl acetate) grafted onto 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 by Kud et al. Suitable commercially available soil release agents of this type include Sokaisn ™ type materials such as Sokalan ™ HP-22. , available from 3ASF (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 are composed of repeating units of ethylene terephthalate and PEOterephthalate in a molar ratio of ethylene terephthalate units to PEO terephthalate units of from about 25:75 to about 35: 65, said polyethylene oxide-containing CEO terephthalate units having molecular weights of about 300 to about 2000. The polymeric soil release agent is in the range of about 25,000 to about 55,000.

See U.S. Patent No. 3959230, Hays, issued May 5, 1976, which is incorporated herein by reference. See also U.S. Patent No. 3,893,929, Sasadur, issued July 8, 1975 (incorporated herein by reference), which discloses similar copolymers.

IN

Another preferred soil release agent is. Polyester with ethylene terephthalate repeating units containing 10 to 15% by weight of ethylene terephthalate units together with 90 to 80% by weight of polyoxyethylene terephthalate units, derived from polyoxyethylene glycol having an average molecular weight of 300-5000, and a molar ratio of ethylene terephthalate units to polyoxyethylene terephthalate units in the polymer compound : 1 and 6: 1. Examples of this polymer include commercially available Zelcon 5126 (from Dupont) and Milease (TM) (from ICI). These polymers and methods for their preparation are described in more detail in US Patent No. 4702857, issued October 27, 1987 to Gosselink, 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 repeating units and a terminal group covalently attached to the chain, wherein the soil release agent is derived from allyl alcohol ethoxylate, dimethylterephthalate, dimethylterephthalate. 2-propylenediol, wherein, after sulfonation, the terminal groups of each oligomer have an average of a total of from about 1 to about 4 sulfonyl groups. Such soil release agents are described 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 Jan. 29, 1990, cited herein for reference for completeness.

Other suitable polymeric soil release agents include the ethyl or methyl-terminated 1,2-propylene terephthalate-polyoxyethylene terephthalate polyesters of U.S. Patent No. 4,711,730, issued December 8, 1987 to Gosselink et al., Anionically terminated oligomeric esters of U.S. Patent No. 4,721,580. , issued Jan. 26, 1988, Gosselink, wherein the anionic terminator comprises sulfo-polyethoxy groups derived from pd polyethylene glycol (PEG), a block polyester oligomeric compound of US Patent No. 4702857, issued Oct. 27, 1987, Gosselink, having a polyethoxy end of formula X- (OCH _n CH _n ) wherein n is from 12 to about 43 and X is C ₁ alkyl, or preferably methyl. The cited patents are all incorporated herein by reference.

Other polymeric soil release agents include the soil release agents of U.S. Patent No. 4,877,896, issued October 5, 1989 to Maldonado et al., Which discloses anionic, especially sulfoaroyl, terminated terephthalate esters, the disclosure of which is incorporated herein by reference. Terephthalate esters contain unsymmetrically substituted-53-substituted oxy-1,2-alkyleneoxy units. Included among the soil release polymers of U.S. Patent No. 4,877,896 are materials with polyoxyethylene hydrophilic components or C 1-6 alkylene terephthalate (propylene terephthalate) repeating units in the range of hydrophobic components

(b) (i) above. These are soil release polymeric agents, characterized by either 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.

When used, soil release agents typically comprise from about 0.01% to about 1.0% by weight of the detergent compositions herein, typically from about 0.1% to about 5%, preferably from about 0.2% to about 3%. , 0

Chelating agents

The detergent compositions of the invention may also optionally contain one or more iron and manganese gelling agents as a builder auxiliary material. Such chelating agents may be selected from the group consisting of aminocarboxylates, aminophosphonates, polyfunctional-substituted aromatic chelating agents, and mixtures thereof, as defined below. While not wishing to be bound by theory, it is believed that the benefit of these materials is due in part to their ability to remove iron and manganese ions from washing solutions by forming soluble chelates.

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

-54ch ₂ \ - (CH _O) -COOM / ¹ wherein M is hydrogen, alkali metal, ammonium or substituted ammonium (e.g. ethanolamine) and x is 1 to about 3, preferably 1. Preferably, these amino carboxylates do not contain alkyl or alkenyl groups with more than 6 carbon atoms. Useful aminocarboxylates include ethylenediaminetetraacetates, N-hydroxyethylethylenediamine triacetates, nitrilotriacetates, ethylenediaminetetra propionates, triethyleneamine hexaacetates, diethylenetriarainpentaacetates and ethanediglycines, their alkali metal salts, and their ammonium salts and their ammonium salts.

Aminophosphonates are also suitable for use as chelating agents in the compositions of the invention when 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

GH n- (ch ₂ ) _x -po ₃ m ₂ where M is hydrogen, alkali metal, ammonium or substituted ammonium and it is 1 to about 3, preferably 1, are suitable and include ethylenediaminetetracies (methylene phosphonates), nitrilotris (methylene phosphonates) ) and diethylenetriaminpentakis (methylene phosphonates). Preferably, these aminophosphonates do not contain alkyl or alkenyl groups having more than about 6 carbon atoms. Alkylene groups may be together with substructures.

Polyfunctional-substituted aromatic chelating agents are also useful in the compositions of the present invention, which materials may contain compounds of the formula:

OH

R wherein at least one R is -SO-1H or -COOH, or soluble salts thereof, and mixtures thereof. U.S. Patent No. 3,812,044, issued May 21, 1974, to Connor et al., Incorporated herein by reference, 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. Alkaline detergent compositions: These materials may contain alkali metal salts, ammonium or substituted ammonium salts (e.g., mono- or triethanolamine salts).

When 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 be from about 0.1% to about 3.0% by weight of these compositions.

Agents that remove clay impurities and counteract their deposition

The compositions of the invention may also optionally contain

-56vat water-soluble ethoxylated amines having the ability to remove clay and counteract deposition. Granular detergent compositions containing these compounds typically contain from about 0.01% to ears < 0.0% by weight of water-dispersible ethoxylated amines; liquid detergent compositions, typically from about 0.01% to about 5%. ^T hese compounds are preferably choose from ny skápiny comprising

1) ethoxylated monoamines having the formula (XL -) - N- (R ² ) ₂

2) ethoxylated diamines having the formula

R ² .HR ^1. NR ² (r ² ) 2 -n-r'-h- (r ² ) 2 ΐ l Ϊ

L L L i I '

XX ^x or (X_L-) ₂ -NR ¹ -N- (R ² ) ₂

3) ethoxylated poles of amines of formula?

R ²

B ³ - / (a ') - <E ⁴ ) _t- N-IV _p

4) ethoxylated amine polymers having the general formula

R ² / (R ²⁾ 2 ⁿ / w ^r1 ^ - ^ R ^ R ¹ -N ¹ -nlx) ₂

L (

X

(-575) mixtures thereof,

O O

-NO-, -NCO-, ‘i

R R where is

OOO tt 1 ^H

-NCN-, -CN-, -OCN-, i:

R R R R

0 0 tt tt tt

-C0-, -0CO-, -0Co o tt tt, -CNC-,

R or -O-,

R is H or alkyl or hydroxyalkyl, R ¹ je- C ₂ _ ₁₂ alkylene, hydroxyalkylene, alkenylene, arylene or alkarylene, or a C ^^ alkyl oxy alkylene group having from 2 to about 20 oxyalkylene units provided that no Vyo tSořeny no ON bonds, each R is C, _A or hydroxyalkyl, the moiety -LX, or two R together form the group

- A ² -CCH 2 J 8 -, wherein A ² is -O- or -CH ₂ -, r is 1 or 2, s is 1 or 2 and r + s is 3 or 4, X is a nonionic group, an anionic group or their mixture, R ^ is? substituted C 1 -C 4 alkyl, hydroxyalkyl, alkenyl, aryl or alkaryl having substitution positions, R ₁ is C ₁ -C ₁₂ alkylene, hydroxyalkylene, alkenylene, arylene or alkarylene or C 8 -C 6 oxyalkylene having 2 to about 20 oxyalkylene units with the proviso that no 0-0 or 0-N bonds are formed,

L is a hydrophilic chain which contains the polyoxyalkylene moiety - / ^(R5 0) m (CH2CH20) n / a - wherein R ⁵ is an _O3-C4 alkylene or hydroxy alkyl en Aman are numbers such that? - (CH ₂ CH ₂ O) - constitutes 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 that

-58diaminy m is from O to about 3 and n is at least about 6 when _R ^ R ^ C 2 alkylene, hydroxyalkylene, or alkenylene, and at least about 3 when R is other than ^C 2 ^{G 3, and y} ^^ ^ ^en * hydroxyalkylene or alkenylene; for said polyamines and emin polymers, m is from 0 to? And d is at least about 3. d is from 3 to 8, q is 1 or 0, t is 1 or O with the proviso that t is 1 when q is 1, w is 1 or 0, x + y + z is at least 2 and y + x is at least 2. The most preferred clay soil release and anti-deposition agent is ethoxylated tetraethylenepentaamine. Examples of ethoxylated amines are further described in US Patent No. 4597898, VanderMeer, issued July 1, 1986, which is incorporated herein by reference. Another group of preferred clay soil removal and deposition agents are the cationic compounds disclosed in European Patent Application No. 111965, Oh and Gosselink, published June 27, 1984, which is incorporated herein by reference for completeness. Other clay soil removal and deposition agents that may be used include the ethoxylated amine polymers described in European Patent Application 111984, Gosselink, published June 27, 1984; The zwitterionic polymers described in European patent application 112592, Goselink, published

July 4, 1984, and the amine oxides described in U.S. Patent No. 4,548,744, Connor ¹ , 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.

-59Polymer 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, more generally from about 1.0% to about 2.0%,

Polycarboxylate materials that can be used as polymeric carboxylate dispersing agents are those polymers or cocolymers that contain at least about 60% by weight of the segments of the general formula

Z i

OCOOM wherein X, Y and Z are each selected from hydrogen, methyl, carboxyl, carboxymethyl, hydroxyl and hydroxymethyl, a salt-forming cation and n is from about 30 to about 400. Preferably X is hydrogen? or hydroxyl, Y is hydrogen or carboxyl, Z is hydrogen and M is hydrogen, alkali metal, ammonium or substituted ammonium.

Polymeric polycarboxylate materials of this type can be prepared by polymerization or copolymerization of suitable

60 unsaturated monomers, preferably in their acid form. The unsaturated monomeric acids to be polymerized to suitable polymeric polycarboxylates include acrylic acid, maleic acid (or maleic anhydride), fimaruvuic acid, itaconic acid, tartaric acid, masaconic acid, citraconic acid, and methylmalonic acid. The presence of monomeric segments in polymeric carboxylates containing no carboxylate radicals such as vinyl methyl ether, styrene, ethylene, etc. is suitable provided that such segments do not constitute more than about 40% by weight.

Particularly suitable polymeric polycarboxylates can be derived from acrylic acid. The acrylic acid-based polymers useful in the compositions of the invention are the water-soluble salts of polymerized acrylic acid. The average molecular weight of such polymers in acid form is preferably in the range of about 2000 to 10000, 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, ammonium salts 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, in U.S. Patent No. 3308067, issued March 7, 1967. This patent is herein incorporated 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 about 200

-61100000, more preferably from about 5000 to 75000, most preferably from about 7000 to 65000. The ratio of acrylic segments to maleate in such a copolymer will be; generally ranging 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, ammonium and substituted ammonium salts. Soluble acrylate / maleate copolymers of this type are known materials as described in European patent application no.

66915, 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 dispersant

clay-like impurities and prevent their deposition. A typical molecular weight range for these purposes is in the range of about 500 to about 100,000, preferably from about 1000 to about 50,000, more preferably from about 1500 to about 10,000.

Clarifying agents

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

The choice of brighteners to be used in the 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 cleaned, such as cotton, synthetic materials, etc. Since most laundry detergent compositions are used to clean various fabrics, detergent compositions should include a blend of bleaching agents. which will be effective for various textiles. Of course, 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 including, but not limited to, stilbene derivatives, pyrazoline, coumarin, carboxylic acids, methinkyanines, 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 Brightening ®, M. Zahradnik, John Wiley and Sons, New York (1982), which is incorporated herein by reference.

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

Some bis (triazinyl) aminostilbene derivatives that can be used in the present invention can be prepared from 4,4'-diaminstilbene-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.

The carboxylic acid derivatives that may be used in the present invention include, but are not limited to, fumaric acid derivatives, benzoic acid derivatives, p-phenylene-bis-acrylic acid derivatives, haftalenedicarboxylic acid derivatives, heterocyclic acid derivatives and cinnamic acid derivatives.

Derivatives of cinnamic acid, kteréimohou be used in the present invention can be further subclassified into groups which include, but are not limited to ^7, cinnamic acid derivatives, styrylazoles, styrylbenzofurans, styryloxaóiazoly, stryryltriazoly and styrylpolyphenyls, as indicated on page 77 of the cited Gardener's publications.

The styrylazoles can be further classified into styrylbenzoxazoles, strylimide azoles and styrylthiazoles as described on page 78 of Zahradhik's work cited. Of course, the three subclasses do not necessarily include an exhaustive list of subgroups into which the styrylazoles can be sorted.

Another group of optical brighteners that can be used in the present invention are the dibenzothiepine-5,5-dioxide derivatives described on pp. 741-749 of The Kirk-Othmer Encyclopedia of Chemical Technology, vol. 3, p. 737-. 750 (John Wiley and Sont, Inc., 1962), the disclosure of which is incorporated herein by reference and includes

3,7-Diaminobenzothiophene-2,8-disulfonic acid 5,5-dioxide *

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

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 pyrazine-derived brighteners and 4-aminonaphthalamide-derived brighteners.

In addition to the brighteners mentioned, mixed agents can also be used as brighteners. Examples of such blending agents are described on pages 93-95 of the Gardener's earlier work and include 1-hydroxy-3,

6,8-pyrentrisulfonic acid, 2,4-dimethoxy-1,3,5-triazin-6-yl-pyrene, 4,5-diphenylimidazolone disulfonic acid and pyrazolinequinoline derivatives.

Other specific examples of optical brighteners that can be used in the present invention are those disclosed in U.S. Patent No. 470856, Wixon, December 13, 1988, which is incorporated herein by reference in its entirety. ^A ato brighteners include the PHORWHITE series of brighteners of the company 'Eron. Other brighteners described in this reference include: Tinopal UNPA, Tinopal CBS and Tinopal 5BM, available from Ciba-Geigy; Arctic White CC and - ^ rctic White?

CWD, available from Hilton-Davis, based in Italy 2- (4-styryl-phenyl) -2H-naphtho [1,2-d] triazoles, 4,4'-bis (1,2,3-triazole-2- yl) -stilbenes, 4,4'-bisistyryl) bisphenyls and γ-aminocoumarins. Specific examples of such brighteners include

4-Methyl-7-diethylaminocoumarin, 1,2-bis (4-benzimidazol-2-yl) ethylene, 1,3-diphenylphrazolines, 2,5-bis-benzoxazol-2-yl) thiophene, 2-styryl-naphtha / 1,2 d) oxazole; and 2. (stilbene-4-yl) 2H-naphtho [1,2-d] triazole.

Other optical brighteners that may be used in the present invention are those described in U.S. Patent No. 3,646,015, issued February 29, 1972 to Hamilton, which is incorporated herein by reference.

-65Other ingredients

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

Combustible 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, propanol and isopropanol. Monofunctional alcohols are preferred for solubilizing surfactants, but polyols such as those containing 2 to about 6 carbon atoms and 2 to about 6 hydroxy groups (e.g., propylene glycol, ethylene glycol, glycerin and 1,2-propanediol) may also be used ).

The detergent compositions herein will preferably be formulated such that during use in aqueous cleaning operations, the wash water will have a pH between about 6 _t 5 and about 11, preferably between about 7.5 and about 10.5. s ^ _n ApaI formulations preferably have a pH between about 7.5 and about 9.5, more preferably between about 7.5 and about 9.0. Techniques for controlling pH at recommended values in use include the use of buffers, alkalis, acids, etc., and are well known to those skilled in the art.

The present invention further provides a method of cleaning substrates such as fibers, textiles, 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 water miscible solvent (e.g. primary and secondary alcohols).

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

DETAILED DESCRIPTION OF THE INVENTION

This experiment provides a process for the preparation of the N-methyl, 1-deoxyglucityl-lauramide surfactant used in the invention. While many variations of the apparatus will be apparent to those skilled in the art, one suitable apparatus for use in this process includes a three-liter four-necked flask equipped with a motor-blade stirrer and a thermometer of sufficient length to contact the reaction medium. The other two flasks are equipped with a nitrogen inlet and a wide-pass secondary arm (note: a wide-pass secondary arm is important in the case of very rapid methane development) to which an efficient collector cooler and vacuum outlet are connected. Τθη is connected to the nitrogen purge and vacuum of the vacuum gauge, then to the hood and trap. The 500 # attac heater with a temperature control unit (Variac) used to heat the reaction is placed on a laboratory jack so that it can be easily raised or lowered while further controlling the reaction temperature.

N-ethyl ethyl glucamine (195 g, 1.0 mol, Aldrich, M470Q-0) and methyl laurate (Procter end Gamble CE 1270, 220.9 g,

1.0 mol) was placed in a flask. The mixture of solid and liquid is heated under stirring under a stream of nitrogen to form a melt (about 25 minutes). When the melt reached 145 ^Q C, catalyst (anhydrous powdered sodium carbonate,

10.5 g, 0.1 mol, J.T.Baker). The nitrogen inlet is closed and the nitrogen outlet is adjusted to create a vacuum of 16.65 kPa. From this point, the temperature is maintained at 150 ° C using Variac A / or increasing or lowering the position

-67coats.

Within 7 minutes, the first bubbles of methanol are visible on the meniscus of the reaction mixture. An intense reaction soon follows. The methanol was distilled off until its flow rate decreased. The vacuum is adjusted to about 50 psi. 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 are discontinued within 11 minutes of detecting methanol evolution with some foaming. The product was 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, alkyl ethoxylated sulfates and antifoaming agents.

Basic Granules 1 2  3 C ₁ 4 ^'C ^ 1jSlky sulfate 11.3 ^G 14-1-alkylethoxy (2,25) sulphate 11.2 16.9 5.6 N-methyl-N-1-deoxyglucityl- 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 sulphate 8.0 8.0 11.1 sodium polyacrylate (4500 mhm) 3.5 3.5 2.1

polyethylene glycol (8000 fahm) 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-foam agents * 1.0 0.5 protease (1.4% of active enzyme) 0.9 0.9 G, 9 perfume 0.3 0.3 0.3 ^ 12 13θΐ ^ ΐΐethoxylate (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 flakes antifoam agent comprise from about 5% dispersion of a silica / silicone oil, encapsulated in flakes, in particular containing PEG (MHM 8000) in an amount greater than 80%, and optionally minor amounts of water-soluble components.

Examples 1-3 are formulations for preferred uses of about

1400 ppm, based on the weight of the wash water, at temperatures below about 50 ° C. The above examples are accomplished by combining the granular base components as a suspension and spray drying to about 4-8% residual moisture. The remaining dry ingredients are admixed in granular or powder form to the spray dried granules in a rotary mixing drum and sprayed with a liquid component (nonionic surfactant and perfume).

Basic granules 4 .5 6 C.. alkyl sulfate 14-15 5, δ C ₁ g- ₁ alkyl ethoxy (2,5) sulphate 6.0 ^ 16-18 ^mas ^ ⁿ ^ ^{k -yelin} 2.2 2.2 Zeolite A 7.0 7.0 7.0

polyacrylate (4500 mhm) 3.3 3.3 3.3 polye thylene 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 A 5.0 5.0 5.0 N-methyl-N-1-deoxyglucitylamide of coconut fat 4.0 6.4 4.4 G ^ ₄ ^ _i alkylsulfate 11, 8 2 igaalkyl sulfate 13.1 16.1 ° 1 2-1 (2) sulphate 5.0 C ₁ _ ₁₄ alkyl ethoxy (2.25) sulfate 4.0 anti-foaming agent flakes ^x 1.0 0.5

various (filler salts, brightener,

enzyme, buffer, zeolite or other activating agent, etc.) 17.2 17.2 16.5 Spray C ₂ _ ^ i- elkyle ethoxy methacrylate (6.5 moles) of 2.0 2,0 2,0 perfume 0,5 θ, 5 0.5 water and various 8.2 9.4 8.4 100.0 100.0 100.0 ^x Anti-foaming Flakes contain approximately 5% dis · Persian silicon dioxide / silicone oil encapsulated in flakes containing mainly PEG (8000 mhm) in quantity- more than 80% and less optionally in the water

soluble ingredients.

The compositions of Examples 4-6 represent condensed granular formulations prepared by suspending and spray drying the granule base ingredients to a moisture content of about 5% and blending with other dry pellets or

-70— granular additives. The resulting mixture is de-dusted by spraying with the liquid components. The product is intended for use at a concentration of about 1000 ppm, at washing temperatures below about 30 ° C.

Examples 7-12

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

Folders  7 8 9 10 N-methyl-N-1-deoxygluci- tylamiď coconut acid fat 4.2 3.1 3.1 8.5 ^C 14-1 (J-alkyl ethoxy (2,25) sulphate 12.6 9.3 8.5 θΐ 2-1 (2.5) sulphate 6.2 C 1-4 alkylsulfate 3.1 C _{1 2} 1-6 alkyl ethoxyethyl 3.4 2.5 dodecyltrimethylammonium- chloride 0.5 0.2 dodecenyl succinate 5.0 sodium citrate 3.4 15.0 5.0 TMS / TDS (80/20) ^x 3.4 ^ fatty acid 3.0 3.0

Oxydisuccinate 20.0 ethoxylated tetraethylene-

pentamine 1,5 2,0 polyacrylate (4500 mhm) 1.5 1.5 Silicone oil (antifoam) agent) 0.9 0.9

various (enzymes, brighteners, releasing agents, stabi-71-

lizators etc.) 15.3 water 52.7 14.0 51.2 14.0 51.2 16.3 54.0 100.0 1 00 | 0 100.0 100.0 ^X TMS / TDS is a tartrate monosuccinate / tartrate disuccinate Folders 1 1 12 N-methyl-N-1-deoxyglucitylamide of coconut fat 5.5 5.5 C1-4 alkyl ethoxylate (6.5 mol) 2.5 2.5 alkyl ethoxylate (2.25) sulfate 1 7.0 17.0 oleic acid 3.0 3.0 dodecyltrimethylammonium chloride 0.2 0.2 citric acid 1.0 1.0 monoethanolamine 2.5 2.5 ethoxylated tetraethylenepantamine 1.5 1.5 protease (3.1% active) 0.5 0.4 amyláaa (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,

based on the wash water, at temperatures below about 50 ° C. They are prepared by combining non-aqueous solvents, aqueous surfactant pastes or solutions, molten fatty acids, aqueous solutions of polycarboxylate activators and other salts, aqueous ethoxylated tetraethylenepentamine, buffering agents, caustic substances and remaining water. The pH is adjusted to about pH 8.5 using an aqueous citric acid solution or sodium hydroxide solution. After pH adjustment, final ingredients such as soil release agents, enzymes, dyes and perfumes are added and the mixture is mixed until a single phase is obtained.

-72Example 13

An alternative method of preparing polyhydroxy fatty acid amides is as follows. Reaction mixture containing 64.67 g of methyiesLe.ru fatty acid (source: Proctcr and Gamble methyl ester CE1270), 75 g of N-methyl-D-glucamine (source: ALdrich Chemical Compsny M47G0-0), 1.04 g of sodium methoxide ( Sources: ALdrich Chemical Company 16, 499-2) and 68.51 g of methanol are used in this procedure. The reaction vessel comprises a reverse flow equipment equipped with a drying tube, a condenser and a stirring bar. In this procedure, N-methylglucamine is mixed with methanol under stirring under argon and heating is started, stirring well (stir 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 completely clear after 63.5 minutes. The reaction is believed to be virtually complete at this point. The reaction mixture is maintained at reflux for 4 hours. Removal of the methanol yielded a crude product weighing 156.6 grams. A total yield of 106.92 grams of purified product is obtained after vacuum drying and purification. However, the percentage yields are not calculated on this basis, since 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 range of detergent compositions using polyhydroxy fatty acid amides.

It will be noted that polyhydroxy fatty acid amides are exposed to some instability under highly basic or highly acidic conditions due to their amide bond. 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 even below 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 necessary to neutralize at least partially the basic catalyst ¹ which was used to form the amide bond. While an acid may be used for this purpose, it will be apparent to the formulator that it is simple and expedient to use an acid that provides the anion and which is otherwise suitable and desirable in the final detergent composition. For example, citric acid may be used for neutralization and the resulting citrate ion (about 1%) is left with a suspension of about 40% polyhydroxy fatty acid amide and pumped to subsequent processing stages of the detergent production process. Similarly, acid forms of materials such as oxydisuccinate, nitrilotriacetate, ethylenediamine tetraacetate, tartrate / succinate and the like can be used.

Polyhydroxy γ-fatty acid anidyls derived from coconut fatty acid alkyl fatty acids (predominantly 3 ^{SOU more} soluble than their alkyl tallow counterparts (predominantly ^G 16 ^-C ₁₈ )) ^, as a result, ₂ ^c 14 materials are somewhat are easier to formulate into liquid compositions and are more dissolving in cold water washing baths, the C ^ΟΟ materiály materials are also quite useful, especially under conditions where warm to hot water is used. their ^ counterparts.

Thus, the formulator can proceed on the basis of the requirement of ease of manufacturing verse. potency in selecting a particular polyhydroxy fatty acid amide for use in a given formulation.

x x ii ii ii ii ii ii ii ii _{A A A A A A A A A A A A A A A A A A A A A A A A A A A A A A} a 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 counterparts. Higher solubility may be particularly useful in formulating liquid preparations. In addition, polyhydroxy fatty acid amides in which the polyhydroxy group is derived from maltose also prove to be particularly good detergents when used in combination with conventional alkylbenzene sulfonate (LAS) surfactants. While not wishing to be bound by any theory, the combination of LAS with higher carbohydrate-derived polyhydroxy fatty acid amides, such as maltose, appears to cause a substantial and unexpected decrease in interfacial tension in aqueous media, thereby promoting detergency performance. (Production of maltose-derived polyhydroxy fatty acid amide is described below).

Polyhydroxy fatty acid amides can be made not only from purified sugars, but also from hydrolyzed starches, e.g., corn starch, potato starch or any suitable starch derived from plant products, which contains the mono-, di-, etc. carbohydrates required by the formulator. This is particularly important from an economic point of view. Thus, high glucose corn syrup, high maltose corn syrup, etc. can be advantageously and economically used. The raw material source for polyhydroxy butyric acid amide can also provide wood-hydrolysed cellulosic pulp.

As mentioned above, polyhydroxy fatty acid amides derived from higher carbohydrates such as maltose, lactose, etc. are more soluble than their glucose counterparts. In addition, it appears that more soluble polyhydroxy fatty acid amides can help solubilize their more soluble counterparts at different rates. Thus, the formulator may choose raw materials containing, for example, a high glucose corn syrup, but may choose a syrup that contains a small amount of maltose (eg, 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 the economic advantages of using sugar mixtures rather than pure sugar starting materials, polyhydroxy fatty acid amides prepared from mixed sugars can provide very substantial advantages in terms of efficiency and ease of formulation. In some cases, however, some grease removal (dishwashing) loss may be observed at fatty acid maltamide levels above about 25% and some foaming loss above about 33% (percentages are percent of polyhydroxy fatty acid amide derived from maltamide v. Polyhydroxy amide). glucose-derived fatty acids in the mixture). This may vary depending on the chain length of the fatty acid moiety. Typically, the formulator choosing to use such mixtures may find the 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: 1.

The production of preferred non-cyclized polyhydroxy fatty acid amides from fatty esters and N-alkyl polyols may be carried out in alcoholic solvents at temperatures from about 30 to 90 ° C, preferably about 50 to 80 ° C. ^It has been determined that it may be appropriate for the formulator of, for example, liquid detergents to carry out such processes in the form of liquid detergents

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, the formulator of, for example, solid, typically granular, detergent compositions may find it advantageous to carry out the process at 30 to 90 ° C in solvents that include ethoxylated alcohols such as ethoxylated (EO 3-8) 2 → 6 alcohols such as NEODOL 23 E06. 5 (Shell). If such ethoxylates are used, it is preferred that they do not contain substantial amounts of unethoxylated alcohol, and most preferably they do not contain substantial amounts of mono-ethoxylated alcohol (Determination T).

While the methods 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 the 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 Nalkylamine 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. While many of the N-alkyl polyhydroxy amines useful in Step 2 can be prepared by various procedures described in the prior art, the following process is preferred, which utilizes an economically advantageous sugar syrup as a raw material. It should be noted that for best results when using such syrups, the manufacturer should choose syrups which are completely light in color or preferably completely colorless (water color)

Preparation of N-alkylpolyhydroxyamine 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 about 50% aqueous methyl amine solution (59.5 g methylamine - 1.92 mol). The methylamine solution (MMA) is bubbled through and protected and cooled to about 10 ° C or lower. The cereal syrup is bubbled through and protected with N 2 at a temperature of about 10 to 20 ° C. Cereal syrup is added slowly to the MMA solution at said reaction temperature. The Gardner color is measured at the indicated approximate times in minutes.

Table 1

Minutes in 1Q 30 60 120 180 240 reaction temperature ° C Gardner Color (approx.) £ 0

1 1 1 1 1 1 1 2

6 10

As can be seen from the above, the Gardner color for the adduct is much worse when the temperature rises above about 30 ° C and about 50 ° G, 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 less than about 4 to obtain a good glucamine color. .

If lower temperatures are used to form the adduct, the time to achieve a substantial equilibrium concentration of the adduct is reduced by using higher amine to sugar ratios. With a molar ratio of 1.5: 1 amine to sugar, the equilibrium was reached for two hours at a reaction temperature of about 30 At a molar ratio of 1.2: 1, under the same conditions, this time was at least about three hours. For good color, the combination of the amino sugar, reaction temperature and reaction time is selected to achieve substantial equilibrium conversion, e.g., greater than about 90, preferably greater than about 95%, and even more preferably greater than about 99%, based on sugar; about 7, preferably less than about 4, more preferably less than about 1, for the adduct.

Using the above process at a reaction temperature below about 20 ° C and corn syrups with different Gardner Colors as indicated, the MMA adduct color (after substantial equilibrium achievement ^ 5 ^ ^r ^ ° ^ ^{3a yes at} least

about two hours) as specified in Table 2. Table 2 Gardnerova color (approximately) corn syrup 1 1 1 1 + Q 0 0+ adduct 3 4/5 7/8 7/8 1 2 1

As can be seen from Table 2, the starting sugar material must be very close to colorless in order to obtain an acceptable adduct. If the sugar has a Gardner color of about 1, the adduct is sometimes acceptable and sometimes unacceptable. If the Gardner color is greater than 1, the resulting adduct is acceptable. The better the initial color of the sugar, the better the color of the adduct.

-79II. Hydrogen Reaction - The adduct mentioned above having a Gardner color of 1 or less is hydrogenated as described below.

About 539 g of the adduct in water and about 23.1 g 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 100 psig 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.

The product after removal of water and MMA evaporation is about 95% N-methylglucamine as a white powder.

The above procedure is repeated with about 23.1 g of Baney-Ni catalyst followed by i. The catalyst is washed three times and the reactor, with the catalyst in the reactor, is purged twice with hydrogen at 1.38 MPa and pressurized with hydrogen at 11 MPa for a period of time. two hours, the pressure is released for one hour and the reactor is re-pressurized to 1 MPa.

The adduct is then pumped to a reactor at pressures of 1.38 MPa and 20 ° C and purged with hydrogen at 1.38 MPa, etc., as above.

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

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

It is important to have a good adduct 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% methylanine in water, which is purged and overlayed with nitrogen at about 10-20 ° C. About 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 below 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 G49B Ni-catalyst were charged into a 200 ml autoclave and purged three times with hydrogen at about 20 ° C. The hydrogen pressure was raised to about 50 psig and the temperature was 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 to about 95% 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 when the hydrogen pressure is less than about 6.88 MPa 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 embodiment similar to that described above for the preparation of the adduct and for carrying out the hydrogen reaction at various reaction temperatures.

The eluate used in the production of glucamine is prepared by combining about 420 g of about 55% glucose (cereal syrup) as a solution (231 g of glucose, 1.28 mol) (the solution is prepared using 99DE cereal syrup from CarGill, the solution is less than 1 color). Gardner) and about 119 g of 50% methyl amine 59.6 g of MiA, 1.92 mol) (from Air Products).

The reaction procedures are as follows:

1. About 119 g of a 50% methyl amine solution was 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 adding all the corn syrup solution, stir for about 1-2 hours.

The eluate is used for the hydrogenation reaction immediately after preparation, 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 5.5 g of G49B Ni into a 200 ml autoclave.

Indole carboxylic second mixture was purged with hydrogen at about 1 38 psig and a temperature of about 20 to 30 ^Q C.

-823. It is pressurized with hydrogen to a pressure of about 2.7 IPa and the temperature is raised to about 50 ° C.

4. The pressure is raised to about 3.45 MPa, allowed to react for about 3 hours. The temperature is maintained at about 50-55 ° C.Sample 1 is taken.

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

6. Decant and filter the Ni-catalyst. Take sample 2.

Conditions for constant temperature reactions:

1. Add about 134 g adduct and about 5.00 g G49B Ni to a 200 ml autoclave.

2. Purge twice with hydrogen at about 50 psi at low temperature.

3. Pressurize to about 100 psig with hydrogen and raise the temperature to about 50 ° C.

4. The pressure is maintained at about 350 psig, allowed to react for about 3.5 hours. The temperature is maintained at that temperature.

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

All experiments yield a similar purity of N-methylglucamine (about 94%), Gardner 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 reaction.

Example 14

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

Stage 1 - Maltose reactant monohydrate (Aldrich, C1318KW) methylamine (40¾ wt% in water) (Aldrich, 03325TM), feyey-nickel, 50% suspension (UAD 52-73D, Aldrich, 12921LW).

The reaction components were placed in a glass cartridge (250 g of maltose, 428 g of methylamine solution, 100 g of catalyst slurry - 50 g of Rane.y-Ni) and placed in a 31 liter swing autoclave purged with nitrogen (3 x 2.78). MPa) and hydrogen (2 x 2.78 MPa) and rocked under a hydrogen atmosphere at room temperature over the weekend at a temperature range of 28 to 50 ° C. The crude reaction mixture was vacuum filtered 2X through a glass microfiber filter with a silica gel plug. 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 is concentrated until a precipitate is formed and stored in a refrigerator overnight. The solid was filtered off and dried under vacuum. This is section 2. The filtrate is again concentrated to half its volume and recrystallized. Very little precipitate is formed. A small amount of ethanol was added and the solution was 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), solidified tallow methyl esters, sodium methoxide (25¾ in methanol), absolute methanol (solvent), molar ratio 1: 1 amine: ester, initial concentration ka-3410 mol %, and increased to 20 mol%, solvent content 50% (w / w).

20.36 g of tallow methyl «Κ - 4 - Μ» are heated in a sealed bottle. -. -. 'I - X. - J_ J f (-3 'Π Z _. * \ 1 * of 1 «.

OC4 and Ucpj-UGU. baiu ^ VUUUl XctZ-body / Vilíci 3β C1U £? ULHJw

3-neck round bottom flasks equipped with a mechanical stirrer. Heat the flask to about 75 ° C to prevent the ester from solidifying. Separately, 25.0 g of N-methyl maltamine was combined with 45.36 g of methanol and the resulting suspension was added to the tallow ester with good stirring. Add 1.51 g of 25¾ sodium methoxide in methanol. After four hours, the reaction mixture was still not clear, so an additional 10 mol% of catalyst (to a total of 20 mol%) was added and the reaction continued overnight (about 66 ° C), after which time the reaction mixture was clear.

in

The reaction flask is then adjusted for distillation. The temperature is raised to about 110 ° C. Distil at atmospheric pressure for 60 minutes. High vacuum distillation is then started 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 was removed on a rotary evaporator and the product was stored in an oven overnight and ground into a powder. Any residual N-methyl maltamine was removed from the product using silica gel. The silica gel slurry in 100¾ methanol is placed in a funnel and washed several times with 100¾ methanol. The concentrated product sample (20 g in 100 mL of 100¾ methanol) is placed on silica gel and eluted several times using vacuum and several methanol washes. The combined eluate was evaporated to dryness (rotary evaporator). Any remaining tallow ester was removed by trituration in 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, the flow of the reaction sequence may be carried out using a commercial cereal syrup containing glucose or a mixture of glucose and typically 5% or more 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 preceding reaction sequence may be performed 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 the formulation of detergent compositions. Again, as required by the formulator, the methoxide catalyst can be neutralized with citric acid to form sodium citrate, which can be left in the fatty acid amide.

Depending on the formulator's requirements, the composition of the invention may optionally contain more or less suds controlling 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 a large degree of foam control may be preferred for front-load washing machines. A wide variety of suds control agents are known in the art and can 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 used, but also on the other surfactants present in the composition. However, it is clear that the use of polyhydroxy fatty acid amides, agents and silicone-based foaming agents of different types (i.e., lower concentrations may be used) are more effective than various other types of agents.

-86 controlling foaming. Silicone suds controlling agents available as X2-3419 and Q2-3302 (Dow Corning) are particularly suitable.

the fabric wash formulator, preferably containing 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). Additional soil release materials which are useful include the nonionic oligomeric esterification products of a reaction mixture comprising a source of C ^ -C ^ alkoxyzakončených polyethoxyjednotek (e.g. CH ^ / ₂ O0H GH _2/1 Goh), a source of terephthaloyl units (např.dimethylterefta- (oxyethylene) oxy units (e.g. polyethylene glycol 1500), a source of oxyiso-prop.ylenoxy units (e.g.

1,2-propylene glycol) and a source of oxyethyleneoxy units (e.g. ethylene glycol), especially wherein the molar ratio of oxyethyleneoxy units: oxyisopropyleneoxy units is at least about 0.5: 1. Such nonionic soil release agents have the general formula

R ^ -ÍÍ (CHgO ^ ^)

CO-CR-CH ₂ O

Ίη o

H

C · o

, -CO (CH_CH_O)

2 y n

O O

G, O-O-OCl (GHgO) -R ¹

-87kde R ¹ is a lower (e.g. _C1 ^ alkyl, especially methyl, x and y are each an integer from about ^ϋ to about 100, m is an integer what about 0.75 to about 30, n is an integer from about 0, 25 to about 20 and R is a mixture of H and GH 2 with the proviso that the molar ratio of oxyeth, ylenoxyoxyisopropylenoxy is at least about 0.5: 1.

Another preferred type of soil release agents are those of the anionic type described in US Patent No. 4,877,896, but provided that they are substantially free of HOROH-type monomers wherein R is prop-ylene or higher alkyl. The soil release agents of U.S. Pat. No. 4,877,896 may include, for example, the reaction product of dimethyl phthalate, ethylene glycol, 1,2-propylene glycol, and 3-sodium sulfobenzoic acid, while such additional soil release reagents may include, for example, the dimethyl terephthalate reaction product, ethylene glycol, 5-sodium sulfoisophthalate and 3-sodium sulfobenzoic acid. 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 for high performance granular laundry detergents. Various ueroxide bleaches are commercially available and can be used, but of these the percarbonate is the most accessible and economical. Thus, the compositions of the invention may contain a solid percarbonate bleaching agent, normally in the form of a 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.

Sodium carbonate is an addition compound having the formula corresponding to 2Na ₂ CO 2. ^and 0 ^is commercially available as a crystalline solid. Most commercially available materials include small amounts of heavy metal scavenger such as EDTA, 1-hydroxyethylidene-1,1-diphosphonic acid (ΗΕΗ) or aminophosphate, which are incorporated during the manufacturing process. For use in the compositions of the invention, the percarbonate may be included in detergent compositions without further protection, but preferred embodiments of the invention are used in stable form of material (FMC). various coatings may be used, the most economical being sodium silicate SiO ₂ : Na 2 O in a ratio of 1.6: 1 to 2.8 µl, preferably 2.0: 1, applied as an aqueous solution and drying to give a concentration of 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 about 400 microns. When coated, the crystals have a size ranging 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, but the percarbonate still requires protection from the heavy metals present as impurities in the other components of the product. 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 in order to avoid adverse effects on the percarbonate stability.

The modern, densified detergent granule has the following composition.

-89Example 15

Ingredient

G ₁ 4 ₁ 13 ^ alkylalkoholsulfonová acid ^G 1 ^to 5 lkylpol 4i, polyethoxylated (2.25) sulfonic acid 5.60 ^g 12-1 ^ al ^ ylpolyethoxylát (6.5) 1.45

C ₁ -fatty acid such as N-methylglucamide 2.50 sodium aluminosilicate <as hydrated

Zeolite A) 25.2 crystalline layered silicate based activator ^{1 2} 23.3 citric acid 10.0 sodium carbonate for washing pH = 9.90 sodium polyacrylate (MW 2000-4500) 3.2 diethvlentriaminepentaacetic acid 0.45

Ssvinase 0.70 6-nonanoyl-6-oxo-peroxycaproic acid 7.40 sodium perborate monohydrate 2.10 nonanoyloxybenzenesulfonic acid 5.00 brightener 0.10

Layered silicate activators are known in the art. Layered sodium silicate is preferred. See, for example, sodium silicate layered active ingredients, U.S. Pat. No. 4,666,459, issued May 12, 1987, to H.P. Rieck, which is incorporated herein by reference. A suitable layered silicate based activator is available as 3KS-6 from Hoechst.

· _T

Available from Novo Nordisk A / S, Copenhagen.

-90—

Significantly preferred granules of said types are those comprising about 0.0001 L to about 2% by weight. % of active enzyme and at least about 1 wt. % of said polyhydroxy fatty acid amide; and most preferably one wherein the anionic surfactant is present.

Described herein are compositions which are liquid and are intended to be washed as compositions of the invention.

It should be noted that the stability of enzymes in such formulations should be less than in granular detergents. By using typical enzyme stabilizers such as formates and boric acid, lipase and cellulose enzymes can be protected from degradation by protease enzymes. However, lipase stability is still relatively poor in the presence of alkylbenzene sulfonate (LA3) surfactants.

LAS partially denatures the lipase and further causes the denatured lipase to be less resistant to protease attack.

In view of these requirements, which, as noted, may be 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. It is difficult to incorporate stably oxidizing enzymes and / or amylase enzymes into such formulations.

It has now been found that various mixtures of lipases, proteases, cellulases, amylases and peroxidases are adequately stable in the presence of some non-alkylbenzene sulfonate surfactant systems so that high performance solid and liquid detergents can be formulated. Formulation of stable, liquid, enzyme-containing

The detergent formulations constitute a very preferred and preferred embodiment achieved by the technology of the invention.

Liquid detergents according to the prior art comprise LAS types or mixtures of LAS with surfactants of the type ROAA4 (AES) described previously, i.e., LAS / AES compositions. 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 noted that this will reduce the stability of the enzymes. Accordingly, it is preferred that the liquid formulations are substantially free (i.e., contain less than about 10%, preferably less than about 5%, more preferably less than about 1%, and most preferably 0%) of the 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 a polyhydroxy fatty acid amide of the formula wherein R ¹ is H, N-hydrocarbyl, 2-hydroxyethyl, 2-hydroxypropyl or a mixture thereof, R ₂ is G ₅ _ ₃₁ hydrocarbyl, and Z is a polyhydroxyhydrocarbyl having a linear hydrocarbyl chain with at least 3 hydroxyls directly connected to the side chain, or an alkoxylated derivative thereof, and said composition is substantially free of alkyl benzene sulfonates.

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

RO (A) of 30 m J wherein R is an unsubstituted C ₁₀ _ ₂ alkyl or hydroxyalkyl · (C 0-24) Slupina, 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 _2- alkyl group, A is ethoxy units, 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, 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: 1, preferably about 1: 1 to about 5: 1, most preferably about 1: 1 to about 4 : 1.

Alternatively, the preparations according to the invention contain polyhydroxy fatty acids, AES, and from about 0.5% to about 5% of the condensation product Cg_ ₂ 2 ^G ^ preferably 10-20 alcohol with between about 1 and about 25, preferably between about 2 and about 18, mol of ethylene oxide per mole of alcohol.

As described previously, the liquid formulations of the present invention have a pH in a 10¾ 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 about 0.1% to about 50 -3 detergent builders. The compositions preferably comprise from about 0.1% to about 20% citric acid or a water-soluble salt thereof and from about 0.1% to about 20% water-soluble succinate-tartrate, in particular its sodium salt and mixtures thereof, or from about 0.1% to about 0.1%;

-9220% oxydisuccinate or mixtures thereof with the above activating agents. 0.1% -50% alkenyl succinate may also be used.

Preferred liquid compositions of the invention comprise from about 0.0001% to about 2%, preferably about (1.0101% to about 1%, most preferably about 0.001% to about 0.5%, based on the active base of the purification enzyme. They are preferably selected from the group consisting of proteases (preferably), lipases (preferred), amylases, cellulases, peroxidases, and mixtures thereof Preferred are preparations with two or more classes of enzymes, most preferably one of which is a protease.

Various purifying proteases, cellulases, etc. are described in the literature, purifying lipases having a slightly smaller extent. Optionally, the formulator may select Amano AIG and Bacillis Sp lipase (e.g., Solvay enzymes). See also lipases described in EP-A-0399681, published Nov. 28, 1990,

EP A 0218272, published April 15, 1987 and PCT / DK 88/00177, published May 18, 1989, which are incorporated herein by reference.

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

From about 2 to about 20,000, preferably about 10 to about 6,000, lipase units of lipase per gram (LU / g) of the product may be used in such formulations. The lipase unit is the amount of lipase that produces 1 µmol of titratable butyric acid per minute in a pH meter, where the pH is 7.0,

The temperature is 30 ° C and the substrate is an emulsion of tribut, yrin and acacia, in the presence of Ga ⁺⁺ and NsCl 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 0.01% to about% by weight of the total composition, although the amounts to be used may be adjusted according to the formulator's requirement to obtain an effective amount (i.e., 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) a surfactant of the RO (A) _m SCyw, as described herein, preferably ROÍCr ^ CI ^ Oj ^ SOyM, wherein R is _{4 _]} (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, a surfactant of the type RCSO-M as described herein, preferably wherein R is G _{12 -1} (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 not preferably, effective amounts of enzyme stabilizers, typically from about 1% to about 10% by weight of the composition,

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

(h) where applicable, various cleaning additives, brighteners, etc.,

Some of which are 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

% By weight

Sulphonic Acid C, 4-15 alkylpolyethoxylate (2.25) 2100

N-methylglucamide C1 2-14 fatty acids ¹ 7,00 mono-tartrate and sodium iso-succinate (mixture

80:20) 4.00 citric acid 3.80

Cl 2-14fatty acid 3.00 Tetraethylenepehfcaaminethoxyl ylate (15-18) 1.50 Ethoxylated polyethylene-polypropylene terephthalate polysulfonic acid copolymer 0.20

Protease 3 (34 g / L) ² 0.68

Lipase (100 KLU / g) ³ 0.47

Cellulase (5000 cevu / g) ^ 0.14 brightener 36 0.15 ethanol 5.20 monoethanolamine 2.00 sodium formate 0.32

1,2-propanediol 8.00 sodium hydroxide 3.10 silicone suds suppressor 0.0375 boric acid 2.00 water / various to 100.00 'prepared as described above.

² Protease 3 is a modified serine protease described in U.S. Pat

European Patent Application No. 87 303761, filed August 28, 1587, in particular pages 17, 24 and 58.

The lipase used herein is a lipase obtained by cloning a gene from Humicola lanuginosa and expressing in? Spergillus oryzae, as described in European Patent Application 0258066, commercially available under the trade name LIFOLASE (from Novo Nordisk A / S, Copenhagen, Denmark).

Cellulose used herein is available under the trademark Garezyme (Nove Nordisk, A / S, Copenhagen, Denmark). Brightener 36 is commercially available as TINOPAL TAS 36.

'V,

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

Examples 17 A-D

The following examples illustrate light duty detergent compositions which are specially formulated for dishwashing or other hard surfaces cleaning. In Examples AD, the surfactants contain various alkyl ethoxy sulfate surfactants which, using standard terminology, are abbreviated to denote their average degree of ethoxylation, ^{σ —} 2-13 E0 (8,8) sulfate means a sulfated mixed C 1-6 alcohol fraction having average degree of ethoxylation 0.8. These anionic ethoxysulfates are widely used in the form of their Na ⁺ or NH 4 ⁺ salts. G 2 - 2 - amine oxide is a mixed (average) dimethylamine oxide. C ^ ₂ -14 APbetain is

0/2 ^H I5 / 29 ^{0Ora (OH} 2 ⁾ 3 ^{N + <0H} 3 ⁾ 2 ^ ^OO 2 ^H · ° 1 ³⁶ ° ^{12/14 H} 25/29 ^{CONH (CIH} 3 ^{> 3I + <OH} 3 ⁾ 2 ^QH 2 ^{OHÍOH)? SO} 3 ^H · ™ ^C 12-14 betaine is <= 2 /, 25/29 ^H 4 ^{N + (CH3>} 2 ^CH 2 ^C0 2 ^H - ^{Ethoxyl0VEné} nonionic surfactant designated C EOťS ^^) is

G alcohols, ethoxylated with an average of 8 moles of ethylene oxide.

9-11

-96 + 4 * ++

Ca and Mg cations are generally introduced into the formulations as CaCl 2 and MgCl 2. The equilibrium of the formulations (i.e., containing up to 100% water and citrate / propylene glycol system in the glucamide surfactant (1-5%) and 1 to 3% of the cumene or xylene sulfonate hydrotropic agent pH is typically in the range 6.8-7.4 (NH4). + salts) or 7-8.2 (Na ⁺ salts).

Component percent (w / w) AND 3 C D ^G 1 4 2-1 ^N - ^meth ylgl ^{u3 <Aini} whose 1 1 8 12.7 9 G _{12 - 13} EO (0,8) sulphate - 16 10.0 9 ₁₂ _ C ₁₄ EO (3) sulfate 1 1 - 2.7 14 C ₁₂ i ₃ EO (6,5) sulphate - - * 3 ^C 12 ^ APbetain - - 2 - G, n-i „APsult ain l 2-1 4 - - 1.0 ₂ ^ amine oxide 2.5 - - 1.0 C _{L2, L4} DMbetain - 2,0 "" G _c .E0 (8) Ca 2 0.5 8 7 0.5 1.0 Mg ⁺⁺ o, 9 0.25 - - balance oo to to to 100 ALIGN! %

Example 18

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

% By weight

N-methylglucamine acid _(C-2) of coconut fat 14

C ₁ _ _{with 5} EO (2.25) sulfate, Na salt 10.0

C _{14 - 15} / EO (7) 4,0

-97 acid anhydrides

2_. | 4alkenyl · amber ¹ 4.0

C12-fatty acid 3.0 citric acid (anhydrous) 4.6

Protease 0.37

Termamyl (enzyme 0.12 Lipolase (enzyme) 0,3 0.36 c

Carezyme (enzyme) ^J 0.12

Deauest 2060S ^ 1.0

NaOH (pH 7.6) 5.5

1,2-propanediol 4.7 ethanol 4.0 sodium metaborate 4.0

CaO1 0.014 ethoxylated tetraethylenepentamine 0.4 brightener ⁸ 0.13

Silane ≥ 0.04 soil release polymer 0.2

Silicone ¹¹ 0.4

Silicone dispersing agent 0.2 water and various to 100, such as SYNPRAX 3 from IGI or DIS A from Proton 3 as described in EPO 0342177, November 1989, percent to 40 g / l.

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

^ Lipase, from Novo, percent to 100 KLU / g ^ Celulase to Novo, percent to 5000 CEVU / l.

^ Available from Monsanto.

⁷ From 3ASF as LUTENSOL Ρ6Φ05.

^S 3LANK0PH0R CPG766, Bayer.

⁹ Silane corrosion inhibitor, available as A1130 from Union Carbide or DYN ASYL AN TRIA1IN0 from Httls.

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

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

2

Silicone antifoam dispersant available as DC-3225C from Dow Corning.

A preferred fatty acid is a proportion of palm oil containing 12% oleic acid and 2% stearic acid and an equal amount of linoleic acid.

Example 19

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

Component % by weight SOK ALAN CPS (100% active as Salt) ¹ 3.52 DEGUEST 2066 (100% as acid) ² 0.45 TINOPAL DMS ³ 0.28 MgS0 ₄ 0.49 Zeolite A (anhydrous 2-5 / µm) 1 7.92 CMC (100% active) ⁴ 0.47 At ₂ GO ₃ 9.44 citric acid 3.5

SKS-6 layered silicate 12.9 tallow alkyl sulfate (100% active, Na salt) 2.82

C. 1-4 alkyl sulfate (100% active, Nasal) 3.5

C _12-15 alkylEO (3) sulphate 1.76-416g N-methylglucamide 4.1

DOBANOL C _{12 - 15} EO (3) 3.54

LIPOLASE (100.00 LU / g) ^δ 0.42

SAVINASE (4.0 KNPU) ⁶ 1.65

-99parfume 0.53

X2-3419 ⁷ 0,22 starch 1 _t 08 stearyl alcohol 0,35 i λ i + on on, r i) oo -i

------- ------ * - '-' - - - ** uř 'H ^W * - *** Exc.4 * J / £. «_ | J Tetraacetylylenediamine (TAED) 5.9 zinc phthalocyanine 0.02 water (ex zeolite) to 100%. SOXALAN is sodium polyacrylate / maleate available from Hoechst.

Monsanto brand for pentaphosphonomethyldiethylenetriamine.

Optical brightener available from Ciba Geigy.

^ Trademark FINNFXX by Metasaliton.

LIPOLASE lipolytic enzyme from NOVO.

SAVXNASE protease enzyme from NOVO.

X2-3419 is a silicone antifoam agent available from

Dow Corning.

The process for preparing the granules includes various tower drying, agglomeration, addition of dry ingredients, etc. as set forth below. The percentages are based on the final formulation.

A. xViening and blowing towers

Using standard techniques, they are mixed and towered

Dries the following ingredients: SOK ALAN CPS 3.52% LEQUEST 2066 0.4 o TINOPAL IBS 0.28% magnesium sulfate 0.49% ZEOLITE And as anhydrous 7.1% CMC 0.47%

-100B. Surfactant thiomerates

31. Agglomeration of sodium tallow alkyl sulfate and sodium 5 ^ 0 (3) sulphate paste

50% active tallow alkyl sulfate paste and 70% paste θ1 2-1 5 ^E Sulfate are agglomerated with Zeolite A and sodium carbonate in the following composition (proportion in detergent composition after agglomerate drying).

Tallow alkyl sulfate 2.82%

C _12-15 EO (3) sulphate 1,18%

Zeolite A 5.3% sodium carbonate 4.5%

B2. ^ ^ J agglomerates alkyl sulfate, C ₁₂ alkyl ethoxy _ ^, DOSANOLu 0 ₂ _ 5 ^ 0 (3) ^and C _{16-1 g} of N-1 methylglukosoamidu ^C 16 GGL ^l Bc ^osoanii ůový nonionic material is synthesized with DOBANOL 0 ^ - (3) present during the reaction of the methyl ester and N-methylglucamine. 0- | ₂ -15 ^{EG <} -3) It acts as a cappressor of melting point as a result of which the reaction proceeds without the formation of cyclic glucosamides, which are undesirable.

A 20% surfactant mixture is obtained.

D03AN0Lu ^G , _{2 -} | ^E 5 ° (3) 80% ^G i6-1S and coagglomerated with 10% sodium carbonate.

Then, the above particles are coagglomerated with a highly active (7076) sodium sulfate and sodium salt paste

G ^ 2 ₁₅ EO (3) sulfate and Zeolite A and sodium carbonate and, in particular, these particles have a good dispersibility in cold water prc C _{1 g} of N-methylglukozoamid.

Throughout the formulation, these particles are represented (proportion in the detergent formulation after drying the agglomerate) as follows:

-101-

6-1g N-methylglucosamide 4.1% D03AN0L C ₁₂ _ ₁₅ EC 0,94% carbonate 4.94% Zeolite A 5.3% Na-5alkyl sulfate 3.5% . , _ - J - Ί. - -. . »-.-S -z aa ⁱⁿ 12_15 wajjsuiibi V, ?? »» C. Dry ingredients The following folders are added: percarbonate 22.3% TAED (tetraacetyl ylethylenediamine) 5.9% SKS 6 layered silicate from Hoechst 12,90% citric acid 3.5% lipolase 0.42% 3AVINA3E 4.0 KNPU 10000OLU / g 1, 65% zinc phthaloc.yanin (photo brightener) 0.02%

D. Spraying on

D03AN0L C ₁₂ _ _{] 5} E0 (3) 2,60% perfume 0,33%

E. Foaming agent

Silicone Foam Suppressor X2-3419 (953-97% high molecular weight silicone, 3% -5% hydrophobic silica) from Dow Corning is coagglomerated with Zeolite A (2-5 µm size), starch and stearyl alcohol binder . The particles have the following composition:

Zeolite A 0.22% starch 1.08% X2-3419 0.22% stearyl alcohol 0.35%

The detergent composition exhibits excellent solubility and excellent foaming control when used in

-102European washing machines, purple. when using 25 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 foregoing examples, the fatty acid glucamide surfactant may be replaced by an equivalent amount of a maltamide surfactant, or a mixture of a glucamine / maltamide surfactant 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. However, the use of sulfobetaine (sultain) surfactants provides increased foaming.

The following examples illustrate other liquid formulations that are particularly suitable for light duty applications such as dishwashers.

Examples 21 A-D

Folders percent A 3 (wt. C D C12-22 Clylethoxysulfate (1 EO) 16 9 12 - ^ 12 14alkylethoxysulfate (3 EO) 14 - 1 1 θ alkyl ethoxylate (SEO) 7 3 7 1 C _{1 2-N-methylglukemid} 8 9 12 6 coconut diethanolamide - - 5 dimethyldodecylamine oxide 1 - 2 koko amidoprop.ylhydroxysultain 1 3 - cocoamidopropylbetain 2 - - , 2+ Mg - - 1 1 ba 0,5 1 - - sodium toluenesulfonate 3 3 3 3 ethanol 4 4 4 4 water -to 1 00—

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

A person skilled in the art intending to add anionic brighteners to liquid cleaning compositions containing relatively high concentrations (e.g.

103 and higher) of anionic and polyanionic substituents, such as polycarboxylate activators, may be advantageous to prepare an optical brightener premix with water and a polyhydroxy fatty acid amide and then add the premix to the final formulation.

Polyglutamic acid or polyaspartic acid dispersants can suitably be used with detergents containing zeolite activating agents. ZE liquid or flakes and DG-544 (Dow Corning) are further examples

-104-

antifoam agents which may 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 (9)

PATENT ^{Z Z} R 0. <Y 1. A detergent composition comprising at least 1% by weight of an alkylalkoxylated sulfate surfactant and optionally surfactants and adjuvants, characterized in that it comprises incorporation into the composition as an improvement? at least 1% by weight of a polyhydroxy fatty acid amide surfactant of the formula OR ¹ 2 ' ^Of R - C - N - Z wherein R ¹ is R 0 -0 alkyl, 2-hydroxyethyl or 2-hydroxy-2 ¹ 4 propyl, R is Cy-G ^ alkyl, and Z is a linear hydrocarbyl ra dicalcium carrying at least three hydrox.ylová groups are directly attached to the hydrocarbon ^- chain, or an alkoxylated derivative thereof, said composition being characterized in that it optionally comprises a suds suppressing agent suppressing foaming and further that it has a weight ratio of polyhydroxy fatty acids: sulfate alkyialkoxylovanému 1:10 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% alkylethoxylated sulfate and said suds suppressor is selected from the group consisting of monocarboxylic fatty acids and salts thereof, silicone agents for suds suppressors, monostearyl phosphate suds suppressors, and hydrocarbon suds suppressors. -1 06- 3. The detergent composition of claim 2 further comprising from about 1% to about 25% of a surfactant. 4. A detergent composition according to claim 3 wherein said surfactant adjuvant comprises an alkyl benzene sulfonate surfactant, an alkyl sulfate surfactant, an alkyl ester sulfonate surfactant, an alkyl ethoxylate, an alkylphenolalkoxylated surfactant, an alkylpolyglycoside, or a surfactant. paraffin sulfonate or mixtures thereof. 5. A detergent composition according to claim 4, wherein said suds suppressor comprises at least 0.5% monocarboxylic acid or salt thereof. 6. A detergent composition according to claim 4 characterized by ui .mu.Ci in that R is methyl, R is C ^ -C ^? Alkyl or alkenyl, Z is -0¾ (CHOH ^ C ^ OH, -GH (GH ₂ OH) - _(CHOH) n _ _{1 -CH2} 0H, or _-CH2- (CHOH) ₂ (ghora *) (GHOH) _-CH2 OH, where n is an integer from 3 to 5, inclusive, and R 'is H or a cyclic or an aliphatic monosaccharide. 7 A detergent composition according to claim 6 bore, ačující in that Z is -CH ₂ (CHOHJ ^ CřLjOH. 8. A composition according to claim 1, wherein, with respect to said polyhydroxy fatty acid amide, Z is derived from maltose. 9. The composition of claim 1 wherein Z is derived from a mixture of monosaccharides, disaccharides, with respect to the polyhydroxy fatty acid amide. and