RU2105790C1 - Detergent composition and method of scouring dishes - Google Patents

Abstract

FIELD: detergents. SUBSTANCE: detergent compositions containing alkylethoxycarboxylate and fatty acid polyhydroxyamide components are characterized by improved detergent and foam-formation properties and exhibit elevated softness to skin. Method of scouring dirty dishes with proposed compositions is also described. EFFECT: improved consumer's properties. 13 cl, 4 tbl

Description

 The invention relates to detergent compositions containing alkylethoxycarboxylates and fatty acid polyoxyamides. In particular, it relates to detergent compositions that possess the desired detergent and foaming properties and are particularly suitable for use in dishwashing.

 Alkylethoxycarboxylates and their use in detergent compositions are known in the art. U.S. Patent Application No. 516,292, "Light liquid detergent dishwashing composition containing an alkyl ethoxy surface active agent," filed May 4, 1989 on behalf of Rodney M. Wise and Thomas A. Kripe, describes such carboxylates and their use in detergent compositions. Although these carboxylates provide improved detergency, the foam they produce usually has a small initial volume and poor stability. Such a small volume of foam and poor stability can cause the wrong feeling among some users that detergent compositions provide worse detergency. Therefore, it would be desirable to combine such carboxylates with a component or components that provide improved foaming ability. It has been found that the compositions of the invention give this desired effect.

 The fatty acid polyoxyamide, which is a component of the claimed composition, is known in the art, as are several of its uses.

 For example, N-acyl-N-methylglucamides are described by J.W. Goodby, M.A. Marcus, E. Chin, and P.L. Finn in "Thermotropic Liquid Crystal Properties of Some Straight-Chain Amphilite Carbohydrates", Liquid Crystals, 1988 , Vol. 3, No. 11, pp. 1569-1581, and A. Muller-Farnow, V. Zabel, M. Steif, and R. Hilgenfeld in "Molecular and Crystal Structure of Non-ionic Detergent: Nonanoyl-N-Methylglucamide", J. Chem. Soc. chem. Commun, 1986, pp. 1573-1574. The use of N-alkylpolyoxyamide surfactants has recently been of considerable interest for use in biochemistry, for example, in the dissociation of biological membranes (see, for example, the journal "N-D-Gluco-N-methylalkanamide compounds, a new class of nonionic detergents in membrane biochemistry" Biochem J. / 1982 /, T. 207, pp. 363-366, J.E.K. Hildreth.

 The use of N-alkyl glucamides in detergent compositions is also described. U.S. Patent 2,965,576, issued December 20, 1960 to E. Wilson, and U.K. Patent 809,060, published February 18, 1959, issued by Thomas Headley and Co. Ltd. relate to detergent compositions containing anionic surfactants and some amide surfactants, which may include N-methylglucamide, added as a foam enhancing agent at low temperatures. These compounds contain a straight chain N-acyl radical of a higher fatty acid having 10-14 carbon atoms. These compositions may also contain auxiliary materials such as alkali metal phosphates, alkali metal silicates, sulfates and carbonates. It is usually also indicated that additional components may also be included in the composition to impart desired properties to the composition, such as fluorescent dyes, bleaching agents, perfumes, and the like.

 U.S. Patent 2,703,798, issued March 8, 1955 to A.A.Schwartz, relates to aqueous detergent compositions containing the product of the condensation reaction of N-alkyl glucamine and the aliphatic effect of a fatty acid. It is indicated that the product of this reaction is applicable in aqueous detergent compositions without further purification. It is also known to produce a sulfuric acid ester of acylated glucamine, as described in US Pat. No. 2,717,894, issued September 13, 1955 to A.M. Schwartz.

PCT International Application WO 83/04412, published December 22, 1983, by J. Hildreth, relates to amphiphilic compounds containing polyoxyaliphatic groups, which, as indicated, can be useful for various purposes, including the use as surfactants in cosmetics , drugs, shampoos, lotions and eye ointments, as emulsifiers and distributing agents for drugs, and in biochemistry for the solubilization of membranes, whole cells or other tissue samples, and for obtaining lysosomes. Included in this description are compounds of the formula R'CON / R / CH ₂ R ″ and R ″ CO / R / R ′, where R ′ is hydrogen or an organic group, R ′ is an aliphatic hydrocarbon group with at least three atoms carbon and R ″ is the remainder of the aldose.

European patent 0 285 768, published October 12, 1988 by H. Kelkenberg et al. relates to the use of N-polyoxyalkylamides of fatty acids as thickening agents in aqueous detergent systems. Included are amides of the formula R ¹ C / O / N / X / R ² , where R ¹ is C ₁ C ₁₇ / preferably C ₁ C ₁₇ / alkyl, R ² is hydrogen, C ₁ C ₁₈ / preferably C ₁ C ₆ / alkyl or alkylene oxide, and X is a polyoxyalkyl having 4 to 7 carbon atoms, for example, coconut fatty acid N-methylglucamide. As indicated, the thickening properties of amides are of particular use in liquid surfactant systems containing paraffin sulfonate, although aqueous surfactant systems may contain other anionic surfactants such as alkaryl sulfonates, olefin sulfonates, salts of sulfosuccinic acid half esters and fatty ether sulfonates alcohols, and nonionic surfactants such as polyglycol ethers of fatty alcohols, polyglycol ethers of alkyl phenols, polyglycol fatty acid esters, mixed polyethylene oxide-polypropylene oxide polymers, etc. Shampoo formulations of coconut fatty acid paraffinsulfonate / N-methylglucamide / nonionic surfactant are given as examples. In addition to the thickening properties, it is indicated that N-polyoxyalkylamides of fatty acids have excellent skin tolerance.

 U.S. Patent 2,982,737, issued May 2, 1961 to Bottner et al. relates to detergent bars containing urea, anionic surfactant sodium lauryl sulfate and non-ionic surfactant N-alkyl glucamide, which is selected from N-methyl-N-sorbityl lauramide and N-methyl-N-sorbityl myristamide.

Other glucamide surfactants are described, for example, in DT 22268272, published December 20, 1973 by H.V. Eckert et al. which relates to detergent compositions containing one or more surfactants and structure-forming salts selected from polymeric phosphates, sequestering agents and detergents, enhanced by the addition of an N-acyl polyoxyalkyl amine of the formula R ¹ C / O / N / R ² / CH ₂ / CHOH / _n CH ₂ OH, where R ¹ is C ₁ -C ₃ alkyl, R ² is C ₁₀ -C ₂₂ alkyl, and n is 3 or 4. N-Acylpolyoxyalkylamine is added as a mud suspending agent.

Known detergent compositions [4] containing at least one surfactant selected in the group of anionic, zwitterionic and nonionic surfactants, and as a textile softener, an N-acyl-N-alkylpolyoxyalkyl compound of the formula R ¹ N / Z / C / O / R ² , where R ¹ is C ₁₀ -C ₂₂ -alkyl, R ² is C ₇ -C ₂₁ -alkyl, R ¹ and R ² in total contain from 23 to 39 carbon atoms, and Z is polyoxyalkyl, which may be —CH ₂ / CHOH / _m CH ₂ OH, where m is 3 or 4.

U.S. Patent 4,021,539, issued May 3, 1977 to H. Muller et al. relates to cosmetic skin compositions containing N-polyoxyalkylamines, which include compounds of the formula R ¹ N / R / CH / CHOH / _m R ² , where R ¹ is hydrogen, lower alkyl, hydroxy lower alkyl, or aminoalkyl, as well as heterocyclic aminoalkyl, R is the same as R ¹ , but both cannot be H, and R ² is CH ₂ OH or COOH.

French patent 1360018 dated April 26, 1963, issued by the Commercial Solvents Corporation, relates to formaldehyde solutions stabilized against polymerization by the addition of amides of the formula RC / O / N / R ₁ / G, where R is the functionality of a carboxylic acid having at least 7 carbon atoms , R ₁ is hydrogen or lower alkyl, and G is a glycitol radical with at least 5 carbon atoms.

The German Federal Patent No. 1261861 dated February 29, 1968 by A. Heinz relates to glucamine derivatives useful as a wetting and dispersing agent of the formula N / R // R ¹ // R ² /, where R is the sugar residue of glucamine, R ¹ is C ₁₀ -C ₂₀ alkyl, and R ² is a C ₁ -C ₅ acyl.

British Patent 745036, issued February 15, 1956, issued by the Atlas Nauder Company, relates to heterocyclic amides and carboxylic esters, which, as indicated, are useful as chemical intermediates, emulsifiers, wetting and dispersing agents, detergents, textile softeners and etc. The compounds are expressed by the formula N / R // R ¹ / C / O / R ² , where R is the residue of anhydrides hexanopentol or a carboxylic ester thereof, R ₁ is a monovalent hydrocarbon radical, and —C / O / R ² is a carboxylic acid acyl having from 2 to 25 carbon atoms.

U.S. Patent 3,312,627, issued April 4, 1967 to D.T. Hooker, describes bars of solid toilet soap that contain virtually no anionic detergents and alkaline soap additives and that contain lithium soap of certain fatty acids, a nonionic surfactant selected from some condensates propylene oxide-ethylene diamine-ethylene oxide, a capacitor propylene oxide-propylene glycol-ethylene oxide and polymerized ethylene glycol, and also contain a non-ionic foaming component, which may include a polyoxyamide of the formula RC / O / NR ¹ / R ² /, where 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, these alkyl groups in total contain from 2 to 7 carbon atoms and the total number of substituting hydroxyl groups from 2 to 6. Essentially a similar description is found in US patent 3312626, also issued April 4, 1967 D.T. Hooker.

 However, none of these references cites a combination of an alkylethoxycarboxylate and a polyoxyamide fatty acid in a detergent composition. In addition, the prior art does not describe an unexpected improvement in foaming performance and improved detergent properties, especially fat cleansing properties of such detergent compositions.

 Also in the prior art there is no indication of softening of the hands indicated by such detergent compositions.

 The aim of the invention is the development of detergent compositions containing alkylethoxycarboxylates and polyoxyamides of fatty acids, which have improved foaming and washing properties and soften the skin.

 Another objective of the invention is to develop a method for cleaning dirty dishes by treating said dishes with specific detergent compositions described herein.

где
R¹ является H, C₂-C₄-углеводородом, 2-оксиэтилом, 2-оксипропилом или их смесями, R² является C₅-C₃₁-углеводородом, и Z является полиоксиуглеводородом, имеющим линейную углеводородную цепь с по крайней мере 3 гидркосильными группами, непосредственно связанными с цепью, или его алкоксилированное производное.The invention relates to detergent compositions containing from about 1%, preferably about 5% to about 65 wt. surfactant mixture consisting of
/ a / from about 5 to about 95 wt. one or more alkylethoxycarboxylates of the general formula
RC / CH ₂ CH ₂ O / ^k CH ₂ COO ^- M ⁺ ,
Where
R is C ₈ -C ₂₂ alkyl; k is an integer from 0 to 10, and M is a cation;
/ b / from about 5 to about 95 wt. one or more polyoxyamide fatty acids of the general formula

Where
R ¹ is H, a C ₂ -C ₄ hydrocarbon, 2-hydroxyethyl, 2-hydroxypropyl or mixtures thereof, R ² is a C ₅ -C ₃₁ hydrocarbon, and Z is a polyoxy hydrocarbon having a linear hydrocarbon chain with at least 3 hydroxy groups directly linked to the chain, or an alkoxylated derivative thereof.

 The invention also relates to a method for cleaning contaminated dishes, comprising treating said dishes with detergent compositions as claimed herein.

 The detergent compositions of the invention are preferably liquid or gel compositions, more preferably light liquid detergent compositions, most preferably light liquid detergent compositions for washing dishes. These detergent compositions contain from about 5 to about 65 wt. preferably about 10-50 wt. even more preferably 20-40 wt. a surfactant mixture consisting of one or more alkyl ethoxycarboxylates and one or more polyoxyamides of fatty acids. These and other optional ingredients commonly found in detergent compositions are listed below.

 Alkylethoxycarboxylate component.

The surfactant mixture of the invention consists of from about 5 to about 95 wt. preferably 20-80 wt. more preferably 40-60 wt. one or more alkylethoxycarboxylates of the general formula
RO / CH ₂ CH ₂ O / _k CH ₂ COO ^- M ⁺ ,
Where
R is C ₈ -C ₂₂ alkyl, preferably C ₁₂ -C ₁₄ alkyl, k is an integer from 0 to 10, preferably 1 5, and M is a cation, preferably ions of an alkali metal, alkaline earth metal, ammonium, lower alkanolammonium and mono -, di- and triethanolammonium, more preferably sodium, potassium and ammonium, more preferably sodium and potassium, and mixtures thereof with magnesium and calcium ions. The number of carbon atoms in the R group and the value of the integer k are interrelated in that if the number of carbon atoms in the R group increases, then preferably the value of k should be increased in order to maintain the solubility of the detergent compound. Usually, when R is C ₁₂ -C ₁₄ alkyl, k is in the range of from about 1 to about 4, when R is C ₁₂ -C ₁₈ -alkyl, k is in the range of from about 1 to about 6, and when R is C ₈ -C ₁₂ alkyl, k is in the range from 0 to about 3.

 The alkylethoxycarboxylate component can be prepared by methods known in the art. One preferred method is described in US patent application Serial No. 354968, entitled "Method for the production of alkylethoxycarboxylates", filed May 22, 1989 in the name of Thomas A. Kripe, the description of which is given here as a prior art.

The alkylethoxycarboxylate component may contain a set of alkyl ethoxycarboxylates. When the composition of the invention contains such a kit, the distribution of ethoxylates will be such that, based on mass, the amount of material where k is 0 will be less than about 20%, preferably less than about 15%, more preferably less than about 10%, and the amount of material where k is greater than 7, is less than about 25%, preferably less than about 15%, more preferably less than about 10%. The average value of k will fall in the range from 1 to 4, when the average R is C ₁₃ or lower, and the average k will fall in the range from 2 to 6, when the average R is greater than C ₁₃ . Such a distribution and its preparation are described in more detail in US patent application N 516292, filed May 4, 1989, the description of which is given here as a prior art.

 When the compositions of the invention include a distribution of ethoxycarboxylates, a desired distribution of carboxylates can be obtained by reacting with a corresponding distribution of the previous ethoxylated alcohols.

 It was found that the presence of divalent cations in the alkyl ethoxycarboxylates in the composition of the invention significantly increases the purification of greasy contaminants. This is especially true when using the composition in softened water, which contains few divalent ions. Bivalent ions are believed to improve the packing of alkyl ethoxycarboxylates at the oil / water interface, resulting in reduced surface tension and improved fat removal. However, liquid detergent compositions used for washing dishes that contain alkylethoxycarboxylates and which do not meet the narrow definition of the present invention will give less effect from the addition of divalent ions and in many cases will in fact exhibit less cleaning ability when adding divalent cations.

 When included in the composition of the invention, divalent ions are preferably added as chlorides, sulfates or hydroxides, more preferably as chloride salts, to compositions containing alkyl ethoxycarboxylates, most preferably sodium or potassium salts, after the composition has been neutralized with a strong base. The concentration of divalent ions is usually in the range from 0 to about 1.5%, preferably from about 0.2 to about 1%, most preferably from 0.3 to about 0.8 wt. Particularly preferred divalent ions are magnesium and calcium ions.

Depending on the method of preparation used to prepare the alkyl ethoxycarbosilate component of the invention and the method of preparing the composition of the invention, such compositions may also contain from 0 to about 5.0%, preferably less than 4.0%, more preferably less than 4.0%, more preferably less 2.5 wt. alcohol ethoxylates of formula II
R'O / CH ₂ CH ₂ O / WH
Where
R 'is C ₁₂ -C ₁₆ alkyl and W is in the range from 0 to about 10 with an average W of less than 6.

 Non-carboxylated alcohol ethoxylates of structure (II) are harmful to the compositions of the invention containing alkyl ethoxycarbosilates. Therefore, it is critical that such compositions contain no more than about 5.0 wt. alcohol ethoxylates from which alkylethoxycarboxylates are derived. Although commercially available alkylethoxycarboxylates contain from 10% or more alcohol ethoxylates, methods are known for producing alkylethoxycarboxylates of the desired high purity. For example, unreacted alcohol ethoxylates can be removed by steam stripping, US Pat. No. 4,098,818 / Example I /, or recrystallization of alkyl ethoxycarboxylates, British Patent No. 1,027,481 / Example I /. Other ways to obtain the desired carboxylates are by reacting sodium hydroxide or metallic sodium and monochloroacetic acid or its salts with alcohol ethoxylates under certain pressure and temperature conditions, as described in US Pat. Nos. 3,992,443 and 4,098,818, and Japanese Patent Application No. 50-24215, all of which are described herein. as a prior art.

 Other ways of obtaining high purity alkylethoxycarboxylates are described in US Patent Application Serial No. 516292, filed May 4, 1989, already mentioned here, which is cited as the prior art.

где
R¹ является H, C₁-C₄-углеводородным радикалом, 2-оксиэтилом, 2-оксипропилом или их смесью, предпочтительно C₁-C₄-алкилом, предпочтительно C₁ или C₂ алкилом, более предпочтительно C₁-алкилом /а именно, метилом/; и R₂ является C₅-C₃₁-углеводородным радикалом, предпочтительно C₉-C₁₇-алкилом или алкенилом с прямой цепью, более предпочтительно C₁₁-C₁₇-алкилом или алкенилом с прямой цепью или их смесью и Z является полиоксиуглеводородом, имеющим линейную углеводородную цепь с по крайней мере 3 гидроксилами, непосредственно связанными с цепью, или ангидропроизводным, полученным дегидратацией такого полиоксиуглеводородного радикала, или его алкоксилированным производным /предпочтительно этоксилированным или пропоксилированным/. Предпочтительно Z будет происходить из восстановленного сахара по реакции восстановительного аминирования, более предпочтительно Z является глицитилом. Подходящие восстанавливаемые сахара включают глюкозу, фруктозу, мальтозу, лактозу, маннозу и ксилозу. В качестве сырья могут быть использованы высококонцентрированный сироп декстрозы кукурузы, высококонцентрированный сироп фруктозы кукурузы и высококонцентрированный сироп мальтозы кукурузы, а также индивидуальные сахара, приведенные выше. Эти кукурузные сиропы могут давать смесь сахарных компонентов для Z. Должно быть понятно, что это не означает исключения других подходящих сырьевых материалов. Предпочтительно должно быть выбран в группе, состоящей из -CH₂-/CHOH/_n-CH₂OH, -CH/CH₂OH/-/CHOH/_n-1-CH₂OH, -CH₂-/CHOH/₂/CHOR''/ /CHOH/-CH₂OH, где n является целым числом от 3 до 5 включительно и R'' является H или циклическим или алифатическим моносахаридом, и их алкоксилированных производных. Наиболее предпочтительными являются глицитилы, где n равно 4.Fatty Acid Polyoxyamide Component
The surface-active mixture of the present invention, in addition, consists of about 5 to 95 wt. preferably 20 to 80 wt. more preferably about 20 to 60 wt. one or more polyoxyamides of fatty acids having the formula

Where
R ¹ is H, a C ₁ -C ₄ hydrocarbon radical, 2-hydroxyethyl, 2-hydroxypropyl or a mixture thereof, preferably C ₁ -C ₄ alkyl, preferably C ₁ or C ₂ alkyl, more preferably C ₁ -alkyl / a namely, methyl /; and R ₂ is a C ₅ -C ₃₁ hydrocarbon radical, preferably a straight chain C ₉ -C ₁₇ alkyl or alkenyl, more preferably a straight chain C ₁₁ -C ₁₇ alkyl or alkenyl, or a mixture thereof, and Z is a polyoxy hydrocarbon having a linear hydrocarbon chain with at least 3 hydroxyls directly attached to the chain, or an anhydro derivative obtained by dehydration of such a polyoxy hydrocarbon radical, or an alkoxylated derivative thereof (preferably ethoxylated or propoxylated). Preferably Z will be derived from reduced sugar by a reductive amination reaction, more preferably Z is glycityl. Suitable reducible sugars include glucose, fructose, maltose, lactose, mannose and xylose. Highly concentrated corn dextrose syrup, highly concentrated corn fructose syrup and highly concentrated corn maltose syrup, as well as individual sugars mentioned above can be used as raw materials. These corn syrups can provide a mixture of sugar components for Z. It should be understood that this does not mean the exclusion of other suitable raw materials. Preferably should be selected in the group consisting of -CH ₂ - / CHOH / _n -CH ₂ OH, -CH / CH ₂ OH / - / CHOH / _n-1 -CH ₂ OH, -CH ₂ - / CHOH / ₂ / CHOR ″ / / CHOH / —CH ₂ OH, where n is an integer from 3 to 5 inclusive and R ″ is H or a cyclic or aliphatic monosaccharide and alkoxylated derivatives thereof. Most preferred are glycityls, where n is 4.

In the formula / I / R ^{1 it} can be, for example, N-methyl, N-ethyl, N-propyl, N-isopropyl, N-butyl, N-2-hydroxyethyl or N-2-hydroxypropyl.

может быть, например, кокамидом, стеарамидом, олеамидом, лаурамидом, миристамидом, каприкамидом, пальмитамидом, таллоуамидом и т.п.

may be, for example, cocamide, stearamide, oleamide, lauramide, myristamide, capricamide, palmitamide, tallowamide and the like.

 Z may be 1-deoxyglucityl, 2-deoxyfructyl, 1-deoxymaltithyl, 1-deoxy lactity, 1-deoxy galactity, 1-deoxymannithyl, 1-deoxy maxotriotyl and the like.

где
R² является C₁₁-C₁₇-алкилом или алкенилом с прямой цепью.The most preferred fatty acid polyoxyamide has the formula

Where
R ² is straight chain C ₁₁ -C ₁₇ alkyl or alkenyl.

 Methods for producing fatty acid polyoxyamides are known in the art. Typically, they can be prepared by reacting an alkylamine with reduced sugar in a reductive amination reaction to form the corresponding 1-alkylpolyoxyamine, and then reacting the 1-alkylpolyoxyamine with an aliphatic ester or triglyceride of a fatty acid in a condensation / amidation step to form 1-alkyl, 1-polyoxyamide fatty acid. Methods for preparing compositions comprising fatty acid polyoxyamides are described, for example, in British Patent 809060, published February 18, 1959, Thomas Headley and Co. Ltd. US patent 2965576, issued December 20, 1960 to E. R. Wilson, and US patent 2703798 [2] Anthony M. Schwartz, issued March 8, 1955 and US patent 1985424, issued December 25, 1934 Piggott, each of which given here as a prior art.

In this method for producing N-alkyl or N-hydroxyalkyl, N-deoxyglycytylamide fatty acids, where the glycityl component is derived from glucose and the N-alkyl or N-hydroxyalkyl functionalities are N-methyl, N-ethyl, N-propyl, N- butyl, N-hydroxyethyl or N-hydroxypropyl, the product is obtained by reacting N-alkyl or N-hydroxyalkylglutamine with a fatty acid ester selected from fatty acid methyl esters, fatty acid ethyl esters and fatty acid triglycerides, in the presence of a catalyst selected in the group consisting of trilithium phosphate, trisodium phosphate, tripotassium phosphate, tetrasodium hypophosphate, pentacalium tripophosphate, lithium hydroxide, sodium hydroxide, calcium hydroxide, lithium carbonate, sodium carbonate, potassium carbonate, disodium artate, dipotassium tartrate, potassium sodium tartrate, basic sodium silicate, basic sodium silicate, basic sodium potassium aluminosilicates and mixtures thereof. A preferred amount is about 0.5-50 wt. more preferably about 2.0 to 10 wt. counting per mole N-alkyl or N-hydroxyalkylglucamine. The reaction is preferably carried out at about 138,170 ^° C., typically about 20 to 90 minutes. When using triglycerides in the reaction mixture as a source of a fatty acid ester, the reaction is also preferably carried out using 1 to 10 wt. phase transfer agent, based on the weight percent by weight of the reaction mixture selected from saturated fatty alcohol polyethoxylates, alkyl polyglucosides, linear glucamide surfactant, and mixtures thereof.

Preferably, this method is as follows:
(a) preheating the fatty ester to about 138,170 ^° C;
(b) add n-alkyl-N-hydroxyalkylglucamine to the heated fatty ester and mix to the extent necessary to form a two-phase liquid / liquid mixture;
(c) mixing the catalyst with the reaction mixture;
/ d / stirred for a certain reaction time.

 It is also preferable to add from the reaction mixture from about 2 to about 20% of the preformed linear N-alkyl N-hydroxyalkyl, N-linear glucosyl fatty amide product by weight of the reactants as a phase transfer agent if the fatty ester is triglyceride. They sow a reaction, as a result of which the reaction rate increases. A detailed experimental procedure is given below in the experimental part.

 The fatty acid polyoxyamides used here also provide benefits to detergent builders because they can be prepared entirely or mainly from natural, renewable, non-petrochemical feeds and are degradable. They also have low toxicity to aquatic life.

 It should be recognized that along with the fatty acid polyoxyamides of the formula [I] in the processes used to prepare them, a certain amount of non-volatile by-products, such as etheramides and cyclic polyoxy fatty acid amides, are usually formed. The content of these by-products will vary depending on the specific reagents and process conditions. Preferably, the polyoxy fatty acid amide included in the detergent composition should be provided in such a way that the composition comprising the polyoxy fatty acid amide added to the detergent contains less than about 2%, preferably less than 0.5% of the cyclic polyoxy fatty acid amide. The preferred methods described above are advantageous in that they can produce lower levels of by-products, including such cyclic amide by-products.

Optional ingredients
Liquid carrier
In a preferred embodiment, the detergent compositions of the invention are liquid detergent compositions. These preferred liquid detergent compositions consist of about 95 to 35 wt. preferably about 90 to 50 wt. most preferably 80 to 60 wt. a liquid carrier, for example water, preferably a mixture of water and a C ₁ -C ₄ monohydric alcohol (for example, ethanol, propanol, isopropanol, butanol and mixtures thereof), ethanol is the preferred alcohol.

pH of the composition
Liquid detergent compositions should preferably be formulated so that during use in water treatment operations, the wastewater should have a pH between about 8 and 10, more preferably between about 8.5 and 9.5. Liquid formulations are prepared at a pH in the range of from about 7.0 to about 11.0, preferably from about 8.5 to about 10.5, more preferably from about 8.8 to about 10.0. You can set the pH of such liquid detergent compositions using methods known to those skilled in the art, for example, adding a base to the composition. Traditionally, liquid dishwashing compositions have a pH of about 7. It has now been found that being in the form of a liquid detergent, the compositions of the invention exhibit improved ability to cleanse fats if they are formulated at an alkaline pH, compared to a pH below 7. Such a beneficial cleansing effect is unique to liquid detergent compositions containing the present alkyl ethoxycarboxylate component. Surprisingly, the compositions of the invention are also very soft on the hands at such an alkaline pH.

 It is desirable to include a buffering agent in the preparation of liquid detergent compositions having increased pH stability. Examples of typical buffering agents include, but are not necessarily limited to, glycine / preferably /, N, N-bis / 2-hydroxyethyl / glycine / preferably /, tri / hydroxymethyl / aminomethane, triethanolamine, monoethanolamine, 2-amino-2-ethyl -1,3-propanediol, 2-amino-2-methyl-1,3-propanediol, N-methyldiethanolamine, 1,3-diamino-2-hydroxypropane and mixtures thereof. When included in the liquid compositions prepared according to this invention, such buffering agents are usually in an amount of from about 0.1% to about 15 wt. preferably from about 1 to about 7 wt. more preferably from about 1.5 to about 5 wt.

Thickeners
The detergent compositions of this invention may also be in the form of a gel. Such compositions are usually formed in the same manner as liquid detergent compositions, with the exception that they contain an additional thickening agent.

 Any material or materials that can be mixed with an aqueous liquid can be used in the compositions to provide low shear compositions having a sufficient flow rate. Materials such as colloidal silica, particulate polymers such as polystyrene and oxidized polystyrene, a combination of certain surfactants and water-soluble polymers such as polyacrylates are known to provide fluidity.

 A preferred thickening agent useful in the compositions of this invention is a high molecular weight polycarboxylate polymer thickener. "High molecular weight" means from about 500,000 to about 5,000,000, preferably from about 750,000 to about 4,000,000.

 The polycarboxylate polymer may be a carboxylic polymer. Such compounds are described in US Pat. No. 2,798,053, which is incorporated herein by reference. Methods for producing carboxyvinyl polymers are also described by Branus and are given here as a prior art.

 Caboxivinyl polymer is an interpolymer of a monomer mixture consisting of monomeric olefinically unsaturated carboxylic acid and from about 0.1 to about 10 wt. of the sum of the monomers of the polyether polyhydric alcohol, said polyhydric alcohol contains at least four carbon atoms to which at least three hydroxyl groups are attached, a polyether containing more than one alkenyl group per molecule. If desired, the monomer mixture may contain other monomer materials, even in a predominant amount. Carboxyvinyl polymers are essentially insoluble in liquid, volatile hydrocarbon polymers and are dimensionally stable upon exposure to air.

где
R является заместителем, выбранным в группе, состоящей из водорода и низших алкилов; наиболее предпочтительной является акриловая кислота.Preferred polyhydric alcohols used to prepare carboxyvinyl polymers include polyols selected in the class consisting of oligosaccharides, from reduced derivatives in which the carbonyl group is converted to an alcohol group, and pentaerythritol, oligosaccharides are more preferred, sucrose is most preferred. Preferably, the hydroxyl groups of the polyol, which are modified, are esterified with allyl groups, polyols having at least two allyl groups per polyol molecule. When the polyol is sucrose, it is preferred that sucrose has at least about five allyl ether groups per sucrose molecule. Preferably, the polyol ether comprises at least about 0.1% of the total monomers, more preferably from about 0.2 to about 2.5%
Preferred monomeric olefinically unsaturated carboxylic acids to produce the carboxyvinyl polymers used herein include monomeric, polymerizable alpha-beta monoolefinically unsaturated lower aliphatic carboxylic acids, more preferred are monomeric acrylic acids of the structure

Where
R is a substituent selected in the group consisting of hydrogen and lower alkyls; most preferred is acrylic acid.

 Carboxyvinyl polymers useful in the formulations of the invention have a molecular weight of at least about 750,000. Preferred are highly crosslinked carboxyvinyl polymers having a molecular weight of at least about 1,250,000. Carboxyvinyl polymers having a molecular weight of at least about 3 are also preferred. 000,000, which may be less stitched.

 Various carboxyvinyl polymers are commercially available from B. F. Goodrich Company, New York, N.Y. under the trade name Carbopol. Carboxyvinyl polymers useful in the formulations of the invention include Carbopol 910 having a molecular weight of about 750,000; Carbopol 941 having a molecular weight of the order of 1,250,000 is preferred, and Carbopol 934 and 940 having molecular weights of the order of 3,000,000 and 4,000,000, respectively, are more preferred.

 Carbopol 934 is a very strongly crosslinked carboxyvinyl polymer having a molecular weight of about 3,000,000. It would be described as a highly molecular crosslinked polyacrylic acid with about 1% polyallyl sucrose, with an average of about 5.8 allyl groups for each sarrose molecule.

An additional polycarboxylate polymer useful in the present invention is Sokolan RNS-25 ^R , a polyacrylic acid available from BASF Corp. and Gantrez ^R poly / methyl vinyl ether / maleic acid / interpolymer, available from GAF Corp.

 Preferred polycarboxylate polymers of the invention are non-linear, water dispersible crosslinked polyacrylic acids crosslinked with a polyalkenyl polyester and having a molecular weight of from about 750,000 to about 4,000,000.

 Clearly preferred examples of these polycarboxylate polymer thickeners are the Carbopol 600 series of resins available from B. F. Goodrich. Carbopol 616 and 617 are particularly preferred. These resins are believed to be more crosslinked than the 900 series resins and have a molecular weight of between about 1,000,000 and 4,000,000. Polycarboxylate polymer blends can also be used in this invention. Particularly preferred is a mixture of the Carbopol 616 and 617 series.

 The polycarboxylate polymer thickener is preferably used with thickening agents substantially free of clay. Indeed, it has been found that when the polycarboxylate polymers of this invention are used with clay in the compositions of this invention, the result is a less desirable product with respect to phase stability. In other words, the polycarboxylate polymer is preferably used instead of clay as a thickening agent / stabilizing agent of the present compositions.

 The polycarboxylate polymer also provides a reduction in what is commonly referred to as a “remainder in a bottle." This term refers to the inability to extract all detergent detergent product from its container. Not bearing in mind the theoretical limit, it is believed that the thickened compositions of this invention provide its advantage because the cohesion force of the composition is greater than the adhesion force to the container wall. For thickening systems with clays, which are the most commercially available products, “residue in the bottle” can be a significant problem in certain conditions.

 Not bearing in mind the theoretical limit, it is also believed that a polycarboxylate polymer thickener with long chain molecules helps to suspend solid products in the thickened detergent compositions of the present invention and helps maintain the expanded matrix. The polymer material is also less sensitive than clay thickeners to degradation due to repeated shifts, such as occur during intensive movement of the composition.

 If the polycarboxylate polymer is used as a quenching agent in the compositions of this invention, it is usually in an amount of from about 0.1% to about 10%, preferably from about 0.2 to about 2 wt.

 Thickeners are used to provide flow rates of from about 50 to about 350, and most preferably from about 75 to about 250.

Determination of yield
The yield strength is an indicator of shear stress at which the gel strength is exceeded and the flow begins. It is changed here on a Brookfield viscometer with an RVT model with a T-spindle B shaft at 25 ^° C using an upward-pointing spiral drive during associated reading. The system is set to 0.5 rpm and the test composition is read after 30 s or after stabilization of the system. The system is stopped and re-set to 1.0 rpm. Read for the same composition after 30 s or after stabilization of the system. The voltage at zero shear is twice the reading at 0.5 rpm minus the reading at 1.0 rpm. The yield strength is calculated as the stress at zero shear, a multiple of 18.8 / conversion factor /.

Other surfactants
Other surfactants, such as anionic, nonionic, ampholytic and zwitterionic surfactants, may be included in the detergent compositions of this invention.

Anionic Surfactants
One type of anionic surfactant that may be used includes alkyl ester sulfonates. Alkyl ether sulfonate surfactants include linear C ₈ -C ₂₀ carboxylic acid esters / t. e. fatty acids / which are sulfonated with gaseous SO ₃ according to "Journal of the American oil chem 1 5 oc ely", 52/1975 /, pp. 323-329. Suitable starting materials may include natural fatty substances derived from tall oil, palm oil and the like.

где
R³ является C₈-C₂₀-углеводородом, предпочтительно алкилом или их сочетанием; R⁴ является C₁-C₆-углеводородом, предпочтительно алкилом или их сочетанием, и M является катионом, который образует водорастворимую соль алкилэфирсульфоната. Подходящие солеобразующие катионы включают металлы, такие как натрий, калий и литий, и замещенные или незамещенные аммонийные катионы, такие как моноэтаноламин диэтаноламин, триэтаноламин. Предпочтительно R³ является C₁₄-C₁₆-алкилом, и R⁴ является метилом, этилом или изопропилом. Особенно предпочтительными являются метиловые эфиры сульфонатов, где R³ является C₁₄-C₁₆-алкилом.Preferably, the alkyl ether sulfonate surfactant, especially for laundry, consists of an alkyl ester sulfonate surfactant of the structural formula

Where
R ³ is a C ₈ -C ₂₀ hydrocarbon, preferably alkyl or a combination thereof; R ⁴ is a C ₁ -C ₆ hydrocarbon, preferably alkyl or a combination thereof, and M is a cation that forms a water-soluble salt of an alkyl ether sulfonate. Suitable salt forming cations include metals such as sodium, potassium and lithium, and substituted or unsubstituted ammonium cations such as monoethanolamine diethanolamine, triethanolamine. Preferably R ³ is C ₁₄ -C ₁₆ alkyl, and R ⁴ is methyl, ethyl or isopropyl. Particularly preferred are sulfonate methyl esters, where R ³ is C ₁₄ -C ₁₆ alkyl.

Alkyl Sulfate Surfactants
Alkyl sulfate surfactants are water-soluble salts or acids of the formula ROSO ₃ M, where R is preferably C ₁₀ -C ₂₄ hydrocarbons, preferably alkyl or hydroxyalkyl having a C ₁₀ -C ₂₀ alkyl component, more preferably C ₁₂ -C ₁₈ - alkyl or hydroxyalkyl, and M is H or an alkali metal cation (for example, sodium, potassium, lithium), or ammonium or substituted ammonium / for example methyl, dimethyl and trimethyl ammonium cations and quaternary ammonium cations such as tetramethyl ammonium and dimethyl piperium dinium cations and quaternary ammonium cations derived from alkylamines such as ethylamine, diethylamine, triethylamine, and mixtures thereof, etc.). Typically, C ₁₂ -C ₁₆ alkyl chains are preferred for low temperature washing (for example, below about 50 ^° C) and C ₁₄ -C ₁₈ alkyl chains are preferred for high temperature washing (for example, above about 50 ^° C).

Alkylalkoxylated Sulfate Surfactants
Alkyl alkoxylated sulfate surfactants are water soluble salts or acids of the formula RO / A / _m SO ₃ M, where R is unsubstituted C ₁₀ -C ₂₄ alkyl or hydroxyalkyl having a C ₁₀ -C ₂₄ alkyl component. preferably C ₁₂ -C ₂₀ alkyl or hydroxyalkyl, more preferably C ₁₂ -C ₁₈ alkyl or hydroxyalkyl; A is an ethoxy or propoxy moiety; m is greater than zero, usually between 0.5 and about 6, more preferably between about 0.5 and about 3, and M is H or a cation, which may be, for example, a metal cation / e.g. sodium, potassium, lithium, calcium, magnesium and the like /, ammonium or a 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 cations and quaternary ammonium cations such as tetramethylammonium and dimethylpiperidinium cations and cations derived from alkylamines such as ethylamine, diethylamine, triethylamine, mixtures thereof and the like. Examples of surfactants are C ₁₂ -C ₁₈ -alkylpolyethoxylate / 1,0 / sulfate / C ₁₂ -C ₁₈ E / 1,0 / M; C ₁₂ -C ₁₈ -alkylpolyethoxylate / 2.25 / sulfate / C ₁₂ -C ₁₈ E / 2.25 / M /, C ₁₂ -C ₁₈ -alkylpolyethoxylate / 3.0 / sulfate / C ₁₂ -C ₁₈ E / 3 , 0 / M / and C ₁₂ -C ₁₈ -alkylpolyethoxylate / 4.0 / sulfate / C ₁₂ -C ₁₈ E / 4.0 / M /, where M is usually selected from sodium and potassium.

Other anionic surfactants
Other anionic surfactants useful for detergents may also be included in the claimed compositions. These may include salts (including, for example, sodium, potassium, ammonium and substituted ammonium salts, such as mono-, di- and triethanolamine salts / soaps, C ₉ -C ₂₀ linear alkylbenzenesulfonates, C ₈ -C ₂₂ primary or secondary alkanesulfonates , C ₈ -C ₂₄ olefin sulfonates, sulfonated polycarboxylic acids obtained by sulfonation of the pyrolyzed product of alkaline earth metal citrates, for example, as described in UK patent N 1085179, C ₈ -C ₂₄ -alkylpolyglycol ether-sulfates (containing up to 10 mol of ethylene oxide); alkilglitserinsulfonaty, fatty acyl glycerol fatty oleilglitserinsulfonaty, alkilfenoletilenoksidnye ether sulfates, paraffin sulfonates, alkyl phosphates, isethionates such as the acyl isethionates, acyl taurates, fatty acid amides of methyl tauride, alkyl succinamates and sulfosuccinates, monoesters of sulfosuccinate / especially saturated and unsaturated C ₁₂ -C ₁₈ monoesters / di-esters of sulfosuccinates (especially saturated and unsaturated C ₆ -C ₁₂ diesters), acyl sarcosinates, sulfates of alkylpolysaccharides such as the sulfates alkilpoligl kozidov (the nonionic nonsulfated compounds being described below), C ₉ -C ₁₇ acyl-N- / C ₁ -C ₄ alkyl / or -N- / C ₂ -C ₄ -oksialkil / glyukaminsulfaty, branched primary alkyl sulfates, and fatty acids esterified with isethionic acid and neutralized with sodium hydroxide. Resin acids and hydrogenated resin acids such as rosin, hydrogenated rosin, and resin acids and hydrogenated resin acids available or derived from tall oil are also suitable. Other examples are described in "Surfactants and Detergents" / t. I and II of Schwartz, Perry and Birch. A set of such surfactants is also described in US Pat. No. 3,929,678, issued December 30, 1975 to Lauglin et al. in column 23, line 58 to column 29, line 23 / is given here as a prior art /.

Nonionic detergent surfactants
Suitable nonionic detergent surfactants are described in US Pat. No. 3,329,9678 to Lauglin et al. issued December 30, 1975 in column 13, line 14 to column 16, line 6, cited here as the prior art. Typical non-limiting classes of beneficial non-ionic surfactants are given below.
1. Condensates of polyethylene, polypropylene and polybutylene oxides with alkyl phenols. Polyethylene oxide condensates are generally preferred. These compounds include condensation products of alkyl phenols having an alkyl group containing from about 6 to about 12 carbon atoms in a straight or branched chain with alkylene oxide. In a preferred embodiment, ethylene oxide is in an amount of from about 5 to about 25 mol of ethylene oxide per 1 mol of alkyl phenol. Commercially available non-ionic surfactants of this type include Igepal ^™ CO-630, sold by GAF Corporation, and Triton ^™ X-45, X-114, X-100, and X-102, all sold by Rom & Haas Company.

2. Condensation products of aliphatic alcohols with 1-25 mol of ethylene oxide. The alkyl chain of an aliphatic alcohol may be straight or branched, primary or secondary and usually contains from about 8 to about 22 carbon atoms. Particularly preferred are the condensation products of alcohols having an alkyl group containing from about 10 to about 20 carbon atoms, from about 2 to 10 mol of ethylene oxide per 1 mol of alcohol. Examples of commercially available nonionic surfactants of this type are Tergitol ^TM 15-S-9 / condensation product of C ₁₁ -C ₁₅ linear alcohol with 9 moles of ethylene oxide /, Tergitol ^TM 24-L-6NMW / condensation product C ₁₂ -C ₁₄ primary alcohol with 6 molar ethylene oxide with a narrow molar mass distribution /, both sold by Union Carbide Corporation; Neodol ^TM 45-9 / condensation product of C ₁₄ -C ₁₅ linear alcohol with 9 mol of ethylene oxide /, Neodol ^TM 23 6.5 / condensation product of C ₁₂ -C ₁₃ linear alcohol with 6.5 mol of ethylene oxide /, Neodol ^TM / condensation product C ₁₄ -C ₁₅ linear alcohol with 7 mol ethylene oxide /, Neodol ^TM 45-4 / condensation product C ₁₄ -C ₁₅ linear alcohol with 4 mol ethylene oxide / sold by Shell Chemical Company, and Kiro ^TM EOB / condensation product C ₁₃ -C ₁₅ alcohol with 9 mol ethylene oxide /, sold by the Procter and Gamble Company.

3. The condensation products of ethylene oxide with a hydrophobic base formed by the 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 water insoluble. The addition of polyoxyethylene fragments to this hydrophobic part gives an increase in water solubility to the molecule as a whole, and the liquid character of the product remains to the point where the polyoxyethylene content is about 50% of the total mass of the condensation product, which corresponds to condensation up to about 40 mol of ethylene oxides. Examples of compounds of this type are some commercially available Pluronic ^TM surfactants sold by BASF.

4. Condensation products of ethylene oxide with the product obtained by the reaction of proplienoxide and ethylenediamine. The hydrophobic fragment of this product consists of the reaction product of ethylenediamine and an excess of propylene oxide and usually has a molecular weight of from about 2500 to about 3000yu. This hydrophobic fragment condenses with ethylene oxide to its content in such a condensation product from about 40 to about 80 wt. polyoxyethylene and has a molecular weight of from about 5,000 to about 11,000. Examples of this type of nonionic surfactant are some commercially available Tetronic ^TM compounds sold by BASF.

 5. Semi-polar non-ionic surfactants are a special category of non-ionic surfactants that include water-soluble amine oxides containing one alkyl moiety with 10 to 18 carbon atoms and 2 moieties selected in the group consisting of alkyls and hydroxyalkyls containing 1 3 atoms carbon; water-soluble phosphine oxides containing one alkyl fragment with 10 18 carbon atoms and 2 fragments selected in the group consisting of alkyls and hydroxyalkyls containing 1 3 carbon atoms; and water-soluble sulfoxides containing one alkyl fragment with 10 18 carbon atoms and a fragment selected in the group consisting of alkyl and hydroxyalkyls with 1 to 3 carbon atoms.

где
R³ является алкилом, оксиалкилом или алкилфенилом, или их смесью, содержащими от 8 до 22 атомов углерода; R⁴ является алкиленом или оксиалкиленом, содержащим от примерно 2 до примерно 3 атомов углерода или их смеси; x равно от 0 до 3, а каждый R⁵ является алкилом или оксиалкилом, содержащим 1 3 атома углерода, или полиэтиленоксидной группой, содержащей 1 3 этиленоксидных групп. Группы R⁵ могут быть присоединены друг к другу, например, через атом кислорода или азота с образованием кольцевой структуры.Semi-polar non-ionic detergent surfactants include surfactant amine oxides of the formula

Where
R ³ is alkyl, hydroxyalkyl or alkylphenyl, or a mixture thereof containing from 8 to 22 carbon atoms; R ⁴ is alkylene or oxyalkylene containing from about 2 to about 3 carbon atoms or mixtures thereof; x is from 0 to 3, and each R ⁵ is alkyl or hydroxyalkyl containing 1 3 carbon atoms, or a polyethylene oxide group containing 1 3 ethylene oxide groups. R ⁵ groups can be attached to each other, for example, through an oxygen or nitrogen atom to form a ring structure.

These surfactant amine oxides in particular include C ₁₀ -C ₁₈ -alkyldimethylamino oxides and C ₈ -C ₁₂ -alkoxyethyldioxyethylamine oxides.

6. The alkyl polysaccharides described in US Pat. No. 4,565,647 to Llenado, issued January 21, 1986, having a hydrophobic group containing from about 6 to about 30 carbon atoms, preferably about 10 to 16 carbon atoms, and a polysaccharide, for example a polyglycoside, a hydrophilic group containing from about 1.3 to about 10, preferably 1.3 to 3, more preferably 1.3 to 2.7 saccharide moieties. Any reduced saccharide containing 5 or 6 carbon atoms, for example glucose, galactose, can be used, and the galactosyl moieties can be replaced by glycosyl moieties. / Optional hydrophobic group attached to 2-, 3-, 4-, etc. positions of predetermined glucose or galactose as opposed to glucoside or galactoside. Intersaccharide bonds can be, for example, between one position of additional saccharide moieties and the 2-, 3-, 4- and / or 6-positions of the preceding saccharide moieties
Optionally and less desirable, the polyalkylene oxide chain may be attached to the hydrophobic moiety and the polysaccharide moiety. A preferred alkylene oxide is ethylene oxide. Typical hydrophobic groups include alkyl groups, saturated or unsaturated, branched or unbranched, containing about 8-18, preferably 10-16 carbon atoms. Preferably, the alkyl group is a straight chain saturated alkyl group. An alkyl group may contain up to about 3 hydroxyl groups and / or a polyalkylene oxide chain may contain up to 10, preferably less than 5 alkylene oxide fragments. Suitable alkyl polysaccharides are octyl, nonildetsil, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl and octadecyl, di-, tri-, tetra-, penta-, and hexaglucosides, galactosides, lactosides, glucosides, fructosides, fructose and / or galactose . Suitable mixtures include coconut alkyl, di-, tri-, tetra- and pentaglucosides and tall alkyl tetra-, penta-, and hexaglucosides.

Preferred alkyl polyglycosides have the formula
R ² O / C _n H _2n O / t / glycosyl / _x ,
Where
R ^{2 is} selected in the group consisting of alkyl, alkyl phenyl, hydroxyalkyl, hydroxyalkyl phenyl and mixtures thereof, in which alkyl contains 10 18, preferably 12 14 carbon atoms; n is 2 or 3, preferably 2; t is from 0 to 10, preferably 0; and x is from 1.3 to about 10, preferably 1.3 to 3, more preferably 1.3 to 2.7. Glycosyl is preferably derived from glucose. To obtain these compounds, alcohol or an alkylpolyethoxy alcohol is first prepared and then reacted with glucose or a glucose source to obtain a glucoside (1-position attachment). Then additional glycosyl moieties can be attached between their 1-position and the preceding glycosyl moieties at the 2-, 3-, 4- and / or 6-positions, preferably mainly at the 2-position.

где
R⁶ является алкилом, содержащим 7 21 атом углерода /предпочтительно 9 17/ и каждый R⁷ выбран в группе, состоящей из водорода, C₁-C₄-алкила, C₁-C₄-оксиалкила и -/C₂H₄O/_xH, где x меняется от 1 до 3.7. Surfactant fatty acid amides have the formula

Where
R ⁶ is alkyl containing 7 21 carbon atoms / preferably 9 17 / and each R ^{7 is} selected in the group consisting of hydrogen, C ₁ -C ₄ alkyl, C ₁ -C ₄ -oxyalkyl and - / C ₂ H ₄ O / _x H, where x varies from 1 to 3.

Preferred amides are C ₈ -C ₂₀ ammonium amides, monoethanolamides, diethanolamides and isopropanolamides.

Ampholytic surfactants
Ampholytic surfactants may be included in detergent / detergent / compositions. These surfactants can be broadly described as aliphatic derivatives of secondary or tertiary amines, or aliphatic derivatives of heterocyclic secondary or tertiary amines in which the aliphatic radical may be straight or branched. One of the aliphatic substituents contains at least 8 carbon atoms, usually 8-18 carbon atoms, and at least one contains an anionic water-soluble group, for example, carboxyl, sulfonate, sulfate (see US patent 3,929,678 Laughlin et al. Issued 30 December 19, column 19, lines 18-35 (cited here as a prior art) for examples of ampholytic surfactants).

Zwitterionic Surfactants
Zwitterionic surfactants can also be included in detergent compositions. These surfactants can be 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 (see U.S. Patent 3,929,678 Lauglin et al., Issued December 30, 1975 column 19, line 38, to column 22, line 48). Given here as a prior art for examples of zwitterionic surfactants.

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

Preferred additional surfactants are anionic and non-ionic surfactants, most preferred are C ₁₁ -C ₂₇ alkyl esters sulfonates, C ₈ -C ₂₂ primary or secondary alkanesulfonates, C ₁₀ -C ₁₈ alkyl dimethyl amino acids, alkyl polysaccharides and their mixtures.

 When included in the compositions of this invention, these optional additional surfactants are usually in a concentration of from about 1.0 to about 10%, preferably from about 2 to about 5, by weight.

Other optional ingredients
Other optional ingredients include detergent components of an organic or inorganic type, although such components are generally not preferred for use in the compositions of this invention. Examples of water-soluble inorganic components that can be used alone or in mixtures with each other, or with organic alkaline binders, are glycine, alkyl and alkenyl succinates, alkali metal carbonates, phosphates, polyphosphates and alkali metal silicates. Specific examples of such salts are sodium tripolyphosphate, sodium carbonate, potassium carbonate, sodium pyrophosphate, potassium pyrophosphate, potassium tripolyphosphate and potassium hexamethophosphate. Examples of organic salts that can be used alone or in a mixture with each other or with the previously mentioned inorganic salts are alkali metal polycarboxylates, examples of which include, but are not limited to, water soluble citrates such as sodium and potassium citrate, sodium and potassium tartrate , sodium and potassium ethylenediaminotetraacetate, sodium and potassium N- / 2-hydroxyethyl / ethylenediamine triacetates, sodium and potassium nitrile diacetates, sodium and potassium N- / 2-hydroxyethyl / nitrile diacetates, sodium and potassium oxide disuccinates and mono- and disodium tartrate sodium and potassium uccinates, such as those described in US Pat. No. 4,663,071 / Bush et al. issued May 5, 1987 /, the description of which is given herein as a prior art. Other organic detergent components, such as water-soluble phosphonates, may be used in the compositions of the invention. However, the detergent components generally have an organic value when the components of the invention are in the form of light liquid dishwashing detergent compositions. When included in the compositions of this invention, these optional components are usually in a concentration of from about 1.0 to about 10%, preferably 2-5 wt.

 Other desirable ingredients include diluents, solvents, colorants, perfumes and hydrotropes / preferably /. The diluents may be inorganic salts such as sodium and potassium sulfate, ammonium chloride, sodium and potassium chloride, sodium bicarbonate, and the like. The diluents useful in the compositions of the invention are usually present in an amount of from about 1 to about 10%, preferably from 2 to 5, by weight.

 Solvents useful herein include water and low molecular weight alcohols such as ethyl alcohol, isopropyl alcohol, and the like. Solvents useful in the compositions of the invention are typically present in an amount of from about 1 to about 60%, preferably from about 5 to about 50, by weight.

 Godrotropes, such as sodium and potassium toluenesulfonates, sodium and potassium xylene sulfonates, sodium and potassium cumene sulfonates, trisodium and tripotassium sulfosuccinates, and related compounds / as disclosed in US Pat. No. 3,915,903, which is described here as the prior art /, can be used in the interest of achieving the desired phase stability and viscosity of the product. It was found that hydrotropes can have a positive effect on washing in soap suds. Although not claiming a theoretical limitation, it is believed that such a beneficial effect is due to the viscosity characteristics of such hydrotropes. Hydrotropes useful in the compositions of this invention are usually present in amounts of from about 1 to about 10 mass. preferably from about 2 to about 5 mass.

 The claimed compositions of the invention are convenient in that they provide unexpected improved detergency when specific fatty acid polyoxyamides are combined with an alkylethoxycarboxylate. Although they do not have a theoretical limit in form, it is believed that the compositions of the invention acquire the additional benefits of improved detergency and are mild to the skin, even when formulated as a liquid and have a high alkaline pH. Also, although they do not mean the theoretical limit, it is believed, moreover, that an additional advantage of the compositions of the inventions is that they clean the dishes without imparting a “greasy” feel to the washed product. It is especially important for market consumers when the cleanliness of dishes is judged by the absence of such a feeling of "greasy". In addition, it is believed that the compositions of the invention provide an additional advantage due to the reduced feeling of "slippery", usually associated with detergent compositions. This is especially important for consumers for whom this feeling is not favorable and is perceived as incomplete washing of the surfactant from the surface of the dishes.

 In an aspect of the method of the invention, the contaminated dishes are contacted with an effective amount, usually from about 0.5 to about 20 ml (per 25 processed plates), preferably 3-10 ml of the composition of the present invention. The actual amount of liquid detergent composition used will be based on the user's desire and will usually depend on factors such as the particular formulation of the composition, including the concentration of the active ingredient in the composition, the number of plates to be washed, the degree of contamination of the plates, etc. The specific formulation of the product, in turn, will depend on a number of factors, such as the specific market / namely, USA, Europe, Japan, etc. / for the composition. The following are typical methods in which the detergent compositions of the invention can be used to wash dirty dishes. These examples are for illustration only and are not limiting.

 For typical US use, from 3 to about 15 ml, preferably 5-10 ml of the liquid detergent composition is combined with about 1000 ml to about 10,000 ml, usually 3,000 to 5,000 ml of water in a sink having a volume of about 5,000 ml, 20,000 ml, usually of the order 10000-15000 ml. The detergent mixture has a surfactant concentration of from about 21 to about 44 mass. preferably 25-40 mass. Dirty dishes are immersed in a sink containing a detergent composition and water, where it is cleaned from contact of the contaminated surface of the plate with a cloth, sponge or similar product. A cloth, sponge or similar product may be immersed in the detergent composition and the aqueous mixture before being contacted with the surface of the dish and it will usually be in contact with the surface of the dish for a period of about 1-10 seconds, although the actual time will vary for each application and user. The contacting of the fabric, sponge or similar product with the surface of the dishes is preferably carried out by competitively wiping the surface of the dishes.

 In typical European market applications, about 3-15 ml, preferably 3-10 ml of liquid detergent composition is combined with about 1000-10000 ml, preferably 3000-5000 ml of water in a sink having a capacity of the order of 5000-10000 ml, usually of the order of 10000-15000 ml . The detergent composition also has a surfactant concentration of about 21-44 masses. preferably about 25-35 mass. Contaminated dishes are immersed in a sink containing the detergent composition in water, where they are cleaned by contacting the contaminated surface with a cloth, sponge or similar product. A cloth, sponge, or similar product may be immersed in a mixture of water and a detergent composition before being contacted with the surface of the dish and it is usually contacted with the surface of the dish for a period of 1-10 seconds, although the actual time will vary for each user and application. The contact of the fabric, sponge or similar product with the surface of the dishes is preferably carried out by specifically wiping the surface of the dishes.

 In typical Latin American and Japanese market applications, from about 1 to about 50 ml, preferably 2-10 ml of the composition, are combined with about 50-2000 ml, usually about 100 to 1000 ml of water in a bowl with a capacity of from about 500 ml to about 5000 ml, usually about 500 to 2000 ml. The detergent composition has a surfactant concentration of from about 5 to about 40 masses. preferably 10-30 mass. Contaminated dishes are cleaned by contacting the contaminated surface of the dishes with a cloth, sponge, or similar product. A cloth, sponge, or similar product can be immersed in a mixture of detergent composition and water before contacting the surface of the dishes and usually wipe the surface of the dishes with them for a period of about 1 to 10 seconds, although the actual time will vary with each use and for each user.

 Another use is to immerse contaminated dishes in a water bath that does not contain any liquid dishwashing detergent. A device for absorbing such a liquid dishwashing detergent, such as a sponge, is placed directly in a separate amount of undiluted liquid composition for a period of about 1 to 5 seconds. The absorbent device, and therefore the undiluted liquid dishwasher composition, is then individually contacted with the surface of each of the contaminated dishes and these impurities are removed. An absorbent device typically contacts each surface of the pan for 1-10 seconds, although the actual processing time will depend on factors such as the degree of contamination of the pan. Contacting the absorbent device with the surface of the dishes is preferably carried out by competitive wiping.

experimental part
An example of a method for producing an N-methyl-1-deoxyglucityllauramide surface substance for a given use. Although a chemist can change the configuration of the equipment, a suitable device for use is a three-liter four-necked cola equipped with a paddle stirrer with an electric drive and a thermometer of sufficient length to contact the reaction medium. The other two necks of the flask are equipped with a nitrogen supply and a lateral branch with a wide opening (a lateral branch with a wide opening is important in case of very fast methanol evolution), to which an efficient collecting capacitor and a vacuum outlet are connected. The latter is connected to a nitrogen purge and a vacuum gauge, then with exhaust ventilation and a trap. A heating casing with a power of 500 W with a temperature control regulator / Variak / used to heat the reaction is placed in such a way on a laboratory jack so that it can be easily raised or lowered to control the reaction temperature.

195 g / 1.0 mol, Aldrich, M4700-0 / and 220.9 g / 1.0 mol, Procter and Gamble CE 1270 / methyl laurate are charged into the flask. The solid / liquid mixture is heated with stirring while purging with nitrogen until a melt is formed (approximately 25 min). When the melt temperature reaches 145 ^° C., 10.5 g / 0.1 mol, JT Baker / anhydrous sodium carbonate powder are added as catalyst. Turns off the nitrogen purge and sets the exhaust and nitrogen purge so as to obtain a vacuum of 5 inches / 5/31 atm / Hg. From this point, the reaction temperature is maintained equal to 150 ^o C, adjusting Variac and / or raising or lowering the casing.

 After 7 minutes, the first vials of methanol are shown on the meniscus of the reaction mixture. Soon a violent reaction develops. Methanol is distilled off until its speed drops. Establish a vacuum to obtain approximately 10 inches / 10/31 atm / Hg. The vacuum is increased approximately as follows / in inches of mercury. in minutes /: 10 at 3, 20 at 7, 25 at 10. After 11 minutes from the start of methanol evolution, heating and stirring are interrupted when foaming occurs. The product is cooled and allowed to harden.

 The following examples are intended to show the compositions of the present invention, but are not necessary to limit or otherwise define the scope of the invention.

 The following examples illustrate the invention, but are not intended to limit it.

 Example 1. The following three formulations A, B, and C were prepared as described below.

Formulation A is prepared by combining initially an alkyl ethoxy carboxylate detergent mixture with a C _12-14 fatty acid-N-methyl glucamide to form a mixture. Then ethanol, sodium chloride and sodium xylene sulfonate are added to this mixture. Then add any desired remaining surfactants. Glycine is added and the pH is adjusted to about 9.0 sodium hydroxide. Finally, magnesium chloride is added, which accordingly lowers the pH. Setting the final viscosity and pH can be done during this time, then add flavoring and dye. The balance is water.

 Formulation B is prepared by adding ethanol, sodium chloride and sodium xylene sulfonate to an alkylethoxycarboxylate detergent / polyoxy fatty acid amide mixture of the type prepared in formulation A. The remaining components of the formulation are added in the order shown in Table. one.

Formulation C is prepared by adding ethanol, sodium chloride and sodium xylene sulfonate to an alkylethoxycarboxylate detergent / polyoxy fatty acid amide mixture of the type prepared in formulation A. C _12-14 monoethanolamide is heated to about 65 ^° C and then added to the mixture. At this time, a slight adjustment of pH and viscosity is carried out, then dye, perfume and water are added to bring the formulation to 100%
1. Enter the reaction of C _12-13 -alkylethoxy / 3.0 sr / alcohol with tert. potassium butoxide and sodium chloroacetate in a ratio of 1: 1.1: 1.1, first mixing the alkyl ethoxylate with tert, potassium butoxide at 60 ^o C at a pressure of about 20 mm Hg within 1 h. After this, tert-butanol is continuously removed from the reaction mixture by distillation. The vacuum is then released and sodium chloroacetate is added with stirring. Again set the pressure to about 18-20 mm RT. Art. and continue the reaction for approximately 3 hours. After this, the reaction pressure is vented to atmospheric level using nitrogen and the steam heating coil is turned off. In this state, the reaction mixture is left overnight. The next day, increase the temperature of the reaction mixture and reduce the pressure to remove tert. butanol from the system. Then the reaction mixture is added to an aqueous solution of hydrochloric acid containing 105% of the theoretically necessary amount to neutralize the initially added tert. potassium butoxide. The acidic aqueous reaction product is heated to accelerate the separation of organic and aqueous materials. Collect the organic phase.

2. Repeat the above step 1 using C _12-13 -alkylethoxy / 2.7 cf. / alcohol and the ratio of this ethoxylate to tert. potassium butoxide and sodium chloroacetate 1: 1.3: 1.3. Potassium tert-butoxide is added to the alkyl ethoxylate, which is at a temperature of about 32.2 ^° C. and then the temperature of the reaction mixture is raised to about 76.7 ^° C. A vacuum pump is then turned on to achieve reduced pressure. The temperature of the reaction mixture was raised to about 104.4 ^° C, distilled off and tert-butanol was collected over about 30 minutes. Sodium chloroacetate is then added to the reaction mixture, which was slightly cooled to 66 ^° C. The reaction is stirred for about 1.5 hours, cooled and a sufficient amount of hydrochloric acid is added to the aqueous solution to obtain a pH of 3.4. Water is added to increase the volume of the reaction mixture by about 50% and the mixture is then heated to about 49 ^° C. The upper organic layer is collected and the washing process is repeated.

 3. The surface-active mixtures obtained in steps 1 and 2 above are mixed in a ratio of 40.4 to 59.6. Part of this large combined surfactant mixture is neutralized with 50% sodium hydroxide to a pH of about 8 and diluted with about 50% a mixture of water and ethanol 25/75 by volume. The resulting solution was continuously extracted at room temperature with hexane for about four days. The lower aqueous phase was collected and some ethanol and water were removed by heating to give a paste containing an alkylethoxycarboxylate containing the surface active mixture described below.

In the above formulations of Example 1, the surface active part contains about 93.9% of the alkyl ethoxycarboxylates of the formula RO / CH ₂ CH ₂ O / _x CH ₂ COO ^- Na ⁺ , where R is C _12-13 -alkyl containing on average 12.5 carbon atoms , X is in the range from 0 to about 10, and the ethoxylate distribution is such that the amount of material where x is 0 is about 2.8% and the amount of material in which x is greater than 7 is less than 2 wt. alkylethoxycarboxylates. The average x in the distribution is 2.8. the surfactant mixture also contains about 6.1% alcohol ethoxylates of the formula RO / CH ₂ CH ₂ O / _x H with R being C _12-13 alkyl, an average of 12.5 and an average of x = 2.8. The surfactant mixture contains 0% soap materials.

 Example 2. Prepare the following three formulations C, D and E of the invention, as well as the formulations of example 1.

 Example 3. An alternative method used to produce fatty acid polyoxyamides as used herein is as follows. Use a reaction mixture consisting of 84.87 g of a fatty acid methyl ester / source: Procter and Gamble, CE1270 methyl ester, 76 g of N-methyl-D-glucamine / source: Aldrich Chemical Company V4700-0 /, and 68.51 g of methyl alcohol. The reaction vessel is a standard distillation flask equipped with a drying tube, a condenser and a rod stirrer. In this procedure, combine N-methyl-glucamine with methanol with stirring in argon and begin to heat with good stirring / rod stirrer, boiling under reflux /. After 15-20 minutes, when the solution reaches the desired temperature, an ester and a methoxide catalyst are added. Samples are taken periodically to monitor the progress of the reaction; it should not be noted that the solution becomes completely transparent after 63.5 minutes. This confirms that the reaction is indeed close to completion at this point. The reaction mixture was refluxed for 4 hours. After removal of methanol, the recovered crude product weighs 156.16 g. After vacuum drying and purification, a total of 106.92 g of purified product is obtained. However, the percentage yield was not calculated for this basis, since regular sampling during the reaction makes the total percentage yield meaningless.

 The following is not intended to limit the invention, but is intended to further illustrate additional aspects of the technology that can be taken into account by the formulator in the production of a variety of detergent compositions using fatty acid polyoxyamides.

 It is easy to understand that fatty acid polyoxyamides are somewhat unstable due to their amide bond under highly alkaline and highly acidic conditions. Although some decomposition may be acceptable, it is preferred that these materials are not exposed to a pH above about 11, preferably 10, but not below about 3 for an indefinitely long time.

 During the production of fatty acid polyoxyamides, it is usually necessary to at least partially neutralize the basic catalyst used to form the amide bond. Although any acid can be used for this purpose, the detergent formulator must take into account that it is simple and convenient to use an acid that provides anion that is useful and desirable in the finished detergent composition. For example, citric acid can be used to neutralize, and the resulting citrate ion (approximately 1%) will allow approximately 40% of the fatty acid polyoxyamide to remain in the paste and pump it to subsequent production steps throughout the detergent manufacturing process. Similarly, acidic forms of materials can be used, such as oxide disuccinates, nitrilotriacetates, ethylenediaminetetraacetates, tartrate / succin, etc.

Fatty acid polyoxyamides derived from coconut alkyl fatty acids (predominantly C ₁₂ -C ₁₄ ) are more soluble than their tall alkyl (predominantly C ₁₆ -C ₁₈ ) duplicates. Therefore, C ₁₂ -C ₁₄ materials are to some extent easier to formulate in liquid compositions and are more soluble in cold water washing baths. However, C ₁₆ -C ₁₈ materials are also useful, especially in conditions where hot to warm water is used for washing. Indeed, C ₁₆ -C ₁₈ materials may be better detergent surfactants than their C ₁₂ -C ₁₄ duplicates. Therefore, the formulator may consider for balance the ease of production relative to production characteristics when a particular fatty acid polyoxyamide is selected for use in a given formulation.

 It should also be borne in mind that the solubility of polyoxyamides of fatty acids can be increased in the presence of points of unsaturation and / or branching of chains in the fatty acid fragment. Thus, materials such as polyoxyamides of fatty acids derived from oleic acid and isostearic acid are more soluble than their n-alkyl duplicates.

 Similarly, the solubility of polyoxyamides of fatty acids derived from disaccharides, trisaccharides, etc. usually there will be more solubility of their monosaccharide duplicates. Such higher solubility may be particularly beneficial in formulating liquid compositions. In addition, fatty acid polyoxyamides, in which the polyhydroxy group is derived from maltose, are able to function particularly well as detergents when used in combination with conventional alkylbenzenesulfonate / LAS / surfactants. Although the theoretical limitation is not meant, it is obvious that the combination of LAS with fatty acid polyoxyamides derived from higher saccharides, such as maltose, causes a significant and unexpected decrease in interfacial tension in the aqueous medium, as a result of which washing ability is also increased. / The production of fatty acids derived from maltose is described below.

 Fatty acid polyoxyamides can be obtained not only from refined sugars, but also from hydrolyzed starches, for example corn starch, potato starch, or any other plant starch that contains mono-, di-, and the like. saccharide desired by the formulator. This is especially important from an economic point of view. So, high glucose corn starch, high maltose corn starch, etc. can be conveniently and economically used. The delignified hydrolyzed cellulose pulp can also be a raw material source for fatty acid polyoxyamides.

 As noted above, fatty acid polyoxyamides derived from higher saccharides such as maltose, lactose and the like. are more soluble than their glucose duplicates. In addition, it is obvious that more soluble fatty acid polyoxyamides can help solubilize their less soluble duplicates, to varying degrees. Therefore, the compiler can select for use raw materials consisting of corn syrup with a high glucose content, for example, he chooses a syrup that contains a small amount of maltose / for example, 1% or more /. the resulting mixture of fatty acid polyoxyamides will usually exhibit more preferred solubility properties over a wider range of temperatures and concentrations than would be the case with a “pure” glucose derived fatty acid polyoxyamide. So, in addition to any economic advantages for using sugar mixtures rather than pure sugar reagents, fatty acid polyoxyamides made from mixed sugars can provide very significant advantages in terms of performance and / or ease of formulation. In some cases, however, some loss of ability to remove impurities / washing dishes / may be noted at levels of fatty acid maltamides higher than about 25% and some loss when washing in soapy foam above about 33% / the percentages indicated are percentages of maltamide derived from fatty polyoxyamide acids relative to the glucose derived polyoxyamyl fatty acids in the mixture. This can be varied to some extent depending on the chain length of the fatty acid moiety. Then, usually the prescriber who chooses to use such mixtures may find it advantageous to choose mixtures of polyoxy fatty acid amides that contain monosaccharides / example, glucose / and di- and higher saccharides / e.g. maltose / in a ratio of from about 4: 1 to about 99: 1 .

The production of preferred non-cyclized fatty acid polyoxyamides from fatty esters and N-alkyl polyols can be carried out in an alcohol solvent at temperatures from about 30 to 90 ^° C., preferably at 50 ^{° to} 80 ^° C. It has now been determined what may be convenient for the compiler, for example liquid formulations, detergents to carry out such processes in a 1,2-propylene glycol solvent, since there is no need to remove the glycol solvent completely from the reaction product before use in the prepared detergent recipes tours. Similarly, the originator of, for example, solid, typically granular detergent compositions, may find it convenient to carry out the process at 30 ^° -90 ^° C. in solvents which consist of ethoxylated alcohols, such as ethoxylated / EO 3-8 / C ₁₂ C ₁₄ alcohols, such as those that are available as NEODOL 23 E 06.5 / Shell /. When using such ethoxylates, it is preferable that they do not contain significant amounts of unethoxylated alcohol, and most preferably do not contain significant amounts of monoethoxylated alcohol / "T" designation /.

 Although the processes per se to produce polyoxyamide fatty acids do not form part of the invention here, the compiler may also note other syntheses of polyoxyamide fatty acids, as described below.

Typically sequential industrial scale reactions to produce preferred acyclic polyoxyamide fatty acids will consist of
Stage 1 of obtaining a derivative of N-alkylpolyoxyamine from the target sugar or sugar mixture by the formation of an adduct of N-alkylamine and sugar, followed by interaction with hydrogen in the presence of a catalyst; then
Stage 2 of the interaction of the above polyoxyamine, preferably with a fatty ester with the formation of an amide bond. Although various N-alkylpolyoxyamines useful in stage 2 of the reaction sequence can be prepared by various known methods, the following process is convenient and economically uses sugar syrup as a raw material. It should be understood that for best results when using such syrup as a raw material, the manufacturer will be able to choose syrups that are completely light in color or preferably almost colorless / "water-white" /.

Preparation of N-alkylpolyoxyamine from plant-derived sugar syrup
I. The formation of the adduct. The following is a standard process in which about 420 g of about 55% glucose solution (corn syrup about 231 g glucose about 1.28 mol), having a Gardner scale of less than 1, are reacted with about 119 g about 50% - aqueous solution of methylamine / 59.5 g of methylamine 1.92 mol /. The methylamine solution (MMA) is purified and protected with N ₂ and cooled to about 10 ^° C. or lower. Corn syrup is cleaned and protected with N ₂ at 10 20 ^o C. Corn syrup is slowly added to the MMA solution at the specified reaction temperature. The color is measured on the Gardner scale at the indicated times in minutes.

As can be seen from the above data, the Gardner color for the adduct is much worse when the temperature rises above about 30 ^° C and at about 50 ^° C, the time at which the adduct has a Gardner color below 7 is only about 30 minutes. For longer reactions and / or holding times, the temperature should be below 20 ^o C. The color on the Gardner scale should be below about 7, preferably below 4 for a good stain of glucamine.

When lower temperatures are used to form the adduct, the time to achieve a significant equilibrium concentration of the adduct is shortened by using higher ratios of amine to sugar. When the ratio of amine to sugar is 1.5-1 in moles, equilibrium is reached in about 2 hours at a reaction temperature of about 30 ^o C. With a molar ratio of 1.2: 1, under the same conditions, this time is at least 3 hours. For good colors, the combination of the amine: sugar ratio, reaction temperature and reaction time is chosen so as to achieve almost equilibrium conversion, for example, more than about 90%, preferably more than about 95%, even more preferably more than 99%, based on sugar, and colors below 7, preferably below note at most 4, more preferably below about 1 for the adduct.

Using the above process at a reaction temperature below about 20 ^° C. and corn syrups with different colors according to Gardner, as indicated, the color of the MMA adduct (after almost equilibrium is reached in at least about 2 hours) is as indicated.

 As can be seen from the above, the starting sugar material must be very close to colorless in order to consistently have an adduct that is acceptable. When sugar has a Gardner color of about 1, the adduct is sometimes acceptable and sometimes not. When the Gardner color is higher than 1, the resulting adduct is unacceptable. The better the initial color of sugar, the better the color of the adduct.

 II. Reaction with hydrogen The adduct from the above step, having a Gardner color of 1 or lower, is hydrogenated according to the following procedure.

About 539 g of adduct in water and about 23.1 g of United Catalyst G 498 Ni catalyst are introduced into a 1 liter autoclave and purged two times with 200 lb / ⁱⁿ² / 14.06 kg / cm ² / H ₂ at 20 ^o C. The hydrogen pressure is increased to about 1400 lb / in ² / 98.4 kg / cm ² /, and the temperature is raised to about 50 ^o C. Then the pressure is raised to about 1600 lb / in ² / 112.5 kg / cm ² /, and the temperature is maintained at about 50 to 55 ^° C. for about 3 hours. At this point, the product is hydrogenated at about 95%. Then, the temperature is raised to about 85 ^° C. for about 30 minutes and the reaction The mixture is decanted and the catalyst is filtered off. After removing water and MMA by evaporation, the product is 95% N-methioglucamine in the form of a white powder.

The above procedure is repeated with approximately 23.1 g of Raney nickel in the form of a catalyst with subsequent changes. The catalyst is washed three times and the reactor, with the catalyst in the reactor was purged twice with hydrogen at 200 lb / ⁱⁿ² / 14.06 kg / cm ² / reactor for 2 hours. The hydrogen is pumped under pressure 1600 lbs / ⁱⁿ² / 112.5 kg / cm ² /, the pressure drops over 1 hour and again set the pressure in the reactor 1600 lbs / in ² / 112.5 kg / cm ² /. Then the adduct is pumped into a reactor that is at 200 lb / in ² / 14.06 kg / cm ² / and 20 ^o C, and the reactor is blown through at 200 lb / in ² / 14.06 kg / cm ² / etc . as above.

 The resulting product in each case is more than 95% composed of N-methylglucamine; it contains less than 10 ppm nickel, counting on glucamine; and the color of the solution is less than 2 on the Gardner scale.

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

 It is important to have a good adduct that has a low sugar content (less than about 5%, preferably less than about 1%) and good color (below about 7, preferably below 4 on the Gardner scale, more preferably below 1 /.

In another reaction, an adduct is prepared based on about 159 g of about 50% methylamine in water, which is purged and protected with N ₂ at about 10 20 ^° C. About 330 g of about 70% corn syrup / near white water / are degassed N ₂ at about 50 ^° C. and slowly added to the methylamine solution at a temperature below 20 ^° C. The solution was stirred for about 30 minutes to obtain about 95% adduct, which is a very light yellow solution.

About 190 g of adduct in water and about 9 g of catalyst G498Ni combined catalyst is added in a 200 ml autoclave and purged three times with H ₂ at about 20 ^o C. The pressure was increased H ₂ to about 200 lb / ^in2, and the temperature was raised to 50 ^o C. The pressure was increased to 250 lb / ⁱⁿ² / 17.6 kN / cm ² / and incubated 50-55 ^o C temperature for 3 hours. The product, which is about 95% hydrogenated at this point, then heated to about 85 ^o C for about 30 min and after removal of water and evaporation, the product is a 95% solution of N-metilglyuka in in the form of a white powder.

Thus it is important to minimize contact between adduct and catalyst when the hydrogen pressure is less than about 1000 lb / in ^2/703 kg / cm ² / to minimize Ni content in 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 reaction with H _{2 is} carried out to directly compare the effect of the reaction temperature.

 A 200 ml autoclave is used in the following type of procedures, similar to those described above, to obtain an adduct and to react with hydrogen at various temperatures.

 The adduct used to produce glucamine is prepared by combining approximately 420 g of an approximately 55% glucose solution / corn syrup // 231 g glucose, 1.28 mol / / the solution is prepared using 99 DE corn syrup from CarGill /, the solution has a color less than 1 according to the Gardner scale / and approximately 119 g of 50% methylamine / 59.9 g of MMA, 1, 92 mol / / from the company Air Products /.

 The reaction procedure is as follows.

1. Add about 119 g of a 50% methylamine solution to a nitrogen-purged reactor protected by nitrogen and cooled to a temperature below 10 ^° C.

2. Degassed and / or purged with nitrogen a solution of corn syrup at 10-20 ^o C with nitrogen to remove oxygen from the solution.

3. Slowly add a solution of corn syrup to a solution of methylamine and maintain the temperature below 20 ^o C.

 4. Add immediately the whole solution of corn syrup with stirring for about 1 to 2 hours

 The adduct is used to react with hydrogen immediately after preparation or stored at a low temperature to prevent further decomposition.

 The hydrogen reactions of the glucamine adduct are as follows.

 1. Download about 134 g of adduct (color below 1 on the Gardner scale) and about 5.8 g of G 49B Ni in an autoclave with a capacity of 200 ml.

2. The reaction mixture is purged twice at about 200 lbs / in ² / 14.06 kg / cm ² / hydrogen at about 20-30 ^o C.

3. Install a hydrogen pressure of about 400 lb / ⁱⁿ² / 28.12 kg / cm ² / and the temperature was raised to about 50 ^o C.

Raise pressure to about 500 lb / ⁱⁿ² / 35.15 kg / cm ² / was reacted for about 3 hours. Keep temperature of 50-55 ^o C. A sample is taken 1.

Raise the temperature to about 85 ^° C. over about 30 minutes.

 6. The nickel catalyst is decanted and filtered. Sample 2 was taken.

 Conditions for a constant reaction temperature.

 1. Approximately 134 g of the adduct and approximately 5.8 g of G498Ni are charged into a 200 ml autoclave.

2. Double purged with hydrogen at about 200 lbs / in ² / 14.06 kg / cm ² / at low temperature.

3. Set the hydrogen pressure to about 400 lb / in ² / 28.12 kg / cm ² / and increase the temperature to about 50 ^o C.

4. Raise the pressure to about 500 lb / in ² / 35.15 kg / cm ² / carry out the reaction for 3.5 hours. Withstand the specified temperature.

5. The nickel catalyst is decanted and filtered. Sample 3 was taken at about 50–55 ^° C; sample 4 at about 75 ^° C. and sample 5 at 85 ^° C. / reaction time at 85 ^° C. is about 45 minutes /.

All experiments give the same purity of N-methylglucamine / about 94% /; Gardner color is similar immediately after the reaction, but only two-stage heat treatment gives good color fastness; and experience at 85 ^o C gives the ultimate color immediately after the reaction.

 Example 4. The preparation of tall / solid / fatty acid amide from N-methylmaltamine for use in detergent compositions according to the invention is carried out as follows.

Stage 1 Reagents: Maltose monohydrate / Aldrich, lot 01318K W /; methylamine / 40% in water / / Aldrich, batch 03325TM /; Raney nickel, 50% paste / and HELL 52-730, Aldrich, lot 12921 LW //
The reagents are loaded into a glass tube / 250 g of maltose, 428 g of methylamine solution, 100 g of catalyst paste 50 g of Raney nickel / and placed in a 3 L rotating autoclave, which is purged with nitrogen / 3 • 500 lb / in ² / 35.15 kg / cm ² / / and hydrogen / 2 • 500 lb / in ² / 35.15 kg / cm ² / and rotate under hydrogen pressure at room temperature during the weekend at a temperature in the range from 28 to 50 ^o C. The crude reaction mixture filtered under vacuum through a glass microfiber filter with silica gel plug. The filtrate is concentrated to a viscous material. Final traces of water by distillation with an azeotrope during dissolution of the material in methanol and subsequent removal of methanol / water on a rotary evaporator. Final drying is carried out in high vacuum. The crude product is dissolved under reflux in methanol, filtered, cooled to recrystallization, filtered and the filter cake dried in vacuo at 35 ^° C. Fraction 1 is obtained. The filtrate was concentrated until a precipitate began to form and left in the refrigerator overnight. The solid product is filtered off and dried in vacuo. Get fraction2. The filtrate is again concentrated to half its volume and crystallization is carried out. Very little precipitate is formed. A small amount of ethanol is added and the solution is left in the refrigerator for the weekend. The solid material is filtered off and dried in vacuo. The combined solid products are N-methylmaltamine, which is used in stage 2 of the general synthesis.

 Stage 2 Reagents: N-methylmaltamine / from stage 1 /; solid tall esters; sodium methoxide (25% in methanol); absolute methanol / solvent /; molar ratio 1: 1 amine: ester; initial level of catalyst 10 mol. / mass./maltamine/, increase to 20 mol. solvent level 50% / wt./.

In a sealed flask, 20.36 g of tall methyl esters are heated to their melting point / water bath / and loaded into a 250 ml three-necked round-bottom flask with mechanical stirring. The flask was heated to about 70 ^° C. to prevent the ester from solidifying. Separately, 25.0 g of N-methylmaltamine is combined with 45.36 g of methanol and the resulting paste is added to the tall ether with good stirring. 1.51 g of 25% sodium methoxide in methanol are added. After 4 hours, the reaction mixture does not clarify, so that an additional 10 mol% of catalyst is added (up to a total of 20 mol%) and the reaction is continued overnight / about 68 ^° C /, after which time the mixture becomes transparent. Then the reaction flask is modified by distillation. Raise the temperature to 110 ^o C. Distillation at atmospheric pressure is continued for 60 minutes Distillation is then started under high vacuum and continued for 14 minutes, during which time the product becomes very viscous. The product was left in the reaction flask at 110 ^° C / external temperature / for 60 minutes. The product is removed from the flask and treated with ethyl ether for the weekend. The ether was removed on a rotary evaporator and the product was left overnight in an oven and pulverized. Any N-methylmaltamine residues are removed from the product using silica gel. Silica gel paste in 100% methanol is loaded into the funnel and washed several times with 100% methanol. A concentrated sample of the product (20 g in 100 ml of 100% methanol) was loaded onto silica gel and eluted several times using vacuum and several methanol washes. The collected eluent is evaporated to dryness (rotary evaporator). Any residues of the tall ester are removed by treatment with ethyl acetate overnight, followed by filtration. The filter residue was dried in vacuo overnight. The product is an alkyl - N-methylmaltamide.

 In an alternative method, step 1 of the above reaction sequence can be carried out using a commercial corn syrup consisting of glucose or a mixture of glucose and usually 5% or more of maltose. The resulting fatty acid polyoxyamides and mixtures can be used in any detergent composition.

 In yet another embodiment, step 2 of the aforementioned reaction sequence can be carried out in 1,2-propylene glycol or NEODOL. At the discretion of the formulator, there is no need to remove propylene glycol or NEODOL from the reaction product before using it to formulate a detergent composition. Again, as desired by the formulator, the methoxide catalyst can be neutralized with citric acid to provide sodium citrate, which can be left in the fatty acid polyoxyamide.

 Depending on the desires of the originator, the compositions may contain more or less different foam control agents. Typically, strong foam is desirable for washing dishes, so it is not necessary to use foam control agents.

Example 5. In any of the above examples of detergent compositions, the surfactant fatty acid glucamide can be replaced with an equivalent amount of surfactant maltamide or surfactant glucamide / maltamide mixtures originating from plant sugar sources. In compositions, the use of ethanolamides contributes to the stability at low temperatures of the finished formulations. In addition, the use of surfactant sulfobetaines (aka "sulfaine") provides excellent foaming. You can use CaCl ₂ / about 1% / in the formulations to improve the removal of greasy contaminants from the dishes. Increases foaming and MgCl ₂ .

Since the invention provides particularly highly foamy compositions, it is preferred that they contain less than about 5%, more preferably less than about 2%, most preferably no C ₁₄ or higher fatty acids are present since they can inhibit foaming. Therefore, it will be desirable for the compiler of highly foamy compositions to avoid introducing suppressive foaming amounts of such fatty acids into highly foamy compositions with polyoxyamide fatty acids, and / or to avoid the formation of C ₁₄ or more higher fatty acids during storage of the finished compositions. This simply means the use of C ₁₂ ester reagents to produce fatty acid polyoxyamides. It is beneficial that the use of surface-active amine or sulfobetaine oxides such as cocoamidopropyl betaine can eliminate some of the negative foaming effects caused by fatty acids.

 A compiler desiring to add anionic optical brighteners to liquid detergents containing relatively high concentrations (for example, 10% or more) of anionic or polyanionic substituents, such as polycarboxylate components, may find it useful to pre-mix the bleach with water and a polyoxyamide fatty acid, and then add this premix in the finished composition.

 The chemist should understand that the preparation of fatty acid polyoxyamides using di- and higher saccharides, such as maltose, will result in the formation of fatty acid polyoxides, in which the linear substituent is “encompassed” by the polyhydroxyl structure. Such materials are fully intended for use herein and do not depart from the spirit and scope of the invention as described and claimed.

Claims (12)

1. Detergent composition containing a surface-active mixture comprising a polyhydroxyamide fatty acid of General formula I

and other detergent components selected from the group consisting of liquid carriers, thickeners, additional anionic, nonionic, ampholytic or zwitterionic surfactants, fillers, diluents, solvents, dyes, perfumes and hydrotropic substances, characterized in that the surface-active mixture contains 5 to 95 wt. a fatty acid hydroxyamide of the general formula I at R ¹ H ₁ (C ₁ - C ₄ ) hydrocarbon, 2-hydroxyethyl, 2-hydroxypropyl or a mixture thereof, R ² - (C ₅ C _{3 1} ) hydrocarbon radical, Z is a polyhydroxy hydrocarbon with a linear hydrocarbon chain with at least three hydroxyl groups associated with this chain, or its alkoxy derivative, and additionally it contains 5 to 95 wt. alkoxycarboxylate of the general formula II
RO (CH ₂ CH ₂ O) _k CH ₂ COO ^- M ⁺ ,
where R (C ₈ C _{2 2} ) alkyl;
k 0 10;
M cation,
in the following ratio of components, wt. Surface active mixture 1 65
other detergent components Up to 100
2. The composition according to claim 1, characterized in that the alkoxycarboxylate has such a distribution that the amount of substance II at k 0 is less than 20%, the amount of substance II at K more than 7 is less than 25.9 wt. and the average value of k 1 4, the average value of RC _{1 3} alkyl or lower and the average value of k 2 6 with an average value of R alkyl more than C _{1 3} .  3. The composition according to claim 1, characterized in that it is liquid, preferably aqueous or hydroalcoholic and contains 10 to 50 wt. surfactant mixture and 50 to 90 wt. liquid carrier.  4. The composition according to claim 3, characterized in that the surface-active mixture comprises 20 to 80 wt. alkoxycarboxylate and 20 to 80 wt. polyhydroxyamide fatty acid.  5. The composition according to p. 4, characterized in that it contains an alkoxycarboxylate at M ion of an alkali metal, alkaline earth metal, ammonium, lower alkanolammonium, mono-, di- and triethanolamine and their mixture with magnesium and calcium ions.  6. The composition according to claim 5, characterized in that its pH is in the range of 7 to 11 and it additionally contains 0.1 to 15 wt. buffer agent and 2 to 5 wt. hydrotrope. 7. The composition according to claim 6, characterized in that it further comprises in an amount of 1 10%, preferably 2 5 wt. one or more anionic or nonionic surfactants selected from the group consisting of C _{1 1} C _{2 7} -alkyl ether sulfonates, C ₈ - C _{2 2} primary or secondary alkanesulfonates, C _{1 0} - C _{1 8} -alkyl dimethyl amine oxides, alkyl polysaccharides and their mixtures.  8. The composition according to claim 7, characterized in that the surface-active mixture contains 40 to 60 wt. alkoxycarboxylate and 20 to 60 wt. polyhydroxyamide fatty acid and as a liquid carrier contains water or its mixture with ethanol. 9. The composition according to p. 8, characterized in that it contains an alkoxycarboxylate of the general formula II at the M-cation selected from the group consisting of sodium, potassium, ammonium and a mixture thereof with calcium and magnesium ions, and a polyhydroxyamide fatty acid of the formula

where R ² C _{1 1} C _{1 7} -alkyl or alkenyl with a straight chain;
Z derivatives of glucose, maltose or mixtures thereof. 10. A method of cleaning dishes by contacting them with a detergent composition, characterized in that as a detergent composition using a composition containing a surface-active mixture comprising 5 to 95 wt. one or more alkoxycarboxylate of the general formula
RO (CH ₂ CH ₂ O) _k CH ₂ COO ^- M ⁺ ,
where RC ₈ C _{2 2 is} alkyl;
k 1 4;
M cation,
and 5 to 95 wt. one or more polyoxyamides of fatty acids of the general formula

where R ¹ H, C ₁ C ₄ hydrocarbon; 2-hydroxyethyl; 2-hydroxypropyl or a mixture thereof;
R ² C ₅ C _{3 1 is a} hydrocarbon,
Z is a polyhydroxy hydrocarbon having a linear hydrocarbon chain with at least three hydroxyl groups directly attached to the chain, preferably C _{1 1} C _{1 7} -alkyl (alkenyl) N - methyl N glucosamide, C _{1 1} C _{1 7} -alkyl (alkenyl) N methyl N maltosamide or a mixture thereof,
or alkoxy derivatives and other detergent components selected from the group consisting of liquid carriers, thickeners, additional anionic, nonionic, ampholytic or zwitterionic surfactants, fillers, diluents, solvents, dyes, perfumes and hydrotropic substances in the following ratio of components, wt. surfactant mixture 1 65; other detergent components up to 100. 11. The method according to claim 10, characterized in that the use of a composition further comprising 1 to 10 wt. preferably 2 to 5 wt. one or more anionic or nonionic surfactants, preferably selected from C _{1 1} C _{2 7} alkyl ether sulfonates, C ₈ C _{2 2} primary and secondary alkanesulfonates, C _{1 0} C _{1 8} alkyl dimethyl amine oxides, alkyl polysaccharides and mixtures thereof.  12. The method according to claim 10, characterized in that a composition is used comprising a polyhydroxyamide fatty acid, in which the Z group is obtained from mixed monosaccharides, disaccharides and polysaccharides obtained from plant sources. 13. The method according to claim 10, characterized in that a composition comprising polyhydroxyamide is used, in which R ² C _{1 5} is C _{1 7} -alkyl, alkenyl or a mixture thereof. Priority by signs:
09/28/90 with a surfactant content of 5 65
09/06/91 when the content of the surface-active mixture from 1 to less than 5%

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