PT99085B - PROCESS FOR THE PREPARATION OF LIQUID DETERGENT COMPOSITIONS FOR LOICA WASHING CONTAINING ALKYL-ETOXICARBOXILATES AND AMIDES OF POLYHYDROXYLIC FATTY ACID - Google Patents

Abstract

Disclosed are detergent compositions comprising and alkyl ethoxy carboxylate component and a polyhydroxy fatty acid amide component. The detergent compositions of the present invention possess improved cleaning and sudsing properties and exhibit enhanced mildness to the skin. Also disclosed is a method for cleaning soiled dishes by treating said dishes with the detergent compositions disclosed herein.

Description

Technical Field The present invention relates to detergent compositions comprising alkyl ethoxycarboxylates and polluted hydroxy fatty acid amides. In particular, it relates to detergent compositions that have desirable cleaning and foaming properties and are especially suitable for use in dishwashing applications.

Background of the Invention

Alkyl-ethoxycarboxylates, and their use in detergent positions, are known in the art. US Patent Application No. ² . Series 516.292, entitled Light -Uuty Liquid Disbwashing Detergent Composition Containing an Alkyl Ethoxy Surfactant, deposited on May 4, 1989 in favor of Rodney M. Wise and Thomas A. Cripe, reveals such carboxylates and their use in detergent compositions . Although these carboxylates provide improved cleaning performance, the foam they produce generally has poor starting volume and stability. This initial foam volume and poor stability can give rise to an incorrect consumer perception that these compositions provide poor cleaning performance. Consequently, it would be desirable to combine such carboxylates with a component or components that provide improved foaming performance, it has been found that the compositions claimed in the present invention provide this desired effect.

amide component of polyhydroxy fatty acid contained in the compositions of the present invention is known in the art as well as several of its uses.

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N-acyl, N-methylglucamide, for example, are disclosed by JW Goody, MA Marcus, E. Chin and PL Finn in The Thermotropico Liquid-Crystalline Properties of Some Straight Chain Carbohydrate Amphiphiles, Liquid Crystals, 1988, Volume 3, N ° . 11, pages 1560-1581, and by A. Iluller-Fahrnov, V. Zabel, M. Steifa and R. Hilgenfeld in Molecular and Crystal Structure of Nonionico Detergent: Nonanoyl-N-methylglucamide, J. Chem: Soc. Chem. Commun, 1986, pages 1573-1574. The use of N-alkylpolyhydroxyamide surfactants has recently been of substantial interest for use in biochemistry, for example in the dissolution of biological membranes. See, for example, the journal article ND-Gluco-N-me ^ · thyl-alkamida Compounds, a New Glass of Non-lonely Detergents For Membrane Biochemistry, Biochem J. (1982), Vol. 207, pages 363-666 , by JEK Hildreth.

The use of N-alkyl-glucamides in detergent compositions has also been discussed. U.S. Patents 2,965,576, issued December 20, 1960 to E.R. Wilson and G.B. 809,060 Patent, published February 18, 1959 and transferred to Thomas Hedley & Co., Ltd, refer to de-detergent compositions; containing anionic surfactants and certain amide surfactants, which may include N-methyl-glucamide, added as a low temperature foam enhancing agent. These compounds include an N-acyl radical of a straight chain fatty acid having 10-14 carbon atoms. These compositions may also contain auxiliary materials such as alkali metal phosphates, alkali metal silicates, alkali metal sulphates and carbonates. It is also indicated, in general, that additional constituent compositions may be included to impart desirable properties to the composition, such as fluorescent pigments; bleaching agents, perfumes, etc.

U.S. Patent 2,703,798, issued on March 8, 1955 to A.M. Schwartz, relates to aqueous detergent compositions containing the reaction product of; ......

condensation of N-alkylglucamide and an aliphatic ester of

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a fatty acid. The product of this reaction is said to be usable in aqueous detergent compositions without further purification. It is also known to prepare an sulfuric ester of acylated glucamide as disclosed in U.S. Patent 2,717,894, issued on September 13, 1955 to A.M. Schwartz.

International application PCI WO 83/04412, published on December 22, 1983, by J. “'RLdreth, refers to amphiphilic compounds containing polyhydroxy aliphatic groups said to be usable for a variety of purposes, including use as surfactants in cosmetics , drugs. Shampoos, lotions and ointments. · Ophthalmic, as emulsifiers and administration agents for medicine, and in biochemistry for solubilizing membranes, global cells and other tissue samples, and for preparing liposomes. 'This disclosure includes compounds of the formula R' CONÍPOCE ^ R and RCON (R) R 'in which R is hydrogen or an organic grouping, R' is an aliphatic hydrocarbon group of at least three carbon atoms and R is the residue of an aldose.

European Patent 0 285 768, published in October 1988, H. Kelkenberg, et al., Refers to the use of N-polyhydroxyalkyl fatty acid amides as thickening agents in aqueous detergent systems. Amides of the formula R ^ C (O) N (X) Rp are included in which is a ^C 1 ^_C 17 alkyl (Preferably Cy-C ^ y), R ^ is hydrogen, a ^ 1 ^- ^ 18 alkyl (preferably ° ^{u UTn} alkylene oxide and X is a polyhydroxyalkyl having four to seven ear atoms, eg, coconut fatty acid N-methylglucamide The thickening properties of the amides are indicated to be of use, particularly in liquid surfactant systems containing paraffin sulfonates, although liquid surfactant systems may contain other anionic surfactants, such as alkylarylsulfonates, olefin sulfonates, partially salts of sulfosuccinic acid and fatty alcohol ether sulfates, and nonionic surfactants such as polyglycolic alcohol ether fatty, alkylphenol polyglycolic ether

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polyglycolic ether of fatty acid, mixed polymers polypropylene oxide-polyethylene oxide, etc. Exemplary paraffin sulfonate shampoo / coconut fatty acid N-netylglucamide / nonionic surfactant formulations are exemplified. In addition to the thickening attributes, N-polyhydroxyalkyl fatty acid amides are said to have skin-tolerant attributes.

U.S. Patent No. 2,298,737 issued on May 2, 1961 to Boetner, et al., Refers to detente bars containing urea, anionic surfactant sodium lauryl sulfate, and a nonionic N-alkylglucamide surfactant that is selected from N-methyl-, N-sorbityl-lauramide and N-methyl-, N-sorbityl-myristamide.

Other glucamide surfactants are disclosed, for example, in DT 2,226,872 published on December 20, 1973, HU Eckert et al., Which refers to washing compositions containing one or more intensifying salts and surfactants selected from polymeric phosphates, agents scavengers and washing alkalis, enhanced by the addition of an N-acyl-polyhydroxyalkylamine of formula (CHOH ^ CI ^ OH, in which it is an O - ^ - Cg, P ^ θ alkyl an ^G 10 ^_G 22 ^en θ 3 alkyl or 4. N-acyl-polyhydroxyalkylamine is added as a stain-suspending agent.

The E.IJ.A. Patent 3,654,166, granted on April 4, 1972 to H.U. Eckert et al., Refers to detergent positions comprising at least one surfactant selected from the group of anionic, zwitterionic and non-ionic surfactants and, as a textile softener, an N-acyl, N-alkyl-polyhydroxyalkyl compound of formula

R ^ N (Z) C (0) R2 in jjual is an alkyl θ ^URQ N -? ^C l ^water it Cy-C ^ Ry and R2 total from 23 to 39 carbon atoms and Ζ is a polyhydroxyalkyl which can be where ra is 3 or 4.

U.S. Patent 4,021,539, issued on May 3, 1977 to H. Mõller et al., Relates to cosmetic compositions for treating it containing N-poly-hi4

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droxyalkylamines that include compounds of formula

R ^ N (R) CH (CH0H ^ R2 ' ^na Φ ¹³ ·! Rq is H, lower alkyl, lower hydroxyalkyl or aminoalkyl, as well as a heterocyclic aminoalkyl, R is the same as Rp but cannot be both

H. and R, is it CH _? OH or COOR.

French Patent 1,360,018 of April 26> ¹⁰ of 1963, transferred to Commercial Solvents Cornoration, refers to formaldehyde solutions stabilized in relation to polymerization with the addition of amides of formula RC (0) N (R ^) G in which R is a carboxylic acid function having at least seven carbon atoms, R3 is hydrogen or a lower alkyl group and a glycitol radical with at least 5 carbon atoms.

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German Patent 1,261,861, February 29, 1968, A. Heins, refers to glucamine derivatives useful as wetting and dispersing agents of formula in which R is a glucamine sugar residue, R 4 is an alkyl radical ^c -lq ^-C 20 '^ 2 θ ^{A ra} ^ ^aca ^ - C ^ -Cp acyl

GB Patent 745,036, published on February 15, 1956, transferred to Atlas Powder Company refers to heterocyclic amides and their carboxylic esters which are said to be useful as chemical intermediates, emulsifiers, wetting and dispersing agents, detergents, textile softeners, etc. The compounds are expressed by the formula N (R) (Rj) C (O) R ', in which R is the residue of a hexanopentol, made anhydrous, or a carboxylic acid ester thereof, is a monovalent hydrocarbon radical and -C (O) R? it is an acyl radical of a carboxylic acid having from 2 to 25 carbon atoms.

U.S. Patent 3,312,627, issued April 4, 1967 to DT Hooker, discloses solid toilet bars that are substantially free of anionic detergents and alkaline intensifying materials and that contain lithium soap of certain fatty acids, a nonionic surfactant selected from certain propylno-ethylenediamine-ethylene oxide condensates, condensate oxide

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J ¹⁰

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Propylene-propylene glycol-ethylene oxide and polymerised ethylene glycol and also contain a foaming component which may include polyhydroxyamide of formula

RC (O) NR ⁱ (R '), in which RC (O) contains from about 10 to about 14 carbon atoms and R and R are each H or C - ^ - C ^ alkyl groups containing the said alkyl groups a total number of carbon atoms of about 2 to about 7 and a total number of hydroxy substituent groups of about 2 to about 6. A substantially similar disclosure is found in U.S. Patent 3,312,626 , also granted on 4 April 1967 to DT Hooker.

However, none of these references explains the combination of an alkyl ethoxycarboxylate and a polyhydroxy fatty acid amide in a detergent composition. Furthermore, nothing in the art explains the unexpected improved foaming characteristics and improved cleaning properties, especially fat-free properties, of such detergent compositions.

There is also nothing in the art to explain the softness to the hands exhibited by these detergent compositions.

It is therefore an object of the present invention to provide preparation for detergent compositions, containing an alkyl ethoxycarboxylate and a polyhydroxy fatty acid amide, which exhibit improved cleaning and foaming properties and are gentle to the skin. .

It is still an object of the present invention to provide a process for cleaning stained dishes by treating said dishes with the particular detergent compositions described herein.

These objectives are achieved by the present invention.

Summary of the Invention This invention is directed to detergent compositions comprising about 1%, preferably 63,878

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about 5% to about 65% by weight of a surfactant mixture comprising:

(a) 'from about 5% to about 95%, by weight, of one or more alkyl ethoxycarboxylates having the general formula ..

RO (CH ₂ CH ₂ O) _k CH ₂ COO- _II + in which R is a C 1 -C 6 alkyl group? , k is an integer in the range 0 to 10 and M is a cation;

(b) from about 5% to about 95%, by weight, of one or more polyhydroxy fatty acid amides having the general formula:

R ¹

² S ij -?] TZ in which R is H, a hydrocarbyl _C₁-Z, 2-hydroxyethyl, 2-hydroxypropyl or mixtures thereof, ^R2 is a C₁-C₄ hydrocarbyl and Z is a poly-hydroxyl -hydrocarbyl having a linear hydrocarbyl chain with at least 3 hydroxyl groups attached directly to the chain or an alkoxylated derivative thereof.

the present invention is also directed to a process for cleaning anodized dishes, said process comprising treating said dishes with the detergent compositions claimed herein.

Detailed Description of the Invention

The detergent compositions of the present invention are preferably detergent compositions in the gel or liquid form, more preferably liquid detergent compositions for light soiling, even more preferably liquid detergent compositions for washing lightly soiled dishes. These detergent compositions comprise from about 5% to about 65%, by weight, preferably from about 10% to about 50%, by weight, even more preferably from about 20% to about 40%, by weight , of a surfactant mixture comprising one or more

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alkyl ethoxycarboxylates and one or more polyhydroxy fatty acid amides. These and other optional ingredients, typically found in detergent compositions, are described below. '

Component Alqui 1-et oxy. carboxy

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The surfactant mixture of the present invention ranges from about 5% to about 95% by weight, preferably from about 20% to about 80% by weight, more preferably from about 40% to about 60% by weight of one or more alkyl ethoxycarboxylates having the general formula:

R0 (CH _? CH ₂ 0) _k CH _? COO-M + in which R is a Cg-C ₂₂ alkyl group, preferably an alkyl group k is an integer within the range 0 to 10, preferably 1 to 5, and M is a cation, preferably an alkali metal, alkali metal - earth, ammonium, lower alkanolammonium and mono-, di- and tri-ethanolammonium, more preferably sodium, potassium and ammonium, even more preferably sodium and potassium, and mixtures with magnesium and calcium ions. The number of carbon atoms in the group R and the value of the integer k are interrelated as far as the number of carbon atoms in the group; R is increased, so it is preferable that the value of the integer k is correspondingly increased to preserve the detergent compound's solubility. Typically, where R is an alkyl group ^ 12 ^{- (} '14''* ^will range from about 1 to about 4, when R is an alkyl group ^and q2 ^_C 18' ^astara on 8 ^ana 1 ^to about 6, and when R is an alkyl group Cg-C ^ _2, k that Ra in the range of 0 to about 3.

The alkyl-ethoxycarboxylate component of the present invention can be prepared by processes known in the art. A preferred process is revealed in U.S. Patent Application no. de Series 354.968, entitled Process for Making Alkyl Ethoxy Carboxylates, deposited on May 22, 1989 for the benefit of Thomas A. Cripe, whose disclosure is hereby incorporated.

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2S.SÍ

M

Mod. 71 - 20,000 βχ.

The alkyl-ethoxycarboxylate component of the present invention can comprise an alkyl-ethoxycarboxylate distribution. When the composition of the present invention comprises such a distribution _,? the ethoxylate distribution will be such that, on a weight basis, the amount of material where k is 0 is less than about 20%, preferably less than about 15%, even 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%, even more preferably less than about 10%. The average k will be in the range of about 1 to 4 when the average R is or less, the average k will be in the range of about 2 to 6, when the average R is greater than

In U.S. Patent Application no. 516,292, filed on May 4, 1989, the disclosure of which is hereby incorporated, describes this distribution, and its preparation, in greater detail. When the detergent compositions of the present invention are comprised of an ethoxycarboxylate distribution, the desired carboxylate distribution can be derived by reacting a corresponding distribution of ethoxylated alcohol precursors.

It has been found that the presence of divalent cations with the alkyl ethoxycarboxylates in the compositions of the present invention greatly increases the cleanliness of fatty stains. This is especially true when using the composition in soft water that contains few divalent ions. Divalent ions are believed to increase the packaging of alkyl ethoxycarboxylates at the interface, water / oil, thus producing reduced interfacial tension and improved fat cleaning. However, liquid detergent compositions used in dishwashing applications that contain alkyl ethoxycarboxylates, and which do not comply with the strict definitions of this invention, benefit less from the addition of divalent ions and, in many cases, in fact exhibit performance of reduced cleaning when adding divalent cations.

When included in the compositions of this in9

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wind, the divalent ions are preferably added as the chloride, sulfate, or hydroxide salt, more preferably the chloride salt, to compositions containing alkali metal or ammonium salts of the alkyl ethoxyearboxylates, more preferably sodium or potassium salts, after neutralization of the composition with a strong base. The concentration of the divalent ion is typically in the range of 0% to about 1.57 (, preferably about 0.27 (to about 1%, more preferably about 0.37 (to about 0.87 ( Particularly preferred divalent ions are by weight magnesium and calcium ions.

Depending on the preparation process used to prepare the alkylethoxycarboxylate component of the present invention, and the process of preparing the compositions of the present invention, such compositions can still contain from 0 to about 5.074, preferably less than 4.0%, more preferably less than 2.5% by weight of ethoxylates alcohol of the formula

R'O (CH ₂ CH ₂ O) H (II) in which R 'is a 0j ₂ -C ₆ gew alkyl group is in the range of about 0 to about 10, the mean w being less than 6.

The non-carboxylated alcohol ethoxylates of structure (II) are a detriment to the alkyl ethoxycarboxylate containing compositions of the present invention. Consequently, it is crucial that such compositions contain no more than about 5.0%, by weight, of alcohol ethoxylates from which the alkyl ethoxyearboxylates are derived. Although alkyl ethoxyearboxylates containing 10% or more alcohol ethoxylates are commercially available, routes are known to obtain the desired high purity alkyl ethoxyearboxylates. For example, unreacted alcohol ethoxylates can be removed by steam distillation, Pat. of E.-TJ.A. No. 4,098,818 (Example 1), or by recrystallization from alkyl-ethoxycarboxylate, Pat. British N ^Q. 1 027-481 (Example 1). Other pathways for the desired carboxylates are the reaction of sodium hydroxide or metallic sodium and monochloroacetic acid, or its salt, with

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ethoxylates alcohol under special conditions of pressure and temperature, as described in Pat. U.S. No. 3,992,443 and 4,098,818; and Japanese Patent Application No. 50-24215, all of which are incorporated herein.

Other routes for high purity alkyl ethoxycarboxylates are disclosed in U.S. Patent Application Serial No. 516,292, filed May 4, 1980, already referred to herein, which is incorporated herein.

Polyhydroxy Fatty Acid Amide Component

The surfactant mixture of the present invention further comprises from about 5% to about 95%, by weight, preferably from about 20% to about 80%, by weight, more preferably from about 20% to about 60% by weight of one or more polyhydroxy fatty acid amides having the general formula,

R ¹

II _(I) R - C. - N - Z ~

in which R and H, C 1 -C 4 hydrocarbyl, 2-hydroxyethyl, 2-hydroxypropyl, or a mixture thereof, preferably C .. -C. alkyl, more preferably C or C ₉ alkyl, even more preferably alkyl (ie, methyl); and R ^z is a straight chain C ^-C ^ hydrocarbyl, preferably straight chain C ^-C ^ alkyl or alkenyl, more preferably straight chain Cg-C. alkyl or alkenyl, even more preferably C ^-C ^ alkyl or alkenyl. linear chain, or mixtures thereof; and Z is a polyhydroxy hydrocarbyl having a linear hydrocarbyl, with at least 3 hydroxyl groups attached directly to the chain, or an anhydrous derivative derived from alkoxylated (preferably ethoxylated or propoxylated). The Z will preferably be derived from a reducing sugar in a reductive amination reaction; more preferably Z is a glycityl. Suitable reducing sugars include glucose, fructose, maltose, lactose, galactose, mannose and xylose. As raw material

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Case: 4262 You can use dextrose-rich wheat syrup, fructose-rich wheat syrup, maytose-rich wheat syrup as well as the individual sugars listed above. These wheat syrups can produce a mixture of sugar components for Z. It should be understood that it is in no way intended to exclude other suitable raw materials. Preferably, Z will be selected from the group consisting of -CH „- (CHO.H) -CPL OH, -CH- (CH ₂ OH) - (CHOH) _τ -σΗ _? ΟΗ, -CH ₂ - (CHOH) _? (CHOH) - (CHOH) CH ₂ 0H, where n is an integer from 3 to 5 inclusive, and R is H or a cyclic or aliphatic monosaccharide and its alkoxylated derivatives. More preferably, they are glycityls where n is 4.

In Formula (I), R can be, for example, N-methyl, N-ethyl, N-propyl, N-isopropyl, N-butyl, Ν-2-hydroxystyl or Ν-2-hydroxypropyl.

R-CO-N <can be, for example, cocamide, stearamide, oleamide, lauramide, myristamide, capricamide, palmitamide, seboamide, etc.

Z can be 1-deoxyglucithyl, 2-deoxyfrutylyl, 1-deoxyltityl, 1-deoxy-lactityl, 1-deoxygalactityl, 1-deoxymanityl, 1-deoxy.maltotriotityl, etc.

The most preferred polyhydroxy fatty acid amide has the general formula

CH ³

R ² - U -Á - CH _? - (CHOH) _Á - CH _? OH in which R ^J is a straight chain alkyl or alkenyl y group.

Processes for producing polyhydroxy fatty acid amides are known in the art. In general, they can be produced by reacting an alkylamine with nn reducing sugar in a reductive amination reaction to form a corresponding N-alkyl-polyhydroxyamine and then by reacting the N-alkyl-polyhydroxyamine with an ester or fatty aliphatic triglyceride in a condensation / amidation step to form the N-alkyl, N-polyhydroxy fatty acid amide product. Processes for the production of color compositions are revealed. 878

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having polyhydroxy fatty acid amides, as an example, in G.B. 809,060 Patent Specification, published in

February 1.8, 1959, by Thomas Redley & Co., Ltd., in U.S. Patent 2,965,576, issued on December 20, 1960 to ER Wilson and in U.S. Patent 2,703,798, Antbony M. Schwartz, issued in March 8, 1955 and U.S. Patent 1,985,424, issued December 25, 1934 to Piggott, each of which is incorporated herein by reference

In a process for producing N-alkyl or N-hydroxyalkyl, N-deoxyglycyl fatty acid amides in which the glyceryl component is derived from glucose and the N-alkyl, or N-hydroxyalkyl function, is N-methyl, N-ethyl, N-pronyl, N-butyl, N-hydroxyethyl or N-hydroxypropyl the product is produced by reacting N-alkyl- or N-hydroxyalkylglucamine with a fatty ester selected from fatty methyl esters, fatty ethyl esters and fatty triglycerides in the presence of a catalyst selected from the group consisting of trilithium phosphate, trisodium phosphate, tripotassium phosphate, tetrasodium pyrophosphate, pentapotassium tripolyphosphate, lithium hydroxide, sodium hydroxide, potassium hydroxide, calcium hydroxide, lithium carbonate, sodium carbonate, potassium carbonate disodium tartrate, dipotassium tartrate, sodium-potassium tartrate, trisodium citrate, tripotassium citrate, basic sodium silicates, basic sodium silicates potassium, basic sodium aluminosilicates and basic potassium aluminosilicates and their mixtures. The amount of catalyst is preferably about 0.5 mol% to about 50 mol%, more preferably about 2.0 mol% to about 10 mol% on a molar base of an N-alkyl or N-hydroxyalkylglucamine The reaction is preferably carried out at about 138 ° C to about 170 ° C for, typically, about 20 to about 90 minutes. When triglycerides are used in the reaction mixture as the fatty ester font, the reaction is preferably still carried out - using from about 1 to about 10% by weight of a phase transfer agent, lime.

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v is based on a weight percentage basis of the total reaction mixture, selected from saturated fatty alcohol polyethoxylates, alkyl polyglucosides, linear glucamide surfactant and mixtures thereof.

This process is preferably carried out as follows:

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

(b) adding the N-alkyl-N-hydroxyalkylglucamine to the heated fatty acid ester and mixing to the extent necessary to form a two-phase liquid / liquid mixture;

(c) mixing the catalyst in the reaction mixture; and (d) stirring for the specified reaction time. Still preferably, about 2% to about 20% of the N-alkyl / N-hydroxyalkyl, N-glycosyl fatty acid amide product is added to the reaction mixture. , preformed, by weight of the reagents, as the phase transfer agent if the fatty ester is a triglyceride. This pulverizes the reaction, increasing its speed. A detailed experimental procedure is provided below, in the section entitled Experimental.

The polyhydroxy fatty acid amide materials used here also offer the advantages to the detergent formulator that they can be prepared entirely or mainly from natural, renewable, non-petrochemical and degradable raw material. They also exhibit low toxicity to aquatic life.

It should be recognized that together with the Formula (I) polyhydroxy fatty acid amides, the processes used to produce them will typically still produce quantities of non-volatile by-products, such as stearides and poly fatty acid amide. cyclic hydroxyl. The level of these by-products will vary depending on the particular reagents and process conditions. Preferably, the polyhydroxy fatty acid amide incorporated in the compositions of

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detergent thereof will be provided in such a form. that the polyhydroxy fatty acid containing composition added to the detergent contains less than about 2%, preferably less than about 0.5%, of the cyclic polyhydroxy fatty acid amide. The preferred processes described above have the advantage that they can preferably produce low levels of by-products, including this cyclic amide by-product.

Optional Ingredients

Liquid Conveyor

In a preferred embodiment, the detergent compositions of the present invention are liquid detergent compositions. These preferred liquid detergent compositions comprise from about 95% to about 35%, by weight, preferably from about 90% to about 50%, by weight, more preferably from about 80% to about 60%, by weight, from a liquid carrier, e.g. water, preferably a mixture of water and a C ^-C _Zi monohydric alcohol (e.g., ethanol, propanol, isopropanol, butanol and mixtures thereof), with ethanol being the preferred alcohol.

Composition pH

These liquid detergent compositions will preferably be formulated such that, during use in aqueous cleaning operations, the washing water will have a pH of between about 8 to about 10, more preferably between about 8.5 to about 9.5. The liquid product formulations of the present invention are prepared at a pH in the range of about 7.0 to about 11.0, preferably about 8.5 to about 10.5, more preferably about 8 , 8 to about 10.0. Liquid detergent compositions can adjust to these pH levels using methods known to those skilled in the art, for example, by adding a base to the compositions. Traditionally, liquid water washing compositions .; you have one. pH. around 7. It was found that when in the form

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Mod. 71 - 20,000 ex. - 90/08 of liquid detergent, the compositions of the present invention exhibit greatly improved fat cleaning if they are fined to an alkaline pH, compared to a pH below 7. This cleaning benefit arises only in relation to those with liquid detergent positions containing the present alkyl ethoxycarboxylate component. Surprisingly, the compositions of this invention are still very smooth compared to hands at this alkaline pH.

It is desirable to include a buffering agent for the purpose of preparing liquid detergent compositions having enhanced pH stability. Examples of typical buffering agents include, but are not necessarily limited to, glycine (preferred), N, 1T-bis (2-hydroxyethyl) glycine (preferred), tri (hydroxymethyl) aminomethane, triethanolamine, monoethanolamine, 2-amino-2 -ethyl-1,3-propanediol, 2-amino-2-methyl -1,3-propanidiol, N-methylldiethanolamine, 1,3-diamino-2-hydroxypronane and mixtures thereof. When included in liquid compositions prepared in accordance with the present invention, such buffering agents are typically present at a level of about 0.1% to about 15% by weight, preferably about 1% to about 7% % by weight, more preferably from about 1.5% to about 5% by weight.

Thickening Agent

The detergent compositions of the present invention can also be in gel form. Such compositions are typically formulated in the same way as liquid detergent compositions, except that they contain an additional thickening agent.

Any material or materials that can be mixed with aqueous liquids can be used in the compositions of this invention to provide shear dilution compositions, having sufficient production values. Materials such as colloidal silica, particulate polymers, such as polystyrene and oxidized polystyrene, combinations of certain surfactants, and water-soluble polymers, such as _ 1 6 _

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such as poly-acrylate are known to provide production values.

A preferred thickening agent useful in the compositions of the present invention is one. high molecular weight polycarboxylate polymer thickener. By high molecular weight we mean from about 500,000 to about 5,000,000, preferably from about 750,000 to about 4,000,000.

polycarboxylate polymer can be a carhoxyvinyl nomer. Such compounds are disclosed in U.S. Patent 2,798,053, which is incorporated herein by reference. Production processes of carboxyvinyl polymers are also revealed in Broun, and are also incorporated by reference.

A carhoxyvinyl polymer is an interpolymer of a monomeric mixture comprising carboxylic acid, olefinically unsaturated, monomeric, and from about 0.18 to about 108, by weight of the total monomers, of a polyether of a polyhydric alcohol, whose polyhydric alcohol contains at least four carbon atoms to which at least three hydroxyl groups are attached, the polyether containing more than one aleenyl group per molecule.

Other mono-olefinic monomeric materials may be present in the monomeric mixture, if desired, even in a predominant proportion.

Carboxyvinyl polymers are substantially insoluble in organic, volatile, liquid hydrocarbons and are dimensionally stable on exposure to air.

Preferred polyhydric alcohols used to produce carboxyvinyl polymers include polyols selected from the class consisting of oligosaccharides, their reduced derivatives in which the carbonyl group converts to an alcohol group, and pentaerythritol; most preferred are oligosaccharides and even more preferred is sucrose. It is preferred that the polyol hydroxyl groups, which are modified, are etherified with allyl groups, the polyol having at least two allyl ether groups in the polyol molecule. When the

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X 26.If/i99 'polyol is sucrose, it is preferred that sucrose has at least about five allyl ether groups per sucrose molecule. It is preferred that the polyether polyether comprises from about 0.1% to about 4% of the total monomers, more preferably. from about 0.2% to about 2.5%.

Carboxylic acids, olefinically unsaturated, monomeric preferred for use in the production of cai polymers. boxivinyls used here include lower aliphatic, mono-olefinically alpha-beta unsaturated, polymerizable, monomeric carboxylic acids; more preferred are acrylic, mono-olefinic, monomeric acids, of structure.

n

I

CH, = C - COOH in which R is a substituent selected from the group consisting of hydrogen and lower alkyl groups; most preferred is acrylic acid.

Carhoxyvinyl polymers useful in formulations of the present invention have a molecular weight of at least 750,000. Highly reticious carboxylic polymers are preferred. sides having a molecular weight of at least 1,250,000. Carbo-vinyl polymers having a molecular weight of at least 3,000,000 are also preferred, which can be less highly cross-linked.

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

Carbopol 934 is a very lightly cross-linked carhoxyvinyl polymer having a molecular weight of about 3,000,000. It has been described as a polyacrylic acid of

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high molecular weight cross-linked with about 1% polyalkyl sucrose all an average of about 5.8 allyl groups for each sucrose molecule.

Additional polycarboxylate polymers useful in the present invention are Sokolaan PHC-25 ^ - ^, a polyacrylic acid available from BASF Corp., and Gantrez ^ \ a poly (methyl vinyl ether / maleic acid) interpolymer available from GAF Corp.

Preferred polycarboxylate polymers of the preser. your invention, non-linear, water-dispersible poly-acrylic acid, cross-linked with a polyalkenyl polyether tends to have a molecular weight of about 750,000 to about 4,000,000.

Highly preferred examples of these thickened polycarboxylate polymers are the Carbopol 600 series of resins available from B.F. Goodrich. Especially preferred are Carbopol 616 and 617. These resins are believed to be more highly cross-linked than the 900 series resins and have molecular weights between about 1,000,000 and 4,000,000. Mixtures of polycarboxylate polymers as described herein can be used in the present invention. Particularly preferred is a mixture of the resins of the Carbopol 616 and 617 series.

The polycarbonate polymer thickener is preferably used with essentially non-clayey thickening agents, in fact, it has been found that if the polycarboxylate polymers of the present invention are used with clay in the composition of the present invention, a less desirable product results. phase instability. In other words, the polycarboxylate polymer is preferably used instead of clay as a thickening / stabilizing agent in the present composition.

polycarboxylate polymer also provides a reduction in what is commonly called bottle grip. This term refers to the inability to remove all dishwashing detergent product from the container that contains it. Without claiming to be limited by theory,

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it is said that the thickened compositions of the present invention provide this benefit because the strength of cohesion of the composition is greater than the strength of adhesion to the walls of the container. With clay thickeners, which the most commercially available products contain, clinging to the bottle can be a significant problem under certain conditions,

Without wishing to be bound by theory, it is believed that the long chain molecules of the polycarboxylate polymer help to suspend solids in the thicker detergent compositions of the present invention and help to keep the matrix expanded. The polymeric material is also less sensitive than clay thickeners to destruction due to repeated shearing, as occurs when. composition is mixed vigorously.

If the polycarboxylate polymer is used as a thickening agent in the compositions of the present invention, it is typically present at a level of about 0.1% to about 10%, preferably about 0.2%, to about; 2 % by weight.

Thickening agents are used to provide a production value of about 50 to about 350, and more preferably, about 75 to about 250.

Production Value Analysis Production value is an indication of the shear stress at which the gel strength is exceeded and flow is initiated. It is measured here with a Brookfield RTV viscometer model with a T-bar type B axis, at 25 ° C, using an upward Helipath pulse during asseed, readings. The system is placed at 0.5 rpm and a reading is made for the composition to be tested after 30 seconds or after the si? theme stabilize. Is the system stopped and the rpm reset? at 1.0 rpm. A reading is made for the same composition after 30 seconds or after the system has stabilized. The stress corresponding to zero shear is equal to twice the reading at 0.5 rpm minus the reading at 1.0 rpm. The production value is calculated as the shear stress at zero times 18.8 (conversion factor).

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£ 26.SEI1991

Other Surfactants

Other surfactants can also be incorporated into the detergent compositions of the present invention, such as anionic, non-ionic, ampholytic and zwitterionic surfactants.

Anionic Surfactant

One type of anionic surfactant that can be used encompasses alkyl ester sulfonates. These alkyl ester sulfonate surfactants including linear esters of carboxylic acids _the C _o -C _ (ie, fatty acids) which are sulfonated with gaseous SO ^ according to The Journal of the American Oil Chemical Society 52 (1975), pages 323 -329. Suitable starting materials should include natural fatty substances such as tallow derivatives, palm oil, etc.

Preferred alkyl-ester-sulfonate surfactant, especially for laundry applications, comprises alkyl-ester-sulfonate surfactants of structural formula:

R '

CH fi c

R 'is ₃ m in which R is a C _o -C' hydrocarbyl, preferably an al4 ° kilo, or combinations thereof, R and a C C-CC hydrocarbyl, preferably an alkyl, or combinations thereof, and M is a cation (J> which forms a water-soluble salt with the alkyl ester-sulfonate. Suitable salt-forming cations include metals such as sodium, potassium and lithium, and substituted or unsubstituted ammonium cations, such as diethanolamine monoethanolamine3 mine and triethanolamine. Preferably, R is a C, .4, ¹⁴ θ alkyl and R is methyl, ethyl or isopropyl. Especially preferred are the methyl estersulfonates in which R ³ is ^C 14 ^C 16 alkyl *

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Alkylsulfate surfactant

Mod. 71 - 20,000 ex. - 3/90

Alkylsulfate surfactants of this are water-soluble salts or acids of the formula ROSO ^ M in which R is preferably hydrocarbyl preferably alkyl or hydroxyalkyl having a C θ alkyl component, more preferably an alkyl or hydroxyalkyl and M is H or a cation, p . eg an alkali metal cation (eg, sodium, potassium, lithium) or substituted ammonium or ammonium (eg, methyl-, dimethyl- and trimethylammonium cations and quaternary ammonium cations, such as tetramethylammonium cations and cations dimethylpiperidinium and quaternary ammonium cations derived from alkylamines such as ethylamine, diethylamine, triethylamine and mixtures thereof, and the like). Typically, C _{2 to 2} g alkyl chains are preferred for low washing temperatures (e.g., below about 50 ° C) and alkyl chains are preferred for high washing temperatures (e.g. ., above about 50 ° C).

Alkylsulfate Alkylsulfate Surfactant

Alkoxylated alkyl sulfate surfactants dis. to salts or acids are soluble in water R0 formula (A) SO ^x m-1 in which R 3 is an alkyl or hydroxyalkyl group pQ ^C 24 ^{-C su} ^ tituido or unsubstituted alkyl having a component .25 ^C 10 ~ ^C

24, preferably C or hydroxyalkyl C

-CgO ^'Maas preferably an alkyl or hydroxyalkyl ^ 12 ^- ^ 18' ^one & ethoxy or propoxy unit, m is greater than zero, typically between about 0.5 and about 6, more preferably between about 0.5 and about 3 and M is H or a cation which can be, for example, a metal cation (eg, sodium, potassium, lithium, calcium, magnesium, etc.), ammonium cation or substituted ammonium. This includes ethoxylated alkyl sulfates as well as propoxylated alkyl sulfates. Specific examples of substituted ammonium cations include methyl-, dimethyl-, trimethylammonium cations and quaternary ammonium cations such as tetramethylammonium and dime35 cations

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tilpiperidinium and the derivatives of alkylamines such as ethylamine, diethylamine, triethylamine and mixtures thereof, and the like. Exemplary surfactants are alkyl polyethoxylate (1,0) alkylsulfate C ^ 2 ^{- (} ^ 18 1? ^- ^ 18 ^E ^ 'polyeth ° xylate (2.25) alkylsulfate ^ q2 ~ ^ 18 alkylsulfate Cy2 ^-C1 ₍ o, alkylsulfate 8 niently selected from sodium and potassium.

(C ₁ 2 ^] gE (2.25) M), polyethoxylate (3.0) (Ci2-Cj.gE (3.0) M) and polyethoxylate (4.0) (C _q nC-, _q E ( 4.0) M), in which M is used Other Anionic Surfactants

Other anionic surfactants useful for detersive purposes may be included in the compositions of this. These may include soap salts (including, for example, sodium, potassium ammonium and substituted ammonium salts, such as mono-, di- and triethanolamine salts), linear Cg-C2g alkylbenzenesulfonates ₅ primary and secondary alkanesulfonates ^ 8 ~ ^ 22 'f ^and fi ° ^nassu sulfonated polycarboxylic acids prepared ffonatos by sulfonating the product pirolizc citrates of alkaline earth metal, p. ex. , as described in the British patent specification N-. 1,082,179, Cg-02 ^ alkylpolyglycol ether sulfates (containing up to 10 moles of ethylene oxide); alkylglycerolsulphonates, fatty acylglycerolsulphonates, fatty oleylglycerolsulphates, alkylphenolylene oxide sulphates, paraffin sulphonates, alkylphosphates, isethionates such as acyl-isethionates, acyltaurates, fatty acid amides of sulfurates and monosaccharides especially ^monoesters ^ q2 ^{- <} ^ 14 i ^{nature <} Tos), di-esters of sulfosuccinates (especially diesters ^ 6 "^ ΐ2 unsaturated and saturated), acylsarcosinates, alkylpolysaccharide sulphates such as sewed alkyl polygluclates (the non-ionic monosulfated compounds described below), acyl-N- (Cy-C ^ alkyl) sulfates Cg-C ^ y or -H- (hydroxyalkyl C ^ -C ^) glucamine, branched primary alkyl sulfates and fatty acids esterified with isethionic acid and neutralized with sodium hydroxide. They are also ade23

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resinous acids and hydrogenated resinous acids, such as rosin, hydrogenated rosin and resinous acids and hydrogenated resinous acids present in or derived from tallow oil derivatives. Additional examples are described in Surface Active Agents and Detergents (Vol. 1 and II by Schwartz, Perry and Berch). A variety of these surfactants are still generally disclosed in U.S. Patent 3,929,678, issued December 30, 1975 to Laughlin, et al., Column 23 line 58 through Column 29, line 23 (incorporated herein by reference).

Nonionic Detergent Surfactants

Suitable non-ionic detergent surfactants are generally disclosed in U.S. Patent 3,992,9,678/, Laughlin et al., Issued December 30, 1975, in cc luna 13, line 14 through column 16, line 6, here , incorporated by reference. Exemplarily, non-limiting classes of non-ionic surfactants are listed below.

1. The polyethylene, polypropylene and polybutylene oxide condensates of alkyl phenols. In general, polyethylene oxide condensates are preferred. These compounds include the condensation products of alkylphenols, having an alkyl group containing from about 6 to about 12 carbon atoms, in either a straight or branched chain configuration, with alkylene oxide. In a preferred embodiment, ethylene oxide is present in an amount equal to about 5 to about 25 moles of ethylene oxide per mole of alkylphenol. Commercially available nonionic surfactants of this type include Igepol / CO-630, marketed by GAF Corporation; and Triton ^ ^M X-45, X-114, X-100 and X-102, all marketed by Rohm & Haas Company.

2. The condensation products of aliphatic alcohols with from about 1 to about 25 moles of ethylene oxide.

The alkyl chain of the aliphatic alcohol can be either straight or branched, primarily or secondarily, and generally contains about 8 to about 22 carbon atoms.

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Particularly preferred are the condensation products of alcohols having an alkyl group, containing from about 10 to about 20 carbon atoms, with about 2 to about moles of ethylene oxide per mole of alcohol. Examples of commercially available non-ionic surfactants of this type include Tergitol 15-S-9 (the condensation product of linear alcohol C. - C._ with 9 moles of ethylene oxide), TM 1 ι 1 □ „_

Tergitol 24-L-6NMW (the condensation product of primary alcohol C ^ ^- with 6 moles of ethylene oxide, with a restricted molecular weight distribution), both marketed by Union Carbide Corporation; Neodol 45-9 (the linear alcohol condensation product C _d . -C. _R with 9 moles „TM 'of ethylene oxide), Neodol 23-6.5 (the linear alcohol condensation product C ₁ „ -C ₁ - _? With 6.5 moles of oxide of

TM ι ζ ι j _ ethylene); Neodol 45-7 (the condensation product of alcohol

- Linear TM C.-C _{d [7} with 7 moles of ethylene oxide), Neodol 14 I 5

45-4 (the condensation product of linear alcohol C., - C.- with 14 1 moles of ethylene oxide), marketed by Shell CheTM mical Company, and Kyro EOB (the condensation product of linear alcohol C. „-C._ with 9 moles of ethylene oxide), marketed by The Procter & Gamble Company.

3. Condensation products of ethylene oxide with a hydrophobic base formed by the condensation of propylene oxide with propylene glycol. The hydrophobic portion of these components preferably has a molecular weight of about 1500 to about 1800 and exhibits insolubility in water. The addition of polyoxyethylene moieties to this hydrophobic moiety tends to increase the water solubility of the molecule as a whole and the liquid character of the product is maintained to the point where the polyoxyethylene content is about 50% of the total weight of the product. condensation, which corresponds to condensation with up to 40 moles of ethylene oxide. Examples of compounds of this type include certain commercially available Pluronic TM τ surfactants, marketed by BASF.

4. Condensation products of ethylene oxide with the product resulting from the propyl oxide reaction25

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not to eti.lenoHianii.na. The hydrophobic portion of these pipelines consists of the ethylene diamine reaction product of the excess of nitropylene oxide and generally has a molecular weight of about 2500 to about 3000. This hydrophobic portion is condensed with ethylene oxide from the condensation product containing from about 40 ^σ ί to about OO '?, nor weight, of polyoxyethylene and has a molecular weight of about 5,000 to about 11,000. Examples of this type of non-ionic surfactant include certain commercially available Tetronic compounds, marketed under SAS ¹⁷ .

5. Semi-nolar nonionic surfactants are a special category of non-tonic surfactants that include water-soluble amine oxides, containing an alkyl norm of about 10 to about 18 carbon atoms and 2 norms selected from the group consisting of groups hydroxyalkyl alkyl containing from about 1 to about 3 carbon atoms, phosphine oxides, water soluble, containing an alkyl portion of about 10 to about 13 carbon atoms and 2 portions selected from the group consisting of alkyl groups and hydroxyalkyl groups containing from about 1 to about 3 carbon atoms; sulfoxides, soluble in water, containing an alkyl portion of about 10 to about 18 carbon atoms and a selected portion of the gruno consisting of alkyl groups and hydroxyalkyl groups containing from about 1 to about 3 carbon atoms.

Semi-polar non-ionic surfactants include amine oxide surfactants

R ³ (orSxn (r ⁵ ) 2 in which R ~ is an alkyl, hydroxyalkyl or alkylphenyl group or mixtures thereof containing from about g to about 22 carbon atoms; R 'is an alkylene or hydroxyalkylene group containing from about 2 to about 3 carbon atoms or mixtures thereof; x is 0 to 3; and each R ³ is an alkyl group or

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hydroxyalkyl, containing from about 1 to about 3 carbon atoms, or a polyethylene oxide group containing, from about 1 to about 3 ethylene oxide groups. Groups 5

R can connect to each other, e.g. through an oxygen or nitrogen atom, to form a ring structure.

These amine oxide surfactants include, in particular, alkyldimethylamine oxides and C _o C ._- oxy -: _

IU of alkoxyethyl di- = ^C 3 ~ ^c -] 2 hydroxyamines

6. Alkyl polysaccharides are disclosed in U.S. Patent 4,565,647, Llenado, issued January 21, 1986, having a hydrophobic group containing from about 6 to about 30 carbon atoms, preferably from about 10 to about 16 atoms carbon and a polysaccharide, e.g. : ex. , a polyglycoside, hydrophilic group containing from about 1.3 to about 10, preferably from about 1.3 to about 3, more preferably from about 1.3 to about 2.7 saccharide units. Any reducing saccharides containing 5 or 6 carbon atoms, e.g. e.g., glucose, galactose and galactosyl moieties can be replaced with glucosyl moieties. (Optionally, the hydrophobic group is attached at positions 2-, 3-, 4-, etc., thus giving glucose or galactose as opposed to a glucoside or galactoside). Intersaccharide bonds can be, e.g. between position one of the additional saccharide units and positions 2-, 3-, 4e and / or 6- in the preceding saccharide units.

Optionally, and less desirably, there may be a polyalkylene oxide chain joining the hydrophobic portion and the polysaccharide portion. The preferred alkylene oxide is ethylene oxide. Typical hydrophobic groups include alkyl groups, whether saturated or unsaturated, branched or unbranched, containing from about 8 to about 18, preferably from about 10 to about 16 carbon atoms. Preferably, the alkyl group is a straight chain saturated alkyl group. The alkyl group contains up to about 3 hydroxy groups and / or the polyalkyl oxide straight chain contains up to about 10, preferably less than 5, δxi portions

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of the alkylene ds. Suitable polysaccharides are octyl, nonildecyl, undecildodscyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl and octadecyl, di-, tri-, tetra-, penta- and hexaglucosides, galactosides, lactosides, glucoses, fruits and nuts and / or. Suitable mixtures include alkyl, di-, tri-, tetra and coconut pentaglucosides and tallow alkyl, tetra-, penta- and hexaglucosides.

Preferred alkyl polyglycosides have the formula

R ² O (C n 2n

0) _t (glycosyl).

in which R is selected from the group consisting of alkyl, alkylphenyl, hydroxyalkyl, hydroxyalkylphenyl and mixtures thereof, in which the alkyl groups contain from about 10 to about 18, preferably from about 12 to about 14, carbon atoms ; n is 2 or 3, preferably 2; t is 0 to about 10, preferably 0; and x is from about 1.3 to about 10, preferably from about 1.3 to about 3, more preferably from 1.3 to about 2.7. The glycosyl is preferably derived from glucose. To prepare these compounds, alcohol or alkyl polyethoxy alcohol is first formed and then reacted with glucose, or a source of glucose, to form the glycoside (bond in position 1). The additional glycosyl units may link between their 1- position and the 2-, 3-, 4 ~ and / or 6- positions of the preceding glycosyl units, preferably predominantly the 2-,

7. Fatty acid amide surfactants having the formula:

c - n (r ') ₂ in which R' is an alkyl group containing from about 7 to about 21 (preferably from about 9 to about 17) carbon atoms and each R ² is selected from the group consisting of hydrogen , C ^-C ^ alkyl, C ^-C ^ hydroxyalkyl and - (CpI ^ O ^H wave x ranges from about 1 to about 3.

2.8

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Preferred amides are ammonia-amides Οη-Ο? Θ, with noethanolamides, diethanolamides and isopropanolamides. Ampholytic Surfactants

Ampholytic surfactants can be incorporated into the detergent compositions thereof. These surfactants can be widely described as aliphatic derivatives of secondary and tertiary amines, or aliphatic derivatives of heterocyclic amines,. secondary and tertiary, in which the aliphatic radical can be linear or branched. One of the aliphatic substituents contains at least 8 carbon atoms, typically 8 to 13 carbon atoms, and at least one contains an anionic water solubilizing group, e.g., carboxy, sulfonate, sulfate. See U.S. Patent U ² . 3,929,678, issued December 30, 1375, to Laughlin et al., In column 19, lines 13-35 (incorporated herein by reference) for examples of ampholytic surfactants. Zwlterionic surfactants

Zwitterionic surfactants can also be incorporated into the detergent compositions thereof. These surfactants can be widely described as derived from secondary and tertiary amines, derived from secondary and tertiary heterocyclic amines or derived from quaternary ammonium, quaternary phosphonium or tertiary sulfonium compounds. -See U.S. Patent ^Nos. 3,929,678, issued on December 30, 1975, to Laughlin et al., In column 19, line 38 through column 22, line 48 (incorporated herein by reference) for examples of zwitterionic surfactants.

In general, zwitterionic and ampholytic surfactants are used in combination with one or more anionic and / or nonionic surfactants.

Further preferred surfactants are anionic and nonionic surfactants with alkyl ester sulfonates C₁-y _9, primary and secondary alkane _C₁-9 2 'alkyldimethylamine oxides alquilpolissa

- 29 Case: 4262 R

and their mixtures are the most preferred.

If included in the compositions of the present invention, these optional additional surfactants are, thioicanically, present in a concentration of about 1.08 to about 108, preferably from about 28 to about 58, by weight

Other Optional Ingredients

Other optional ingredients include intensifi. Detergent cleaners, both organic and inorganic, although in general, such enhancers are not preferred for use in the composition of the present invention. Examples of water-soluble inorganic intensifiers that can be used, either alone or mixed with each other or with intensifying salts. alkaline, organic sequestering scavengers are glycine, alkyl and alkenyl silicates, alkali metal carbonates, phosphates, polyphosphates and silicates. Specific examples of such salts are sodium tripolyphosphate, sodium carbonate, potassium carbonate, sodium pyrophosphate, potassium pyrophosphate, potassium tripolyphosphate and hexanetaphosphate alone. hate. Examples of organic intensifier salts that can be used alone, or in mixture with each other or with the preceding inorganic alkaline intensifier salts, are alkali metal polycarboxylates, examples of which include, but are not limited to, water soluble citrates such as citrate sodium and potassium tartrate, sodium and potassium tartrate, ethylenediaminetetra. sodium and potassium acetate, sodium and potassium N- (2-hydroxyethyl) -ethylenediaminetriacetates, sodium and potassium nitrilotriacetates, sodium N- (2-hydroxyethyl) -nitrilodiacetates and potassium, sodium and potassium oxisuecinates, tartaratomone- and sodium and potassium di-succinates, such as those described in U.S. Patent 4,663,071 (Bush et al., issued May 5, 1937), the disclosure of which is here incorporated. Other organic detergency enhancers, such as water-soluble phosphonates, can be used in the compositions of the present invention. However, detergency enhancers in general have an IjL value

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broken when the compositions of the present invention are in the form of liquid detergent combinations for washing lightly soiled dishes. If included in the compositions of the present invention, these optional enhancers are typically present in a concentration of about 1.0% to about 10%, preferably from about 2% to about 5% by weight.

Other desirable ingredients include diluents, solvents, pigments, nerfunes and hydrotopes (preferred). Diluents can be inorganic salts, such as sodium and potassium sulfate, ammonium chloride, sodium and notassium chloride, sodium bicarbonate, etc. Diluents useful in the compositions of this invention are typically present in levels of about 1% to about 10%, preferably about 2% to about 5%, by weight.

Solvents useful here include water and low molecular weight alcohols, such as ethyl alcohol, isopropyl alcohol, etc. Solvents useful in the compositions of the present invention are typically present in levels of about 1% to about 60%, preferably> to about 5% ' ^y ''' about '^; 50% by weight.

Hydrotropes such as sodium and potassium toluenesulfonate, sodium and potassium xylenesulfonate, sodium and potassium cumenesulfonate, trisodium and tripotassium sulfosuccinate and related compounds (as disclosed in U.S. Patent 3,915,903, the disclosure of which is incorporated herein, may be used. ) in the interest of achieving a desired viscosity and phase stability of the product. Hydrotropes have been found to have a positive effect on the foam benefit of the present invention. Although not intended to be limited by theory, it is believed that this benefit is due to the viscosity characteristics of such hydrotropes. Hydrides useful in the compositions of the present invention are typically present at levels from about 1% to about 10% by weight, preferably from about 2% to about 5% by weight.

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Mod. 71 - 20,000 ex. - 8/90

The claimed compositions of the present invention are advantageous in that they provide unexpectedly improved foaming performance when the particular polyhydroxy acid acid amide combines with the alkyl ethoxycarboxylate. While not intended to be limited in theory, it is believed that the compositions of the present invention have the added benefit of improved cleaning performance and are gentle to the skin, even when formed as a liquid and having a high alkaline pH. In addition, although not intended to be limited by theory, it is further believed that the additional benefit of the compositions of the present invention is that they clean dishes without imparting a greasy feeling to the finished product. this is especially important in consumer markets where the cleanliness of dishes is assessed by the deficiency of such a greasy sensation. In addition, it is believed that the compositions of the present invention still have the benefit of a slippery feel, typically associated with de-detergent compositions. This is especially important in consumer markets where such a sensation is not favored and is seen as an uncompromising rinse of surfactants from the surface of the dishes.

From the point of view of the process of the present invention, the anode is contacted with an effective amount, typically from about 0.5 ml to about 20 ml (per 25 pieces of dishes to be treated), preferably about 3 ml at about 10 ml of the composition of the present invention. The actual amount of detergent composition used will be based on the user's discretion and will typically depend on factors such as the particular product formulation of the composition, including the active ingredient composition in the composition, the number of pieces of sodden dishes to be cleaned, the degree of staining of dishes and the like. In turn, the formulation of a particular product will depend on a minimum of factors, such as the market for the composition of the product (eg, Europe, Japan, etc.). The following examples 32

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26. T.1991> ’°

Mod. 71 - 20,000 ex. - 90/08 .20 tees are typical processes in which the detergent compositions of the present invention can be used to clean anodized dishes. These examples are for illustrative purposes and are not intended to be limiting.

In a typical US order, from about 3 ml to about 15 ml, preferably from about 5 ml to about 10 ml, a liquid detergent composition with from about 1,000 ml to about 10,000 ml is combined, more typically from about 3,000 ml to about 5,000 ml, of water in a basin having a volumetric capacity in the range of about 5,000 ml to about 20,000 ml, more typically from about 10,000 to about 15,000 ml. The detergent composition has a surfactant concentration of about 21% to about 44% en weight, preferably from about 25% to ^J 40% by weight. The anodized dishes are immersed in the basin containing the detergent and water composition where they are cleaned by contacting the anodized surface of the dishes with a cloth, sponge or similar article. The cloth, sponge or similar article can be immersed in the mixture of the detergent and water composition before being put in contact with the surface of the dishes and, typically, it is contacted with the surface of the dishes for a period of time in the range of about 1 to about 10 seconds, although our real time will vary with each order and user.

Contact of the cloth, sponge or similar article with the surface of the dishes is accompanied by a simultaneous brushing of the dishes.

In a typical European market application, from about 3 ml to about 15 ml, preferably from about 3 ml to about 10 ml, are combined with a liquid detergent composition from about 1,000 ml to about 10,000 ml , preferably from about 3,000 ml to about 5,000 ml, of water in a bowl having a volumetric capacity ranging from about 5,000 ml to about 20,000 ml, more typically from about 10,000 ml to about 15,000 ml. The detergent composition has a surfactant concentration of about 21% to about 44% by weight, preferably 35

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from about 25% to 35% by weight. The anodized crockery is tightened in the basin containing the detergent and water composition, where it is cleaned by contacting the crocheted surface of the crockery with a cloth, sponge or similar article. The nano, sponge or similar article can be immersed in the mixture of the detergent and water composition before being brought into contact with the surface of the dishes and, typically, made contact with the surface of the dishes for a period of time in the range of about 1 to about 10 seconds, although the actual time may vary with each application and user. The contact of the cloth, sponge or similar article with the surface of the dishes is accompanied by a simultaneous brushing of the surface of the dishes.

In a typical auction in the Latin American and Japanese market, from about 1 ml to about

Mod. 71 - 20,000 ex. - 90/08 ml, preferably from about 2 ml to about 10 ml, of a liquid detergent composition with from about 50 ml to about 2,000 ml, more typically from about 1,000 ml, of water in a bowl having a

100 ml volumetric capacity in the range of about more typically about 500 ml to about 5,000 ml, 500 ml to about 2,000 ml. The detergent composition has a surfactant concentration of about 5% to about 40% by weight, preferably from about 10% to about 30% by weight. The anodized dishes are immersed in the basin containing the detergent and water composition, where they are cleaned by contacting the anodized surface of the dishes with a cloth, sponge or similar article. The cloth, sponge or similar article can be immersed in the mixture of the detergent and water composition before being put in contact with the surface of the dishes and, typically, it is contacted with the surface of the dishes for a period of time in the range. about 1 to about 10 seconds, although the actual time may vary with each application and user. The contact of the cloth, sponge or similar article with the surface of the dishes is preferably accompanied by a simultaneous brushing of the surface of the dishes.

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26.SEfl991

Another method of use will comprise immersion of crockery in a water bath in which there is no liquid dishwashing detergent. A device for absorbing liquid dishwashing detergent, such as one, is placed. sponge, directly in a separate amount of undiluted liquid dishwashing composition for a period of time, typically in the range of about 1 to about. 5 seconds. The absorbent device, and consequently the diluted liquid dishwashing composition, is then individually contacted with the surface of each anodized dishware to remove said dirt.

absorbent disoositive will typically be put in contact with each ¹ Oeca of dishes for a period of time in the range of about 1 to about 10 seconds, although the actual time of application will depend on factors such as the degree of soiling of the crockery. The contact of the absorbent device with the surface of the dishes is accompanied by a simultaneous brushing.

EXPERIMENTAL

This exemplifies a process for producing an N-methyl, 1-deoxyglucityl-lauramide surfactant for use here. Although an expert chemist can vary the configuration of the apparatus, a suitable apparatus for use here comprises a three-liter, four-necked glass flask fitted with a motor-driven paddle stirrer and a thermometer of sufficient length to contact the medium. reaction. The other two glass tube necks are fitted with a nitrogen circuit and a wide orifice side arm (warning: a wide orifice side arm is important in the case of very rapid evolution of methanol) to which it is attached an efficient collection condenser and vacuum outlet. Connect σ · preceding a nitrogen purge and a vacuum indicator, then a vacuum cleaner and a siphon. A heating blanket is then placed35

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500 watt unit with a variable transformer temperature controller, (Variac), used to heat the reaction in a mobile laboratory support that can easily be lifted or lowered for additional control of the reaction temperature.

(195 g, 1.0 & Gamble CE

Place in a soft flask, Aldrich, M47OO-O) and 1270, 220.9 g, 1.0 mole).

glass N-methylglucamine methyl laurate (Procter The solid / liquid mixture is heated with stirring under a nitrogen circuit to form a melt (approximately 25 minutes).

(powdered sodium carbonate, anhydrous, 10.5 g, 0.1 mole, J.T. Baker). The nitrogen circuit is removed and the aspirator and nitrogen purge are adjusted to give 5 inches (5/31 atm) of vacuum Hg. From this point, the temperature of the

and / or raising or lowering the blanket.

Within 7 minutes, the first methanol bubbles are seen in the meniscus of the reaction mixture. A vigorous reaction soon follows. The methanol is distilled until its speed drops. The vacuum is adjusted to give 10 inches of Hg (10/31 atm) of vacuum. The vacuum is increased approximately as follows (in inches of Hg to minutes): 10 to 3.20 to 7.25 to 10. After 11 minutes from the beginning of the evolution of methanol, heating and stirring are discontinuous, coinciding with some foaming. Cool and solidify the product.

The following examples are intended to emulate compositions of the present invention, but are not intended to limit or in any way define the scope of the invention, said scope being defined according to the following claims.

EXAMPLES

The following examples illustrate the practice of the present invention but are not intended to limit it.

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The following three formulations A, B and

EXAMPLE I

C of the present invention are prepared according to the description presented below:

Formulation A is produced by initially combining a mixture of alkyl ethoxycarboxylate detergent with a C-fatty acid N-methylglucamide | ₂ _ ^ ₍ , _; to form a mixture. Then sodium chloride and sodium xylenesulfonate are added to that mixture. Then any desired surfactants are added. Glycine is added and the pH is adjusted to about 9.0 with sodium hydroxide Finally, magnesium chloride is added which consequently reduces the nH. At this point, the final adjustments of viscosity and pH are made, followed by the addition of perfume and pigment. The rest is water.

Formulation B is produced by adding sodium chloride ethanol and sodium xylenesulfonate to a mixture of polyhydroxy fatty acid alkyl-ethoxycarboxylate / amide, of the type prepared in Formulation A. The remaining components of the formula are added in order given in the table below.

Formulation C is produced by adding sodium chloride ethanol and sodium xylenesulfonate to a mixture of polyhydroxy fatty acid alkyl-ethoxycarboxylate / amide, of the type prepared in Formulation A. Nonoethanolamide C ₁ '2-] is heated 4 ^{at about} 65 ° C and then added to the mixture. At this time minor adjustments are made to the pH and viscosity followed by the addition of pigment, perfume and water to bring the formulation to 100%.

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Case: 4262 R z Zr / · / d. // - 0 0 Λ. \ z ^j #z O ~] • 26. SET. 1991 ^% ok? V s in Weight Formulation Formulation Formulation THE B Ç Component Alkyl-ethoxy (med.2,8) carboxylate C, _η , from ζ,. 13-1 '4 sodium 20.0 20.0 15.0 C ₁₉ fatty acid N-methylglucamide 5.0 5.0 5.0 C ₁₀ alkylethoxy alcohol - - 5.0 Alkyl-ethoxy (med.0,3) sodium sulfate 3.0 - - Methyl ester sulfonate ^ C- fatty acid-, D ', Sodium ^{12' 14} 4.0 Alkyl-ethoxy (med.3,0) C sulfate, _{9 q} „sodium 4.0 A1qu i1d ime t ilb ata ina ^C 12-14 3.0 - Alkyldimethylamine oxide ' 3.0 5.0 5.0

Acid monoethanolamine

fat C _l2 _ _u "- 4.0 So magnesium (added as MgCly.ôHyO) 'o; 76 0.76 0.76 Glycine 4.0 - - Trisodium sulfosuccinate 2.0 2.2 2.0 Ethanol 7.5 7.0 7.0 Sodium chloride 1.5 <1 2.25 product pill 9.0 9.0 9.0 Perfume and pigment 0.15 0.15 0.15 Water Remaining Remaining Restant

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Mod. 71 - 20,000 ex. - 90/08 * The surfactant mixture containing sodium alkyl ethoxycarboxylate is prepared according to the process outlined below XO ·

1. An alkylethoxy alcohol (med.3,0) 2-1 'is reacted with sodium t-butoside and sodium chloroacetate in a 1: 1.1: 1.1 ratio in the initial mixture of the alkyl ethoxylate with sodium otoxide at about 60Â ° C and an incidence of about 3.67 x 10 Pa (20 mm Hg) for about 1 hour. After that, 0 t-butanol is continuously removed from the reaction mixture by distillation. The vacuum is then broken and sodium chloroacetate is added with mixing. The pressure is restored at about 2.40-2.67x10 ³ Pa (13-20 mm Hg) and the reaction is allowed to proceed for about 3 hours. Subsequently, the reaction pressure is brought to the level of atmospheric stress and the forged heating coils are removed. the reaction mixture is left in this state overnight. The next day, the temperature is increased and the pressure of the reaction mixture is decreased to remove t-butanol from the system. The reaction mixture is then added to a? aqueous solution of hydrochloric acid containing 105% of the amount theoretically necessary to neutralize the sodium t-butoside added initially. The aqueous, acidic reaction product is heated to force the phase separation of the organic and aqueous materials. The organic phase is collected.

2. Repeat Step 1, above, using an alkyl ethoxyl alcohol (med. 2.7) C ^ 2_-3 ° a ratio of this ethoxyl alcohol to sodium t-butoxide and sodium chloroacetate of 1 : 1.3: 1.3. Sodium t-butoxide is added to the alkyl ethoxylate, which is at a temperature of 32.2 ° C, and then the reaction mixture is increased to about 76.7 ° C. The vacuum pump is then switched on to reduce stress. The reaction temperature is increased to about 104.4 ° C and the t-butanol which is collected over a period of about 30 minutes is removed. Sodium chloroacetate is then added to the mixture.

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Mod. 71 -20,000 ex. - 8/90>

reaction mixture, which was cooled slightly to about 66 ° C. The reaction is mixed for about 1.5 hours, cooled and then added to an aqueous solution of hydrochloric acid sufficient to reach 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 49θΟ. The top organic layer is collected and the washing process is repeated.

3. The surfactant mixtures produced in Steps 1 and 2 above are mixed, in a ratio of 40.4 to 59.6. A larger portion of this surfactant mixture combined with. 50% sodium hydroxide at a pH of about 8 and about 50% diluted with a 25/75 mixture, by volume and water and ethanol. The resulting solution is continuously extracted at room temperature with hexanes for about 4 days. The lower aqueous phase is collected and some ethanol and water are removed by heating to produce a slurry containing the alkyl ethoxycarboxylate containing the des-_ surfactant mixture. below.

In the formulations of Example 1, above, the surfactant moiety contains about 93.9% alkyl-ethoxycarboxylate of formula RO (CE ^Cí ^O) Cí ^C00-Na ⁺ , in which R is ^C 12 ~alkyl 13 ^{in an} average of 12.5, x is from 0 to about 10 and the distribution of ethoxylate is such that the amount of material where x is 0 is about 2.8% and the amount of material where x is greater than 7 is less than about 2% by weight of the alkyl ethoxylates. The average x in the distribution is .2.8.

The surfactant mixture also contains about 6.1% alcohol ethoxylates of formula R0 (CH „CH„ 0) H, R being alkyl

Ct Ct X ^C 12 ~ 13 ^{at an} average of 12.5 average eox = 2.8. The surfactant mixture contains 0% · of soap materials.

EXAMPLE ΙΙΞ

The following three formulations C, D and E of the present invention were prepared in the same way as the formulations of Example I:

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Case: 4262 R

Oa?

Uf> .sÉT.fl | i in neso

Component C

Alkyl ethoxy (med.2.8) C- _{] 9} _ ₁ / sodium carboxylate * ⁴ 15.0

F,

Mod. 71 - 20,000 ex. - 8/90

Alkyl-N-methylglucide C-, _o ,

12-14

Alkylethoxy alcohol (med.8) C-, θ

Alkyl-ethoxy (med.0.8) sodium sulfate

ÉsterQf methyl-sulfone fatty acid to 12-14 ^ ^c ^ ^and

Alkyl-ethoxy (med.3,0) C ₁₂ _, ₄ sodium sulfate

Alkildimet ilbetaine ^C 12-14

Alkylldiniethylbetaine ^C 14-16

C ₁₂ _ _u fatty acid diethanolamine

C ^ ₂ _ ₁₄ fatty acid monoethanolamine

Magnesium ion (added as MgCl ₂ .6H _? 0)

Glycine

Ν, N-b i s (2-bi dr ox i and t i1) glycine

Me t i1d i e t ano1amIna

CocoamidopropildimetH betaine

5.0

5.03.0

4.0

0? 76

4.0

20.0 15.0 10.0 12.0

5.0 5.0 10.0 10.0

4.0

5.0

5.0

5.0 - 10.0

4.0

4.0

3.0

1.0

3.0

10.0 - 10.0

3.0

1.0

1.0

0.'76 0.76 0.3 0.5 0.5

5.0 3.0

- 10.0

3.0

3.0

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Dimethylamine oxide ^C 12-14

Trisodium sulfosuccinate 2.0 2.2 2.0 - - - Ethanol 7.5 7.0 7.0 5.0 5.0 5.0 Sodium chloride 1.5 <1 2.25 - - - product pH 9.0 9.0 9.0 9.0 3.0 8.0 Perfume and pigment 0.15 0.15 0.15 0.15 0.15 0.15 Monoethanolamine - - - 5.0 5.0 - Triethanolamine - - - 5.0 - 4.0 Water - Remaining until 100% - -

* The surfactant mixture containing sodium alkyl ethoxycarboxylate is prepared according to the process disclosed in Example I.

EXSMPLO III

An alternative process for repairing polyhydroxycarboxylic fatty acid amides used herein is as follows. A reaction mixture consisting of 84.87 g of fatty acid methyl ester (source: Procter Sc Gamble methyl ester CE127O), 75 g of N-methyl-D-glucamiia (source: Aldrich Chemical Company M4700-0) is used , 1.04 g of sodium methoxide (source: Aldrich Chemical Company 16.499-2) and 68.51 g of methyl alcohol. The reaction vessel comprises a standard reflux assembly fixed with a drying tube and a stir bar. In this procedure, N-methylglucamiria is combined with methanol with stirring under argon and heating is started with a good mixture (stir bar) : reflux). After 12 _T 20 minutes, when the solution reaches the desired temperature, the ester and sodium methoxide catalyst are added. Samples are taken periodically to control the reaction, but note that the solution is completely clear in 63.5 minutes. The reaction is judged,

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in fact close to being finished at this point. The reaction mixture is refluxed for 4 hours. After removal of methanol, the recovered crude product weighs 156.16 grams. After drying under vacuum and purification, a total purified product production of 106.92 grams is recovered. However, the percentage of yield in this ha is not calculated, since as regular sampling throughout the course of the reaction a less significant overall yield value is obtained ·.

The following is not intended to limit the invention included here, but it is simply still to illustrate additional aspects of the technology that can be considered by the formulator in the production of a wide variety of detergent compositions using polyhydroxy fatty acid amides.

Appreciate

It is easily understood that polyhydroxy fatty acid amides are, due to their amide bond, subject to some instability under highly basic or highly acidic conditions. Although some decomposition can be tolerated, it is preferred that these materials are not subjected to pH above 11, preferably 10, or below about 3 for excessively long periods. The pH of the final product (liquids) is tinically 7.0-9.0.

During the introduction of amides the

of polyhydroxy fatty acid it will typically be necessary to neutralize, at least partially, the basic catalyst used to form the amide bond. Although no acid can be used for this purpose, the detergent formulator will recognize that it is a simple and convenient matter to use an acid that provides an anion that is otherwise useful and desirable in the finished detergent composition. For example, citric acid can be used for neutralization purposes and the resulting citrate ion (ca. 1%) is left with a polyhydroxy fatty acid amide slurry. 40% and is pumped into the final production steps of the overall detergent production process. Similarly, acidic forms of materials such as oxisuccinate, nitrile-43 can be used

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Case: 4262 R

'4 H' 5} ^V 26.If/i99^ you

I triaetate, ethylenediaminetetraacetic, tartrate / succinate and the like.

The polyhydroxy fatty acid amylates derived from coconut alkyl fatty acids (predominantly 'CC-C ^)) are more soluble than their tallow alkyl additives (predominantly' C ^-Cp _p ). h is according to the materials t2 ^ '^ ^s * 14 ° nal ^{un nouco} easy to formulate in liquid compositions , and are more soluble in laundry baths of cold water. However, C ^^ - C ^ materials are also quite useful, especially under circumstances where tepid-hot wash water is used. In fact, Cj ^ “C ·, g materials may be better detersive surfactants than their complementary ones and according to this, the formulator may want to make a balance between ease of production vs. performance when selecting products. a particular polyhydroxy fatty acid amide for use in a given formulation.

It will also be appreciated that the solubility of the polyhydroxy fatty acid amides can be increased by having unsaturation points and / or branched chain in the fatty acid portion. Thus, materials such as polyhydroxy fatty acid amides derived from oleic acid and isostearic acid are more soluble than their complementary n-allylics.

In a similar manner, the solubility of polyhydroxy fatty acid amides prepared from disaccharides, trisaccharides, etc., will generally be greater than the solubility of their complementary monosaccharide-derived materials. This increased solubility can be of particular help when formulating liquid compositions. In addition, the polyhydroxy fatty acid amides in which the polyhydroxy group is derived from maltose appear to function especially as detergents when used in combination with alkylbenzenesulfonate surfactants. (LAS). Although not intended to be limited in theory, it appears that the combination of LAS with poly / z fatty acid amides

63,873

-hydroxyl derivatives derived from superior de-saccharides, such as maltose, give rise to a substantial and unexpected decrease in interfacial tension in an aqueous medium, thus reinforcing the overall detergency performance. (The production of a maltose-derived polyhydroxy fatty acid amide is described hereinafter).

Polyhydroxy fatty acid amides can be produced not only from purified sugars but also from hydrolyzed starches, o-, e.g. , wheat starch, potato starch or other starch derived from a suitable plant containing the mono-, dl, etc., saccharide desired by the formulator. This is of particular importance from an economic point of view. Thus, glucose-rich wheat syrup, glucose-rich wheat syrup etc. can conveniently and economically be used. The de-defaced cellulose pulp can also provide a source of raw material for the polyhydroxy fatty acid amides.

As noted above, polyhydroxy fatty acid amides derived from higher saccharides, such as maltose, lactose, etc., are more soluble than their glucose complementary. In addition, it has been found that the more soluble polyhydroxy fatty acid amides can help to solubilize their less soluble complementary substances, to varying degrees. Accordingly, the formulator may elect for use a raw material comprising glucose syrup rich in wheat, for example, but not salify a syrup that contains a small amount of maltose (eg, 1% or more). The resulting mixture of polyhydroxy acids will generally exhibit lower solubility properties. wounds over a wider range of temperatures and concentrations than a polyhydroxy fatty acid amide derived from other glucose. Thus, in addition to any economic advantages o using sugar mixtures more than any pure sugar reagents, polyhydroxy fatty acid amides prepared from mixed sugars can offer many substantial advantages with respect to

63,878

Case: 4262 R to performance and / or ease of formulation. On some occasions, however, you may notice some loss of fat removal (dishwashing) performance at fatty acid maltamide levels above about 25% and some loss in foaming above about 33% (said percentages being the percentage of polyhydroxy fatty acid amide derived from maltamide vs. polyhydroxy fatty acid amide derived from glucose in the mixture). This can vary slightly, depending on the chain length of the fatty acid portion. Typically, after the formulator chooses such mixtures for use, he may discover advantages in selecting mixtures of polyhydroxy fatty acid amide which contain monosaccharide ratios (eg, glucose) over higher di-saccharides (eg ., maltose) from about 4: 1 to about 99: 1.

The production of non-cyclized, preferred polyhydroxy fatty acid amides from fatty esters and N-alkylpolyols can be carried out in solvent solvents at temperatures of about 30 ° C to about 90 ° C, preferably about 50 ° C. ° C-80 ° C. It has now been determined that it may be convenient for the formulator of, for example, liquid detergents to conduct such a process in 1,2-propylene glycol solvent, provided that the glycol solvent does not need to be completely removed from the reaction product before use in the formulation of finished detergent. Similarly, the formulator of, for example, detergent compositions, typically granular, solid may find it convenient to carry out the process at 30 ° C-90 ° C, in solvents comprising ethoxylated alcohols, such as ^c ^ ₂ “- alcohols C ^ ethoxylates (E0 3-8), such as those available as NEODOL 23 EO6.5 (Shell). When such ethoxylates are used.,; it is preferable that they do not contain substantial amounts of non-ethoxylated alcohol: and, more preferably, they do not contain substantial amounts of mono-ethoxylated alcohol. (Designation T).

Although the production processes of polyhydroxy fatty acid amides per se are not part of the invention.

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Mod. 71 - 20,000 βχ.

included herein, the formulator may also take into account other syntheses of polyhydroxy fatty acid amides, as described hereinafter.

Typically, the industrial-scale reaction sequence for preparing the preferred polyhydroxy fatty acid amides will comprise: Step 1 - preparation of the N-alkylpolyhydroxyamine derivative from the sugar, or mixture of sugars, desired by forming an adduct of the N-alkylamine and sugar, followed by the reaction with hydrogen in the presence of a catalyst, followed by Step 2 reaction of the aforementioned polyhydroxyamine with, preferably, a fatty ester to form an amine bond. Although a variety of N-alkylpolyhydroxyamines useful in Step 2 of the reaction sequence can be prepared by various processes disclosed in the art, the following process is convenient and makes use of economical sugar syrup as raw material. It must be understood. that, for best results when using such raw syrup materials, the manufacturer must select syrups that have a slight color or, preferably, are almost colorless (water bank).

Preparation of N-alkylpolyhydroxyamine. THE : ____

From Sugar Syrup Derived from Plants.

I. Adduct Formation - The following is a standard process in which about 420g of about 55% glucose solution is reacted (wheat syrup - about 231g of glucose - about 1.28 moles), having a Gardner color of less than 1, with about 119 g of 50% aqueous methylamine solution (59.5 g of methylamine - 1.92 moles). Purge the methylamine solution (ΝΜΆ), protect with N ₂ and cool to about 10 ° C, or less. Purge the wheat syrup, protect with N ₂ at a temperature of about 10 ° C-20 ° C. Wheat syrup is added slowly to the MMA solution at the indicated reaction temperature, as seen.

Color Gardner is measured in the approximate terms indicated in minutes.

63,378 Case:

4262 R

TABLE 1

Time in minutes 10 30 60 120 130 240 Temp. reaction ⁰ Ç Gardner Color (Approximate) 0 1 1 1 1 1 1 20 1 i 1 1 1 1 30 Ί J. 1 2 2 4 5 50 Zj 6 10 - - As if can see peies above data, í ι Color Gardner for the adduct is much worse when the temperament gg Θ take here

at 30 ° C and around 50 ° C, the time the adduct has a Gardner Color below 7 is only about 30 minutes. For longer reactions and / or waiting times, the temperature must be less than about 20 ° C. Gardner Color must be less than 7 and preferably less than 4 for good glucamine staining.

.When low temperatures are used for the formation of the adduct, the time to achieve substantial balance of concentration of the adduct is shortened by the use of higher ratios of amine to sugar .. With the molar ratio of amine to sugar of 1 , 5: 1 mentioned, the equilibrium is reached in about two hours and the reaction temperature is about 30 ° C. At a 1.2: 1 molar ratio, under the same conditions, the time is at least about three hours. For a good coloring, the combination of the amine: sugar ratio is selected; reaction temperature; and reaction time to achieve substantially a. equilibrium conversion, e.g., more than about 90.11, preferably more than about 95%, even more preferably more than about 99%, based on sugar, and a color that is less than about 4 of 7, preferably less than about 4, more preferably less than about 1, for the adduct.

Using the above process, at a reaction temperature of less than 20 ° C and wheat syrups with different

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> 26-SE »

Gardner colors as indicated, the color of the MMA adduct (after substantial equilibrium, achieved in at least about two hours) is as indicated.

TABLE 2

Gardner Color (Approximate)

Xarooe ds wheat

Adduct

4/5

1+ 7/8 7/0

0+

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

II. Hydrogen Reaction - The adduct obtained above is hydrogenated, having a Gardner Color of 1 or less, according to the following procedure.

About 539 g of adduct in water are added and

adduct is hydrogenated in about 95%. Then you have it

decant the reaction mixture and remove the catalyst by filtration. The product, after removing water and MMA by evaporation, is a white powder of about 95% N-methylglucamine.

The above procedure is repeated with about 23.1 g of Ni Raney catalyst with the following changes. There

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Case: 4262, R

26 “SEfite91, / · Check the catalyst three times and flush the reactor, with the 6 catalyst in the rector, twice with 1.38x10 '· Pa (200 psig 7 of Hy) and pressurize the reactor with H? at 1.10x10 Pa (160C psig) for two hours, the pressure is released in one hour and the reactor is repressurized at 1.10x10? Pa (1600 usxg). Bomheií 7

the nara adduct is then inside the reactor which is at 1.38x10 'Pa (200 psig) and 20 G and the reactor is purged with 1.33 x 10' Pa (200 psig) H ₉ , etc., as above, The resulting product in each case is more than about 95% of N-methylglucamine, has less than about 10 ppm Ni, based on glucamine; a has a solution color less than about 2 Gardner.

The crude N-netylglucamine is color stable at about 140 ° C for a short exposure time.

It is important to have a good adduct that is low in sugar (less than 5%, preferably less than 1%) and a good color (less than about 7, preferably less than about 4 Gardner, more preferably less than about 1 ).

In another reaction, the adduct is prepared starting with about 159 g of about 50% methylamine in water, which is purged and protected with N ?. at about 10-20 ° C. Degas with N _? , at about 50Â ° C, about 330 g of about 70% wheat syrup (close to white water) and slowly added to the methylamine solution at a temperature of less than about 20Â ° C. -Mix the solution for about 30 minutes to give about 95% adduct which is a very slightly yellow solution.

About 190 g of adduct in water and about 9 g of Ni catalyst, United Catalys G49B, are added to a 200 ml autoclave and purged three times with H ₉ at approximately

20 $ C. The pressure of Hy is raised to about 1.38x10 ^ Pa (200 psi) and the temperature is raised to about 50 ° C. Elevates6

the pressure is maintained to about 1.72x10 'Pa (250 psi) and the temperature is maintained at about 50-55 ° C for about three hours. The product that is hydrogenated by about 95%.

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Case: 4262 R

At this point, a temperature of about 85 ° C is then raised for about 30 minutes and the product, after removal of water and evaporation, is a white powder of about 95% N-methyl glucamine.

It is also important to minimize the contact between adduct, ecatalyst when the pressure of H ₉ is less than about 6.88x10 'Pa (1000 psig) to minimize the Ni content in glucamine. The nickel content in N-methylglucaminu in this reaction is about 100 ppm compared to less than 10 ppm in the previous reaction.

The following reactions with H ₉ proceed by directly comparing the effects of the reaction temperature ·.

A 200 ml autoclave reactor is used following typical procedures, similar to those presented above, to produce the additive and the hydrogen reaction takes place at various temperatures.

adduct used in the production of glucamine is prepared by combining about 420 g of glucose solution (wheat syrup) to about 55% (231 g of glucose; ^z t ^ 28 moles) (the solution is made using syrup 99DE wheat from CarGill, the solution having a Gardner color less than 1) and about 119 g of 50% methylamine (59.5 g of MMA; 1.92 moles) (from Air Products).

reaction procedure is as follows:

1. About 119 g of the 50% methylamine solution is added to a reactor purged with N2, protected with N2 and cooled to less than 10 ° C.

2. Decontaminate and / or purge the 55% wheat syrup solution at 10-20 ° C with N? to remove oxygen from the solution.

3. The wheat syrup solution is slowly added to the methylamine solution and the temperature is kept below 20 ° C.

4. Once the wheat syrup solution is added, stir for 1-2 hours.

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The adduct for the hydrogen reaction is used immediately after production or is stored at low temperature to prevent further degradation.

The hydrogen reactions of adduct glucamine are as follows:

1. Add about 134 g of adduct (color less than about Gardner 1) and about 5.3 g of Ui G49B to a 200 ml autoclave.

2. Purge the reaction mixture with about 1.33x10 ^ Pa (200 psi H 2 O twice at about 20-30 ° C.

3. Are you pressurized with R? at about 2.75x10 ° Pa (400 psi) and the temperature is raised to about 50 ° C.

4. The pressure is raised to about 3.44x10 ^ Pa (500 psi), reacted for about 3 hours. The temperature is maintained at about 50-55 ° C. Sample 1 is taken.

5. Raise the temperature to about 35 ° C for 30 minutes.

6. Decrease and remove the Ni catalyst by filtration. Sample 2 is taken.

Conditions for reactions at constant temperature:

1. Add 134 g of adduct and about 5.8 g of Ni G49B to a 200 ml autoclave.

2. Purge with about 1.38x10 ° Pa (200 psi H?) Twice at low temperature.

3- Pressurize to about 2.76x10 'Pa (400 psi) and raise the temperature to about 50 ° C.

4. The pressure is raised to about 3.44x10 'Pa (500 psi), reacted for about 3.5 hours. The temperature is maintained at the indicated temperature.

5. Decant and remove the Ni catalyst by filtration. Sample 3 is at about 50-55 ° C; Sample 4 is at about 75 ° C; and Sample 5 is at about 85 ° C. (The reaction time to about 85 ° C is about 45 minutes.)

All reactions give similar purity of N-methylglucamine (about 94%); Gardner Colors of reactions are

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similar immediately after the reaction but only two-stage heat treatment gives good

EXAMPLE IV

The preparation of the N-methylmaltamine tallow fatty acid (hardened) amide, for use in the detergent compositions according to this invention, is as follows.

Step 1 - Reagents: maltose, monohydrate, (Aldrich, batch

01318KW); methylamine (40% by weight in water)

The reagents are added to a glass coating (250 g of · maltose, 428 g of methylamine solution, 100 g of catalyst paste - 50 g of Ni Raney) and placed in a 3 L oscillating autoclave that is purged with nitrogen

psig) and oscillate under, at room temperature for a period of

weekend, the temperature within the range of 28 ° C a Crude reaction mixture is vacuum filtered 2x through a glass microfiber filter with a silica gel stopper. The filtrate is concentrated to a viscous material. The final traces of water are removed by azeotropic distillation, dissolving the material in methanol and then removing the methanol / water in a rotary evaporator. Is it done? final drying under high vacuum. The crude product in the metabolite is dissolved at reflux, filtered, cooled until it crystallizes, filtered and the filter cake is dried under vacuum at 35 ° C. This is fraction # 1. Concentrate the filtrate until a precipitate begins to form and store in a refrigerator overnight. Filter the solid and dry in vacuo. This is fraction # 2. The filtrate is concentrated again to half its volume and re-crystallized. Very little precipitate is formed. A small amount is added

quantity of ethanol and leave the solution in a refrigerator for the weekend. Filter the solid material and dry in vacuo. The combined solids comprise N-methylamine, which is used in Step 2 of the overall synthesis.

Step 2 - Reagents: N-methylamine (from Step 1); hardened tallow methyl esters; sodium methoxide (25% in methanol); absolute methanol (solvent); amine: ester molar ratio 1: 1; initial catalyst level 10%, molar, (w / r ds maltamine), increased to 20%, molar; solvent level 50% (weight).

In a sealed flask, heat 20.36 g of tallow methyl ester to its melting point (water bath) and load into a 250 ml 3-neck round bottom flask with mechanical stirring. The flask is heated to ca.

70 ° C to prevent the ester from solidifying. Separately, 25.0 g of N-methylmaltamine are combined with 45.36 g of methanol and the resulting slurry is added to the tallow ester with good mixing. 1.51 g of 25% sodium methoxide in methanol is added. After four hours the reaction mixture is not clear, so add 10 mol% of additional catalyst (up to a total of 20 mol%) and allow the reaction to continue overnight (ca 68 ° C) , time after which the · mixture is clear. The reaction flask is then modified. for distillation. The temperature is increased to 110 ° C. Distillation at atmospheric pressure continues for 60 minutes. Then, a high vacuum distillation begins, which lasts for 14 minutes, at which point the product is very thick, the product is allowed to remain in the reaction flask at 110 ° C (external temperature) for 60 minutes. Scrape the product from the flask and crush it in ethyl ester for a week. Evaporate the ester on a rotary evaporator, store the product in an oven overnight and grind to a powder. Any remaining N-methylmaltamine is removed from the product using silica gel. A silica gel paste in 100% methanol is loaded into a funnel and washed several times with 100% methanol. A concer sample is loaded onto the silica gel.

54 '63,878

Case: 4262 R

.lET.199l χ

the product (20 g in 1008 methanol) and eluted several times using vacuum and several washes with methanol. Evaporate the collected eluent to dryness (rotary evaporator). Any remaining tallow ester is removed by trituration in ethyl acetate overnight, followed by filtration. The filtrate holo is dried in vacuo overnight. The product is tallow alkyl N-methylmaltaraide.

In an alternative way, Step 1 of the previous reaction sequence can be carried out using wheat syrup. commercial product comprising glucose or mixtures of glucose and typically 58 or more maltose. The resulting polyhydroxy fatty acid amides and mixtures can be used in any of the detergent compositions included herein.

In yet another method, Step 2 of the previous reaction sequence can be carried out in 1,2-propylene glycol or NEODOL. At the formulator's discretion, 1,2-propylene glycol NEOPOL · does not need to be removed from the reaction product before use to formulate detergent compositions. Again, according to the formulator's wishes, the methoxide catalyst can be neutralized by citric acid to provide sodium citrate which can remain in the polyhydroxy fatty acid amine.

Depending on the formulator's wishes, the positions included here may contain more or less foam-controlling agents. Typically, for washing dishes with high foaming it is desirable that no foam controlling agent is used.

EXAMPLE V

In any of the examples of the detergent compositions, the fatty acid glucamide surfactant may be replaced with an equivalent amount of maltamide surfactant or glucanide / maltamide surfactant mixtures derived from vegetable sources of sugar. In the compositions, the use of etauolamides seems to help the low temperature stability of the finished formulations. In addition, the use

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of sulfobetaine surfactants (also known as suitain) provides superior foaming. CaCl ^ (ca. 1%) can be used in formulations to intensify the removal of greasy stains from dishes. 0 MgCl _? intensifies foaming.

Since the present invention provides especially high foaming compositions, it is preferable that less than 5%, more preferably less than 2%, even more preferably no higher fatty acids are present, as these can suppress the foam. Accordingly, the formulator of high foaming compositions will desirably avoid introducing foam suppression amounts of such fatty acids into high foaming compositions with polyhydroxy fatty acid amides and / or avoid formation of C -, - or higher fatty acids in the storage of the finished compositions. A simple way is to use C | 2 ester reagents to prepare the poly, hydroxylic fatty acid amides included here. Fortunately, the use of amine oxide surfactants. or sulfobetaine, such as cocoamido propyl betaine can overcome some of the negative foaming effects caused by fatty acids.

If the formulator wishes to add optical brighteners to liquid detergents containing concentrations. relatively high (eg, 10% and greater) of anionic or polyanionics, such as polycarboxylate enhancers, may find it useful to pre-mix the rinse aid with water -and the polyhydric fatty acid amide and then add the pre-mixture to the final composition.

It will be appreciated by those skilled in the art of chemistry that the preparation of the polyhydroxy fatty acid amides included here using disaccharides or higher, such eomomaltose, will result in the formation of polyhydroxy fatty acid amides in which the linear substituent Z is involved by ring structure of the polyhydroxy. Such materials are fully contemplated to use aaui and do not depart from

63.87-8

Case: 4262 R

26.SEW9ÍV of the spirit e. scope of the invention as disclosed. · and claimed

Claims (10)

R Ε I V I N Τ) I C Process for the preparation of an alkoxycarboxylate detergent composition for washing dishes, characterized in that the composition comprises from 1% to 65%, by weight, of a surfactant mixture comprising: (a) from 5% to 95%, by weight of one or more alkyl ethoxycarboxylate having the general formula CH _? C00IH in which R is a C ^-C ?? alkyl group, k is an integer in the range 0 to 10 and M is a cation; and (b) from 5% to 95%, by weight, of one or more polyhydroxy fatty acid amides having the general formula is a 0 ^ -Co- ^ hydrocarbyl and Z is a polyhydroxyhydrocarbyl having a chain linear hydrocarbyl with at least 3 hydroxyl groups attached directly to the chain or an alkoxylated derivative thereof. 2 ^§ . Process for the preparation of a composition according to claim 1, characterized in that the alkyl alkoxycarboxylate component (a) is distributed in such a way that the amount of material where k is 0 is less than 20% and the amount of material where k is greater than 7 is less than 25%, ok average is in the range of 1 to 4 when the average R is C ^ or less and the average k is in the 63,878 Case: 4262 R 26.Sf.199i range from 2 to 6 when the average R is greater than C. ^. 3 ^§ . Process for preparing a composition according to claim 1, characterized in that said detergent composition is liquid, preferably contains water or a mixture of water and an alcohol Cj-C _/} and comprises from 10% to 50% % by weight of a surprising mixture and from 90% to 50% by weight of a liquid vehicle. 4 ⁹ . Process for the preparation of a composition according to claim 3, characterized in that the surfactant mixture comprises from 20% to 80%, by weight, of the alkyl alkoxycarboxylate component and from 20% to 80%, by weight, of the amide component of noli-hydroxylic fatty acid. 5®. Process for preparing a composition according to claim 4, characterized in that the M occasion for the alkyl ethoxycarboxylate (a) is selected from the group consisting of an alkali metal, alkaline earth metal, ammonium, lower to mono-, alkanolammonium di and tri-ethanolammonium, and their mixtures with calcium and magnesium ions 6 ^a . Process for preparing a composition according to claim 5, characterized in that the composition of the composition is in the range of 7.0 to 11.0 and, preferably, additionally contains from 0.1% to 15%, by weight , of a buffering agent and still preferably and additionally contain from 2% to 5%, by weight, of a hydrotrope. 7®. Process for the preparation of a composition according to claim 6, characterized in that the liquid detergent contains one or more additional anionic or non-ionic surfactants selected from the group consisting of primary and secondary alkyl estersulfonates, Qq-C ^^, alkyldimethylamines θ10 ^- ^ 18 'alkyl polysaccharide oxides and mixtures thereof. 3®. Process for the preparation of a composition according to claim 7, characterized in that the surfactant mixture comprises from 4074 to 60%, by weight, of an alkyl ethoxycarboxylate 9 component from 20% to 60%, by weight, of a component polyhydroxy fatty acid amide58 63,870 Case: 4262 with the liquid vehicle comprising water or a mixture of water and ethanol. 9 ^S. Process for the preparation of a composition according to claim 8, characterized in that the cation M nara the alkyl-ethoxycarhoxylate component (a) is selected from sodium, potassium and ammonium, and their mixtures with calcium and magnesium ions, and in that the polyhydroxy fatty acid amide (h) has the formula in which R is a straight chain alkenyl or C C--C- alkyl, and in which Z is derived from glucose, maltose or mixtures thereof. 10 ^ã . Process for the preparation of a composition according to the preceding claims, characterized in that the composition comprises from 5% to 65%, by weight, of a surfactant mixture comprising: (a) from 5% to 95%, by weight, of one or more xicarboxylated alkyl ethoes having the general formula in which R is an alkyl group> h is an integer averaged from 1 to 4 and M is a cation; and (h) from 5% to 95%, by weight of one or more amides of polyhydroxy fatty acid having the formula in which xiethyl R is h, a C, -C ,, 2-hydro * 4 2 hydrocarbyl 2-hydroxypropyl or mixtures thereof, R 63,878 Case: 4262 R is a C ^-C ^ hydrocarbyl and Z is a nolihydroxy-hydrocarhyl having a linear hydricarhyl chain with at least 3 hydroxyl groups attached directly to the chain, preferably N-methyl Cn ^-C- ^ y, N -metiimaltamide ^ 11 ^ 17 ' ^{or n:} ' - ^strips of said glucamide, and maltamide, or an alkoxylated derivative thereof; and, optionally, (c) one or more non-carboxylate anionic surfactants. ll ^s . Process according to claim 10, characterized in that said portion 7, in said polyhydroxy fatty acid amide is derived from disaccharide monosaccharides and mixed polysaccharides available from plant sources. 12. A process according to claim 10, wherein said R ^J portion in said polyhydroxy fatty acid amide is alkenyl, C-, ^ -C ^ y alkyl or mixtures thereof.