PT99101B - PROCESS FOR THE PREPARATION OF DETERGENT COMPOSITIONS CONTAINING ANIONIC THRESHOLD AGENTS, POLYHYDROXYAMIDES OF FATTY ACIDS AND MAGNESIUM - Google Patents

Abstract

The present invention provides a detergent composition comprising one or more anionic sulfate or sulfonate surfactants; one or more polyhydroxy fatty acid amides having formula (I) wherein R<1> is H, a C1-C4 hydrocarbyl, 2-hydroxy ethyl, 2-hydroxy propyl, or mixtures thereof, R<2> is a C5-C31 hydrocarbyl, and Z is a polyhydroxyhydrocarbyl having a linear hydrocarbyl chain with at least 3 hydroxyl groups directly connected to the chain, or an alkoxylated derivative thereof; and magnesium in a molar amount corresponding to 0.1X-2.0X, wherein X is the number of moles of anionic sulfate or sulfonate surfactant present in said composition. The present invention also provides for 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 one or more anionic sulfate or sulfonate surfactants, one or more polyhydroxy. fatty acid and magnesium amides. In particular, it relates to detergent compositions which have the desirable cleaning and foaming properties, which are gentle on the hands, and which are especially suitable for dishwashing applications.

REFERENCE TO RELATED PATENT APPLICATIONS

This order is a partial continuation of the co-pending order with the serial ^Q 590 617, filed on 28 September 1990.

BACKGROUND OF THE INVENTION

It is known to use anionic, sulfated or sulfonated surfactants in detergent compositions. However, it would be desirable to incorporate such surfactants into detergent compositions that have improved cleaning and foaming performance.

It has now been found that detergent compositions containing one or more detergent, anionic, sulfated or sulfonated surfactants, one or more fatty acid, and magnesium polyhydroxyamides, have foaming and cleaning performances which, surprisingly, are superior to the performances of anionic, sulfated or sulfonated surfactants alone.

In addition to these performance benefits, such compositions when compared to anionic, sulfated or sulfonated surfactants, are softer for the hands, have improved rinsing capacity, no

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TECHNICAL BACKGROUND use of anionic surfactants, sulfate or sulfonate, in detergent compositions is known in the art. U.S. Patent 4,435,317 to (Gerritson et al., March 6, 1984); describes liquid detergent compositions containing alkyl sulfate, alkyl ether sulfate and benzenesulfonate alkyl surfactants. U.K. 809 060 Patent Description, issued to Hedley & Co. Ltd., and published on February 18, 1959, describes detergent compositions containing a sulfate or sulfonate surfactant with a specific fatty acid polyhydroxyamide.

polyhydroxyamide component of fatty acid contained in the composition of the present invention is also known in the art, as are several of its uses.

For example, N-acyl and N-methyl-glucamides are described by JW Goodby, Μ. A. Marcus, E. Chin and P. L Finn in The Thermotropic Liquid-Crystalline Properties of Some Sraight Chain Carbohydrate Amphiphiles, Liquid Crystals, 1988, Volume 3, N ^Q 11, p. 1569-1581, and by A. Muller-Fahr now, V. Zabel, M. Steifa and R. Hilgenfeld, in Molecular and Crystal Structure of a Nonionic Detergent: Nonanoyl-N-methyl glucamide, J. Chem. Soc. Chem. Commun., 1986, p.1573-1574. The use of N-alkyl-polyhydroxy hydroxide surfactants has recently been of immense interest in biochemistry, for example, for the dissociation of biological membranes. See, for example, the article ND-gluco-N-methyl-alkanami_ by Compounds, the New Class of Non-Ionic Detergents For Membrane Biochemistry, in the journal Biochem. J. (1982), Vol. 207, on pages 363-366, by JEK Hildreth.

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use of N-alkyl-glucamides in detergent compositions has also been appreciated. US Patent 2,965,576, issued on December 20, 1960, to ER Wilson, and UK Patent Description 809 060 referred to herein, describe 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 a straight chain N-acyl radical of a fatty acid with 10-14 carbon atoms. These compositions can also contain auxiliary materials such as alkali metal phosphates, alkali metal silicates, sulphates and carbonates. It also refers generally, that they can also be included in the compositions, and for them to confer the desirable properties, additional constituents such as fluorescent dyes, bleaching agents, perfumes, etc.

US Patent 2 703 798, issued on March 8, 1955, to AM Schwartz, relates to aqueous detergent compositions containing the product of the N-alkyl-glucamine condensation reaction and an aliphatic ester of a fatty acid . The product of this reaction is said to be usable in aqueous detergent compositions without further purification. The preparation of acylated glucamine sulfuric ester is also known, as described in the U.S. Patent

717,894, issued on September 13, 1955, to A.M. Schwartz.

PCT International application W0 83/04412, published on 22 December 1983 by J. Hildreth, refers to amphiphilic compounds containing polyhydroxy aliphatic groups considered useful for a variety of purposes, including use as surfactants. active in cosmetics, drugs, shampoos, lotions and ointments for the eyes, as emulsifiers and distribution agents for medicines, and in biochemistry for solubilization of membranes, complete cells or other tissue samples, and for preparation

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breeding of liposomes. Included in this description are compounds of the formula R 'C0N (R) CH ₂ R and R C0N (R) R', in which R is hydrogen or an organic grouping, R 'is an aliphatic hydrocarbon group with at least three atoms of carbon, and R is a residue of an aldose.

European Patent 0 285 768, published on October 12, 1988, by H. Kelkenberg, et. al., refers to the use of N-polyhydroxyalkyl fatty acid amides as thickening agents in aqueous detergent systems. Included are amides of the formula R ^ C (0) N (X) R ₂ , where R ^ is alkyl (preferably, C7-C27), R ₂ is hydrogen, a C4 -C / alkyl (preferably, C1-) C5) or an alkylene oxide, and X is a polyhydroxyalkyl having four to seven carbon atoms, namely, N-methyl glucamide of coconut fatty acid. It is reported that the thickening properties of amides have special use in liquid surfactant systems containing paraffin sulfonate, although aqueous surfactant systems may contain other anionic surfactants, such as alkylaryl sulfonates, olefin sulfonate, salts of sulfosuccinic acid hemi-esters and fatty alcohol ether-sulfonates, non-ionic surfactants such as polyglycol and fatty alcohol, polyglycol and alkylphenol ether, fatty acid polyglycol ester , mixed polypropylene oxide polyethylene oxide, etc. exemplifications of paraffin sulfonate / N-methyl glucamide shampools of coconut fatty acid / non-ionic surfactant are exemplified. In addition to the thickening attributes. N-polyhydroxyalkyl fatty acid amides are said to have superior attributes with respect to skin tolerance.

US Patent 2 982 737, issued on May 2, 1961, to Boettner et al., Refers to detergent bars containing urea, anionic sodium lauryl sulfate surfactant, and a nonionic surfactant of N-alkyl-glucamide which is selected from N-methyl õa

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N-sorbityl-lauramide and N-methyl or N-sorbityl-myristamide.

Other glucamide surfactants are described, for example, in DT 2 226 872, published on December 20, 1973, by HW Eckert, et al., Which refers to washing compositions comprising one or more surfactants -active agents and adjuvant salts selected from polymeric phosphates, sequestering agents and alkaline washing bases, improved by the addition of an N-acyl-polyhydroxyalkylamine of the formula RiC (0) N (i? 2) CH2 (CH0H) _n CH20H , in which it is a C1-C3 alkyl, R2 is a ^C 1 ^{O _C} 22 ' ^en θ 3 or 4 alkyl. N-acyl-polyhydroxyalkylamine is added as a soil suspending agent.

US Patent 3,654,166, issued on April 4, 1972, to HW Eckert, et al., Relates to detergent compositions comprising at least one surfactant selected from the group of anionic surfactants. , zwitterionic and non-ionic and, as a textile softener, an N-acyl or N-alkyl-polyhydroxyalkyl compound of the formula R | N (Z) C (0) R2 <in which R ^ is a Cjq-C22 alkyl '^ 2 ® ^a C7-C21 alkyl, Rj θ R2 total between 23 and 39 carbon atoms, and Z is a polyhydroxyalkyl which can be -CH2 (CH0H) _m CH20H, where m is 3 or 4.

US Patent 4,021,539, issued on May 3, 1977, to H. Moller et al., Refers to cosmetic compositions for the treatment of skin containing N-polyhydroxyalkylamines that include compounds of the formula R R N (R) CH (CHOEl · π®2, in which R | is H, lower alkyl, hydroxy-alkyl or aminealkyl, as well as heterocyclic aminoalkyl, R is equal to R |, although both cannot be H, and R2eCH2OH or COOH.

French Patent 1 360 018, of April 26, 1963, issued to Coromerciál. Solvents Corporation, I refer to formaldehyde solutions stabilized against polymerization by the addition of amides of the formula RC (0) N (Ri) G, where R is a carboxylic acid function with at least seven carbon atoms, R ^ is hydrogen or an lower alkyl group

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above, and G is a glycitol radical with at least 5 carbon atoms.

German Patent 1,261,861, February 29, 1968, to. A. Heins, refers to glucamine derivatives, useful as wetting and dispersing agents, of the formula N (R) (Ri) (R ₂ ), where R is a glucamine sugar residue, Ri is a C10 alkyl radical -C20 ' ^{and R} 2 θ ^a C1-C5 acyl radical.

GB 745 036, issued on February 15, 1956, issued to Atlas Powder Company, refers to heterocyclic amides and their carboxylic esters considered useful as chemical intermediates, emulsifiers, wetting and dispersing agents, detergents, textile softeners , etc. The compounds are represented by the formula N (R) (Ri) C (0) R2, in which R is the residue of an anhydrized hexanopentol or its carboxylic acid ester R1 is a monovalent hydrocarbon radical, and -C (O) R ₂ is the acyl radical of a carboxylic acid having 2 to 25 carbon atoms.

US Patent 3 312 627, issued on April 4, 1967, to DT Hooker, describes bars of soap that are substantially free of anionic detergents and alkaline adjuvant materials, and which contain lithium soap of certain fatty acids, an agent non-ionic surfactant selected from certain condensates of propylene-ethylene diamine-ethylene oxide, condensates of propylene-propylene-glycol-ethylene oxide, and polymerized ethylene glycol, and which also contain a non-ionic foaming component which may include polyhydroxyamide of the formula RC (0) NR ^ (R ² ), where RC (0) contains from about 10 to about 14 carbon atoms, R ^ and R ² are each H or alkyl groups C ^ -Cg; said alkyl groups contain a total number of carbon atoms from 2 to about 7, and such a number of hydroxyl substituent groups from 2 to about 6. A substantially similar description is found.

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similar to U.S. Patent 3,312,626, also issued on April 4, 1967, to D. T. Hooker.

The use of magnesium in detergent compositions is also known in the art. The U. S. Patent

435 317, already referred to herein, describes detergent compositions comprising magnesium and anionic surfactants.

However, there is nothing in the technique to refine the unexpectedly superior cleaning and foaming performance, easy rinsing, absence of slippery touch and softness for the hands, associated with the compositions of the present invention that contain surfactants aqionic, sulfated or sulfonated, polyhydroxyamides of fatty acids and magnesium.

It is therefore an object of the present invention to provide such detergent compositions that exhibit such properties.

It is another object of the present invention to provide a process for cleaning dirty dishes, by treating said dishes with the specific detergent compositions described herein.

These objects are realized with the present invention.

SUMMARY OF THE INVENTION the present invention relates to detergent compositions comprising from 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 anionic surfactants, sulfate or sulfonates; and (b) from about 5% to about 95%, by weight, of one or more fatty acid polyhydroxyamides of the formula

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%

R ¹ II I

R ² -C -N -Z in which R 1 is H, a C 1 -C / j hydrocarbyl, 2-hydroxyethyl, 2-hydroxypropyl or mixtures thereof; R2 is a C5-C31 hydrocarbyl; and Z is a polyhydroxyhydrocarbyl having a linear hydrocarbyl chain with at least 3 hydroxyl groups attached directly to the chain, or an alkoxylated derivative thereof;

the composition should contain magnesium in a molar amount corresponding to O, 1X-2, OX, where X is the number of moles of anionic surfactant, sulfate or sulfonate, present in said composition · the present invention also refers , to a process for washing dirty dishes, a process that includes the treatment of said dishes with the detergent compositions claimed herein.

DETAILED DESCRIPTION OF THE INVENTION

The detergent compositions of the present invention comprise from about 5% to about 65% by weight, preferably from about 10% to about 50% by weight, and most preferably from about 20% to about 40% by weight of a surfactant mixture comprising one or more anionic, sulfated or sulfonated surfactants, and one or more fatty acid polyhydroxyamides. These compositions additionally contain magnesium in a molar amount corresponding to 0.1X-2.0X, preferably O, 2X-1.7X, and more preferably still, 0.3X-1.5X where X is the number of moles of anionic, sulfate or sulfonate surfactant present in said composition. These and other ingredients normally found in detergent compositions are presented below. Compositions hold-363905

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People of the present invention are preferably in the form of a liquid or gel, more preferably being liquid detergent compositions for delicate purposes, or, more preferably still, liquid detergent compositions for delicate purposes, for dish washing.

Anionic Surfactant

The surfactant mixture of the present invention comprises from about 5% to about 95%, preferably from about 20% to about 80%, and, most preferably, from about 40% to about 60%, by weight of one or more anionic surfactants, sulphate or sulphonate. The anionic surfactants, sulfate or sulfonate, can be any surfactant sulphate or organic sulphonate, but are preferably selecciç births from among alkyl C ^^ - ^ C -benzonossulfonatos, alkyl sulfates Cio ^{- C} 16 ^{and its} ethoxy analogs containing up to twelve moles of ethylene oxide per mole of alkoxy alkoxy sulfates, C ^ gC ^ g sulfonates and secondary alkane sulfonates, C ^ QC ^ g olefin sulfonates, Clo ~ ^c alkylglyceryl ether sulfonates 2O 'Cg-C4 ç-N- (C1-C4 alkyl) or -N- (C2-C4 hydroxyalkyl) sulfates glucamine and mixtures of any of the above substances. More preferably, the anionic surfactant is selected from alkyl ethoxy sulfates, alkyl glyceryl ether sulfonates and paraffin sulfonates.

The alkylbenzenesulfonates useful in the compositions of the present invention are those in which the alkyl group, which is substantially linear, contains 10-16 carbon atoms, preferably 10-13 carbon atoms, with a material having an average carbon chain length being preferred. of 11.2. The distribution of the phenyl isomer, i. e., the point of attachment of the alkyl chain to the benzene core, are not critical, but alkylbenzenes with a high content of the 2-phenyl isomer are preferred.

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Suitable alkyl sulfates are the primary alkyl sulfates in which the alkyl group contains 10-16 carbon atoms, more preferably an average of 12-14 carbon atoms, preferably in a straight chain. The ^Cio-C 16 alcohols "derived from natural fats, or Ziegler ofelínica construction or synthesis 0X0 constitute suitable sources for the alkyl group. Examples of synthetically derived materials are Dobanol 23 (Trademark) sold by Shell Chemicals (UK) Ltd., Ethyl 24, sold by Ethyl Corporation, a mixture of C13-C25 alcohols at 67% C13, 33% C15 , sold under the trademarks of Lutensol, by BASF GmbH, and Synperonic (Registered Trademark), by ICI Ltd., and Liai 125, sold by Liquichimica Italiana. Examples of naturally occurring materials from which alcohols can be derived are coconut oil and palm kernel oil, and the corresponding fatty acids.

The surfactants of sulfate alquiletoxilo compreedem primary alquiletoxilo a sulfate derivative of the condensation product of a Cio alcohol ^c ~ lg up to 7 ethylene oxide groups on average. The C ^ q--Cgg alcohol, in itself, can be obtained from any of the sources previously described for the alkyl sulfate component. C12-C13 ethoxy alkyl sulfates are preferred.

Conventional ethoxylation processes, catalyzed by base, for the production of an average degree of ethoxylation of 12 result in a distribution of the individual ethoxylates varying between 1 and 15 ethoxyl groups per mole of alcohol, so that the desired average can be obtained by a variety of modes. Mixtures of materials with different degrees of ethoxylation and / or different distributions of ethoxylate can be made that result from the specific ethoxylation techniques employed and subsequent processing steps, such as distillation. For example, it has been found that foaming and removal performance

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In preferred compositions, according to the present invention, an alkylethoxy sulfate is used which has an average degree of ethoxylation from 0.4 to 6.5 which (decreases the turbidity of the product ^ more preferably, from 0.4 to 3 , 0.

Secondary alkanesulfonates, useful in the present invention, have from 13 to 18 carbon atoms per molecule, more desirably, from 13 to 16 carbon atoms per molecule. These sulfonates are prepared, preferably, by subjecting a paraffinic fraction, corresponding to the chain lengths specified above, to the action of sulfur dioxide and oxygen, according to the well-known sulfoxidation process, the product of this reaction is a secondary sulfonic acid which is then neutralized with a suitable base to provide a secondary alkyl sulfonate. Similar secondary alkylsulfonates can be obtained by other processes, such as, for example, by the sulfochlorination process, in which chlorine and sulfur dioxide are reacted with paraffins, in the presence of actinic light, the resulting sulfonyl chlorides being hydrolyzed and neutralized to form the secondary alkyl sulfonates. Whichever technique is employed, it is usually desirable to produce the sulfonate as the monosulfonate, without any initial hydrocarbons left unreacted or with only a limited proportion present, and with little or no by-product of inorganic salt. In the same way, the proportions of disulfonate or super-sulfonated material should be minimized, although some may be present. The monosulfonate may be terminally sulfonated, or the sulfonate group may be attached to carbon 2 or another carbon in the linear chain. The same

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Thus, any accompanying disulfonate, usually produced when an excess of sulfonating agent is present, may have the sulfonate groups distributed on different carbon atoms of the paraffinic base, and mixtures of monosulfonates and disulfonates may be present.

Particularly preferred are mixtures of monoalkanesulfonates, where the alkanes have 14 and 15 atoms, and where the sulfonates are present in a maximum ratio of C14-C15 paraffins between 1: 3 and 3: 1.

The olefin sulfonates useful in the present invention are mixtures of alkene-1-sulfonates, alkene-hydroxysulfonates, alkenedisulfonates and hydroxy-disulfonates, and are described in US Patent 3,332,880, issued to PFPflauner and A. Kessler on July 25, 1967 .

Suitable alkylglyceryl ether sulfonates are those derived from tallow and coconut oil ethers.

Other sulphate surfactants include C 1 -C 4 -C 4 acyl sulfates (C 1 -C 4 -alkyl) or -N (C 1 -C 2 hydroxyalkyl) -glucamine, preferably those in which the C 5 -C 4 acyl group is derived from coconut or palm oil. These materials can be prepared by the process described in U.S. Patent 2,717,894, issued on September 13, 1955, to Schwartz.

counterion for the anionic surfactant component is preferably selected from sodium, potassium, magnesium, ammonium or alkanol-ammonium, and mixtures thereof, with magnesium being preferred.

Fatty Acid Polyhydroxyamide Component

The surfactant mixture of the present invention comprises from about 5% to about 95%, preferably from about 20% to about 80%, and, most preferably, from about 40% to about 60%, by weight of one or more fatty acid polyhydroxyamides with the structural formula:

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R1, II I r2 _ c - N - Z in which: R1 is H, C1-C4 hydrocarbyl, 2-hydroxyethyl, 2-hydroxypropyl, or a mixture thereof, preferably 0χC4 alkyl, more preferably, alkyl or C ₂ alkyl, and most preferably, C alkyl | (iemethyl); and R ² is a straight chain C5-C31 hydrocarbyl, preferably straight chain C7-C17 alkyl or alkenyl, more preferably straight chain C7-C49 alkyl or alkenyl, and most preferably straight chain C11-C17 alkyl or alkenyl. mixture; and Z is a polyhydroxyhydrocarbyl having a linear hydrocarbyl chain with at least 3 hydroxyls attached directly to the chain, or an alkoxylated derivative thereof (preferably ethoxylated or propoxylated). Preferably, Z will 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. High-dextrose corn syrup, high-fructose corn syrup and high-maltose corn syrup can be used as raw materials, as well as the individual sugars listed above. These corn syrups may give rise to a mixture of sugar components for Z. However, 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 -CH2- (CH0H) _n -CH20H, -CH (CH2OH) -. (CHOH) _n _ ₁ -CH ₂ OH, -CH ₂ - (CHOH) ₂ ( CHOR ') (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 ethoxylated derivatives. Most preferred are glycityls where n is 4, particularly -CH ₂ - (CHOH) 4 ~ CH ₂ OH.

In formula (I), R3 · can be, for example, N-methyl, N-ethyl, N-propyl, N-isopropyl, N-butyl, N-2 *

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-hydroxyethyl or Ν-2-hydroxypropyl.

R2_co ~ N <can be, for example, cocamide, stearamide, oleamide, lauramide, myristamide, capricamide, palmitamide, sebamide, etc.

Z can be 1-deoxyglucityl, 2-deoxyfructityl, 1-deoxyltityl, 1-deoxylactityl, 1-deoxygalactityl, 1-deoxymanityl, 1-deoxyltotriotithyl, etc.

The preferred fatty acid polyhydroxyamide has the general formula

CHo the I! ^!

R ² - C - N - CH ₂ - (CHOH) ₄ CH ₂ OH where R ² is a straight chain alkyl or alkenyl group.

Methods for producing fatty acid polyhydroxyamides are known in the art. In general, they can be produced by reacting an alkylamine with a reducing sugar, in a reductive amination reaction, to form the corresponding N-alkyl-polyhydroxyamine and then reacting the N-alkyl-polyhydroxyamine with a triglyceride or aliphatic fatty ester in a condensation / amidation step, to form the product N-alkyl, N-polyhydroxyamide of fatty acid. Processes for producing fatty acid polyhydroxyamides are described, for example, in GB 809 060 Patent Descriptions, published on February 18, 1959, by Thomas Hedley & Co., Ltd., US Patent 2 965 576 , issued on December 20, 1960 to ER Wilson, US Patent 2 703 798, issued on March 8, 1955, to Anthony M. Schwartz and US Patent 1 985 424, granted on December 25, 1934, Piggott, all of which are incorporated by reference.

In a N-alkyl or N-hydroxyalkyl, fatty acid N-deoxyglycylamides process in which the glyceryl component is derived from glucose and the N-alkyl or N-hydroxyalkyl functionality is N-methyl, N-ethyl,

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N-propyl, N-butyl, N-hydroxyethyl or N-hydroxypropyl, the product is made by reacting N-alkyl- or N-hydroxyalkyl-glucamine With a fatty ester selected from fatty methyl esters, fatty ethyl esters and triglycerides fatty acids, in the presence of a catalyst selected from the group consisting of tri-lithium phosphate, tri-sodium phosphate, tri-potassium phosphate, tetra-sodium pyrophosphate, penta-potassium tri-polyphosphate, hydroxide lithium, sodium hydroxide, potassium hydroxide, calcium hydroxide, lithium carbonate, sodium carbonate, potassium carbonate, di-sodium tartrate, di-potassium tartrate, sodium and potassium tartrate, tri-sodium citrate, tri-potassium citrate, basic sodium silicates, basic potassium silicates, basic sodium aluminum silicates, basic potassium aluminum silicates and mixtures thereof. The amount of catalyst is preferably between about 0.5 mol% and about 50 mol%, more preferably between about 2.0 mol% and about 10 mol%, on a molar basis of N-alkyl or N-hydroxyalkyl-glucamine. The reaction is preferably carried out between about 138 ° C and about 170 ° C for, typically, about 20 to about 90 minutes. When triglycerides are used in the reaction mixture as a fatty ester source, the reaction is also preferably carried out with about 1 to about 10%, by weight, of a phase transfer agent, calculated on a percentage by weight basis. total reaction mixture, which agent is selected from the saturated alcohol polyethoxylates, alkyl-poly-glucosides, linear glucamine surfactants and mixtures thereof.

Preferably, this process is carried out as follows:

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

(b) addition of N-alkyl or N-hydroxyalkyl-glucamine to the fatty acid ester.35

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eido 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.

Preferably from about 2% to about 20% by weight of the reagents, preferably the pre-formed linear product of N-alkyl / N-hydroxyalkyl, linear N-glycosyl acid-amide is also added to the reaction mixture. fat, as a phase transfer agent, if the fatty ester is a triglyceride. This starts the reaction by increasing its speed. A detailed experimental procedure is indicated below in the section entitled Experimental Part.

The fatty acid polyhydroxyamide materials used here also offer the detergent formulator the advantages of being able to be prepared wholly or mainly from natural, renewable, and not petrochemical raw materials, and of being degradable. They also exhibit low toxicity to aquatic life.

It should be recognized that, together with the fatty acid polyhydroxyamides of Formula (i), the processes used for their production also typically give rise to quantities of non-volatile by-products such as cyclic styramides and polyhydroxyamides. fatty acid.0 The level of these by-products varies depending on the specific type of reagents and the process conditions. Preferably, the fatty acid polyhydroxyamide incorporated in the present detergent compositions should be such that the composition containing the fatty acid polyhydroxyamide added to the detergent contains less than about 10%, preferably less than 4%. % fatty acid cyclic polyhydroxyamide. The preferred processes described above have the advantage of having relatively low yields of secondary products, including these products.

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Magnesium Component>

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The detergent compositions of the present invention contain magnesium in a molar amount corresponding to 0.1X-2.0X, preferably 0.2X-1.7X, and most preferably 0.3X-1.5X, in that X is the number of moles anionic, sulfate or sulfonate surfactant present in these detergent compositions.

The magnesium incorporation technique in the positions of the present invention is not considered critical, and can be performed in a number of ways.

Thus, the individual anionic surfactants can be produced as aqueous solutions of alkali metals or ammonium salts which are then mixed together with the hydrotrope, after which magnesium can be introduced as a water-soluble salt, such as like chloride or sulfate. Optional secondary ingredients can then be added before adjusting the pH and viscosity. This process has the advantage of using conventional techniques and equipment, but results in the introduction of additional chloride or sulfate ions that can increase the temperature of the precipitation point (the temperature at which inorganic salts precipitate, like crystals, in the liquid).

If the anionic surfactants are in acidic form, then magnesium can be added by neutralizing the acid with a slurry of magnesium oxide or magnesium hydroxide in water. This technique avoids the addition of chloride and sulfate ions. The neutralized surfactant salts and the hydrotrope are then introduced into the final mixing tank and any optional ingredients are added before adjusting the pH.

A third, and preferred, technique is the addition of the anionic surfactant, sulfate or sulfonate, as a magnesium sulfate salt. When es-1163,905

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If the magnesium addition method is used, it can be added as much magnesium as desired, in molar excess over the anionic surfactant, by one of the other methods identified herein, or by methods known to those skilled in the art.

Liquid Conveyor

In a preferred embodiment, the detergent compositions of this 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, and most preferably from about 80% to about 60% % by weight of a liquid carrier, eg water, but preferably a mixture of water and a monohydric alcohol Οχ-C4 (eg ethanol, propanol, isopropanol, butanol and their mixtures), with ethanol being the preferred alcohol.

Composition pH

The liquid compositions of the invention are preferably formulated in such a way that, during use in cleaning operations in an aqueous medium, the washing water has a pH between about 5.5 and about 9.5, more preferably, between about 6.5 and about 8.0. Liquid product formulations preferably have a pH in the range of about 5.0 to about 10.5, preferably of about 6.0 to about 9.0 and most preferably, of about 6, 5 to about 7.5. Techniques for controlling the pH at the recommended usage levels include the use of buffers, alkalis, acids, etc., and are well known to those skilled in the art.

Thickening Agent

The detergent compositions of the present invention can also be in the form of a gel. These compositions are typically formulated in the same way as liquid detergent compositions, but they also contain a thickness agent.

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Any material or materials that can be mixed with the aqueous liquid to provide shear thinning positions and sufficient yield values can be used in the compositions of this invention. It is known that materials such as colloidal silica, particulate polymers, such as polystyrene and oxidized polystyrene, combinations of certain surfactants and water-soluble polymers such as polyacrylate, provide due yield values.

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

polycarboxylate polymer can be a carboxyvinyl polymer. These compounds are described in U.S. Patent 2,798,053, which is incorporated herein by reference. Processes for the production of carboxyvinyl polymers are also described in Brown and are also incorporated herein by reference.

A carboxyvinyl polymer is an interpolymer of a monomeric mixture comprising a carboxylic acid, olefinically unsaturated and monomeric, and from about 0.1% to about 10%, by weight of the total monomers, of a polyether of a polyether alcohol hydric, containing that polyhydric alcohol, at least four carbon atoms to which at least three hydroxyl groups are attached, the polyether containing more than one alkenyl 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 liquid, volatile, organic hydrocarbons, and are dimensionally stable on exposure.

63,905

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air.

Preferred polyhydric alcohols used for the production of carboxyvinyl polymers include polyols selected from the class consisting of oligosaccharides, their reduced derivatives in which the carbonyl group is converted to an alcohol group, and pentaerythritol, · most preferred are oligosaccharides, and especially preferred is sucrose. It is preferred that the hydroxyl groups of the polyol that are modified are etherified with allyl groups, the polyol having at least two allyl ether groups per polyol molecule. When the polyol is sucrose, it is preferred that sucrose has at least about five groups of allyl ether per sucrose molecule. It is preferred that the polyol polyether constitutes from about 0.1% to about 4% of the total monomers, more preferably, from about 0.2% to about 2.5%.

Preferred monomeric, olefinically unsaturated carhoxy acids for use in the production of the carboxyvinyl polymers used herein include lower, monomeric, polymerizable, aliphatic carhoxy acids, mono-olefinically unsaturated alpha-beta; more preferred are acrylic, monomeric mono-olefinic acids, of structure ch ₂ = c-cooh where R is a substituent selected from the group consisting of hydrogen and lower alkyl groups; Especially preferred is acrylic acid.

The carboxyvinyl polymers useful in the formulations of the present invention have a molecular weight of at least about 750,000. Carboxyvinyl polymers which are highly cross-linked and have a molecular weight of at least 1,250,000 are preferred. Also preferred are the póllí

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carboxyvinyl dimers with a molecular weight of at least about 3,000,000, which may not be as highly retained.

Various carbaxivinyl polymers are commercially available from B.F. Goodrich Company, New York,

N.Y., under the trademark Carbopol. Carboxyvinyl polymers useful in formulations of the present invention include Carbopol 910, with a molecular weight of about 750,000; Carbopol 941, with a molecular weight of about 1 250 000 is preferred; and even more preferred are Carbopol 934 and 940, with molecular weights of about 3,000,000 and 4,000,000C respectively.

Carbopol 934 is a very lightly cross-linked carboxyvinyl polymer, with a molecular weight of about 3 000 000. It has been described as a high-molecular, cross-linked poly (acrylic acid), with about 1% polyallysaccharose having an average about 5.8 allyl groups per sucrose molecule.

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

The preferred polycarboxylate polymers in the present invention are non-linear, water-dispersible, poly (acrylic acid) cross-linked polymers with a polyalkenyl-polyether, and having a molecular weight of about 750,000 to about 4,000,000.

Most preferred examples of these polycarboxylate polymer thickeners are the Carbc pol 600 series resins, available from B.F. Goodrich. Especially preferred are Carbopol 616 and 617. These resins are believed to be more cross-linked than the 900 series resins, and have molecular weights between about 1,000,000 and 4,000,000. They can also be used in the present invention. mis35

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Mod. 71 - 23,000 βχ. - 8/90>

Polycarboxylate polymer thickener is preferably used essentially without clay 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 in terms of phase instability is obtained. In other words, the polycarboxylate polymer is preferably used, in the present compositions, instead of clay, as a thickening / stabilizing agent.

polycarboxylate polymer also provides a reduction in what is commonly called bottle hang-up. This term refers to the inability to obtain the distribution of the entire dishwashing detergent product from its container. Without wishing to be bound by theory, it is believed that the thickened compositions of the present invention provide this benefit because the cohesive strength of the composition is superior to adhesion to the container wall. With clay thickening systems, which most commercially available products contain, container retention can be a significant problem under certain conditions.

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

If the polycarboxylate polymer is used as a thickening agent in the compositions of the present invention35

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However, it should typically be present at a level of about 0.1% to about 10%, preferably from about 0.2 to about 2%, by weight

The thickening agents are used to provide a yield value of about 50 to about 350 and, more preferably, about 75 to about 250.

Assignment value analysis

Mod. 71 - 20,000 ex. - 90 (06 yield value is an indicator of the shear stress at which the gel resistance is exceeded and the flow starts. It is here measured with a Brookfield viscometer model RVT with a B spindle at T, at 25 ° C, and using a Helipath ascending actuator during the associated readings, the system is set to 0.5 rpm, and the composition to be tested is read after 30 seconds or after the system has been stalied. the rotation is reset to 1.0 rpm. A reading is made for the same composition after 30 seconds, or after the system is stabilized. The zero cut voltage is equal to twice the reading at 0.5 rpm less. the reading 1.0 rpm The yield value is calculated as the shear stress zero times 18.8 (conversion factor).

Optional Components

Other anionic surfactants, useful for detergent purposes, may also be included in the positions of the present invention. Useful anionic surfactants include, by way of example and without limitation, salts (eg sodium, potassium, ammonium and substituted ammonium salts, such as soap mono-, di- and triethanolamine salts), sulfonated polycarboxylic acids, prepared by sulfonation of the alkaline earth metal citrate pyrolysate product, eg, as described in British Patent specification 1,082,179, Cg-C22 alkyl sulfates / C8-C24 alkyl polyglycol ether sulfates (containing up to 10 moles of ethylene oxide); alkylglycerolsulfonates, sul35

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Mod. 71 - 20,000 ex. - 90/08 fatty acylglycerol phonates, fatty acylglycerol sulphates, ethylene oxide and alkylphenol ether sulphates, alkyl phosphates, isethionates such as acyl isethionates, acyl tau rats, fatty acid amides, succinates and alkyl sulfosuccinates , acyl sarcosinates, alkyl poly-saccharide sulphates, such as alkyl polyglucoside sulphates (the non-ionized non-sulphated compounds having already been described herein), alkyl ether carbonates, alkyl ethoxycarboxylates, fatty acids esterified with acid isethionic and neutralized with sodium hydroxide, and fatty acid amides and methyl tauride. Additional examples are described in Surface Active Agents and Detergents (Vol. I and II, by Schwartz, Perry and Berch). A variety of such surfactants are also generally described in US Patent 3,929,678, issued on December 30, 1975, to Laughlin et al., From respective Column 23, line 58 to Column 29 , line 23 (incorporated here for reference).

Surfactants Non-ionic detergents

Nonionic detergent surfactants are generally described in the U.S. Patent

929 678 by Laughlin et al., Issued on December 30, 1975, respective Column 13, line 14 to Column 16, line 6, incorporated herein, for reference. Listed, by way of example, are classes of useful nonionic surfactants.

1. The condensates of polyethylene oxide, polypropylene and polybutylene of alkyl phenols. Polyethylene oxide condensates are generally preferred. These compounds include the condensation products of alkylphenols, having an alkyl group having 6 to 12 carbon atoms in a straight or branched chain configuration, with alkylene oxide. In a preferred embodiment, ethylene oxide is present in an amount of 5 to 25 moles of ethylene oxide per mole of alkylphenol. The tensile agents

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non-ionic actives of this type, commercially available, include Igepal ^ 00-630, marketed by GAF Corporation; and Triton MR _X _4 ₅ , χ-114, X-100 and X-102, ^all marketed by Rohm & Mas company.

2- The condensation products of aliphatic alcohols with from 1 to about 25 moles of ethylene oxide. The alkyl chain of the aliphatic alcohol can be straight or branched, primary or secondary, and generally contains 8 to 22 carbon atoms. Particularly preferred are condensation products of alcohols having a primary alkyl group having from about 10 to about 20 carbon atoms, with from about 2 to about 10 moles of ethylene oxide per mole of alcohol. Examples of commercially available nonionic surfactants of this type include Tergitol MRi5_s_g (the condensation product of a linear alcohol C11-C15 with 9 moles of ethylene oxide), Tergitol MR24; .lg NMW (0 product of condensation of a primary alcohol Ci2 “Cl4 with 6 moles of ethylene oxide with a limited molecular weight distribution), both marketed by Union Carbi of Corporation; Neodol MR45_g (the condensation product of a linear alcohol C14-C15 with 9 moles of ethylene oxide), Neodol MR 23-6.5 (the condensation product of a linear alcohol Ci2- ^C l3 ^c ° ni 6/5 moles of oxide ethylene), Neodol ^MR 45-7 (the condensation product of a linear alcohol C14-C15 with 7 moles of ethylene oxide), Neodol 45-4 (the condensation product of a linear alcohol 0 ^ 4-0 ^ 5 with 4 moles of ethylene oxide), marketed by Shell Chemical Company, and Kyro ^MR EOB (the condensation product of a C13-C15 alcohol with nine moles of ethylene oxide), marketed by The Protíter & Gamble Company.

3. Condensation products of ethylene oxide with a hydrophobic base formed by condensation of propylene oxide with propylene glycol. The hydrophobic portion of these compounds preferably has a molecular weight of about 1500 to about 1800 and is insoluble in water.

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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 extent that the polyoxyethylene content is about 50% of the total weight of the product. condensation, which corresponds to condensation with up to about 40 moles of ethylene oxide. Examples of compounds of this type include some of the commercially available Pluronic ^MR surfactants and marketed by BASF.

4. The condensation products of ethylene oxide with the product resulting from the reaction of propylene oxide and ethylenediamine. The hydrophobic portion of these products consists of the reaction product of ethylenediamine and excess propylene oxide, and generally has a molecular weight of about 2500 to about 3000. This hydrophobic portion is condensed with ethylene oxide as that condensation product containing from about 40% to about 80% by weight of polyoxyethylene, and has a molecular weight of about 5000 to about 11000. Examples of this type of nonionic surfactants include certain of the Tetronic MR compounds commercially available and marketed by BASF.

5. Semi-polar nonionic surfactants are a special category of nonionic surfactants that include water-soluble amine oxides, containing an alkyl portion of 10 to 18 carbon atoms and two portions selected from the group consisting of alkyl groups and hydroxyalkyl groups containing from 1 to 3 carbon atoms; phosphine oxides, soluble in water, containing an alkyl portion of 10 to 18 carbon atoms and 2 portions selected from the group consisting of alkyl groups and hydroxyalkyl groups containing from 1 to 3 carbon atoms; and water-soluble sulfoxides containing an alkyl portion of 10 to 18 carbon atoms and a portion selected from the group consisting of alkyl and hydroxyalkyl moieties

-21Λ

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Non-ionic, semi-polar detergent surfactants include the amine oxide surfactants of the formula

R ³ (OR ⁴ ) _X N (R5) 2

Mod. 71 - 20,000 ex. · 90/08 where R ³ is an alkyl, hydroxyalkyl or alkylphenyl group or mixtures thereof, containing 8 to 22 carbon atoms; R4 is an alkylene or hydroxyalkylene group containing from 2 to 3 carbon atoms, or mixtures thereof; X is 0 to 3; and each of R ³ is an alkyl or hydroxyalkyl group containing from 1 to 3 carbon atoms, or a polyethylene oxide group containing from about 1 to about 3 ethylene oxide groups. The RÓ groups can be linked to each other, eg through an oxygen or nitrogen atom, to form a ring structure.

These surfactants include amine oxide, in particular ^C 1O alkyl dimethylamine oxides ^"C 18 oxides ^and Cg-di-alkoxyethyl-C₄ - hydroxyethylamine.

6. The alkyl polysaccharides described in US Patent 4,565,647, to Llenado, issued January 21, 1986 with a hydrophobic group containing from about 6 to about 30 carbon atoms, preferably from about 10 to about 16 carbon atoms, and a polysaccharide, eg, a hydrophilic, polyglycoside group containing from about 1.3 to about 10, preferably, from about 1.3 to about 3, and, most preferably, about 1.3 to about 2.7 units of saccharide. Any reducing saccharide containing 5 or 6 carbon atoms can be used, e.g., glucose, lactose and galactosyl moieties can replace the glucosyl moieties. (Optionally, the hydrophobic group is attached at positions 2-, 3-, 4-, etc., thus giving rise to glucose or galactose as opposed to a glucoside or galactoside)

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Intersaccharide bonds can be, e.g. between the uir position of the additional saccharide units and the 2-, 3-, 4e / or 6- positions of the preceding saccharide units.

Optionally, and less desirably, there may be a polyalkylene oxide chain linking the hydrophobic portion and the polysaccharide portion. The preferred alkylene oxide is ethylene oxide. Typical hydrophobic groups include alkyl groups, saturated or unsaturated, branched or unbranched, containing from 8 to 18, preferably from 10 to 16 carbon atoms. Preferably, the alkyl group is a straight chain saturated alkyl group. The alkyl group can contain up to 3 hydroxyl groups and / or the polyalkylene oxide chain can contain up to 10, preferably less than 5, alkylene oxide moieties. Suitable alkyl polysaccharides are octyl, monildecyl, undecildodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl and octadecyl, di-, tri-, tetra-, penta- and hexaglu sewn, galactosides, lactosides, glucoses, fruits and fruits / or galactoses. Suitable mixtures include coconut alkyl, di-, tri-, tetra- and pentaglucosides and tallow alkyl tetra-, penta- and hexaglucosides.

Preferred alkyl polyglucosides have the formula

R ² O (C _n H2 _n O) _t (glycosyl) _x wherein R2 is selected from the group consisting of alkyl, alkylphenyl, hydroxyalkyl, hydroxyalkylphenyl and mixtures thereof, in which the alkyl groups contain from 10 to 18, preferably , from 12 to 14 carbon atoms; n is 2 or 3, preferably 2; t is from 0 to about 10, preferably 0; ex is about 1.3 to about 10, preferably about 1.3 to about 3, and most preferably, about 1.3 to about 2.7. The glycosyl is preferably derived from glucose. To prepare these compounds, the alcohol or alkyl polyethoxy alcohol is first formed and

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therefore, it is reacted with glucose or with a glucose source, to form the glucoside (bond in position 1). The additional glycosyl units can be linked between their position 1 and the preceding glycosyl units, in positions 2-, 3-, 4- and / or 6-, preferably in position 2.

7. Fatty acid amide surfactants with the formula:

I I

R ⁶ - C - N (R ⁷ ) 2 where r6 is an alkyl group containing from 7 to 21, preferably 9 to 17 carbon atoms, and each R ⁷ is selected from the group consisting of hydrogen , C1-C4 alkyl, C1-C4 hydroxyalkyl and - (C2H40) _x H, where x varies between about 1 and about 3.

The preferred amides are the ammonia amides Cg-C2Qz monoethanolamides, diethanolamides and isopropanolamides.

Other surfactants

Ampholytic surfactants can also be incorporated into the detergent compositions of the invention. These surfactants can be broadly described as aliphatic derivatives of secondary, tertiary or tertiary amines, or aliphatic derivatives of heterocyclic, secondary and tertiary amines, in which the aliphatic radical. can be linear-branched. One of the aliphatic substitutes contains at least 8 carbon atoms, typically from 8 to 18 carbon atoms, and at least one contains an anionic water-solubilizing group, e.g., carboxyl, sulfonate, sulfate. See U.S. Patent 3,929,678, to Laughlin et al., Issued December 30, 1975, in column 19, lines 18-35 (incorporated herein by reference), where examples of useful ampholytic surfactants are given.

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The zwitterionic surfactants can also be incorporated into the present detergent compositions. These surfactants can be broadly described as derived from secondary and tertiary amines, derived from heterocyclic, secondary and third amines, or derived from quaternary ammonium, quaternary phosphonium or tertiary sulfonium compounds. See US Pat ^. . 3 929 678, by Laughlon et al., Issued on December 30, 1975, from column 19, line 38 to column 22, line 48 (incorporated here for reference), to obtain examples of surfactants, zwitterionic agents Useful.

These ampholytic and zwitterionic surfactants are generally used in combination with one or more anionic and / or nonionic surfactants. especially preferred for use in the present invention are betaine and sulfobetaine (sultaine) surfactants.

Preferred, additional, surfactants are anionic and nonionic. Preferred nonionic surfactants include condensates of polyethylene oxide, polypropylene and polybutylene of alkyl phenols; the alkyl ethoxylate products of condensation of aliphatic alcohols with ethylene oxide? condensation products of ethylene oxide with a hydrophobic base formed by the condensation of propylene oxide with propylene glycol; the condensation product of ethylene oxide with the product resulting from the reaction of propylene oxide and ethylenediamine; alkyl polysaccharides, more preferably alkyl polysaccharides with a hydrophobic group containing from about 6 to about 30 carbon atoms and a polysaccharide group containing from about 1.3 to about 10 units of saccharide; fatty acid amides; and their mixtures.

If included in the compositions of the present invention, these optional additional surfactants are typically present, at a concentration of about

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from 1.0% to about 15%, preferably from about 2% to about 10%, by weight.

Other optional ingredients include detergent aids, of the organic or inorganic type, although these aids are generally not preferred for use in the compositions of the present invention, they are examples of water-soluble inorganic aids that can be used, alone or in mixtures of their own or with organic, alkaline and sequestering salts, are glycine, alkyl and alkenyl succinates, alkali metal carbonates, phosphates, polyphosphates and silicates. specific examples of these salts are sodium tri-polyphosphate, sodium carbonate, potassium carbonate, sodium pyrophosphate, potassium pyrophosphate, potassium tri-phosphate and sodium hexametaphosphate. Examples of organic adjuvant salts that can be used alone or in admixture with each other or with the aforementioned inorganic and alkaline adjuvant salts are the alkali metal polycarboxylates, of which water-soluble citrates are non-limiting examples. such as sodium and potassium citrate, sodium and potassium tartrate, sodium and potassium ethylenediaminetetraacetate, οε N- (2-hydroxyethyl) -ethylenediaminetriacetates sodium and potassium, sodium and potassium nitrilotriacetates, Sodium and potassium N- (2-hydroxyethyl) -nitrilodiacetates, sodium and potassium oxydisuccinates and potassium and sodium tartrate mono- and di-succinates, such as those described in US Patent 4 663 071 to ( Bush et al., Issued on May 5, 1987), the description of which is incorporated herein for reference. Other organic detergent aids, such as water-soluble phosphonates, can be used in the compositions of the present invention. However, detergent aids, in general, have limited value when the compositions of the present invention are in the form of dishwashing detergent compositions for delicate purposes. If they are included35

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In the compositions of the present invention, these optional adjuvants 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 are diluents, solvents, dyes, perfumes and hydrotropes (preferred Diluents can be inorganic salts, such as sodium and potassium sulfate, ammonium chloride, sodium and potassium chloride, sodium bicarbonate, etc. The diluents Useful for the compositions of the present invention are present, typically at levels from about 1% to about 10%, preferably from about 2% to about 5% by weight.

Solvents useful to the invention 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, from about 5% to about 50% by weight.

Hydrotropes such as sodium and potassium toluenesulfate, sodium and potassium xylenesulfate, sodium and potassium cumenesulfate, tri-sodium and tri-potassium sulfosuccinate and related compounds (as per US Patent 3 915 903, whose description is hereby incorporated by reference), in order to achieve the desired phase stability and viscosity in the product. It has been found that hydrotropes can have a positive effect on the foam-producing benefits of the present invention. Although it is not intended to be limited by theory, it is believed that these benefits are due to the viscosity characteristics of those hodrotropes. Hydrotropes useful in the compositions of the present invention are typically present at levels from about 1% to about 10%, preferably from about 2% to about 7% by weight.

Optional useful ingredients when the compositions of the present invention are used in applications

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for liquid dishwashing detergents, they include flow-promoting ethoxylated nonionic surfactants, of the type described in U.S. Patent 4,316,824, issued to Pancheri on February 23, 1982, a patent for which the description is incorporated herein.

Although it is not intended to be limited by theory, it is believed that the claimed compositions of the present invention are beneficial in that they provide improved foaming and grease cleaning performances, and for washing dishes without leaving a greasy touch on the washed dishes. it is especially important for consumers, for whom dishwashing is appreciated due to the absence of that greasy touch. Furthermore, although it is not intended, once again, to be limited by theory, it is believed that there are additional benefits in the compositions of the present invention, reflected in their ease of rinsing and in the fact that they reduce the slippery touch associated with typical liquid detergent compositions. This is important for consumers who do not like that slippery touch, seen as the result of an incomplete rinsing of the surfactants on the surface of the dish.

From the point of view of the process of the present invention, dirty dishes are contacted with an effective amount, typically from about 0.5 ml to about 20 ml (per 25 dishes to be treated), preferably about 3 ml to about 10 ml, of the composition of the present invention. The actual amount of liquid detergent composition used will be based on the user's judgment and will typically depend on factors such as the specific formulation of the composition product, including the concentration of active ingredient in the composition, the number of dirty dishes to be washed, the degree of dirtiness of the dishes, and others. The particular formulation of the product, in turn, will depend on a number of factors, such as the placement market (i.e., USA, Europe, Japan, etc.) of the product of the composition. The following are examples of typical processes in which detergent compositions of

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Mod. 71 - 20,000 ex. - 90/08 feels invention can be used for washing dishes. These examples are for illustrative purposes and are not limiting.

In a typical US application, from about 3 ml to about 15 ml, preferably from about 5 ml to about 10 ml, a liquid detergent composition of about 1000 ml to about 10,000 ml is combined , more typically / from about 3000 ml to about 5000 ml of water, in a dishwasher with a volumetric capacity in the range of 5000 ml to about 20 000 ml, more typically, from about 10 000 ml to about 15 000 ml. The detergent composition has a surfactant mixture concentration of about 21% to about 44% by weight, preferably from about 25% to about 40% by weight. Dirty dishes are immersed in the sink containing the detergent and water composition, and are then washed by contacting the dirty surface of the dish with a cloth, sponge or similar article. The cloth, sponge or similar article can be immersed in the mixture of detergent and water composition before contacting the surface of the dish, and normally contacts the surface of the dish for a period of time ranging from about 1 to about 10 seconds / although the real time varies in each application and with each user. When the cloth, sponge or similar article is contacted with the surface of the plate, it is preferably rubbed simultaneously.

In a typical application for the European market, from 3 ml to 15 ml, preferably

te of about 3 ml about of 10 ml in an composition in- liquid detergent with fence in 1000 ml The fence in 10,000 ml, more typically, in fence in 3000 ml The fence in 5000 ml in

water, in a sink with a volumetric capacity between about 5000 ml and about 20 000 ml, more typically, between about 10 000 ml and about 15 000 ml. THE

MJ ~ detergent composition has a tensile-active mixture concentration of about 21% to about 44% by weight, preferable-3563,905

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about 25% to about 35% by weight. The dirty dishes are immersed in the sink containing the detergent and water composition, and there they are washed by contacting the dirty surface of the dish with a cloth, sponge or similar article. The cloth, sponge or similar article can be immersed in the mixture of detergent and water composition before contacting the surface of the dish, normally contacting the surface of the dish for a period ranging from about 1 to about 10 seconds, although the real time varies with each application and with each user. During the contact of the cloth, sponge or similar article with the surface of the plate, it is preferably rubbed.

In a typical application for the Latin American and Japanese markets, from about 1 ml to about 50 ml are combined, preferably from about 2 ml to about 10 ml of a liquid detergent composition with about 50 ml at about 2000 ml, more typically, with about 100 ml to about 1000 ml of water, in a container with a volumetric capacity between about 500 ml and about 5000 ml, more typically, between about 500 ml and about 2000 ml. The detergent composition has a surfactant mixture concentration of about 5% to about 40% by weight, preferably from about 10% to about 30% by weight. Dirty dishes are washed by contacting the dirty surface of the dish with a cloth, sponge or similar article. The cloth, sponge or similar article can be immersed in the mixture of detergent and water composition before contacting the surface of the dish, and contacts, usually with the surface of the dish for a period of time ranging from about 1 to about 10 seconds. although the real time varies in each application and with each user. During the contact of the cloth, sponge or similar article with the surface of the plate, it is preferably rubbed.

Another use process will include immersing dirty dishes in a water bath without any

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Mod. 71 - 20,000 βχ. - 90/08 liquid dishwashing detergent. A device for absorbing liquid dishwashing detergent, such as a sponge, is placed directly in a separate amount of undiluted liquid dishwashing composition for a period of time that typically ranges from about 1 at about 5 seconds.0 absorption device and, consequently, the undiluted liquid dishwashing composition then individually contact the surface of each dirty dish to remove dirt. The absorption device is normally contacted with the surface of each plate for a period of time from about 1 to about 10 seconds, although the actual application time depends on factors such as the degree of dirt on the plate. During the contact of the absorber with the surface of the plate, it is preferably rubbed.

EXPERIMENTAL PART

An example of a process for preparing an N-methyl surfactant, 1-deoxy-glucityl-lauramide for use in the present invention is exemplified below. Although any chemical expert may vary the configuration of the device, a device suitable for use here comprises a three-liter, four-necked flask equipped with a paddle stirrer driven by an engine and with a thermometer of sufficient length to contact with the reaction medium. The other two necks of the flask are equipped with a nitrogen inlet and a large side tube (be careful: a large side tube is important in the case of very fast methanol release), to which a collection condenser is connected effective and a vacuum outlet. The latter is connected to a nitrogen purge and a vacuum gauge and then to a vacuum cleaner and a trap. A 500-watt heating mantle with a transformer temperature controller is placed

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variable (Variac), used to heat the reaction, on a laboratory jack, so that it can be raised or lowered for additional control of the reaction temperature.

Place in an N-methyl-glucamine flask (195g, 1.0 mole, Aldrich, M4700-0) and methyl laurate (Procter & Gamble CE 1270, 220.9 g, 1.0 mole). The solid / liquid mixture is heated with stirring under a stream of nitrogen to form a melt (approximately 25 minutes). When the melt temperature reaches 145 ° C, catalyst (anhydrous sodium carbonate powder, 10.5 g, 0.1 mole, J.T. Baker) is added. The nitrogen stream is cut and the vacuum cleaner and nitrogen purge are adjusted to a vacuum of 5 inches Hg (16 kPa). From this moment on, the reaction temperature is maintained at 150 ° C by adjusting the Variac and / or raising or lowering the blanket.

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

In 7 minutes, the first methanol bubbles are observed in the meniscus of the reaction mixture. A vigorous reaction follows almost immediately. The methanol is distilled until its flow rate drops. The vacuum is adjusted to obtain a vacuum of about 10 inches Hg (32 kPa). The vacuum is increased more or less as follows (in inches of Hg (kPa), in minutes): 10 (32kPa) in 3, 20 (65 kPa) in 7, (82 kPa) in 10. Stop the heating and stirring 11 minutes after the start of methanol release, then some foam formation. The product is cooled, which solidifies.

The following examples are intended to exemplify compositions of the present invention, but are not intended to limit or otherwise define the scope of the invention, this scope being determined in accordance with the claims that follow.

EXAMPLES

The following examples illustrate the practice of the invention, but do not limit it.

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Mod. 71 - 20,000 ex.

The following compositions are formulated on a weight percentage basis. These compositions are prepared according to the description below:

Initially, a surfactant paste is formed by combining any desired surfactants with water and alcohol. The surfactants contained in this surfactant paste include the fatty acid polyhydroxyamides of the present invention. Ideally, the surfactant paste should be pumpable at room temperature or at elevated temperatures. Separately, in a large mixing bowl with a propeller stirrer, combine, with the mixture to obtain a clear solution, three quarters of water of the formulated product, half of the alcohol of the formulated product and any necessary hydrotropes (eg xylene, cumene, toluenesulfonates). Then, magnesium is added, followed by the surfactant paste, to form a mixture.

Magnesium can be added directly to the mixing vessel as magnesium chloride, magnesium sulfate or as magnesium oxide or hydroxide powder. The magnesium oxide or hydroxide powder is added to the acid form of the salts of surfactants (e.g. alkylbenzenesulfonates, alkyl sulfates, ethoxylated alkyl sulfates, methyl estersulfonates, etc.) in the surfactant paste. When magnesium is added as an oxide or hydroxide powder, a smaller amount than that which is chiometrically necessary is added, with mixing, to ensure complete dissolution. The pH of the magnesium-containing surfactant paste is then adjusted using NaOH or KOH solutions.

The mixture is mixed until a clear and homogeneous product solution is obtained. Then more water, alcohol and any additional hydrotopes (added as a solution) can be added to cut the viscosity of the

-3963,905

4263

R

Case:

>

product solution to the desired level, ideally between 0.05 Pa.s (50 cps) and 1 Pa.s (1000 cps), as measured by a Brookfield visaosimeter, at 21, 1 ^and C (70 ^s F). The pH of the product solution with HCl or NaOH is then adjusted to a level of 7.0 + 0.7, in the case of formulas containing ammonium ions, and to 8.5j; 1.5, for the for formulas that do not contain ammonium ions.

Finally, perfume, dye and other ingredients are added, e.g., opacifying agents such as Lytron and ethylene glycol distearate. Lytron can be added directly as a dispersion, with mixing. The ethylene glycol distearate must be added in a molten state, with rapid mixing, to form the desired pearl-shaped crystals.

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

Component A

N-methyl-C1-2 alkyl ^_ 14 "-glucamide 5.0

Linear alkyl

-sodium benzenesulfonate 15.0

Ammonium coconut-ethoxylate alcohol sulphate (1.0 med.)

B

12.5

Ç D E

9.0 10.0 20.0

10.0

10.0 15.0 10.0

10.0

10.0

Ammonium coconut alcohol sulphate - - 5.0

MgO

2.0 2.0 1.5

2.5

2.0

Dodecyl-dimethylamine oxide

4.0 3.5 - 3.0 _'40_

63,905

Case: 4263 R

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

Amidopropyl dimethyl betaine dp cocn

Coconut monoethanolamide

Coconut diethanolamide

Sodium cumenesulfonate

Potassium toluenesulfonate

Propylene glycol

Ethanol

Water & div.

(dye, perfume, opacifier, etc.)

2.0

2.0

2.0

3.0

2.0 4.0

1.0 2.0

1.0

4.0 3.0 2.0 4.0

3.0

4.0 5.0 5.0 5.0

3.0

2.0

--- the rest to 100% - 25

EXAMPLE II

The following compositions are formulated in one; weight percentage basis. These compositions are prepared in the same way as the compositions of Example I.

Component

N-methyl-C ^ ₂ ~ 14 ^- alkyl

-glucamine 5.0 5.0 10.0 10.0

6, / 0

- <H63.905

Case: 4263 Έ

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

Linear alkyl Cjj ₍ sodium _2- benzenesulfonate

Ammonium coconut-ethoxylate sulfate (1.0 med.)

Ammonium coconut alcohol sulphate

Coconut acid methyl ester-sulfonate sodium salt

MgCl ₂

Alpha-olefin C14-I6-sodium sulfonate

Coconut polyglycoside (med. 1.6 glucose units per molecule)

10.0

25.0

8.0

10.0 5.0

15.0

8.0

0.5 1.5 0.8 0.6 1.8

Dodecyldimethyl amine oxide 3.0

Coconut starch propylimethyl-betaine

3.0

Coconut monoethanolamide 2.0

Sodium cumenesulfonate

5.0

3.0

3.0

20.0

5.0 1.6

2.0 3.0 3.0 3.0

4.0

-4263,905

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1992

Mod. 71 - 29,000 ex. - 8/90

Potassium toluenesulfonate

Ethanol

Water & div.

Dye, perfume, opacifier, etc.)

5.0 4.0

2.0

3.0 2.5

--- the rest to 100% -

EXAMPLE III

The following compositions are formulated on a weight percentage basis. These compositions are prepared in the same way as the compositions of Example I.

Component

N-methyl-C1-2 alkyl ^- 14'-glucamide

Linear alkyl Cji ^ -sodium benzenesulfonate

Ammonium coconut-ethoxylate alcohol sulphate (1.0 med.)

Coconut acid methyl ester sulfonate sodium salt

MgCl ₂

15.0 20.0 12.5 5.0

5.0

15.0 5.0

15.0

0.5 0.7 2.0 1.9

I í

'92

63,905

Case: 4263 R

Coconut polyglycoside (med. 1.6 glucose units per molecule)

15.0 dodecyldimethyl amine oxide 3.0 6, Ώ

Mod. 71 - 20,000 ex. -? 0/08

Coconut starch propylimethyl-betaine

Hexadecildimethyl-betaine

Coconut diethanolamide

Sodium cumenesulfonate

3.0

- - - 5.0

3.0 2.0

3.0

Sodium Xylenesulfonate

Potassium toluenesulfonate

Ethanol

Water & div.

(dye, perfume, opacifier, etc.)

3.0

2.0 2.0

4.0 3.0

3.0 4.0

--- the rest to 100% - 30

EXAMPLE IV

The following compositions are formulated on a weight percentage basis. These compositions are prepared in the same way as the compositions of Example I.

63,905

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

Component THE B ç D AND Linear alkyl Cll, 2 benzenesulfonate ammonium - 10.0 8.0 13.5 13.5 Ci2 ~ 14 fatty acid N-methylglucamide 16.5 12.5 10.0 12.5 10.0 Alkyl sulfate ^C 12- ^C 14 ^(E °), 8 Ammonium 12.5 11.0 10.0 6.0 Coconut-starch-propyl -betaine 1.5 4.0 3.0 2.0 2.0 Hexadecildimethyl- -betaine 2.0 3.5 3.0 3.0 2.5 Monoethanolamide Of coconut 3.8 3.8 3.8 2.0 - alkyl oxide 0 ^ 2- ^ 14 -dimethylamine - - 4.0 2.0 3.0 Cumenesulfonate sodium 1.0 1.0 1.0 1.0 2.0 Ethanol 4.5 5.0 5.0 4.0 4.0 Urea 0.5 - - - 0.7 Magnesium hydroxide 1.6 1.5 1.5 1.5 1.5

- 4T7 / 5

63,905

Case: 4263 R /

''

--- the rest to 100% - Water & div. (dye, perfume, opacifier, etc.

EXAMPLE V

The following compositions are formulated on a weight percentage basis. These compositions are prepared in the same way as the compositions of Example I.

Component

Alpha-olefin ^c 14 ~ 16 sulfonate

5.0

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

Alpha-olefin

magnesium sulfonate 5.0

Dodecylbenzenesulfonate

C12 ~ i4 fatty acid N-methylglucamide 12.0

C1-2 alkyl- ^e t ° ^x i (0.8 med) -Magnesium sulfate 12.0

C1-2 alkyl-ethoxy (1.0 med)-magnesium sulfate

Etoxylate (0.8 med) of primary alcohol C ^ q

10.0 10.0 5.0

5.0

12.0 5.0 10.0 10.0 12.0

12.0

15.0

5.0

5.0

4.0

-4é63,905

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Mod. 71 - 20,000 ex. - 5Ό / Ο8

Dimethyl- -Beta2 Ci2 ~ 14 4.0 - - - - - Starch ^ dimethyl- -betaine C22 ~ 14 3.0 3.0 3.0 3.0 Monoethanolamide of coconut acid - - - 2.0 - - Diethanolamide from coconut acid - - 2.0 2.0 - - dimethyl oxide coconut amide - 3.0 - - 3.0 3.0 Cumenesulfonate sodium 3.0 2.0 2.0 3.0 5.0 2.0 Xylenesulfonate sodium 1.0 3.0 3.0 - - - Ethanol 5.0 5.0 3.0 4.0 5.0 4.0 Diestearate ethylene glycol - - - 1.0 - - Urea 2.0 1.5 - - - - Water & div. (dye, opacifying perfume, etc. l ) ---O remaining for 100% ---

EXAMPLE VI

The following compositions are formulated in a

63,905

Case: 4263 R

27JAN.1992 weight percentage basis. These compositions are prepared in the same way as the compositions of Example I.

Component A

^C 1214 fatty acid N-methylglucamide

10.0 14.0

8.0

10.0 10.0

C22-14 ~ alkyl ^and toxi (0.8 med) - magnesium sulfate 5.0

C1-13 alkyl-ethoxy (1.0 med)-magnesium sulfate 5.0

10.0 13.0

10.0

Mod. 71 - 23,000 ex. - 8/90

C1-13 alkyl _ ^and toxi (6.5 med) - magnesium sulfate 5.0

13.0

Magnesium C14-16 paraphosulfonate

Methyl ester sulfonate ^c 12 “14 magnesium

5.0

5.0 10.0

5.0 10.0

C14-2 £ -5 polyglycoside, O 5.0

5.0

Primary alcohol ethoxylate (med 8.0)

Dimethylbetaine

C12-14 - 3.0

4.0

-45 ¹ 63,905

Case: 4263 R! Í27 JãN.’í992

L /

Amidopropxldimeti1

-betaine C12-14 2.0 - - - 2.0 - Monoethanolami of coconut acid 1.0 2.0. 2.0 - - - Diethanolamide of coconut acid 1.0 2.0. 2.0 - - - dimethyl oxide coconut amine 1.0 - 3.0 5.0 2.0 4.0 Cumenesulfonate sodium 2.0 2.0 2.0 - - 2.0 Xylenesulfonate sodium 2.0 2.0 2.0 3.0 4.0 2.0 Ethanol 3.0 - 4.0 4.0 5.0 4.0 Diestearate ethylene glycol - - 1.0 - - - Dimeti lbetaí at C ^ g 3.0 -

Water & debt

(dye, perfume, opacifier, etc.) —c remaining to 100%) -

EXAMPLE VII

The following detergent compositions are formulated on a weight percentage basis. These compositions are prepared in the same way as the compositions of Example I.

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Case: 4263 R

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A B

D E F

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

Component

Paraffin sulfonates ¢ 44-45 sodium

Paraffin sulfonates ¢ 44-45 sodium

Sodium salt of a sulfated coconut alcohol, ethoxy side, with 3 moles of ethoxylated oxide

Magnesium salt of a sulfated coconut alcohol, ethoxylated, with 3 moles of ethylene oxide, coconut glycerin ether sulfonate, sodium

Magnesium coconut glyceryl ether sulfonate

C ₁₂ ~ i4 fatty acid N-methylglucamide

26.0

26.0

14.0

34.0

15.0

5.0

15.0 10.0

5.0

15.0 12.0 12.0 15.0 10.0 3.0

10.0

-W63.905

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

Dimethyl oxide dodecyl-amine 4.0 4.0 4.0 4.0 4.0 4.0 2.0 Acylamide- propyl dimethylbetaine C12-14 5.0 5.0 5.0 Triethanolamine 3.5 3.5 3.5 3.5 3.5 3.5 - Ethanol 5.0 5.0 5.0 5.0 5.0 5.0 - Carbopol ^R 616 - - - 1.0 - - Carbopol ^R 617 - - - - 2.0 - Water & div. (dye, perfume, opacifier, etc.) --- 0 remaining for 100% ---

EXAMPLE VIII

An alternative process for the preparation of the fatty acid polyhydroxyamides usable here is the following. A reaction mixture consisting of 84.87 g of fatty acid methyl ester (source: CE1270 Procter & Gamble methyl ester) is used 75 g of N-methyl-D-glucamine (source: M4700-0 from Aldrich Chemical Company) , 104 g of sodium methoxide (source: 16.499-2 from Aldrich Chemical Company) and 68.51 g of methyl alcohol. The reaction vessel comprises a standard reflux assembly, with a drying tube, a condenser and a stir bar. In this procedure, N-methyl-glucamide is combined with methanol, with stirring, under argon, and heating is started with a good mixture (stir bar; reflux). After 15-20 minutes, when the solution reaches the desired temperature, the sodium methoxide and ester catalysts are added. Samples are taken periodically to control the reaction, checking that the solution is completely clear at 63.5 minutes.

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

The reaction is thought to be, in fact, almost complete on that point. The reaction mixture is refluxed for 4 hours. After removal of methanol, the recovered crude product weighs 156.16 grams. After vacuum drying and purification, a total of 106.92 grams of purified product is recovered. However, percentage yields are not calculated on this basis, as regular sampling during the reaction makes a percentage value of total yield meaningless. The reaction can be carried out at reagent concentrations of 80% and 90%, for periods up to 6 hours, to obtain products with very low formation of secondary products.

It is not intended, with the following, to limit this invention, but simply to illustrate additional aspects of the technology that can be considered by the formulator in the manufacture of a wide variety of detergent compositions using fatty acid polyhydroxyamides.

It will soon be understood that fatty acid polyhydroxyamides, due to their amide bond, are, in very basic or very acidic conditions, subject to some instability. Although some decomposition can be tolerated, it is preferable that these materials are not subjected to pH's greater than about 11, preferably 10, or less than 3, for too long periods. The pH of the final product (liquids) is typically 7.0-9.0.

During the manufacture of fatty acid polyhydroxyamides, it is usually necessary to neutralize, at least partially, the catalyst base used in the formation of the amide bond. Although any acid can be used for this purpose, the detergent formulator easily recognizes that it is simpler and more convenient to use an acid that provides an anion that is useful and desirable in the composition to hold finished people. For example, citric acid can be used for neutralization purposes, and the resulting citrate ion (ca.1%) can be left in a polyhydroxyamide slurry of ca. 40%, and be pumped to the later phases

-5Zi

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Mod. 71 - 23,000 ex. - 8/90

the overall detergent manufacturing process. Acidic forms of materials such as oxidisuccinate, nitrilotriacetate, ethylene diaminetetraacetate, tartrate / succinate and the like can be used in the same way.

Fatty acid polyhydroxyamides, derived from coconut alkyl fatty acids (predominantly C12-C14) are more soluble than their tallow acid counterparts (predominantly Cig-Cig). Consequently, Ci2 ^-C l4 materials are somewhat easier to formulate in liquid compositions, and are more soluble in cold water baths. However, C ^ gC ^ g materials are also quite useful, especially in circumstances where warm or hot wash water is used. In fact, Cig-C ^ g materials can be better detergent surfactants than their C12-C14 counterparts · In these terms, the formulator may wish to balance ease of manufacture with performance by selecting a poly - fatty acid hydroxyamide for use in a given formulation.

It should also be noted that the solubility of the fatty acid polyhydroxyamides can be increased by the existence of points of unsaturation and / or chain branching in the fatty acid portion. Thus, materials such as fatty acid polyhydroxyamides derived from oleic acid and isostearic acid are more soluble than their corresponding n-alkyl compounds.

Similarly, the solubility of the fatty acid polyhydroxyamides prepared from disaccharides, trisaccharides, etc., is generally superior to the solubility of the corresponding materials derived from monosaccharides. This higher solubility may be of particular interest when formulating liquid compositions. In addition, fatty acid polyhydroxyamides, in which the polyhydroxy group is derived from maltose, appear to act especially well as detergents when used in combination with alkylbenzenesulfonate surfactants.

-5Ò63,905

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

Conventional (Las). Although it is not intended to be limited by theory # it seems that the combination of LAS with fatty acid polyhydroxyamides derived from higher saccharides, such as maltose, causes an unexpected and substantial lowering of the interfacial tension in aqueous media, thus intensifying performance real detergency. (The manufacture of a maltose-derived fatty acid polyhydroxyamide is described hereinafter).

Fatty acid polyhydroxyamides can be made not only from purified sugars, but also from hydrolyzed starches, eg, corn starch, potato starch or any other suitable plant-derived starch containing mono-, di - etc., saccharide desired by the formulator. This is of particular importance from an economic point of view. Thus, corn syrup with high glucose content, corn syrup with high maltose content, etc. The hydrolyzed and delignified cellulose pulp can also be a source of raw material for fatty acid polyhydroxyamides.

As noted earlier, fatty acid polyhydroxy derivatives derived from higher saccharides, such as maltose, lactose, etc., are more soluble than their corresponding glucose derivatives. Furthermore, does it appear that the more soluble fatty acid polyhydroxyamides can help to solubilize their less soluble counterparts? to varying degrees. Consequently, the formulator may choose to use a raw material comprising a corn syrup with a high glucose content, for example, but choose a syrup that contains a small amount of maltose (e.g. 1% or more). The resulting mixture of acid polyhydroxyamides will, in general, exhibit preferable solubility properties over a wider range of temperatures and concentrations than a pure fatty acid polyhydroxyamide derived from glucose. So, in addition to any

-Ò “V

63,905

Case: 4263 R, · Λ. * * Λ,

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

edonomic advantages in using mixtures of sugars instead of pure sugars, fatty acid polyhydroxyamides prepared from mixed sugars can offer very substantial advantages in terms of performance and / or ease of formulation. However, in some cases, some loss in fat removal performance (dishwashing) at fatty acid maltamide levels greater than about 25%, and some loss of foaming above about 33% may be noted. (said percentages corresponding to the percentage of fatty acid polyhydroxyamides derived from maltamide vs. fatty acid polyhydroxyamides derived from glucose in the mixture). This may vary slightly, depending on the chain length of the fatty acid portion. Thus, typically, the formulator who chooses to use these mixtures may find it advantageous to select mixtures of fatty acid polyhydroxyamides containing monosaccharide (eg glucose) ratios for higher disaccharides and salts (eg maltose) between about 4: 1 and about 99: 1.

The manufacture of the preferred, non-cyclized fatty acid polyhydroxyamides from fatty esters and N-alkylpolyols can be carried out in alcoholic solvents, at temperatures of about 30 ° C-90 ° C, preferably about 50 ° C-80 ° C. It has now been found to be convenient. for the formulator of, for example, liquid detergents to conduct these processes in 1,2-propylene glycol solvent, since the glycol solvent does not need to be completely removed from the reaction product before use in the finished detergent formulation. Likewise, the formulator of, for example, solid detergent compositions, typically granular, may find it convenient to carry out the process at 30 ° C-90 ° C in solvents comprising ethoxylated alcohols, namely ethoxylated alcohols (E0 3-8 Cx2 ^{- C} 14 'as □ s that are available as NEODOL 23 E06.5 (Shell). When using these ethoxylates, it is preferable that they do not

-ifíT63,905

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have substantial amounts of non-ethoxylated alcohol, and it is more preferable that they do not contain substantial amounts of monoethoxylated alcohol. (Designation T).

Although the processes for producing fatty acid polyhydroxymines per se are not part of the present invention, the formulator may also consider other syntheses of fatty acid polyhydroxymines, such as those described hereinafter.

Typically, the industrial-scale reaction sequence for the preparation of acyclic fatty acid polyhydroxyamides comprises: Step 1 - preparation of the N-alkylpolyhydroxyamine derivative from the desired sugar or sugar mixtures, by forming an adduct N-alkylamine and sugar, followed by reaction with hydrogen, in the presence of a catalyst; followed by Step 2-reaction of said polyhydroxyamine with, preferably, a fatty ester, to form an amide bond. Although a variety of N-alkyl-polyhydroxymines useful in Step 2 of the reaction sequence can be prepared by various processes described in the art, the following process is convenient and uses economical sugar syrup as a raw material. It should be understood that, in order to obtain the best results when using this sugar syrup as a raw material, the manufacturer must select syrups that are quite clear in terms of color or, preferably, almost colorless (transparent as water).

Preparation of N-alkyl-polyhydroxyamine from Plant-derived Sugar Syrups

I. Adduct Formation - The following is a standardized process in which about 420 g of about 56% glucose solution is reacted (corn syrup - about 231 g of glucose - about 1.28 moles) as a Gardner color of less than 1, with about 119 g of aqueous solution of

63,905

Case: 4263 R

Ρ Λ

Τ '; * 1 P /% &

50% methylamine (59.5 g of methylamine - 1.92 moles). The methylamine solution (MMA) is purged and protected with N2, and cooled, to about 10 ° C, or less. The corn syrup is purged and protected with N2 at a temperature of about 10 ° -20 ° C. Corn syrup is added slowly to the MMA solution, at the indicated reaction temperature, as shown. Gardner color is measured at approximate times, indicated in minutes.

TABLE 1

Time in minutes: 10 30 60 120 180

240

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

Reaction temperature ° C

Gardner color (approximate)

As can be seen from the previous data, the Gardner color for the adduct is much worse when the temperature rises above 30 ° C and, at around 50 ° C, the time during which the adduct has a Gardner color less than 7 is only about 30 minutes. For longer reaction and / or retention times, the temperature should be less than about 20 ° C. The Gardner color should be less than 7 and, preferably, less than 4 for a good colored glucamine.

When lower temperatures are used for adduct formation, the time required to reach a substantially equilibrium concentration of the adduct is shortened by using higher amine to sugar ratios. With the said 1.5: 1 molar ratio of amine to sugar, equilibrium is reached in about two hours, at a reaction temperature of about 30 ° C. At a molar ratio of 1.2: 1, under the same conditions, the time is at least

-Π63,905

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Mod. 71 - 23,000 ex. - 8/8 less, about three hours. For good color, the combination of amine: sugar; the reaction temperature; and the reaction time

Λ / rv, are selected to achieve a substantial equilibrium conversion, eg, more than about 90%, preferably more than about 95%, and, more preferably still, more than about 99 %, based on sugar, and a color of less than about 7, preferably less than about 4, and more preferably still less than about 1, for the adduct.

Using the above process at a reaction temperature of less than about 20 ° C, and corn syrups with different Gardner colors as indicated, the color of the MMA adduct (after substantial equilibrium has been reached in at least two hours) is as indicated.

TABLE 2

Gardner Color (Approximate)

Corn syrup 1

Adduct 3

111 +

4/5 7/8 7/8

As can be seen from the table above, the starting sugar material must be almost colorless, in order to have a consistently acceptable adduct. When sugar has a Gardner color of about 1, the adduct is sometimes acceptable and sometimes unacceptable. When the Gardner color is greater than 1, the resulting adduct is unacceptable. The better the initial color of the sugar, the better the color of the adduct.

II. Reaction with hydrogen- The previous adduct is hydrogenated with a Gardner color of 1 or less, according to the following procedure.

About 539 g of adduct in water and about 23.1 g of United Ca-6-S53.905 are added to a one-liter autoclave.

Case: 4263 R

Mod. 71 - 20,000 ex. - 90/08 talyst G49B Ni, and purged twice with 1397 kPa (200 psig) of H2, at about 20 ° C. The H2 pressure is raised to about 9778 kPa (1400 psi), and the temperature is raised to about 50 ° C. Thereafter, the pressure is raised to about 11174 kPa (1600 psig), and the temperature is maintained at about 50-55 ° C for about three hours. At this point, the product is hydrogenated by about 95%. The temperature is then raised to about 85% ° C, for about 30 minutes, the reaction mixture is decanted and the catalyst is filtered off. The product, after removal of water and MMA by evaporation, consists of about 95% N-methyl-glucamide, as a white powder.

The previous procedure is repeated with about 23.1 g of Ni Raney catalyst, with the following changes. The catalyst is washed three times and the reactor, with the catalyst in the reactor, is purged twice with 1397 kPa (200 psig) of H2, being pressurized with H2 at 11174 kPa (1600 psig) for two hours, the pressure is broken at one hour, and the reactor pressurized again at 11174 kPa (1600 psig). The adduct is then pumped into the reactor which is at about 1397 kPa (200 psig) and 20 ° C, and which is purged with 1397 kPa (200 psig) of H2, etc., as before.

the resulting product has, in each case, more than 95% N-methyl-glucamine; has less than about 10 ppm Ni, based on glucamine; and has a solution color less than about Gardner 2.

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

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

In another reaction, the adduct is prepared from about 159 g of 50% methylamine in water, which is purged

63,905

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

and protected with N2 at about 10-20 ° C. About 330 g of about 70% corn syrup (qua, if transparent like water) are degassed with N2 at about 50 ° C and slowly added to the methylamine solution at a temperature of less than about 20 ° C. The solution is mixed for about 30 minutes, obtaining about 95% adduct which is a light yellow solution.

About 190 g of the adduct in water and about 9 g of United Catalyst G49B Ni catalyst are added to a 200 ml autoclave and purged three times with H2 at about 20 ° C. The H2 pressure is raised to about 1397 kPa (200 psig), and the temperature is raised to about 50 ° C. The pressure is increased to about 1746 kPa (250 psi) and the temperature is maintained at about 50-55 ° C for about three hours. The product, which at this point, is 95% hydrogenated, is then subjected to a temperature of about 85 ° C for about 30 minutes, and the product, after removal of water and evaporation, consists of about 95% N-methyl-glucamine, as white powder.

It is also important to minimize the contact between the adduct and the catalyst when the H2 pressure is less than about 6984 kPa (1000 psig), to minimize the Ni content of glucamine. The nickel content of N-methyl-glucamine in this reaction is about 100 ppm, when compared to less than 10 ppm from the previous reaction.

The following reactions with H2 are carried out to directly compare the effects of the reaction temperature.

A 200 ml autoclave is used, following the typical procedures similar to those previously presented for the preparation of the adduct and for carrying out the reaction with hydrogen, at various temperatures.

The adduct for the production of glucamyl is prepared by combining about 420 g of 55% glucose solution (corn syrup) (231 g of glucose; 1.28 moles) (a so-6063.905

Case: 4263 R

THE

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

Solution is made using Cargill's 99DE corn syrup, the solution having a water color less than Gardner 1) and about 119 g of 50% methylamine (59.9 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 about 10 ° C.

2. Degass and / or purge the 55% corn syrup solution at 10-20 ° C with N2 to remove oxygen from the solution.

3. The corn syrup solution is added slowly to the methylamine solution, maintaining the temperature below about 20 ° C.

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

adduct is used for the reaction with hydrogen shortly after it has been prepared, or is stored at low temperature to prevent further degradation.

The adduct / glucamine reaction with oxygen is as follows:

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

2. Purge the reaction mixture with about 1397 kPa (200 psi) of H2, twice, at about 20-30 ° C.

3. Pressurize with H2 at about 2794 kPa (400 psi), and raise the temperature to about 50 ° C.

4. The pressure is raised to about 3492 kPa (500 psi), and reacted for about 3 hours. The temperature is maintained at about 50-55 ° C. Sample 1 is taken.

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

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

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

Conditions for reactions at constant temperature are:

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

2. Purge with about 1397 kPa (200 psi) of H2, twice, at low temperature.

3. Pressurize with H2 at about 2794 kPa (400 psi), and raise the temperature to about 50 ° C.

4. Raise the pressure to about 3492 kPa (500 psi), and react for about 3.5 hours. Keep the temperature at the indicated value.

5. Decant and filter the Ni catalyst by filtration. Sample 3 is for a temperature of 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 tests give similar purity for N-methyl-glucamine (about 94%); Gardner colors for all tests are similar after the reaction, but only the two-stage heat treatment produces good color stability; and the test at 85 ° C gives marginal color immediately after the reaction.

EXAMPLE IX

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

Step 1-Reagents: maltose monohydrate (Aldrich, lot 01318KW); methylamine (40% by weight in water) *

(Aldrich, lot 03325TM); Raney nickel, 50% sludge (UAD 52-73D, Aldrich, lot 12921LW).

The reagents are added to a glass coating tube (250 g of maltose, 428 g of methylamine solution, 100 g of catalyst slurry - 50 g of Ni Raney) and

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they are placed in a 3 1 oscillating autoclave, which is purged with nitrogen (3X3492 kPa (500 psig)) and hydrogen 2X3492 kpa (500 psig), and gently stirred under H2 at room temperature for a weekend at room temperatures ranging between 28 ° C and 50 ° C. The crude reaction mixture is vacuum-filtered 2X through a glass microfiber filter with a silica gel plug. Concentrate the filtrate until a viscous material is obtained. The final traces of water are removed by azeotropic distillation, dissolving the material in methanol and then removing the methanol / water on a rotary evaporator. The final drying is carried out under high vacuum. The crude product is dissolved in refluxing methanol, filtered, cooled to recrystallize, filtered and the filter cake dried under vacuum at 35 ° C. This is the fraction; # !. Concentrate the filtrate until a precipitate begins to form, and store in a refrigerator overnight. Filter the solid and dry in vacuo. This is the fraction ^ 2. The filtrate is again filtered to half its volume and recrystallized. Very little precipitate is formed. A small amount of ethanol is added and the solution is left in the freezer for a weekend. Filter the solid material and dry in vacuo. The combined solids comprise N-methyl-maltamine which is used in Step 2 of the overall synthesis.

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

Heat, in a sealed ampoule, 20.36 g of tallow methyl ester to its melting point (water bath) and load in a 250 ml round bottom flask, with three necks, with mechanical stirring. The flask is heated to ca. 70 ° C to prevent the ester from solidifying. Separate-6363,905

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In addition, 25.0 g of N-methyl maltamine 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 are added. After four hours, the reaction mixture is still not ..... clarified, so an additional 10 mol% of catalyst is added (for a total of 20 mol%) and the reaction is allowed to continue overnight (ca. 68 ° C), after which the mixture is clear. The reaction flask is then modified for distillation. The temperature is raised to 110 ° C. Distillation at atmospheric pressure is continued for 60 minutes. Thereafter, high vacuum distillation begins and continues for 14 minutes, after which the product is very thick. The product is left in the reaction flask, at 110 ° C (external temperature), for 60 minutes. Scrape the product off the flask and soak in ethyl ether for a weekend. The ether is removed on a rotary evaporator and the product is stored in an oven overnight, grinding to a powder. Any remaining N-methyl-maltamine is removed from the product using silica gel. A silica gel slurry in 100% methanol is loaded into a funnel and washed several times with 100% methanol. A sample of the product is loaded onto silica gel (20 g in 100 ml of 100% methanol) and eluted several times using vacuum and several washes with methanol. The collected eluent is evaporated to dryness (rotary evaporator). Any remaining tallow ester is removed by maceration with ethyl acetate overnight, followed by filtration. The filter cake is then dried under vacuum. The product is tallow N-methyl-alkyl-maltamine.

Alternatively, Step 1 of the previous reaction sequence can be conducted using commercial corn syrup, comprising glucose or mixtures of glucose and, typically, 5% or more, maltose. The resulting fatty acid polyhydroxyamides and mixtures can be used in any of the detergent compositions of the invention

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In yet another form, Step 2 of the previous reaction sequence can be carried out in 1,2-propylene glycol or NEODOL. Depending on the formulator's preference, propylene glycol or NEODOL does not need to be removed from the reaction product before use in the formulation of 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 fatty acid polyhydroxyamide.

Depending on the formulator's wishes, the present compositions may contain more or less of a number of foam control agents. Typically, for dishwashing, the formation of a lot of foam is desirable, thus, no foam control agent is used. For washing fabrics in top-loading washing machines, some foam control may be desirable, and for front-loading washing machines, a considerable degree of foam control may be preferred. A wide variety of foam control agents are known in the art and can be chosen for use in this invention according to the routine of the art. In fact, the selection of the foam control agent, or mixtures of foam control agents, for any specific detergent composition depends not only on the presence and amount of fatty acid polyhydroxyamide used therein, but also on the other surfactants. active ingredients in the formulation. However, it appears that, for use with fatty acid polyhydroxyamides, silicone based foam control agents of various types (which can therefore be used at lower levels) are more effective than several other types of foam. foam control agents. Available silicone foam control agents, such as AE, X2-3419, Q2-3302 and DC-544 (Dow Corning) are particularly useful.

formulator of compositions for washing fabrics, which may advantageously contain an agent for the

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Mod. 71 - 20,000 ex. - 90/08 dirt-free, has a wide variety of known materials to choose from (see, for example, US Patents 3 962 152, 4 116 885, 4 238 531, 4 702 857, 4 721 580 and 4 877 Additional dirt release materials useful for this invention include the nonionic and oligomeric product from the esterification of a reaction mixture comprising a source of polyethoxy unit terminated by ale.g. CH3 [OCH2CH2] i6OH), a source of terephthaloyl units (e.g., dimethyl terephthalate); a source of poly (oxyethylene) oxy units (e.g., polyethylene glycol 1500) a source of oxy-iso-propylene-oxy units (e.g., 1,2-propylene glycol); and a source of oxy-ethylene-oxy units (eg ethylene glycol), especially those in which the molar ratio of oxy-ethylene-oxy units: oxy-iso-propylene-oxy units is at least about 0.5: 1. These non-ionic dirt release agents have the general formula coxy C1-C4 (1

R ¹ 0- (CH ₂ CH ₂ 0) X 0 0 U- ^ J ^ Ío-CH-C ^ O l - 0 0 11 / = \ II cZ A-co (ch ₂ ch ₂ o) y R ² m -

0

C - 0 (CH ₂ CH ₂ 0) X-r1 in which R1 is lower alkyl (eg, C1-C4), especially methyl; X and Y are each integers from about 6 to about 100; m is an n? integer from about 0.75 to about 30; n is an integer from about 0.25 to about 20; and R4 is a mixture of H and CH3, providing an oxy-ethylene-oxy: oxy-iso-propylene-oxy molar ratio of at least about 0.5: 1.

Another preferred type of soil release agents useful in this invention is the general anionic type described in U.S. Patent 4,877,896, provided that these agents are substantially free of HOROH-type monomers, where R is propylene or higher alkyl. Thus, the agents of

-6 is 10

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The 1992 release of dirt from US Patent 4,877,896 may comprise, for example, the reaction product of dimethyl terephthalate, ethylene glycol, 1,2-propylene glycol and 3-sodium sulfobenzoic acid, while these additional soil release agents they may comprise, for example, the reaction product of dimethyl terephthalate, ethylene glycol] 5-sodium sulfophisophthalate and 3-sodium sulfobenzoic acid. These agents are preferred for use in granular laundry detergents.

The formulator may also consider it advantageous to include a non-perborate bleach, especially in granular, strongly-acting laundry detergents. Numerous branMod are commercially available. 71 - 23,000 ex. - 8/90

peroxygen binders that can be used in the present invention, but, of all, percarbonate is the most convenient and economical. Thus, the present compositions may contain a solid percarbonate bleach, usually in the form of the sodium salt, incorporated at a level of about 3% to 20% by weight, more preferably from 5% to 18% by weight, and, more preferably, from 8% to 15%, by weight of the composition.

Sodium percarbonate is an addition compound with the formula corresponding to 2Na2CO3.3H2O2, and is commercially available as a crystalline solid. Most commercially available materials include a low level heavy metal scavenger, such as EDTA, 1-hydroxyethylidene, 1,1-diphosphonic acid (HEDP), or an amino phosphate, which is incorporated during the manufacturing process. in this invention, percarbonate can be found in detergent compositions without additional protection, but preferred embodiments of the invention use a layer coated with the material. Although a series of coatings can be used, the most economical is sodium silicate with Si02: Na20 in the ratio of 1.6: 1 to 2.8: 1, preferably 2.0: 1, applied as a solution aqueous, and dried to give a level of 2% to 10%, (usually 3% to 5%), of only 35

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silicate lipids by weight of percarbonate. The magnesium silicate can also be used, a chelator such as one of those mentioned may be included in the coating.

particle size of the crude crystals percarbonate ranges from 350 microns to 450 microns, with an average of approximately 400 microns. When coated, the crystals have a size of the order of 400 to 600 microns.

Although the heavy metals present in the sodium carbonate used in the manufacture of percarbonate can be controlled by the inclusion of scavengers in the reaction mixture, percarbonate still needs protection against the heavy metals present as impurities in other ingredients of the product. It was found that the total level of iron, copper and manganese ions in the product should not exceed 25 ppm and, preferably, should be less than 20 ppm, in order to avoid an unacceptable adverse effect on the stability of the percarbonate.

The use of magnesium ion (eg, 1% MgCl2, typically 0.15% -3.0%) provides especially preferred liquid dishwashing compositions, which are characterized by their especially desirable foaming properties. The following Examples XA and B illustrate these compositions. Examples XC and D illustrate superior fat removal compositions containing calcium ions. It is within the scope of the present technology to provide mixed Mg / Ca compositions containing Ca ⁺⁺ and Mg ⁺⁺ ions.

EXAMPLES X A-D

The following Examples illustrate liquid, mild-acting detergent compositions that are specially adapted for dishwashing and other hard surface cleaning operations. In Examples AD, the surfactant agents comprise various alkyl ethoxide sulphate agents which, using common technology, are abbreviated to indicate their average degree of ethoxylation; thus C12-13EO (0.8) sulphate indicates a fraction of sulphated Ci ₂ ^-C 13 alcohol

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Mod. 7) - 20,000 ex. - Mixed 90/08, containing an average degree of ethoxylation of 0.8. These anionic ethoxysulfates are preferably used in the form of their Na ⁺ or NH4 ⁺ salt. The CX2-14 amine oxide is a mixed CX2 ^- 13 (medium) dimethylamine oxide. AP-betaine C12-14 is Ci ₂ / 14H ₂ 5 / 29CONH (CH ₂ ) ₃ N ⁺ (CH3) 2CH2CO2H. The AP-sulfin C12-J4 is C12 / C14H35 / 29CONH (CH2) 3N ⁺ (CH3) 2CH ₂ CH (OH) CH2 S0 ₃ H. DM-betaine Ο ₁₂ ~ 14 is C ₁₂ / 14H ₂ 5 / 29N ⁺ (CH3) 2CH2CO2H. The nonionic ethoxylated surfactant, called Cg-XEO (8), refers to C9-Cxx ethoxylated alcohols with 8 moles of ethylene oxide, respectively. The Ca ⁺⁺ and Mg ⁺⁺ cations are conveniently introduced into positions with CaCl2 and MgCl ₂ · The rest of the compositions comprise water and citrate / propylene glycol present in the glucamide surfactant (1-5%), and 1- 3% cumenesulfate and xylenesulfate hydrotrope. pH is typically 6.8-7.4 (NH4 ⁺ salts) or 7-8.2 (Na ⁺ salts).

Ingredients

Percentage (weight)

THE B Ç D N-methylglucamide C _X2 “14 11 8 12.7 9 ^c 12-13EO (0.8) sulfate - 16 10.0 9 ^c 12 “14 ^e0 (3) sulfate 11 - 2.7 14 Ci2-i3EO (6.5) sulfate - - - 3 AP-betaine C _X2 -14 - - 2 - AP-sultein C _X2 - _X 4 - - - 1.0 amine oxide C _x2 - _X3 2.5 - - 1.0 DM-betaine Ci ₂ ^- 14 - 2.0 - - E0 (8) Cg- _xx 0.5 8 7 - Ca ⁺⁺ - - 0.5 1.0 Mg ⁺⁺ 0.9 0.25 - - Remaining Rest. Rest. Rest. Rest Although the effects of Mg ion ⁺⁺ reveals itself rem, more significantly , in compositions net from you

dishwashing powder, the following example illustrates the use of MgS04 in a granular composition.

-is?-

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EXAMPLE XI

A granular laundry detergent composition suitable for use at the relatively high concentrations that are characteristic of automatic front-loading laundry machines, especially in Europe, and over a wide range of temperatures, is as follows.

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Ingredients

SOKALAN CP5 (100% active as Na salt) ¹ DEQUEST 206'6 (100% as acid) ² TINOPAL DMS 3

MgS0 ₄ *

Zeolite A (anhydrous)

CMC (100% active) 4

Na ₂ C0 ₃

Citric acid

SKS-6 layered silicate

Tallow alkyl sulfate (100% active; Na salt) C14-C15 alkyl sulfate (100% active; Na salt) Cl2 " ^c 15 E0 alkyl sulfate (3) N-methyl-glucamide Οχθ-Οχθ

DOBANOL C12-C15 E0 (3)

LIPOLASE (100,000 LU / g) ⁵

SAVINASE (4.0 KNPU) ⁶

perfume

X2-3419

Starch

Stearyl alcohol

Sodium percarbonate (coated)

Tetraacetylethylenediamine (TAED)

Zinc Phthalocyanine

Water (ex zeolite)% weight

3.52 0.45 0; 28 0.49

17.92

0.47

9.44

3.5

12.9

2.82

3.5

1.76

4.1

3.54

0.42

1.65

0.53

0.22

1.08

0.35

22.3

5.9

0.02

Remaining ^ SOKOLAN is polyacrylate / sodium maleate, available from

Hoechst.

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^ Monsanto's brand of pentafosphonomethyl-diethylenetriamine.

³ Optical brightener, available from Ciba Geigy.

^ FINNFIX trademark, available in Metasaliton. ⁵ LIPOLASE N0V0 lipolytic enzyme.

^ SAVINASE N0V0 protease enzyme.

”7x2-3419 is a silicone foam suppressant available from Dow Corning.

The procedure for preparing the granules comprises various tower drying, agglomeration, dry additions, etc., as follows.

The percentages are based on the finished composition.

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

A. Mixing and Pneumatic Passage through the Tower

Using standard techniques, the following components are mixed (crutched) and dried in a tower.

SOKOLAN CP5 3.52%

DEQUEST 2066 0.45%

TINOPAL DMS 0.28%

Magnesium sulfate 0.42%

Zeolite A as anhydrous 7.1%

CMC 0.47%

B. Surfactant Agglomerates

BI. Agglomeration of sodium salt of tallow alkyl sulfate and sodium salt of C12 ~ 1E0 (3) sulfates

-A 50% active paste of tallow alkyl sulfate and a 70% paste of ^Ci2_c 15 E0 (3) sulfate are agglomerated with Zeolite A and sodium carbonate, according to the following formula (contribution to the formulation detergent after drying the chipboard).

2.4% tallow alkyl sulfate

-7Í19 <%

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Ci2-i5E0 (3) sulfate 1.18%

Zeolite A 5.3%

4.5% sodium carbonate

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B2. Agglomerate of the C alkyl Smlfato | g-CI5 'of Alquiletoxilo sulfate C ₁₂ _C ₁₅ Dobanol Cio-CIC EO (3) and N-methyl-qlucoseamida Cik-Cir-0 glucoseamida equipment ^C16 18' is not ionic, it is synthesized with DOBANOL Ci2 ^- 15 ^E ° ( ³ ) present during the reaction of methyl ester and N-methyl-glucamide. The C | 2 ~ 15 ^E ° ( ³ ) acts as a melting point depressant and allows the reaction to proceed without the formation of cyclic glucoseamides, which are undesirable.

A surfactant mixture of 20% DOBANOL C ^ 2 “15 ^E ° ( ³ ) ^{and 80} % N-methylglucoseamide Cjg-Cjg is obtained, and co-agglomerates with 10% sodium carbonate.

Then, the above particle is co-agglomerated with a slurry of high activity (70%) of a sodium salt of C14-15 alkyl sulphate and still Ci2 ° ^_ L5 ^{and (3)} more sulfatoj zeolite A and sodium carbonate . This particle shows a good cold water dispersibility of the N-methyl-glucoseamide C ^gC ^g.

The overall formulation of this particle (contribution to the detergent formulation after drying the agglomerate) is:

N-methyl-glucoseamide C ^ g-C ^ g 4.1% DOBANOL C ₁₂ -i5 E0 (3) 0.94% Sodium carbonate 4.94% Zeolite A 5.3% Na C14-C15 alkyl sulfate 3.5% E0 (3) Na2 ~ 15 Na2 sulfate 0.59%

C. Dry Additives

The following ingredients are added.

Percarbonate

22.3%

-U-

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TAED (tetraacetylethylenediamine) 5.9%

Hoechst SKS 6 layered silicate 12.90%

Citric acid 3.5%

Lipolase 0.42%

100,000 LU / g

SAVINASE 4.0 KNPU 1.65%

Zinc phthalocyanine (photo-brightener) 0.02%

D. Sprayed

DOBANOL Ci2-15 E0 (3) Perfume

2.60%

0.53%

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E. Foam Suppressor, silicone foam suppressor, X2-3419 (95-97% high molecular weight linear silicone; 3% -5% hydrophobic silica), from Dow Corning, is co-agglomerated with Zeolite A ( size 2-5 pm), starch and astearyl alcohol binder. Es. This particle has the following formulation:

Zeolite A 0.22% Starch 1.08% X2-3419 0.22% Stearyl alcohol 0.35% The detergent preparation exhibits excellent solubility, of

superior performance and excellent foam control when used in European washing machines, e.g., using 85 g of detergent in an AEG brand washing machine in cycles of 30 ° C, 40 ° C, 60 ° C and 90 ° C,

EXAMPLE XII

In any of the previous examples, the fatty acid glucamide surfactant can be replaced with an equivalent amount of maltide surfactant or a mixture of glucamide / maltamide surfactants derived from sugar sources.

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plants. In the compositions, the use of ethanolamides seems to reinforce the stability, the cold temperature, of the finished formulations. In addition, the use of sulfobetaine and / or amine oxide surfactants provides superior foaming.

The following Examples further illustrate the liquid compositions (both Mg ⁺⁺ and Ca ⁺⁺ , as mentioned above) which are especially suitable for use for delicate purposes, such as for washing dishes.

EXAMPLE XIII A-D

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Ingredients

THE

C12-14 ( ^1E °) ¹⁶ alkylethoxy sulfate

C ^ 2-14 alkylethoxy sulfate (3E0)

Alkylethoxylate Cjq (8E0) 7

N-methyl-glucamide Ci2 “14 ⁸

Coconut diethanolamide dimethyldodecylamine oxide

Cocoamide-propylhydroxy-sultaine

Percentage (weight)

B C D

12 - 11

7 1

12 6

1—2

3

Cocoamide-propyl-betaine 2 Mg2 +

Ca ²⁺ 0,5 Sodium toluenesulfate 3 Ethanol 4 Water · ·, ------- 30

Remaining --------- For compositions where especially high foaming is desired (eg, dishwashing), it is preferable that less than 5%, preferably less than 2%, are present, and, more preferably still no C14 or higher fatty acids, as these can suppress foaming. Consequently, the formulator of 35 high foaming compositions

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ve prevent the introduction of quantities of suppressing foaming of these fatty acids in those compositions with the polyhydroxy fatty acid as well as prevent the formation of A * C? ₄ fatty acids or greater in the storage of the finished compositions. A simple means is the use of C ^ ₂ ester reagents ^{in the} preparation of the fatty acid polyhydroxyamides of the invention. Fortunately, the use of amide oxide or beta-sulphate surfactants can overcome some of the negative foaming effects caused by fatty acids.

formulator wishing to add optical, anionic brighteners to liquid detergents containing relatively high concentrations (eg 10% or more ^ If anionic or poly-anionic substituents, such as polycarboxylate adjuvants, you may find it useful to pre-mix the brightener with water and poly - fatty acid hydroxyamide and then add the premix to the final composition.

Those skilled in the chemical arts will readily understand that the preparation of the fatty acid polyhydroxyamides of the invention using a variety of higher saccharides, such as maltose, will result in the formation of fatty acid polyhydroxyamides in which the linear substituent Z is covered ( capped) by a polyhydroxy ring structure. The use of these materials is fully contemplated in this invention and does not depart from the spirit and scope of the mesur, as it is presented and claimed.

Lisbon, 21

Claims (13)

- CLAIMS Mod. 7] - 20,000 ex. - 8/90 £ 1. - Process for the preparation of a detergent composition comprising between 5% and 65% by weight of a mixture of surfactants characterized by mixing: (a) between 5% and 95% by weight of one or more sulfonate or anionic sulfate surfactants; and (b) between 5% to 95% by weight of one or more fatty acid polyhydroxyamides having the general formula: 0 R ^Z ~ C - NZ where R and H, a C C-C ^, 2-hydroxyethyl, 2-hydroxy-propyl hydrocarbyl group, or corresponding mixtures, R ** is a C ^C ^ hydrocarbyl group, and Z is a polyhydroxyhydrocarbyl group having a hydrocarbyl chain with at least 3 hydroxyl groups directly attached to the chain or a corresponding alkoxylated derivative and that said composition contains magnesium ion in a molar amount corresponding to C, 1X - 2.0X, where X is the number of moles of sulfonate or anionic sulfate surfactants present. 2 ε. Process according to claim 1, characterized in that between 10% to 50% by weight of the mixture of surfactants and between 90% to 50% by weight of a vehicle are mixed and in that said composition contains magnesium ion in a corresponding molar amount at 0.2X - 1.7X. 3 e. Process according to claim 2, characterized in that the mixture of surfactants comprises between 20% to 80% by weight of the anionic sulfonate or sulfate surfactant and between 20% to 80% by weight of the fatty acid polyhydroxyamide. 4 §. Process according to claim 3, characterized in that the vehicle comprises water or a mixture of water and a C ^-C ^ monohydric alcohol. 5e. _ p_r.access according to claim -7663,905 Case: 4263 R JV /! 9Ç’2 ' Mod. 71 - 20,000 ex. - 90 (08 4, characterized in that R ¹ is an alkyl group O2 -02 θ R ² is an alkyl or alkenyl group of straight chain Cg-C4 ç or corresponding minorities. 6. A process according to claim 1, characterized in that a fatty acid polyhydroxyamide is used in which Z is derived from maltose. Process according to Claim 1, characterized in that a fatty acid polyhydroxyamide is used in which Z is derived from a mixture of monosaccharides, disaccharides and, optionally, saccharides with a high number of carbon atoms, comprising said mixture at least 1% of a disaccharide, preferably maltose. - Process according to claim 1, characterized in that additionally a betaine and sultaine surfactant is mixed, or corresponding mixtures. 9. A process according to claim 5, characterized in that one or more additional nonionic or anionic surfactants selected from polyethylene, polypropylene and polybutylene oxides condensed from alkyl phenols are mixed; condensation products of alkyl ethoxylate of aliphatic alcohols with ethylene oxide; condensation product of ethylene oxide with a hydrophobic base formed by the condensation of propylene oxide with propylene glycol; condensation product of ethylene oxide with the product resulting from the reaction of propylene oxide and ethylenediamine; alkyl polysaccharides, preferably alkyl polysaccharide having a hydrophobic group containing between 6 to 30 carbon atoms and a hydrophilic polysaccharide containing between 1.3 to 10 saccharide units; fatty acid amides; and corresponding mixtures » 10. A process according to claim 9, characterized in that a betaine or sultaine surfactant is further mixed, or corresponding mixtures. -7763,905 Case: 4263 R ll ^ã - Process according to claim I, characterized in that it additionally mixes between 2% to 5% by weight of a hydrotrope. 12 ^ _ Process according to claim II, characterized in that the mixture of surfactants comprises between 40% to 60% by weight of the anionic sulfonate or sulfate surfactant and between 40% to 60% by weight of the fatty acid polyhydroxyamide. 13. The process of claim 12 wherein the fatty acid polyhydroxyamide has the general formula. Mod. 71 - 20.OCO ex. - 8/90 B R ² - C -N - CH2 - Z where R ² is a straight chain of C11-C17 alkyl or alkenyl, Z is derived from glucose, maltose or corresponding mixtures, and the hydrotrope is selected from toluene-sodium toluene sulfonate - potassium sulphonate, sodium xylene sulphonate, potassium xylene sulphonate, sodium cumene sulphonate, potassium cumene sulphonate, trisodium sulfo succinate and tripotassium sulfo succinate. 14. ^A process according to claim 13, characterized in that in the fatty acid polyhydroxyamide used, Z is derived from maltose. 15A - Process according to claim 13, wherein the polyhydroxy used fatty acid, Z is derived from a mixture of monosaccharides, disaccharides and, optionally saccharides with a high number of carbon atoms, said mixture comprising at at least 1% of a disaccharide, preferably maltose.