SK25793A3 - Detergent composition containing alkylethoxy carbozylates and polyhydroxy fatty acid amides - Google Patents

Abstract

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

Description

Technical field

The invention relates to cleaning compositions comprising alkyl ethoxycarboxylates and polyhydroxy fatty acid amides. In particular, the invention relates to detergent compositions which have desirable cleaning and foaming characteristics and are particularly suitable for dishwashing.

BACKGROUND OF THE INVENTION

Alkyl ethoxycarboxylates and their use in detergent compositions are known. U.S. application Ser

516,292 entitled “Light-Duty

Liquid Diswashing Detergent

composition

Containing an Alkyl detergent

Ethoxy surfactant, filed May 4, 1989 (Rodney M. Vise and Thomas A. Cripe) discloses carboxylates and their use in detergent compositions. Although these carboxylates provide improved purification characteristics, they generally produce a small initial foam volume and this foam has poor stability. This low volume of foam and its poor stability can lead to a misconception among the part of consumers who believe that the detergent has a worse cleaning effect. Therefore, it may be desirable to combine such carboxylates with a component or components that improve foaming characteristics. The detergent compositions of the invention have been found to meet this requirement.

The polyhydroxy fatty acid amide contained in the composition of the invention is also known per se, as is its numerous uses.

N-acyl, N-methylglucamides are described, for example, by J.V. Goodby, M.A. Marous, E. Chin and P.L. Finn in 'The Thermotropic Liquid-Crystal1ine Properties of Some Straight Chain Carbohydrate Ämphiphiles' (Liquid-Crystalline Properties of Some Straight Chain Carbohydrate Amphiphiles), Liquid

Crystals, 1988, Volume 3, Number 11, p. 1569 až

1581 and A.

Muller-Fahrnow, M. Zabel, M.

Steifa and R.

Hilgenfeld v

Molecular

Structure

Nonionic of

Detergent ^:

Crystal

Nonanoyl-N-Methylglucamide and nonionic detergents: Nonanoyl-N-methylglucamide, J.

Chem. Soc. Chem. Commun., And (Molecular and crystal structure

1986, p. 1573 až

1574. Use

N-alkyl polyhydroxyamide surfactants have recently received great attention for the use of biochemistry, for example in the dissociation of biological membranes by a journal (e.g.

J.E.K.

Hildreth

N-D * Gluco-N-methyl-alkanamide Compounds, a

Nev

Class of

Non-Ionic

Detergents

for

membrane

Biochemistry "

N-D-Gluco-N-methylalkanamide compounds, novel detergents for membrane biochemistry, Biochem. J.

nonionic class

1982, Vol. 207, p. 363 to 366.

The use of N-alkyl glucamides in detergent compositions is also described. U.S. Patent No. 2,965,576 (ER Vilson, Dec. 20, 1960) and British Patent Application No. 809060, cited above, disclose detergent compositions containing anionic surfactants and certain amide surfactants which may contain N-methylglucamide added as low temperature foaming agent. These compounds contain an N-acyl group of a higher straight chain fatty acid having 10 to 14 carbon atoms. These compositions may also contain adjuvants such as alkali metal phosphates, alkali metal silicates, sulfates and carbonates. It is also generally stated that the compositions may contain additional ingredients to impart desirable properties of the composition, such as fluorescent dyes, bleaching agents and perfumes.

U.S. Patent No. 2,707,898 (Mar. 8, 1955) to A. Schwartz relates to aqueous cleaning compositions comprising the condensation reaction product of an N-alkylglucamine and an aliphatic fatty acid ester. The product of this reaction is said to be usable in aqueous cleaning compositions without further purification. It is also known to prepare a sulfuric acid ester of an acylated glucamine, as described by A. M. Schwartz in U.S. Patent 2,717,894 (September 13, 1955).

International Application PCT WO 83/04412. published

December 22, 1983 (J. Hildreth) relates to amphiphilic compounds containing polyhydroxylaliphatic groups, which are said to be useful for a variety of purposes, including as surfactant compounds in cosmetics, in pharmaceutical compositions in shampoos, lotions, eye ointments, as emulsifiers and release agents for drugs and biochemistry for solubilizing membranes, whole cells or other tissue samples, and for preparing liposomes. Included are compounds of the general formula R (R (R) CH 2 R and RCON (R) R 1 where R is hydrogen or an organic group, R is an aliphatic hydrocarbon group of at least 3 carbon atoms and R is an aldose residue.

European Patent Application No. 0 285768, published October 12, 1988 (H-Kekkenberg et al.), Relates to the use of N-polyhydroxyalkylamides of fatty acid as thickeners in aqueous cleaning systems. Included are amides of the formula R 1 C (O) N (X) R 2, wherein R 1 is C 1 -C 17 alkyl (preferably C 7 -C 17), R 2 is hydrogen, C 1 -C 18 alkyl ( preferably 2 to 6 carbon atoms) or an alkylene oxide group and X a polyhydroxyalkyl group having 4 to 7 carbon atoms, for example Coconut oil fatty acid N-methyl glucamide.

The thickening properties of the amides are said to be particularly useful

Agents in liquid surfactant systems that paraffin sulfonates, although aqueous surfactant systems may contain other anionic surfactants such as alkylarylsulfonates, olefin sulfonates, sulfosuccinic acid polyester salts, and nonionic surfactant ether sulfonates. as fatty alcohol are fatty alcohol polyglycol ether, alkylphenol polyglycol ether, polyglycol fatty acid ester, polypropylene oxide polyethylene oxide blend polymers. By way of example, shampoo compositions based on the paraffin sulphonate / coconut fatty acid glucamide / nonionic surfactant system are mentioned. In addition to the thickening action, N-polyhydroxyalkylamides of the fatty acid are said to contribute to better skin tolerance of the compositions.

U.S. Patent No. 2,982,237 (May 2, 1961)

CBoettner et al.) Refers to urea, sodium lauryl sulfate reagent and N-alkyl glucamide which is selected from N-sorbitol lauramide and N-methyl,

Other glucamide surfactants, for example, in DT et al., Published Dec. 20, compositions comprising active agents and salts polymerized with a detergent bar additive, a nonionic surfactant surfactant, including N-sorbitylmyristamide.

active number 2

1973), one builder phosphate, sequestering agents,

N-acy1po1yhydroxya1ky1am yne RLC (0) NCR2) CH2 CCH0H) _n CH ₂ 0H containing the active agent, N-methyl agents include 226,872 (HV Eckert which relates to washing or more surfactants from the group consisting of washing alkalis, improved by the formula wherein R is alkyl of 1 to 3 carbon atoms, R2 is alkyl of 10 to 22 carbon atoms and n is 3 or 4. N-acylpolyhydroxyamino amine is added as a soil suspending agent.

U.S. Patent 3,654,166 to H.V. Eckert et al., U.S. Pat.

(April 4, 1972) discloses detergent compositions comprising at least one surfactant selected from the group consisting of anionic, zwitterionic and nonionic surfactants and as textile softener N-acyl, N-alkylpolyhydroxyalkyl compound of the general formula R1N (Z) C (O) R2 . wherein R 1 is C 10 -C 22 alkyl, R 2 is C 7 -C 21 alkyl, and R 1 and R 2 comprise a total of 23 to 39 carbon atoms and Z is a polyhydroxyalkyl group which may be of the formula -CH 2 CCHOH; 3 or 4.

U.S. Patent No. 4,021,139 to CH. Môller et al.,

May 3, 1977) relates to cosmetic compositions for skin care, containing the N-polyhydroxy, comprising a compound of the formula RiN (R) CHCCH0H) _m R 2, wherein R is H, lower alkyl, hydroxy-lower alkyl, or aminoalkyl, as well as the heterocyclic aminoalkyl group, R has the same meaning as R 1, but cannot be hydrogen and R 2 is CH 2 OH or COOH.

French Patent Specification No. 1 360018 (April 26, 1963) (CCommercial Solvents Corporation) relates to formaldehyde solutions.

stabilized against polymerization by the addition of amides of formula RC (O) N (R 1) G, wherein R is a carboxylic acid group and at least carbon atoms and G a glycitol group of at least 5 carbon atoms.

German Patent Specification No. 1 261861 (No. Heins, Feb. 29, 1968) relates to glucamide derivatives useful as wetting and dispersing agents of the general formula (RCR) (R 1) (R 2) wherein R is a glucamine sugar moiety, R 1 is a C 10 alkyl group and R 2 is an acyl group having 1 to 5 carbon atoms.

British Patent Specification No. 745036 (Atlas Povder Company, published February 15, 1956) relates to heterocyclic amides and their carboxylic esters useful, for example, as chemical intermediates of emulsifiers, wetting and dispersing agents, detergents and textile emollients. These compounds have the general formula N (R) (R1) C (O) R2. wherein R is a residue of an anhydrized hexanpentol or carboxylic acid ester, R 1 is a monovalent hydrocarbon group, and -C (O) R 2 is an acyl group of a carboxylic acid having 2 to 25 carbon atoms.

U.S. Pat. No. 3,312,627 to D. T. Hooker, U.S. Pat.

(April 1967) relates to solid toilet bars which are substantially free of anionic detergents and alkaline builders and which contain lithium non-ionic surfactants of certain fatty agents from the group consisting of certain propylene oxide and d-ethylenediamine and amine-ethylenediox The condensates, propylene oxide-propylene glycol-ethylene oxide condensates and polymerized ethylene glycol and also contain a nonionic foaming component which may contain a polyhydroxyamide of formula RC (O) NR 1 (R 2). wherein R c (O) contains about 10 to about 14 carbon atoms and R 1 and R 2 are each hydrogen or C 1 -C 6 alkyl, wherein the alkyl groups have a total carbon atom number of 2 to about 7 and a total number of hydroxyl substituents 2 to about 6. Essentially similar is the subject-matter of the invention

312626 (D. T. Hooker, April 4, 1967).

However, nowhere in the known art is the concomitant use of alkyl ethoxycarboxylates and polyhydroxy fatty amides to unexpectedly improve the foaming characteristics and improved acids in the detergent composition. There is no mention of a cleaning action, particularly improved fat removal by such cleaning agents. Likewise, no mild skin action is shown anywhere in the present invention.

Accordingly, the present invention relates to cleansing compositions comprising an alkyl ethoxycarboxylate and a polyhydroxy fatty acid amide having favorable cleansing and foaming characteristics while having a mild skin action. The invention also relates to a method for washing dirty dishes using the detergent according to the invention.

SUMMARY OF THE INVENTION

Accordingly, the present invention provides a cleaning composition comprising about 1% by weight. preferably about 5% to about 65% by weight of a surfactant composition

a) about 5 to about 95% of one or more alkyl ethoxycarboxylates of the formula

R 0 (CH 2 CH 2 O) to CH 2 CO-M, where is

R is an alkyl group of 8 to 22 carbon atoms, k is an integer of 0 to 10, and an M cation,

b) about 5 to about 95% of one or more polyhydroxy fatty acid amides of the formula

R ¹

R ² - C - N - Z where is

R ¹ is H, a hydrocarbon group having 1 to 4 carbon atoms,

A 2-hydroxyethyl group, a 2-hydroxypropyl group, or a mixture thereof

R ² hydrocarbon group of 5-31 carbon atoms, and

Z is a linear hydrocarbon chain polyhydroxy hydrocarbon group having at least three hydroxyl groups directly bonded to the chain or an alkoxylated derivative thereof.

As mentioned above, the invention also relates to a method of dishwashing using the above-mentioned detergent. The cleaning composition according to the invention is preferably in the form of a liquid or gel and in particular in the form of a liquid dishwashing composition (low hollow). The cleaning composition comprises from about 5 to about 65%, preferably from about 10 to about 50, and more preferably from about 20 to about 40%, of a surfactant composition containing one or more alkyl ethoxycarboxylates and one or more polyhydroxy fatty acid amides. □ both these components as well as other possible components are discussed below.

Alky 1 ethoxy car boxes are a component

The surfactant composition of the invention comprises from about 5 to about 95%, preferably from about 20 to about 80%, and more preferably from about 40 to about 60%, by weight, of one or more alkyl ethoxycarboxylates of formula (RO) (CH ₂ CH ₂ O) to CH ₂ COO-M ⁺ Cl). where it means

R is an alkyl group having 8 to 22 carbon atoms, preferably an alkyl group having 12 to 14 carbon atoms, to an integer of 0 to 10, preferably 1 to 5, and

A cation, preferably an alkali metal, alkaline earth metal cation, ammonium, lower alkanolammonium and monoethanolammonium, diethanolammonium or triethanolammonium cations, especially sodium, potassium and ammonium cations, and in particular sodium and potassium cations and mixtures thereof with magnesium and calcium ions.

The number of carbon atoms of the R group and the integer value of k are correlated so that when the number of carbon atoms increases, it is preferable that the integer value of k 'increases accordingly to maintain the solubility of the detergent composition. Generally, when R is C 12 -C 14 alkyl, k is about 1 to about 4, when R is C 12 -C 18 alkyl, k is about 1 to about 6, and when R is alkyl a group having 8 to 12 carbon atoms, k has a value of 0 to about 3.

The alkyl ethoxycarboxylate component of the invention can be prepared by itself in a known manner. A preferred method is described in U.S. Patent Application Serial No. 354968, entitled Process for Making Alkyl Ethoxy Carboxylates, filed May 22, 1989 (Thomas A. Cripe).

The alkyl ethoxycarboxylate component of the invention may include a distribution of alkyl ethoxycarboxylates. If the cleaning composition according to the invention contains such a distribution. the ethoxylate distribution is such that on a weight basis the amount of materials where k is zero is less than about 20%, preferably less than about 15% and in particular less than about 10% and the amount of material where k is greater than 7 is less than about 25%, preferably less than about 15%, and more preferably less than about 10%. The mean value of k will be in the range of 1 to 4 when the mean number of carbon atoms of the group R is 13 or less, and the mean value of k will be in the range of 2 to 6 when the mean number of carbon atoms of R is greater than 13. are described in detail in U.S. Patent Application Serial No. 516,292. filed May 4, 1989. Where the compositions of the invention include the ethoxycarboxylate resolution, the desired carboxylate resolution is derived by reaction corresponding to the distribution of ethoxylated alcohol precursors.

It has been found that the presence of divalent cations in connection with alkyl ethoxycarboxylates in the detergent compositions of the invention greatly improves the removal of greasy dirt. This is particularly true when the detergent compositions of the present invention are used in softened water containing few divalent ions. It should be; It is believed that divalent ions increase the accumulation of alkyl ethoxycarboxylates at the oil / water interface, thereby reducing the interfacial tension and improving the possibility of fat removal. However, liquid dishwashing compositions containing alkyl ethoxycarboxylates and not meeting the definition of the present invention show minor improvements upon addition of divalent ions and in many cases even reduced cleaning characteristics upon addition of divalent cations.

When divalent cations are added to the detergent composition of the invention, divalent ions are preferably added in the form of chloride or sulfate salts, or in the form of hydroxides. preferably, however, in the form of a chloride salt in a cleaning composition comprising alkyl ethoxycarboxylates in the form of an alkali metal salt or in the form of an ammonium salt, in particular in the form of a sodium or potassium salt. after neutralizing the detergent with a strong base. The divalent ion concentration is generally about 0 to about 1.5% by weight. preferably about 0.2 to about 1.0% by weight, and particularly about 0.3 to about 0.8% by weight. Magnesium and calcium ions are mentioned as particularly preferred divalent ions.

Depending on the process for preparing the alkyl ethoxycarboxylate component of the invention and the process for preparing the detergent composition of the invention, such a detergent composition may contain from about 0% to about 5.0% by weight. preferably less than 4.0% and especially less than 2.5% of the alcohol ethoxylates of formula II

R 10 (CH ₂ CH ₂ O) _w H (II) wherein R * represents an alkyl group having 12 to 16 carbon atoms and w 0 to about 10, the mean number v being less than 6.

The uncarboxylated alcohol ethoxylates of the formula II are unfavorable for the detergent compositions of the invention containing alkyl ethoxycarboxylates. It is therefore important that such cleaning compositions contain at most about 0.5% by weight of the alcohol ethoxylates. from which alkyl ethoxycarboxylates are derived. However, commercial alkyl ethoxycarboxylates contain 10% by weight or more alcohol ethoxylates. methods for achieving the desired purity of alkyl ethoxycarboxylates are known. For example, unreacted alcohol ethoxylates can be removed by steam distillation according to U.S. Pat. No. 4,089,818 (Example 1). or by recrystallization of alkyl ethoxycarboxylates by the method of British Patent Specification No. 1,027,481 (Example 1). Other methods for preparing the desired carboxylates include reacting sodium or sodium metal hydroxide and monochloroacetic acid or a salt thereof with alcohol ethoxylates under special pressure and temperature conditions as described in U.S. Patent Nos. 3,992,443 and 4098818 and Japanese Patent Application Publication No. 24,215th

Another method for preparing high purity alkyl ethoxycarboxylates is described in U.S. Patent Application Ser.

May 4, 1989.

Fatty acid polyhydroxyamide

The surfactant composition of the invention contains from about 5 to about 95% by weight, preferably about. 20 to »

about 80%, and especially about 40 to about 60%, of one or more polyhydroxy fatty acid amides of formula I

R ¹ - R 2 - c - N - Z (I) where is

R ^{@ 1} is hydrogen, C1 -C4 hydrocarbon, 2-hydroxyethyl. A 2-hydroxypropyl group or a mixture thereof, preferably an alkyl group having 1 to 4 carbon atoms, especially an alkyl group having 1 to 2 carbon atoms, and in particular an alkyl group having 1 carbon atom (i.e. a methyl group),

R ² is a C 5 -C 31 hydrocarbon group, preferably a C 7 -C 19 straight chain alkyl or alkenyl group, especially a C 9 -C 17 straight chain alkyl or alkenyl group, and in particular a straight chain alkyl or alkenyl group with Or a mixture thereof.

Z is a linear hydrocarbon chain polyhydroxy hydrocarbon group having at least three hydroxyl groups directly bonded to the chain or an alkoxylated (preferably ethoxylated or propolylated) derivative thereof.

The group Z is preferably derived from a reducing sugar in a reductive amination reaction. Preferably Z is a glycityl group. 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, such as the individual sugars listed above, may be used as starting material. Corn syrups may be obtained as a mixture of the Z sugar components. However, the above calculation does not exclude other suitable raw materials. Of Z preferably will be selected from the group consisting of -CH2- (CH0H) _n -CH 2 OH, -CHCCH ₂ 0H> - (CHOH) n -CH ₂ OH ICH

-CH ₂ - (CHOH) ₂ C (CHOR 1) (CHOH) -CH ₂ OH wherein n is an integer from 3 to 5 and R is a hydrogen atom or a cyclic or aliphatic monosaccharide and its alkoxylated derivatives. Most preferred are glycityls wherein n is 5, especially of the formula

-CH ₂ -CH ₂ OH -CH ₂ OH

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

R ² -CO-N can be, for example, cocamide, stearamide, oleamide.

lauramide, myristamide.

Z symbol

1-deoxyglucyl capricamide, palmitamide, tallow amide can be, for example, a group

2-deoxyfructyl, 1-deoxymethyl,

2-deoxylactityl,

1-deoxygalactityl, 1-deoxymanityl or

1-deoxymaltotriotityl.

Most preferred are polyhydroxy fatty acid amides of the general formula

CH ₂ aa

R ² - C - N - CH ₂ - (CHOH) 4 CH ₂ OH wherein R ₂ represents an alkyl or alkenyl group having 11 to 17 straight-chain carbon atoms.

These polyhydroxy fatty acid amides are prepared by known methods. Generally, they are prepared by reacting an alkylamine with a reducing sugar by a reductive amination reaction to give the corresponding N-alkyl polyhydroxyamine and then reacting the N-alkyl polyhydroxyamine with a fatty acid ester or triglyceride in a condensation amidation step to form an N-alkyl, N-polyhydroxyalkylamide. Methods for preparing mixtures containing polyhydroxy fatty acid amides are described, for example, in British Patent Application No. 809060 (Thomas Nedlay & Co., Ltd.) published Feb. 18, 1959; U.S. Patent No. 2,965,576 (ER Wilson, Dec. 20, 1960); No. 2,703798 (Anthony M. Schwartz, Mar. 8, 1955) and U.S. Patent No. 1,985,424 (Piggott, Dec. 25, 1934).

In one method of preparing N-alkyl or N-hydroxyalkyl

N-depoxyglycityl amides of fatty acid, glucose wherein the glycityl component is derived from

N-alkyl or

N-hydroxyalkyl N-propyl,

N-hydroxypropyl,

The group is a group

N-methyl,

N-ethyl,

N-butyl,

N-hydroxyethyl or the product is prepared by reaction

N-alkylglucamine or selected from

N-hydroxyalkylglucamine with a fatty acid ester.

a fatty acid methyl ester group.

fatty acid ethyl esters and fatty triglycerides in the presence of a catalyst selected from the group consisting of tri lithium phosphate, trisodium phosphate, tricalcium phosphate, tetranium pyrophosphate, pental potassium tripolyphosphate, lithium hydroxide, sodium hydroxide, potassium carbonate, calcium carbonate, calcium carbonate, , sodium potassium tartrate, trisodium citrate.

tricalcium citrate, basic sodium silicate, basic potassium silicate, basic sodium aluminum silicate, and basic potassium aluminum silicate, and mixtures thereof. The amount of catalysts preferably corresponds to about 0.5 mol% to about 50 mol%, preferably about 2.0 mol% to about 10 mol%, based on N-alkylglucamine, or

N-hydroxyalkylglucamine on a molar basis. The reactions are preferably carried out at a temperature of about 138 to 170 ° C, generally for 20 to 90 minutes. When triglycerides are used in the reaction mixture as a fat ester source, the reaction can also be advantageously carried out at about 1% to about 10% by weight of the phase transfer agent, based on the weight of the reaction mixture as a whole, selected from saturated surfactants. fatty alcohol polyethoxylates, alkyl polyglucosides, linear glycamines, and mixtures thereof.

Preferably, the method is carried out such that:

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

b) add N-alkylglucamine or N-hydroxyalkylglutamine to the heated fatty acid ester and mix until a biphasic liquid / liquid mixture is formed,

c) adding the catalyst to the reaction mixture.

d) stirring the reaction mixture for a given time.

When triglycerides are used as the fatty acid ester, it is also preferable to add the prepared% pre-weight of about 2 to about 20% by weight.

N-alkyl / N-hydroxyalky1,

N-linear glucosylamide product based on the weight of the reaction fatty acids into the reaction mixture, components as phase transfer agents.

This inoculates the reaction and thus increases the reaction rate.

A detailed description of this procedure is given in the Examples section of the invention.

The polyhydroxy fatty acid amide of the present invention provides the advantage to those skilled in the art that it can be fully prepared from primary additional degradable raw materials, i.e. not

These feedstocks are also poorly toxic from petrochemical feedstocks.

for the environment of natural watercourses.

It is recalled that in addition to the polyhydroxy fatty acid amides of formula I, some nonvolatile by-products, such as ester amides and cyclic polyhydroxy fatty acid amides, are also prepared by the process for their preparation. The concentration of these by-products varies depending on the reactants selected and the reaction conditions. Preferably, the polyhydroxy fatty acid amide introduced into the detergent composition is formulated in a composition comprising a polyhydroxy fatty acid amide composition to contain less than about 10% by weight and preferably less than about 4% cyclic polyhydroxy fatty acid amide. The preferred process described above has the advantage of providing a rather low amount of by-products, including such a cyclic amide by-product.

Liquid carrier

According to a preferred embodiment, the cleaning agent according to the invention may be a liquid cleaning agent. These preferred liquid compositions comprise from about 95 to about 35%, preferably from about 90 to about 50%, and more preferably from about 80 to about 60% by weight of a liquid carrier such as water, more particularly mixtures of water and a C 1 -C 4 monohydric alcohol (e.g. isopropanol, butanol and mixtures thereof), with ethanol being preferred.

PH of the composition

The liquid cleaning compositions of the invention are preferably formulated such that when used in an aqueous cleaning operation, the wash water has a pH of about 8 to about 10, and in particular about 8.5 to about 9.5. Liquid cleaning compositions preferably have a pH of about 7.0 to about 11.0, preferably about 8.5 to about 10.5, and particularly about 8.8 to about 10.0. The methods for controlling the pH of the liquid detergent compositions of the invention are possible in a known manner, as known to those skilled in the art, for example by adding a base to the detergent composition. Dishwashing compositions generally have a pH of 7. It has been found that the liquid cleaning compositions of the present invention provide improved greasy soil removal when formulated in an alkaline pH range as opposed to a pH of 7 or less than 7. This improvement The cleaning action appears unique in the case of the liquid cleaning compositions of the invention containing an alkyl ethoxycarboxylate component. Surprisingly, the detergent compositions of the present invention remain mild for the skin even in this alkaline pH range.

thickening

The detergent compositions of the invention may also be used in the form of a gel. Such compositions are generally formulated in the same manner as liquid cleaning compositions, but a thickener is added thereto.

Any material or materials may be admixed with an aqueous liquid to provide dilute cleaning compositions of the invention having sufficient slip. Such materials that provide slip values include colloidal silicon dioxide, particulate polymers such as polystyrene and oxidized polystyrene, mixtures of certain surfactants, and water-soluble polymers such as polyacrylate.

A preferred thickener for the detergent compositions of the present invention is a high molecular weight polycarbonate polymer thickener. By high molecular weight is meant a molecular weight of about 500,000 to 5,000,000, preferably about 750,000 to about 4,000,000.

The polycarbonate polymer may be a carboxyvinyl polymer. Such compounds are described in U.S. Pat. No. 2,779,553. Brown has also described the preparation of carboxyvinyl polymers.

The carboxyvinyl polymer is an iriterpolymer of a monomer blend containing a monomeric olefinically unsaturated carboxylic acid and a weight of about 0.1 to about 10% by weight based on the total monomers of the polyether polyether, the polyhydric alcohol containing at least 4 carbon atoms to which at least three hydroxyl groups are bound; the polyether contains more than one alkenyl group per molecule. Optionally, other monoolefinic materials may also be present in the monomer mixture, even in a predominant amount. Carboxyvinyl polymers are substantially insoluble in liquid, volatile organic hydrocarbons and are dimensionally stable when exposed to air.

Preferred polyhydric alcohols suitable for the preparation of carboxyvinyl polymers include polyols selected from the group consisting of oligosaccharides, reduced derivatives thereof, wherein the carbonyl group is converted to an alcohol group and pentaerythritol, more preferably oligosaccharides and most preferably sucrose. It is preferred that the hydroxyl groups of the polyol that have been modified be etherified with allyl groups.

wherein the polyol has at least two allyl ether groups per polyol molecule. When the polyol is sucrose. it is preferred that the sucrose has at least five allyl ether groups per sucrose molecule. It is preferred that the polyether polyol contain from about 0.1 to about 4% by weight of the monomers as a whole, and in particular from about 0.2 to 2.5.

Preferred olefinically unsaturated carboxylic acids for use in the preparation of carboxyvinyl polymers are the monomeric, poly-convertible alpha-beta monoolefinically unsaturated lower aliphatic carboxylic acids. In particular, monomeric monoolefinic acrylic acids of the general formula are mentioned

R

CH 2 = C-COOH wherein R represents a hydrogen atom or a lower alkyl group. Most preferred is acrylic acid.

Carboxyvinyl polymers suitable for the detergent compositions of the invention have a molecular weight of at least about 750,000. Preferred are the higher saturated carboxyvinyl polymers having a molecular weight of at least about 1,250,000. Also preferred are carboxyvinyl polymers having a molecular weight of at least about 3,000,000. highly saturated.

Various carboxyvinyl polymers are commercially available from B.F. Goodrich Company, Nev. under the trade name Carbopol. Carbopolinyl polymers suitable for the detergent compositions of the present invention include Carbopol 910 having a molecular weight of about 750,000, preferably Carbopol 941 having a molecular weight of about 1,250,000, and particularly Carbopol 934 and 940 having a molecular weight of about 3,000,000 and 4,000,000.

Carbopol 934 is a very slightly saturated carboxyvinyl polymer having a molecular weight of about 8,000,000. It is described as a high molecular weight polyacrylic acid saturated with about 1% polyallylsaccharose with a mean content of about 5.0 allyl groups per sucrose molecule.

Additional polycarbonate polymers useful in the present invention

.17 are Sokolan PHC-25 ^B , a polyacrylic acid of BASF Corp.. and Gantrez®, poly (methyl vinyl ether / maleic acid), an interpolymer of GAF Corp.

Preferred polycarboxylate polymers for the detergent compositions of the present invention are nonlinear water dispersible polyacrylic acids. saturated polyalkenyl polyether and have a molecular weight of about 750,000 to about 4,000,000.

Highly preferred examples of such polycarboxylate polymeric thickeners include Carbopol 600 resins from B.F. Goodrich. Particularly preferred thickeners are Carbopo 616 and 617. It appears. These resins are much more saturated than the 900 series resins and have a molecular weight of approximately 1,000,000 to 4,000,000. The polycarboxylate polymer compositions herein are also suitable for the detergent compositions of the invention. Particularly preferred is a feed mixture of Carbopol 616 and 617 series.

Polycarboxylate polymeric thickeners are preferably used substantially in the absence of clays as thickeners. In fact, it was found. According to the invention, if polycarboxylate polymers with clay are used in the detergent compositions of the invention, a less stable product is obtained with respect to phase instability. In other words, polycarboxylate polymer is used instead of clay as a thickener / stabilizer in the detergent compositions of the invention.

The polycarboxylate polymer also reduces the well-known sticking phenomenon in the bottle (hang-up). This is understood to mean the impossibility of pouring out the entire contents of the dishwashing composition from the packaging. Without intending to be bound by the invention to any theory, it is believed that the thickened detergent compositions of the invention provide this advantage because the cohesive force of the composition is higher than the adhesive force to the walls of the package. Using clay-based thickeners, which are included in most commercially available formulations, adhering to the walls of packages can be a serious problem under certain conditions.

Without intending to be bound by any theory, it also appears that the long-chain polycarboxylate polymer thickener molecules help to suspend solids in the thickened detergent composition of the invention and maintain the expanded matrix. The polymeric material is also less sensitive than clay thickeners to destruction due to repeated shear, which occurs with vigorous mixing.

When a polycarboxylate polymer is used as a thickening agent in the detergent compositions of the invention, the polymer is typically present in an amount of about 0.1 to about 10.0% by weight, preferably about 0.2 to about 2% by weight.

Thickeners are used to achieve a slip value of about 50 to about 350, and preferably about 75 to about 250.

Sliding value

The slip value (Yield value) is an indication of the shear stress that exceeds the gel strength and begins to flow. It is measured with a Brookfield model RVT viscometer with a B-spindle and T-bars at 25 ° C using a rising screw drive with simultaneous subtraction. The system is set to 0.5 rpm. and subtraction for the test device is performed after 30 seconds or after system stabilization. The system stops and the speed is reset to 1.0 / min. Subtraction is performed for the same device after 30 seconds or after system stabilization. The zero shear voltage is equal to twice the reading at 0.5 rpm. minus reading at 1.0 rpm. The yield value is calculated as zero shear stress times 18.8 (conversion factor).

Other surfactants

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

Anionic surfactants

One type of anionic surfactants that can be used. includes alkyl ester sulfonates. Alkyl ester sulfonate surfactants include linear esters of carboxylic acids having 8 to 20 carbon atoms (i.e. fatty acids) that are sulfonated with sulfur trioxide gas as described in The Journal of the American Oil Chemist Society, 52 (197), p.

323 to 329. Natural fats such as tallow and palm kernel oil are mentioned as suitable starting materials.

Preferred alkyl ester sulfonate surfactants, especially for laundry purposes, include alkyl ester sulfonate surfactants of the general formula ^0- I.

R ³ -CH-C-OR ⁴

Where SO3M means

R ³ is a C 8 -C 20 hydrocarbon group, preferably an alkyl group or a mixture of such alkyl groups.

R ⁴ is a C 1 -C 6 hydrocarbon group, preferably an alkyl group or a mixture of such alkyl groups, and a M soluble salt-forming cation.

Sodium, potassium and ammonium salts are suitable as such.

salts include metal salts such as lithium salts and substituted or unsubstituted such as methyl ammonium, trimethylammonium and quaternary ammonium cations such as tetramethylammonium and dimethylpiperidinium cations derived from alkanolamines such as and triethanolamine. With carbon atoms, for example, preferably R ^{3 represents a} C 10 to alkyl group and R ^{4 represents a} methyl, ethyl or isopropyl group. Particularly preferred are methyl ester sulfonates wherein R ^{3 is} monoethanolamine, diethanolamine C 14 -C 16 alkyl.

Alkyl sulfate surfactants

Alkyl sulfate surfactants useful in the detergent compositions of the present invention are the water-soluble salts or acids or acids of the formula ROSO3M wherein R is preferably a C 10 -C 24 hydrocarbon group, preferably a C 10 -C 20 alkyl or hydroxyalkyl group. an alkyl moiety, especially an alkyl or hydroxyalkyl group of 12 to 18 carbon atoms and M represents a hydrogen atom or a cation, for example an alkali metal cation (for example sodium, potassium, lithium), a substituted or unsubstituted ammonium cation for example a methyl ammonium, dimethylammonium and trimethylammonium cation cations such as tetramethylammonium and dimethylpyperidinium and cations derived from alkanolamines such as ethanolamine, diethanolamine, triethanolamine and mixtures thereof. Generally, an alkyl chain of 12 to 16 carbon atoms is preferred for low temperature washing (e.g., below about 50 ° C), and alkyl chains of 16 to 18 carbon atoms are preferred for washing at higher temperatures (e.g., above about 50 ° C) .

Alkylalkoxylated sulfate surfactants

Another category of active agents are active agents. Such usable anionic surface alkylalkoxylated sulfate surfactants are water-soluble salts or acids of the general formula

R0 (A) mSO3M, wherein R represents an unsubstituted alkyl group of 10 to 24 carbon atoms or a hydroxyalkyl group of 10 to 24 carbon atoms in the alkyl moiety, especially an alkyl group or a hydroxyalkyl group of 12 to 20 carbon atoms, and in particular an alkyl or hydroxyalkyl group The symbol A represents an ethoxy group or a propoxy group, m a number greater than zero, generally about 0.5 to about 6, in particular about 0.5 to about 3, and M a hydrogen atom or a cation, which may be, for example, a metal cation (e.g., sodium, potassium, lithium, calcium, magnesium cation) and an ammonium or substituted ammonium cation. Alkyl ethoxylated sulfates as well as alkyl propoxylated sulfates are contemplated herein. Specific examples of substituted ammonium cations include methyl ammonium, ethylammonium and trimethylammonium cations and quaternary ammonium cations such as tetramethylammonium, dimethylpiperidinium and alkanolamine-derived cations. for example, from monoethanolamine, diethanolamine and triethanolamine and mixtures thereof. Exemplary C12 -C12 alkylpolyethoxylate (10) sulfate surfactants include carbon atoms in the alkyl moiety (C12-C18E (1, O) M), C12-18 alkyl (C12-C18 alkyl) alkylpolyethoxylate (2.25). 2.25). alkylpolyethoxylates (alkyl) (3,0) sulfate of 12 to 18 carbon atoms in alkyl portion (C12-C18EC3,0 M) and alkylpolyethoxylate (4,0) carbonates of 12 to 18 carbon atoms in alkyl portion (C12-C18E ( 4.0) M), wherein M generally means sodium or potassium.

Other anionic surfactants

Salts (including potassium, ammonium, and substituted monoethanolamine) may also be included in the detergent composition of the invention may also include other anionic surfactants.

for example triethanolamine salts) with carbon atoms up to carbon atoms.

X ^ X detergent purposes.

for example sodium.

ammonium salts.

diethanolamides, linear alkylbenzenesulfonates, primary and secondary alkanesulfonates, C8-olefin sulfonates, sulfonated polycarboxylic acids.

prepared by sulfonating a pyrolyzed citrate product such as that described in British alkaline earth metals.

carbon

082179, alkyl polyglycol ether sulfates having an alkyl moiety (containing up to 10 to 24 moles of ethylene oxide, alkyl glycerol sulfonates, fatty acylglycerol sulfonates, fatty oleyl acyl glycerol sulfonates, alkylsulfonate fatty acids, alkyl acyl sulfonates, acyl sulfonates, acyl sulfonates, acyl sulfonates, paraffin sulfates, paraffin sulfates, methyl tauride, alkyl succinamates and sulfosuccinates, sulfosuccinate monoesters (especially saturated and unsaturated monoesters having 12 to 18 carbon atoms), sulfosuccinate diesters (especially saturated and unsaturated diers having up to carbon atoms),

N-acyl sarcosinates, alkylpolysaccharide sulphates such as alkylpolyglucoside sulphates of acyl-N-alkylglucine sulphates having 9 to (nonionic unsulphated compounds hereinafter), acyl carbon atoms and 1 to 4 carbon atoms in the alkyl portion, or acyl to 17-hydroxy sulphates carbon atoms in the acyl moiety and with up to 4 carbon atoms in the alkyl moiety branched primary alkyl sulfates and fatty acids esterified with isethionic acid and neutralized with sodium hydroxide. Also suitable are bitumen acids and hydrogenated bitumen acids such as rosin acids, hydrogenated rosin, and bitumen acids contained in such anionic surface bitumen, acids and oils. Further examples of reagents are described hydrogenated in the ta-active

Agents and

Detergents

in Surface Actlve (Volume I and II, Schwartz, Perry and Berch). A variety of such surfactants are also described in U.S. Pat. No. 3,929,678 (Laughlin et al., Dec. 30, 1975), column 23, line 58 through column 29, line 23.

Non - ionic surfactants

Suitable nonionic surfactant detergents are generally described in U.S. Pat. No. 3,929,668 (Laughlin et al., Dec. 30, 1975), column 13, line 14 to column 16, line 6. The following are exemplary but not limiting classes of suitable nonionic surfactants. surfactants:

Polyethylene oxide, polypropylene oxide and polybutylene oxide condensates of alkylphenols. These compounds include the condensation products of alkylphenols having an alkyl moiety of 6 to 12 carbon atoms in a straight or branched chain configuration and an alkylene oxide. According to a preferred embodiment, the ethylene oxide is present in an amount of about 5 to about 25 moles of ethylene oxide per mole of alkyl phenol. Commercially available nonionic surfactants of this type are, for example

Igepal ™ C0-630 by GAF Corporation and Triton ™, X-45,

X-114, X-100 and X-102, all Rohm & Haas products

Company.

2- The condensation products of aliphatic alcohols with about 1 to 25 moles of ethylene oxide. The alkyl chain of the aliphatic alcohol may be either straight or branched, primary or secondary, and generally contains 8 to 22 carbon atoms. Particularly preferred are the condensation products of an alkyl alcohol of about 10 to about 20 carbon atoms and about 2 to about 10 moles of ethylene oxide per mole of alcohol. Examples of commercially available nonionic surfactants of this type are Tergitol (TM) 15-S-9 (a 9 to 10 mol linear ethylene oxide condensation product), Tergitol (TM) 24-L-6-NMV (a primary alcohol condensation product) 12 to 14 carbon atoms with 6 moles of ethylene oxide and narrow molecular weight distribution), both of which are products of Union Carbide Corporation; Neodol ™ 45-9 (condensation product of linear alcohol with 14 to 15 carbon atoms with 9 moles of ethylene oxide), Neodol ™ 23-6.5 (condensation product of linear alcohol with 12 to 13 carbon atoms with 6.5 moles of ethylene oxide), Neodol ™ 45- 7 (the condensation product of a linear C14-C15 alcohol with 7 moles of ethylene oxide). Neodol ™ 45-4 (condensation product of a linear alcohol of 14 to 15 carbon atoms with 4 moles of ethylene oxide) always from Shell Chemical Company and Kyro ™ EOB (condensation product of an alcohol of 13 to 15 carbon atoms with 9 moles of ethylene oxide) from Procter & Gambie Company .

3. The condensation products of ethylene oxide and 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 1,500 to 1,800 and exhibits water insolubility. Addition of the polyoxyethylene moiety to this hydrophobic moiety results in an increase in the water solubility of the molecule as a whole and a liquid nature of the product to a point where the polyoxyethylene content is about 50% by weight with respect to the total weight of the condensation product. Examples of compounds of this type include certain commercially available Pluronic ™ surfactants from BASF.

4. The condensation products of ethylene oxide and the product formed by the reaction of propylene oxide and ethylenediamine. The hydrophobic portion of this product consists of the reaction product of ethylenediamine and an excess of propylene oxide and generally has a molecular weight of about 2,500 to about 3,000. This hydrophobic portion is condensed with ethylene oxide to such an extent that the condensation product contains an approximate molecular weight of this type up to about 80% of about 5,000 to nonionic surfactant polyoxyethylene and had about 11,000. The commercially available Tetronic ™ compounds of BASF are mentioned as active agents.

5. Semi-polar nonionic surfactants of a special category of nonionic surfactants which include water-soluble amine oxides containing an alkyl moiety of 10 to 18 carbon atoms and two moieties specially selected from the group consisting of alkyl groups and hydroxyalkyl groups having 1 to 3 carbon atoms each: water-soluble phosphine oxides containing an alkyl moiety of 10 to 18 carbon atoms and two moieties selected from the group consisting of alkyl groups and hydroxyalkyl groups of 1 to 3 carbon atoms each; and water-soluble sulfoxides containing an alkyl moiety of from 10 to 18 carbon atoms and a moiety selected from the group consisting of alkyl and hydroxyalkyl moieties of from 1 to 3 carbon atoms.

Semi-polar nonionic detergent surfactants include the amine oxide surfactants of the formula:

R 3 (0R ⁴⁾ x N (R ⁵⁾ 2 wherein

R ³ an alkyl, hydroxyalkyl, or alkyl phenyl group or mixtures thereof containing from 8 to 22 carbon atoms,

R ^{4 is an} alkylene or hydroxyalkylene group having 2 to 3 carbon atoms or mixtures thereof, up to 3; and

R ^{5 is in} each case an alkyl or hydroxyalkyl group having 1 to 3 carbon atoms or a polyethylene oxide group having approximately 1 to 3 ethylene oxide groups. wherein the R ⁵ groups can be bonded to each other, for example, through oxygen or nitrogen atoms to form a ring structure.

These amine oxide surfactants especially include C 10 -C 18 alkyldimethylamine oxides and C 8 -C 12 alkoxyethyldihydroethylamine oxides.

6. Alkyl polysaccharides. described in U.S. Patent 4,556,547 (Llenado, Jan. 21, 1986) have a hydrophobic group containing from about 6 to about 30 carbon atoms, preferably about 10 to about 16 carbon atoms, and a polysaccharide, for example a polyglycoside as a hydrophilic group containing 1.3 to about 10, preferably about 1.3 to about 3, and especially about 1.3 to about 2.7 carbohydrate units. Any reducing saccharide containing 5 or 6 carbon atoms can be used, for example glucose, galactose and galectosyl moieties can be replaced by glycosyl moieties. (An optional hydrophobic moiety is attached at the 2, 3, 4 position, etc. and also provides glucose or galactose over the glucoside or galactoside.) The intersaccharide linkages may, for example, be between the position of the additional carbohydrate units and the positions 2, 3, 4 and / or 6 of the preceding. carbohydrate units.

Alternatively, but less desirable, the polyalkylene oxide chain may bind a hydrophobic moiety and a polysaccharide moiety. A preferred alkylene oxide is ethylene oxide. Typical hydrophobic groups are alkyl groups, either saturated or unsaturated, branched or unbranched, containing from 8 to 18 carbon atoms, preferably from 10 to 16 carbon atoms. Preferably, the alkyl group is a straight chain saturated alkyl group. The alkyl group may contain up to 3 hydroxyl groups and / or the polyalkylene oxide chain may contain up to 10 alkylene oxide moieties, preferably at most 5 alkylene oxide moieties. Suitable alkyl polysaccharides include octyl. nonyldecyl.

undecy1dodecy1. three decy1, tetradecy1. pentadecy1. hexadecyl, heptadecyl and octadecyl, di-, tri-, tetra-, penta and hexaglucosides, galactosides, lactosides, glucose, fructoside, fructose and / or galactose. Suitable mixtures include coconut alkyl, di-, tri-, tetra- and pentaglucosides and tallow alkyl tetra-, penta- and hexaglucosides.

Preferred alkyl polyglycosides have the general formula

R 20 (C _n H ² O 10) (glycosyl) x wherein R ² is alkyl, alkylphenyl, hydroxyalkyl, hydroxyacylphenyl, and mixtures thereof, wherein the alkyl moiety contains 10 to 18 carbon atoms, preferably 12 to 14 carbon atoms, n 2 or 3 preferably about 2 to about 10, preferably about 0 to about 1.3 to about 10, preferably about 1.3 to about 3, and especially about 1.3 to about 2.7. The glycosyl is preferably derived from glucose. To prepare these compounds, an alcohol or an alkylpolyethoxy alcohol is first prepared and then reacted with glucose or a source of glucose to form a glucoside (bound at position 1). The additional glucosyl units may then bind between their 1-position and the preceding glycosyl units at the 2, 3, 4 and / or 6 position, preferably predominantly at the 2-position.

7. Fatty acid amide as a surfactant of the general formula

II

^R6 - C - N ^(R7) 2 wherein ^R6 is an alkyl group having 7-21 carbon atoms, preferably 9-17 carbon atoms and R ⁷ is H, alkyl of 1 to 4 carbon atoms, hydroxyalkyl And (C 2 H 4 O) x H wherein x is about 1 to about 3.

Preferred amides are those having 8 to 20 carbon atoms, monoethanolamides, diethanolamides and isopropanolamides.

Ampholytic surfactants

Ampholytic surfactants can also be incorporated into detergent compositions. These surfactants are described as aliphatic derivatives of secondary or tertiary amines or aliphatic derivatives of heterocyclic secondary and tertiary amines in which the aliphatic moiety may have a straight or branched chain. One of the aliphatic substituents contains at least 8 carbon atoms, as a rule 8 to 18 carbon atoms, and at least one contains an anionic water-solubilizing group, for example a carboxy group, ¹ sulfonate group and a sulfate group. According to U.S. Pat. No. 3,929,678 to Laughlin et al., Dec. 30, 1975, column 19, lines 18-35, ampholytic surfactants are used, for example.

Both surfactants

Both surfactants can also be incorporated into the detergent compositions of the invention. These surfactants are described as derivatives of secondary and tertiary amines, derivatives of heterocyclic secondary and tertiary amines, or derivatives of quaternary ammonium. quaternary phosphonium or tertiary sulfonium compounds. Examples of useful zwitterionic surfactants are described in U.S. Pat. No. 3,929,678 to Laughlin et al.

30 December 1975) column 19, line 38 to column 22, line 48.

Such ampholytic and zwitterionic surfactants are generally used with one or more anionic and / or nonionic surfactants.

Preferred additional surfactants are anionic and nonionic surfactants, with alkyl esters sulfonates having from 11 to 27 carbon atoms in the alkyl moiety, primary and secondary alkanesulfonates having from 8 to 22 carbon atoms, alkyldimethylamine oxides having from 10 to 18 carbon atoms in the alkyl moiety being most preferred. . alkyl polysaccharides and mixtures thereof i.

When the compositions of the invention contain these additional surfactants, these additional surfactants are included in an amount of about 1 to about 10% by weight, preferably about 2 to about 5% by weight.

Other possible ingredients

Other optional ingredients are detergent builders (builders) of either organic or inorganic type, although not generally, it is preferred to use such builders in the detergent compositions of the invention. Examples of water-soluble inorganic builders that can be used either alone or in admixture with each other or with organic alkaline sequestering builder salts include glycine, alkyl succinates and alkenyl succinates, alkali metal carbonates, phosphates, polyphosphates and silicates. Specific examples of such salts include tripolyphosphate, sodium carbonate, potassium carbonate, potassium pyrophosphate, potassium hexametaphosphate, pyrophosphate, tripolyphosphate builder salts. which sodium. By way of example, they can be used organic alone or in mixtures with other substances or in mixtures with the above-mentioned builder salts. alkali metals, exemplified by inorganic polycarboxylates, include, but are not limited to, sodium citrate and potassium soluble citrates, sodium and, for example, potassium tartrate, sodium or potassium ethylenediaminetetraacetate.

Potassium sodium N- (2-hydroxyethyl) ethylenediamine triacetate, sodium and potassium nitrilotriacetate N-C2-hydroxyethyl) sodium and potassium nitrilodiacetate, sodium and potassium oxydisuccinate and sodium and potassium tartrate monosuccinate and sodium and potassium tartrate disuccinate as described in U.S. Pat. No. 4,666,171 (Bush et al., May 5, 1987). Other organic builders, such as water-soluble phosphonates, may be used in the detergent compositions of the invention. Generally, however, in the detergent compositions of the present invention, the builders have compositions according to the light-cleaning compositions

If they are then present in such compositions according to the invention, they are optional for the series.

The cleaning compositions in the form of liquid builders are generally included in an amount of about 1 to about 10% by weight, preferably about 2 to about 5% by weight.

Other desirable components include diluents, solvents, colorants, perfumes, and hydrotropic agents (preferred), the diluents being inorganic salts such as sodium and potassium sulfate, sodium, potassium and ammonium chloride, sodium bicarbonate. Diluents are generally present in the detergent compositions of the present invention in an amount of about 1 to about 10% by weight, and in particular about 2 to about 5% by weight.

Suitable solvents for the detergent compositions of the present invention include, for example, water and low molecular weight alcohols such as ethyl alcohol and isopropanol. Solvents for the detergent compositions of the present invention are generally present in an amount by weight of about 1 to about 60%, preferably about 5 to about 50%.

Hydrotropic agents such as sodium and potassium toluenesulfonate, sodium and potassium xylene sulfonate, sodium and potassium cumenesulfonate, trisodium and trisulphate sulfosuccinate and the like (see U.S. Pat. No. 3,915,903) can optionally be used to achieve the desired product stability and viscosity. It has been found that hydrotropic agents can have a positive effect on the foaming of the detergent compositions of the invention. Although it is not intended to bind the invention to any theory. this is probably due to the viscosity characteristics of such hydrotropic agents. The hydrotropic agents used in the detergent compositions of the invention are generally included in an amount of about 1 to about 10% by weight, preferably about 2 to about 5% by weight.

The detergent compositions of the invention have an unexpected advantage in their foaming when a certain fatty acid polyhydroxamide is combined with an alkyl ethoxycarboxylate.

Although it is not intended to be bound by theory, the detergent compositions of the present invention appear to be mild with respect to the skin, in addition to the improved cleansing characteristics, even though they are formulated as liquid with a high alkaline pH. Although it is not intended to bind the invention to any theory.

the cleaning compositions of the invention are likely to be advantageous in that they exhibit an unexpectedly high foaming and fat-removing ability and provide washed dishes which do not have a greasy touch, which is particularly important for the consumer when the cleanliness of the cookware is judged by removal of the "greasy" touch. In addition, again without wishing to be bound by theory, the additional advantages of the detergent compositions of the invention appear to be easy to rinse and reduce the slippery feel typically associated with liquid detergents. This is important for the consumer market where such a slippery touch is unfavorable and is perceived as insufficient rinsing of surfactants from the surface of the dishes.

According to the invention, the dirty dishes are contacted with an effective amount as a rule with approximately

0.5 ml to about 20 ml (per 25 washed containers). With about 3 cleaning liquid preferably with the composition of the invention, the cleaning composition depends on up to about 10 ml

The actual amount of user judgment and, as a rule, depends on such factors as the formulation of the detergent composition, including the concentrations of the active ingredient in the detergent composition, the number of containers washed and the degree of soiling of the containers. On the contrary, the particular formulation of the detergent composition of the invention depends on many factors depending on market requirements (for example in the United States of America, Japan and Europe). The following examples describe typical dishwashing methods using the detergent composition of the invention. However, these examples are intended to illustrate and not to limit the invention.

According to a typical use in the United States of America, about 3 ml to about 15 ml, preferably about 5 ml to about 10 ml of a liquid detergent are used together with about 1,000 to about 10,000 ml of water, typically about 3,000 to about 5,000 ml. ml of water in the sink with a capacity of about 5,000 ml to about 20,000 ml, typically about 10,000 ml to 15,000 ml. The detergent composition comprises a surfactant composition in an amount of about 21 to about 20 weight percent

The soiled dish is immersed in a sink containing an approximately% cleaning, preferably about 25 to about 40%.

detergent and water and are cleaned by contacting the soiled surface of the dish with, for example, a cloth or sponge. The cloth, sponge, or the like can be immersed in the detergent / water mixture prior to contact with the surface of the seconds, although the time varies. according to the user, or the like, in contact with the surface of the container is preferably accompanied by simultaneous scrubbing of the surface of the container.

According to a typical use in Europe, about 3 ml to about 15 ml, preferably about 3 ml to about 10 ml, of a liquid detergent together with about 1,000 to about 10,000 ml of water, typically about 3,000 to about 5,000 ml of water, are used. in a sink having a volume capacity of about 5,000 ml to about 20,000 ml, typically about 10,000 ml to 15,000 ml. The cleaning composition comprises a surfactant composition in an amount by weight of about 21 to about 44%, preferably about 25 to about 24%. The soiled dish is immersed in a sink containing detergent and water and is cleaned by contacting the soiled dish surface with, for example, a cloth or sponge.

A cloth, sponge, or the like may be immersed in the detergent / water mixture prior to contact with the cookware surface and generally then contacted with the cookware surface for about 1 to 10 seconds, although the time varies depending on usage and user. The contacting of the cloth, sponge or the like with the dish surface is preferably accompanied by simultaneous scrubbing of the dish surface.

Depending on the typical use in Latin America and Japan, about 1 ml to about 50 ml, preferably about ml to about 10 ml, of a liquid detergent are used in total about 50 ml to about 50 ml.

000 ml of water, as a rule about 100 to approximately

000 water in a container with a capacity of approx

500 ml approx

500 ml to 2000 to about ml. cleansing

As a rule, the composition contains a surface-active dirt of active ingredients with a mixture in an amount of about 5 to preferably about 10 to about 30% by weight. cleans by touching the soiled surface of the dishes by contacting, for example, a cloth or sponge. A cloth, sponge, or the like may be immersed in the detergent / water mixture prior to contact with the cookware surface and generally thereafter contacted with the cookware surface for about 1 to 10 seconds, although the time varies depending on usage and user. The contacting of the cloth, sponge or the like with the dish surface is preferably accompanied by simultaneous scrubbing of the dish surface.

According to other uses, dirty dishes are immersed in a water bath in the absence of any dishwashing detergent. The aid for absorbing a liquid dishwashing composition, such as a sponge, is introduced directly into a separate amount of undiluted liquid dishwashing composition for a period of about 1 to 5 seconds. Washing aid as well as undiluted liquid detergent to remove dirt. The absorbent device is generally contacted with each dish surface for about 1 to 10 seconds, although the time varies according to usage and user. Putting cloths. the sponge or the like in contact with the cookware surface is preferably accompanied by simultaneous scrubbing of the cookware surface.

DETAILED DESCRIPTION OF THE INVENTION

The N-methyl 1,1-deoxyglucityl lauramide surfactant used according to the following examples is prepared as follows:

Although one skilled in the art may vary the configuration, it comprises a suitable three-liter four-necked flask apparatus equipped with a reaction mixture-driven motor. The other two flasks are fitted with a nitrogen purge side arm and a large orifice side arm (note: a large orifice side arm is important in the case of very rapid methanol evolution) to which an efficient collector condenser and vacuum outlet are connected. The vacuum outlet is connected to a nitrogen source and to a vacuum meter and to a suction and trap. Heater 500 Watt jacket with temperature control via a control transformer ('Variac'). used to heat the reaction, it is placed on the laboratory preparation so that it can be easily lifted or lowered to further control the temperature of the reaction.

N-methylglucamine (195 g, 10 mol, Aldrich, M4700-0) and methyl laurate (Procter & Gambia CE 1270, 220.9 g, 1.0 mol) were charged to a flask. The mixture of solid and liquid is heated with stirring and flushing with nitrogen to form a melt (approximately 125 minutes). When the melt temperature reached 145 ° C, a catalyst (anhydrous powdered sodium carbonate, 10.5 g, 0.1 mol, J. T. Baker) was added. The nitrogen purge is stopped and the aspirator and the nitrogen outlet are set to obtain a vacuum of 16.95 kPa. From now on, the reaction temperature is maintained at 150 ° C by adjusting the Variac and / or raising or lowering the jacket.

Within seven minutes, the first methanol bubbles appeared on the meniscus of the reaction mixture. Then there is an almost violent reaction. The methanol is distilled off until it is formed. The vacuum is set to about 33.86 kPa., The vacuum is increased approximately as follows (in kPa for a given minute): 33.86 kPa for 3 minutes, 67.72 kPa for 7 minutes, 84.65 for 10 minutes. After a few minutes from the start of the methanol formation, heating and stirring are interrupted simultaneously with some foaming. The product is cooled and allowed to solidify.

The following examples illustrate the invention but do not limit it in any way.

Example 1

The following three preparations, A, B and C, are prepared according to the process of the invention.

Detergent A and prepared by initially mixing an alkyl ethoxycarboxylate cleaning composition with an N-methylglucamide of a C 12 -C 14 fatty acid to obtain a mixture. Ethanol, sodium chloride and sodium xylene sulfonate are added to this mixture. Any remaining surfactant is then added. Glycine is added and the pH is adjusted to 9.0 with sodium hydroxide. Finally, magnesium chloride is added to lower the pH. At this point, the final viscosity and pH can also be adjusted, after which perfume and dye are added. Water was added to 100%.

Detergent B is prepared by adding ethanol, sodium chloride, and sodium xylene sulfonate to a mixture of an alkyl ethoxycarboxylate detergent component and a polyhydroxamide fatty acid type as per detergent A. The remaining ingredients are added in the order shown in the table.

Detergent C is prepared by adding ethanol, sodium chloride, and sodium xylene sulfonate to a mixture of an alkyl ethoxycarboxylate detergent component and a polyhydroxy fatty acid amide of the type of Detergent A. The C 12 -C 14 monoethanol amide is heated to about 65 ° C and introduced into the mixture. At the same time, a minor adjustment of viscosity and pH is made. whereupon perfume and dye are added. Water was added to 100%.

component Quantity (¾) Device A B C sodium C12-13alkylethoxy (middle- No 2,8) carboxylate 20.0 20.0 15.0 N-methylglucamide C12-14 fatty of 5.0 5.0 5.0 C10 alkyloxyethoxy; - - 5.0 umCi2-13 alkyloxyethoxy (middle- no 0.8) sulfate 3.0 - - sodium α-sulfonate methyl ester C12-14 fatty acids - 4.0 - ci2-i3alkylethoxy sodium (middle- no 3.0) sulfate - - 4.0 Ci2-14a1ky1d imethy1beta i n 3.0 - - C12-14 Alkyldimethylaminoxid 3.0 5.0 5.0 monoethanolamide C12-14 fatty of - - 4.0 magnesium ion (added as he- magnesium chloride xahydrate) 0.76 0.76 0.76 glycine 4.0 - - trinátriumsulfosukcinát 2.0 2.2 2.0 ethanol 7.5 7.0 7.0 sodium chloride . 1.5 <1.0 2.25 pH value of the product 9.0 9.0 9.0 perfume and dye 0.15 0.15 00:15 water to 100 %

^{Λ A} surfactant mixture containing sodium alkyl ethoxycarboxylate. it is prepared as follows:

1. Allow an alkyl ethoxy alcohol of 12 to 13 carbon atoms in the alkyl moiety and a medium of 3.0 ethoxy groups with tert-butoxide and potassium chloroacetate in a ratio of 1 = 1.1 to react:

1.1 by first mixing the alkyl ethoxylate with potassium tert-butoxide at a temperature of about 60 ° C and at a pressure of about 26 mm Hg for one hour. Then the tert. butanol is continuously removed from the reaction mixture by distillation. The vacuum was discontinued and sodium chloroacetate was added with stirring. The pressure is readjusted to about 25 mm Hg to 26 mm Hg and the reaction is allowed to proceed for three hours. The pressure is then brought to ambient pressure by introducing nitrogen and the heating by the steam coil is switched off. The reaction mixture is left overnight at this stage. The next day the temperature of the reaction mixture is increased and the pressure is reduced to remove tert-butanol from the system. The reaction mixture is then added to an aqueous hydrochloric acid solution containing 105% of the theoretical amount required to neutralize the initially added potassium tert-butoxide. The acidic reaction mixture is heated to support phase separation of the organic and aqueous material. An organic phase is thus obtained.

2. Repeat step 1 using a C12-C13 alkyl ethoxy alcohol having an average of 2.7 ethoxy groups, with the ratio of the ethoxy alcohol to potassium tert-butoxide and sodium chloroacetate 1 ^: 1.3 · 1.3. Potassium tert-butoxide is added to the alkyl ethoxylate at a temperature of approx

32.2 ° C and the temperature of the reaction mixture is then raised to about 76.7 ° C. Adjust the vacuum pump to achieve the required pressure reduction. The reaction temperature is raised to about 104.4 ° C and the tert-butanol is expelled and collected for about 30 minutes. Sodium chloroacetate is then added to the reaction mixture, cooled slightly to about 66 ° C. The reaction mixture is stirred for about 1.5 hours, cooled and added to an aqueous solution with sufficient hydrochloric acid to give a pH of 3.4. Water is added to increase the reaction mixture volume by approximately 50% and the mixture is heated to approximately 49 ° C by heating. The upper organic layer is collected and the washing process is repeated.

3. The surfactant mixtures prepared in accordance with paragraphs 1 and 2 are mixed in a ratio of 40.0 to 59.6. A portion of this surfactant mixture is neutralized with 50% sodium hydroxide solution to a pH of about 8 and diluted to about 50% by adding a 25/75 v / v mixture of water and alcohol. The resulting solution was continuously extracted at room temperature with hexanes for about 4 days. The lower aqueous phase is collected and some ethanol and water are removed by heating to give an alkyl ethoxycarboxylate-containing paste containing the surfactant mixture described below.

In the compositions of Example 1, the surfactant comprises about 93.9% by weight of the alkyl ethoxycarboxylates of the formula

RO (CH 2 CH 2 O x CH 2 CO-Na ⁺ wherein R represents an alkyl group having 12 to 13 carbon atoms, an intermediate having 12.5 carbon atoms, x an integer of 0 to 10 and an ethoxylate distribution is such that the amount of material where x 0 is about 2.8% and the amount of material where x is greater than 7 is less than 2%, based on the weight of the alkyl ethoxycarboxylates, the mean value x in the distribution is 2.8. alcohol ethoxylates of the general formula

R 0 (CH ₂ CH ₂ O) x H where R represents an alkyl group having 12 to 13 carbon atoms, an average of 12.5 carbon atoms, and an average of 2.8. This surfactant mixture contains no soaps.

Example 2

In the same manner as in Example 1, three other detergents according to the invention C, D and E and F, G and H are prepared.

component Quantity (%) Composition C D E sodium C 12-13 alkylethoxy (middle- no 2,8) carbosylate ´ * 15.0 20.0 15.0 C 12-14 Alkyl-N-methylglucamide d 5.0 5.0 5.0 Cioalkylethoxy (middle 8) alcohol 5.0 5.0 coating of aluminum-13 alkyloxyethoxy (middle- no 0.8) sulfate 3.0 - - sodium α-sulfonate methyl ester 012-14 fatty acids - 4.0 - ci2-i3alkylethoxy sodium (middle- no 3.0) sulfate - - 4.0 CI2-i4alkyldimety1betaín 4.0 - - C 1-6 Alkyldimethylaminoxide d - 5.0 - monoethanolamide C12-14 fatty of - - 4.0 magnesium ion (added as he- magnesium chloride xahydrate) 0.76 0.76 0.76 glycine 4.0 - - N, N-bis (2-hydrokyety1) glycine - - - methyldimethanolamine - - - kokoam i dopropy1d i methy1beta í ή - - 3.0 CI2-i4dimetylamínoxid - - - trinátriumsulfosukcinát 2.0 2.2 2.0 ethanol 7.5 7.0 7.0 sodium chloride 1.5 <1.0 2.25 pH value of the product 9.0 9.0 9.0 perfume and dye 00:15 0.15 0.15 monoethanolamine - - - triethanolamine - - - water to 100 %

** A surfactant composition containing sodium alkyl ethoxycarboxylate is prepared in the same manner as in Example 1.

component Quantity (%) Composition F G H sodium C 12-13 alkyl ethoxy (middle- no 2,8) carbosylate ' 10,0 12.0 8.0 C 12-14 alkyl-N-methylglucamide d 10,0 10,0 10,0 Cioalkylethyls (middle 8) alcohol - 5.0 - sodium C12-C13 alkyl ethoxy (middle- no 0.8) sulfate 10.0 - - sodium α-sulfonate methyl ester 0ΐ2 — ι · 4 fatty acids - - 10,0 sodium C12-13alkylethoxy (middle- no 3.0) sulfate - - - CI2-i4alkyldimety1betaín 3.0 - - C12 I6alkyldimetylamínoxid - 3.0 - diethanolamide C12-14 fatty of 1.0 - 1.0 monoethanolamide C12-14 fatty of - 1.0 magnesium ion (added as he- magnesium chloride xahydrate) 0.3 0.5 0.5 glycine - - - N, N-bis (2-hydroxyety1) glycine 5.0 3.0 - methyldi ethanolamine - 10,0 - cocoam i dopropy1d imethy1betaine n - - 3.0 CI2-i4dimetylamínoxid - - 3.0 three paints umsu1f osukc i paint - - - ethanol 5.0 5.0 5.0 sodium chloride - '- - pH value of the product 9.0 8.0 8.0 perfume and dye 0.15 0.15 0.15 monoetano1amín 5.0 5.0 - triethanolamine 5.0 - 4.0 water to 100 %

^x surfactant mixture comprising nátriurnalky1etoxykarboxy methacrylate, was prepared in the same manner as in the example first

Example 3

An alternative process for preparing polyhydroxy fatty acid amides is as follows.

A reaction mixture containing 84.87 g of fatty acid methyl ester (supplied by Procter & Gambia) is used.

CE1270), 75.00 g of N-methyl-D-glucamine (supplied by Aldrich Chemical

Company M4700-0), 1.04 g sodium methoxide (supplier: Aldrich

Chemical Company 16, 499-2) and 68.51 g of methanol (30% by weight based on the reaction mixture). The reaction vessel has standard equipment for reflux, a drying tube, a condenser mixing bar. In this process, N-methylglucamine is mixed with methanol under stirring under argon and heating is started with good stirring (stirring bar, reflux). After 15-20 minutes the solution is at the desired temperature and the ester and sodium methoxide are added as catalyst. Samples are taken periodically to monitor the progress of the reaction, with the solution clearing well in 63.5 minutes. It is believed that at this point the reaction is virtually complete. The reaction mixture is refluxed for 4 hours. The reaction mixture obtained weighs 156.16 g. After vacuum drying, the overall yield is 106.92 g of granulated purified product, which can be easily crushed into small particles. The percentage yield is not calculated on this basis since sampling during the reaction affects the overall yield.

The following is not intended to limit the invention, but merely to further elucidate the technological aspects to be taken into account by one skilled in the art in the manufacture of a variety of detergent compositions using polyhydroxy fatty acid amides.

It is clear that polyhydroxy fatty acid amides are unstable under highly basic or highly acidic conditions because of their amide bond. Although some decomposition can be tolerated, it is preferred that these materials are not exposed to pH values above 11, preferably above 10 or below 3, for an unsuitable period of time. The pH of the final product (liquid) is generally 7.0 to 9.0.

In the preparation of polyhydroxy fatty acid amides, it is generally necessary to at least partially neutralize the basic catalyst used for the formed amide bonds. Although any acid may be used for this purpose, it will be apparent to those skilled in the art that it is simple and convenient to use acids whose anion is otherwise useful and desirable in the finished detergent composition. For example, citric acid may be used for neutralization and the resulting citrate ion (approximately 1%) suspended in approximately 40% of the polyhydroxy fatty acid amides and pumped to the next stage of the finished detergent production process. Similarly, acid forms of chemicals such as oxydisuccinate can be used. nitrilotriacetate, ethylenediaminetetraacetate and the tartrate / succinate system.

Polyhydroxy fatty acid amides derived from coconut fatty acid alkyls (predominantly 12 to 14 carbon atoms) are more soluble than their tallow fatty acid alkyl counterparts (predominantly 16 to 18 carbon atoms), so materials with 12 to 14 carbon atoms are somewhat easier to formulate in liquid compositions and are more soluble in cold water wash liquors. However, materials having 16 to 18 carbon atoms are also good, especially in circumstances where warm to hot water is used in the wash. Therefore, C16-C18 materials can be better detergent compositions than their C12-C14 counterparts. A person skilled in the art can therefore balance the ease of preparation with the utility properties by choosing a particular polyhydroxy fatty acid amide for a particular detergent composition.

It is also noted that the solubility of polyhydroxyamides into fatty acids may increase depending on the unsaturation and / or branching of the fatty acid portion of the chain. Materials such as oleic and isostearic acid polyhydroxy fatty acid amides are much more soluble than their n-alkyl counterparts.

Similarly, the solubility of polyhydroxy fatty acid amides.

prepared disaccharides, trisaccharides, etc. is generally greater than the solubility of their monosaccharide counterparts.

derived from

This higher solubility can particularly assist in the formulation of liquid compositions. In addition, the polyhydroxy fatty acid amides whose polyhydroxy compounds are derived from maltose appear to be particularly detergent when used in admixture with conventional alkyl benzene sulfonate (LAS) surfactants. Although not intended to be limited by theory, a mixture of LAS with polyhydroxy fatty acid amides derived from higher saccharides, such as maltose, appears to exhibit a substantial and unexpected decrease in interfacial tension in the aqueous environment, thereby promoting a cleansing action. (The process for preparing maltose-derived polyhydroxy fatty acid amide is described below.)

Polyhydroxy fatty acid amides may be prepared not only from purified sugars, but also from hydrolysed starches, for example, corn starch, potato starch or other suitable vegetable starch containing the necessary monosaccharides, disaccharides and the like. This is of particular importance from an economic point of view. For example, such high glucose corn syrup, high maltose corn syrup can be used easily and economically. The feedstock for the preparation of polyhydroxy fatty acid amides may also be deligified hydrolyzed pulp.

As mentioned above, polyhydroxy fatty acid amides derived from higher carbohydrates, such as maltose and lactose, are much more soluble than their counterparts. In addition, it appears that the more soluble polyhydroxy fatty acid amides may assist in varying degrees of solubilization of their less soluble counterparts. A person skilled in the art may therefore choose, for example, as a raw material instead of a high glucose corn syrup, a syrup containing a small amount of maltose (e.g., 1% by weight or more). The polyhydroxy fatty acid mixture obtained generally has more advantageous solubility characteristics over a wide range of temperatures and concentrations than polyhydroxy fatty acid amide, preferably derived from the use of pure mixtures of glucose sugars. In addition to economical compared to pure polyhydroxy amide sugar, sugars also have the advantage of fatty light acids prepared from a mixture of handling operations. In some cases, however, there is a decrease in fat removal (at dishwashing) at a fatty acid maltamide concentration above about 25% about 33% (some loss of foaming at a concentration by percentage of maltamides derived polyhydroxy fatty acid amides as opposed to polyhydroxy fatty acid amines derived glucose). Some variations are possible depending on the chain length of the fatty acid moiety. One of ordinary skill in the art can choose those compositions which he considers preferred for polyhydroxy fatty acid amides that vary the ratio of monosaccharides (e.g. glucose) to disaccharides and to higher carbohydrates (e.g. maltose) of about 99-1.

Preparation of non-cyclized approximately 4 · 1 to polyhydroxyamides

Preferred fatty acids from fatty acid esters may be carried out in alcoholic solvents at a temperature, and the N-alkyl polyols may be approximately up to about 90 ° C. preferably about 50 to 80 ° C.

For example, it has now been found that liquid detergents may be suitable in a 1,2-propylene glycol solvent for the preparation of the skilled artisan since the glycol solvent may not be completely removed from the reaction product prior to use in the preparation of the finished detergent composition. Similarly, it is appropriate for those skilled in the art to prepare a solid, generally granulated, detergent composition at a temperature of 30 to 90 ° C in solvents containing ethoxylated alcohols, for example ethoxylated (EO 3-8) alcohols having 12 to 14 carbon atoms, which are a commercial product of NEODOL 23 E06.5 (Shell). When ethoxylates are used, it is preferred that they do not contain a substantial amount of the unethoxylated alcohol, and in particular. to contain no significant amounts of monoethoxylated alcohol (T).

Although methods for preparing polyhydroxy fatty acid amides per se are not within the scope of the present invention, other possibilities for preparing polyhydroxy fatty acid amides are also discussed and are described below.

Typically, the reaction sequence on an industrial scale for the preparation of preferably acyclic polyhydroxy fatty acid amides comprises the following steps: Step 1. Preparation of an N-alkyl polyhydroxyamine derivative from the desired sugar or desired sugar mixture by forming an adduct of N-alkylamine and sugar, followed by reaction with hydrogen in the presence of a catalyst. degree

2. - Reaction of the aforementioned polyhydroxyamine, preferably with a fatty acid ester, to form an amide bond. Although a wide variety of N-alkyl polyhydroxyamines are suitable for the Stage 2 reaction sequence, sugar syrups are suitable for the process and for economic reasons. The best results when using such syrups as raw material are obtained when selecting syrups which are light in color or preferably colorless (water white).

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

1. Adduct preparation

According to a standard method, about 420 g of about 55% glucose solution (corn syrup of about

231 g g of glucose - about 1.28 mol) with a Gardner color of less than 1 and about 119 g of an approximately 50% aqueous solution of methylamine (59.5 g of methylamine 1.92 mol). The methylamine (MMA) solution is purged with nitrogen and cooled to about 10 ° C or below. Corn syrup is poured and nitrogen is introduced at a temperature of about 10 to 20 ° C. Corn syrup is added slowly to the methylamine solution at the above reaction temperature. The Gardner color number is measured at the following time intervals, in minutes.

Table I

From the above, it is apparent that the Gardner color for the adduct is much worse when the temperature rises above 30 ° C and at about 50 ° C the time during which the Gardner adduct is below 7 is only 30 minutes. For the next reaction and / or duration, the temperature should be less than about 20 ° C. The Gardner color should be less than about 7 and preferably less than about 4 to achieve a good glucamine color.

When a lower temperature is used to form an adduct, the time to reach equilibrium adduct concentration is reduced using a higher amine to sugar ratio. At a molar ratio of 1.5 - 1 amine to. The sugar is equilibrated in about two hours at a reaction temperature of about 30 ° C. At a 1.2: 1 molar ratio under the same conditions, the time is at least about three hours. For good color, the combination of amine to sugar ratio, reaction temperature and reaction time to achieve a substantially equilibrium conversion, for example greater than about 90, preferably greater than about 95%, and even greater than about 99%, based on sugar and adduct color are chosen. which is less than about 7, preferably less than about 4, and most preferably less than about 1.

In the above process, the reaction temperature is less than about 20 ° C and corn syrup of different Gardner color and MMA adduct color (after reaching substantially equilibrium within at least two hours) is shown in Table II.

Table II

Gardner color (About) corn syrup 1 1 1 1+ 0 0 0+ adduct 3 4/5 7/8 7/8 1 2 1

As can be seen from the table, the starting sugar must be almost colorless to produce an acceptable adduct. If the sugar has a Gardner number of about 1, the adduct is sometimes acceptable, sometimes unacceptable. If the Gardner number is above 1, the adduct obtained is unacceptable. The better the initial color of the sugar, the better the color of the adduct.

II. Reaction with hydrogen

The adduct obtained by the above process and with Gardner color or lower is hydrogenated by the following process:

Approximately 539 g of the adduct in water and about 23.1 g of the G49B nickel catalyst (United Catalysts) are charged into a one liter autoclave and purged twice with hydrogen at positive pressure.

380 kPa at 20 ° C. The hydrogen pressure is increased to 9 660 kPa and the temperature is raised to 50 ° C. The overpressure is raised to 110 mm Hg and the temperature is maintained at 50-55 ° C for three hours. At this point the product is 95% hydrogenated. The temperature is then raised to about 85 ° C for about 30 minutes and the reaction mixture is decanted and the catalyst is filtered off. The product and water and methylamine were removed by evaporation to give 95% N-methylglucamine as a white powder.

The above process is repeated with about 23.1 g of Raney nickel catalyst as follows. The catalyst is washed three times and the reactor with the catalyst in the reactor is purged twice with hydrogen at an atmospheric pressure of 1480 kPa, after which the hydrogen pressure in the autoclave is adjusted to 11040 kPa for two hours, relieved in one hour and repressurized in the reactor.

II 040 kPa. The adduct is then pumped to a reactor at a hydrogen pressure of 1480 kPa and a temperature of 20 ° C and the reactor is purged with hydrogen at a pressure of 1380 kPa, which is repeated.

In any case, the resulting product is more than 95% of N-methylglucamine, which contains less than 10 ppm nickel, based on globulin, and which has a Gardner color of less than 2.

Crude N-methylglucamine is color stable under short term exposure to temperatures up to about 140 ° C.

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

In another method, the adduct is prepared from about 159 g of about 50% methylamine in water, which is washed and washed with water. nitrogen at about 10 to 20 ° C. About 330 g of about 70% corn syrup (almost white water) is degassed with nitrogen at about 50 ° C and slowly added to the methylamine solution at a temperature of less than about 20 ° C. The solution is stirred for about 30 minutes until about 95% adduct is obtained which is a very slightly yellow solution.

About 190 g of this adduct in water and about 9 g of the GE9B nickel catalyst (United Catalyst) are charged into a 200 ml autoclave and purged three times with hydrogen at about 20 ° C. The hydrogen pressure is raised to about 1380 kPa and the temperature is raised to about 50 ° C. The pressure is raised to 1715 kPa and the temperature is maintained at about 50-55 ° C for three hours. The temperature of the product, which is hydrogenated to about 95%, is increased to about 85 ° C for about 30 minutes and the product after removal of water and evaporation: about 95% N-methylglucamine as a white powder.

It is also important to minimize contact of the adduct and catalyst under a hydrogen pressure of less than 6.9 MPa to minimize the nickel content of the glucamine. The nickel content of N-methylglucamine in this reaction is approximately 100 ppm compared to less than 10 ppm in the previous reaction.

The following reaction with hydrogen is performed to directly compare the effect of the reaction temperature.

An autoclave containing 200 ml is used in a typical process similar to that described above for the preparation of the adduct and the reaction with hydrogen is carried out at different temperatures.

Glucamine adduct is prepared by mixing approximately 420 g of approximately 55% glucose solution (corn syrup) (231 g glucose, 1.28 mol) (prepared using CarBill 99DE corn syrup, Gardner color number less than 1 ) and about 119 g of 50% methylamine (59.5 g MMA, 1.92 mol) (from Air Products).

The reaction is carried out as follows:

1. Charge about 119 g of a 50% methylamine solution to a nitrogen-purged nitrogen shielded reactor and cool to less than about 10 ° C,

2. degassing and / or flushing the 55% corn syrup solution at 10 to 20 ° C with nitrogen to remove oxygen from the solution;

3. slowly add the corn syrup solution to the methylamine solution and maintain the temperature below about 20 ° C.

4. when all the corn syrup solution is added, stir for one to two hours.

The adduct is used to react with hydrogen directly as it is produced or after storage at low temperature to prevent degradation.

The reaction of the glucamine adduct is carried out as follows:

1. Charge approximately 134 g of adduct (Gardner color number less than 1) and approximately 5.8 g of G49B nickel catalyst into a 200 ml autoclave,

2. The reaction mixture is purged with hydrogen at a pressure of about 50 psig twice at 20-30 ° C;

3. The hydrogen pressure is raised to about 2760 kPa and the temperature is raised to about 50 ° C.

4. The pressure is raised to about 3.45 MPa, the reaction is allowed to proceed for three hours, maintaining the temperature at about 50 to 55 ° C, and sampling 1 is taken.

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

6. decant and filter the catalyst, take a sample

Second

The conditions for the reaction at a constant temperature ¹

1. Charge about 134 g of adduct and about 5.8 g of nickel catalyst into an autoclave containing 200 ml,

2. The reaction mixture is purged with hydrogen at a pressure of about 50 psig twice at low temperature.

3. The hydrogen pressure is raised to about 2760 kPa and the temperature is raised to about 50 ° C.

4. The pressure is raised to about 3.45 MPa, the reaction is allowed to proceed for three and a half hours while maintaining the temperature as above;

5. Decant and filter the catalyst. Sample 3 corresponds to about 50-55 ° C, sample 4 corresponds to about 75 ° C, and sample 6 corresponds to about 85 ° C. (The reaction time for about 85 ° C is about 45 minutes.)

All processes give N-methylglucamine of similar purity (approximately 94%) and a similar Gardner color number. However, only a two-stage heat treatment provides good color fastness, and in the reaction at 85 ° C there is only a slight coloration immediately after the reaction.

Example 4

The tallow (hardened) N-methylmaltamine fatty acid amide for use in detergent compositions is prepared as follows:

Step 1. Reagents: Maltose monohydrate (Aldrich lot 01318KV), methylamine (40% by weight in water) (Aldrich lot 03325 ™), Raney nickel, 50% suspension (UAD 52-73D, Aldrich lot 12921LV).

The reactants are placed in a glass cartridge (250 g of maltose,

428 g of methylamine solution, 1200 g of catalyst suspension

50 g of Raney nickel) and the insert is placed in a 3 liter autoclave with a nitrogen purge pressure of 3.45 liters.

MPa three times) and hydrogen (at an overpressure of 3.45 MPa, twice) and the autoclave fluctuates in a hydrogen atmosphere at 28-50 ° C for the weekend. The crude reaction mixture is filtered under vacuum twice through a glass microfiber filter with a 1 µg layer. The filtrate was concentrated to give a viscous material. The final traces of water are removed azeotropically by dissolving the material in methanol and then removing the methanol / water system on a rotary evaporator. Final drying is carried out under high vacuum. The crude product was dissolved in refluxing methanol, filtered, cooled to crystallization, filtered, and the filter cake was dried under vacuum at 35 ° C. This is a section = 1. The filtrate is concentrated until a precipitate is formed and stored in a refrigerator overnight. The solid was filtered off and dried in vacuo. This is cut = 2. The filtrate is again concentrated to half its volume and crystallization occurs. A very small amount of precipitate is formed. A small amount of ethanol is added and the solution is left in the freezer over the weekend. The solid material was filtered off and dried in vacuo. The combined solids contained n-methylmaltamine which was used in step 2.

Step 2- - Reagents: N-methylmaltamine (from Step 1).

hardened tallow methyl esters, sodium methoxide (25% solution in methanol), absolute methanol (solvent) mole ratio of amine: ester 1 = 1, initial catalyst concentration of 10 mol% (based on the weight of maltamine) is increased to 20 mol, solvent concentration by weight 50

In a sealed flask, 20.36 g of tallow methyl ester is heated to its melting point (in a water bath) and placed in a 250 ml three-necked round-bottomed flask with mechanical stirring. The flask is heated to about 75 ° C to avoid ester stiffening. Separately, 25.0 g of N-methylamine is mixed with 45.36 g of methanol and the suspension obtained is added to the tallow fatty acid ester with good stirring. 1.51 g of 25% sodium methoxide in methanol is added. After four hours, the reaction mixture did not clear, so an additional 10 mol% catalysts (to a total of 20 mol%) were added and the reaction was allowed to proceed overnight (approximately 68 ° C), after which time the mixture clarified. The reaction flask is then adjusted for distillation. The temperature was raised to 110 ° C. Distillation at ambient pressure was continued for 60 minutes. High vacuum distillation is then started for 14 minutes, at which time the product becomes highly dense. The product is kept in the reaction flask at 110 ° C (outside temperature) for 60 minutes. The product was removed from the flask and triturated in ethyl ether over the weekend. The ether is removed on a rotary evaporator and the product is stored in an oven overnight and ground to a powder. Any residual N-methyl maltamine is removed from the product using silica gel. The silica gel slurry in 100% methanol was added to the funnel and washed several times with 100% methanol. A concentrated sample of the product (20 g in 100 mL of methanol) is loaded onto a silica gel and eluted several times under vacuum and washed several times with methanol. The collected eluent was evaporated to dryness (rotary evaporator). Any tallow fatty acid ester was removed by trituration in ethyl acetate overnight and filtered. The filter cake is dried under vacuum overnight. The product is tallow alkyl N-methyl maltamide.

In a varied process of Step 1, the above reaction sequence may be carried out using a commercial corn syrup containing glucose or glucose mixtures and typically 5% or more maltose. The polyhydroxy fatty acid amides obtained and the compositions can be used in any detergent.

In another method, step 2 of the above reaction can be carried out in 1,2-propylene glycol or NEODOL. At the discretion of the worker, propylene glycol or NEODOL need not be removed from the reaction product prior to use in the formulation of the detergent composition. Again, at the discretion of the operator, the methoxide catalyst can be neutralized with citric acid to form sodium citrate. which does not have to be separated from the polyhydroxy fatty acid amide.

Depending on the needs of a person skilled in the art, the cleaning composition of the invention may contain a greater or lesser amount of various suds suppressors. However, it is usually desirable. so that the detergent is not used to reduce foaming.

in

Example 5

In all of the preceding examples, the fatty acid glucamide surfactant can be replaced with an equivalent amount of maltamide surfactant or a surfactant glucanide / maltamide mixture derived from natural sugar sources. In the detergent compositions of the invention, the use of ethanolamides appears to help maintain cold stability of the finished detergent compositions. In addition, the use of sulfobetaine (such as sultaine) surfactants shows increased foaming. Calcium chloride (approximately 1% by weight) may be used in the detergent compositions of the invention to promote the removal of greasy soils from the dishes. Magnesium chloride also promotes foaming.

For high suds cleaning compositions, it is preferred that they contain less than about 5%, preferably less than about 2%, especially that they contain no C 14 or more fatty acids, since these fatty acids suppress the foaming. Therefore, those skilled in the art, in the case of high suds cleaners, avoid introducing a plurality of such suds suppressing fatty acids into high suds cleaners containing polyhydroxy fatty acid amides and / or avoid the formation of C 14 or more fatty acids when storing finished cleaners. according to the invention. A simple method is to use 12-carbon ester reagents to prepare polyhydroxy fatty acid amides. Fortunately, the use of amine oxide or sulfobetaine surfactants can prevent the negative effects on foaming caused by fatty acids.

Worker in the field. intending to add anionic brighteners to liquid cleaning compositions containing relatively high concentrations (e.g., 10% or greater) of anionic or polyanionic substituents such as polycarboxylate builders, may find it beneficial to prepare an optical brightener premix with water and polyhydroxy fatty acid amide and then this premix into the finished detergent.

Those skilled in the art are clear,. that the preparation of polyhydroxy fatty acid amides using disaccharides and higher carbohydrates such as maltose results in the formation of polyhydroxy fatty acid amides wherein the linear substituent Z is protected (capped) polyhydroxy ring structure. Such materials are fully encompassed within the scope of the invention and thus do not depart from the scope of the invention.

Industrial usability

Detergents containing an alkyl ethoxycarboxylate component and a polyhydroxy fatty acid amide as an additional component exhibit improved cleansing performance and improved foaming characteristics while having a mild skin action and are well suited for dishwashing.

such that the amount of materials where k is zero is less than 20% and the amount of material where k is greater than 7 is less than 25%, the mean k is 1 to 4 when the mean number of carbon atoms in the group R 13, or lower, and the mean k is 2 to 6, when the mean number of carbon atoms of the R group is greater than 13.

A cleaning composition according to claim 1, characterized in that it is liquid, preferably based on water or a mixture of water and alcohol having 1 to 4 carbon atoms, and contains 10 to 50% by weight of surfactant mixture and 90 to 50% by weight liquid carrier.

4. A detergent composition according to claim 3, comprising 20 to 80% by weight of an alkyl alkoxycarboxylate component and 20 to 80% by weight of a polyhydroxy fatty acid amide.

5. A detergent composition according to claim 4 wherein the M cation of the alkyl ethoxycarboxylate component (a) is selected from the group consisting of alkali metal, alkaline earth metal, ammonium, lower alkanolammonium and monoethanolammonium, diethanolammonium, triethanolammonium, and mixtures thereof with calcium. fever ions.

A detergent composition according to claim 5, characterized in that its pH is 7.0 to 11.0 and contains an additional weight of 0.1 to 15% buffer and preferably an additional weight of 2 to 5% hydrotropic agent.

7. A detergent composition according to claim 6 which is liquid and comprises one or more additional anionic or nonionic surfactants selected from the group consisting of C12-C27 alkyl ester sulfonates, primary and secondary C8-C22 alkane sulphonates. . (C až-C 18) alkyldimethylamine oxides and alkylpolysaccharides and mixtures thereof.

¹¹ ϋοο? mo

Claims (2)

F-REFERENCE TOOLS 1C Y A cleaning composition comprising alkyl ethoxycarboxylates and polyhydroxy fatty acid amides, characterized in that they contain from 1% to 65% by weight of a surfactant composition containing by weight a) 5 to 95% of one or more alkyl ethoxycarboxylates of the formula ROCCH2CH ₂ O) kCH2COO-M + wherein R is an alkyl group having 8 to 22 carbon atoms, k is an integer 0 to 10 and M cation a b) 5 to 95% of one or more polyhydroxy fatty acid amides of the general formula OR ¹ *> r2 _ c - N - Z where is R ¹ is H, a hydrocarbon group having 1 to 4 carbon atoms, 2-hydroxyethyl, 2-hydroxypropyl or a mixture thereof, R ² hydrocarbon group of 5-31 carbon atoms, and Z is a polyhydroxy hydrocarbon group having a linear hydrocarbon chain and at least three hydroxyl groups directly bonded to the chain or an alkoxylated derivative thereof. A detergent composition according to claim 1, wherein the alkyl ethoxylate component (a) is divided on a weight basis 8. A detergent composition according to claim 7 comprising 40 to 60% by weight of an alkyl ethoxycarboxylate component and 20 to 60% by weight of a polyhydroxy fatty acid amide, and the liquid carrier is water or a mixture of water and ethanol. 9. A detergent composition according to claim 8, wherein the M cation of the alkyl ethoxycarboxylate component (a) is selected from the group consisting of sodium, potassium and ammonium, and mixtures thereof with calcium and magnesium ions and the polyhydroxy fatty acid amide (b) having the general formula: 0 CH3 ^R2 - C - N - Z wherein R ² is an alkyl or alkenyl group, a straight chain with 11 to 17 carbon atoms, and Z is derived from glucose, maltose or mixtures thereof. 10. A method of washing dirty dishes, characterized in that the dishes come into contact with an effective amount of a cleaning composition comprising a) 5 to 95% of one or more alkyl ethoxy carboxylates of the formula I R 0 (CH2CH20) KCH ₂ C00-M ⁺ wherein R * is an alkyl group having 8 to 22 carbon atoms, k is an integer from 0 to 10 and M cation a, b) 5 to 95% of one or more polyhydroxy fatty acid amides of the general formula 0 R ¹ _R 2 - C - N - Z where is R ¹ is H, a hydrocarbon group having 1 to 4 carbon atoms, A 2-hydroxyethyl group, a 2-hydroxypropyl group, or a mixture thereof R ² hydrocarbon group of 5-31 carbon atoms, and Z is a linear hydrocarbon chain polyhydroxy hydrocarbon group having at least three hydroxyl groups directly bonded to the chain, preferably derived from N-methylglucamide having 11 to 17 carbon atoms. N-methylmaltamide having 11 to 17 carbon atoms or from a mixture of glucamide and maltamide, or an alkoxylated derivative thereof, and optionally * c) one or more monocarboxylate anionic surfactants. Process according to claim 10, characterized in that the proportion of the fatty acid polyhydroxyamides is derived from a mixture of monosaccharides, disaccharides and polysaccharides from plant sources. Process according to claim 10, characterized in that R 2 in the polyhydroxy fatty acid is an alkyl or alkenyl group in each case having 15 to 17 carbon atoms or a mixture thereof.