HU213735B - Detergent compositions containing alkoxyethoxyacetates and n-polyhydroxyalkyl-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

The present invention relates to detergent compositions comprising alkoxyethoxyacetates and N-polyhydroxyalkyl fatty acid amides. More particularly, the present invention relates to detergent compositions having the desired cleaning effect and foaming properties, which are particularly suitable for washing dishes.

Alkoxyethoxyacetates are known in the art and are currently used in detergent compositions. Such acetates and their use in detergent formulations are described in U.S. Patent No. 5,230,833 to Light-Duty Liquid Dishwashing Detergent Composition Containing an Alkyl Ethoxy Surfactant. These acetates have an improved cleaning effect, but generally form a foam with a low initial volume and poor stability. This low foam volume and poor stability can cause the consumer to feel that the cleaning effect of the formulation is inadequate. It is therefore desirable to mix these acetates with one or more components that improve the foaming properties. It has now been found that the compositions of the invention are suitable for this purpose.

The N-polyhydroxyalkyl fatty acid amide component of the composition of the present invention is known in the art for many purposes.

For example, N-acyl-N-methylglucamides are described in JW Goodby, MA Marcus, E. Chin and PL Finn, "The Thermothropic Liquid-Crystalline Properties of Somme Straight Chain Carbohydrate Amphiphiles", [Liquid Crystals, 3, No. 11 1569 1581 (1988)] and A. Muller-Fahmow, V. Zabee, M. Steifa and R. Hilgenfeld, Molecular and Crystal Structure of a Nonionic Detergent; Nonanoil-N-methylglucamide ”, [J. Chem. Soc. Chem. Commun. 1573-1574 (1986)]. Recently, the biochemical use of N-polyhydroxyalkylamide surfactants has become very important, for example in the dissociation of biological membranes, see, e.g., J. Ε. K. Hildreth, "N-D-Gluco-N-methylalkanamide Compounds, New Class of Nonionic Detergents for Foam Membrane Biochemistry" [Biochem. J. 207: 363-366 (1982)].

The use of N-alkylglucamides in detergent formulations has also been investigated. U.S. Patent No. 2,965,576 discloses detergent compositions comprising anionic and amide surfactants such as N-methylglucamide. These surfactants are added to the formulation to enhance low-temperature foaming, which may further include alkali metal phosphates, alkali metal silicates, sulfates and carbonates. The composition may also contain other ingredients which enhance its properties, such as fluorescent dyes, bleaching agents, perfumes.

U.S. Patent 2,703,798 discloses detergent compositions comprising a condensation product of N-alkylglucamine with an aliphatic fatty acid ester. As described herein, this reaction product can be used without further purification in aqueous detergent compositions.

Further, the preparation of an sulfuric acid ester of acylated glucamine is disclosed in U.S. Patent No. 2,717,894.

PCT International Publication No. WO 83/04412 discloses amphiphilic compounds having aliphatic polyhydroxy groups, which are described herein as having various uses, such as in cosmetics, pharmaceuticals, shampoos, lotions and ointments as surfactants, emulsifiers and dispersants in medicaments, solubilizing membranes, whole cells, or other tissue samples and producing liposomes. The present invention includes within its scope R'CON (R) CH ₂ R "and R" CON (R) R where R is hydrogen or an organic group, R is an aliphatic hydrocarbon group containing at least 3 carbon atoms and R "is an aldose residue group.

EP 0 285 768 discloses the use of N-polyhydroxyalkyl fatty acid amides as a thickener in aqueous detergents. These compounds are amides of the formula R ₁ C (O) N (X) R ₂ - wherein R 1 is C 1 -C 17, preferably C 7 -C 17 alkyl, R ₂ is hydrogen, C 1 -C 18, preferably C 1 -C 6 alkyl or an alkylene oxide group and X is a C 4 -C 7 polyhydroxyalkyl group such as N-methyl coconut fatty acid glucamide. According to the disclosure, the density-enhancing effect of amides is particularly useful in liquid surfactant systems containing paraffin sulfonates, but aqueous surfactant systems may also contain other anionic surfactants such as alkylaryl sulfonates, olefin sulfonates, sulfobenzoic acid esters, nonionic surfactants such as fatty alcohol polyglycol ether, alkylphenol polyglycol ether, fatty acid polyglycol ether or polypropylene oxide-poly (ethylene oxide) mixed polymers.

U.S. Patent No. 2,982,737 relates to a bar detergent comprising urea, sodium lauryl sulfate anionic surfactant and an N-alkylglucamide nonionic surfactant, namely N-methyl-N-sorbityl lauramide or Contains N-methyl-N-sorbityl myristamide.

Other glucamide surfactants are described, for example, in German Patent No. 2,226,872, which contains one or more surfactants and washing aid salts, namely polymeric phosphates, sequestering agents or wash soda, and one of R, C (O) N (R _2). ) CH ₂ (CHOH) _n CH ₂ OH N-acyl (polyhydroxyalkyl) amine - wherein R 1 is C 1 -C 3 alkyl, R ₂ is C 10 -C 22 alkyl and n is improved by the addition of 3 or 4 applies to detergent formulations. N-acyl (polyhydroxyalkyl) amine is added as a soil suspending agent.

U.S. Patent No. 3,654,166 discloses detergent compositions2

Comprising at least one anionic, zwitterionic or nonionic surfactant and, as a fabric softener, a compound of the formula RiN (Z) C (O) R ₂ - wherein R 1 is C 10 -C 22 alkyl, R ₂ is C 7 -C 21 alkyl, such that R, and R ₂ total from 23 to 39 carbon atoms, and Z is a polyhydroxy alkyl group which may be _CH2 (chome) _{m -CH2} OH wherein m is 3 or 4, - comprising .

U.S. Patent 4,021,539 discloses skin care compositions containing N-polyhydroxyalkylamine. These compounds have the general formula R, N (R) CH (CHOH) _m R ₂ , wherein R 1 is is hydrogen, lower alkyl, hydroxy (lower alkyl), aminoalkyl, or heterocyclic aminoalkyl, R is the same as R 1 but one other than H, and R? is CH ₂ OH or COOH.

French Patent No. 1,360,018 relates to solutions stabilized against polymerisation with formaldehyde containing amides of the formula RC (O) N (Ri) G wherein R is a carboxylic functionality containing at least 7 carbon atoms, R 1 is hydrogen or lower alkyl, And G is a glycogen group having at least 5 carbon atoms.

German Patent No. 1,261,861 relates to glucamine derivatives of the formula N (R) (R 1) (R ₂ ) for use as a wetting and dispersing agent, wherein R is a sugar moiety of glucamine, R 1 is a C 10-20 alkyl group, and R ₂ is C 1 -C 5 alkyl.

British Patent No. 745,036 relates to heterocyclic amides and their carbocyclic esters which are used, inter alia, as chemical intermediates, emulsifiers, wetting agents, dispersants and detergents, and as fabric softeners. The compounds may be represented by the formula N (R) (R 1) C (O) R ₂ , wherein R is a radical derived from anhydrated hexane pentol or its carboxylic acid ester and the moiety -C (O) R ₂ is a 2-25 moiety. acyl group of a carboxylic acid.

U.S. Patent No. 3,312,627 discloses a solid toilet perfume bar, which is substantially free of anionic detergents and washing-up alkalis, but contains lithium soaps of certain fatty acids, a nonionic surfactant, and a propylene oxide ethylene diamine-ethylene. oxide condensate, propylene oxide-propylene glycol-ethylene oxide condensate or polymerized ethylene glycol; and a nonionic foaming agent, which may be a polyhydroxyamide of formula RC (O) NR '(R ² ), wherein RC (O)

C 10 -C 14, and each of R ¹ and R ² is hydrogen or C 1 -C 6 alkyl having a total number of carbon atoms from 2 to 7 and the total number of hydroxyl groups being substituted is between 2 and 6. U.S. Pat. No. 3,312,626 has a substantially similar subject.

However, none of the above literature discloses detergent compositions containing an alkoxyethoxyacetate together with an N-polyhydroxyalkyl fatty acid amide. Thus, no reference is made to the surprisingly good foaming properties of such detergent compositions, their enhanced washing effect, especially as regards the degreasing effect.

Similarly, no prior art teaches about the gentle effect of such detergent compositions.

Thus, the present invention relates to skin-friendly detergent compositions having improved foaming properties and washing properties comprising alkoxyethoxyacetates and N-polyhydroxyalkyl fatty acid amides.

BACKGROUND OF THE INVENTION The present invention relates to a detergent composition containing alkoxyacetates comprising 99-35% by weight of a conventional detergent component, characterized in that it contains from 1% to 65% by weight of a surfactant mixture consisting of:

(a) one or more alkoxyethoxyacetates of formula (I) wherein R is an alkyl group having 8 to 22 carbon atoms, k being an integer from 0 to 10, and M being an alkali metal, an alkali metal, ammonium, lower alkyl a cation selected from the group consisting of ammonium, mono-, di- and triethylammonium ions in an amount of from 5 to 95% by weight, (b) one or more N-polyhydroxyalkyl fatty acid amides of formula (III): wherein R ¹ is hydrogen, C 1-4 alkyl, 2-hydroxyethyl, 2-hydroxypropyl, R ² is C 7-19 alkyl or alkenyl, and Z is polyhydroxy derived from a reducing sugar in a reductive amination reaction. hydrocarbon group in an amount of 5 to 95% by weight.

The compositions of the invention are preferably liquid or gels, more preferably liquid delicate detergents, most preferably liquid delicate detergents. The compositions contain from 5% to 65%, preferably from 10% to 50%, most preferably from 20% to 40%, by weight of a surfactant mixture containing one or more alkoxyethoxyacetates and one or more N-polyhydroxyalkyl fatty acid amides. These and other optional additives commonly used in detergent formulations are described below.

The surfactant mixture according to the invention comprises from 5 to 95, preferably from 20 to 80, most preferably from 40 to 60% by weight of one or more alkoxyethoxyacetates of the formula (I) wherein R is a C8-C22, preferably 12- C 14 alkyl, k is an integer from 0 to 10, preferably from 1 to 5, and M is a cation which is preferably an alkali metal, alkaline earth metal, ammonium, lower alkyl ammonium ion, more preferably sodium -, potassium or ammonium, most preferably sodium or potassium, or mixtures thereof with magnesium and calcium. The number of carbon atoms in the R group is related to the values of the integer k if it is advisable to increase the value of k simultaneously by increasing the number of carbon atoms R

The solubility of the detergent compound is maintained. Generally, when R is a C 12 -C 14 alkyl group, k is 1 to 4, if R is a C 12 -C 18 alkyl group, then k is 1 to 6, and if R is a C 8 -C 12 alkyl group, k is 0 to 3 between.

The alkoxyethoxy acetate component of the compositions of the invention may be prepared by methods known in the art.

The alkoxyethoxyacetate component of the compositions of the invention may comprise a series of alkoxyethoxyacetates. In this case, the distribution of the ethoxylates is such that the part of the substance having a value of 0 is less than 20% by weight, preferably less than 15% by weight, most preferably less than 10% by weight, and wherein k is greater than 7, less than 25% by weight, preferably less than 15% by weight, most preferably less than 10% by weight. If R is an average of 13, then the mean of k is between 1 and 4, and if the average of R is greater than 13, the mean of k is between 2 and 6. Such a distribution and its preparation are described in U.S. Patent No. 5,230,833. When the composition of the present invention contains a series of alkoxyethoxyacetates, the desired distribution of the acetate can be achieved by using ethoxylated alcohol precursors of appropriate distribution as starting materials.

It has been found that the presence of divalent cations in addition to alkoxyethoxyacetates greatly enhances the cleaning effect of the composition against fatty impurities. This is especially true when the composition is used in softened water containing little divalent ions. This is probably due to the fact that divalent ions increase the density of alkoxyethoxyacetates at the water / oil interface, thereby reducing the surface tension and improving the cleaning effect. However, for liquid detergent formulations containing alkoxyethoxyacetates that do not meet the narrow definition of the invention, the addition of divalent ions has fewer benefits and in many cases even reduces the cleaning effect of the composition.

When divalent ions are used in the compositions of the invention, they are preferably added in the form of chloride or sulfate salts or hydroxides which, after neutralization with a strong base, contain the alkoxyethoxyacetates in the form of alkali metal or ammonium salts, preferably sodium or potassium salts. . The concentration of divalent ions is generally 0-1.5% by weight, preferably 0.2-1% by weight, more preferably 0.3-0.8% by weight. Particularly preferred are the divalent ions magnesium and calcium.

Depending on the method used to prepare the alkoxyethoxy acetate component of the composition of the invention and the method used to prepare the composition, the composition may contain from 0 to 5.0%, preferably from 4.0% to less than 1%, more preferably from less than 2.5%. Alcohol ethoxylates of formula (II) wherein R 'is a C 12 -C 16 alkyl group and w is from 0 to 10 and less than 6 on average.

The unesterified alcohol ethoxylates of the formula (II) have a deleterious effect on the alkoxyethoxyacetate-containing compositions of the present invention. It is therefore essential that these formulations contain no more than 5.0% by weight of the alcohol ethoxylates from which the alkoxyethoxyacetates are derived. Although commercially available alkoxyethoxyacetates contain 10% or more alcohol ethoxylates, there are known methods for obtaining alkoxyethoxyacetates of the desired purity. For example, unreacted alcohol ethoxylates can be removed by steam distillation according to Example 1 of U.S. Patent 4,098,818 or by recrystallization of alkoxyethoxyacetate according to Example 1 of British Patent 1,027,481. A further method is disclosed in U.S. Patent No. 3,992,443, which discloses that alcohol ethoxylates are reacted with sodium hydroxide or metal sodium and monochloroacetic acid under specific pressure and temperature conditions to obtain the desired acetates.

Still other ways of preparing high purity alkoxyethoxyacetates are described in U.S. Patent 5,230,833, already mentioned.

The surfactant mixture according to the invention further comprises 5-95, preferably 20-80, more preferably 20-60% by weight of N- (polyhydroxyalkyl) fatty acid amide of formula (III) wherein R ¹ is hydrogen, C 1-4 alkyl, 2-hydroxyethyl, 2-hydroxypropyl, preferably alkyl having 1 or 2 carbon atoms, most preferably methyl; R ² is straight-chained C 7 -C 19 alkyl or alkenyl, more preferably straight-chained C 9 -C 17 alkyl or alkenyl, more preferably straight-chained C 11 -C 17 alkyl or alkenyl; and Z is a linear polyhydroxy hydrocarbon chain having at least 3 hydroxy groups directly attached to the chain or anhydride or alkoxylated (preferably ethoxylated or propoxylated) derivative obtained by dehydration of such a chain. Preferably Z is derived from a reducing sugar converted by a reductive amination reaction, more 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, high maltose corn syrup, or any of the individual sugars listed above may be used as starting materials. From these corn syrups a mixture of sugar components for Z can be obtained. Of course, other suitable starting materials may be used without exceeding the scope. Preferably Z is -CH ₂ - (CHOH) _n -CH ₂ OH, -CH (CH ₂ OH) - (CHOH) _n -] - CH ₂ OH or -CH ₂ - (CH ₂ OH) - (CHOH) ₂ -. (CHOR ") (CHOH) -CH ₂ OH wherein n is an integer from 3 to 5, R" is hydrogen or a cyclic or aliphatic monosaccharide or alkoxylated derivatives thereof. Most preferred are glycityl groups, where n is 4.

HU 213 735 Β

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

Examples of the formula R ² -CO-N < 1 &gt; include coconut amide, stearyl amide, oleyl amide, lauryl amide, myristyl amide, caprylamide, palmityl amide or tallow amide and the like.

Z can be 1-deoxyglucityl (sorbityl), 2-deoxyglucyl, 1-deoxymaltityl, 1-deoxylactyl, 1-deoxygalactyl, 1-deoxymannnityl, or 1-deoxy-maltotriotithyl.

Most preferred are polyhydroxy fatty acid amides of formula (IV) wherein R ² is a straight chain,

C 1 -C 17 alkyl.

Polyhydroxy fatty acid amides can be prepared by methods known in the art, generally by reacting an alkylamine with a reducing sugar in a reductive amination reaction to form the corresponding N-polyhydroxyalkylamine followed by condensation with an aliphatic fatty acid ester or triglyceride. the amidation step gives the N-alkyl-N- (polyhydroxyalkyl) fatty acid amide product. Methods for preparing compositions containing N-polyhydroxyalkyl fatty acid amides are described, for example, in British Patent Nos. 809,060, 2,965,576, 2,703,798 and 1,985,424.

In one process for the preparation of N-alkyl or N-hydroxyalkyl-N- (deoxyglycityl) fatty acid amides having a glycityl component derived from glucose and N-alkyl or N- (hydroxyalkyl) ) is N-methyl, Ν-ethyl, N-propyl, Ν-butyl, N- (hydroxyethyl) or N- (hydroxypropyl), N-alkyl or N- ( hydroxyalkyl) glucamine catalysts such as trilithium phosphate, trisodium phosphate, tri-potassium phosphate, tetrasodium pyrophosphate, pentakotassium tripolyphosphate, lithium hydroxide, sodium hydroxide, potassium hydroxide, calcium, -carbonate, potassium carbonate, disodium tartrate, dipotassium tartrate, sodium potassium tartrate, trisodium citrate, tricalcium citrate, basic sodium silicates, basic potassium silicates, basic sodium aluminum silicates, silicates or mixtures thereof - with a fatty acid ester such as methyl or ethyl ester or triglycerides of fatty acids. The amount of catalyst is preferably 0.5 to 50 mol%, more preferably 2.0 to 10 mol%, based on one mode of N-alkyl or N-hydroxyalkyl glucamine. The reaction is preferably carried out at a temperature of from 138 to 170 ° C, preferably from 20 to 90 minutes. When triglycerides are used as the source of the fatty acid ester in the reaction mixture, it is also preferable to use a phase transfer reagent such as saturated fatty alcohol polyethoxylates, alkyl polyglycosides, linear chain glucamide surfactants or mixtures thereof in an amount of 1-10% by weight of the total reaction mixture.

The reaction is preferably carried out as follows:

(a) preheating the fatty acid ester to 138-170 ° C;

(b) adding N-alkyl or N-hydroxyalkylglucamine under heating and stirring until a biphasic liquid / liquid mixture is formed;

(c) adding the catalyst to the reaction mixture; and (d) stirring until the indicated reaction time.

When the fatty acid ester is a triglyceride, preferably 2 to 20% by weight of the linear N-alkyl-N-hydroxyalkyl-N- (linear glycosyl) fatty acid amide is added to the reaction mixture as the phase transfer reagent. This inoculates the reaction, thereby increasing the reaction rate. The experimental part describes the procedure in detail.

The N-polyhydroxyalkyl fatty acid amides used in the process of the present invention are also advantageously used in the formulation of detergent formulations because they are completely or predominantly made from natural, renewable, non-petrochemical starting materials and are only slightly degradable to aquatic life. they are highly toxic.

It should be noted that the N-polyhydroxyalkyl fatty acid amides of formula (III) are formed in significant amounts by-products such as ester amides and cyclic polyhydroxy fatty acid amides. The amount of these depends on the materials involved and the reaction conditions. The N-polyhydroxyalkyl fatty acid amide is preferably added to the detergent composition in a composition which contains less than 2% by weight, more preferably 0.5% by weight, of cyclic polyhydroxy fatty acid amide. The above processes are advantageous because they result in small amounts of by-products, including such cyclic amide by-products.

The additives that may be used in the formulation are described below.

In a preferred embodiment of the invention, the composition of the invention is a liquid detergent composition. These liquid detergent compositions contain from 95% to 35%, preferably 90% to 50%, more preferably 80% to 60%, by weight of a liquid carrier such as water and a C 1 -C 4 monovalent alcohol such as ethanol, propanol, isopropanol, butanol or mixtures thereof. They included. Of the alcohol, ethanol is preferred.

Preferably, the liquid detergent compositions of the present invention are formulated to have a pH of the wash water of from 8 to 10, more preferably from 8.5 to 9.5, when used in aqueous cleaning applications. The formulation of the liquid formulations is formulated to have a pH of from 7.0 to 11.0, more preferably from 8.5 to 10.5, more preferably from 8.8 to 10.0. The pH of the liquid detergent compositions can be adjusted to this level by methods known in the art, for example by adding a base. Liquid detergents generally have a pH of 7. It has now been found that the compositions of the present invention will have a much greater lipid solubility in liquid form when their pH is alkaline than when they are below pH 7. This increase in cleaning effect is only seen in liquid detergent compositions containing the alkoxyethoxy acetate component of the invention. It is surprising that the compositions of the present invention, despite this alkaline effect, are highly gentle.

In order to increase the pH stability of the liquid preparation, it is advisable to use a buffer material. For this purpose, for example, N, N-bis (2-hydroxyethyl) glycine, tris (hydr

EN 213,735 (oxymethyl) aminomethane, triethanolamine, monoethanolamine, 2-amino-2-ethyl-1,3-propanediol, 2-amino-2-methyl-1,3-propanediol, N methyl diethanolamine, 1,3-diamino-2-hydroxypropane, preferably glycine or mixtures thereof. When the composition according to the invention contains such a buffer, it is present in an amount of 0.1 to 15% by weight, preferably 1 to 7% by weight, more preferably 1.5 to 5% by weight.

The compositions of the invention may also be in gel form. Such formulations are formulated in the same manner as liquids except that they also contain a thickening agent.

Any material that can be mixed with the aqueous solution may be used to form a thixotropic (fluidized by shear) and sufficiently high flow composition. Suitable materials for forming the yield point include colloidal silica, particulate polymers such as polystyrene or oxidized polystyrene, combinations of certain surfactants and water-soluble polymers such as polyacrylates.

For example, a high molecular weight polycarboxylate polymer may be used as a thickening agent in the compositions of the present invention. By "high molecular weight" is meant 500,000 to 5,000,000, preferably 750,000 to 4,000,000.

The polycarboxylate may be a carboxyvinyl polymer. Such compounds are described in U.S. Patent No. 2,798,053.

The carboxyvinyl polymer is an interpolymer of a mixture of monomers which, in addition to an olefinically unsaturated carboxylic acid monomer, contains from 0.1 to 10% by weight, based on the total weight of the monomers, of a polyether having at least 4 carbon atoms, polyol (polyhydric alcohol) at least 3 hydroxy groups are attached to the carbon atoms of the alcohol chain, and the polyether contains more than one alkenyl group. The monomer mixture may optionally contain significant amounts of other monoolefinic monomers. Carboxyvinyl polymers are practically insoluble in liquid, volatile organic hydrocarbons, and retain their size when exposed to air.

Preferred polyhydric alcohols for the preparation of carboxyvinyl polymers are oligosaccharides, reduced derivatives thereof in which the carbonyl group is converted to an alcohol group, and pentaerythritol, more preferably oligosaccharides, most preferably sucrose. The modified hydroxyl groups of the polyols are preferably etherified with allyl groups and the polyol contains at least two allyl ether groups per molecule. When the polyol is sucrose, it preferably contains at least five allyl ether groups per molecule. The polyetherated polyol preferably comprises from 0.1 to 4%, more preferably from 0.2 to 2.5%, by weight of the total monomers.

Preferred olefinically unsaturated carboxylic acid monomers for use in the preparation of carboxyvinyl polymers include monolefin-aliphatic unsaturated, lower aliphatic carboxylic acid monomers which are polymerizable, more preferably monoolefin acrylic acid monomers of formula (V); the most preferred of these being acrylic acid.

The carboxyvinyl polymers used in the compositions of the present invention have a molecular weight of at least 750,000. Preferred cross-linked carboxyvinyl polymers having a molecular weight of at least 1,250,000 are preferred. Also preferred are cross-linked carboxyvinyl polymers having a molecular weight of at least 3,000,000, which may be less cross-linked.

Various carboxyvinyl polymers are available from the B. F. Goodrich Company (New York, N.Y.) under the tradename Carbopol. Carboxyvinyl polymers useful in preparing the compositions of the present invention include Carbopol 910 having a molecular weight of 750,000; larbopol 941 having a molecular weight of 1,250,000 is preferred; more preferably, Carbopol 934 and Carbopol 940 having a molecular weight of 3,000,000 and 4,000,000, respectively.

Carbopol 934 is a very weak crosslink,

000,000 molecular weight carboxyvinyl polymer. It consists of a high molecular weight polyacrylic acid crosslinked with 1 mol% of a polyallyl sucrose with an average of 5.8 allyl groups per sucrose molecule.

Other polymers that can be used in the compositions of the invention include the polyacrylic acid commercially available from BASF Corp. under the tradename Sokolan PHC-25 ^R and the Gantarez ^R poly (methyl vinyl ether / maleic acid) interpolymer from GAF Corp.

Non-linear, water-dispersible, polyalkenyl polyether crosslinked polyacrylic acids having a molecular weight of 750,000 and more preferably used as polycarboxylates in the compositions of the invention

000,000.

Of these polycarboxylate thickeners, the Carbopol 600 series resins available from BF Goodrich, particularly Carbopol 616 and 617, are highly preferred. These resins are presumably much more crosslinked than the 900 series and have molecular weights of 1,000,000 and 4,000. 000,000. Polyester blends can also be used in the compositions of the present invention, with Carbopol 616 and 617 being particularly preferred.

The polycarboxylate thickeners are preferably used in such a way that the composition is substantially free of material thickeners. It has been found that the use of the polyesters of the invention in combination with the material in the composition of the present invention results in a product which is less favorable in terms of phase stability. In other words, the polyester is preferably used as a thickener / stabilizer instead of clay in the compositions of the invention.

Polycarboxylate polymer also reduces so-called "bottle residue". This term means that the detergent cannot be completely emptied from the container. Without wishing to be bound by theory, it is believed that the compressed compositions of the present invention behave so favorably because the composition has a greater cohesive strength than the adhesion strength of the container wall. The clay

In the case of formulations containing a bulking agent such as most commercially available detergents, "bottle residue" may in certain circumstances cause significant problems.

Without wishing to be bound by theory, long chain molecules of apolycarboxylate thickener are also believed to help suspend solids in the concentrated detergent compositions of the present invention and to help keep the matrix in an extended state. Furthermore, the polymer is less susceptible to repeated shear than clay thickeners that occur when the composition is vigorously mixed.

The polycarboxylate thickener is generally used in the composition of the invention in an amount of 0.1 to 10% by weight, preferably 0.2 to 2% by weight.

The yield range with thickeners is 50-350, preferably 75-250.

The yield point refers to the shear stress that exceeds the strength of the gel at which the flow begins. This value was measured with a Brookfield RTV type viscometer, T-bar and needle B using a Helipath type slide at readings at 25 ° C. The system was set to 0.5 rpm and read after 30 seconds or after the system stabilized. At this point, the system was stopped and the speed was reset to 1.0 / min. Readings were made again after 30 seconds or after system stabilization. The zero shear stress is obtained by subtracting the reading at 1.0 rpm from twice the reading at 0.5 rpm. The yield stress is calculated by multiplying the zero shear stress by 18.8 (conversion factor).

Other surfactants such as anionic, nonionic, ampholytic and zwitterionic surfactants may also be used in the compositions of the invention.

One type of anionic surfactant that can be used is alkyl ester sulfonates. Alkyl ester sulfonate surfactants as used herein refer to straight chain esters of C 8 -C 20 carboxylic acids (fatty acids) as described in "The Journal of the American Oil Chemists Society" (52, 323-329 (1975)). sulfonated with trioxide. Suitable starting materials for this purpose are natural fats derived from, for example, tallow or palm oil.

The alkyl ester sulfonates of formula (VI), wherein R ³ is a C 8-20 hydrocarbon, preferably a alkyl or a combination of alkyl groups, and R ^{4 is a} C 1-6 hydrocarbon, are particularly suitable as surfactants for alkyl esters. -, preferably an alkyl group or a combination of alkyl groups, and M is a cation which forms a water soluble salt with the alkyl ester sulfonate. Suitable salt-forming cations are metal ions such as sodium, potassium or lithium and substituted or unsubstituted ammonium cations such as monoethanolamine, diethanolamine, or triethanolamine. Preferably R ³ is C 14 -C 16 alkyl and R ⁴ is methyl, ethyl or isopropyl. Particularly preferred are methyl ester sulfonates wherein R ³ is C 14 -C 16 alkyl.

The alkylsulfate surfactants useful in the compositions of the present invention are water soluble salts or acids of the formula ROSO3M, wherein R is preferably a C 10 -C 24 hydrocarbon, more preferably C 10 -C 20 alkyl or hydroxyalkyl group, most preferably a C 12 -C 20 alkyl or hydroxyalkyl group. -C 18 alkyl or hydroxyalkyl, M is hydrogen or a cation such as an alkali metal such as sodium, potassium or lithium, ammonium or substituted ammonium such as methyl, dimethyl or trimethyl ammonium cation or a quaternary ammonium ion such as tetramethylammonium or dimethylpiperidinium cation or quaternary ammonium ion derived from alkylamines such as ethylamine, diethylamine, triethylamine and mixtures thereof. C12-C16 alkyl chains are generally preferred at low wash temperatures (e.g., below 50 ° C) and C14-C18 alkyl chains are preferred at higher wash temperatures (e.g., above 50 ° C).

Used in compositions of the invention, alkyl alkoxy sulfate surfactants of R0 (A) ms0 _3M water soluble salts or acids of the formula wherein R is preferably an unsubstituted 10 to 24 carbon atoms or a hydroxyalkyl containing carbon atoms 10-24 , more preferably a C 12 -C 18 alkyl or hydroxyalkyl group. A is an ethoxy or propoxy moiety, m is greater than 0, preferably between 0.5 and 3, and M is hydrogen or a cation which may be, for example, a metal ion such as sodium, potassium, lithium, calcium or a magnesium ion, an ammonium or a substituted ammonium cation. These include alkyl ethoxylated and alkyl propoxylated sulfates. The substituted ammonium cation may be, for example, a methyl, dimethyl or trimethylammonium cation or a quaternary ammonium ion such as tetramethylammonium or dimethylpiperidinium cation or alkylamines such as ethylamine, diethylamine, triethylamine and the like. Mixtures of quaternary ammonium ions. Such surfactants can include (C12-18) alkyl polyethoxylate (l, 0) sulfate [(C _{2 -C! 8} E (1,0) M], a (C12-18) alkyl polyethoxylate ( 2,25) sulfate [(C ₁₂ C [ ₈ E (2,25) M], C 12 -C 18 alkyl polyethoxylate (3,0) sulfate [(C ₁₂ -C ₁₈ E (3, 0) M], and a (C12-18) alkyl polyethoxylate (4.0) sulfate [(C ₂ -C ₈ E (4.0) M], where M is sodium or potassium atom.

Other anionic surfactants suitable for purification may also be used in the compositions of the invention. These may be salts, for example sodium, potassium, ammonium or substituted ammonium salts of soaps, such as mono-, di- or triethanolamine salts, C 9 -C 20 straight-chain alkylbenzene sulfonates, C 8 -C 22 primary or secondary alkane sulfonates, C 8 -C 24 olefm sulfonates, sulfonated polycarboxylic acids, prepared by sulfonation of up to 10 moles of ethylene carbonate containing up to 10 moles of ethylene oxide in sulfonated polycarbonate pyrolysis product of United Kingdom Patent 1,082,179; alkyl glycerol sulfonates, fatty acids and fatty oils glice7

EN 213 735 Β rinsulfonates, alkyl phenol ethylene oxide ether sulfates, paraffin sulfonates, alkyl phosphates, isethionates such as acyl isethionates, acyl taurates, methyl tauride fatty acid amides, alkyl succinates and preferably C12-C18 saturated and unsaturated monoesters; diesters of sulfosuccinates, preferably C 6 -C 12 saturated and unsaturated diesters; acyl sarcosinates, sulfates of alkyl polysaccharides, such as alkyl polyglycoside sulfates (nonionic, non-sulfated compounds described below), (C 9 -C 17) acyl, -N- (C 1 -C 4) alkyl, or -N- (2) C 4 -Chydroxyalkyl) glucamine sulfates, branched primary alkyl sulfates, and fatty acids esterified with isethionic acid and neutralized with sodium hydroxide. Also suitable for this purpose are resin acids and hydrogenated resin acids, such as rosin and hydrogenated rosin, and resin acids and hydrogenated resin acids present in or derived from tall oil. Further examples are found in Schwartz, Perry, and Berch's Surface Active Agants and Detergents. and II. Vol. In addition, a generic description of a number of such surfactants can be found in U.S. Pat. No. 3,929,678, column 23, line 58 to column 29, line 23.

Non-ionic surfactant detergents for use in the compositions of the present invention are described in general in column 13, line 14 through column 16, line 6 of U.S. Patent 3,929,678. The following are non-limiting examples of nonionic surfactants that may be used, without limitation:

CLAIMS 1. Condensates of alkyl phenols with polyethylene, poly (propylene) and poly (butylene oxide), preferably poly (ethylene oxide), including alkylene of alkyl phenols having 6 to 12 carbon atoms in the straight or branched chain. Ethylene oxide is preferably present in an amount of 5 to 25 mol per mole of alkylphenol, of which Igepal ™ CO-630 is commercially available from GAF Corporation and Triton. ™ X-45, Xl 14, X-100, and X-102, marketed by Rohm & Haas Company.

2. Condensates of aliphatic alcohols with 1-25 moles of ethylene oxide. The alkyl chain of the aliphatic alcohol may be straight or branched, primary or secondary and generally has from 8 to 22 carbon atoms. Particularly preferred are the condensation products formed by alcohols having from 10 to 20 carbon atoms containing from 2 to 10 moles of ethylene oxide per mole of alcohol. Of these types of surfactants are commercially available Tergitol ™ 15-S-9 (a condensation product of straight chain alcohols of 11 to 15 carbon atoms with 9 moles of ethylene oxide), Tergitol ™ 24-L-6 NMW (C12-C14 primer). a narrow molecular weight condensation product of alcohol with 6 moles of ethylene oxide), both available from Union Carbide Corporation; Neodol ™ 23-6.5 (a condensation product of straight chain alcohol of 12-13 carbon atoms with 6.5 moles of ethylene oxide),

Neodol ™ 45-7 (a condensation product of C14-C15 straight chain alcohol with 7 moles of ethylene oxide), Neodol ™ 45-4 (a condensation product of C14-15 straight chain alcohol with 4 moles ethylene oxide) Shell Chemical Company and Kyro ™ EOB (a condensation product of C13-C15 straight chain alcohol with 9 moles of ethylene oxide) marketed by Procter & Gamble Company.

3. Condensation products of ethylene oxide with hydrophobic bases obtained by condensation of propylene oxide with propylene glycol. The hydrophobic moiety of these compounds preferably has a molecular weight of 1500-1800 and is insoluble in water. Addition of the polyoxyethylene moieties to this hydrophobic moiety increases the water solubility of the molecule as a whole and maintains the liquid nature of the product until its polyoxyethylene content is 50% by weight, up to 40 moles. corresponds to condensation with ethylene oxide. This type of compound includes, for example, certain commercial Pluronic ™ surfactants marketed by BASF.

4. The condensation product of the reaction product of propylene oxide and ethylenediamine with ethylene oxide. The hydrophobic moiety of these compounds is a reaction product of ethylenediamine and excess propylene oxide and generally has a molecular weight of between 2500 and 3000. This hydrophobic moiety is condensed with ethylene oxide to such an extent that the condensation product contains 40 to 80% by weight of polyoxyethylene and has a molecular weight of between 5,000 and 11,000. Examples of such nonionic surfactants are certain Tetronic ™ compounds sold by BASF.

5. Semi-polar nonionic surfactants are a special class of nonionic surfactants. These include, for example, water-soluble amine oxides having one C 10 -C 18 alkyl moiety and 2 other groups which are C 1 -C 3 alkyl or hydroxyalkyl groups; water-soluble phospho-oxides containing one C 10 -C 18 alkyl moiety and 2 other groups, namely C 1 -C 3 alkyl or hydroxyalkyl groups; and water-soluble sulfides having a C 10 -C 18 alkyl moiety and a C 1 -C 3 alkyl or hydroxyalkyl group.

Semi-polar nonionic detersive surfactants are, for example, amine oxides of formula (VII) wherein R ³ is C 8 -C 22 alkyl, hydroxyalkyl, or phenyl, or a mixture thereof; R ⁴ is C 2 -C 3 alkylene or hydroxyalkylene, or a mixture thereof; x is from 0 to 3; and each R ⁵ is a C 1 -C 3 alkyl or hydroxyalkyl group or a polyethylene oxide group having 1 to 3 ethylene oxide groups. The ^R5 groups are joined together to form a ring via an oxygen or nitrogen atom.

Preferred amine oxide surfactants include (C 10 -C 18) alkyldimethylamine oxides and (C 8 -C 12) alkoxyethyl (dihydroxyethyl) amine oxides.

6. The alkyl polysaccharides described in U.S. Patent 4,565,647,

Having a hydrophobic group of 6 to 30, preferably 10 to 16, carbon atoms and a hydrophilic group of polysaccharide having 1.3 to 10, preferably 1.3 to 3, most preferably 1.3 to 2.7, polysaccharide units, preferably polyglycoside. it is. Glycoside moieties may be substituted by any reducing C 5 or C 6 reducing saccharide such as glucose, galactose or galactosyl. (The hydrophobic group optionally binds at the 2-, 3-, or 4-position to give glucose or galactose instead of the glycoside or galactoside.) The inter-saccharide linkages may be, for example, the added saccharide moiety one and the preceding saccharide moiety 2-, 3- 4and / or 6th position.

In certain cases, and less desirably, the hydrophobic moiety is linked by a poly (alkylene oxide) - preferably ethylene oxide - chain to the polysaccharide moiety. Hydrophobic groups are generally saturated or unsaturated, branched or unbranched, preferably linear, saturated alkyl groups having from 8 to 18 carbon atoms, preferably from 10 to 16 carbon atoms. The alkyl group may have up to 3 hydroxy groups and / or the polyalkylene oxide chain may contain up to 10, preferably less than 5, alkylene oxide moieties. Polysaccharides suitable for this purpose include octyl, nonyl decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl and octadecyl di-, tri-, tetra-, penta- and -hexaglycosides, -galactosides, -lactosides, -fructosides, -fructoses and / or -galactoses. Suitable mixtures include, for example, coconut alkyl di-, tri-, tetra- and pentaglycosides and tallow alkyl tetra-, penta- and hexaglycosides.

Preferred are alkyl polyglycosides of formula (VIII) wherein R ² is alkyl, alkylphenyl, hydroxyalkyl, hydroxyalkylphenyl, or mixtures thereof, wherein the alkyl groups are 10 to 18, preferably

They contain from 12 to 14 carbon atoms; n is 2 or 3, preferably 2; t is from 0 to 10, preferably 0; and x is from 1.3 to 10, preferably from 1.3 to 3, more preferably from 1.2 to 2.7. The glycosyl group is preferably derived from glucose. In preparing this compound, the alcohol or alkyl polyethoxy alcohol is first prepared and then reacted with glucose or a source of glucose to form the glycoside (linkage 1). The additional glycosyl moieties are then linked such that their carbon at position 1 is bonded at positions 2, 3 or 4 and / or 6, preferably predominantly at position 2, of the preceding glycosyl moieties. ring.

7. The fatty acid amide surfactants of formula (IX) wherein R ⁶ is C ⁷ -C 21, preferably C 9 -C 17 alkyl, and R ⁷ is hydrogen, C 1 -C 4 alkyl, C 1 -C 4 hydroxyalkyl, or - (C ₂ H ₄ O) _X H, wherein x is from 1 to 3.

Preferred amides include C8-20 ammonia, mono- and diethanolamides, and isopropanolamides.

The composition of the invention may also contain ampholytic surfactants. These surfactants are generally described as aliphatic derivatives of secondary or tertiary amines or aliphatic derivatives of heterocyclic secondary or tertiary amines in which the aliphatic moiety may be straight or branched. One of the aliphatic substituents contains at least 8, usually 8 to 10, carbon atoms, and at least one of them contains an anionic water-solubilizing group such as a carboxyl, sulfonate or sulfate group. Examples of ampholytic surfactants are found in U.S. Pat. No. 3,929,678, column 19, pages 18-35. line.

The composition of the invention may also contain zwitterionic surfactants. These surfactants are generally characterized as derivatives of secondary or tertiary amines, derivatives of heterocyclic secondary or tertiary amines, or quaternary ammonium, quaternary phosphonium or tertiary sulfonium compounds. Examples of zwitterionic surfactants are found in U.S. Pat. No. 3,929,678, column 19, line 38 to column 22, line 48.

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

The additional surfactants used are anionic or nonionic, preferably (C 11 -C 27) alkyl ester sulfonates, C 8 -C 22 primary or secondary alkane sulfonates, (C 10 -C 18 alkyl) dimethylamine oxides, alkyl polysaccharides or mixtures thereof.

These optional additional surfactants are present in the composition in a concentration of 1.0 to 10, preferably 2 to 5% by weight.

The composition of the invention may optionally contain other additives, such as builder inorganic or organic materials, although their use in the composition of the invention is generally not preferred. Glycine, alkyl and alkenyl succinates, alkali metal carbonates, phosphates, polyphosphates and silicates may be used as the water soluble inorganic detergent inorganic substance, either alone or in combination with organic alkaline soil retention detergents. Specific examples of such salts are: sodium tripolyphosphate, sodium carbonate, potassium carbonate, sodium pyrophosphate, potassium pyrophosphate, potassium tripolyphosphate and sodium hexametaphosphate. Alkali metal salts of polyhydric carboxylic acids, for example water-soluble cyphydrates such as sodium or potassium citrate, sodium or potassium tartrate, may be used as organic detergent salts, alone or in combination, or with the above alkaline detergent inorganic salts. ethylenediaminetetraacetate, sodium or potassium N- (2-hydroxyethyl) ethylenediaminetetriacetates, sodium or potassium nitrilotriacetates, sodium or potassium N- (2-hydroxy) ethyl ethyl nitrilodiacetates, sodium or potassium oxide succinates, sodium or potassium tartrate (mono- or di) succinates, as disclosed in U.S. Patent 4,663,071. Other organic detergent enhancing agents, such as water soluble phosphonates, may also be used in the compositions of the present invention.

HU 213 735 Β

However, detergent enhancers are of limited value when the composition of the invention is a liquid delicate detergent. These substances are optionally present in the composition in a concentration of 1.0 to 10, preferably 2 to 5% by weight.

Other preferred additives include diluents and solvents, dyes, fragrances, and, most preferably, hydrotropizing agents. The diluents may be inorganic salts, such as sodium or potassium sulfate, ammonium chloride, sodium or potassium chloride, sodium bicarbonate. The diluents are present in the compositions of the invention in a concentration of 1.0 to 10, preferably 2 to 5% by weight.

Solvents for use in the composition of the invention include water and low molecular weight alcohols such as ethyl alcohol or isopropyl alcohol. Solvents are present in the compositions in a concentration of 1.0-60%, preferably 5-50%.

To obtain the desired phase stability and viscosity of the formulation, hydrotropizing agents, such as sodium and potassium toluenesulfonate, sodium and potassium xylene sulfonate, sodium and potassium coumenesulfonate, trisodium and tricalcium sulfosuccinate, and the like are described in U.S. Pat. It has been found that the hydrotropizing agents have a beneficial effect on the foaming properties of the composition of the invention. Without wishing to be bound by theory, we believe that this beneficial effect is due to the viscosity characteristics of these hydrotropic substances. The hydrotropizing agents are present in the compositions in a concentration of 1.0 to 10, preferably 2 to 5% by weight.

The compositions of the present invention are advantageous in that their foaming properties show a surprising improvement when the given polyhydroxy fatty acid amide is used in combination with alkoxyethoxyacetate. Without wishing to be bound by theory, the compositions of the present invention are believed to retain their enhanced cleansing properties and skin-friendly properties even when formulated in the form of a highly alkaline liquid. Furthermore, without the theory, it is a further advantageous feature of the compositions of the invention that after washing, the washed dish will not be "greasy". This is particularly important in consumer markets, where the purity of a dish is judged by its lack of this "greasy" feeling. It is a further advantage of the compositions of the invention that, after use, the "slippery" sensation commonly found in detergents is reduced. This is especially important in consumer markets where this feeling is not liked because it creates the feeling that detergent cannot be completely removed from the surface of the container by rinsing.

As far as the process of the present invention is concerned, the contaminated vessels are contacted with an effective amount of the composition of the invention. The effective amount is 0.5-20 ml, preferably 3-10 ml, for 25 dishes to be washed. The actual amount of liquid detergent to be used is based on the user's judgment and will generally depend on factors such as the composition of the particular composition, including the concentration of active ingredient, the amount of dishes to be washed and the degree of soiling. However, the composition of the formulation depends on a number of factors, such as the target market area (e.g. USA, Europe, Japan). The following examples describe typical methods of using the compositions of the invention for washing purposes. The examples are intended to illustrate the invention but are not intended to limit its scope.

In a typical US application, 3 to 15 ml, preferably 5 to 10 ml of liquid detergent composition is added to 1000 to 10,000, preferably 3,000 to 5,000 ml of water in a 5,000 to 20,000, preferably 10,000 to 15,000 ml sink. The concentration of surfactant in the detergent composition is 21 to 44%, preferably 25 to 0% by weight. Dirty dishes are immersed in a sink containing detergent composition and water, and the soiled surface is cleaned using a cloth, sponge, or similar. The cloth, sponge, or similar device may be dipped in a mixture of detergent and water before being brought into contact with the surface of the container; the contact time between the device and the container is 1-10 seconds, although the actual duration varies depending on the application and the user. While the cloth, sponge or the like is touching the surface of the container, it is preferable to rub the surface simultaneously with it.

In a typical European application, 3 to 15 ml, preferably 3 to 10 ml of liquid detergent composition is added to 1000 to 10,000, preferably 3,000 to 5,000 ml of water in a 5,000 to 20,000, preferably 10,000 to 15,000 ml sink. The detergent composition has a surfactant concentration of 21% to 44%, preferably 25% to 35% by weight. The dirty dishes are placed in a sink containing the detergent composition and water, and the soiled surface is cleaned using a cloth, sponge or similar. The cloth, sponge, or similar device may be dipped in a mixture of detergent and water before being brought into contact with the surface of the container; the contact time between the device and the container is 1-10 seconds, although the actual duration varies depending on the application and the user. While touching the cloth, sponge or the like with the surface of the container, it is preferable to rub the surface simultaneously with it.

In a typical Latin-American and Japanese application, 3-50 ml, preferably 2-10 ml of liquid detergent composition is added to 50-2000 ml, preferably 500-2000 ml of water in a 500-5000 ml, preferably 500-2000 ml dishwasher. The concentration of surfactant in the detergent composition is 5 to 40%, preferably 10 to 30% by weight. Dirty dishes are immersed in a sink containing detergent composition and water, and the soiled surface is cleaned using a cloth, sponge, or similar. The cloth, sponge, or similar device may be dipped in a mixture of detergent and water before being brought into contact with the surface of the container; the duration of contact between the device and the vessel

HU 213 735 Β

1-10 seconds, although actual duration varies depending on usage and user. While the cloth, sponge or the like is touching the surface of the container, it is preferable to rub the surface simultaneously. 5

In another method, the dirty dishes are immersed in a dishwashing liquid which does not contain any liquid detergent. A device for absorbing liquid detergent, such as a sponge, is immersed in a separate, undiluted liquid detergent for a period of 1-5 seconds. The suction device, and consequently the liquid undiluted detergent, is then brought into contact with the surface of each dirty dish to remove contamination. The duration of this contact is between 15 and 10 seconds, although the actual duration varies depending on the use and the user. While the suction means is touching the surface of the container, it is preferable to rub the surface simultaneously with it.

The following example illustrates a process for preparing a N-methyl-1-deoxyglucityl lauramide surfactant for use in a composition of the invention. Although one skilled in the art can freely change the arrangement, one of the devices suitable for this purpose is a four-neck, 3-liter round-bottomed flask equipped with 25 motor-driven paddle stirrers and a thermometer long enough to incorporate the reaction mixture. The other two necks of the flask are equipped with a nitrogen inlet and a wide inside diameter sidewall (note: for very rapid methanol development, the wide inside diameter sidewall to which a high-performance condenser cooler and a vacuum tube is connected. and connected to a vacuum manometer and then to a suction device and a filter trap. To heat the reaction mixture, we use a 500 Watt heating jacket equipped with a temperature regulator ("Variac") which operates with a variable secondary voltage transformer and is mounted thereon. for easy lifting and lowering, providing additional control over the reaction temperature.

A flask was charged with 195 g (1.0 mol) of N-methylglucamine (Aldrich M4700-0) and 220.9 g (1.0 mol) of methyl laurate (Procter & Gamble CE 1270). The liquid / solid mixture was thawed under a stream of nitrogen (25 minutes). When the melt temperature reaches 145 ° C, 10.5 g (0.1 mol) of anhydrous powdered sodium carbonate (JT Baker) are added as a catalyst. The nitrogen sweep is shut off, the suction device 50 and nitrogen bleed are adjusted to give 1,6χ 10 ⁴ Pa vacuum formed. The reaction temperature is then maintained at 150 ° C by adjusting the Variac and raising / lowering the heating jacket.

within minutes, the first methanol bubbles 55 appear on the surface of the reaction mixture. The reaction will soon become very vigorous. Methanol is distilled until the rate of evolution slows down. The pressure was adjusted to 3,2x 10 ⁴ Pa, and then gradually increased as follows: After 3 minutes, 3.2 ^χ 10 ⁴ Pa, 7 minutes later 6,4xl0 ^4, After 60 minutes, 8.0 ^χ 10 ⁴ Pa. After 11 minutes from the onset of methanol evolution, heating and stirring were discontinued, with some foaming occurring. The product was allowed to solidify on cooling.

The following examples are intended to illustrate the compositions of the present invention and are not intended to limit the scope of the invention.

Example 1

The preparation of three compositions of the present invention is described below.

Preparation of Formulation A begins by mixing an alkoxyethoxyacetate detergent mixture with an N-methylglucamide of a C12-C14 fatty acid, followed by the addition of ethanol, sodium chloride and sodium xylene sulfonate. Further, any desired surfactant may be added to the mixture. Glycine was then added and the pH adjusted to 9 with sodium hydroxide. Finally, magnesium chloride was added, which lowered the pH to a sufficient extent. The final pH and viscosity can then be adjusted and the perfume and colorants added and the amount of water required for proper dilution added.

To prepare Formulation B, ethanol, sodium chloride and sodium xylene sulfonate are added to the alkoxyethoxyacetate / N-polyhydroxyalkyl fatty acid amide mixture prepared as described in Formulation A. Further components of the composition are added in the order shown in Table 1 below.

To prepare Formulation C, ethanol, sodium chloride and sodium xylene sulfonate are added to the alkoxyethoxyacetate / N-polyhydroxyalkyl fatty acid amide mixture prepared as described in Formulation A. The C12-C14 monoethanolamine is added to the mixture by heating to about 65 ° C. After fine-tuning the pH and viscosity, the perfume and colorants are added and the water is added to 100% by weight.

Table 1

weight Percent

component THE B C preparation Sodium [(C12 -C13 alkoxy) - ((average 2.8) ethoxy) acetate) * 20.0 20.0 15.0 (C12-C14 fatty acid) -N-methylglucamide 5.0 5.0 5.0 (C 10 -alkoxy) -ethoxy alcohol 5.0 Sodium [(C12-C13) alkoxy] ((average 2.8) ethoxy) sulfate) 3.0 Sodium (C 12 -C 14 fatty acid α-sulfonate methyl ester) 4.0 Sodium [(C 12 -C 13 alkoxy) - (average 3.0) ethoxy] sulfate] _ 4.0

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weight Percent

component THE B C preparation (C 12 -C 14 alkyl) dimethyl betaine 3.0 (C 12 -C 14 alkyl) dimethylamine oxide 3.0 5.0 5.0 (C12-C14 fatty acid) monoethanolamide 4.0 Magnesium ion (added as MgCl ₂ · 6H ₂ O) 0.76 0.76 0.76 glycine 4.0 - - Trisodium sulfosuccinate 2.0 2.2 2.0 ethanol 7.5 7.0 7.0 NaCI 1.5 <1 2.25 PH of the preparation 9.0 9.0 9.0 Fragrances and coloring agents 0.15 0.15 0.15 Water equilibrium quantity

* The surfactant mixture containing sodium alkoxyethoxy acetate is prepared as follows:

1. A C12-C13 alkoxy / (average 3.0) ethoxy / alcohol is reacted with potassium tert-butoxide and sodium chloroacetate in a 1: 1.1: 1.1 molar ratio. by first stirring the alkoxyethoxylate with tert-butoxide for 1 hour at 60 ° and 2600 Pa. The tert-butoxide is then gradually distilled off from the mixture. At this time, the vacuum was removed and sodium chloroacetate was added with stirring. The pressure was restored to 2400-2600 Pa and the reaction was allowed to proceed for 3 hours. The reaction pressure is then raised to atmospheric with nitrogen and the steam heating tubes switched off. The reaction mixture was allowed to stand overnight. The next day, the temperature of the reaction mixture was raised and the pressure was reduced to remove more tert-butanol from the system. The reaction mixture is then poured into an aqueous solution containing 105% by weight hydrochloric acid in an amount which would be theoretically necessary to neutralize the potassium tert-butoxide originally added to the system. To facilitate the separation of the organic and aqueous phases, the acid-aqueous reaction product is heated. The organic phase is then separated.

2. Repeat step 1 above using a (C 12 -C 13 alkoxy) / (average 2.7) ethoxy / alcohol with potassium tert-butoxide and sodium chloroacetate. tal in the ratio of 1: 1.3: 1.3 mol. Potassium tert-butoxide was added to the alkoxyethoxylate at 32.2 ° C and the reaction mixture was heated to 76.7 ° C. The vacuum pump was then turned on, the reaction temperature was raised to 104.4 ° C, and the t-butanol was distilled off over 30 minutes and collected. The reaction mixture was carefully cooled to 66 ° C and sodium chloroacetate was added. The reaction mixture was stirred for 1.5 hours, then cooled and poured into aqueous hydrochloric acid solution sufficient to reach pH 3.4. Water was added to increase its volume by 50% and then heated to 0 ° C. The upper organic layer was separated and the washing steps repeated.

3. The surfactant mixtures prepared in steps 1 and 2 above are mixed in a weight ratio of 40.4: 59.6. The pH of a portion of the resulting surfactant mixture was adjusted to 8 by the addition of a 1% sodium hydroxide solution and then diluted 50% by volume with aqueous ethanol (25: 75). The resulting solution was extracted continuously with hexane for 4 days. The lower aqueous layer was separated and heated to remove some water and alcohol to give a paste containing the alkoxyethoxyacetate surfactant mixture described below.

In the formulations of Example 1 above, the surfactant moiety contains 93.9% by weight of the alkoxyethoxyacetates of the formula R16CH3CTTOkC ^ COCUNa® wherein R is 12 to 13, on average 12.5 carbon atoms, x is 0 and 10, and the ethoxylates are present in such a distribution that the amount of the moiety where x is 0.2 is 2.8 wt.% And the moiety where x is greater than 7 is less than 2 wt. by weight of ethoxyacetates. The average value of X in this distribution is 2.8. The surfactant mixture further comprises 6.1% by weight of the aclohol ethoxylates of the formula RO (CH ₂ CH ₂ O) _X H, wherein R is 12 to 13, C 12 -C 12 alkyl having an average x of 2.8 . The surfactant mixture contains 01% soap.

Example 2

Table 2

weight Percent

component C D E F G H preparation Sodium [(C12-C13) alkyl] ((average 2.8) ethoxy) acetate * 15.0 20.0 15.0 10.0 12.0 8.0 (C 12 -C 14 alkyl) -N-methylglucamide (C 10 -C 10 alkoxy) - 5.0 5.0 5.0 10.0 10.0 10.0 - (average 8 ethoxy) alcohol Sodium - [(C12-C13) alkoxy] - 5.0 - 5.0 - 5.0 - - / (average 0.8) ethoxy / sulfate] 3.0 - - 10.0 - -

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weight Percent

Component preparation

Sodium (C 12 -C 14 fatty acid α-sulfonate)

methyl ester) Sodium [(C 12 -C 13 alkoxy) - ((average 3.0) ethoxy / sulfate)] (C 12 -C 14 alkyl) dimethyl betaine (C 14 -C 16 alkyl) dimethyl betaine 4.0 4.0 3.0 3.0 10.0 5.0 4.0 (C12-C14 fatty acids) - diethanol amide - - - 1.0 - 1.0 (C12-C14 fatty acids) - monoethanol amide - - 4.0 - - 1.0 Magnesium ion (MgCly 6H ₂ O) added as) 0.76 0.76 0.76 0.3 0.5 0.5 glycine 4.0 - - - - - N, N-bis (2-hydroxyethyl) - glycine - - - 5.0 3.0 - Methyl diethanolamine - - - - 10.0 - Coco amido propyl dimethyl betaine - - 3.0 - - 3.0 (C 12 -C 14 alkyl) - N-oxide - - - - - 3.0 T trisodium sulfosuccinate 2.0 2.2 2.0 - - - ethanol 7.5 7.0 7.0 5.0 5.0 5.0 NaCI 1.5 <1 2.25 - - - PH of the preparation 9.0 9.0 9.0 9.0 8.0 8.0 Fragrances and coloring agents 0.15 0.15 0.15 0.15 0.15 0.15 Monoethanolamine - - - 5.0 5.0 - Triethanolamine - - - 5.0 - 4.0 Water - equilibrium unit - * The surfactant mixture containing sodium alkoxyethoxy acetate was prepared as in Example 1.

Example 3 4Q

Used in the compositions of the invention

N-polyhydroxyalkyl fatty acid amides can also be prepared by the following procedure, starting from 84.87 g of methyl fatty acid ester (Procter & Gamble CE 1270 methyl ester), 75 g of N-methyl D-glucamine (Aldrich 45). Chemical Company M4700-0), 1.04 g of sodium methoxide (Aldrich Chemical Company 16,499-2) and 68.51 g of methanol are used. The reaction vessel is equipped with a standard reflux system comprising a dryer, a reflux condenser and a stir bar. 5Q N-Methyl-D-Glucamine is added to methanol with stirring under argon and heating is started. After 15-20 minutes, when the solution has reached the desired temperature, the ester and the sodium methoxide catalyst are added. From time to time, a sample is taken to require progress of the reaction, but it is noted that the solution is completely clear within 63.5 minutes. We believe that by this time the reaction will be almost complete. The reaction mixture was refluxed for 4 hours.

The crude product obtained after removal of methanol yielded 156.16 g. After vacuum drying and purification, the final product yield is 106.92 g. The yield is not given in% because the occasional sampling makes the calculation of this value meaningless.

In the following, it is intended to provide further aspects which can be used to prepare a wide variety of detergent compositions containing N-polyhydroxyalkyl fatty acid amides. These aspects are not intended to limit the scope of the invention.

It is readily apparent that N-polyhydroxyalkyl fatty acid amides are somewhat unstable in highly basic and highly acidic media due to their amide linkages. Although some degradation is permissible, it is not advisable to expose these materials to OH higher than 11, preferably lower than 10, for prolonged periods. The pH of the (liquid) final product is generally from 7.0 to 9.0.

In preparing N-polyhydroxyalkyl fatty acid amides, the basic catalyst used to form the amide bond will generally need to be at least partially neutralized. Although any acid can be used for this purpose, the preparation13

The formulator of this recipe can easily recognize that it is simple and convenient to use an acid that is otherwise useful and desirable in the formulation. For example, citric acid can be used for neutralization, the resulting citrate ion (1% by weight) is left in a 40% suspension of N-polyhydroxyalkyl fatty acid amide, which can then be used again at a later stage of detergent production. Likewise, acidic forms of substances such as oxydisuccinate, nitrilotriacetate, ethylenediaminetetraacetate, tartrate / succinate can be used.

N-polyhydroxyalkyl fatty acid amides (mainly C12-C14) derived from coconut fat fatty acids are more soluble than those derived from tallow (especially C16-C18). Therefore, C12-C14 materials are slightly easier to incorporate into liquid formulations and are more soluble in cold wash water. But C 16-18 materials are also quite useful, especially when washing in hot or hot water. In fact, these materials may have better detergent surfactants than their C12-C14 counterparts. Thus, the formulator, when selecting a particular N-polyhydroxyalkyl fatty acid amide for use in a particular formulation, will need to find a balance between good processability and performance in use.

It should also be noted that the solubility of N- (polyhydroxyalkyl) fatty acid amides will be higher if the fatty acid chain is unsaturated and / or branched. Therefore, for example, N-polyhydroxyalkyl fatty acid amides derived from oleic acid and isostearic acid are more soluble than the corresponding n-alkyl derivatives.

Similarly, N-polyhydroxyalkyl fatty acid amides prepared from disaccharides, trisaccharides, generally have a higher solubility than their monosaccharide counterparts. In addition, N-polyhydroxyalkyl fatty acid amides having a polyhydroxyalkyl group derived from maltose are particularly good detergents when used in combination with conventional alkylbenzene sulfonates (LAS). While not wishing to be bound by theory, the combination of LAS with N- (polyhydroxyalkyl) fatty acid amides derived from oligosaccharides such as maltose appears to cause an unexpected and surprising reduction in surface tension and thereby an increase in washing effect. (The preparation of N-polyhydroxyalkyl fatty acid amides from maltose is described below.)

The N-polyhydroxyalkyl fatty acid amides may be prepared not only from purified sugars, but also from hydrolyzed starches, such as corn starch, potato starch or any suitable starch of plant origin containing the mono-, di- or oligosaccharides desired by the formulator. This is extremely important from an economic point of view. For example, high glucose corn syrup, high maltose corn syrup and the like can be conveniently and economically used. Lignite-depleted, hydrolyzed cellulose pulp may also be used as starting material for the preparation of N-polyhydroxyalkyl fatty acid amides.

As stated, N-polyhydroxyalkyl fatty acid amides from oligosaccharides such as maltose or lactose are more soluble than the corresponding glucose derivatives. In addition, it appears that the more soluble N-polyhydroxyalkyl fatty acid amides may, to varying degrees, contribute to the solubilization of their less soluble counterparts. Thus, the formulator may select a high glucose corn syrup as the raw material, but also containing a small amount (e.g., 1% or more) of maltose. The resulting mixture of N-polyhydroxyalkyl fatty acid amides generally exhibits better solubility properties over a wide range of temperatures and concentrations than N-polyhydroxyalkyl fatty acid amides obtained from "pure" glucose. Thus, if sugar mixtures are used as the raw material instead of pure sugar compounds, the N-polyhydroxyalkyl fatty acid amides thus obtained, in addition to economic advantages, also offer considerable advantages in terms of performance and ease of formulation. However, in some cases, the concentration of maltamide above 25% by weight decreases to a certain extent the scrubbing effect of washing, and above 33% it reduces to a certain extent the foaming [these are% N- (polyhydroxyalkyl) fatty acid amides from maltose concentration in the mixture relative to N-polyhydroxyalkyl fatty acid amides derived from glucose. This effect may vary slightly depending on the chain length of the fatty acid moiety. In general, it is preferred that the monosaccharides (e.g., glucose) are present in the N-polyhydroxyalkyl fatty acid amide mixture in a weight ratio to di- and oligosaccharides (e.g., maltose) of from 4: 1 to 99: 1.

Preferred non-cyclized N-polyhydroxyalkyl fatty acid amides can be prepared from fatty acid esters and N-alkyl polyols in alcoholic solvents at temperatures of from 30 to 90, preferably from 50 to 80 ° C. It has been found that 1,2-propylene glycol is well suited as a solvent for the preparation of liquid detergents because glycol does not need to be completely removed from the reaction mixture before it is used in the detergent final product. Likewise, solid, generally granular, detergents are preferably prepared at a temperature in the range of 30 to 90 ° C in a solvent containing ethoxylated alcohols, such as C 12 -C 14 alcohols containing ethoxy groups 3 to 8 such as NEODOL 23 E006.5 by Shell. If such ethoxylated alcohols are used, they preferably do not contain significant amounts of non-ethoxylated alcohols, and more preferably, they do not contain significant amounts of monoethoxylated alcohols. ("T" symbol).

Although the preparation of N-polyhydroxyalkyl fatty acid amides is not within the scope of the present invention, further methods of preparation are described below.

The preferred industrial preparation of N-polyhydroxyalkyl fatty acid amides comprises the following steps:

In step 1, the N-polyhydroxyalkylamine derivative is prepared from the desired sugar or sugar mixture by combining the N-alkylamine and the sugar.

HU 213 735 Β

If the above procedure is carried out at below 20 ° C and with different Gardner color corn syrups, the resulting

The color of the MMA adduct (after equilibration, i.e. at least 2 hours) shows the values listed in Table 4 below.

Table 4 forms an adduct and reacts with hydrogen in the presence of a catalyst; in the subsequent step 2, the above (polyhydroxyalkyl) amine is preferably reacted with a fatty acid ester to form the amide bond. Although the N-alkylpolyhydroxyalkylamines useful in Step 2 of the above reaction may be prepared by a variety of methods known in the art, the following procedure may conveniently be carried out using inexpensive sugar syrup as the raw material. It should be noted that if such syrups are used as a raw material, a very clear or preferably almost colorless syrup should be selected in order to obtain better results.

Preparation of N-alkyl polyhydroxyamine from sugar syrup of plant origin

I. Adduct Formation: In the following routine procedure, 420 g of a 55% solution of glucose [corn syrup, 231 g (1.28 mol) glucose] having a Gardner color value of less than 1, 119 g of 50% aqueous methylamine solution (59.5 g, 1.92 mol) in methylamine. The methylamine (MMA) solution was purged with nitrogen and cooled to 10-20 ° C or lower with nitrogen. The corn syrup is slowly added to the MMA solution at the reaction temperature shown in Table 3. At the times shown in Table 3, measure the Gardner color.

Table 3

Time, minutes 10 30 60 120 180 240

Of reaction. ° C Gardner color

1 1

1 1

1 2

6 10

As can be seen from the above data, as the temperature is raised above 30 ° C, the Gardner color of the adduct becomes worse and, at temperatures around 50 ° C, the Gardner color value of the adduct is only under 30 seconds. If the reaction and / or residence time is longer, the temperature should be kept below 20 ° C. The Gardner color value of the glucamine solution should be less than 7, preferably less than 4.

When the adduct is formed at a lower temperature, the time required to reach the equilibrium concentration of the adduct can be reduced by increasing the ratio of the amine to the sugar. For a 1: 5 molar ratio of amine to sugar at 30 ° C, equilibrium is required for 2 hours. Under the same conditions, at a molar ratio of 1.2: 1, this time is at least 3 hours. In order to obtain a satisfactory level, the ratio of amine to sugar, reaction temperature and reaction time should be chosen so that it is practically equilibrium, that is, above 90%, preferably above 95%, more preferably above 99% based on sugar and the color of the adduct. less than 4, preferably less than 4, more preferably less than 1.

Gardner Color (Approx.) —---- Corn Syrup 1 1 1 1+ 0 0 0+

Addukt 3 4/5 7/8 7/8 1 2 1

As can be seen from the above, the sugar-containing starting material must be almost perfectly colorless in order to obtain a consistently acceptable adduct. If the Gardner color value of the sugar is 1, the adduct will be acceptable at one time and not at other times. If the Gardner color value is above 1, the resulting adduct is unacceptable. The better the initial color of the sugar, the better the adduct.

Hydrogenation Reaction: The adduct prepared above having a Gardner color value of 1 or less is hydrogenated as follows.

539 g adduct and 23.1 g of United Catalyst G498 Ni catalyst in water, in a 1 liter autoclave at 20 ° C, purged twice with 1.3 × 10 ^{6 * 1 * 4 * 7} psi hydrogen. The hydrogen pressure was then raised to 9.5 10 ⁶ Pa and the temperature raised to 50 ° C, followed by a pressure of 10.910 ⁶ Pa.

The temperature was raised to about 50-55 ° C for 3 hours. By this time the product was already 95% hydrogenated. The temperature was raised to 85 ° C for 30 minutes, then the reaction mixture was decanted and the catalyst removed by filtration. The product obtained after evaporation of water and MMA is a white powder containing 95% N-methylglucamine.

The above procedure is repeated with about 23.1 g of Raney Ni catalyst with the following changes: The catalyst is washed three times and purged twice with the reaction vessel together with the catalyst therein 1.3 · 10 ⁶ psi of hydrogen for 2 hours and then 10.9 to 10 ^{It is} maintained under a hydrogen pressure of ⁶ hours by releasing the pressure after one hour and raising it again to 10,910 mmHg. The adduct is then pumped in from 1.3 to 10 ⁶ Pa pressure reactor to 20 ° C, the reactor is purged from 1.3 to 10 ⁶ psi with hydrogen, and thereafter the process as described above.

In both cases, the final product contains more than 951% N-methylglucamine, less than 10 ppm nickel per glucamine, and the solution has a Gardner color value of less than 2.

The color of the crude N-methylglucamine is stable up to 140 ° C when exposed to temperature for a short time.

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

Alternatively, the adduct is prepared from 159 g of a 501% aqueous solution of methylamine. The solution is purged with nitrogen at 10 to 20 ° C

EN 213 735 Β cover. 330 g of a 70% (almost anhydrous purity) corn syrup is degassed with nitrogen at 50 ° C and then slowly added to the methylamine solution at a temperature below 20 ° C. The solution was stirred for 30 minutes to give 95% adduct as a very pale yellow solution.

190 g of the adduct and 9 g of United Catalyst G498 Ni catalyst in water in a 200 ml autoclave were purged three times with hydrogen at 20 ° C. Then the hydrogen pressure is raised to 50 ° C 1.3 10 ⁶ Pa, the temperature and the pressure was raised from 1.7 to 10 ⁶ Pa, the temperature was maintained for 3 hours at 50 to 55 ° C. The temperature of the already 95% hydrogenated product was raised to 85 ° C for 30 minutes. The product obtained after evaporation of water and MMA is a white powder containing 95% N-methylglucamine.

It is also important that the contact between the adduct and the catalyst is kept to a minimum while the hydrogen pressure does not reach 6.8 · 10 6 Pa, in order to minimize the nickel content of glucamine. The N-methylglucamine obtained in this reaction had a nickel content of 100 ppm, whereas the product obtained in the previous reaction had a nickel content of less than 10 ppm.

The following hydrogenation reactions were performed to test the effect of temperature.

In the methods, as above, a 200-milliliter autoclave is used to prepare the adduct and hydrogenate at various temperatures.

The adduct to be used in the preparation of the glucamine was prepared by adding 420 g of 55% glucose solution (corn syrup, 231 g, 1.28 mol glucose) (prepared from CardeG 99DE corn syrup with a Gardner color value 119 g of a 50% solution of methylamine (59.5 g, 1.92 mol MMA, product of Air Products) are mixed.

The procedure consists of the following steps:

1. A reactor purged with nitrogen and charged to a reactor cooled to below 10 ° C was charged with 119 g of a 50% solution of methylamine.

2. 55% corn syrup solution is degassed with nitrogen at 10-20 ° C and / or blown to remove oxygen.

3. Slowly add the corn syrup solution to the methylamine solution while maintaining the temperature below 20 ° C.

4. After complete addition of the corn syrup solution, the reaction mixture is stirred for 1-2 hours.

The adduct is used immediately after preparation in the hydrogenation reaction or stored at low temperature to avoid further degradation.

The hydrogenation reaction of glucamine consists of the following steps:

1. Add 134 g (less than 1 adduct Gardner color) of adduct and 5.8 g of nickel G498 to a 200 mL autolab.

2. The reaction mixture is purged twice with hydrogen at ²⁰ psi at 20-30 ° C.

3. Raise the hydrogen pressure to 2.6 to ¹⁰ psig and the temperature to 50 ° C.

4. The pressure was raised to 9.8 mmHg and the reaction was continued for 3 hours. The temperature is maintained between 50 and 55 ° C. Remove sample 1.

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

6. The nickel catalyst is removed by decantation and filtration. Remove sample 2.

Conditions for reactions at constant temperature:

1. Add 134 g of adduct and 5.8 g of G498 nickel into a 200 ml autoclave.

2. The reaction mixture is purged twice with low hydrogen at 1.3 x 10 ⁶ P at low temperature.

3. The hydrogen pressure of 2.6 · 10 ⁶ Pa and the temperature was raised to 50 ° C.

4. After raising the pressure to 9.8-10 ⁶ Pa, the reaction was continued for 3.5 hours. The temperature is maintained at the specified value.

5. The nickel catalyst is removed by decantation and filtration. Sample 3 at 50-55 ° C, Sample 4 at 75 ° C, and Sample 5 at 85 ° C. (The reaction time is 85 minutes at 85 ° C.)

Each method yields the same 941% pure N-methylglucamine; immediately after the reaction, the Gardner color value of the products obtained by the various methods is the same, but only treatment with biphasic heating gives good color stability; slight discoloration was observed after treatment at 85 ° C.

Example 4

The (hardened) tallow fatty acid amide of N-methyl maltamine for use in the detergent compositions of the present invention is prepared as follows:

Step 1 - Reagents used: maltose monohydrate (Aldrich, item no. 01318KW); methylamine (40% w / w aqueous solution) (Aldrich, item no. 03325 ™); Raney Nickel in a 50% suspension (UAD 52-730, Aldrich, item no. 12921LW).

The reactants are added to glass beads (250 g maltose, 428 g methylamine solution, 100 g catalyst slurry containing 50 g Raney Ni) and the mixture was placed in 3 L rocking autoclave, which is 3.4 x 10 ⁶ psi with nitrogen three times and 3.4 x 10 ⁶ Pa pressure purged twice with hydrogen, and shaken over the weekend at a temperature between 28 and 50 °. The crude reaction mixture was vacuum filtered twice through a silica gel glass fiber microfilter. The filtrate was evaporated to a viscous material. Azeotropically removes the last traces of water by dissolving it in methanol and distilling off the methanol / water mixture in a rotary evaporator. The final drying is carried out under high vacuum. The crude product was dissolved in methanol under reflux, filtered, recrystallized by cooling, filtered again and the filter cake dried in vacuo at 35 ° C. This is the first dose. The filtrate was evaporated until precipitation started and stored overnight in a refrigerator. The solid was filtered off and dried in vacuo. This is the 2nd dose. The filtrate was again evaporated to half its original volume and the recrystallization was repeated. Very few substances are precipitated. To this is added a little ethanol and the solution is left in the refrigerator for a weekend. Then the

The solid was filtered and dried in vacuo. The N-methyl maltamine-containing solids obtained in each step were collected and used in Step 2 of the synthesis.

Step 2: - Reagents used: N-methyl maltamine (from Step 1); hardened tallow methyl esters; sodium methoxide (25% in methanol); absolute methanol (solvent); 1: 1 molar amide: ester; an initial catalyst concentration of 10 mol% (based on maltamine) and subsequently increased to 20 mol%; solvent: 50% by weight.

In a sealed flask, 20.36 g of tallow methyl ester was thawed under water and transferred to a 3-necked round bottom flask equipped with a mechanical stirrer. The flask was heated to 70 ° C to prevent the ester from solidifying. In a separate vessel, 45.36 g of methanol are mixed with 25.0 g of N-methyl maltamine and the resulting suspension is added to the tallow ester with vigorous stirring. Then 1.51 g of 25% sodium methoxide are added. After 4 hours, the reaction mixture still does not purify, so an additional 10 mol% (20 mol%) of catalyst is added and the reaction is allowed to continue overnight (68 ° C). By this time the mixture is clarified. Transfer the flask for distillation and raise the temperature to 110 ° C. Distillation was continued at atmospheric pressure for 60 minutes. At this point, the high vacuum distillation was started and continued for 14 minutes. During this time, the product thickens strongly. The product was allowed to stand at 110 ° C (external temperature) for 60 minutes, then vented and triturated with diethyl ether over the weekend. The ether was then removed in a rotary evaporator, the product was stored overnight in an oven and ground to a powder. Any remaining N-methylmaltamine is removed with silica gel. The silica gel suspended in 100% methanol was transferred to a funnel and washed several times with 100% methanol. A concentrated sample of the product (20 g in 100 ml of 100% methanol) was poured onto silica gel and eluted with methanol under vacuum several times. The collected eluent is evaporated to dryness in a rotary evaporator. Any residual tallow ester was removed by trituration with ethyl acetate and standing overnight, followed by filtration. The filtrate cake was dried overnight in vacuo. The product thus obtained is tallow alkyl N-methyl maltamide.

In another embodiment of the process, Step 1 of the above reaction sequence uses commercially available corn syrup containing glucose or glucose mixtures and generally 51% or more maltose. The resulting N-polyhydroxyalkyl fatty acid amides can be used in any of the detergent compositions of the invention.

Alternatively, Step 2 of the above reaction sequence can be carried out in 1,2-propylene glycol or NEODOL. The formulator does not deem it necessary to remove propylene glycol or NEODOL from the product prior to use in detergent formulations. It is also within the skill of the art to neutralize the methoxide catalyst with citric acid, and the resulting sodium citrate may also remain in the N-polyhydroxyalkyl fatty acid amide.

The formulations of the present invention may contain more or less antifoaming agents as desired by one skilled in the art. In the case of detergents, strong foaming is generally desirable and an antifoam agent is not required.

Example 5

In the formulations according to any of the preceding examples, the fatty acid glucamide surfactant may be replaced by an equivalent amount of maltamide or a surfactant mixture of glucamide / maltamide derived from plant sugar-containing substances. The use of ethanolamides in the compositions can improve the stability of the final product at low temperatures. In addition, the use of sulphobetaine ("sultaine") surfactant can give the product excellent foaming properties. Removal of greasy impurities from vessels may be facilitated by the use of 1% calcium chloride. Magnesium chloride enhances foaming of the preparation.

Because of the extremely high foaming of the compositions of the present invention, fatty acids having 14 or more carbon atoms are preferably present in the compositions in amounts of less than 5%, more preferably less than 2%, and most preferably none at all, suppress. Thus, the formulator will preferably avoid incorporating an antifoam amount of N-polyhydroxyalkyl fatty acid amides into the formulation of the highly effervescent formulation and / or forming 14 or more carbon fatty acids during storage of the final product. One simple way is to prepare the N-polyhydroxyalkyl fatty acid amides to be used in the composition from 12 carbon esters. Fortunately, the use of amine oxide or sulfobetaine surfactants, such as coconut amidopropylhydroxysultain, or betaines, such as coconut amidopropyl betaine, can overcome some of these bad foaming properties caused by fatty acids.

If anionic optical bleach is to be added to formulations containing anionic or polyanionic detergents such as polycarboxylate detergent in relatively high concentrations (101% or greater), it is preferable to remove the bleach with water and N-polyhydroxyalkyl fatty acid amide, added to the final product.

One skilled in the art will recognize that when di- or oligosaccharides such as maltose are used to prepare the N-polyhydroxyalkyl fatty acid amides to be used in the composition, polyhydroxy fatty acid amides are obtained wherein the straight-chain Z substituent is a polyhydroxy ring. ". These materials are intended to be wholly within the scope of the invention and do not depart from the spirit and spirit thereof as set forth in the specification and claims.

Claims (18)

PATENT CLAIMS A detergent composition comprising alkoxyacetates comprising 99-35% by weight of a conventional detergent component, characterized in that it comprises from 1% to 65% by weight of a surfactant mixture consisting of: (a) one or more alkoxyethoxyacetates of formula (I) wherein R is an alkyl group of 8 to 22 carbon atoms, k is an integer from 0 to 10, and M is an alkali metal, alkaline earth metal, ammonium, a cation selected from the group consisting of alkylammonium, mono-, di- and triethylammonium ions in an amount of from 5 to 95% by weight, and (b) one or more N-polyhydroxyalkyl of formula (III) fatty acid amide wherein R 'is hydrogen, C 1-4 alkyl, 2-hydroxyethyl, 2-hydroxypropyl, R ² is C 7-19 alkyl or alkenyl, and Z is a reducing sugar in a reductive amination reaction Polyhydroxy hydrocarbon radicals from 5 to 95% by weight (Priority 06/09/1991) Composition according to claim 1, characterized in that component (a) comprises a mixture of alkyl-alkoxyacetates having a distribution, wherein the part where k is 0 is less than 201%, the part where k is It is greater than 7, less than 25%, and if R has an average of 13 carbon atoms, then the mean value of k is between 1 and 4, and if R has more than 13 carbon atoms in general, the average value of k is between 2 and 6. (Priority: 06/09/1991) Liquid composition according to claim 1, characterized in that it contains 90-50% by weight of a liquid carrier, preferably water or water, and a mixture of 1 to 4 carbon atoms and 10-50% by weight of a surfactant mixture. (Priority: 06/09/1991) Composition according to claim 3, characterized in that it contains a surfactant mixture comprising 20-80% by weight of alkoxyethoxyacetate and 20-80% by weight of N-polyhydroxyalkyl fatty acid amide. (Priority: 09/06/1991) Composition according to claim 4, characterized in that component (a) comprises an alkoxyethoxyacetate in which the cation M is an alkali metal, alkaline earth metal, ammonium, lower alkyl ammonium, preferably mono-, di- or triethylammonium ions or mixtures thereof with calcium and magnesium ions. (Priority: 06/09/1991) 6. The composition of claim 5, wherein the pH is between 7.0 and 11.0, optionally with 0.1-15% by weight of buffer material and optionally with 2 to 5% by weight of hydrotropizing agent. contains material. (Priority: 06/09/1991) 7. The composition of claim 6, wherein the liquid composition comprises one or more additional anionic or nonionic surfactants, namely C 12 -C 27 alkyl ester sulfonates, C 8 -C 22 primary or secondary alkali sulfonates, C 10 -C 18 alkyl dimethylamine oxides, alkyl polysaccharides or mixtures thereof. (Priority: 06/09/1991) 8. A composition according to claim 7, characterized in that it comprises a surfactant mixture consisting of 40-80% by weight of alkoxyethoxyacetate and 20-60% by weight of N-polyhydroxyalkyl fatty acid amide and water as a liquid carrier. or a mixture of ethanol and water. (Priority: 06/09/1991) 9. A composition according to claim 8, wherein component (a) comprises a mixture of alkoxyethoxyacetate, wherein the cation M is sodium, potassium, ammonium, calcium or magnesium, and component (b). contains an N-polyhydroxyalkyl fatty acid amide wherein R ² is a straight chain alkyl or alkenyl group containing from 11 to 17 carbon atoms and the substituent Z is glucose or maltose. (Priority: 06/09/1991) 10. A detergent composition comprising alkoxyacetates comprising from 95 to 35% by weight of a conventional detergent component, characterized in that it contains from 5 to 65% by weight of a surfactant mixture consisting of: (a) one or more alkoxyethoxyacetates of formula (I) wherein R is an alkyl group having 8 to 22 carbon atoms, k is an integer from 0 to 10, and M is an alkali metal, alkaline earth metal, ammonium, low carbon atom; alkyl is selected from the group consisting of ammonium, mono-, di- and triethylammonium ions in an amount of from 5 to 95% by weight, and (b) one or more N-polyhydroxyalkyl of formula (III) fatty acid amide - wherein R ¹ is hydrogen, C 1 -C 4 alkyl, 2-hydroxyethyl, 2-hydroxypropyl, R ² is C 7 -C 19 alkyl or alkenyl, and Z is polyhydroxy hydrocarbon from a reducing sugar in a reductive amination reaction -5% to 95% by weight. (Priority: 06/09/1991) 11. A composition according to claim 10, wherein component (a) comprises an alkyl alkoxyacetate mixture having a distribution wherein the portion wherein k is 0 is less than 201%, the portion where k is It is greater than 7, less than 25%, and if R contains an average of 13 carbon atoms, then the average value of k is between 1 and 4, and if R contains more than 13 carbon atoms, the average value of k is between 2 and 6. (Priority: September 28, 1991) Liquid composition according to claim 10, characterized in that it comprises 90-50% by weight of a liquid carrier, preferably a mixture of water or water and a C 1 -C 4 alcohol, and 10-50% by weight of a surfactant mixture. (Priority: September 28, 1990) 13. A composition according to claim 12, wherein the surfactant mixture is comprised of 20-80% by weight of alkoxyethoxyacetate and 20-80% by weight of N-polyhydroxyalkyl fatty acid amide. (Priority: September 28, 1990) 14. The composition of claim 13, wherein component (a) comprises alkoxyethoxyacetate wherein the cation M is an alkali metal, alkaline earth metal, ammonium, EN 213 735 Β alkyl) ammonium, preferably mono-, di- or triethylammonium ions or mixtures thereof with calcium and magnesium ions. (Priority: September 28, 1990) 15. The composition of claim 14, wherein the pH is between 7.0 and 11.0, optionally with 0.1-15% by weight of buffer material and optionally with 2 to 5% by weight of additional ingredient. contains hydrotropizing agent. (Priority: September 28, 1990) 16. The composition of claim 15, wherein the liquid composition comprises one or more additional anionic or nonionic surfactants, C 12 -C 27 alkyl ester sulfonates, C 8 -C 22 primary or secondary alkali sulfonates, C 10 -C 18 alkyl dimethylamine oxides, alkyl polysaccharides or mixtures thereof. (Priority: September 28, 1991) 17. A16. Composition according to claim 1, characterized in that it comprises a surfactant mixture consisting of 40-80% by weight of alkoxyethoxyacetate and 20-60% by weight of N- (polyhydroxyalkyl) fatty acid amide, and the liquid carrier is water or ethanol-water. contains a mixture. (Priority: 9/28/90) 18. The composition of claim 17, wherein component (a) comprises a mixture of alkoxyethoxyacetate, wherein the cation M is sodium, potassium, ammonium, calcium or magnesium, component (b). and contains an N-polyhydroxyalkyl fatty acid amide wherein R ² is a straight-chain alkyl or alkenyl group containing from 11 to 17 carbon atoms and the substituent Z is glucose or maltose. (Priority: September 28, 1990) HU 213 735 Β Int Cl ⁶ : C 11 D 1/65 Θ © RO (CH ₂ CH ₂ O) _k CH ₂ COO M (I) 0 R ¹ R2-C- _z (III) R'O (CH ₂ CH ₂ O) _w H (II) 0 CHo, 1 I ³ R2-C - N-CH - (CHOH) _a - _CH2 OH (IV) CH ₂ = C-COOH (V) r 3 -CH-C-O ^{4 S} ° 3 ^M (VI) R ³ (OR ⁴ ) x N (R ⁵ ) 2 (VII) R ² 0 (C _n H _2n 0) _t (glycosyl) _χ (VII) E «7 R ⁶ -C -N (R ⁷ ) ₂