KR100225999B1 - Detergent compositions containing anionic surfactants, polyhydroxy fatty acid amides, and limited select foaming enhancers - Google Patents

Abstract

The present invention provides one or more anionic sulfate or sulfonate surfactants Wherein R ¹ is H, C ₁ -C ₄ hydrocarbyl, 2-hydroxyethyl, 2-hydroxy propyl or a mixture thereof, R ² is C ₅ -C ₃₁ hydrocarbyl, Z is 3 or more And one or more polyhydroxy fatty acid amides of polyhydroxyhydrocarbyl or alkoxylated derivatives thereof, wherein the hydroxyl group is a straight chain hydrocarbyl chain directly linked to the chain and a carefully selected foaming agent. . The invention also relates to a method for cleaning contaminated tableware by treating the tableware with the detergent composition described herein.

Description

[Name of invention]

Detergent composition containing anionic surfactant, polyhydroxy fatty acid amide and a limited selection of foaming enhancer

Detailed description of the invention

[Field of Invention]

The present invention relates to detergent compositions comprising at least one anionic sulfate or sulfonate surfactant, at least one polyhydroxy fatty acid amide and a limited selection of foaming enhancers. In particular, the present invention relates to detergent compositions having enhanced cleaning and foaming properties, no hand irritation, and particularly suitable for dish washing.

[Background of invention]

The use of anionic sulfated or sulfonated surfactants in detergent compositions is known. However, it is desirable to incorporate such surfactants into cleaning compositions that exhibit improved cleaning and foaming capabilities under variable temperature and humidity conditions.

In accordance with the present invention one or more anionic sulfated or sulfonated detergent surfactants, one or more polyhydroxy fatty acid amides and foaming enhancers (which are amine oxides, betaines, steines, certain nonionic materials and mixtures thereof) It was found that the detergent composition containing the present invention exhibits better foaming and detergent performance than that of detergent compositions having only surfactants that are sulfated or sulfonated with anions. In addition to these performance advantages, these compositions are compared to anionic sulfated or sulfonated surfactants. These compositions are easier to formulate because they are more irritating to the hands, have improved cleaning power, are not slippery to the touch, and the need to use process additives such as solvents and hydrotropes is reduced.

A further advantage associated with this composition is that its foaming ability is exceptionally uniform even with changes in temperature and humidity conditions.

The use of anionic sulfates or sulfonate surfactants in cleaning compositions is known in the art. United States Patent No. 4.535.317 (Gerritson et al. March 6, 1984) discloses alkyl pate. Liquid detergent compositions containing alkyl ether sulfates and alkylbenzene sulfonate surfactants are described. British Patent No. 809.060, assigned to Hedley and Corporation Limited and published on February 18, 1959, describes a detergent composition containing a sulfate or sulfonate surfactant and certain polyhydroxy fatty acid amides.

The polyhydroxy fatty acid amide components contained in the compositions of the present invention are also known in the art for various uses.

N-acyl. N-methyl glucamide is described, for example, in J. Chem. W. Goofby. M. a. Markus (M.A.Marcus). E. Chin. And The Thermotropic Liquid-Crystalline Properties of Some Straight Chain Carbohydrate Amphiphiles by P.L.Finn. Liquid Crystals, 1988. Volume 3. 11, pp 1569-1581 and A. Muller-Fahrnow. V. Zabel. M. M. Steifa. And al. Molecular and Crystal structure of a Nonionic Dedtergent by R. Hilgenfeld: Nonaroyl-N-methylglucamide. J. Chem. Soc. Chem. commun..1986. pp 1573-1574. The use of N-alkyl polyhydroxyamide surfactants has recently been biochemical. For example, it is remarkably advantageous for dissociation of biological membranes (N-Gluco-N-methyl-alkanamide Compounds. A New Class of Non-lonic Detergents For Membrane Biochemistry, Biochem. J. (1982). Vol. 207.pp. 363 to 366. JEK Hldreth].

The use of N-alkyl glucamides in detergent compositions has also been discussed. This egg on December 20, 1960. US Patent No. 2.965.576 to ER wilson and British Patent Specification No. 809.060, already discussed, may contain N-methyl glucamide and may be added as a low temperature foaming enhancer. And detergent compositions containing certain amide surfactants. Such compounds include N-acyl radicals of higher straight fatty acids having 10 to 14 carbon atoms. Such compositions are also alkyl metal phosphates. Alkyl metal silicates. sulfate. And auxiliary substances such as carbonates. Also generally, fluorescent dyes impart desirable properties to the composition. bleach. It is pointed out that additional ingredients such as perfumes and the like may also be contained in the composition.

March 8, 1955 A Mei. U.S. Patent No. 2.702.798, issued to A. M. Schwartz, relates to an aqueous detergent composition containing a condensation product of an N-alkyl glucamine with an aliphatic ester of a fatty acid. Such reaction products are described that can be used in aqueous detergent compositions without further purification. September 13, 1955 A Mei. M. It is also known to prepare sulfuric acid esters of acylated glucamines as described in US Pat. No. 2.717.894 to Schwarz.

Jay was released on December 22, 1983. Hildresser's PCT International Application No. WO83 / 04412 is a cosmetic, pharmaceutical. shampoo. Lotion. As surfactants in eye ointments, as emulsifiers and dispersants for pharmaceuticals, and membranes in biochemistry. Amphoteric compounds containing polyhydroxyl aliphatic groups that have been described as useful for a variety of purposes, including use for lysing whole cells, or other tissue samples, and dissolution for preparing liposomes. The technique includes compounds of the general formulas R'CON (R) CH ₂ R and RCON (R) R 'wherein R is hydrogen or an organic group. R' is an aliphatic hydrocarbon group having at least 3 carbon atoms, and R is an aldose residue Is included).

Published on October 12, 1988. European Patent No. 0.285.768 to H. Kelkenberg et al. Relates to the use of N-polyhydroxy alkyl fatty acid amides as thickening agents in aqueous detergent systems. Amide of the general formula R ₁ C (O) N (X) R ₂ , wherein R ₁ is C ₁ -C ₁₇ (preferably C ₇ -C ₁₇ ) alkyl and R ₂ is hydrogen. C ₁ -C ₁₈ (preferably C ₁ -C ₁₆ ) alkyl. Or alkylene oxide, X is polyhydroxy alkyl having 4 to 7 carbon atoms.] For example, N-methyl, coconut fatty acid glucamide. While the thickening properties of amides have been pointed out as having special use in necessarily liquid surfactant systems containing paraffin sulfonates, aqueous surfactant systems are alkylaryl sulfonates. Olefin sulfonates. Fatty acid alcohol polyglycol ethers and other anionic surfactants such as sulfosuccinic acid half ester salts and fatty acid alcohol ether sulfonates. Alkylphenol polyglycol ethers. Fatty acid polyglycol esters. Nonionic surfactants such as polypropylene oxide-polyethylene oxide mixed polymer and the like. Paraffin sulfonate / N-methyl coconut fatty acid glucamide / nonionic surfactant shampoo detergent is illustrated. In addition to the thickening characteristics. N-polyhydroxy alkyl fatty acid amides are described as having good skin resistance.

U.S. Patent No. 2.982.737, issued May 2, 1961 to Boettner et al., Is a urea, natmul lauryl sulfate anionic surfactant. And N-methyl, N-sorbitol lauamide and N-methyl. A cleaning bar containing an N-alkylglukamide nonionic surfactant selected from N-sorbitol myrmidamide.

Other glucamide surfactants are. N-acylpolyhydroxy of, for example, one or more surfactants and polymeric phosphates, enhancer salts selected from metal ion sequestrants, and the general formula R ₁ C (O) N (R ₂ ) CH ₂ (CHOH) nCH ₂ OH To a cleaning composition comprising an improved cleaning alkali by addition of an alkylamine, wherein R ₁ is C ₁ -C ₃ alkyl. R ₂ is C ₁₀ -C ₂₂ alkyl and n is 3 or 4. H was released on December 20, 1973. DT by W. Eckert et al. 2.226. 872. N-acylpolyhydroxyalkylamine is added as a dirt washing agent.

H on April 4, 1972. W. U.S. Patent No. 3.654.166, issued to Actu et al., Is anionic, zwitterionic. And at least one surfactant and a fiber softener selected from nonionic surfactants, N-acyl, N-acyl polyhydroxyalkyl compounds of the general formula R ₁ N (Z) C (O) R ₂ , wherein R ₁ is C _10- C ₂₂ alkyl, R ₂ is C ₇ -C ₂₁ alkyl, the total carbon number of R ₁ and R ₂ is 23-39, Z is the formula-CH ₂ (CHOH) mCH ₂ OH wherein m is Polyhydroxyalkyl, which may be 3 or 4).

On May 3, 1977. U.S. Patent No. 4.021.539 to H. Moller et al. Discloses a compound of the general formula R ₁ N (R) CH (CHOH) mR ₂ , wherein R ₁ is H. lower alkyl. Hydroxy-lower alkyl. Or skin containing N-polyhydroxyalkylamine, including aminoalkyl as well as heterocyclic aminoalkyl and R is the same as R ₂ but neither can be H and R ₂ is CH ₂ OH or COOH The present invention relates to a treatment cosmetic composition.

French Patent No. 1.360.018, accepted on 26 April 1963 and assigned to Commercial Solvents Corporation, discloses an amide of the general formula RC (O) N (R ₁ ) G, wherein R Carboxylic acid functionality, R ₁ is hydrogen or a lower alkyl group, G is a glycitol radical having at least 5 carbon atoms), and a formaldehyde solution stabilized against polymerization.

Federal Republic No. 1.261.861, issued to A. Heins on February 29, 1968, discloses a glucamine derivative of the general formula N (R ₁ ) (R ₂ ), useful as a humectant and dispersant. R is a sugar moiety of glucamine, R ₁ is a C ₁₀ -C ₁₀ alkyl radical and R ₂ is a C ₁ -C ₅ acyl radical.

British Patent No. 745.036 to Atlas Powder Copany, published February 15, 1956, is a chemical intermediate. Emulsifier. Wetting and dispersing agents. Detergent. Heterocyclic amides and carboxylic acid esters thereof which are described as useful as fabric softeners and the like. The compound is represented by the general formula N (R) (R ₁ ) (RS ₂ ) C (O) R ₂ , wherein R is a residue of anhydrous hexane pentol or a fumaric acid ester thereof, and R ₁ is monovalent Is a hydrocarbon radical, and -C (O) R ₂ is an acyl radical of a carboxylic acid having 2 to 25 carbon atoms.

D. on April 4, 1967. United States Patent No. 3.312.627 to DT Hooker contains substantially free of anionic detergents and alkaline enhancer materials, lithium soaps of certain fatty acids and certain propylene oxide-ethylene diazine-ethylene oxide condensates. Propylene oxide-propylene glycol-ethylene oxide condensate. And a nonionic surfactant selected from polymerized ethylene glycol, and also a polyhydroxyamide of the general formula RC (O) NR ¹ (R ² ), wherein RC (O) has from about 10 to about 14 carbon atoms R ¹ and R ² are each H or a C ₁ -C ₆ alkyl group, wherein the total carbon number of the alkyl group is from 2 to about 7 and the total number of substituent hydroxyl groups is from 2 to about 6. Solid toilet bars are also described which may also contain nonionic foaming components. Substantially similar technology was described on April 4, 1967 by D. US Pat. No. 3.312.626 to Tea Hooker.

Amine oxides. Betaine. Sultines and methods of using the nonionic materials of the present invention are also known in the art. US Pat. No. 4.55.360, issued November 26, 1985 to Bissett et al., Discloses certain sulfated and sulfonated surfactants. Detergent compositions comprising betaine surfactants and amineoxides are described. These compositions may also optionally contain certain nonionic cleaning surfactants. US Pat. No. 3.351.557, issued November 7, 1967 to Almstead et al., Is a nonionic detergent. Enhancer latex. Enhanced liquid detergent compositions are described that contain a detergent selected from the group of detergents including stabilizers, moisture, and steines.

However, anionic sulfated or sulfonated surfactants. Exceptional cleaning and foaming power associated with detergent compositions of the invention containing polyhydric fatty acid amides and a limited selection of foaming enhancers. Reduced slippery touch. Ease of washing. Detergent compositions that are hypoallergenic for hands are not taught in the art.

Also substantially uniform under variable temperature and humidity conditions. Compositions that provide improved foaming forces are also not taught in the art.

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

Another object of the present invention is to provide a method for cleaning contaminated tableware by treating the tableware with the characteristic detergent composition described herein.

These objects are realized by the present invention.

[Summary of invention]

(A) about 5% to about 95% by weight of at least one anionic sulfate or sulfonate surfactant:

(b) general formula Wherein R ¹ is H. C ₁ -C ₄ hydrocarbyl. 2-hydroxy ethyl, 2-hydroxy propyl or mixtures thereof. R ² is C ₅ -C ₃₁ hydrocarbyl, Z is at least 3 high About 5% to about 95% by weight of one or more polyhydroxy fatty acid amides of the desyl group is a polyhydroxyhydrocarbyl or alkoxylated derivative thereof having a straight chain hydrocarbyl chain directly linked to the chain; and

(C) amine oxides: betaine, steine, and alkyl phenols and polyethylene. Condensates of polypropylene and polybutylene oxide. Alkyl ethoxylate condensation products of aliphatic alcohols and ethylene oxide. A condensation product of a hydrophobic base and ethylene oxide formed by a condensation reaction of propylene oxide and propylene glycol, a product of a condensation product of propylene oxide with ethylene oxide by a reaction of propylene oxide and ethylenediamine. Nonionic compounds selected from alkylpolysaccharides and fatty acid amides: and from about 5% to about 65% of a surfactant mixture comprising from about 1% to about 20% by weight foaming enhancer selected from the group consisting of: and mixtures thereof It relates to a detergent composition comprising%.

The present invention also relates to a method of cleaning contaminated tableware, including treatment with the detergent composition claimed herein.

Detergent compositions of the present invention comprise from about 5% to about 65% by weight of a surfactant mixture comprising at least one anionic sulfated or sulfonated surfactant and at least one polyhydroxy fatty acid amide and a limited selected foaming enhancer. , Preferably from about 10% to about 50%, more preferably from about 15% to about 40% by weight. These and other components typically found in liquid detergent compositions are described below. The detergent composition of the present invention is preferably in the form of a liquid or gel, more preferably a hard liquid detergent composition, most preferably a hard liquid dishwashing detergent composition.

[Anionic Surfactant]

The surfactant mixture of the present invention comprises from about 5% to about 95%, preferably from about 20% to about 80%, more preferably from about 40% by weight of one or more anionic sulfates or sulfonate surfactants. About 60% by weight. The anionic sulfate or sulfonate surfactant may be any organic sulfate or sulfonate surfactant, but is preferably ethylene oxide per mole of C ₁₁ -C ₁₅ alkyl benzene sulfonate, C ₁₀ -C ₁₆ alkyl sulfate and alkyl ethoxy sulfate Ethoxy homologs thereof containing up to 12 moles, C ₁₃ -C ₁₈ paraffin sulfonate, C ₁₀ -C ₁₆ olefin sulfonate, C ₁₀ -C ₂₀ alkyl glyceryl ether sulfonate, C ₉ -C ₁₇ acyl-N -(C ₁ -C ₄ alkyl) or -N- (C ₂ -C ₄ hydroxyacyl) glucamine sulfate and mixtures thereof. More preferably, the anionic surfactant is selected from straight chain alkyl benzene sulfonates, alkyl ethoxy sulfates, alkyl glyceryl ether sulfonates and paraffin sulfonates.

Alkyl benzene sulfonates useful in the compositions of the present invention are materials wherein the alkyl group is substantially linear and contains 10 to 16, preferably 10 to 13, carbon atoms, and the most preferred average carbon chain length is 112. Although the phenyl isomer distribution, ie the point of attachment of the alkyl chain to the benzene nucleus, is not critical, alkyl benzenes having a high 2-phenyl isomer content are preferred.

Suitable alkyl sulfates are primary alkyl sulfates in which the alkyl group is preferably straight-chain and having from 10 to 16 carbon atoms, more preferably on average 12 to 14 carbon atoms. C ₁₀ -C ₁₆ alcohols are natural fats. Or Ziegler olefin formation. Or is induced by OSO synthesis to form a suitable source for alkyl groups. Examples of materials derived by synthesis are Dobanol 23 (RTM) sold by Shell Chemicals. UK. Ethyl 24 (RTM), plated by Ethyl Corporation. Blends of C ₁₃ -C ₁₅ alcohols (C ₁₃ 67%, C ₁₅ 33% proportions) and Synperonic (RTM) and Liquikimika sold by ICI Limited sold under the trade name Lutensol by Basmb Gmbh Lial 125 sold by Italiana (Liquichimica Italiana). Examples of natural substances that can be derived from alcohols are coconut oil and palm kernel oil and corresponding fatty acids.

Alkyl ethoxy sulfate surfactants include primary alkyl ethoxy sulfates derived from condensation products of C ₁₀ -C ₁₆ alcohols having an average of up to six ethylene oxide groups. The C ₁₀ -C ₁₆ alcohol itself can be obtained from any of the raw materials for the alkyl sulfate component described above. Preference is given to C ₁₂ -C ₁₄ alkyl ethoxy sulfates.

A conventional base catalyzed ethoxylation process with an average degree of ethoxylation of 12 allows for the distribution of each ethoxylate with 1 to 15 ethoxy groups per mole of alcohol so that the desired average degree of ethoxylation can be obtained in various ways. Have The blend may be composed of materials having different degrees of ethoxylation and / or different ethoxylate distributions resulting from the particular process of ethoxylation used and the subsequent process steps such as distillation. For example. The same foaming and stain removal performance as given by the blend of alkyl sulphate and alkyl triethoxy sulphate can be obtained by reducing the concentration of alkyl sulphate and using ethyl ethoxy sulphate having approximately an average of two ethoxy groups per mole of alcohol. Turned out to be. In a preferred composition according to the invention, alkyl ethoxy sulfates are used which have an average degree of ethoxylation of 0.4 to 5, more preferably 0.4 to 3.0.

Secondary alkane sulfonates useful in the present invention have 13 to 18 carbon atoms per mole, more preferably 13 to 16 carbon atoms. These sulfonates are preferably by cleaving paraffins corresponding to the chain lengths described above. It is prepared by the action of sulfur dioxide and oxygen according to the well-known sulfoxylation method. The product of this reaction is secondary sulfonic acid which is neutralized with a suitable base to give a water soluble secondary alkyl sulfonate. Similar secondary alkyl sulfonates are another method. For example, it can be obtained by a sulfochlorination reaction in which chlorine and sulfur dioxide are reacted with paraffins in the presence of actinic radiation to hydrolyze and neutralize the resulting sulfonyl chloride to form a secondary alkyl sulfonate. Whatever method you use. It is usually desirable to produce the sulfonates as monosulfonates which are free or present in only a limited proportion of unreacted starting hydrocarbons and little or no inorganic salt by-products. Similarly. Disulfonates or higher sulfonated materials may be present somewhat, but will be minimized. The monosulfonate may be sulfonated at the end or the sulfonate group may be linked to a straight 2-carbon or other carbon phase. Similarly, disulfonates, which are generally produced and accompanying, usually in the presence of excess sulfonating agent, may have sulfonate groups distributed over different carbon atoms of paraffin bases, and mixtures of monosulfonates and disulfonates May also be present.

Mixtures of alkanes of monoalkane sulfonates having 14 to 15 carbon atoms are particularly preferred when the sulfonate to C ₁₄ -C ₁₅ paraffins are present in a weight ratio of 1: 3 to 3: 1.

Olefin sulfonates useful in the present invention are mixtures of alken-1-sulfonates, alkenes hydroxysulfonates alkenes disulfonates and hydroxydisulfonates, p. F. US Patent No. 3.332.880, issued July 25, 1967 to P. F. Pflauner and A. Kessler.

Suitable alkyl glyceryl ether sulfonates are those derived from ethers of coconut oil and tallow.

Other sulfate surfactants are C ₉ -C ₁₇ acyl-N- (C ₁ -C ₄ alkyl) or N- (C ₁ -C ₂ hydroxyalkyl) glucamine sulfate, wherein the C ₉ -C ₁₇ acyl group is preferred. Preferably derived from coconut oil or palm kernel oil). These materials can be prepared by the method described in US Pat. No. 2.725.894, issued to Schwart on September 13, 1955.

The counter ion for the anionic surfactant component is preferably sodium, potassium, magnesium, ammonium or alkanol-ammonium and mixtures thereof, with magnesium being most preferred.

In a preferred composition in which C ₁₀ -C ₁₆ alkyl ethoxy sulfates are mixed as anionic surfactants, the molar equivalents of the magnesium ions of the crude product are 0.35-0.65X, where X is the C ₁₀ -C ₁₆ alkyl sulfate Molar number). The most preferred magnesium ion content is adjusted to be half the stoichiometric equivalent, ie, the molar equivalent of alkyl sulfate present. In such conditions, magnesium ions are present at a concentration of about 0.15% to about 3.0% by weight, preferably 0.25% to 1.5% by weight of the composition.

[Polyhydroxy Fatty Acid Amide Component]

The surfactant mixture of the present invention comprises from about 5% to about 95% by weight of at least one polyhydroxy fatty acid amide of formula (I). Preferably from about 20% to about 80% by weight. More preferably about 40% to about 60% by weight.

In the above formula

R ¹ is H, C ₁ -C ₄ hydrocarbyl, 2-hydroxyethyl. 2-hydroxypropyl or mixtures thereof. Preferably .C ₁ alkyl (ie methyl):

R 1 is H. C ₁ -C ₄ hydrocarbyl. 2-hydroxyethyl. 2-hydroxypropyl. Or alkenyl. More preferably straight chain C ₇ 0C1 ₉ hydrocarbyl. C ₉ -C ₁₇ -alkyl or alkenyl. Most preferably straight chain C ₁₁ -C17 alkyl or alkenyl. Or a mixture thereof and Z is a polyhydroxyhydrocarbyl or alkoxylated (preferably ethoxylated) derivative thereof having at least three hydroxyls having a straight chain hydrocarbyl directly linked to the chain.

Z is preferably derived from reducing sugars in a reductive amination reaction: more preferably Z. is glycidyl. Suitable reducing sugars are glucose. Fructose. Maltose, lactose, galactose, mannose and xylose. High dextrose corn syrup as well as the respective sugars described above as raw materials. High fructose corn syrup and maltose corn syrup are available. Such corn syrup may provide a mixture of sugar components for Z. Z is preferably a general formula

-CH _2- (CHOH) _n- CH ₂ OH. CH (CH ₂ OH)-(CHOH) _n-1 -CH ₂ OH-CH _2- (CHOH) ₂ (CHOR ') (CHOH) -CH ₂ OH, wherein n is an integer from 3 to 5 and R is Is H or a cyclic or aliphatic monosaccharide). And alkoxylated inducers thereof. glycidyl with n equals 4. In particular _{-CH 2 - (CHOH) 4 -CH} 2 OH are most preferred.

In formula (I). R ¹ is for example. N-methyl. N-ethyl. N-propyl. N-isopropyl. N-butyl. N-2-hydroxyethyl, or N-2-hydroxy propyl.

R ² -CO-N is. For example cocoamide. Stearamide. Oleamide. Laurylamide. Myristicamide. Capricamide. Palmitamide, uziamide, and the like.

Z is 1-deoxyglucityl. 2-deoxyfructitil. 1-deoxymaltyl. 1-deoxylactyl. 1-deoxygalactityl. 1-deoxymannityl 1-deoxymalto trirotidyl and the like.

Most preferred polyhydroxy fatty acid amides are compounds of the general formula

In the above formula

R ² is a C ₁₁ -C ₁₇ straight alkyl or alkenyl group.

Methods of preparing polyhydroxy fatty acid amides are known in the art. In general, they react alkyl amines with reducing sugars in a reductive amination reaction to form the corresponding N-alkyl polyhydroxyamines, followed by N-alkyl polyhydroxyamines in fatty acid aliphatic esters or triglycerides in the condensation / amidation step. Reacted with N-alkyl. It can be prepared by forming an N-polyhydroxy fatty acid amide product. Methods for preparing compositions containing polyhydroxy fatty acid amides are described, for example, in Thomas Hedley and Co., published February 18, 1959, each of which is incorporated herein by reference. British Patent Specification No. 809.060, Limited. This egg on December 20, 1960. US Patent No. 2.965.576 to E. R. Wilson and Anthony M. on March 8, 1955. US Patent No. 2.703.798, granted to Anthony M. Schwartz. US Patent No. 1.985.424, issued to Piggott on December 25, 1934.

The glycidyl component is derived from glucose and the N-alkyl or N-hydroxy alkyl functional group is N-methyl. N-ethyl. N-propyl. N-butyl. N-alkyl or N-hydroxyalkyl, which is N-hydroxyethyl or N-hydroxypropyl. In one of the processes for the preparation of N-deoxyglycityl fatty acid amide, trilithium phosphate. Trisodium phosphate. Tripotassium phosphate. Tetrasodium pyrophosphate, pentapotassium tripolyphosphate. Lithium hydroxide. Sodium hydroxide. Potassium hydroxide, calcium hydroxide. Lithium carbonate, sodium carbonate. Potassium carbonate, disodium tartrate. Dipotassium tartrate. Sodium potassium tartrate. Trisodium citrate. Tripotassium citrate. Sodium base silicate. Potassium Base Silicate. Sodium base aluminosilicate. And fatty acid methyl esters of N-alkyl- or N-hydroxyalkyl-glucamine in the presence of a catalyst selected from the group consisting of potassium based aluminosilicates and mixtures thereof. The product is prepared by reacting with a fatty acid ester selected from fatty acid ethyl esters and fatty acid triglycerides. The amount of catalyst is preferably from about 0.5 mol% to about 50 mol%, more preferably from about 2.0 mol% to about 10 mol%, based on the molar equivalent of N-alkyl or N-hydroxyalkyl-glucamine. The reaction is preferably carried out at about 138 ° C. to about 170 ° C., typically for about 20 to about 90 minutes. When trglycerides are used in the reaction mixture as the fatty acid ester source, the reaction is also saturated fatty alcohol polyethoxylate. Alkylpolyglycosides. It is preferably carried out using from about 1 to about 10 weight percent of a phase transfer agent calculated in weight percent relative to the total reaction mixture selected from the linear glycamide surfactants and mixtures thereof.

The method is preferably carried out as follows:

(a) preheating the fatty acid ester to about 138 ° C to about 170 ° C:

(b) N-alkyl or N-hydroxyalkyl glucamine is added to the heated fatty acid ester and mixed to the extent necessary to form a two-phase liquid / liquid mixture:

(c) mixing the catalyst with the reaction mixture:

(d) Stir for a specific reaction time.

Also preferably when the fatty acid ester is triglyceride, from about 2% to about 20% by weight of the pre-reduced straight chain N-alkyl / N-hydroxyalkyl relative to the weight of the reactants. N-linear glucosyl fatty acid amide product is added to the reaction mixture as a phase transfer agent. This promotes the reaction and increases the reaction rate. Detailed experimental methods are provided in the following experiments.

As used herein, the polyhydroxy fatty acid amide material is also wholly or mostly natural. play. It can be manufactured from chemical raw materials other than petroleum. Provide degradable benefits to detergent manufacturers. They are also less toxic to aquatic organisms.

It should be recognized that the methods used to prepare them using the polyhydroxy fatty acid amides of formula (I) also generally produce large amounts of nonvolatile byproducts such as ester amides and cyclic polyhydroxy fatty acid amides. The concentration of these byproducts depends on the particular reactants and process conditions. Preferably. The polydihydroxy fatty acid amide incorporated in the detergent composition of the present invention is less than about 10% of the polyhydroxy fatty acid amide containing composition added to the detergent. It is preferably provided in a form containing less than about 4% cyclic polyhydroxy fatty acid amides. The preferred methods described above are advantageous in that they can produce by-products including these cyclic amide by-products at lower concentrations.

[Foam Formation Enhancer]

The surfactant mixtures of the present invention further comprise amine oxides. Betaine. From about 1% to about 20%, preferably from about 2% (more preferably, 5%) to about 20% by weight foaming neutralizer selected from the group consisting of steine and certain nonionic compounds do.

Amine oxides useful in the present invention include compounds having the general formula:

In the above formula

R ³ is alkyl having 8 to 26 carbon atoms, preferably 8 to 16, hydroxyalkyl. And acylamidopropyl and alkyl phenyl group 4 or mixtures thereof: R ⁴ is an alkylene or hydroxy alkylene group having 2 to 3 carbon atoms, preferably 2, or a mixture thereof: X is 0 to 3, preferably Preferably 0: each R ⁵ is an alkyl or hydroxyalkyl group having preferably 1 to 3 carbon atoms or a polyethylene oxide group having 1 to 3. carbon atoms or preferably an ethylene oxide group.

The R ⁵ groups may be bonded to one another via, for example, oxygen or nitrogen atoms to form a ring structure.

These amine oxide surfactants include in particular C ₁₀ -C ₁₈ alkyl dimethylamine oxides and C ₈ -C ₁₂ alkoxy ethyl dihydroxy ethylamine oxides. Examples of such materials are dimethyl octylamine oxide. Diethyldecylamine oxide. Bis- (2-hydroxyethyl) dodecylamine oxide. Dimethyldodecylamine oxide. Dipropyltedradecylamine oxide. Ethylethylexaheyl amine oxide, dodecylamidopropyl dimethylamine oxide and dimethyl-2-hydroxyoctadecylamine oxide. Preferred are C ₁₀ -C ₁₈ alkyl dimethylamine oxide and C ₁₀ -C ₁₈ acylamido alkyl dimethylamine oxide.

Betaines useful in the present invention are compounds of the general formula R (R ¹ ) ₂ N ⁺ -R ² -COO ^_ where R is a C ₆ -C ₈ hydrocarbyl group, preferably a C ₁₀ -C ₁₆ alkyl group, Each R ¹ is typically C ₁ -C ₃ alkyl, preferably methyl, R ² is a C ₁ -C ₅ hydrocarbyl group, preferably a C ₁ -C ₃ alkylene group, more preferably C ₁ -C ₂ alkylene group). Examples of suitable betaines include coconut acylamidopropyldimethyl betaine: hexadecyldimethyl betaine: C ₁₂ -C ₁₄ acylamidopropylbetaine: C ₈ -C ₁₄ acylamidohexyldiethyl betaine: 4 [C _14- C ₁₆ acylmethylamidodiethyl ammonio] -1-carboxybutane: C ₁₆ -C ₁₈ acylamidodimethylbetaine: C _12-16 acylamido pentanediethyl betaine: [C ₁₂ -C ₁₆ acylmethyl Amidomethyl] betaine. Preferred are C ₁₂ -C ₁₈ dimethyl-ammoniohexanoate and C ₁₀ -C ₁₈ acyl amidopropane (or ethane) dimethyl (or diethyl) betaine.

Sultains useful in the present invention are compounds of the general formula R (R ¹ ) ₂ N ⁺ R ² SO ₂ , wherein R is a C ₆ -C ₁₈ hydrocarbyl group, preferably a C ₁₀ -C ₁₆ alkyl group. Preferably a C ₁₂ -C ₁₃ alkyl group, each R is typically C ₁ -C ₃ alkyl, preferably methyl, and R ² is a C ₁ -C ₆ hydrocarbyl group, preferably C ₁ -C ₃ Alkylene, preferably a hydroxyalkylene group). Examples of suitable sulfines are C ₁₂ -C ₁₄ dimethyl ammonio-2 hydroxypropyl sulfonate. C ₁₂ -C ₁₄ amidopropyl ammonio-2 hydroxypropyl sultine. C ₁₂ -C ₁₄ dihydroxy ethyl ammonio propane sulfonate and C ₁₆ -C ₁₈ dimethylammonio hexane sulfonate. Preferred is C _12-14 amido propyl ammonio-2 hydroxyl propyl sultaine.

Suitable nonionic cleaning surfactants are generally cited herein by reference. US Patent No. 3.929.678, column 13 line 14 to column 16. line 6, issued December 30, 1975. Exemplary non-limiting groups of useful nonionic surfactants are illustrated below.

1. Polyethylene of alkyl phenols. Polypropylene. And polybutylene oxide condensates. In general, polyethylene oxide condensates are preferred. Such compounds include condensation products of alkyl phenols with alkylene oxides having alkyl groups containing about 6 to about 12 carbon atoms in a straight or branched chain arrangement. In a preferred embodiment. Ethylene oxide is present in an amount equivalent to about 5 to about 25 moles per mole of alkyl phenol. That this type of nonionic surfactants on the market are GAF Corporation is a commercially available [gepa] ^TM CO-630: and Rohm and Haas Co. Needle (Rohm Hass Company) the Triton ^TM X-45, which are all commercially available. X-114. X-100. And X-102.

2. About 1 to about 25 moles of alkyl ethoxylate condensation product of aliphatic alcohol and ethylene oxide. The alkyl chain of aliphatic alcohol is straight or branched chain. May be first or second class. It generally contains 8 to 22 carbon atoms. Particular preference is given to condensation products of alcohols having alkyl groups containing 10 to 20 carbon atoms with about 2 to about 10 moles of ethylene oxide per mole of alcohol. Most preferred is a product of a condensation of an alcohol having an alkyl group having 10 to 14 carbon atoms with about 6 to about 10 moles of ethylene oxide per mole of alcohol. Examples of commercially available nonionic surfactants of this kind are both Tergitol ^™ 15-S-8 (C ₁₁ -C ₁₅ straight-chain alcohols and 9 moles of ethylene oxide and commercially available from Union Carbide Corporation). Condensation reaction product). Tergitol ^™ 24-L-6 NMW (condensation product of 6 moles of ethylene oxide with narrow molecular weight distribution of C ₁₂ -C ₁₄ primary alcohol): Neodol ^TM 45-9 (available from Shell Chemical Company) Condensation product of 9 moles of ethylene oxide with C ₁₄ -C ₁₅ linear alcohol). Neodol ^™ 23-6.5 (condensation product of C ₁₂ -C ₁₃ straight chain alcohol with ethylene oxide alcohol). Condensation reaction product of 6.5 moles of ethylene oxide) Neodol 45-7 (condensation reaction product of 7 moles of C ₁₄ -C ₁₅ linear alcohol with ethylene oxide). Neodol 45-4 (condensation product of 4 moles of C ₁₄ -C ₁₅ linear alcohol with ethylene oxide) and Kyro ^TM EOB (C ₁₃ -C ₁₅ ) alcohol sold by The Procter Gamble Company 9 moles of ethylene oxide condensation product).

3. Condensation product of ethylene oxide with hydrophobic base formed by the condensation reaction of propylene oxide with propylene glycol. The molecular weight of the hydrophobic portion of such compounds is preferably about 1500 to about 1800 and exhibits water insolubility. The addition of polyoxy ethylene moieties to these hydrophobic moieties generally tends to increase the water solubility of the molecules, and the liquid properties of the product are maintained up to the point where the polyoxyethylene content is about 50% of the total weight of the condensation reaction product, This corresponds to condensation with up to about 40 moles of ethylene oxide. Examples of compounds of this kind include certain Pluronic ^™ surfactants commercially available from BASF.

4. Condensation product of ethylene oxide with a product obtained from the reaction of propylene oxide with ethylenediamine. The hydrophobic moiety of this product consists of the reaction product of ethylenediamine and excess propylene oxide and has a molecular weight of about 2500 to about 3000 in one. These hydrophobic moieties are condensed with ethylene oxide to about 40 to about 80 weight percent polyoxyethylene and have a molecular weight of about 5,000 to about 11.000. Examples of nonionic surfactants of this kind include certain Tetronic ^™ compounds sold by BASF.

5. Hydrophobic groups and polysaccharides having from about 6 to about 30 carbon atoms, preferably from about 10 to about 16 carbon atoms. For example polyglycosides. From about 1.3 to about 10. Preferably from about 1.3 to about 3. Most preferably having hydrophilic groups containing from about 1.3 to about 2.7 saccharide units. Alkylpolysaccharides described in US Pat. No. 4.565.647 to Llenado, issued January 21, 1986. Any reducing saccharide of 5 or 6 dehydration number can be used. For example. Glucose. Galgaltose glucosyl residues may be substituted with galgaltosyl residues (optionally a hydrophobic group is attached at a position such as 2-.3-.4-, etc. to provide glucose or galactose as opposed to glucoside or galgaltoside). The linkage between the saccharides is, for example, 1-position of additional saccharide units and 2-. 3-. It may be present between the 4- and / or 6-positions.

Randomly. Less preferably. There may be a polyalkylene oxide chain connecting the hydrophobic moiety to the polysaccharide moiety. Preferred alkylene oxides are ethylene oxides. Typical hydrophobic groups are saturated or unsaturated having 8 to 18 carbon atoms, preferably 10 to 16 carbon atoms. Branched or straight chain alkyl groups. Preferably. Alkyl groups are straight chain saturated alkyl groups. Alkyl groups contain up to 3 hydroxy groups and / or up to 10 polyalkylene oxides. It may preferably contain less than 5 alkylene oxide residues. Suitable alkyl polysaccharides are octyl. Nonyldecyl. Undecyldodecyl. Tridecyl. Tetradecyl. Pentadecyl. Hexadecyl. Heptadecyl. And octadecyl. D-. Tri-tetra. Penda-, and hexaglucoside. Galactoside. Lactoside. Glucose, fructoside. Fructose and / or galactose. Suitable mixtures are coconut alkyl. D-. Tri-tetra- and pentaglucoside and tallow alkyl tetra- penta-. And hexaglucoside.

Preferred alkylpolyglycosides have the general formula

Wherein R ² is 10 to 18 carbon atoms in the alkyl group, preferably 12 to 14 alkyl. Alkylphenyl. Hydroxyalkyl. Hydroxyalkylphenyl. And mixtures thereof: n is 2 or 3. preferably 2 and t is 0 to about 10. Preferably 0 and x is about 1.3 to about 10. preferably about 1.3 to about 3. Most preferably from about 1.3 to about 2.7.

Glycosyl is preferably derived from glucose. To prepare such compounds, alcohols or alkylpolyethoxy alcohols are first formed and then reacted with glucose or glucose sources to form glucosides (attached at the 1-position). Additional glycosyl units are then substituted in their 1-position with said glycosyl units 2-. 3-. 4- and / or 6-position. Preferably it can be attached mainly between the 2-positions.

6. Fatty acid amide surfactants of the general formula:

In the above formula

R ⁶ is an alkyl group having 7 to 21 carbon atoms, preferably 9 to 17, and R ⁷ is each hydrogen. C ₁ -C ₄ alkyl. C ₁ -C ₄ hydroxyalkyl. And-(C ₂ H ₄ O) H, where X is in the range of 1-3.

Preferred amides are C ₈ -C ₂₀ ammonia amides. Monoethanolamide. Diethanolamide and isopropanolamide.

Preferred foaming enhancers are C ₁₀ -C ₁₈ alkyl dimethylamine oxides, C ₁₀ -C ₁₈ acyl amide alkyl dimethyl amine oxadides. Betaine. Stein. Condensation products of aliphatic alcohols and ethylene oxide. Alkylpolysaccharides and mixtures thereof.

[Liquid carrier]

In a preferred embodiment, the detergent composition of the present invention is a liquid detergent composition.

These preferred liquid detergent compositions are, for example, water. Preferably from about 95% to about 35% by weight of a liquid carrier, such as a mixture of water and C ₁ -C ₄ alcohols (eg, ethanol. Propanol isopropanol. Butanol and mixtures thereof, ethanol being the preferred alcohol). Preferably about 90% by weight. Most preferably from about 85% to about 60% by weight.

[Composition ph]

The liquid detergent composition herein is preferably formulated such that the pH of the wash water is from about 6 to about 9. More preferably from about 7 to about 8 during use in the aqueous cleaning process. The liquid body of the invention is about 5.0 to about 10.5. Preferably from about 6.0 to about 9.0 more preferably from about 6.5 to about 7.5. A method of adjusting the pH to the desired use concentration is a buffer. Carly. It is known in the art, including the use of acids and the like.

Thickening Agent

The detergent composition of the present invention may also be in the form of a gel. Such compositions are formulated in the same manner as liquid detergent compositions, except that they contain additional thickening agents.

Any material or materials that can be combined with an aqueous liquid to provide a shear-thinning composition with sufficient yield values is used in the compositions of the present invention. Substances such as colloidal silica. Particular polymers such as polystyrene and oxidized polystyrene. Water soluble polymers such as blends of certain surfactants and polyacrylates are known to have yields.

Preferred thickening agents useful in the compositions of the present invention are high molecular weight polycarboxylate polymer thickening agents.

High molecular weight is about 500.000 to about 5.000.000. Preferably a molecular weight of about 750.000 to 4.000.000.

The polycarboxylate aggregate may be a carboxyvinyl polymer. Such compounds are described in US Pat. No. 2.798.053, which is incorporated herein by reference. Methods for making carboxyvinyl polymers are described in Brown's literature, which is incorporated herein by reference.

The carboxyvinyl polymer is composed of monomeric olefinically unsaturated carboxylic acids and from about 0.1% to about 10% by weight of a polyhydric alcohol, wherein the polyhydric alcohol contains four carbon atoms having three or more hydroxyl groups bonded thereto. Interpolymers of monomeric mixtures comprising polyethers, wherein the polyethers contain one or more alkenyl groups per molecule. Other monoolefinic monomeric materials may be present in the monomeric mixture in a predominant proportion if necessary. The carboxyvinyl polymer is substantially liquid. Volatile oils are insoluble in hydrocarbons and dimensional safe when exposed to air.

Preferred polyhydric alcohols used to prepare the carboxyvinyl polymers are polyols selected from the group consisting of oligosaccharides, reduced derivatives of which carbonyl groups are converted to alcohol groups, and pentaerythritol, more preferably oligosaccharides, most Preferably it is sucrose. It is preferred that the hydroxyl groups of the modified polyols are etherified to allyl groups and the polyols have at least two allyl ether groups per polyol molecule. If the polyol is sucrose, sucrose preferably has at least 5 allyl ether groups per molecule. The polyether of the polyol comprises from about 0.1% to about 4%, more preferably from about 0.2% to about 2.5% by weight of the total monomers.

Preferred monomeric olefinically unsaturated carboxylic acids for use in preparing the carboxyvinyl polymers used herein are monomeric, polymerizable. a- monoolefinically unsaturated lower aliphatic carboxylic acid is included: more preferably monomeric monoolefinic acrylic acid of the general formula: most preferably acrylic acid.

In the above formula

R is a substituent selected from the group consisting of hydrogen and lower alkyl groups.

Carboxyvinyl polymers useful in the formulations of the present invention have a molecular weight of at least about 750.000. Preference is given to highly crosslinked carboxyvinyl polymers having a molecular weight of at least about 1.250.000. Also preferred are carboxyvinyl polymers having a molecular weight of less than about 3.000.000 that are less crosslinked.

Various carboxyvinyl polymers are based in New York, New York. F. Carbopol is commercially available from B. F. Goodrich. Carboxyvinyl polymers useful in the formulations of the present invention include Carbopol 910 having a molecular weight of about 750.000: Carbopol 941 having a molecular weight of about 1.250.000 is preferred, and more preferably Carbopol having a molecular weight of about 3.000.000 to 4.000.000, respectively. 934 is a few 940.

Carbopol 934 is a very lightly crosslinked carboxyvinyl polymer with a molecular weight of about 3.000.000. Sucrose has been described as high molecular weight polyacrylic acid crosslinked with about 1% polyallyl sucrose with an average of about 5.8 allyl groups for each molecule.

Further polycarboxylate polymers useful in the present invention are Sokolan PHC-25 ^R. Polyacrylic acid commercially available from BASF Corporation and Gantrez ^R commercially available from GAF Corporation. Poly (methyl vinyl ether / maleic acid) interpolymer.

Preferred polycarboxylate polymers of the present invention have a molecular weight of about 750.000 to about 4.000.000. Side-chain water dispersible polyacrylic acids crosslinked with polyalkenyl polyethers.

Very preferred examples of these polycarboxylate polymer thickening agents are B. a. Carbopol 600 family resin commercially available from B. F. Goodrich. Especially preferred are Carbopol 616 and 617. These resins are more highly crosslinked than 900 series resins and have a molecular weight of about 1.000.000 to 4.000.000. Mixtures of the polycarboxylate polymers described herein can also be used in the present invention. Preferred are mixtures of Carbopol 616 and 617 series resins.

It is preferable that the polycarboxylate polymer thickener is not used together with a clay thickener. In fact when the polycarboxylate polymers of the invention are used with clay in the compositions of the invention. It has been found that less desirable products are obtained in terms of phase instability. That is, the polycarboxylate polymers are preferably used in the compositions of the present invention as thickeners / stabilizers instead of clays.

Polycarboxylate polymers also reduce the shape, commonly referred to as bottlehang-up. This term means the ability to remove all dishwashing detergent products from the detergent container. Without being bound by theory, it is believed that the thickener compositions of the present invention are advantageous because the cohesion of the composition is greater than the adhesion to the container wall. When using the clay thickener system found in most commercial products. Bottle hang-up can be a major problem under certain conditions.

Without being bound by theory, it is believed that the long chain molecules of the polycarboxylate polymer thickeners facilitate the deposition of solids in the thickener detergent compositions of the present invention and facilitate the maintenance of an expanded matrix. The polymerizable material is also less sensitive than clay thickeners to breakdown by repeated shearing, such as occurs when the composition is mixed vigorously.

When the polycarboxylate polymer is used as a thickening agent in the composition of the present invention, it is typically about 0.1% to about 10% by weight. Preferably at a concentration of about 0.2% to about 2% by weight.

Thickening agents are used to provide a yield of about 50 to about 350. Most preferably about 75 to about 250.

Yield Analysis

Yield is an indicator of the shear stress at which flow begins beyond the gel strength. Yield values are measured here using a Brookfield RVT model viscometer equipped with a T-B spindle at 25 ° C. using a Helipath drive top during the relevant calibration. Set the system to 0.5 rpm and read the scale for the composition to be tested after 30 seconds or after the system has stabilized. Stop the system and set the rpm back to 1.0 rpm. After 30 seconds or after the system has stabilized read the eyes for the same composition. At zero shear force the stress is equal to or twice the scale minus 1.0 rpm to the scale of 0.5 rpm. The yield value is selected as the stress x18.8 (conversion factor) at zero shear force.

[Optional ingredients]

The compositions of the present invention may optionally contain other anionic and nonionic compounds, which refer to compounds other than those already described herein.

Other anionic surfactants useful for detergent purposes can also be included in the compositions thereof. Examples of useful anionic surfactants include salts of soaps such as sodium. Potassium, ammonium salts, and substituted ammoniums such as mono-di- and triethanolamine salts. For example. Sulfonated polycarboxylic acids made by sulfonating a pyrolysis product of alkaline earth metal citrate as described in British Patent Duty Free No. 1.082.179. C ₈ -C ₂₂ alkyl sulfates. C ₈ -C ₂₄ alkylpolyglycolethersulfate containing 10 moles or less of ethyl oxide: alkyl glycerol sulfonate. Fatty acid acyl glycerol sulfonate. Fatty acid acyl glycerol sulfate isethionate (eg acyl isethionate). Acyl taurate. Fatty acid amides, alkyl succinates and sulfosuccinates. Sulfates of alkyl polysaccharides such as acyl sarcosinate, sulfates of alkyl polyglucosides (nonionic non-sulfurized compounds described below). Alkyl ether carbonates. Fatty acid amides of methyl tauide and fatty acids esterified with acetionic acid and neutralized with sodium hydroxide. Examples of stock prices are described in Surface Active Agents and Detergents (Vol. 1 and [1. Schwartz. Perry and Berch). Various surfactants are also generally described in US Pat. No. 3.929.678, column 23. lines 58 to column 29. line 23, issued December 30, 1975 to Laughlin et al. Cited).

Amphoteric surfactants may be admixed in the detergent compositions of the present invention. Such surfactants can be broadly described as aliphatic derivatives of secondary or tertiary amines or aliphatic derivatives of heterocyclic secondary and tertiary amines in which the aliphatic radicals can be straight or branched. One of the aliphatic substituents is eight or more carbon atoms. Typically contains 8 to 18 carbon atoms. At least one substituent is an anionic water soluble group. For example carboxy. Sulfonates. Sulfates. See, for useful amphoteric surfactants. United States Patent No. 3.929.678, column 19 lines 18-35, issued to Raulin et al. On Dec. 30, 1975 (incorporated herein by reference).

Zwitterionic surfactants may also be mixed into the detergent compositions of the present invention. Such surfactants are derivatives of secondary and tertiary amines. Derivatives of heterocyclic secondary and tertiary amines. Or quaternary ammonium. It can be described broadly as a derivative of quaternary phosphonium or tertiary sulfonium compounds. [US Pat. No. 3..929.678 to Raulin et al., Issued Dec. 30, 1975, for a reference zwitterionic surfactant. Column 19 line 38 to column 22. line 48]

Amphoteric and zwitterionic surfactants are generally used as mixtures with one or more anionic and / or nonionic surfactants.

When used in the compositions of the present invention, these optional additional surfactants typically range from about 1% to about 10% by weight. Preferably from about 2% to about 5% by weight.

Other optional ingredients include cleaning enhancers in oily or inorganic form. Such enhancers are generally undesirable for use in the compositions of the present invention. Examples of water soluble inorganic enhancers that can be used alone or in admixture thereof or in admixture with organic alkali metal ion sequestrant enhancer salts include glycine, alkyl and alkenyl succinates, alkali metal carbonates, phosphates, polyphosphonates and It is a silicide. Specific examples of such salts are sodium tripolyphosphate, sodium carbonate, potassium carbonate, sodium pyrophosphate, potassium pyrophosphate potassium tripolyphosphate and sodium hexametaphosphate. Examples of organic enhancer salts that can be used alone or in admixture with each other or in admixture with the inorganic alkaline enhancer salts are water soluble citrate (eg sodium and potassium citrate). Sodium and potassium tartrate, sodium and potassium ethylenediaminetetraacetate, sodium and potassium N- (2-hydroxy-ethyl) -ethylenediamine triacetate, sodium and potassium nitrilotriacetate, sodium and potassium N- (2-hydroxy Ethyl) -nitrile, including but not limited to diacetate, sodium and potassium oxydisuccinate, and sodium and potassium tartrate mono- and disuccinate, which are incorporated herein by reference in US Pat. No. 4,663,071 (bush). (Bush et al., Issued May 5, 1987). Other organic detergent enhancers such as water soluble phosphonates can be used in the compositions of the present invention. However, cleaning enhancers typically have limited value when the composition of the present invention is in the form of a hard liquid wash detergent composition. When included in the compositions of the present invention, these optional enhancers are typically present at from about 1.0% to about 10% by weight, preferably from about 2% to about 5% by weight.

Other preferred components include diluents, solvents, dyes, fragrances and hydrotropes (preferably). Diluents can be inorganic salts such as sodium and potassium sulfate, ammonium chloride, sodium and potassium chloride, sodium bicarbonate and the like. Diluents useful in the compositions of the present invention are typically present in about 1% to about 10% by weight, preferably from about 2% to about 5% by weight.

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

Hydrofts are for example sodium and potassium toluene sulfonates, sodium and potassium xylene sulfonates, sodium and potassium cumenesulfonates, trisodium and tripotassium sulfosuccinates and related compounds (US Pat. No. 3,915,903, incorporated herein by reference). ) Can be used with the advantage that the product achieves the desired phase stability and viscosity. It has been found that hydrotrope has a positive effect on this advantage of the present invention. Although not based on theory, it is believed that this advantage is due to the viscosity characteristics of this hydrotrope. Hydrotropes useful in the compositions of the present invention are typically present in about 1% to about 10% by weight, preferably from about 2% to about 5% by weight.

Any component that is useful when the composition of the present invention is used in liquid dish washing detergent applications is the wastewater described in US Pat. No. 4,316,824 (Pancheri, issued February 23, 1982), which is incorporated herein. Promoted ethoxylated nonionic surfactants.

Without wishing to be bound by theory, the claimed compositions of the present invention have a foaming and oil washing performance that does not impart a greasy feeling to the washed dishes, which is important in the consumer market where the cleanliness of the dishes is judged to be lacking this greasy feeling. It is believed that there is an advantage of providing an unusual improvement. In addition, although not based on theory, it is believed that a further advantage of the compositions of the present invention is the ease of rinsing and the advantage that they reduce the slippery feeling associated with typical liquid compositions. This is important in the consumer market as it is not preferred to have such a slippery feel and the surfactant has been washed unstable from the tableware surface.

In addition, although not being bound by theory, it is believed that the compositions of the present invention exhibit exceptionally uniform foaming forces under varying temperature and humidity conditions, particularly in the preferred dishwashing temperature range of about 100 ° F. to about 120 ° F. .

In terms of the method of the present invention, the stained tableware is contacted with an effective amount of the composition of the present invention, typically from about 0.5 ml to about 20 ml (per 25 dishes to be treated), preferably from about 3 ml to about 10 ml. The actual amount of liquid detergent composition used is based on the judgment of the user and typically depends on factors such as the specific product formulation of the composition, including the concentration of active ingredients in the composition, the number of contaminated utensils to be cleaned, the degree of contamination of the utensils, and the like. Will be. Next, the particular product formulation will depend on many factors, such as the intended market for composition production (ie, United States, Europe, Japan, etc.). Examples of typical methods in the detergent compositions of the present invention that can be used to wash dishes are as follows. These examples are for purposes of citation, not limitation.

When targeting the typical United States market, a sink having a volume size of from about 3 ml to 15 ml, preferably from about 5 ml to about 10 ml, from about 5000 ml to about 20,000 ml, more typically from about 10,000 ml to about 15,000 ml In an amount from about 1,000 ml to about 10,000 ml, more typically from about 3,000 ml to about 5,000 ml. The detergent composition has a surfactant mixture at a concentration of about 21% to about 44% by weight, preferably about 25% to about 40% by weight. Preferred water temperatures are from about 80 ° F to about 125 ° F, and more preferred water temperatures are from about 100 ° F to about 120 ° F. The stained utensils are immersed in a sink containing detergent composition and water and are washed by contacting the soiled surfaces of the utensils with a cloth, sponge or the like. A cloth, sponge or the like may be immersed in and in the mixture of detergent composition and water before contacting the surface of the dish, typically contacting the dish surface for about 1 to about 10 seconds but the actual time varies with each application and user. do. Contacting the surface of the dish with a cloth, sponge or the like is preferably carried out by wiping the surface of the dish at the same time.

If you are targeting a typical European market. From about 5000 ml to about 20.000 ml of from about 3 ml to about 15 ml, preferably from about 3 ml to about 10 ml of the liquid detergent composition. More typically from about 1.000 ml to about 10.000 ml of water in a sink having a volume size of about 10.000 ml to about 15.000 ml. More typically from about 3.000 ml to about 5.000 ml. Detergent composition is about 21% to about 44% by weight. Preferably from about 25% to about 35% by weight of the surfactant mixture. Preferred water temperatures are about 80 ° F. to about 125 ° F., and more preferred water temperatures are about 100 ° F. to 120 ° F. Contaminated tableware is immersed in a sink containing detergent composition and water, and they are clothed. Clean by touching the stained surface of the dish with a sponge or similar object. The cloth, sponge or the like may be in and mixed with the detergent composition and water prior to contact with the dish surface, typically in contact with the dish surface for about 1 to about 10 seconds, but the actual time varies with each application and user. Cloth on the table. Contacting the sponge or the like is preferably performed while wiping the surface of the tableware with a bowl.

From about 1 ml to about 50 ml of detergent composition when targeting the typical Latin American and Japanese markets. Preferably from about 2 ml to about 10 ml from about 500 ml to about 5.000. More typically about 50 ml to about 2.000 ml of water in a sink having a volume size of about 500 ml to about 1.000 ml. More typically from about 100 ml to about 1.000 ml. Detergent composition is about 5% to about 40% by weight. Preferably from about 10% to about 30% by weight of the surfactant mixture. Clean contaminated utensils by touching the stained surface of the utensils with a cloth, sponge or similar object. A cloth sponge or the like may be immersed in and in a mixture of detergent composition and water before contacting the dish surface, and typically contacting the dish surface for about 1 to about 10 seconds is preferably performed by simultaneously wiping the dish surface.

Another use is specifically made by immersing dishware and immersing in a bath without liquid dishwashing detergent. Appliances that absorb liquid dishwashing detergents, such as sponges, are placed directly in separate amounts of undiluted liquid dishwashing composition, typically for about 1 to about 5 seconds. The absorbent device and consequently the undiluted liquid dishwashing composition are then brought into contact with each surface of the contaminated tableware to remove the contamination. The absorber is typically in contact with each dish surface for about 1 to about 10 seconds, but the actual application time will depend on factors such as the contamination of the dish. The contacting of the absorption mechanism on the surface of the dish is preferably performed by simultaneously wiping the surface of the dish.

[Experiment]

It is N-methyl for use in the present invention. The method of manufacturing the 1-deoxyglucityl lauryl surfactant is illustrated. Although a skilled chemist can change the arrangement of the device. Suitable devices for use in the present invention include a 3-liter four-necked flask equipped with a motor-operated paddle stirrer and a thermometer of sufficient length to conform to the reaction medium. Nitrogen sweeps and wide-bore side-arms (Note wide-bore side-arms are important when methanol is released very quickly) and other effective capture to other two-necked flusks Connect the condenser and vacuum outlet. Connect citron to nitrogen bleed and vacuum gauge. Connect to aspirator and trap. The reactant, which is placed on a lab-jack with a 500-watt heating mantle with a variable transformer temperature variable used to heat the reactants, can be further controlled by easily raising or lowering the temperature.

N-methylglucamine (195 g, 1.0. Aldrich. M4700-0) and 1270.9 g of methyllaurate Procter Gamble CE. 1.0) is placed in the flask. The solid / liquid mixture is heated with stirring under a nitrogen sweep to form a melt. (About 25 minutes). The melting temperature reaches 145 ° C. and the catalyst [anhydrous powdered sodium carbonate. 10.5. 0.1 mol. second. tea. Baker (J. T. Baker). Stop the nitrogen sweep and adjust the aspirator and nitrogen bleed to 5 inches (5/31 bar) Hg. Provide a vacuum. At this point the Variac is adjusted and / or the mantle is raised or strongly maintained at 150 ° C.

Within 7 minutes. Methanol bubbles are preferentially observed in the meniscus of the reaction mixture. Intense reactions soon follow. Methanol is distilled until its rate decreases. Adjust the vacuum to obtain about 10 inHg. (10/31 atm). The vacuum is increased approximately as follows: 10 inHg at 3 minutes, 20 inHg at 7 minutes, 25 inHg at 10 minutes. 11 minutes after the onset of methanol release. Heating and stirring are stopped upon stopping foaming. The product is cooled and solidified.

The following examples merely illustrate the compositions of the present invention. It is not meant to limit or limit the scope of the invention, which is determined in accordance with the following claims.

EXAMPLE

The following examples describe aspects of the invention and are not so limited.

Example I

The following compositions are formulated based on weight percent. These compositions are prepared according to the description set out below.

Surfactant pastes are initially formed by mixing the desired surfactant with water and an alcohol. Surfactant contained in the said surfactant paste contains polyhydroxy fatty acid amide and the foaming promoter of this invention. The ideal surfactant paste should be capable of pumping at room or elevated temperatures. Separately, in large mixing vessels without a propulsion mixer. 3/4 of the moisture in the formulation product. A combination of alcohol 1/2 in the formulation product and the required hydrotropes (eg xylene, silica, toluene sulfonate) are combined to obtain a clear solution. Preferred optional magnesium is added next. The surfactant is then added to form a mixture.

If magnesium is included. It can be added directly to the mixing vessel as magnesium chloride. It may also be added as magnesium oxide or hydroxide powder. The magnesium oxide or hydroxide powder is added to the acid form of the surfactant salt (e.g., alkyl benzene sulfonate, alkyl sulfate, alkyl ethoxylated sulfonate, methyl ester sulfonate, etc.) in the surfactant paste. When magnesium is added as an oxide or hydroxide powder. If it is mixed with less than stoichiometric amount, it will be completely decomposed. The pH of the magnesium containing surfactant paste is then adjusted using NaOH or KOH solution.

Mix until the mixture is a homogeneous and clear solution product. Then additional water, alcohol and preferred additional hydrotrope (added as solution) are added to bring the viscosity of the solution product to the desired level. Ideally, the Brookfield viscometer is adjusted to a viscosity of 50 to 1000 cps at 70 ° F. The pH of the solution product is about 7.0 ± 0.7 when it contains ammonium ions by HCI or NaOH. If it does not contain ammonium ions, adjust to about 8.5 ± 1.5.

Spices. Dyestuffs and other ingredients such as opacifiers such as litrone and ethylene glycol may be added as a final step. Litron can be added directly as a dispersion while mixing. Ethylene glycol distearate must be added in a molten state with rapid mixing to form the desired pearlescent crystals.

Example II

The following compositions are formulated based on weight percent. These compositions are prepared by the same method as the composition of Example 1.

Example III

The following compositions are formulated based on weight percent. These compositions are prepared in the same manner as the compositions of Example I.

Example IV

The following compositions are formulated based on weight percent. These compositions are prepared in the same manner as the compositions of Example I.

Example V

The following compositions are formulated based on weight percent. These compositions are prepared in the same manner as the compositions of Example I.

Example VI

The following compositions are formulated based on weight percent. These compositions are prepared in the same manner as the compositions of Example I.

Example VII

The following compositions are formulated based on weight percent. These compositions are prepared in the same manner as the compositions of Example I.

Example VIII

Another method for preparing the polyhydroxy fatty acid amides used in the present invention is as follows. 84.87 g of fatty acid methyl ester (source: Procter & Gamble Methyl Ester CE 1270), N-methyl-D-glukamine (source: Aldrich Chemital Campani M4700-0.sodium methoxide (source: Aldrich Chemical Campa 16.499-2) 1.04 g and 68.51 g methyl alcohol The reaction vessel contains a dry tube, a standard reflux apparatus equipped with a cooler and a stirring rod, in which the N-methyl glucamine is stirred under argon. Mix with ethanol and begin to heat with sufficient mixing (stirring bar: reflux) After 15 to 20 minutes, when the solution reaches temperature for the purpose, add ester and sodium methoxide catalyst Samples are taken periodically and reacted Note the progress, but note that the solution becomes completely clear by 63.5 min.In use the reaction is judged to be almost complete 4 hours while refluxing the reaction mixture. Is maintained. After removal of the methanol. The weight of the recovered crude product is 156.16g. Is vacuum dried, and collected in a purified and then this overall yield 106.92 crude product.

But. The yield (%) is not calculated based on the above since regular sampling throughout the reaction makes the total yield value meaningless. By running the reaction for six months at 80% and 90% reaction concentrations, products with very little byproduct formation can be obtained.

The following is not intended to limit the present invention and merely briefly describes additional aspects of the technology that may be considered by manufacturers in the preparation of various detergent compositions using polyhydroxy fatty acid amides.

It is readily understood that polyhydroxy fatty acid amides are readily unstable under very basic or very acidic conditions by semantic amide linkages. Some degradation may be tolerated, but such materials are at least about 11. Preferably at least 10. Or not applied to a pH of about 3 or less for an excessively long time. The pH of the (liquid) final product is typically 7.0 to 9.0.

It is typically necessary to at least partially neutralize the catalyst used during the preparation of the polyhydroxy fatty acid amides to form amide bonds. Although you can use certain acids for this purpose. Detergent manufacturers will appreciate the simplicity and convenience of using acids that provide useful and desirable anions in processed detergent compositions. For example. Citric acid can be used for the neutralization reaction and the resulting citrate ions (about 1%) are maintained with about 40% of the polyhydroxy fatty acid amide slurry and introduced into later stages of manufacture of the overall detergent-making process. Acid forms of materials such as oxydisuccinate, nitrile triacetate, ethylenediaminetetraacetate, tartrate / succinate and the like can be similarly used.

Polyhydroxy fatty acid amides derived from (primarily C ₁₂ -C ₁₄ ) coconut alkyl fatty acids are more soluble than their counterparts (primarily C ₁₆ -C ₁₈ ) resin alkyls. C ₁₂ -C ₁₄ materials are more easily formulated to some extent in liquid compositions and are more soluble in cold water wash baths. But. C ₁₆ -C ₁₈ materials are also very useful, especially in the context of using wash water which is hot or hot water. Indeed, the C ₁₆ -C ₁₈ material can be a better washable surfactant than its C ₁₂ -C ₁₄ counterpart. Thus, a manufacturer may want to balance ease of manufacture with respect to performance when selecting a particular polyhydroxy fatty acid amide for use in a provided formulation.

It is also recognized that the solubility of polyhydroxy fatty acid amides can be increased by having unsaturated and / or decondensation points on fatty acid residues. therefore. Materials such as polyhydroxy fatty acid amides derived from oleic acid and iso-stearic acid are more soluble than the n-alkyl counterparts.

Similarly, Disakara Dit. The solubility of polyhydroxy fatty acid amides prepared from trisaccharides and the like will typically be higher than the solubility of their monosaccharide-derived counterparts. Such high solubility can be particularly helpful when formulating liquid compositions. In addition, polyhydroxy fatty acid amides in which the polyhydroxy group is derived from maltose exhibit particularly suitable functions as detergent compositions used as a mixture with conventional alkylbenzen sulfonate (LAS) surfactants. Without being bound by theory, mixtures of unfolded hydroxy fatty acid amides derived from higher saccharides such as LAS and maltose have been shown to improve net detergent performance by causing substantial and unexpected degradation of surface tension in aqueous media. (The preparation of polyhydroxy fatty acid amides from malcos is described below).

Polyhydroxy fatty acid amides are refined sugars as well as hydrolyzed starch. For example, it may be prepared from corn starch, potato starch, or certain other convenient plant-derived starches containing saccharides such as mono-di- as desired by the manufacturer. This is especially important from an economic point of view. Thus high glucose corn syrup. It can be conveniently and economically used, such as high maltose corn syrup. Delignified and hydrolyzed cellulose pulp may also provide a source official for polyhydroxy fatty acid amides.

As noted above, polyhydroxy fatty acid amides derived from higher saccharides such as maltose, lactose and the like are more soluble than their glucose counterparts. It also appears that more soluble polyhydroxy fatty acid amides can help to varying degrees the solubilization of their less soluble counterparts.

Therefore, the manufacturer can select and use a substance containing high glucose corn syrup except for example, selecting a syrup containing a small amount of maltose (for example, 1% or more). The resulting mixture of polyhydroxy fatty acids generally exhibits more desirable solubility properties over a wider temperature range and concentration than pure glucose-derived polyhydroxy fatty acid amides. Thus, in addition to certain economic advantages when using sugar mixtures rather than pure sugar reactants, polyhydroxy fatty acid amides prepared from mixed sugars can provide very substantial advantages in terms of performance and / or ease of formulation. However, in some cases it can be noted that the degreasing performance (dish wash) is slightly reduced at fatty acid melt-amide levels of at least about 25%, and the susceptibility is somewhat reduced at or above about 33% (the% is glucose-derived in the mixture) % Of maltamide-derived polyhydroxy fatty acid amide relative to polyhydroxy fatty acid amide). This may vary depending on the chain length of the fatty acid residue. Then, manufacturers who typically choose and use such mixtures have prepared polyhydroxy fatty acid amide mixtures containing a ratio of monosaccharides to di- and higher saccharides such as maltose from about 4: 1 to about 99: 1. One may find it advantageous to choose.

Preferred non-closed polyhydroxy fatty acid amides are prepared from fatty acid esters and N-alkyl polyols from about 30 ° C to 90 ° C. Preferably it may be carried out in an alcohol solvent at a temperature of about 50 ℃ to 80 ℃. Since the glycol solvent does not need to be completely removed from the reaction product prior to use in the processed detergent formulation, it has now been determined that the producer of liquid detergent, for example, can conveniently carry out this process in 1.2-propylene glycol solvent. Likewise, even producers of solid, typically granular detergent compositions, for example, contain ethoxylated alcohols such as ethoxylated (EO 308) CC alcohols, such as those marketed as NEODOL 23EO6.5 (cell). One may find it convenient to carry out the process at 30 ° C. to 90 ° C. in a solvent. When using such ethoxylates. They preferably do not contain substantial amounts of non-ethoxylated alcohols, and more preferably do not contain substantial amounts of mono-ethoxylated alcohols (denoted as T).

The process for producing the polyhydroxy fatty acid amides itself is not part of the present invention, but producers may also note the synthesis of polyhydroxy fatty acid amides as described below.

Typically, industrial scale reaction sequences for the preparation of the preferred bicyclic polyhydroxy fatty acid amides will include the following.

[Step 1] An N-alkyl polyhydroxyamine derivative is prepared from a desired sugar or sugar mixture by forming an additive of -N-acyl amine with a sugar and then reacting with hydrogen in the presence of a catalyst. Reacting hydroxy amines, preferably with fatty acid esters, to form amide bonds. Although various N-alkyl polyhydroxy amines useful in step 2 of the reaction sequence can be prepared by methods described in various fields. The following method is convenient and economical sugar syrup is used as a raw material. For best results, manufacturers use very bright colors when using these syrup raw materials. Or preferably a syrup that is almost colorless (light-white).

Preparation of N-Alkyl Polyhydroxy Amine from Vegetable Sugar Syrup

I. Adduct Formation—The following is about 420 g of about 55% glucose solution with Gardner Color <1 (corn syrup-glucose about 23 lg-about 1.28 moles) about 50% methylamine aqueous solution about 119 g (59.5 g of methylamine). -1.92 mole). The methylamine (MMA) solution is purged, masked with N ₂ and cooled to 10 ° C or less. Purge corn syrup and shield with N ₂ at a temperature of about 10-20 ° C. Corn syrup is slowly added to the MMA solution at the indicated reaction temperatures indicated above. Measure the color in Gardner at the approximate minutes indicated.

Table 1

As can be seen from the data, the Gardner killer of the adduct is much worse when the temperature rises above about 30 ° C. and about 50 ° C., and the time when the Gardner color of the adduct is below 7 is only about 30 minutes. Longer response. And / or for retention time the temperature should be less than about 20 ° C. The Gardner color should be less than about 7 and preferably less than about 4 for good color glucamine.

When lower temperatures are used to form the adducts, the use of higher ratios of amines to sugars shortens the time for the adducts to reach substantial flat concentrations. The molar ratio of amine to sugar mentioned is used at 1.5: 1 and equilibration is reached in about 2 hours at a reaction temperature of about 30 ° C. Under the same conditions, the time at a molar ratio of 1.2: 1 is about 3 hours or more. For excellent color. The reaction time is the substantial equilibrium conversion on a sugar basis. For example about 90% or more. Preferably at least about 95%. More preferably, it is selected to acquire more than about 99%, and the color of the adduct is less than about 7. Preferably less than about 4. More preferably less than about 1.

The color of the MMA adduct is indicated as indicated above using corn syrup having a different Gardner color as described above and at the reaction temperature below about 20 ° C. (after attaining substantial equilibrium in at least about 2 hours).

[Table 2]

As can be seen from the above, the joule sugar material should be nearly colorless so that the adduct continues to be accepted. If our Gardner color is approximately 1. Adjuncts are sometimes allowed and sometimes not allowed. If the Gardner color is one or more, the resulting adduct is not allowed. The better the initial color of the sugar. The color of the adduct is excellent.

II. Hydrogen, the above adduct having a reaction-Gardner color of 1 or less, is hydrogenated according to the following method.

Additives in Water About 539 g United catalyst About 23.1 g of the United States G49B Ni catalyst are added to a 1 L volume of ochoclave and purged twice with 200 psig H ₂ at about 20 ° C. The H ₂ pressure was raised to about 1400 psig and the temperature was raised to about 50 ° C. The pressure is then elevated to about 1600 psig and the temperature is maintained at about 50 to 55 ° C. for about 3 hours. The product is about 95% hydrogenated at this point. The temperature is raised at about 85 ° C. for about 30 minutes, the reaction mixture is decanted and the catalyst is filtered off. After evaporation removes water and MMA. The product is about 95% N-methyl glucamine, white powder.

The following method is repeated using about 23.1 g of Raney Ni catalyst with the following changes. The catalyst is washed three times and the reactor containing catalyst in the reactor is purged twice with 200 psig H ₂ and the reactor is pressurized from 1600 psig to H ₂ for 2 hours, releasing pressure for 1 hour and repressurizing the reactor to 1600 psig.

The adduct is then introduced to the reactor at 200 psig and 20 ° C. and the reactor is purged with ₂₀₀ psig H ₂ as above.

The product obtained in each case is at least about 95% N-methyl glucamine: contains less than about 10 ppm Ni based on the glucamine: a solution with a Gardner color of less than about 1.

The color of the crude N-ketyl gluamine is stable to about 140 ° C. for a short exposure time.

Having good adducts with low (less than about 5%, preferably less than about 1%) sugar content and good color (Gardner color is less than about 7, preferably less than about 4, more preferably less than about 1) It is important.

In another reaction, the adduct is prepared starting with about 159 g of about 50% methylamine in water, which is purged at about 10-20 ° C. and masked with N ₂ . About 330 g of about 70% corn syrup (almost water-white) is stripped with N ₂ at about 50 ° C. and slowly added to the methyl amine solution at a temperature below about 20 ° C. The solution is mixed for about 30 minutes to obtain about 95% of an adduct which is a very bright yellow solution.

About 190 g of adduct in water and about 9 g of United Catalyst G49B Ni catalyst are added to a 200 ml autoclave and purged three times with H ₂ at about 20 ° C. Raise the H ₂ pressure to about 200 psi and raise the temperature to about 50 ° C. The pressure is raised to 250 psi and the temperature is maintained at about 50-55 ° C. for about 3 hours. At this point, the product is about 95% N-methyl glucamine, white powder, after about 95% hydrogenated product is heated to 85 ° C. temperature for about 30 minutes, water is removed and evaporated.

It is also important to minimize the Ni content in the glucamine by minimizing contact between the adduct and the catalyst when the H ₂ pressure is less than about 1000 psig. The nickel content in N-methyl glucamine in this reaction is about 100 ppm, compared to less than 10 ppm in the reaction.

The following reaction with H ₂ is carried out for a direct comparison of the reaction temperature effects.

The adduct is prepared in a similar manner as described above using a 200 ml autoclave reactor and the hydrogen reaction is carried out at various temperatures.

An adduct for use in the preparation of glucamine was prepared by using about 420 g of glucur (corn syrup) solution of about 420 g (glucose 231 g: 1.28 moles) [99DE corn syrup commercially available from CarGill. The solution is prepared by mixing Gardner color is less than 1] and 50% methyl amine about 119 G (59.5 g MMA: 1.92 moles) (available from Air Products).

The reaction method is as follows.

1. N ₂ is added about 119 g of a 50% methylamine solution to the purged reactor, shielded with N ₂ and cooled to less than about 10 ° C.

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

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

4. Add all corn syrup all at once and stir for about 1 to 2 hours.

The adducts are used for hydrogen reaction as appropriate after preparation or stored at low temperature to prevent further decomposition.

The glucamine adduct hydrogen reaction is as follows:

1. Add 135 g of adduct (with Gardner color less than about 1) and about 5.8 g of G49B Ni to a 200 ml autoclave.

2. Purge the reaction mixture twice with H ₂ at about 200 psi at about 20-30 ° C.

3. Pressurize to about 400 psig with H ₂ and raise the temperature to about 50 ° C.

4. Raise pressure to about 500 psi and allow to react for about 3 hours. The concentration is maintained at about 50-55 ° C. Take sample 1.

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

6. Tilt out and filter the Ni catalyst. Take sample 2.

Conditions for Constant Temperature Reaction:

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

2. Purge twice with about 400 psi H ₂ at low temperature.

3. Pressurize to about 400 psi with H _{2 and} raise the temperature to about 50 ° C.

4. Boost up to about 500 psi and react for about 3.5 hours. Maintain temperature at the indicated temperature.

5. Tilt out and filter Ni catalyst. Sample 3 is about 50-55 ° C .: Sample 4 is 75 ° C. Sample 5 is 85 ° C. (about 85 ° C. reaction time is about 45 minutes).

All runs provide N-methyl glucamine of similar purity (about 94%): The Gardner color of the run is similarly appropriate after the reaction, but provides excellent color stability by -stage heat treatment: 85 ° C. run after reaction Provide limit color immediately.

Example IX

The preparation of the resin (cured) fatty acid amides of N-methyl maltamine for use in the detergent composition according to the invention is as follows.

Step 1-Reactant: Maltose monohydrate (Aldrich. Lot 013KW): Methylamine (40% by weight in water) (Aldrich. Lot 03325 ™): Raney Nickel. 50% slurry (UAD 52-73D. Aldrich. Lot 12921LW).

The reaction was added to a glass liner (250 g of maltose. 428 g of methylamine solution. 100 g of catalyst slurry-50 g of Raney Ni), placed in a 3L vibrating oatclave, purged with nitrogen (3x500 psig) and hydrogen (2x 500 psig) and ranged from 28 ° C. to 50 ° C. Vibrate under H ₂ at room temperature over 1 week at temperature. The crude reaction mixture is vacuum filtered twice through a glass microfiber filter fitted with a silica gel plug. The filtrate is concentrated to a viscous material. The material is dissolved in methanol to azeotrope the final traces of water and then the methanol / water is removed on a rotary evaporator. Final drying under high vacuum. The crude product is dissolved in reflux methanol, cooled to recrystallize, filtered and the filter cake is dried in vacuo at 35 ° C. This is Kit # 1. And the filtrate is concentrated and stored overnight in the freezer until field begins to form. The solid is filtered off and dried under vacuum. This is cut # 2. The filtrate is again concentrated to its half volume and recrystallization is performed. Very little and the whole thing is formed. A small amount of ethanol is added and the solution left in the freezer for one week. The solid material is filtered off and dried in vacuo. The collected solids were used in step 2 of the overall synthesis N-methyl maltamine (from step 1): cured resin methylester: sodium methoxide (25% in methanol): anhydrous metalol (solvent): amine: ester molar ratio 1 : 1% W / r maltamine per 10 moles of initial catalyst). Rise to 20 mol%: solvent 50% by weight

In a sealed bottle, 20.36 g of tallow methyl ester is heated to its melting point (water bath) and placed in a 250 ml three-neck round bottom flask with mechanical stirring. The flask is heated to about 70 ° C. to prevent the ester from solidifying. Separately, 25.0 g of N-methyl maltamine is combined with 45.36 g of metalol, and the resulting slurry is added to the resin ester with appropriate mixing. 1.51 g of 25% sodium methoxide in metalol is added. After 4 hours the reaction mixture is not purified, additional 10 mole% (up to 19 mole% total) of catalyst is added and the reaction continues overnight (about 68 ° C.) and the mixture becomes clear. The reaction flask is then reformed for distillation. Increase the temperature to 110 ° C. Distillation is continued for 60 minutes at atmospheric pressure. High vacuum distillation then commences and continues for 14 minutes, where the viscosity of the product is very high. The product is kept in the reaction flask at 110 ° C. (external temperature) for 60 minutes. The product is scraped from the flask and polished with ethyl ether over one week. The ether is removed on a rotary evaporator and the product is stored overnight in the oven and ground to a powder. Silicakel is used to remove residual N-methyl maltamine from the product. The silica gel slurry in 100% methanol is placed in a funnel and washed several times with 100% methanol. A concentrated product sample (20 g in 100 ml of 100% methanol) is placed on silica gel and eluted several times using vacuum and washed several times with methanol. The collected eluate is evaporated to dryness (rotary evaporator). The remaining resin ester is removed by grinding overnight in ethyl acetate and filtered. The filter cake is vacuum dried overnight. The product is resin alkyl N-methyl maltamide.

In another embodiment, reaction sequence step 1 is carried out using commercially available corn syrup comprising glucose or a mixture of glucose and maltose, typically at least 5%. The obtained polyhydroxy fatty acid amides and mixtures can be used in the detergent composition of the present invention. In another embodiment step 2 of the above reaction sequence can be carried out in 1,2-propylene glycol or NEODOL. At the discretion of the manufacturer, propylene glycol or NEODOL need not be removed from the reaction product prior to formulating the detergent composition using it. Again according to the manufacturer's wishes. The methoxide catalyst may be neutralized with citric acid to provide sodium citrate which may remain in the polyhydroxy fatty acid amide.

Advantageously, manufacturers of fabric laundry compositions which may contain antifouling agents have a variety of known materials selected from the following. United States Patents 3.962.152: 1.116.885: 4.238.531: 4.702.857: 4.721.580 and 4.77.896]. Further antifouling materials useful in the present invention include a source of C ₁ -C ₄ alkoxy-terminated polyethoxy units (CH ₃ LOCH ₂ CH ₁₆ OH). Sources of derephthaloyl units (eg dimethyl terephthalate): Sources of poly (oxyethylene) oxy units (eg polyethylene glycol 1500): Sources of oxyiso-propyleneoxy units (eg 1,2-propylene glycol and ) A source of oxyethyleneoxy units (eg, butylene glycol), in particular. Wherein the molar ratio of oxyethyleneoxy units: oxyiso-propyleneoxy units is at least about 0.5: 1. Such nonionic antifouling agents are compounds of the following general formula.

Wherein R ¹ is lower (eg C ₁ -C ₄ ) alkyl. In particular methyl: x and y are each an integer from about 6 to about 100: m is an integer from about 0.75 to about 30: n is an integer from about 0.25 to about 20: R ² is oxyethyleneoxy: oxyisopropylene A mixture of H and CH ₃ that provides a molar ratio of oxy of at least about 0.5: 1

Another preferred type of antifouling agent useful in the present invention is the general anionic material described in US Pat. No. 4,77,896. Such detergents must be conditionally free of monomers of type HOROH wherein R is propylene or alkyl. Thus, the antifouling agent of US Pat. No. 4,77,896 is for example. Dimethyl terephthalate. Ethylene glycol. These additional protective agents may for example contain 1.2-propylene glycol and 3-sodiosylfobenzoic acid. Dimethyl terephthalate. Ethylene glycol. 5-sodiosulfoisophthalate and 3-sodiosulfobenzoic acid reaction products. Such detergents are preferred for use in granular laundry detergents.

It is also advantageous for the manufacturer to include non-perborate bleach in particular in granular laundry detergents for mass production. Various peroxygen bleaches are commercially available and can be used in the present specification, of which percarbonate is convenient and economical. Thus, the compositions of the present invention may contain solid percarbonate bleach, typically in the form of sodium salts, wherein 3 to 20% by weight of the composition. More preferably, it is mixed at a level of 5 to 18% by weight and most preferably 8 to 15% by weight.

Sodium perborate is an additive compound having the general formula corresponding to 2Na ₂ co ₃ h ₂ o ₂ and is commercially available as a crystalline solid. Most commercially available materials are EETA. It contains low levels of heavy metal ion disintegrants, such as 1-hydroxyethylidene 1,1-diphosphonic acid (HEDP) or amino-phosphonate, which are mixed during the manufacturing process. For use in the present invention, percarbonate can be mixed into the detergent composition without further protection. Preferred embodiments of the invention use a safe form of the material (FMC). Although various coatings can be used, sodium silicate having a Sio ₂ : Na ₂ O ratio of 1.6: 1 to 2.8: 1 1, preferably 2.0: 1, is the most surfactant, applied as an aqueous solution and dried, based on the weight of percarbonate Silicate solids are provided at levels of 2% to 10% (typically 3% to 5%). Magnesium silicate may also be used and chelating agents such as those described above may also be included in the coating.

The particle size range of the percarbonates determined is 350 to 450 pm and the average value is about 400 pm. At the time of covering. The size of the crystals ranges from 400 to 600 pm.

Heavy metals present in the sodium carbonate used to make the percarbonate can be adjusted by containing metal ion sequestrants in the reaction mixture, but the percarbonates still must be protected from heavy metals present as impurities in the other components in the product. Iron in the product. It has been found that the total level of copper and manganese ions should not exceed 25 ppm and preferably below 20 ppm to prevent an unacceptable adverse effect on percarbonate stability.

The condensed washing detergent granules are as follows.

Generalized silicate builders are known in the art. Layered sodium silicate is preferred. Reference. For example, H. P., incorporated herein by reference and dated May 12, 1987. Layered sodium silicate as described in US Pat. No. 4.66.895 to Rick. Suitable layered silicate builders are commercially available as SKS-6 from Hext.

Available from Novo Nordisk A / S in Copenhagen

Very preferred granules of this kind are granules comprising from about 0.0001% to about 2% by weight of the active enzyme and at least about 1% by weight of the polyvalent fatty acid amide. The anionic surfactant here is not an alkylbenzene sulfonate surfactant.

The compositions provided by the present invention can be used in a variety of cleaning methods. It is most preferable to use these for dish washing. The following describes some preferred dish cleaning solutions according to the present invention.

Example X A-D

The following examples are particularly suitable for dishwashing and other hard surface cleaning operations. The liquid detergent composition at light operation is described. In Examples A-D. Surfactants are various alkyl ethoxy sulfate surfactants abbreviated to represent their average degree of ethoxylation using standard terms (hence, C _12-13 EO (0.8 sulfate has a sulfated mixed C with an average degree of ethoxylation of .0.8). _12- C ₁₃ alcohol fraction.) These anionic ethoxy sulfates are preferably used in the form of their Na ⁺ or NH ₄ ⁺ salts C _12-13 amine oxides are mixed C _12-13 (average ) are the methyl amine oxide, C ₁₂ -. ₁₄ Ap betaine is

C _12-14 H _25/29 CONH (CH ₂ ) ₃ N ⁺ (CH ₃ ) ₂ CH ₂ CO ₂ H. C _12-14 AP betaine is C _12/14 H _25/29 CONH (CH ₂ ) ₃ N ⁺ (CH ₃ ) ₂ CH ₂ CH (OH) CH ₂ SO ₃ H. C _12-14 DM betaine is _12/14 H _25/29 N ⁺ C (CH) CHCO. Ethoxylated nonionic surfactants denoted C _9-1 EO (8) refer to C ₉ -C ₁₁ alcohols ethoxylated with an average of 8 moles of ethylene oxide. Ca ⁺⁺ and Mg ⁺⁺ cations are conveniently introduced into the composition as CaCl ₂ and MgCl ₂ . The remaining materials of the composition include water and citrate / propylene glycol (1-5%) and 1-3% cumene sulfonate or xylene sulfonate hydrotropes present in the glucamide surfactant. The pH is typically 6.8 to 7.4 (NH salt ⁺ ) or 7 to 8.2 (Na ⁺ salt).

Example XI

In any of the above embodiments. Maltamide surfactant in equimolar amounts of fatty acid glucamide surfactant. Or a mixture of glucamide / maltamide surfactants derived from vegetable sugar sources. In the composition, the use of ethanolamide may contribute to the cold stability of the processed formulation. Furthermore. Foam formability is excellent by using a sulfobetaine (alias steine) surfactant.

Example XII A-D

As mentioned above. In particular, the more foam is formed, the more preferable the composition (eg dishwashing) it is preferable not to use the foam suppression at all. The higher fatty acids of C ₁₄ or higher may act as antifoam, so the dishwashing composition contains less than about 5% of C ₁₄ or higher fatty acids. It is preferably to contain less than about 2%, most preferably substantially free of it. therefore. Manufacturers of large foam-forming composition is preferably a polyhydroxy avoid the composition having a fatty acid amide that for introducing the fatty acid as a foam inhibiting amount / avoid or to avoid that during storage C of ₁₄ fatty acids in the final composition is formed Do. One simple method is to prepare polyhydroxy fatty acid amides of the present disclosure using C ₁₂ ester reactants. Fortunately, the use of amine oxides or sulfobetaine surfactants can overcome some of the antifoam effects caused by fatty acids.

Manufacturers wishing to add anionic optical varnishes to liquid detergents containing relatively high concentrations (eg 10% or more) of anionic or polyvalent anionic substituents (e.g. polycarboxylate enhancers) are required to add gloss to water and polyhydroxy fatty acids. It may be useful to premix with amides and then add the premix to the final composition.

Polyglutamic acid or polyaspartic acid dispersants may be usefully used with zeolite based detergents.

Those skilled in the chemistry have made polyhydroxy fatty acid amides of the present disclosure using di- and higher saccharides such as maltose, resulting in polyhydroxys in which the linear substituent Z is capped by the polyhydroxy ring structure. It will be appreciated that fatty acid amides are formed. Such materials have been fully contemplated for use herein and are without departing from the spirit and limitations of the invention as set forth in the specification and claims.

Claims (16)

(a) 5% to 95% by weight of at least one anionic sulfate or sulfonate surfactant (b) general formula At least one polyhydroxy fatty acid amide wherein R ¹ is H. C ₁ -C ₄ hydrocarbyl. 2-hydroxy ethyl. 2-hydroxy propyl or a mixture thereof. R ² is C ₅ -C ₃₁ hydroxy. Hydroxycarbyl, Z is a polyhydroxycarbyl or alkoxylated derivative thereof having a straight chain hydrocarbyl chain in which at least three hydroxyl groups are directly attached to the chain) 5% to 95% by weight and (c) amine oxides: polyetherylene of betaine, sultine, and alkyl phenols. Polypropylene and polybutylene oxide condensates. Alkyl ethoxylate condensation products of aliphatic alcohols and ethylene oxide. Condensation product of hydrophobic base and ethylene oxide formed by the condensation reaction of propylene oxide with propylene glycol. Condensation product of ethylene oxide with a product resulting from the reaction of propylene oxide with ethylenediamine. Nonionic compounds selected from alkylpolysaccharides and fatty acid amides: foam comprising from 5% to 65% by weight of a surfactant mixture comprising from 1% to 20% by weight of a foaming enhancer selected from the group consisting of: and mixtures thereof Detergent composition with improved formation properties The detergent composition of claim 1 in liquid form and comprising 10% to 50% by weight of the surfactant mixture and 90% to 50% by weight of the liquid carrier. The composition of claim 1 wherein Z in the polyhydroxy fatty acid amide is derived from maltose. The monosaccharide of claim 1 wherein Z in the polyhydroxy fatty acid amide. A composition derived from a mixture of disaccharides and higher saccharides, the mixture comprising at least 1% of one or more disaccharides. The 20% to 80% by weight of the surfactant mixture of claim 2, wherein the surfactant mixture is anionic sulfate or sulfonate component. A composition comprising 20% to 80% by weight of a polyhydroxy fatty acid amide component and 2% to 20% by weight of a foaming enhancer. The method of claim 1. A composition further comprising at least one anionic or nonionic surfactant. 7. The foaming enhancer of claim 6 wherein the foaming enhancer is C ₁₀ -C ₁₈ alkyl dimethyl amine oxide. C ₁₀ -C ₁₈ acyl amide alkyl dimethyl amine oxide. Betaine. Sultine aliphatic alcohol ethylene oxide condensation product. Composition selected from alkylpolysaccharides and mixtures thereof. 8. The composition of claim 7, wherein the polyhydroxy fatty acid amide is a compound of the general formula In the above formula R ² is a straight chain C ₁₁ -C ₁₇ altyl or alkenyl group. Z is glucose. Derived from maltose or mixtures thereof. The method of claim 1. Composition substantially free of C ₁₄ or higher higher fatty acids (a) 5% to 95% by weight of at least one anionic sulfate or sulfonate surfactant (b) general formula At least one polyhydroxy fatty acid amide, wherein R ¹ is H. C ₁ -C ₄ hydrocarbyl. 2-hydroxy ethyl. 2-hydroxy propyl or mixtures thereof, R ² is C ₅ -C ₃₁ Z is C ₁₁ -C ₁₇ N-methyl glucamide, C ₁₁ -C ₁₇ N-methyl, which is a polyhydroxyhydrocarbyl having a straight chain hydrocarbyl chain in which at least three hydroxyl groups are directly attached to the chain. Maltamide, a mixture of said glucamide and maltamide or an alkoxylated derivative thereof) 5% to 95% by weight and (c) amine oxides; Betaine; Stein; And polyethylene, polypropylene and polybutylene oxide condensates of alkyl phenols, alkyl ethoxylate condensation products of aliphatic alcohols and ethylene oxide, hydrophobic base and ethylene oxide condensation products formed by condensation of propylene oxide and propylene glycol, propylene 1% to 20% by weight of a foaming enhancer selected from the group consisting of a product resulting from the reaction of the oxide with ethylenediamine and a condensation product of ethylene oxide, an alkylpolysaccharide and a fatty acid amide: and mixtures thereof A method for cleaning contaminated tableware, comprising contacting the dishware with water containing an effective amount of a detergent composition comprising 5% to 65% by weight of the surfactant mixture. The method of claim 10 wherein the Z moiety in the polyhydroxy fatty acid amide is derived from a mixture of monosaccharides, polysaccharides, and polysaccharides that can be obtained from a vegetable source. The method of claim 10 wherein the R ² residues in the polyhydroxy fatty acid amide are C ₁₆ -C ₁₇ alkyl, alkenyl or mixtures thereof. The method of claim 10, wherein the water further contains one or more sulfate or sulfonate cleaning surfactants. The method of claim 10, wherein the composition is substantially free of C ₁₄ or higher higher fatty acids. The composition of claim 4 wherein Z in the polyhydroxy fatty acid amide is derived from a mixture of monosaccharides, disaccharides and higher saccharides, the mixture comprising at least 1% maltose. The composition of claim 2 wherein the carrier is water or a mixture of water and C ₁ -C ₄ alcohols.