CN1061042A - Polyhydroxy fatty acid amide surfactants for enhanced enzyme performance - Google Patents

Abstract

Disclosed is a kind of improvement detergent composition that comprises one or more anion surfactants, nonionogenic tenside or the mixture of the two and detergency enzyme, and its improvement comprises that the structural formula that will improve enzyme performance is

The polyhydroxy fatty acid amide material be added in the described composition R wherein ¹Be H, C ₁-C ₄The combination of alkyl, 2-hydroxyethyl, 2-hydroxypropyl or these groups, R ²Be C ₅-C ₃₁Alkyl, and Z is polyhydroxy alkyl or its alkoxy derivative with straight-chain alkyl chain (having at least 3 hydroxyls directly to link on this chain).

Description

The present invention relates to enzyme-containing detergent compositions and, more importantly, the present invention relates to enzyme-containing detergent compositions containing polyhydroxy fatty acid amide surfactants.

It is common industry practice to add various enzymes to liquid and granular laundry detergents in order to enhance cleaning performance. Most commonly used are proteases, but other enzymes such as amylases, cellulases, lipases, peroxidases, mixtures of these enzymes have also been suggested for this purpose. The literature and standard recipe books contain numerous references to the use of enzymes in fabric laundering compositions.

Since enzymes are biological substances, they are prone to denaturation and inactivation, especially after prolonged contact with other ingredients in formulated detergent compositions. Thus, freshly formulated enzyme-containing detergent compositions often exhibit exceptionally higher cleaning performance than older products that have been stored or placed on the shelf. For manufacturers, the stability of enzyme-containing detergent compositions, especially liquid detergents, is an important consideration, and various enzyme stabilizers have been developed. For example, various boron compounds, formate salts, ethanolamines, and/or various short chain fatty acids are often added to detergent compositions to provide enzyme stability. These stabilizers are commonly used in enzyme-containing liquid detergent compositions.

In addition, enzymes are relatively expensive, and the addition of enzymes to detergent compositions means increased costs for manufacturers, and the increased costs will ultimately be borne by users. Therefore, it would be interesting to improve enzyme performance with relatively inexpensive additives.

With the help of various additives, it is theoretically possible to not only stabilize enzymes from degradation but also to enhance their performance. However, whether it is to stabilize enzymes or improve performance, the basic goal is the same, that is, to fully consider the long-term activity of enzymes from the market point of view-to provide users with detergent compositions with good performance.

There is a constant search for materials for stabilizing or otherwise improving the performance of enzymes in formulated detergent compositions; this is because almost all enzymes are expensive and almost all will lose at least some activity on storage .

Without intending to be bound by theory, it appears that polyhydroxy fatty acid amide surfactants of the type disclosed herein provide a stabilizing and/or performance enhancing effect on the enzyme. It is likely that polyhydroxy fatty acid amides work by removing molecular "debris" produced by enzymes attacking soils, thus allowing enzymes to function more efficiently. Regardless of the mechanism of action, the present invention achieves the ultimate goal of providing robust removal of enzyme-labile soils in fully formulated enzyme-containing detergent compositions, thereby improving overall performance.

In addition to enhancing enzyme performance, polyhydroxy fatty acid amides are excellent detersive surfactants in their own right. Furthermore, surfactants of this type can be obtained mostly or entirely from natural, renewable raw materials and can replace petroleum product-based surfactants in whole or in part without loss of cleaning power.

Various polyhydroxy fatty acid amides have been described in the prior art. For example N-acyl, N-methylglucamide, by J.W.Goodby, M.A.Marcus, E.Chin, and P.L.Finn in "Thermotropic liquid crystal properties of some linear carbohydrate amphiphiles" (Liquid Crystals, 1988, Volume 3, No.11, pp1569-1581) and A. MullerFahrnow, V. Zabel, M. Steifa, and R. Hilgenfeld in "Nonionic detergents: Molecular and crystal structure of nonanoyl-N-methylglucamide "(J.Chem.Soc.Chem.Commun., 1986, pp1573-1574). Recently, the use of N-alkyl polyhydroxyamide surfactants in biochemistry, for example in biofilm breakdown, has been of particular importance, see, for example, the journal article "N-D-glucose-N-methyl-alkanamides" by J.E.K. Hildreth Compound, a novel nonionic detergent for membrane biochemistry" (Biochem. J. (1982), Vol. 207, pp363-366).

The use of N-alkyl glucamides in detergent compositions has also been discussed. U.S. Patent 2,965,576 of E.R.Wilson published on December 20, 1960, and British Patent 809,060 issued to Thomas Hedley & Co., Ltd. published on February 18, 1959, are about containing anionic surfactants detergent compositions and certain amide surfactants, which may include N-methyl glucamide added as a low temperature suds booster. These compounds contain N-acyl groups of higher linear fatty acids having 10-14 carbon atoms. These compositions may also contain auxiliary substances such as alkali metal phosphates, alkali metal silicates, sulfates and carbonates. It is also generally noted that additional components which impart desirable properties to the composition may also be included in the composition, such as fluorescent dyes, bleaching agents, perfumes, and the like.

U.S. Patent 2,703,798, A.M. Schwartz, issued March 8, 1955, relates to aqueous detergent compositions containing condensation products of N-alkylglucamines and aliphatic esters of fatty acids. The reaction product is said to be useful in aqueous detergent compositions without further purification. It is also known to prepare sulfate esters of acylated glucosamines as disclosed in U.S. Patent 2,717,894, A.M. Schwartz, issued September 13, 1955.

PCT International Application WO 83/04412 by J. Hildreth, published December 22, 1983, relates to amphiphilic compounds containing polyhydroxy aliphatic groups which are said to be used for various purposes, including in cosmetics, medicines, shampoos, shampoos, It is used as a surfactant in medicaments and eye ointments, as an emulsifier and formulation agent for solubilizing membranes, whole cells or other tissue samples, and for preparing liposomes in medicine and biochemistry. Included in this disclosure are compounds of the formula R'CON(R) _CH2R " and R"CON(R)R', wherein R is hydrogen or an organic group, R' is an aliphatic hydrocarbon group of at least 3 carbon atoms, R " is the residue of an aldose.

European Patent 0285768, H. Kelkenberg et al., published October 12, 1988, relates to the use of N-polyhydroxyalkyl fatty acid amides as thickeners in aqueous detergent systems. Amides comprising the formula _R1 (CO)N(X) _R2 , wherein _R1 is _C1 - _C17 (preferably _C7 - _C17 ) alkyl, _R2 is hydrogen, _C1 - _C18 (preferably _{C1 -C₆} )alkyl, or alkylene oxide, x is a polyhydroxyalkyl group having 4-7 carbon atoms, such as N-methyl coco fatty acid glucamide. The thickening properties of the amide represent particular utility in liquid surfactant systems containing alkyl sulfonates, although the aqueous surfactant systems may contain other anionic surfactants, e.g., alkylaryl sulfonates, Alkenyl sulfonates, sulfosuccinic acid monoester salts and fatty alcohol ether sulfonates, and nonionic surfactants, such as fatty alcohol polyethylene glycol ethers, alkylphenol polyethylene glycol ethers, fatty acid polyethylene glycol ethers, Glycol esters, polyoxypropylene/polyoxyethylene mixed polymers, etc. Alkyl Sulfonate/N-Methyl Coco Fatty Acid Glucamide/Nonionic Surfactant Shampoo as an example. In addition to thickening properties, N-polyhydroxyalkyl fatty acid amides are said to have super skin tolerance properties.

U.S. Patent 2,982,737 to Boettner, issued May 2, 1961, relates to detergent bars containing urea, sodium lauryl sulfate anionic surfactants, and N-alkylglucamide nonionic surfactants , which is selected from N-methyl-N-sorbityl lauramide and N-methyl-N-sorbityl myristamide.

Other glucamide surfactants are disclosed, for example, in DT 2,226,872, HWEckert et al., published December 20, 1973, on detergent compositions containing one or more surfactants and builder salts _{, builder} salts are selected from polymeric phosphates _, chelating agents and detergent bases, _the composition is obtained by adding N _-acyl polyhydroxyl Alkylamines are improved, wherein R ₁ is C ₁ -C ₃ alkyl, R ₂ is C ₁₀ -C ₂₂ alkyl, and n is 3 or 4. The N-acyl polyhydroxyalkylamines are added as soil suspending agents.

U.S. Patent 3,654,166 issued April 4, 1972 to HWEckert et al. is about comprising at least one surfactant selected from anionic, zwitterionic and nonionic surfactants, and as a fabric softener of the formula R ₁ N (Z) N-acyl, -N-alkyl polyhydroxyalkyl compounds of C(O) _R2 , where _R1 is _C10 - _C22 alkyl, _R2 is _C7 - _C21 alkyl, R ₁ and _R2 have a total of 23-39 carbon atoms, and Z is a polyhydroxyalkyl group which may be _-CH2 (CHOH) _mCH2OH , where m is 3 or 4.

ller等的美国专利4，021，539是关于皮肤治疗化妆品组合物。含有包括式R₁N（R）CH（CHOH）mR₂化合物的N-多羟基烷基胺，式中R₁是H、低级烷基、羟基低级烷基，或氨基烷基，以及杂环氨基烷基，R与R₁相同，但二者不能都是H，R₂是CH₂OH或COOH。HM published May 3, 1977

U.S. Patent 4,021,539 to Iller et al. relates to cosmetic compositions for skin treatment. N-polyhydroxyalkylamines containing compounds of the formula _R1N (R)CH(CHOH) _mR2 , wherein _R1 is H, lower alkyl, hydroxylower alkyl, or aminoalkyl, and heterocyclic amino Alkyl, R is the same as _R1 but both cannot be H, _R2 is _CH2OH or COOH.

French Patent 1,360,018, issued April 26, 1963, assigned to Commercial Solvents Corporation, relates to solutions of formaldehyde stable to polymerization with added amide of the formula RC(O)N(R ₁ )G, where R is Carboxylic acid functionality having at least 7 carbon atoms, _R1 is hydrogen or lower alkyl, and G is a sugar alcohol group having at least 5 carbon atoms.

German Patent 1,261,861 of A. Heins published on February 29, 1968 is about glucosamine derivatives of the formula N(R)(R ₁ )(R ₂ ) for use as wetting and dispersing agents, the formula wherein R is a sugar residue of glucosamine, R ₁ is a C ₁₀ -C ₂₀ alkyl group, and R ₂ is a C ₁ -C ₅ acyl group.

British Patent 745,036, assigned to Atlas Powder Company, published February 15, 1956, relates to heterocyclic amides and their carboxylic acid esters, which are said to be useful as chemical intermediates, emulsifiers, wetting agents, dispersants, detergents, fabric softener, etc. The compound is represented by the formula N(R)(R ₁ )C(O)R ₂ , where R is the residue of dehydrated hexanepentol or its carboxylate, R ₁ is a monovalent hydrocarbon group, -C(O) R ₂ is an acyl group of a carboxylic acid having 2-25 carbon atoms.

U.S. Patent 3,312,627 to DTHooker, issued April 4, 1967, discloses a solid bathroom soap bar that is substantially free of anionic detergent and alkaline builder materials, and lithium soap containing some fatty, nonionic Surfactants selected from certain propylene oxide/ethylenediamine/ethylene oxide condensates, propylene oxide-propylene glycol-ethylene oxide condensates and polyethylene glycols, also containing nonionic foaming groups , which may include polyhydroxy amides of the formula RC(O)NR ¹ (R ² ), where RC(O) contains about 10-14 carbon atoms, and R ¹ and R ² are H or C ₁ -C ₆ Alkyl, the total number of carbon atoms contained in the above-mentioned alkyl group is 2 to about 7, and the total number of hydroxy substituents is 2 to about 6. A substantially similar disclosure is also found in U.S. Patent 3,312,626, DTHooker, issued April 4, 1967.

The present invention provides an improved detergent composition comprising one or more anionic surfactants, nonionic surfactants, or mixtures thereof and a detersive enzyme. Wherein the improvement comprises adding a structural formula whose amount can improve enzyme performance in the described composition is

The polyhydroxy fatty acid amide substance, wherein R ¹ is H, C ₁ -C ₄ hydrocarbyl, 2-hydroxyethyl, 2-hydroxypropyl, or a combination of these groups, R ² is C ₅ -C ₃₁ hydrocarbyl, and Z is a polyhydroxyhydrocarbyl having a straight hydrocarbyl chain (at least 3 hydroxyl groups directly attached to the chain) or an alkoxylated derivative thereof.

The present invention also provides a method for improving the cleaning performance of a detergent composition containing a detersive surfactant, such as an anionic, nonionic or cationic surfactant, especially an anionic surfactant, in the presence of an aqueous medium by adding Add the above-mentioned polyhydroxy fatty acid amide to improve the energy of enzyme performance in the detergent composition.

The present invention further provides a method of cleaning substrates such as fibers, fabrics, hard surfaces, skin, etc., by reacting said substrate with a detergent comprising one or more anionic, nonionic or cationic and detersive enzymes A composition is contacted, wherein said composition contains a polyhydroxy fatty acid amide surfactant that enhances the energy of the enzyme.

Polyhydroxy fatty acid amide surfactant

The detergent compositions herein contain "enzyme energy enhancing" polyhydroxy fatty acid amides. "Enhancing enzyme performance" means that the formulator of the composition can select the amount of polyhydroxy fatty acid amide added to the composition to enhance the enzymatic cleaning performance of the detergent composition. Typically, for detergents containing normal amounts of enzymes, the addition of about 1% by weight of polyhydroxy fatty acid amides improves enzyme performance.

The detergent compositions herein generally comprise at least about 1% by weight of polyhydroxy fatty acid amide surfactant, preferably at least about 3%, more preferably comprise from about 3% to about 50%, most preferably about 3% - about 30% polyhydroxy fatty acid amides.

The polyhydroxy fatty acid amide surfactant composition of the present invention comprises structural formula as

The compound, wherein: R ¹ is H, C ₁ -C ₄ hydrocarbyl, 2-hydroxyethyl, 2-hydroxypropyl, or a combination of these groups, preferably C ₁ -C ₄ alkyl, more preferably is C ₁ or C ₂ alkyl, most preferably C ₁ alkyl (i.e. methyl); R ² is C ₅ -C ₃₁ hydrocarbon, preferably straight chain C ₇ -C ₁₉ alkyl or alkenyl, more is preferably a straight chain C ₉ -C ₁₇ alkyl or alkenyl group, most preferably a straight chain C ₁₁ -C ₁₅ alkyl or alkenyl group, or a combination of these groups; and Z is a poly Hydroxyhydrocarbyl (at least 3 hydroxyl groups directly attached to the chain) or their alkoxylated derivatives (preferably ethoxylated or propoxylated derivatives). Z is preferably derived from a reducing sugar by reductive amination; more preferably, Z is a glycityl. Suitable reducing sugars include glucose, fructose, maltose, lactose, galactose, mannose and xylose. As raw materials, in addition to using the individual sugars listed above, high dextrose corn syrup, high fructose corn syrup, and high maltose corn syrup can be used. These corn syrups can produce mixed sugar ingredients for Z. It should be understood that there is no intention to exclude other suitable starting materials. Z is preferably selected from the group _-CH2- (CHOH)n- _CH2OH , -CH( _CH2OH )-(CHOH) _{n-1- CH2OH} , _-CH2- (CHOH) ₂ (CHOR' )(CHOH) _-CH2OH and alkoxylated derivatives thereof, wherein n is an integer from 3 to 5 inclusive, and R' is H or a cyclic or aliphatic monosaccharide. Most preferred are glycityls wherein n is 4, especially _-CH2- (CHOH) ₄ - _CH2OH .

In the formula (I), R' can be, for example, N-methyl, N-ethyl, N-propyl, N-isopropyl, N-butyl, N-2-hydroxyethyl or N-2 - Hydroxypropyl.

R ² -CO-N< can be, for example, cocoamide, stearamide, oleamide, laurylamide, lactamide, capricamide, palmitamide, tallowamide, and the like.

Z can be 1-deoxyglucosyl, 2-deoxyfructosyl, 1-deoxymaltosyl, 1-deoxylactosyl, 1-deoxygalactosyl, 1-deoxymannosyl, 1-deoxymaltotriosyl, etc. .

Methods of preparing polyhydroxy fatty acid amides are known in the art. In general, they can be prepared by reacting an alkylamine with a reducing sugar in a reductive amination reaction to give the corresponding N-alkylpolyhydroxylamine, followed by reacting the N-alkylpolyhydroxylamine in a condensation/amidation step. Reaction with fatty esters or triglycerides yields N-alkyl, N-polyhydroxy fatty acid amide products. Methods for preparing polyhydroxy fatty acid amide-containing compositions are disclosed, for example, in British Patent Specification 809,060 of Thomas Hedley & Co., Ltd., published February 18, 1959; issued December 20, 1960, to E.R. Wilson In U.S. Patent 2,965,576 issued on March 8, 1955 to Anthony M. Schwartz in U.S. Patent 2,703,798 and in U.S. Patent 1,985,424 issued to Piggott on December 25, 1934, All of these patents are incorporated herein by reference.

In a method of preparing N-alkyl or N-hydroxyalkyl, N-deoxyglycosyl fatty acid amides, wherein the glycosyl component is derived from glucose and the N-alkyl or N-hydroxyalkyl functional group is N-form base, N-ethyl, N-propyl, N-butyl, N-hydroxyethyl or N-hydroxypropyl, the product is obtained by making N-alkyl or N-hydroxyalkyl-glucose in the presence of a catalyst Prepared by reacting amines with fatty esters selected from fatty methyl esters, fatty ethyl esters and fatty triglycerides. Above-mentioned catalyst is selected from 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, potassium sodium tartrate, trisodium citrate, tripotassium citrate, basic sodium silicate, basic potassium silicate, basic sodium aluminosilicate, and basic potassium aluminosilicate and mixtures thereof. The amount of catalyst used is preferably from about 0.5 mole percent to about 50 mole percent, calculated on a mole basis of N-alkyl or N-hydroxyalkyl-glucamine. More preferably from about 2.0 mole% to about 10 mole%. Preferably, the reaction is carried out at a temperature of from about 138°C to about 170°C, generally for about 20 to about 90 minutes. When triglycerides are used as the source of fatty esters, the reaction is also preferably carried out using about 1 to about 10% by weight of a phase transfer agent (calculated as a percentage of the total weight of the reaction mixture) selected from saturated Fatty alcohol polyethoxylates, alkyl polyglycosides, linear sugar amide surfactants and mixtures thereof.

Preferably, the method is carried out in the following steps:

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

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

(c) mixing the catalyst into the reaction mixture; and

(d) Stir for the specified time.

Also preferably, when the fatty ester is a triglyceride, about 2% to about 20% by weight of the reactants of a pre-formed linear N-alkyl/N-hydroxyalkyl, N-straight Alkyl glucosyl fatty acid amides as phase transfer reagents. This activates the reaction, which increases the rate of the reaction. The detailed experimental procedure is given below.

The polyhydroxy fatty acid amide materials used herein also offer advantages to detergent manufacturers in that these polyhydroxy fatty acid amide materials can be produced in whole or in part from natural, renewable, non-petrochemical sources and are capable of degrading. They also show lower toxicity to aquatic life.

It should be recognized that the processes used to produce the polyhydroxy fatty acid amides of formula (I) generally also produce certain amounts of non-volatile by-products, such as ester amides and cyclic polyhydroxy fatty acid amides, along with the production of these amides. The amount of these by-products will vary with the particular reactants and reaction conditions. Preferably, the polyhydroxy fatty acid amide added to the detergent compositions herein is provided in such a form that the detergent-added polyhydroxy fatty acid amide composition comprises less than about 10%, preferably less than about 4% cyclic polyhydroxy fatty acid amides. The preferred methods described above have the advantage that they produce relatively small amounts of by-products.

enzyme

Detergent enzymes are included in detergent formulations for a variety of purposes including, for example, the removal of protein-type, carbohydrate-type or triglyceride-type soils and prevention of color cross contamination. Enzymes to be added include proteases, amylases, lipases, cellulases and peroxidases and mixtures of these enzymes, and may also include other types of enzymes. They may be of any suitable origin, such as of vegetable, animal, bacterial, fungal and yeast origin. However, the choice of enzyme depends on several factors, such as pH-activity and/or stability optima, thermostability, stability with active detergents, builders, etc. In this regard, bacterial or fungal enzymes are preferred, such as bacterial amylases and proteases, and fungal cellulases.

Enzyme is usually added in an amount sufficient to provide up to about 5 mg by weight per gram of composition, more typically from about 0.05 mg to about 3 mg of active enzyme.

Suitable examples of proteases are subtilisins, which are obtained from particular strains B. subtilis and B. licheniforms. Another suitable protease is obtained from a Bacillus strain having maximum activity throughout the pH range of 8-12, developed and sold by Novo Industries A/S under the registered trade name ESPERASE. British Patent Specification No. 1,243,784 to Novo describes the preparation of this and similar enzymes. Proteases suitable for removing proteinaceous type soils are commercially available and include enzymes sold under the trade names ALCALASE and SAVINASE by Novo Industries A/S (Denmark) and under the trade name MAXATASE by International Bioproducts (Netherlands) enzymes.

With respect to the class of proteases, especially for liquid detergent compositions, the enzymes are referred to herein as Protease A and Protease B. Protease A and methods for its preparation are described in European Patent Application 130,756, published January 9, 1985, incorporated herein by reference. Protease B is a protease different from Protease A by substituting leucine for tyrosine at position 217 of its amino acid sequence. Protease B is described in European Patent Application Serial No. 87303761.8 filed April 28, 1987, which is hereby incorporated by reference. The preparation of Protease B is also disclosed in European Patent Application 130,756, Bott et al., published January 9, 1985, incorporated herein by reference.

Amylases include, for example, the alpha-amylases obtained from a particular strain of B. licheniforms which are described in more detail in British Patent Specification No. 1,296,839 (Novo), incorporated herein by reference. . Amylolytic proteins include, for example, RAPIDASE (Biologics International) and TERMAMYL (Novo Industries).

Cellulases useful in the present invention include bacterial or fungal cellulases. Preferably, the optimum pH of these cellulases is between 5 and 9.5. Suitable cellulases are disclosed in U.S. Patent 4,435,307 (Barbesgoard et al.), which was incorporated herein by reference, issued March 6, 1984, which discloses fungal cellulase from Humicola insolens . Suitable cellulases are also disclosed in GB-A-2,075,028; GB-A-2,095,275 and DE-OS-2,247,832.

Examples of such cellulases are cellulases produced from Humicola insolens (Humicola grisea Var. thermoidea) strains, in particular Humicola strain DSM1800; Cellulase produced by fungi; and Cellulase extracted from the hepatic pancreas of aquatic molluscs (Dolabella Auricula Solander).

Suitable lipases for use in detergents include those produced by microorganisms of the Pseudomonas group, such as Pseudomonas Stutzeri ATCC 19.154 disclosed in British Patent 1,372,034, which is hereby cited as references. Suitable lipases include those enzymes produced by microorganisms of the genus Pseudomonas fluorescens IAM 1057 that show positive immunological cross-reactivity to lipase antibodies. This lipase and its purification method are described in Japanese Patent Application No. 53-20487, laid open to the public on February 24, 1978. This lipase is available from Amano Pharmaceutical Co. Ltd. of Nagoya, Japan under the trade name Lipase P "Amano", hereinafter referred to as "Amano-P". The enzymes of the invention should show positive immunological cross-reactivity to the Amano-P antibody, as determined by the standard and well known immunodiffusion method of Ouchterlony (Acta. Med. Scan., 133, p. 76-79 (1950)). These lipases and their methods of immunological cross-reactivity with Amano-P are also described in U.S. Patent 4,707,291, Thom et al., issued November 17, 1987, incorporated herein by reference. Typical examples of these enzymes are Amano-P lipase; lipase ex Pseudomonas fragi FERM P 1339 (available under the trade name Amano-B); lipase ex Psuedomonas nitroreducens var. lipolyticum FERM P 1338 (available under the trade name Amano-CES); Lipase ex Chromobacter viscosum, such as Chromobacter viscosum var. lipolyticum NRRLB 3673, commercially available from Toyo Jozo Co. of Tagata, Japan; and Chromobacter viscosum lipases from U.S. Biochemical Corp. of the United States and Disoynth Co. of the Netherlands, and Lipase ex Pseudomonas gladioli.

Peroxidase is used in combination with an oxygen source such as percarbonate, perborate, persulfate, hydrogen peroxide, etc. They are used for "solution bleaching", i.e. preventing the transfer of dyes or pigments that have been removed from a substrate during washing to other substrates in the wash solution. Peroxidases are known in the art and include, for example, horseradish peroxidase, ligninase and haloperoxidases such as chloro- and bromo-peroxidases. For example, peroxidase-containing detergent compositions are disclosed in PCT International Application WO89/099813 (O. Kirk, published October 19, 1989), assigned to Novo Industries A/S, which is hereby incorporated by reference literature.

Enzyme materials and methods for their incorporation into synthetic detergent granules are also disclosed in U.S. Patent 3,553,139, issued January 5, 1971 to McCarty et al. (incorporated herein by reference). Enzymes are also disclosed in U.S. Patent 4,101,457, Place et al., issued July 18, 1978, and U.S. Patent 4,507,219, Hughes, issued March 26, 1985, both of which are incorporated herein by reference. Enzyme materials useful in liquid detergent formulations and methods for their incorporation into formulations are disclosed in Hora et al., U.S. Patent 4,261,868, issued April 14, 1981, which is also incorporated herein by reference.

For granular detergents, the enzymes are preferably coated or granulated with auxiliaries which are inert to the enzymes to minimize dust formation and improve storage stability. These techniques are well known in the art. In liquid formulations, enzyme stabilization systems are preferably employed. Enzyme stabilization techniques for aqueous liquid detergent compositions are also well known in the literature. For example, one of the enzyme stabilization techniques in aqueous solution is the use of free calcium ions derived from calcium acetate, calcium formate and calcium propionate. Calcium ions may be used in combination with short chain carboxylates, preferably formate. See, for example, U.S. Patent 4,318,818 (published March 9, 1982) to Letton et al, incorporated herein by reference. It has also been proposed to use polyols like glycerol and sorbitol. Alkoxy alcohols, dialkyl glyceryl ethers, mixtures of polyols with polyfunctional fatty amines (such as diethanolamine, triethanolamine, diisopropanolamine, etc.) and boric acid or alkali metal borates. Other enzyme stabilization techniques and examples are in Horn et al. U.S. Patent 4,261,868 (published April 14, 1981), Gedge et al. U.S. Patent 3,600,319 (published August 17, 1971), both of which are cited here as references, and in European Patent Application Venegas, published October 29, 1986 (publication number 0199405, application number 86200586.5). Non-boric acid and borate stabilizers are preferred. U.S. Patent Nos. 4,261,868: 3,600,319 and 3,519,570 also describe enzyme stabilization systems.

To aid detersive performance, the compositions herein may contain other detersive surfactants in addition to the polyhydroxy fatty acid amides. The particular surfactant employed can vary widely, using any detersive surfactant desired for the particular end use. The most common ones are enzymatic detergents, which are used to wash clothes, textiles, fibers, hard surfaces, and more. Suitable surfactants include anionic, nonionic, cationic and other surfactants, which are exemplified below. Preferably, the composition includes one or more anionic surfactants, one or more other nonionic surfactants, or mixtures thereof. It is particularly pointed to the advantage of the present invention that the compositions contain surfactants or other ingredients which are harsh to enzymes. Typically they include, but are not limited to, anionic surfactants such as alkyl ester sulfonates, linear alkylbenzene sulfonates, alkyl sulfates, and the like. Generally, detersive surfactants are added in amounts of from about 3% to about 40% by weight of the detergent compositions, preferably from about 5% to about 30% by weight. Suitable surfactants are described below.

anionic surfactant

One type of anionic surfactant that can be used includes alkyl ester sulfonates. They are desirable because they can be produced from renewable, non-petroleum feedstocks. Alkyl ester sulfonate surfactant components can be prepared according to methods disclosed in the technical literature. For example, according to "The Journal of the American Oil Chemists Society", 52 (1975), pp. 323-329, linear esters of _C8 - _C20 carboxylic acids can be sulfonated with gaseous _SO3 . Suitable starting materials include natural fatty materials derived from tallow, palm oil and coconut oil, among others.

Preferred alkyl ester sulfonate surfactants, especially for laundry use, include those of the formula

Alkyl ester sulfonate surface detergents, wherein R ³ is a C ₈ -C ₂₀ hydrocarbon group, preferably an alkyl group, or a combination of these groups: R ⁴ is a C ₁ -C ₆ hydrocarbon group, preferably an alkyl group, or these groups combination of groups; and M is a cation that forms a soluble salt. Suitable salts include metal salts such as sodium, potassium and lithium; substituted or unsubstituted ammonium salts such as methyl, dimethyl, trimethyl and quaternary ammonium cations (e.g. tetramethyl and dimethylpiperidinium) , and salts formed from cations derived from alkanolamines such as monoethanolamine, diethanolamine, and triethanolamine. Preferably, R ³ is C ₁₀ -C ₁₆ alkyl and R ⁴ is methyl, ethyl or isopropyl. Particularly preferred are methyl ester sulfonates, wherein R ³ is C ₁₄ -C ₁₆ alkyl.

Alkyl sulfate surfactants are another anionic surfactant that finds important use herein. When water-soluble salts or acids of the formula ROSO ₃ M are used in combination with polyhydroxy fatty acid amides, in addition to providing excellent overall detergency, including good detergency over a wide range of temperatures, wash concentrations and wash times /Oil ability, can also dissolve alkyl sulfates, and improve the formulation ability of liquid detergent formulations. In the structural formula ROSO ₃ M, R is a C ₁₀ -C ₂₄ hydrocarbon group, preferably an alkyl group or a hydroxyalkyl group with a C ₁₀ -C ₂₀ alkyl component, more preferably a C ₁₂ -C ₁₈ alkyl group or a hydroxyalkyl group and M is H or a cation, for example, an alkali metal cation (such as sodium, potassium, lithium), a substituted or unsubstituted ammonium cation, such as methyl, dimethyl and trimethyl ammonium ions, and a quaternary ammonium cation (such as tetra methylammonium and dimethylpiperidinium), cations derived from alkanolamines such as ethanolamine, diethanolamine, triethanolamine, combinations of these ions, etc. Generally, _C12 - _C16 alkyl chains are suitable for lower wash temperatures (for example, below about 50°C) and _C16 - _C18 alkyl chains are suitable for higher wash temperatures (for example, above about 50°C).

Alkyl alkoxylated sulfate surfactants are another class of useful anionic surfactants. These surfactants are water-soluble salts or acids having the formula RO(A)mSO ₃ M, where R is an unsubstituted C ₁₀ -C ₂₄ alkyl or hydroxyalkyl with a C ₁₀ -C ₂₄ alkyl component, Preferably C ₁₂ -C ₂₀ alkyl or hydroxyalkyl, more preferably C ₁₂ -C ₁₈ alkyl or hydroxyalkyl; A is an ethoxy or propoxy unit, m is greater than zero, preferably from about 0.5 to about 6 , more preferably from about 0.5 to about 3: M is H or a cation, for example, may be a metal ion (such as sodium, potassium, lithium, calcium, magnesium, etc.), ammonium or a substituted ammonium cation. Alkyl ethoxylated sulfates as well as alkyl propoxylated sulfates are contemplated herein. Specific examples of substituted ammonium cations include methyl, dimethyl, trimethylammonium, and quaternary ammonium cations such as tetramethyl and dimethylpiperidinium, derived from alkanolamines such as monoethanolamine, diethanolamine, and triethanolamine. cations, and combinations of these ions. Typical surfactants are C ₁₂ -C ₁₈ alkyl polyethoxy (1.0) sulfate, C ₁₂ -C ₁₈ alkyl polyethoxy (2.25) sulfate, C ₁₂ -C ₁₈ alkyl polyethoxy base (3.0) sulfate and C ₁₂ -C ₁₈ alkyl polyethoxy (4.0) sulfate, wherein M is conveniently selected from sodium and potassium.

Other anionic surfactants

Other anionic surface detergents useful for cleaning purposes may also be included in the compositions herein. These surfactants include soap salts (for example, salts including sodium, potassium, ammonium and substituted ammonium salts such as mono-, di- and triethanolamine), C ₉ -C ₂₀ linear alkylbenzene sulfonates, C ₈ -C ₂₂ Primary or secondary alkane sulfonates, _C8 - _C24 alkene sulfonates, sulfonated polycarboxylic acids obtained by sulfonating pyrolysis products of alkaline earth metal citrates (for example, as in British Patent Specification No. 1,082 , 179), alkyl glycerol sulfonates, fatty acyl glycerol sulfonates, fatty oleoyl glycerol sulfonates, alkylphenol oxide ethylene ether sulfates, paraffin sulfonates, alkyl phosphates, hydroxyl Ethylates such as acyl isethionates, N-acyl taurates, fatty acid amides of methyl taurine, alkyl succinamates and thiosuccinates, thiosuccinate monoesters (especially Sulfuric acid of saturated and unsaturated C ₁₂ -C ₁₈ monoesters) and sulfosuccinic acid diesters (especially saturated and unsaturated C ₆ -C ₁₄ diesters), N-acyl glycinates, alkyl polysaccharides Salts such as sulfates of alkyl polyglucosides (non-ionic and non-sulfated compounds are described below), branched primary alkyl sulfates, alkyl polyethoxy carboxylates such as RO (CH ₂ CH ₂ O) Those salts of kCH ₂ COO ^- M ⁺ (wherein R is a C ₈ -C ₂₂ alkyl group, K is an integer from 0 to 10, and M is a cation that forms a water-soluble salt), and esterified with isethionate and oxidized with hydroxide Sodium neutralized fatty acids. Resin acids and hydrogenated resin acids are also suitable, such as rosin present in or derived from tall oil, hydrogenated rosin, and resin acids and hydrogenated resin acids. Additional examples are described in "Surface Active Agents and Detergents" (Vol. I & II, by Schwartz, perry & Berch). U.S. Patent 3,929,678 to Laughlin et al., issued December 30, 1975, also generally discloses many such surfactants at column 23, line 58 through column 29, line 23 (this patent is incorporated herein by reference).

Nonionic Detergent Surfactants

Suitable nonionic detergent surfactants are generally disclosed in U.S. Patent 3,929,678 to Laughlin et al., issued December 30, 1975, at column 13, line 14 through column 16, line 6, which patent is incorporated herein by reference. Typical, non-limiting classes of useful nonionic surfactants are listed below.

1. Polyethylene oxide, polypropylene oxide and polybutylene oxide condensates of alkylphenols. In general, polyethylene oxide condensates are preferred. These compounds include the condensation products of alkylphenols with alkylene oxides having alkyl groups having from about 6 to about 12 carbon atoms in a straight or branched configuration. In a preferred embodiment, the ethylene oxide is present in an amount from about 5 to about 25 moles of ethylene oxide per mole of alkylphenol. Commercially available nonionic surfactants of this type include IGEPAL CO-630 sold by GAF, and TRITON X-45, X-114, X-100 and X-102 sold by Rohm & Haas. These compounds are commonly referred to as alkylphenol alkoxylates (eg, alkylphenol ethoxylates).

2. Condensates of fatty alcohols with from about 1 to about 25 moles of ethylene oxide. The alkyl chain of the fatty alcohol can be straight or branched, primary or secondary, and generally contains from about 8 to about 22 carbon atoms. Particularly preferred are the condensation products of alcohols, often having an alkyl group of from about 10 to about 20 carbon atoms, with from about 2 to about 18 moles of ethylene oxide per mole of alcohol. Examples of commercially available nonionic surfactants of this type include TERGITOL 15-S-9 (condensation product of C ₁₁ -C ₁₅ linear secondary alcohols with 9 moles of ethylene oxide), TERGITOL 24-L-6NMW ( Condensation product of C ₁₂ -C ₁₄ primary alcohol with 6 moles of ethylene oxide with narrow molecular weight distribution), both of which are sold by Union Carbide: NEODOL 45-9 (C ₁₄ -C ₁₅ linear alcohol with 9 moles of cyclic Condensation product of ethylene oxide), NEODOL 23-6.5 (condensation product of C ₁₂ -C ₁₃ linear alcohol with 6.5 moles of ethylene oxide). NEODOL 45-7 (condensation product of C ₁₄ -C ₁₅ linear alcohol with 7 moles of ethylene oxide). NEODOL 45-4 (condensation product of a C ₁₄ -C ₁₅ linear alcohol with 4 moles of ethylene oxide), both sold by Shell Chemical Company; and KYRO EOB (C ₁₃ -C ₁₅ condensation product of alcohol with 9 moles of ethylene oxide). Nonionic surfactants of this type are often referred to as "alkyl ethoxylates".

3. Condensation product of ethylene oxide and hydrophobic base (condensed from propylene oxide and propylene glycol). The hydrophobic portion of these compounds preferably has a molecular weight of from about 1500 to about 1800 and exhibits water insolubility. The addition of a polyoxyethylene moiety to this hydrophobic moiety will increase the water solubility of the entire molecule, and the liquid properties of the product will remain at a level corresponding to about 50% of the total weight of the polyoxyethylene component of the condensation product, which corresponds to condensation of up to about 40 molar of ethylene oxide. Examples of compounds of this type include certain of the commercially available PLURONIC surfactants sold by BASF.

4. Condensation products of ethylene oxide with the product resulting from the reaction of propylene oxide and ethylenediamine. The hydrophobic portion of these products consists of the reaction product of ethylenediamine and excess propylene oxide and generally has a molecular weight of from about 2500 to about 3000. The hydrophobic moiety is condensed with ethylene oxide to such an extent that the condensation product contains from about 40% to about 80% by weight polyoxyethylene and has a molecular weight of from about 5,000 to about 11,000. Examples of nonionic surfactants of this type include certain of the commercially available TETRONIC compounds sold by BASF.

5. Semi-polar nonionic surfactants are a special class of nonionic surfactants, which include water-soluble amine oxides containing a part of an alkyl group of about 10 to about 18 carbon atoms and two parts selected from the group consisting of Alkyl and hydroxyalkyl groups of about 1 to about 3 carbon atoms; water-soluble phosphine oxides containing a moiety of alkyl groups of about 10 to about 18 carbon atoms and two moieties selected from the group consisting of about 1 to about Alkyl and hydroxyalkyl groups of 3 carbon atoms; and water-soluble sulfoxides containing a portion of alkyl groups of about 10 to about 18 carbon atoms and a portion selected from the group consisting of about 1 to about 3 carbon atoms Alkyl and hydroxyalkyl groups.

Semi-polar nonionic detergent surfactants include the structural formula

Amine oxide surfactants, wherein R ³ is an alkyl group, hydroxyalkyl group, alkylphenyl group or a combination of these groups containing about 8 to about 22 carbon atoms; R ⁴ is a group containing about 2 to about 3 carbon atoms Atoms of alkylene or hydroxyalkylene or combinations of these groups; x is from 0 to about 3; and each ^R is an alkyl or hydroxyalkyl group containing about 1 to about 3 carbon atoms or containing about 1 to about 3 polyethylene oxide groups of oxirane groups. The ^R5 groups may be linked to each other, for example via an oxygen or nitrogen atom, thereby forming a ring structure.

These amine oxide surfactants include in particular C ₁₀ -C ₁₈ alkyl dimethyl amine oxides and C ₈ -C ₁₂ alkoxyethyl dihydroxyethyl amine oxides.

6. Alkyl polysaccharides disclosed in Llenado's U.S. Patent 4,565,647 (published on January 21, 1986), with about 6 to about 30 carbon atoms, preferably about 10 to about 16 carbon atoms and polysaccharides (e.g. polyglycosides), and hydrophilic groups containing about 1.3 to about 10, preferably about 1.3 to about 3, most preferably about 1.3 to about 2.7 saccharide units. Any reducing sugar containing 5 or 6 carbon atoms can be used, for example, glucose, galactose and galactosyl moieties can be substituted for the glucosyl moiety. (Hydrophobic groups are arbitrarily attached to the 2-, 3-, 4-, etc. positions so that glucose or galactose is on the other side of the glucoside or galactose.) For example, the chemical bond between saccharides can be in the latter Between one position of the saccharide unit and the 2-, 3-, 4- and/or 6-position of the preceding saccharide unit.

Optionally, but not necessarily, polyalkylene oxide chains may be embedded in the hydrophobic portion and the polysaccharide portion. A preferred alkylene oxide is ethylene oxide. Typical hydrophobic groups include saturated or unsaturated, branched or unbranched alkyl groups having from about 8 to about 18, preferably from about 10 to about 16 carbon atoms. Preferred alkyl groups are straight chain saturated alkyl groups. The alkyl group may contain up to 3 hydroxyl groups and/or the polyalkylene oxide chain may contain up to 10, preferably less than 5 alkylene oxide units. Suitable alkyl polysaccharides are octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl and octadecyl, di-, tri-, tetra-, penta-, and hexa-glucosides, galactosides, lactosides, glucose, fructosides, fructose, and/or galactose. Suitable mixtures include coconut alkyl di, tri, tetra and pentaglucosides and tallow alkyl tetra, penta and hexaglucosides.

Preferred alkyl polyglycosides have the formula

^R2O ( _CnH2nO )t(glycosyl) _x

Wherein ^R is selected from alkyl, alkylphenyl, hydroxyalkyl, hydroxyalkylphenyl or a combination of these groups, wherein the alkyl group contains about 10 to about 18, preferably about 12 to about 14 carbon atoms; n is 2 or 3, preferably 2; t is from 0 to about 10, preferably 0; x is from about 1.3 to about 10, preferably from about 1.3 to about 3, most preferably from about 1.3 to about 2.7. The glycosyl is preferably derived from glucose. To prepare these compounds, alcohols or alkylpolyethoxylated alcohols are first prepared and then reacted with glucose or a source of glucose to obtain glucosides (attached at the 1-position). A subsequent glycosyl unit may have its 1-position attached to the 2-, 3-, 4- and/or 6-position of the preceding glycosyl unit, preferably mostly at the 2-position.

7. Has a structural formula

Fatty acid amide surfactants, wherein R ⁶ is an alkyl group containing about 7 to about 21 (preferably about 9 to about 17) carbon atoms, each R ⁷ is selected from hydrogen, C ₁ -C ₄ alkyl, C ₁ -C ₄ hydroxyalkyl and -(C ₂ H ₄ O)xH wherein x varies from about 1 to about 3.

Preferred amides are C ₈ -C ₂₀ aminoamides, monoethanolamides, diethanolamides and isopropanolamides.

cationic surfactant

Cationic detersive surfactants can also be included in the detergent compositions of the present invention. Cationic surfactants include ammonium ionic surfactants such as alkyldimethylammonium halides, which have the formula:

[ ^R2 ( ^OR3 )y][ ^R4 ( ^OR3 )y] _2R5N ⁺ X ^- where ^R2 is an alkyl or alkylbenzyl having ^from about 8 to about 18 carbon atoms in the alkyl chain group; each R ³ is selected from -CH ₂ CH ₂ -, -CH ₂ CH(CH ₃ )-, -CH ₂ CH(CH ₂ OH)-, -CH ₂ CH ₂ CH ₂ - and combinations of these groups : Each R ⁴ is selected from C ₁ -C ₄ alkyl, C ₁ -C ₄ hydroxyalkyl, benzyl, a ring structure formed by two R ⁴ groups joined together, -CH ₂ CHOH-CHO HCOR ⁶ CHOHCH ₂ OH (wherein R ⁶ is any hexose sugar or a hexose sugar polymer with molecular weight less than about 1000), and when y is not 0 is selected from hydrogen; R ⁵ is the same as R ⁴ or an alkyl chain, wherein R ² plus The total number of carbon atoms on ^R is not greater than about 18; each y is from 0 to about 10, and the sum of the y values is from 0 to about 15; and x is any compatible anion.

U.S. Patent 4,228,044, Cambre, issued October 14, 1980, incorporated herein by reference, also describes other cationic surfactants useful herein.

other surfactants

Amphoteric surfactants can be added to the detergent compositions herein. These surfactants can be broadly described as aliphatic derivatives of secondary or tertiary amines, or aliphatic derivatives of heterocyclic secondary and tertiary amines, where the aliphatic substituents may be straight chain or branched. One of the aliphatic substituents contains at least about 8 carbon atoms, generally from about 8 to about 18 carbon atoms, and at least one of the substituents contains an anionic water-solubilizing group, such as carboxy, sulfonate, sulfate groups. See column 19, lines 18-35 of U.S. Patent 3,929,678, Laughlin et al., issued December 30, 1975, incorporated herein by reference, for examples of amphoteric surfactants.

Zwitterionic surfactants can also be incorporated into the detergent compositions herein. These surfactants can be broadly described as derivatives of secondary and tertiary amines, derivatives of heterocyclic secondary and tertiary amines, or derivatives of quaternary ammonium, quaternary phosphonium or tertiary sulfonium compounds. See column 19, line 38 through column 22, line 48 of U.S. Patent 3,929,678, Laughlin et al., issued December 30, 1975, incorporated herein by reference, for zwitterionic surfactants.

Amphoteric and zwitterionic surfactants are often used in combination with one or more anionic and/or nonionic surfactants.

In order to aid or enhance cleaning performance, treat substrates to be washed, or improve the aesthetic properties of detergent compositions or to improve, the detergents herein include, in addition to enzymes, polyhydroxy fatty acid amides and any detersive surfactants, one or more other detergent additive substances or other substances (e.g. fragrances, colorants, dyes, etc.).

builder

To assist in controlling mineral hardness, the compositions herein can optionally include detergent builders. Inorganic and organic builders can be used.

The amount of builder used can vary widely depending on the end use of the composition and its desired physical form. The compositions, if used, generally include at least about 1% of builder. Liquid formulations generally comprise from about 5% to about 50%, more typically from about 5% to about 30%, by weight, of detergent builder. Granular formulations generally comprise from about 10% to about 80%, more typically from about 15% to about 50%, by weight, of detergent builder. However, this does not mean that lower or higher levels of builder are excluded.

Inorganic detergency builders include, but are not limited to, alkali metal, ammonium and alkanolammonium polyphosphates (such as tripolyphosphates, pyrophosphates and glassy polymeric metaphosphates), phosphates, Phytates, carbonates (including bicarbonates and sesquicarbonates), sulfates and aluminosilicates. Both borate builders and builders containing borate-forming substances which produce borate under detergent storage or wash conditions can be used, both of which are hereinafter collectively referred to as "borate builders". lotion". For use at wash conditions below about 50°C, especially below about 40°C, the compositions of the present invention preferably employ non-borate builders.

Examples of silicate builders are alkali metal silicates, especially alkali metal silicates and multilayer silicates having a _SiO2 : _Na2O ratio of 1.6:1 to 3.2:1, as incorporated herein by reference. The multilayer sodium silicates described in U.S. Patent 4,664,839 issued May 12, 1987 to HP Rieck. However, other silicates can also be used, such as magnesium silicate, which can be used as curling agents for granular formulations, stabilizers for oxygen bleaches, and as a component of suds control systems.

Examples of carbonate builders are alkaline earth metal and alkali metal carbonates, including sodium carbonate and sodium sesquicarbonate containing ultrafine calcium carbonate and mixtures thereof, described in German Patent Application No. 2,321,001 (November 1973 published on May 15), the contents of which are incorporated herein by reference.

Aluminosilicate builders are especially useful herein. Aluminosilicate builders are of great importance in currently marketed heavy duty granular detergent compositions and are also an effective builder ingredient in liquid detergent formulations. Aluminosilicate builders include materials having the empirical formula:

Mz (zAlO ₂ ySiO ₂ )

wherein M _is sodium, potassium, ammonium, or substituted ammonium, Z is from about 0.5 to about 2; y is 1; and the material has a magnesium ion exchange capacity of at least about 50 milliequivalents of CaCO hardness per gram of anhydrous aluminosilicate . Preferred aluminosilicates are those of the formula:

Naz [(AlO ₂ ) _z (SiO ₂ ) y]·xH ₂ O

The zeolite filter aid of , wherein z and y are integers of at least 6, the molar ratio of z to y is in the range of 1.0 to about 0.5, and x is an integer of about 15 to about 264.

Useful aluminosilicate ion exchange materials are commercially available. These aluminosilicates are crystalline or amorphous in structure and may be naturally occurring aluminosilicates or synthetically derived. Methods for preparing aluminosilicate ion exchange materials are disclosed in U.S. Patent 3,985,669, Krummel et al., issued October 12, 1976, which is incorporated herein by reference. Preferred synthetic crystalline aluminosilicate ion exchange materials for use herein are available under the designations Zeolite A, Zeolite P(B) and Zeolite X. In particularly preferred embodiments, the crystalline aluminosilicate ion exchange materials have the following general formula:

Na ₁₂ [(AlO ₂ ) ₁₂ (SiO ₂ ) ₁₂ ]·xH ₂ O

wherein x is from about 20 to about 30, especially about 27. This substance is called ZeoliteA. Preferably, the aluminosilicate has a particle size of about 0.1-10 microns in diameter.

Specific examples of polyphosphates are alkali metal tripolyphosphates, sodium, potassium, and ammonium pyrophosphates, sodium and potassium orthophosphates, sodium polymetaphosphates having a degree of polymerization ranging from about 6 to about 21, and phytic acid salts .

Examples of phosphate builder salts are the water-soluble salts of ethane 1-hydroxy-1,1-diphosphonate, especially the sodium and potassium salts, the water-soluble salts of methylene diphosphonic acid, such as trisodium and Tripotassium salt, and water-soluble salts of substituted methylene diphosphonic acids, such as trisodium and tripotassium ethylene, isopropylidene, benzylmethylene, and halomethylene phosphonates. Phosphonate builder salts of the above type are disclosed in U.S. Patent Nos. 3,159,581 and 3,213,030 (issued to Diehl on December 1, 1964 and October 19, 1965); , 422,021 (issued to Roy on January 14, 1969); U.S. Patent Nos. 3,400,148 and 3,422,137 (issued to Quimby on September 3, 1968 and January 14, 1969) . The disclosure is incorporated herein by reference.

For purposes of the present invention, suitable organic detergent builders include, but are not limited to, a wide variety of polycarboxylate compounds. As used herein, "polycarboxylate" means a compound having a plurality of carboxylate groups, preferably at least 3 carboxylate groups.

Polycarboxylate builders are usually added to the compositions in acid form, but may also be added in neutralized salt form. When employed in salt form, alkali metal such as sodium, potassium and lithium salts or alkanolammonium salts are preferred.

Polyhydroxylate builders include various types of useful materials. One important class of polycarboxylate builders includes the ether polycarboxylates. A number of ether polycarboxylates have been disclosed for use as detergency builders. Examples of useful ether polycarboxylates include oxydisuccinates disclosed in Berg U.S. Patent 3,128,287 (issued April 7, 1964) and Lamberti et al. U.S. Patent 3,635,830 (1972 issued on January 18, 2010), which are hereby incorporated by reference.

A particular class of ether polycarboxylates useful as builders in the present invention also includes compounds having the general formula:

CH(A)(COOX)-CH(COOX)-O-CH(COOX)-CH(COOX)(B) where A is H or OH; B is H or -O-CH(COOX) _-CH2 (COOX ); X is H or a salt-forming cation. For example, if A and B are both H in the above general formula, the compound is oxydisuccinic acid and its water-soluble salts. If A is OH and B is H, the compound is tartrate-succinic acid (TMS) and its water-soluble salts. If A is H and B is -O-CH(COOX) _-CH2 (COOX), then the compound is tartrate disuccinic acid (TDS) and its water-soluble salts. Particular preference is given here to using mixtures of these builders. Particularly preferred are mixtures of TMS and TDS wherein the weight ratio of TMS to TDS is from about 97:3 to about 20:80. These builders are disclosed in U.S. Patent 4,663,071, issued May 5, 1987 to Bush et al.

Suitable ether polycarboxylates also include cyclic compounds. Especially cycloaliphatic compounds, as disclosed in U.S. Patent Nos. 3,923,679; 3,835,163; 4,158,635; Reference.

Other useful detergency builders include ether hydroxy polycarboxylates represented by the formula: HO-[C(R)(COOM)-C(R)(COOM)-O]nH where M is hydrogen or a cation, and The salts formed by the anions are water-soluble, preferably alkali metal, ammonium or substituted ammonium cations, n is from about 2 to about 15 (preferably n is from about 2 to about 10, more preferably n is on average from about 2 to about 4), each R is the same or different and is selected from hydrogen, C _1-4 alkyl or C _1-4 substituted alkyl (R is preferably hydrogen).

Other ether polycarboxylates include copolymers of maleic anhydride with ethylene or vinyl methyl ether, 1,3,5-trihydroxybenzene-2,4,6-trisulfonic acid and carboxymethoxysuccinic acid.

Organic polycarboxylate builders also include the various alkali metal, ammonium and substituted ammonium polyacetates. Examples of polyacetate builders are the sodium, potassium, lithium, ammonium and substituted ammonium salts of ethylenediaminetetraacetic acid and nitrilotriacetic acid.

Polycarboxylates also include, for example, mellitic acid, succinic acid, oxydisuccinic acid, polymaleic acid, benzene-1,3,5-tricarboxylic acid and carboxymethoxysuccinic acid, and the water-soluble salts thereof.

Citric acid builders, such as citric acid and its water soluble salts (especially the sodium salt), are polycarboxylate builders of importance in heavy duty liquid detergent formulations, but can also be used in granular compositions middle.

Other carboxylate builders include carboxylated carbohydrates as disclosed in U.S. Patent 3,723,322, Diehl, issued March 28, 1973, incorporated herein by reference.

Also suitable as builders for the detergent compositions of the present invention are 3,3-dicarboxy-4-oxa-1,6-hexanedioates and related compounds disclosed in U.S. Patent 4,566,984 (Bush, issued January 28, 1986), which is incorporated herein by reference. Useful succinic acid builders include _C5 - _C20 alkyl succinic acids and salts thereof. A particularly preferred compound of this type is dodecenylsuccinic acid. Alkyl succinic acid generally has the general formula R-CH(COOH) _CH2 (COOH), that is, a derivative of succinic acid, wherein R is a hydrocarbon group such as C ₁₀ -C ₂₀ , alkyl or alkenyl, preferably C ₁₂ -C ₁₆ , or where R can be substituted by hydroxyl, sulfo, sulfenyl or sulfone. All of these are described in the aforementioned patents.

Succinate builders are preferably used in the form of their water-soluble salts, which include sodium, potassium, ammonium and alkanolammonium salts.

Specific examples of succinate builders include: lauryl succinate, myristyl succinate, palmityl succinate, 2-dodecenyl succinate (preferred), 2-pentadecene base succinate, etc. Lauryl succinates are preferred in this group of builders and are described in European Patent Application 86200690.5/0,200,263, published November 5,1986.

Examples of useful builders also include sodium and potassium carboxymethoxymalonates, carboxymethoxysuccinates, ciscyclohexane hexacarboxylates, ciscyclopentane tetracarboxylates, water soluble polyacrylates (those polyacrylates having a molecular weight greater than about 2,000 are also useful as effective dispersants), and copolymers of maleic anhydride and vinyl methyl ether or ethylene.

Other suitable polycarboxylates are the polyacetal carboxylates disclosed in U.S. Patent 4,144,226, Crutchfield et al., issued March 13, 1979, incorporated herein by reference. These polyacetal carboxylates can be prepared by bringing together under polymerization conditions a glyoxylic acid ester and a polymerization initiator, and the resulting polyacetal carboxylates are attached to chemically stable end groups, thereby making the polyacetal Acetal carboxylates are stabilized against rapid depolymerization in alkaline solutions and converted into the corresponding salts and added to surfactants.

Polycarboxylate builders are also disclosed in U.S. Patent 3,308,067, Diehl, issued March 7, 1967, incorporated herein by reference. These materials include the water-soluble salts of homopolymers and copolymers of aliphatic carboxylic acids such as maleic acid, itaconic acid, mesaconic acid, fumaric acid, aconitic acid, citraconic acid and methylenemalonic acid.

Other organic builders known in the art can also be used. For example, monocarboxylic acids with long chain hydrocarbyl groups and their water soluble salts may be used; this would include what are commonly referred to as "soaps" and generally use chain lengths of _C10 to _C20 , the hydrocarbyl groups may be saturated or unsaturated.

Bleaching Compounds - Bleach and Bleach Activators

The detergent compositions of the present invention may contain a bleaching agent or a bleaching composition comprising a bleaching agent and one or more bleach activators. When present, bleaching compounds generally comprise from about 1% to about 20%, more typically from about 1% to about 10%, of the detergent compositions. Typically, bleaching compounds are optional components in non-liquid formulations such as granular detergents. If present, the amount of bleach activators will generally be from about 0.1% to about 60%, more typically from about 0.5% to about 40%, of the bleaching composition.

The bleaching agent used herein may be any bleaching agent used in detergent compositions for fabric laundering, hard surface cleaning or other cleaning purposes which are now known or will become known. These include oxygen bleaches as well as other bleaching agents. For wash conditions below about 50°C, especially below about 40°C, the compositions of the present invention preferably do not contain borate or materials capable of forming borate in situ under detergent storage or wash conditions (i.e., form borate substances). Therefore, it is best to use a non-borate, non-borate-forming bleach under these conditions. Preferably, detergents used at these temperatures are substantially free of borate and borate-forming species. The term "substantially free of borate and borate-forming substances" means that the composition contains no more than about 2% by weight of any type of borate-containing and borate-forming substances, preferably no more than 1%, more preferably 0%.

One type of bleach that can be used includes percarboxylic acid bleaches and their salts. Suitable examples of such agents include magnesium monoperoxyphthalate hexahydrate, magnesium m-chloroperbenzoate, 4-nonylamino-4-oxoperoxybutyric acid and diperoxydodecane di acid. These bleaching agents are disclosed in U.S. Patent 4,483,781 (Hartman, issued November 20, 1984), U.S. Patent Application 740,446 (Burns et al., filed June 3, 1985), European Patent Application 0,133 , 354 (Banks et al., issued February 20, 1985) and U.S. Patent 4,412,934 (Chung et al., issued November 1, 1983). All of these patents are hereby incorporated by reference. Particularly preferred bleaching agents also include 6-nonylamino-6-oxoperoxycaproic acid, which is described in U.S. Patent 4,634,551, issued January 6, 1987 to Burns et al., This patent is hereby incorporated by reference.

Another type of bleach that can be used includes halogen bleach. Examples of hypohalite bleaches include trichloroisocyanuric acid, sodium and potassium dichloroisocyanurates, and N-chloro and N-bromoalkanesulfonamides. These substances are generally added at 0.5-10% by weight of the final product, preferably 1-5% by weight.

Peroxygen bleach can also be used. Suitable peroxygen bleaching compounds include sodium carbonate peroxyhydrate, sodium pyrophosphate peroxyhydrate, urea peroxyhydrate and sodium peroxide.

The peroxygen bleach is preferably mixed with a bleach activator, resulting in the in situ generation of peroxyacid corresponding to the bleach activator in aqueous solution (ie during the wash).

Preferred bleach activators for incorporation into compositions of the present invention have the general formula:

wherein R is an alkyl group containing from about 1 to about 18 carbon atoms, wherein the longest straight alkyl chain extending from and including the carbonyl carbon contains from about 6 to about 10 carbon atoms, and L is a leaving group , whose conjugate acids have a pKa ranging from about 4 to about 13, these bleach activators have been described in U.S. Patent 4,915,854 (issued to Mao et al. on April 10, 1990), which patent is hereby incorporated as Reference, and U.S. Patent 4,412,934, which was previously incorporated by reference.

Bleaching agents other than oxygen bleaching agents are also known in the art and may be used herein, one non-oxygen bleaching agent of particular interest includes photoactivated bleaching agents such as sulfonated zinc and/or aluminum phthalocyanines . These substances are deposited on the substrate during the washing process, and the sulfonated zinc phthalocyanine is activated under light irradiation in the presence of oxygen, such as hanging clothes in the sun, so that the substrate is bleached. A preferred zinc phthalocyanine and photoactivated bleaching process are described in U.S. Patent 4,033,718, issued July 5, 1977 to Holcombe et al., which patent is incorporated herein by reference. Typically, detergent compositions contain from about 0.025% to about 1.25% by weight of the sulfonated zinc phthalocyanine.

polymer soil remover

Any polymeric soil release agent known in the art may be used in the practice of the present invention. Polymeric soil removers are characterized by having hydrophilic segments, which make the surface of hydrophobic fibers such as polyester and nylon hydrophilic, and hydrophobic segments, which deposit on hydrophobic fibers and remain adhered to them throughout the wash and rinse cycle. On top of that, the hydrophobic segment acts as a "binder" for the hydrophilic segment. This makes it easy to wash off the soil present after the treatment with the soil remover in the subsequent washing process.

At the same time, the use of polymeric soil release agents in any detergent composition of the present invention is beneficial, especially in those detergent compositions for laundry or other uses where it is desired to remove grease and oil from hydrophobic surfaces The presence of polyhydroxy fatty acid amides in detergent compositions which also contain anionic surfactants can enhance the performance of most of the more commonly used types of polymeric soil release agents. Anionic surfactants affect the ability of certain soil removal agents to deposit thereon or adhere to hydrophobic surfaces. These polymeric soil release agents have nonionic hydrophilic or hydrophobic segments which interact with the anionic surfactants.

The performance of polymeric soil release agents can be improved through the use of polyhydroxy fatty acid amides for the compositions of the present invention. The compositions of the present invention are those comprising an anionic surfactant system, a soil removal agent interacting with the anionic surfactant and a polyhydroxy fatty acid amide (PFA) in an amount capable of enhancing the performance of the soil removal agent, where: (I) the anionic surfactant interaction between the soil remover of the detergent composition and the anionic surfactant system, can be compared by comparing (A) "control" experiments and (B) "SRA/anionic surfactant The amount of deposition of soil removal agent (SRA) in aqueous solution on hydrophobic fibers (such as polyester) of detergent" experiment was observed that in (A), the deposition amount of SRA in aqueous solution of the detergent composition was in the absence of Measured in the case of other detergent ingredients, in (B), the same type and amount of anionic surfactant system used in the detergent composition is mixed with SRA in aqueous solution, so that SRA and anionic surfactant The weight ratio of the system is the same as that of the detergent composition, so that the reduced deposition amount in (B) relative to (A) shows the interaction between the anionic surfactants; and (II) whether the detergent composition contains its amount The ability of polyhydroxy fatty acid amides to enhance soil release can be determined by comparing SRA deposition in (B) SRA/anionic surfactant experiment with (C) soil removal agent deposition in "SRA/anionic surfactant/PFA experiment" , in (C), the same kind and amount of polyhydroxy fatty acid amides as in the detergent composition are mixed with the soil remover and anionic surfactant corresponding to the SRA/anionic surfactant test, so that the soil The increased deposition of the remover in experiment (C) relative to experiment (B) indicates the presence of polyhydroxy fatty acid amide in an amount capable of enhancing the performance of the soil remover. For the purpose of the experiment, the experiment should be carried out under the condition that the concentration of the anionic surfactant in the aqueous solution is greater than its critical micelle concentration (CMC), preferably greater than about 100 ppm. The polymeric soil release agent concentration should be at least 15 ppm. A small bundle of polyester fabric should be used as a source of hydrophobic fibers. For each experiment, the same fiber bundles were soaked and agitated in 35 °C aqueous solution for 12 min, then removed and analyzed. Deposition of the polymeric soil release agent was determined by radiolabeling the soil release agent prior to treatment, followed by radiochemical analysis, according to techniques known in the literature.

As an alternative to the radiochemical analysis methodology discussed above, the deposition of soil-detergents can also be performed in the series of experiments described above (i.e., series A, B, and C), according to techniques well known in the literature, by assaying the experimental solution It is measured by the absorption of ultraviolet light (UV). The decrease in UV absorption of the experimental solution after removal of the hydrophobic fiber material corresponds to increased SRA deposition. Those skilled in the art will recognize that UV analysis cannot be used for experimental solutions that contain certain types and levels of substances that cause excessive UV absorption interference, such as high levels of surfactants with aromatic groups (such as alkylbenzene sulfonate, etc.).

The so-called "enhance the amount of soil removal agent" of polyhydroxy fatty acid amide means that the amount of this kind of surfactant can increase the deposition of soil removal agent on the hydrophobic fiber, which is just as described above; For fabrics washed by the detergent composition, the amount of the surfactant is such that the grease/oil cleaning performance in subsequent washing steps is improved.

The amount of polyhydroxy fatty acid amide required to enhance deposition will vary with the anionic surfactant chosen, the amount of anionic surfactant used, the particular soil release agent chosen, and the particular polyhydroxy fatty acid amide chosen. Typically, the compositions comprise from about 0.01% to about 10%, typically from about 0.1% to about 5%, by weight of a polymeric soil release agent, and from about 4% to about 50%, more typically from about 5% to about 30% weight of anionic surfactant. Although not necessarily intended to be limiting, these compositions will generally contain at least about 1%, preferably at least about 3%, by weight, of the polyhydroxy fatty acid amide.

Polymeric soil-removing agents whose performance has been improved by polyhydroxy fatty acid amides in the presence of anionic surfactants, comprising soil-removing agents comprising: (a) one or more nonionic hydrophilic ingredients which are primarily Consisting of (i) polyoxyethylene segments having a degree of polymerization of at least 2, or (ii) propylene oxide or polyoxypropylene segments having a degree of polymerization of 2-10, wherein said hydrophilic segment does not include any propylene oxide units, unless adjacent moieties are linked at each end by ether linkages, or (iii) a mixture of propylene oxide units comprising propylene oxide and from 1 to about 30 propylene oxide units, wherein said mixture contains a sufficient number of propylene oxide units , so that the hydrophilic component is sufficiently hydrophilic to increase the hydrophilicity of the surface of ordinary polyester synthetic fibers on which the soil removal agent is deposited. Said hydrophilic segment preferably comprises at least about 25% oxypropylene units, more preferably, especially for components having about 20-30 propylene oxide units, at least about 50% oxyethylene units; or (b) a One or more hydrophobic components, including (i) C ₃ oxyalkylene terephthalate fragments, wherein, if the hydrophobic component also includes ethylene oxide terephthalate, then oxyethylene terephthalate: C ₃ propylene oxide terephthalate units in a ratio of about 2:1 or less, (ii) _C4 - _C6 alkene or _C4 - _C6 alkene oxide fragments, or mixtures thereof, (iii) poly( vinyl ester) fragments, preferably poly(vinyl acetate), with a degree of polymerization of at least 2, or (iv) C ₁ -C ₄ alkyl ether or C ₄ hydroxyalkyl ether substituents, or combinations of these substituents, wherein Said substituents are present in the form of C ₁ -C ₄ alkyl ether or C ₄ hydroxyalkyl ether cellulose derivatives or mixtures thereof, and these cellulose derivatives are amphiphilic so that they have a sufficient amount of C ₁ -C ₄ alkyl ethers and/or C ₄ hydroxyalkyl ethers are deposited on the surface of ordinary polyester synthetic fibers and maintain enough hydroxyl groups that once they stick to the surface of the ordinary synthetic fibers, they will enhance the fiber Hydrophilicity of the surface; or a mixture of (a) and (b).

Generally, the polyoxyethylene segments of (a)(i) have a degree of polymerization of from 2 to about 200 (although higher degree segments can be used), preferably from 3 to about 150, more preferably from 6 to about 100. Suitable oxidized _C4 - _C6 alkene hydrophobic segments include, but are not limited to, capping of polymeric soil release agents as disclosed in U.S. Patent 4,721,580 (issued to Gosselink on January 26, 1988) MO ₃ S(CH ₂ )nOCH ₂ CH ₂ O- in which M is sodium and n is an integer from 4 to 6, which is incorporated herein by reference.

Polymeric soil release agents useful in the present invention include cellulose derivatives such as hydroxyether cellulose polymers, ethylene terephthalate or propylene terephthalate in combination with polyethylene oxide or polypropylene oxide. Block copolymers of phthalates, etc.

Cellulose derivatives useful as soil release agents are commercially available and include hydroxyethers of cellulose such as Methocel ^R (Dow).

Cellulosic soil removers useful herein also include materials selected from C ₁ -C ₄ alkyl and C ₄ hydroxyalkyl celluloses, such as methyl cellulose, ethyl cellulose, hydroxypropyl methyl cellulose and Hydroxybutyl methylcellulose. Various cellulose derivatives useful as soil release polymers are disclosed in U.S. Patent 4,000,093, issued December 28, 1976 to Nicol, et al., which is incorporated herein by reference.

Soil removal agents characterized by polyvinyl ester hydrophobic segments include graft copolymers of polyvinyl esters such as C ₁ -C ₆ vinyl esters, preferably polyvinyl acetate attached to a polyalkylene oxide backbone, Such as polyethylene oxide backbone. These substances are known in the art and have been described in European Patent Application 0219048 (published April 22, 1987, kud, et al.). Suitable commercially available soil removers of this type include SOKALAN materials such as SOKALAN HP-22, available from BASF (West Germany).

A preferred soil release agent is a random block copolymer having ethylene terephthalate and polyethylene oxide (PEO) terephthalate. More specifically, these polymers are composed of repeating units of ethylene terephthalate and PEO terephthalate, where the ethylene terephthalate unit is combined with the PEO terephthalate unit The molar ratio is about 25:75 to about 35:65, and the PEO terephthalate unit contains polyethylene oxide with a molecular weight of about 300 to about 2000. The polymeric soil release agents have a molecular weight ranging from about 25,000 to about 55,000. See U.S. Patent 3,959,230, issued May 25, 1976 to Hays, incorporated herein by reference. See also U.S. Patent 3,893,929, issued July 8, 1975 to Basadur, incorporated herein by reference, which discloses similar copolymers.

Another preferred polymeric soil release agent is a polyester having repeating units of ethylene terephthalate containing 10-15% by weight of ethylene terephthalate units and 90-80% by weight of Polyoxyethylene terephthalate units derived from polyethylene oxide glycol with an average molecular weight of 300-5,000. The molar ratio of ethylene terephthalate units to polyoxyethylene terephthalate units in the polymer is from 2:1 to 6:1. Examples of such polymers include the commercially available materials ZELCON 5126 (from Dupont) and MILEASE T (from ICI). These polymers and their method of preparation are fully described in U.S. Patent 4,702,857, issued October 27, 1987 to Gosselink, which is incorporated herein by reference.

Another preferred polymeric soil release agent is a sulfonation product of a substantially linear ester oligomer comprising an oligomer ester backbone of terephthaloyl and oxyalkylene oxide repeating units with terminal Moieties are covalently linked to this backbone. The soil remover is derived from allyl alcohol ethoxylate, dimethyl terephthalate and 1,2-propylene glycol, wherein after sulfonation, the terminal portion of each oligomer contains an average of total From about 1 to about 4 sulfonate groups. These soil removal agents are fully described in U.S. Patent 4,968,451 (issued November 6, 1990 to J.J. Scheibel and E.P. Gosselink), U.S. Patent Application No. 07/474,709 (filed January 29, 1990), All of which are incorporated herein by reference.

Other suitable polymeric soil release agents include the ethyl- or methyl-terminated 1,2-propylene terephthalate-polyethylene terephthalates of U.S. Patent 4,711,730 (issued December 8, 1987 to Gosselink et al.). Oxyethylene terephthalate polyesters, anionically terminated oligomeric esters of U.S. Patent 4,721,580 (issued to Gosselink on January 26, 1988), wherein the anionically terminated comprises polyethylene glycol ( PEG) _derived sulfopolyethoxy groups, block polyester oligomers of the formula X-( _OCH2CH2 ) n-polyethoxy group-terminated, wherein n is 12 to about 43, X is C ₁ -C ₄ alkyl or preferably methyl. All of these patents are hereby incorporated by reference.

Other polymeric soil release agents include those of U.S. Patent 4,877,896 (issued to Maldonado et al. on October 31, 1989) which discloses anionic, especially sulfoaroyl, terminated terephthalic acid esters, said patent is hereby incorporated by reference. These terephthalates contain asymmetrically substituted oxy-1,2-alkyleneoxy units. The soil release agent polymers included in U.S. Patent No. 4,877,896 have polyoxyethylene hydrophilic moieties or C ₃ oxyalkylene terephthalates within the hydrophobic moieties of (b)(i) above (trimethylene terephthalate) repeating unit substances. The characteristics of these polymeric soil release agents are measured by one or two evaluation criteria, which means that in the presence of anionic surfactants, polymeric soil release agents especially benefit from the inclusion of the polyhydroxy fatty acid amide.

If used, soil release agents will generally comprise from about 0.01% to about 10.0% wt, typically from about 0.1% to about 5% wt, preferably from about 0.2% to about 3.0% wt, of the detergent compositions herein.

Chelating agent

The detergent compositions herein may also optionally contain one or more iron and magnesium chelating agents as a builder additive material. Such chelating agents can be selected from aminocarboxylates, aminophosphonates, polyfunctionally substituted aromatic chelating agents and mixtures thereof, all of which are explained below. Without wishing to be bound by theory, it is believed that the benefit of these materials is due in part to their exceptional ability to remove iron and magnesium ions from wash solutions by forming soluble chelates.

Aminocarboxylate can have one or more, preferably at least two of the following substructural units as an optional chelating agent in the composition of the present invention:

wherein M is hydrogen, alkali metal, ammonium or substituted ammonium (eg ethanolamine) and x is from 1 to about 3, preferably 1. Preferred such aminocarboxylates do not contain alkyl or alkenyl groups having more than about 6 carbon atoms. Practical aminocarboxylates include EDTA, N-hydroxyethylethylenediaminetriacetate, nitrilotriacetate, ethylenediaminetetrapropionate, triethylenetetraminehexaethylene salt, diethylenetriaminepentaacetate, and ethanol diglycine, their alkali metal, ammonium, and substituted ammonium salts, and mixtures thereof.

Amino phosphonates are also suitable for use as chelating agents in the compositions of the invention when their total phosphorus levels are at least as low as to permit their presence in detergent compositions. Useful compounds have one or more, preferably at least two, of the following substructural units:

wherein M is hydrogen, alkali metal, ammonium or substituted ammonium, and x is from 1 to about 3, preferably 1, such compounds include ethylenediaminetetrakis(methylenephosphonate), nitrilotris(methylene Phosphonates) and Diethylene Triamine Penta(methylene phosphonates). Preferred of these amino phosphonates are those whose alkyl or alkenyl group contains not more than 6 carbon atoms. Alkylene groups can be shared by substructures.

Polyfunctionally substituted aromatic hydrocarbon chelating agents may also be used in the compositions of the present invention. These substances may include compounds of the general formula

wherein at least one R is -SO ₃ H or -COOH or their soluble salts and mixtures thereof. U.S. Patent 3,812,044, Connor et al., issued May 21, 1974, incorporated herein by reference, discloses polyfunctionally substituted aromatic chelating and sequestering agents. Preferred compounds of this type in acid form are dihydroxydisulfobenzenes, such as 1,2-dihydroxy-3,5-disulfobenzene. Alkaline detergent compositions may contain such materials in the form of alkali metal, ammonium or substituted ammonium (eg mono- or triethanolamine) salts.

In practical use, these chelating agents are generally used in an amount of about 0.1% to about 10% (based on the weight of the detergent composition herein), and more preferably the chelating agent is used in an amount of about 0.1% to about 3.0% by weight of the detergent composition. (Heavy).

Clay Stain Remover/Anti-Redeposition Agent

The compositions of the present invention may also optionally contain water-soluble ethoxylated amines having clay soil release and antiredeposition properties. Granular detergent compositions containing these compounds generally contain from about 0.01% to about 10.0% by weight of the water-soluble ethoxylated amine; liquid detergent compositions generally contain from about 0.01% to about 5% by weight. Such compounds are preferably selected from the following substances:

(1) Ethoxylated monoamines having the following structural formula:

(XL-)-N-(R ² ) ₂

(2) Ethoxylated diamines having the following structural formula:

or (XL-) ₂ -NR ¹ -N-(R ² ) ₂

(3) Ethoxylated polyamines having the following structural formula:

(4) Ethoxylated amine polymers having the following structural formula:

and

(5) mixtures thereof; where A ¹ is

or -O-; R is H or C ₁ -C ₄ alkyl or hydroxyalkyl; R ¹ is C ₂ -C ₁₂ alkylene, hydroxyalkylene, alkenylene, arylene, or alkylene aryl, or a C ₂ -C ₃ oxyalkylene moiety having 2 to about 20 oxyalkylene units (as long as no ON bonds are formed); each R ² is C ₁ -C ₄ or hydroxyalkyl, a -LX moiety, or both ^R2 combine to form a (( _CH2 )r, ^-A2- ( _CH2 )s- moiety, where ^A2 is -O- or _-CH2- , r is 1 or 2, s is 1 or 2, And r+s is 3 or 4; x is a nonionic group, anionic group or their mixture; ^R3 is a substituted C ₃ -C ₁₂ alkyl, hydroxyalkyl, alkenyl, aryl, or an alkane with a substitution position Aryl; ^R4 is C1 _{- C12} alkylene, hydroxyalkylene, alkenylene, arylene or alkarylene, or C2- _C3 oxide having ₂ to about 20 alkylene oxide units alkene moiety (as long as no OO or _ON bonds are formed); L is a hydrophilic chain containing a polyoxyalkylene moiety -[( ^R5O )m( _CH2CH2O )n]-, where ^R5 is _C3 -C ₄ alkylene or _{hydroxyalkylene} , and m and n are such numbers that the -( _CH2CH2O )n- moiety comprises at least about 50% by weight of said polyoxyalkylene moieties; For monoamines, m is 0 to about 4, and n is at least about 12; for said diamines, m is 0 to about 3, and when R ¹ is C ₂ -C ₃ alkylene, hydroxyalkylene , or n is at least about 6 for alkenylene, and n is at least about 3 when ^R is other than _C2 - _C3 alkylene, hydroxyalkylene or alkenylene; for said polyamines and amine polymers m is from 0 to about 10, n is at least about 3; p is from 3 to 8; q is 1 or 0; t is 1 or 0, as long as t is 1 when q is 1; w is 1 or 0; x+y+z is at least 2; and y+z is at least 2. A particularly preferred soil release and anti-redeposition agent is ethoxylated tetraethylenepentamine. Ethoxylated amine Examples of the invention are further described in the U.S. Patent 4,597,898 of VanderMeer issued July 1, 1986, which is incorporated herein by reference.Another class of preferred clay soil release/anti-redeposition agents are cationic compounds , and disclosed in European Patent Application 111,965 of Oh and Gosselink, published June 27, 1984, incorporated herein by reference. Other clay soil release/anti-redeposition agents that can be used include ethoxylated amine polymers , which was disclosed in European Patent Application 111,984 of Gosselink published on June 27, 1984; zwitterionic polymers were disclosed in European Patent Application 112,592 of Gosselink published on July 4, 1984; in 1985 Amine oxides are described in U.S. Patent 4,548,744, Connor, issued October 22, all of which are incorporated herein by reference.

Other clay soil release and/or antiredeposition agents known in the art may also be employed in the compositions of the present invention. Another preferred type of anti-redeposition agent includes carboxymethylcellulose (CMC) materials. Such substances are well known in the art.

polymer dispersant

Polymeric dispersants are well suited for use in the compositions of the present invention. These substances help control calcium and magnesium hardness. Suitable polymeric dispersing agents include polymeric polycarboxylates and polyethylene glycols, although others known to those skilled in the art can also be used. It is believed, although not wishing to be bound by theory, that when used with other builders, including low molecular weight polycarboxylates, polymeric dispersants improve The builder performance of the entire detergent.

Polycarboxylates useful as polymeric dispersants in the present invention are the following polymers or copolymers which contain at least about 60% by weight of segments of the general formula:

wherein X, Y, and Z are independently selected from hydrogen, methyl, carboxyl, carboxymethyl, hydroxy, and hydroxymethyl; salt-forming cations, and n is from about 30 to about 400. Preferably, X is hydrogen or hydroxy, Y is hydrogen or carboxy, Z is hydrogen and M is hydrogen, alkali metal, ammonia or substituted ammonium.

Polymeric polycarboxylate materials of this type can be prepared by polymerizing or copolymerizing suitable unsaturated monomers, preferably in their acid form. Unsaturated monomeric acids that can be polymerized into suitable polymeric polycarboxylates are acrylic acid, maleic acid (or maleic anhydride), fumaric acid, itaconic acid, aconitic acid, mesaconic acid, citraconic acid and methylene Malonate. The monomeric segments present in the polymeric polycarboxylates of this invention may contain non-carboxy groups such as vinylmethyl ether, styrene, ethylene, etc., provided such segments do not constitute more than 40% by weight.

Particularly useful polymeric polycarboxylates can be derived from acrylic acid. The acrylic acid-based polymers used herein are water-soluble salts of polymerized acrylic acid. The average molecular weight of such polymers in the acid form is preferably from about 2,000 to 10,000, more preferably from about 4,000 to 7,000, most preferably from about 4,000 to 5,000. Water-soluble salts of such acrylic acid polymers include, for example, the alkali metal, ammonium and substituted ammonium salts, such soluble polymers being known materials. Such polyacrylates for use in detergent compositions are disclosed, for example, in U.S. Patent 3,308,067, Diehl, issued March 7,1967. This patent is incorporated herein by reference.

Acrylic/maleic acid based copolymers can also be used as a preferred component of the dispersing/anti-redeposition agent. Such materials include the water-soluble salts of copolymers of acrylic acid and maleic acid. The average molecular weight of such copolymers in the acid form is preferably from about 2,000 to 100,000, more preferably from about 5,000 to 75,000, most preferably from about 7,000 to 65,000. The ratio of acrylate to maleate segments in such copolymers is generally from about 30:1 to about 1:1, preferably from about 10:1 to 2:1. Water-soluble salts of acrylic acid/maleic acid copolymers include, for example, alkali metal, ammonium and substituted ammonium salts. Soluble acrylate/maleate copolymers of this type are known materials and are described in European Patent Application No. 66915, published December 15, 1982, which is incorporated herein by reference.

Another polymer that may also be included is polyethylene glycol (PEG). PEG has dispersant properties and acts as a clay soil release/anti-redeposition agent, and for this purpose generally has a molecular weight of about 500 to 100,000, preferably about 1,000 to about 50,000, more preferably about 1,500 to about 10,000.

brightener

Any optical brightener or other brightening or brightening agent known in the art can be incorporated into the detergent compositions of the present invention.

The selection of the whitening agent used in the detergent composition depends on various factors, for example, the type of detergent, the properties of other components in the detergent composition, the temperature of the washing water, the intensity of the agitation, and the degree of separation of the laundry and the The ratio of wash basin size.

The choice of brightener also depends on the type of material being washed, for example, cotton, synthetics, etc. Since most laundry detergent products are used to clean a variety of fibers, the detergent composition should contain a blend of brighteners that is effective on a variety of fibers. Of course, the individual components of the whitener mixture must be compatible.

The industrial optical brighteners that can be used in the present invention can be divided into the following groups, but not limited to these, including derivatives of stilbene, pyrazoline, coumarin, carboxylic acid, methine anthocyanin, thiofluorene - 5,5-dioxides, pyrroles, 5- and 6-membered ring heterocycles, and other heterochromants. Examples of such brightening agents are disclosed in "The Production and Application of Fluorescent Brightening Agent", M. Zahradnik, Published by John Wiley & Sons, New York (1982), the contents of which are incorporated herein by reference.

Stilbene derivatives that can be used in the present invention include, but are not limited to, derivatives of bis(triazinyl)amino-stilbene; bisamido derivatives of stilbene; triazole derivatives of stilbene; Azole derivatives; oxazole derivatives of stilbene; styryl derivatives of stilbene.

Certain bis(triazinyl)aminostilbene derivatives useful in the present invention can be prepared from 4,4'-diamine-stilbene-2,2'-disulfonic acid.

Coumarin derivatives that can be used in the present invention include, but are not limited to, derivatives substituted at the 3-position, at the 7-position, and at the 3- and 7-positions.

Carboxylic acid derivatives that can be used in the present invention include (but are not limited to) fumaric acid derivatives; benzoic acid derivatives; para-phenylene-bis-acrylic acid derivatives; naphthalene dicarboxylic acid derivatives; derivatives; and cinnamic acid derivatives.

The cinnamic acid derivatives that can be used in the present invention are further subdivided into the following groups, including (but not limited to) cinnamic acid derivatives, styrene pyrrole, styrene benzofuran, styrene oxadiazole, styrene triazole , and styrene polyphenylene, are described on page 77 of Zahradnik's reference.

Styrenated pyrroles can be further subdivided into styrenated benzoxazoles, styrenated imidazoles and styrenated thiazoles and are described on page 78 of the Zahradnik literature. It should be understood that the three subclasses mentioned do not reflect the full subclass of styrenated pyrroles.

Another class of optical brighteners that can be used in the present invention are derivatives of thiofluorene-5,5-dioxides, described in The Kirk-Othmer Encyclopedia of Chemical Technology, volume 3, pages 737-750 (John Wiley & Son Inc., 1962), which is hereby incorporated by reference and includes 3,7-diaminothiofluorene-2,8-disulfonic acid 5,5 dioxide.

Another class of optical brighteners that can be used in the present invention includes pyrroles, which are derivatives of 5-membered heterocycles. Pyrroles can be further subdivided into monopyrroles and bispyrroles. Examples of monopyrroles and bispyrroles are described in the Kirk-Othmer literature.

Another class of brighteners which may be used in the present invention are 6-membered heterocyclic derivatives and are described in the Kirk-Othmer literature. Examples of such compounds include whitening agents derived from pyrazine and whitening agents derived from 4-aminonaphthylamide.

In addition to the brighteners already mentioned, staining agents can also be used as brighteners. Examples of such heterochromants are described in Zahradnik, pages 93-95, and include 1-hydroxy-3,6,8-pyrenetrisulfonic acid; 2,4-dimethoxy-1,3, 5-Triazin-6-yl-pyrene; 4,5-diphenylimidazolinone disulfonic acid; and pyrazolinequinoline derivatives.

Specific examples of other optical brighteners which may be used in the present invention are described in U.S. Patent 4,790,856, Wixon, issued December 13, 1988, incorporated herein by reference. These brighteners include the PHORWHITE series of brighteners available from Verona. Other brighteners disclosed in this document include: Tinopal UNPA, Tinopal CBS and Tinopal 5BM; available from Ciba-Geigy; Arctic White CC and Artic White CWD, available from Hilton-Davis (in Italy); 2-(4- Styryl-phenyl)-2H-naphtho[1,2-d]triazole; 4,4′-bis-(1,2,3-triazol-2-yl)stilbene; 4,4′- bis-(styryl)bisphenyl; and y-aminocoumarin. Specific examples of whitening agents include 4-methyl-7-diethyl-aminocoumarin; 1,2-bis(benzimidazol-2-yl)ethane; 1,3-diphenyl-methazol 2,5-bis-(benzoxazol-2-yl)thiophene; 2-styrylnaphth[1,2-d]oxazole; and 2-(stilbene-4-yl)2H -Benzo-[1,2-d]triazole.

Other optical brighteners which may be used in the present invention include those disclosed in Hamilton, U.S. Patent 3,646,015, issued February 29, 1972, which is incorporated herein by reference.

Foam suppressor

Compounds known, or to become known, for reducing or inhibiting suds formation may be incorporated into the compositions of the present invention. Incorporated materials, hereinafter "suds suppressors" are desirable because the polyhydroxy fatty acid amide surfactants herein enhance suds stability in detergent compositions. Suds suppression is of particular importance when the detergent composition includes relatively high sudsing surfactants in conjunction with polyhydroxy fatty acid amide surfactants. Suds suppression is most desirable when the composition is intended to be used in a front load automatic washing machine which generally features a drum containing laundry and wash water which has a horizontal axis and rotates about that axis. This form of agitation can create a lot of foam, thereby reducing cleaning performance. The use of suds suppressors is also especially important under hot water wash conditions and under high surfactant concentration conditions.

Suds suppressors useful in the compositions of the present invention are a variety of materials. Suds suppressors are well known to those of ordinary skill in the art and are generally described, for example, in Kirk Othmer Encyclopedia of Chemical Technology, Third Edition, Volume 7, pp. 430-447 (John Wiley & Sons, Inc, 1979). One very important class of suds suppressors includes monocarboxylic fatty acids and their soluble salts. Such materials are described in U.S. Patent 2,954,347, Wayne St. John, issued September 27, 1960, which is incorporated herein by reference. The monocarboxylic fatty acids and salts thereof useful as suds suppressors generally have from 10 to about 24 carbon atoms, preferably from 12 to 18 carbon atoms, in the hydrocarbon chain. Suitable salts include alkali metal salts such as sodium, potassium, and lithium, ammonium and alkanolammonium salts. These materials are a preferred class of suds suppressors for detergent compositions.

The detergent compositions can also contain non-surfactant suds suppressors. Examples include the following: high molecular weight hydrocarbons such as paraffins, fatty acid esters (e.g. fatty acid triglycerides), fatty acid esters of monovalent alcohols, C ₁₈ -C ₄₀ aliphatic ketones (e.g. stearyl ketone) and the like. Other types of suds suppressors include N-alkylated aminotriazines such as three to six alkyl melamines or two to four alkyl diamine chlorotriazines (composed of cyanuric chloride and two or three moles containing 1 to 24 carbon atoms products of primary or secondary amines), propylene oxide, and monostearyl phosphates such as monostearyl alcohol phosphate and monostearyl dialkali metal (e.g., K, Na, and Li) phosphates and phosphoric acid ester. Hydrocarbons such as paraffins and halogenated hydrocarbons may be used in liquid form. Liquid hydrocarbons are liquid at room temperature and pressure, with a pour point ranging from about -40°C to about 5°C, and a minimum boiling point of not less than about 110°C (atmospheric pressure). Paraffinic hydrocarbons may also be used, preferably having a boiling point below about 100°C. Hydrocarbons constitute a preferred class of suds suppressors for detergent compositions. Hydrocarbon suds suppressors are described in U.S. Patent 4,265,779, Gandolfo et al., issued May 5, 1981, which is incorporated herein by reference. Hydrocarbons thus include aliphatic hydrocarbons, alicyclic hydrocarbons, aromatic hydrocarbons and heterocyclic saturated or unsaturated hydrocarbons having from about 12 to about 70 carbon atoms. The term "paraffin" (as used in suds suppressor discussions) includes mixtures of linear alkanes and cyclic hydrocarbons.

Another preferred class of non-surfactant suds suppressors includes silicone suds suppressors. Such suds suppressors include the use of polyorganosiloxane oils such as polydimethylsiloxane, emulsions or dispersions of polyorganosiloxane oils or resins, and polyorganosiloxanes with silica particles A combination in which polyorganosiloxane is chemisorbed and melted onto silica. Silicone suds suppressors are well known to those skilled in the art, for example, U.S. Patent 4,265,779 to Gandolfo et al., issued May 5, 1981, and Starch, M.S., issued February 7, 1990. Both are described in European Patent Application No. 89307851.9, both of which are incorporated herein by reference.

Other silicone suds suppressors are described in U.S. Patent 3,455,839, which relates to the composition and processing of antifoam fluids incorporating small amounts of polydimethylsiloxane liquids.

Mixtures of siloxanes and silanized silicas are described, for example, in German Patent Application DOS 2,124,526. Silicone antifoam and suds control agents in granular detergent compositions are described in Bartolotta et al. U.S. Patent 3,933,672 and Baginski et al. is introduced.

The application example of silicone base suds suppressor in the present invention is the foam control agent of suds suppressing amount, and its main composition is:

(i) polydimethylsiloxane fluids having a viscosity at 25°C of from about 20 ^cs to about 1500 ^cs ;

(ii) Per 100 parts by weight of (i), about 5 to 50 parts by weight of silicone resin consisting of (CH ₃ ) ₃ SiO1/2 units and SiO ₂ units, (CH ₃ ) ₃ SiO The ratio of _1/2 units to _SiO2 units is from about 0.6:1 to about 1.2:1; and

(iii) from about 1 to about 20 parts by weight of solid silica gel per 100 parts by weight of (i).

For any detergent composition used in an automatic washing machine, suds formation should not overflow the washing machine. When using a suds suppressor, it is best to use a "foam suppressing amount" of the suds suppressor. As used herein, "suds suppressing amount" means an amount of suds control agent, selectable by the formulator of the composition, sufficient to control suds so that low sudsing detergents are used in automatic washing machines. The amount of suds control varies with the choice of detergent surfactant. For example, where there is a large amount of sudsing surfactant, a relatively high amount of suds control agent is used to obtain a more desirable suds control effect than a small amount of sudsing surfactant. Generally, sufficient amounts of suds suppressors are incorporated into low sudsing detergent compositions such that suds are generated during the wash cycle (i.e., agitation of the detergent in an aqueous solution at a predetermined wash temperature and concentration) using an automatic washing machine. Not more than about 75% of the void volume of the drum volume of the washing machine, preferably the amount of foam is not more than about 50% of said void volume, where the void volume refers to the difference between the volume of the drum of the washing machine and the volume of the laundry plus washing water .

The compositions of the present invention generally contain from about 0% to about 5% suds suppressor. When used as suds suppressors, monocarboxylic fatty acids and their salts are generally used at levels of about 5% by weight of the detergent compositions. Preferably from about 0.5% to about 3% fatty monocarboxylate suds suppressor is used. Silicone suds suppressors are typically used at levels up to about 2.0% by weight, based on the weight of the detergent composition, although greater amounts can be used. The upper limit is practical in fact, primarily in relation to cost reduction and effectiveness in effectively controlling foam. Preferably from about 0.01% to 1% silicone suds suppressor is used, more preferably from about 0.25% to about 0.5%. These weight percents of suds suppressor as used herein include silica which may be used with the polyorganosiloxane, and any additive materials which may be used. Monostearyl phosphate is generally used in amounts of from about 0.1% to about 2% by weight of the composition.

Typical levels of hydrocarbon suds suppressors range from about 0.01% to about 5.0%, although higher levels can also be used.

other components

Various other ingredients useful in detergent compositions can be included in the compositions of the present invention, including other active ingredients, carriers, hydrotropes, processing aids, dyes or pigments, solvents for liquid formulations, etc.

Liquid detergent compositions may contain water and other solvents as carriers. Low molecular weight primary or secondary alcohols such as methanol, ethanol, propanol, and isopropanol are suitable. Monohydric alcohols are preferred for solubilizing surfactants, but polyols containing 2 to about 6 carbon atoms and 2 to about 6 hydroxyl groups (for example, propylene glycol, ethylene glycol, glycerol, and 1,2-propanediol) can also be used .

The detergent compositions of the present invention are preferably formulated for use in liquid phase cleaning operations. The pH of the wash water may be from about 6.5 to about 11, preferably from about 7.5 to about 10.5. Liquid product formulations have a pH of from about 7.5 to about 9.5, preferably from about 7.5 to about 9.0. Methods of controlling pH at recommended levels include the use of buffers, bases, acids, etc., and are well known to those skilled in the art.

The present invention also provides a method for improving the performance of detergents containing anionic, nonionic, and/or cationic surfactants, and detergent enzymes, by using the above-mentioned polyhydroxy fatty acid amides in the detergent to increase enzyme performance energy Surfactant is realized, generally contains at least about 1% of this kind of surfactant.

The present invention also provides a method of cleaning a substrate, said substrate being fibres, fabrics, hard surfaces, skin, etc., in the presence of a solvent such as water or a water-miscible solvent (such as primary and secondary alcohols) with a detergent containing Enzyme and one or more anionic, non-ionic, or the detergent composition contacting said substrate of cationic surfactant, wherein said detergent composition contains the polyhydroxy fatty acid amide that improves enzyme performance energy, generally at least About 1% by weight of the composition. Stirring can better improve the cleaning effect. Suitable means for providing agitation include rubbing or preferably using a brush, sponge, cloth, mop, or other cleaning device, automatic washing machine, automatic dishwasher, and the like.

Example

This example is a procedure for the preparation of N-methyl, 1-deoxyglucosyl lauramide surfactant for use in the compositions of the present invention. Although a chemist skilled in the art can vary the configuration of the apparatus, one suitable apparatus for use in the present invention comprises a three-liter, four-necked flask equipped with a motor-driven paddle stirrer and a thermometer long enough to access the reaction medium. The other two necks of the flask are equipped with nitrogen purge tubes and a thick hollow side tube (note: the thick hollow side tube is important in quickly venting the methanol), said hollow side tube is connected to the effective collection condenser and the vacuum outlet . The latter is connected with nitrogen remover and vacuum gauge, and then connected with extraction pipe and steam valve. A 500 W heating mantle with an adjustable temperature controller for heating the reaction was placed in the experimental jacket so that the temperature could be easily raised or lowered to further control the reaction.

N-methylglucamine (195 g, 1.0 mol, Aldrich, M4700-0) and methyl laurate (Procter & Gamble CE 1270, 220.9 g, 1.0 mol) were placed in a flask. The solid/liquid mixture was stirred and heated with a stirrer under a nitrogen purge to form a melt (approximately 25 minutes). When the temperature of the melt reached 145°C, the catalyst (anhydrous powdered sodium carbonate, 10.5 g, 0.1 mole, J.T. Baker) was added. The nitrogen purge was turned off and the aspirator and nitrogen remover were regulated to a vacuum of 5 inches (5/31 atm) Hg. At this point, the reaction temperature was maintained at 150°C by adjusting the Variac and/or raising or lowering the hood.

Within 7 minutes, the first methanol bubbles were observed at the meniscus of the reaction mixture, followed by a vigorous reaction. Methanol evaporates until its velocity drops. Adjust the vacuum to a vacuum of about 10 inches Hg. (10/31 atmospheres). The vacuum was increased approximately as follows (in.Hg/minute): 10 inches Hg at 3 minutes, 20 inches Hg at 7 minutes, and 25 inches Hg at 10 minutes. After 11 minutes from the start of methanol evolution, heating and stirring were stopped while some foaming occurred. The product cooled and solidified.

The following examples are intended to illustrate the compositions of the present invention, but not to limit or define the scope of the invention, which scope will be determined according to the following claims.

Example I-III

These examples represent heavy duty granular detergent compositions comprising polyhydroxy fatty acid amides and protease.

Basic particles Ⅰ Ⅱ Ⅲ

C _14-15 alkyl sulfate 16.9 16.9

C _14-15 Alkyl Ethoxylate (2.25) Sulfate 16.9

N-methyl N-1-deoxyglucosyl cocoamide 5.6 5.6 5.6

Zeolite A 30.1 18.8 18.8

Sodium citrate 11.3 11.3

Sodium carbonate 16.9 16.9 16.9

Sodium silicate 5.6 5.6 5.6

Sodium sulfate 15.1 15.1 15.1

Sodium polyacrylate (4500MW) 1.1 1.1 1.1

Polyethylene glycol (8000MW) 1.1 1.1 1.1

Animal fatty acids 1.1 1.1 1.1

Brightener 0.2 0.2 0.2

Blend and Spray

Protease (1.4% active enzyme) 2.1 0.9 0.9

Spices 0.3 0.3 0.3

_C12-13 alkyl ethoxylate (6.5 moles) 1.1 1.1 1.1

Water and other 3.8 3.8 3.8

100.0 100.0 100.0

The formulations of Examples I-III preferably use about 1400 ppm (by weight of wash water) and wash temperatures below about 50°C. The above examples were prepared by mixing the base granular detergent as a slurry and spray drying to about 4-8% residual moisture. These remaining dry detergent ingredients are mixed in granular or powder form with the spray-dried granules in a tumbler mixer and the liquid ingredients (nonionic surfactant and perfume) are sprayed on.

Embodiment IV-IX

The following examples illustrate heavy duty liquid compositions containing polyhydroxy fatty acid amides and protease and amylase.

Component Ⅳ Ⅴ Ⅵ

N-methyl N-1-deoxyglucosyl cocoamide 10.0 5.5 5.5

_C12-13 alkyl ethoxylate (6.5 moles) 15.0 2.5 2.5

C _14-15 Alkyl Ethoxylate (2.25) Sulfate 17.0 17.0

C _12-14 fatty acids 3.0 3.0 3.0

Dodecyltrimethylammonium chloride 0.2 0.2 0.2

Citric acid 1.0 1.0 1.0

Monoethanolamine 2.5 2.5 2.5

Ethoxylated tetraethylenepentamine 1.5 1.5 1.5

Protease (3.1% activity) 0.4 0.5 0.4

Amylase (11.5% activity) 0.2

Other and Solvent Balance Balance Balance

100.0 100.0 100.0

Component VII VIII IX

N-methyl N-1-deoxyglucosyl cocoamide 4.2 3.1 3.1

C _14-15 Alkyl Ethoxylate (2.25) Sulfate 12.6 9.3

C _12-18 Alkyl Ethoxylate (2.5) Sulfate 6.2

C _12-14 Alkyl Sulfate 3.1

C _12-14 Alkyl Ethoxylates 3.4

Dodecyltrimethylammonium chloride 0.5

Dodecenylsuccinate 5.0

Citrate 3.4 15.0

TMS/TDS (80/20)* 3.4

C _12-14 fatty acids 3.0

Oxydisuccinate 20.0

Ethoxylated tetraethylenepentamine 1.5

Polyacrylate (4500MW) 1.5 1.5

Protease (3.1% activity) 0.5 0.2 0.2

Amylase (11.5% activity) 0.2

Others and Solvents Balance Balance Balance

100.0 100.0 100.0

*TMS/TDS is tartrate monosuccinate/tartrate disuccinate.

Examples IV-IX are preferably used at about 2000 ppm (by weight of wash water) and at a wash temperature below about 50°C.

Embodiment IV-IX is by non-aqueous solvent, aqueous surfactant paste or solution, the fatty acid of melting, the aqueous solution of polycarboxylate builder and other salt, aqueous ethoxylated tetraethylene pentamine, buffer Agent, hydroxide, and remainder are mixed with water to prepare. The pH was adjusted to about pH 8.5 with aqueous citric acid or sodium hydroxide. After the pH is adjusted, the final ingredients such as soil remover, enzymes, colorants, and fragrance are added and the mixture is stirred until a single phase is formed.

Example X

The following is an additional and particularly preferred method for preparing the polyhydroxy fatty acid amides used herein. A method consisting of 84.87 g of fatty acid methyl esters (source: Procter and Gamble methyl esters CE1270), 75 g of N-methyl-D-glucosamine (source: Aldrich Chemical Company M4700-0), 1.04 g of sodium methoxide (source: : Aldrich Chemical Co. 16, 499-2), and a reaction mixture consisting of 68.51 g of methanol. The reaction vessel consisted of a standard reflux unit with drying tube, condenser and stir bar. In this step, N-methylglucamine is mixed with methanol under argon atmosphere with stirring and heated with good mixing (stir bar; reflux). After 15-20 minutes, when the solution reached the desired temperature, the ester and sodium methoxide catalyst were added. Samples were withdrawn intermittently to control the progress of the reaction, but it was noted that the solution was completely transparent for 63.5 minutes. In fact, this was judged to be near completion of the reaction. The reaction mixture was kept at reflux for 4 hours. After removal of the methanol, the recovered crude product weighed 156.16 grams. After vacuum drying and purification, a total of 106.92 g of purified product was recovered. However, percent yields cannot be calculated on this basis because periodic samples taken throughout the course of the reaction render the percent total yield meaningless. The reaction can go to completion at 80% and 90% reactant concentrations and up to 6 hours to give products with very little by-products.

A new, concentrated laundry detergent granule follows.

Example XI

Component

C _14-15 alkyl alcohol sulfonic acid 13

C _14-15 alkyl polyethoxy (2.25) sulfonic acid 5.60

C _12-13 Alkyl Polyethoxylate (6.5) 1.45

C _12-14 Fatty Acid N-Methyl Glucamide 2.50

Sodium aluminosilicate (like hydrated zeolite A) 25.2

Crystalline layered silicate builder ¹ 23.3

Citric acid 10.0

Sodium carbonate to obtain washing pH = 9.90

Sodium polyacrylate (m.w.2000-4500) 3.2

Diethylenetriaminepentaacetic acid 0.45

savinase ² 0.70

6-Nonanoylamino-6-oxo-peroxycaproic acid 7.40

Sodium perborate monohydrate 2.10

Nonanoyloxybenzenesulfonic acid 5.00

Brightener 0.10

¹ Layered silicate builders are known in the art. Preference is given to layered sodium silicates. See, for example, the layered sodium silicate builders of U.S. Patent 4,664,859, issued May 12, 1987 to HP Rieck. Suitable layered silicate builders are commercially available from Hoechst (trademark SKS-6).

² Available from Novo Nordisk A/S, Copenhagen.

Particularly preferred granules of the above type contain from about 0.0001% to about 2% by weight of active enzyme and at least about 1% by weight of said polyhydroxy fatty acid amide, and most preferably said anionic surfactant is not an alkane benzenesulfonate surfactants.

The following relates to the preparation of preferred liquid heavy duty laundry detergents according to the present invention. It is known that the stability of the enzymes in such compositions will be much less than in granular detergents. However, lipases and cellulases are protected from degradation by proteases by using common enzyme stabilizers such as formate and boric acid. However, the stability of lipases is still relatively poor in the presence of alkylbenzenesulfonate ("LAS") surfactants. Apparently, LAS partially denatures the lipase, or further, since the lipase is denatured, it is more susceptible to attack by proteases.

Based on the above considerations, which are particularly difficult in liquid compositions, it has been a challenge to provide liquid detergent compositions containing lipase, protease and cellulase simultaneously. A greater challenge is to provide a stable liquid detergent with a ternary enzyme system with effectively incorporated detersive surfactants. Additionally, it is difficult to stably incorporate peroxidases and/or amylases in such compositions.

Various mixtures of lipases, proteases, cellulases, amylases and peroxidases have been found to be fairly stable in the presence of certain non-alkylbenzenesulfonic acid surfactant systems, allowing the formulation of Effective heavy duty solid and even liquid detergents. Indeed, the formulation of stable enzyme-containing liquid detergent compositions constitutes a highly advantageous and preferred embodiment provided by the technology of the present invention.

In particular, prior art liquid detergent compositions typically contain LAS or a mixture of LAS and a surfactant of the RO(A) _mSO₃M type ("AES") described above, ie a LAS/AES mixture. In contrast, the liquid detergents of the present invention preferably comprise a binary mixture of AES and a polyhydroxy fatty acid amide of the type disclosed. When small amounts of LAS are present, it is known that the stability of the enzyme will be reduced accordingly. Therefore, the liquid composition is preferably substantially free (ie, contains less than about 10%, preferably less than about 5%, more preferably less than about 1%, and most ideally 0%) of LAS.

A kind of liquid detergent composition provided by the invention comprises:

(a) from about 1% to about 50%, preferably from about 4% to about 40%, of anionic surfactants;

(b) from about 0.0001% to about 2% active detergent enzymes;

(c) Enzyme energy enhancing (preferably from about 0.5% to about 12%) polyhydroxy fatty acid amide substances of the formula

Wherein R ¹ is H, C ₁ -C ₄ hydrocarbon group, 2-hydroxyethyl, 2-hydroxypropyl, or their combination, R ₂ is C ₅ -C ₃₁ hydrocarbon group, Z is a polyhydroxy hydrocarbon group (containing a linear hydrocarbon chain and at least 3 hydroxyl groups are directly attached to said chain), or alkoxylated derivatives thereof;

And the composition is virtually free of alkylbenzene sulfonates.

Preferred water-soluble anionic surfactants herein include ("AES"):

RO(A)mSO ₃ M

wherein R is an unsubstituted C _10-24 alkyl or hydroxyalkyl (C ₁₀ -C ₂₄ ) group, A is ethoxy or propoxy, m is an integer greater than 0, and M is hydrogen or a cation. Preferably, R is unsubstituted _C12 - _C18 alkyl, A is an ethoxy unit, m is from about 0.5 to about 6, and M is a cation. The cation is preferably a metal cation (eg, sodium (preferred), potassium, lithium, calcium, magnesium, etc.) or ammonium or substituted ammonium cations.

Here the ratio of the above surfactant ("AES") to polyhydroxy fatty acid amide is preferably from about 1:2 to about 8:1, preferably from about 1:1 to about 5:1, most preferably from about 1:1 to about 4:1.

In another aspect the present composition also contains polyhydroxy fatty acid amide, AES, and from about 0.5% to about 5% of a condensation product of a C ₈ -C ₂₂ (preferably C ₁₀ -C ₂₀ ) linear alcohol with ethylene oxide, wherein Ethylene oxygen is condensed with about 1 to about 25, preferably about 2 to about 18 moles per mole of alcohol.

As noted above, the liquid composition preferably has a pH of from about 6.5 to about 11.0, preferably from about 7.0 to about 8.5 in 10% aqueous solution at 20°C.

The instant compositions also preferably contain from about 0.1% to about 50% detergency builder. These compositions preferably contain from about 0.1% to about 20% of citric acid, or a water-soluble salt thereof, and from about 0.1% to about 20% of a water-soluble succinic acid tartrate, especially its sodium salt, and mixtures thereof, Or from about 0.1% to about 20% by weight of oxydisuccinates or mixtures thereof with the above builders. 0.1% to 50% alkenyl succinate can also be used.

Preferred liquid compositions herein contain from about 0.0001% to about 2%, preferably about 0.0001% to 1%, most preferably about 0.001% to about 0.5% (on an active agent basis) of detergent enzymes. These enzymes are preferably selected from proteases (preferred), lipases (preferred), amylases, cellulases, peroxidases, and mixtures thereof. The composition preferably has two or more enzymes, and most preferably one is a protease.

While various descriptions of detergent proteases, cellulases, etc. are available in the literature, detergent lipases are less well known. Therefore, to aid formulators, lipases of interest include Amano AKG and Bacillis Sp lipases (such as Solvay enzymes). See also EP A 0399 681 (published on November 28, 1990), EPA 0218 272 (published on April 15, 1987), and lipases described in PCT/DK88/00177 (published on May 18, 1989), all of which All literatures are listed as references in this paper.

Suitable fungal lipases include those produced by Humicola Lanuginosa and Thermomyces Lanuginosus. Most preferred is a lipase obtained by cloning genes in Humicola Lanuginosa and expressed in Aspergillus oryzae, as described in European Patent Application 0258068 (herein incorporated by reference), commercially available under the trademark LIPOLASE The product.

From about 2 to about 20,000, preferably from about 10 to about 6,000 lipase units per gram of product (Lu/g) may be used in these compositions. 1 lipase unit is the amount of lipase that produces 1 micromole of titratable butyric acid per minute at pH 7.0 at 30°C, and the substrate is in phosphate buffer in the presence of Emulsion of tributyrin and gum arabic in the presence of Ca ⁺⁺ and NaCl.

The following examples describe preferred heavy duty liquid detergent compositions comprising:

(a) Enzymes selected from proteases, cellulases and lipases, or preferably mixtures thereof, generally comprising from about 0.01% to about 2% (based on total composition weight), although the amount used may vary according to the desires of the formulator to provide an "effective" amount (i.e. soil removal amount) of said enzyme or enzyme mixture;

(b) A polyhydroxy fatty acid amide surfactant as disclosed herein, generally comprising at least about 2% by weight of the composition; more typically comprising from about 3% to about 15%, preferably from about 7% to about 14% ;

(c) A surfactant of the type RO(A)mSO ₃ M (disclosed herein), preferably RO(CH ₂ CH ₂ O)mSO ₃ M, wherein R is C ₁₄ -C ₁₅ (average) and m is 2 -3 (average), wherein M is H or a water-soluble salt-forming cation, such as Na ⁺ , said surfactants generally comprising from about 5% to about 25% by weight of the composition;

(d) Optionally, surfactants of the ROSO ₃ M type (disclosed herein), preferably wherein R is C ₁₂ -C ₁₄ (average), said surfactants preferably contain from about 1% to about 10 %, by weight of the composition;

(e) a liquid carrier, especially water or a water-alcohol mixture,

(f) optionally (but preferably), an effective amount of an enzyme stabilizer, generally from about 1% to about 10%, by weight of the composition;

(g) optionally (but preferably), water-soluble builders, especially polycarboxylate builders, generally from about 4% to about 25% by weight of the composition;

(h) optionally, containing various detergent additives, brighteners, etc. (as described above), generally (if used) from about 1% to about 10%, by weight of the composition; and

(i) The composition is virtually free of LAS.

Example XII

Component Weight %

C _14-15 Alkyl Polyethoxy (2.25) Sulfonic Acid 21.0

C _12-14 fatty acid N-methylglucamide ¹ 7.0

Sodium tartrate mono and disuccinate (80:20 mix) 4.00

Citric acid 3.80

C _12-14 fatty acids 3.00

Tetraethylenepentamine ethoxylate (15-18) 1.50

Ethoxylated polyethylene-polypropylene terephthalate copolymer polysulfonic acid 0.20

Protease B (34g/l) ² 0.68

Lipase (100KLU/g) ³ 0.47

Cellulase (5000cevu/g) ⁴ 0.14

Brightener 36 ⁵ 0.15

Ethanol 5.20

Monoethanolamine 2.00

Sodium formate 0.32

1,2 propylene glycol 8.00

Sodium hydroxide 3.10

Silicone foam suppressor 0.0375

Boric acid 2.00

Water/other balance to 100

¹ was prepared by the method disclosed above.

² Protease B is a denatured bacterial serine protease described in European Patent Application Serial No. 87303761 (filed April 28, 1987), particularly pages 17, 24 and 98.

³ The lipase used here is the lipase derived from the cloned gene of Humicola Lanuginosa and the gene expressed in Aspergillus oryzae, described in European Patent Application 0258068 and available under the trademark LIPOLASE (available from Novo Nordisk A/S, Copenhagen Denmark ) are available in the market.

⁴ Cellulases used herein are sold under the trade mark CAREZYME (Novo Nordisk, A/S, Copenhagen Denmark).

^5Brightener 36 is commercially available under the trademark TINOPAL TAS 36.

The brightener was added to the composition by additional premixing of brightener (4.5%), monoethanolamine (60%) and water (35.5%).

The following examples are not intended to limit the present invention, but are provided for the reference of formulators in the use of polyhydroxy fatty acid amides to make various detergent compositions, ie, to further illustrate other aspects of the present technology.

It is easy to know that polyhydroxy fatty acid amides are somewhat unstable under strong alkaline or acidic conditions due to their own amide bonds. Although some decomposition is allowed, it is preferred that the materials have a pH no higher than 11, preferably no higher than 10, nor lower than about 3 for unduly prolonged periods of time. The final product pH (liquid) is typically 7.0-9.0.

During the preparation of polyhydroxy fatty acid amides, it is generally necessary to at least partially neutralize the basic catalyst used to form the amide bond. Since any acid can be used for this purpose, the detergent formulator will recognize that it is a simple and convenient matter to use an acid which provides a useful and desirable anion in the final detergent composition. For example, citric acid is used for neutralization purposes and the resulting citrate ions (approximately 1%) are allowed to remain in approximately 40% polyhydroxy fatty acid amide slurry and pumped to the next preparation process of the full detergent preparation process middle. It is also possible to use acid forms such as oxydisuccinate, nitrilotriacetate, ethylenediaminetetraacetate, tartaric acid/succinate and the like.

Polyhydroxy fatty acid amides derived from coconut alkyl fatty acids (predominantly C ₁₂ -C ₁₄ ) are more soluble than their tallow alkyl (predominantly C ₁₆ -C ₁₈ ) counterparts. Thus, _C12 - _C14 species are sometimes more readily formed in liquid compositions and are more soluble in cold water wash sinks. However, C ₁₆ -C ₁₈ materials are also useful, especially in warm to hot water washes. In fact, _C16 - _C18 materials are better detersive surfactants than their _C12 - _C14 counterparts. Therefore, a formulator will desire a comparison of both ease of manufacture and performance in selecting a particular polyhydroxy fatty acid amide for use in a given formulation.

It will also be appreciated that the solubility of polyhydroxy fatty acid amides is enhanced by the presence of points of unsaturation and/or chain branching in the fatty acid moiety. Thus, materials such as the polyhydroxy fatty acid amides derived from oleic acid and iso-stearic acid are more soluble than their n-alkyl counterparts.

Likewise, polyhydroxy fatty acid amides prepared from disaccharides, trisaccharides, etc. are generally more soluble than their monosaccharide-derived counterpart materials. This higher solubility is of great help in forming liquid compositions. Furthermore, polyhydroxy fatty acid amides, in which the polyhydroxy groups are derived from maltose, exhibit particularly good performance as detergents when combined with conventional alkylbenzenesulfonyl salt ("LAS") surfactants. Without wishing to be bound by theory, it appears that the combination of LAS with polyhydroxy fatty acid amides derived from higher sugars such as maltose causes a significant and unexpected reduction in interfacial tension in aqueous media, thus improving net cleaning performance. (The preparation of polyhydroxy fatty acid amides from maltose will be described below.)

Polyhydroxy fatty acid amides can be prepared not only from pure sugars, but also from hydrolyzed starches such as corn starch, potato starch or any other convenient plant-derived starch containing mono-, di-, etc.-saccharides desired by the formulator. This is very important from an economic point of view. Therefore, it is convenient and economical to use "high dextrose" corn syrup, "high maltose" corn syrup, etc. De-lignified hydrolyzed cellulose pulp may also provide a source of raw material for the preparation of polyhydroxy fatty acid amides.

As noted above, polyhydroxy fatty acid amides derived from higher sugars, such as maltose, lactose, etc., are more soluble than their glucose counterparts. Furthermore, it appears that the more soluble polyhydroxy fatty acid amides may aid in dissolving their less soluble counterparts to varying degrees. So, for example, a formulator may choose to use an ingredient that contains high dextrose corn syrup rather than a syrup that contains a small amount of maltose (such as 1% or more). The resulting hydroxy fatty acid mixtures generally exhibit better solubility over a wider range of temperatures and concentrations than "pure" glucose derived polyhydroxy fatty acid amides. Thus, in addition to any economic advantages of using sugar mixtures rather than pure sugar reactants, polyhydroxy fatty acid amides derived from mixed sugars offer substantial advantages in terms of performance and/or ease of manufacture. In some cases, however, some loss of degreasing performance (dishwashing) may be indicated by a maltamide fatty acid content of greater than about 25%, and some loss of greater than about 33% in lathering (the stated percentages are maltamide in the mixture). Percentage of polyhydroxy fatty acid amides obtained to polyhydroxy fatty acid amides obtained from glucose). This value is sometimes variable, depending on the chain length of the fatty acid moiety. In general, then, a formulator choosing to use such a mixture may find it desirable to select a polyhydroxy fatty acid amide mixture containing a ratio of monosaccharide (such as glucose) to di- and higher sugar (such as maltose) from about 4:1 to about 99:1. There are advantages.

The preparation of preferred, non-cyclized polyhydroxy fatty acid amides from fatty esters and N-alkyl polyols can be accomplished in alcoholic solvents at temperatures from about 30°C to 90°C, preferably from about 50°C to 80°C. It has now been determined that it is convenient for the formulator, for example for liquid detergents, to carry out such a process in 1,2-propylene glycol, since said propylene glycol solvent is used prior to use in the final detergent composition. It does not have to be completely removed from the reaction product. Likewise, for example, formulators of solid, especially granular detergent compositions will find it useful to include ethoxylated alcohols, such as ethoxylated (EO3-8) C ₁₂ -C ₁₄ alcohols at 30°C-90°C [as available from the market It is convenient to carry out such a process in a solvent such as NEODOL23EO6.5 (Shell)]. When such ethoxylates are used, they preferably do not contain significant amounts of non-ethoxylated alcohols and most preferably do not contain significant amounts of monoethoxylated alcohols. (“T” designation.)

Although the preparation of polyhydroxy fatty acid amides per se is not part of the present invention, formulators may also be aware of other methods of synthesizing polyhydroxy fatty acid amides described below.

A general industrial-scale reaction procedure for the preparation of the preferred acyclic polyhydroxy fatty acid amides would include: first step - preparation of polyhydroxy fatty acid amide derivatives from the desired sugar or sugar mixture by N-alkylamide and sugar addition, followed by Reaction with hydrogen in the presence of a catalyst; followed by the second step - reaction of said polyhydroxylamine with (preferably) fatty ester to form an amide bond. Since the various N-alkyl polyhydroxylamines used in the second step reaction process can be prepared by various existing processes, the subsequent process is convenient and economical syrup can be used as a raw material. It is known that for best results with this syrup material the manufacturer should select a syrup that is fairly light in color, preferably nearly colorless ("water white").

Preparation of N-Alkyl Polyhydroxylamines from Plant-Derived Sugar Syrups

1. Adduct formation - the following is the standard method: with about 420 grams of about 55% dextrose solution (corn syrup - about 231 grams of glucose - about 1.28 moles) [its Gardner Color (Gardner Color) is less than 1] with about 119 grams About 50% methylamine (59.5 g methylamine - 1.92 moles) aqueous solution was reacted. Purge and isolate the methylamine (MMA) solution with _N , and cool to about 10 °C, or lower. Wash and isolate the corn syrup with _N2 at a temperature of about 10°-20°C. The corn syrup was slowly added to the MMA solution at the desired reaction temperature (indicated). Gardner color can be measured at the approximate times (minutes) shown.

Table 1

Time (minutes): 10 30 60 120 180 240

Reaction temperature °C Gardner color (approximate)

0 1 1 1 1 1 1

20 1 1 1 1 1 1

30 1 1 2 2 4 5

50 4 6 10 - - -

As can be seen from the above data, the Gardner color of the adduct is poor when the temperature is raised above about 30°C, and the Gardner color of the adduct is below 7 for only about 30 minutes at about 50°C. For longer reactions, and/or durations, the temperature should be below about 20°C, and the Gardner color should be below 7, preferably below 4 for good color glucosamine.

Using a higher ratio of amine to sugar results in a shorter time to reach a substantial equilibrium concentration of the adduct when lower temperatures are used to form the adduct. When the amine to sugar ratio is 1.5:1 molar, equilibrium will be reached in about 2 hours at a reaction temperature of about 30°C. At a 1.2:1 molar ratio, the time to reach equilibrium is at least about 3 hours under the same conditions. For good color, the amine:sugar ratio; reaction temperature; and reaction time are selected such that the combination achieves a substantially equilibrium conversion (as sugar), e.g., greater than about 90%, preferably greater than about 95%, more preferably Greater than about 99%, the color of the adduct is less than about 7, preferably less than about 4, more preferably less than about 1.

Conducting the above process at a reaction temperature of less than about 20°C, given the different Gardner colors of the corn syrup, gives the color of the MMA adduct (after reaching substantial equilibrium for at least about 2 hours).

Table 2

Gardner color (approximate)

Corn Syrup 1 1 1 1+ 0 0 0+

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

As can be seen from the above data, the starting sugar material must be nearly colorless in order for the adduct to consistently pass. When the sugar Gardner color is about 1, the adduct is sometimes acceptable and sometimes not acceptable. When the Gardner color is greater than 1, the resulting adduct is unacceptable. The better the starting color of the sugar, the better the color of the adduct.

II. Hydrogenation reaction - The adduct obtained above having a Gardner color of 1 or less was hydrogenated in the following manner.

About 539 grams of adduct in water and about 23.1 grams of United Catalyst G49BNi catalyst were charged to a 1 liter autoclave and purged ₂ times with 200 psig H2 at about 20°C. The hydrogen pressure was raised to about 1400 psi and the temperature was raised to about 50°C. The pressure was then raised to about 1600 psig and the temperature was maintained at about 50-55°C and maintained at these conditions for 3 hours. At this point about 95% of the product is hydrogenated. The temperature was then raised to about 85°C for 30 minutes, the reaction mixture was decanted and the catalyst was filtered off. After removal of water and MMA by evaporation, the product of about 95% N-methylglucamine was obtained as a white powder.

The above procedure was repeated using about 23.1 grams of Raney Ni catalyst with the following changes. The catalyst was washed 3 times, the reactor (the one containing the catalyst) was rinsed 2 times with 200 psig H ₂ , the reactor was pressurized with 1600 psig H ₂ for 2 hours, depressurized at 1 hour and then repressurized to 1600 psig. The adduct was then pumped into a reactor at 200 psig and 20°C, and 200 psig _H2 was fed into the reactor, etc., as described above.

The product obtained in each case had greater than about 95% N-methylglucamine; had less than about 10 ppm Ni (based on glucosamine); and had a solution color of less than about 2 Gardner.

Crude N-methylglucamine is color stable up to about 140°C with brief exposure times.

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

In another reaction, starting with about 159 g of methylamine in about 50% water, the adduct was prepared at about 10-20°C with a _N2 purge and isolation. About 330 grams of about 70% corn syrup (approximately water white) was deoxygenated with _N2 at about 50°C and the methylamine solution was added slowly at a temperature below about 20°C. The solution was mixed for about 30 minutes to give about 95% adduct as a pale yellow solution.

About 190 g of the adduct in water and about 9 g of United Catalyst G49B Ni catalyst were added to a 200 mL autoclave and purged ₃ times with H at about 20 °C. The hydrogen pressure was raised to about 200 psi and the temperature was raised to about 50°C. The pressure was raised to 250 psi and the temperature was maintained at about 50-55°C for about 3 hours. The about 95% hydrogenated product obtained at this time was then raised to about 85°C for 30 minutes. After removal of water and steam, the product was about 95% N-methylglucamine and was a white powder.

When the hydrogen pressure is less than about 100 psig, reducing the contact between the adduct and the catalyst is also important to reduce the Ni content of the glucosamine. In this reaction, the nickel content in N-methylglucamine was about 100 ppm, a decrease of 10 ppm compared to the previous reaction.

The following reactions were performed with _H2 to directly compare the effect of reaction temperature.

The adducts were prepared and the hydrogenation was carried out at various temperatures in a 200 ml autoclave reactor following a general procedure similar to that already described above.

The adduct used in the preparation of glucosamine was prepared by passing about 420 grams of about 55% dextrose (corn syrup) solution (231 grams of glucose; 1.28 moles) (the solution was made with 99DE corn syrup commercially available from CorGill, which The solution had a color less than Gardner 1) and about 119 g of 50% methylamine (59.5 g MMA; 1.92 moles) (obtained from Air Products).

The reaction process is as follows:

1. Add about 119 grams of 50% methylamine solution to the _N2 purged reactor, blanket with _N2 and cool to below about 10°C.

2. At 10-20°C, deoxygenate and/or purge the 55% corn syrup solution with _N2 to remove oxygen from the solution.

3. Slowly add the corn syrup solution to the methylamine solution, keeping the temperature below about 20°C.

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

The adducts were used in hydrogenation reactions immediately after preparation, or were stored at low temperature to prevent further degradation.

The hydrogenation reaction of glucosamine adducts is as follows:

1. Add about 134 grams of adduct (color less than about 1 Gardner) and about 5.8 grams of G49BNi to a 200 mm autoclave.

2. Purge the reaction mixture twice with about 200 psi _H2 at about 20-30°C.

3. Pressurize to about 400 psi. with _H2 and raise temperature to about 50°C.

4. Increase the pressure to about 500 psi, react for 3 hours, and keep the temperature at 50-55°C. Take out sample 1.

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

6. Decant and filter off the Ni catalyst. Take out sample 2.

Constant temperature reaction conditions:

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

2. Rinse twice with about 200 psi _H2 at low temperature.

3. Pressurize to about 400 psi with _H2 and raise temperature to about 50°C.

4. The pressure was raised to about 500 psi and the reaction was carried out for 3.5 hours. Keep the temperature at the specified temperature.

5. Decant and filter off the Ni catalyst. Sample 3 was about 50-55°C; Sample 4 was about 75°C; Sample 5 was about 85°C. (Reaction time is about 45 minutes at about 85°C.)

All tests gave N-methylglucamine of similar purity (approximately 94%); the Gardner colors of the tests after reaction were very similar, but only two heat treatments gave good color stability; and the 85°C test Gives the border color immediately after the reaction.

Example XIII

According to the present invention, the greasy (hardened) fatty acid amides of N-methylmaltamine for use in detergent compositions are prepared as follows:

Step 1 - Reactants: Maltose-hydrate (Aldrich, lot 01318KW); Methylamine (40% by weight in water) (Aldrich, lot 03325TM); Raney Nickel, 50% slurry (UAD 52-73D, Aldrich, lot 12921LW).

The reactants were added to a glass lined (250 g maltose, 428 g methylamine solution, 100 g catalyst slurry - 50 g Raney nickel) 3 liter shaking autoclave fed with nitrogen (3 x 500 psig) and hydrogen (2 ×500 psig) and shaken over a weekend at room temperature under a hydrogen atmosphere that can vary from 28°C to 50°C. The crude reaction mixture was vacuum filtered twice through a glass microfiber filter with a silica gel plug. The filtrate was concentrated to a viscous mass. The remaining traces of water were removed by dissolving the material in methanol followed by azeotroping (methanol/water) on a rotary evaporator. Finally dry under high vacuum. The crude product was dissolved in refluxing methanol, filtered, cooled to recrystallize, filtered and the filter cake dried under vacuum at 35°C. This is Fraction 1#. The filtrate was concentrated until a precipitate started to form and stored overnight in a refrigerator. The solid was filtered and dried under vacuum. This is Fraction 2#. The filtrate was again concentrated to half volume and recrystallization formed. Little precipitate formed. A small amount of ethanol was added and the remaining solution was left in the refrigerator for a weekend. The solid material was filtered and dried under vacuum. The combined solids constitute the N-methylmaltamine used in step 2 of the total synthesis.

Step 2 - Reactants: N-methyl maltamine (obtained from step 1); hardened tallow methyl ester: sodium methoxide (25% in methanol); anhydrous methanol (solvent); amine in molar ratio 1:1 : ester; initial catalyst content 10 mol% (w/v maltamine): increased to 20 mol%; solvent content 50% by weight.

In a sealed bottle, 20.36 g of tallow methyl ester was heated to its melting point (water bath) and charged to a 250 ml 3-neck round bottom flask equipped with mechanical stirring. The flask was heated to about 70°C to prevent solidification of the ester. Separately, 25.0 grams of N-methyl maltamine was mixed with 45.36 grams of methanol, and the resulting slurry was added to the tallow ester with good stirring. 1.51 g of 25% sodium methoxide in methanol was added. After 4 hours, the reaction mixture was not clear, so an additional 10 mole % catalyst was added (20 mole % total) and the reaction was allowed to continue overnight (about 68°C), after which time the mixture cleared. The reaction flask was then switched to distillation and the temperature was raised to 110°C. Distillation at atmospheric pressure lasted 60 minutes. High vacuum distillation was then started and continued for 14 minutes during which time the product was very thick. The product was kept in the reaction flask at 110°C (external temperature) for 60 minutes. The product was scooped out of the flask and triturated in ether over a weekend. The ether was removed on a rotary evaporator and the product was stored in an oven overnight and ground to a powder. Any remaining N-methylmaltamine was removed from the product using silica gel. The silica gel slurry in 100% methanol was placed in a funnel and washed several times with 100% methanol. A concentrated sample of the product (20 g in 100 mL of 100% methanol) was placed on silica gel, eluted several times with vacuum, and washed several times with methanol. The collected eluate was evaporated to dryness (rotary evaporator). Any remaining tallow esters were removed by trituration in ethyl acetate overnight followed by filtration. The filter cake was vacuum dried overnight. The product is tallow alkyl N-methyl maltamide.

In a modified example, the above-mentioned reaction process of step 1 can be carried out using commercially available corn syrup (containing dextrose or a mixture of dextrose, and generally also containing 5% or higher maltose). The resulting polyhydroxy fatty acid amides and mixtures can be used in any of the detergent compositions herein.

In another modified example, the above-mentioned second step reaction process is carried out in 1,2-propanediol or NEODOL. At the discretion of the formulator, the propylene glycol or NEODOL used need not be removed from the reaction product prior to formulating the detergent composition. Alternatively, at the desire of the formulator, the methoxide catalyst can be neutralized with citric acid to obtain sodium citrate, which can be preserved in polyhydroxy fatty acid amides.

The compositions herein may contain more or less of a variety of suds control agents according to the desires of the formulator. Generally, high suds are desired for dishwashing, so suds control agents are not used. Certain suds control agents are desirable for fabric laundering in top loading washing machines, with a maximum degree of suds control being preferred for front loading machines. There are a variety of foam control agents in the existing technology, which can be selected and used by conventional methods. In practice, the choice of suds control agent or mixture of suds control agents for any particular detergent composition will depend not only on the presence or amount of polyhydroxy fatty acid amide, but also on the presence of other surfactants in the formulation. However, it appears that the various types of silicone-based suds control agents used with polyhydroxy fatty acid amides are more effective (ie, lower levels are available) than the other various suds control agents. In particular the commercially available X2-3419 and Q2-3302 (Dow Corning) were used here as silicone suds control agents.

Formulators of fabric washing compositions containing advantageous soil release agents have a wide variety of known materials to choose from (see, e.g., U.S. Patents 3,962,152; 4,116,885; 4,238, 531; 4,702,857; 4,721,580 and 4,877,896). Other detergency materials useful herein include those containing polyethoxy units derived from C ₁ -C ₄ alkoxy-terminated units (e.g., CH ₃ [OCH ₂ CH ₂ ] ₁₆ OH); (e.g., dimethyl terephthalate); derived from poly(oxyethylene) oxygen units (e.g., polyethylene glycol 1500); derived from oxypropylene oxide units (e.g., 1,2-propylene glycol) and derived from oxidized Nonionic oligomer esterification products of reaction mixtures of ethylene oxide units such as ethylene glycol, especially wherein the molar ratio of oxyethylene oxide units to isopropylene oxide units is at least 0.5:1. Such nonionic soil removers have the general formula:

wherein R ¹ is lower (e.g. C ₁ -C ₄ ) alkyl, especially 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 from about an integer from 0.25 to about 20; and ^R is a combination of H and _CH to provide a molar ratio of oxyethylene oxide to isopropylene oxide of at least about 0.5:1. Another preferred type of soil remover for use herein is the common anionic type described in U.S. Patent 4,877,896, provided that the soil remover is substantially free of the HOROH type (wherein R is sub- Propyl or higher alkyl) monomers. Thus, the soil release agents in U.S. Patent No. 4,877,896 may include, for example, the reaction product of dimethyl terephthalate, ethylene glycol, 1,2-propanediol and 3-sodiosulfobenzoic acid, and In one aspect such additional soil release agents may include, for example, dimethyl terephthalate, ethylene glycol, the reaction product of 5-sodiosulfoisophthalate and 3-sodiosulfobenzoic acid. The soil removers are preferably used in granular laundry detergents.

Formulators may also decide that the inclusion of non-perborate bleach is beneficial, especially in heavy duty granular laundry detergents. Various peroxygen bleaches are commercially available and can be used herein, however, of these, percarbonate is convenient and economical. Accordingly, the detergent compositions herein may contain solid percarbonate bleach, usually in the form of the sodium salt, at an added level of from 3% to 20% by weight, preferably from 5% to 18% ( weight), most preferably from 8% to 15% by weight (based on the weight of the composition).

Sodium percarbonate is _an additional compound having the corresponding formula _{2Na2CO3.3H2O2} and is _{commercially available} as a crystalline solid. Most commercially available materials include low levels of heavy metal chelating agents such as EDTA, 1-hydroxyethylidene 1,1-diphosphonic acid (HEDP) or ammonium phosphonate, which are introduced during the preparation process. As used herein, percarbonate can be incorporated into detergent compositions without additional protection, whereas the preferred embodiment of the present invention utilizes a stabilized form of the material (FMC). Although various coatings can be used, the most economical is sodium silicate, with a SiO ₂ :Na ₂ O ratio of 1.6:1 to 2.8:1, preferably 2.0:1, used as an aqueous solution and dried to give 2% to 10 % (typically 3% to 5%) silicate solids content (by weight of percarbonate). Magnesium silicate can also be used, and any of the chelating agents described above can be included in the coating.

The particle size of the crystalline percarbonate ranges from 350 microns to 450 microns with an average of about 400 microns. When coated, the crystals have a particle size in the range of 400 to 600 microns. Since the presence of heavy metals in the sodium carbonate used to make percarbonate can be controlled by introducing chelating agents into the reaction mixture, there remains a need for percarbonate to prevent heavy metals from being present as impurities in other components of the product. It has been found that the total content of iron, copper and manganese ions in the product should not exceed 25 ppm and preferably should be below 20 ppm in order to avoid unacceptable detrimental effects on percarbonate stability.

Example XIV

The following illustrates the preparation of perborate bleach plus bleach activator detergent compositions of the present invention by mixing the following ingredients in a mixing drum.

In this example, Zeolite A refers to hydrated crystalline Zeolite A containing about 20% water and having an average particle size of 1 to 10, preferably 2 to 5 microns; LAS refers to sodium C _12.3 linear alkylbenzene sulfonate; AS refers to Sodium C _14-15 Alkyl Sulfate; nonionic means non-ethoxylated and monoethoxylated coconut alcohols condensed with about 6.5 moles of ethylene oxide per mole of alcohol and stripped, and abbreviated C _n AE6 .5T; and DTPA means sodium diethylenetriaminepentaacetate.

Granular of the final composition

Parts by weight Percentage

Basic particle ¹ 51.97 100.00

AS 9.44 18.16

LAS 2.92 5.62

Humidity 4.47 8.60

Sodium silicate (1.6 ratio) 1.35 2.60

Sodium sulfate 6.47 12.45

Sodium polyacrylate (4500MW) 2.61 5.02

PEG 8000 1.18 2.27

Nonionic 0.46 0.89

Sodium carbonate 13.29 25.57

Brightener 0.20 0.38

Sodium aluminosilicate 9.11 17.53

DTPA 0.27 0.52

Spices 0.20 0.38

Particle ² 6.09 100.00

NAPAA 2.86 46.96

LAS 0.30 4.93

Sulfates and others 2.93 48.11

Particle ³ 3.88 100.00

NOBS 3.15 81.19

LAS 0.12 3.09

PEG 8000 0.19 4.90

Other 0.42 10.82

Zeolite particles ⁴ 12.00 100.00

Sodium aluminosilicate 7.39 61.58

PEG 8000 1.50 12.47

Nonionic 1.16 9.70

Humidity 1.66 13.83

Other 0.29 2.42

mix

Sodium SKS-6

Layered silicate 15.84

Protease (0.78mg/g activity) 0.52

sodium perborate

-hydrate 1.33

Citric acid 6.79

C ₁₂ -C ₁₄ N-Methyl Glucamide 1.58

Total amount of final composition 100.00

¹ Base granules are prepared by spray drying an aqueous stirred mixture of the listed ingredients.

² Obtain a freshly prepared sample of NAPAA wet cake, which usually consists of about 60% water, about 2% peroxyacid (for oxygen acquisition) (AVO) (equivalent to about 36% NAPAA), and the remaining (about 4%) consisted of unreacted starting material. The wet cake is the crude reaction product of NAAA (monononyl adipate), sulfuric acid, and hydrogen peroxide, which is sequentially quenched with the addition of water followed by filtration, washed with distilled water, washed with phosphate buffer and finally aspirated. The wet cake is recovered by filtration. A portion of the wet cake was air dried at room temperature to obtain a dry sample, which typically consisted of about 5% AvO (equivalent to about 90% NAPAA) and about 10% unreacted starting material. When dry, the sample pH was approximately 4.5.

NAPAA granules are prepared by mixing about 51.7 parts of dry NAPAA wet cake (containing about 10% unreacted matter), about 11.1 parts of C _12.3 sodium linear alkylbenzene sulfonate (LAS) paste (45% active matter) in a CUISINART mixer , about 43.3 parts of sodium sulfate, and about 30 parts of water. After drying, the granules (containing about 47% NAPAA) were sieved through a No. 14 Tyler mesh sieve, retaining all granules that did not pass through a No. 65 Tyler mesh. The size of the amide peroxyacid particles (agglomerates) is about 5-40 microns, with a median particle size of about 10-20 microns, as determined by Malvern particle analysis.

³ NOBS (nonanoyloxybenzenesulfonate) particles were prepared according to U.S. Patent 4,997,596, Bowling et al., issued March 5, 1991, incorporated herein by reference.

⁴ Zeolite particles having the following composition can be prepared by mixing Zeolite A with PEG8000 and CnAE6.5T in an Eirich R08 energy tumbler mixer.

parts by weight

before drying after drying

Zeolite A (including bound water) 70.00 76.99

PEG 8000 10.80 12.49

CnAE6.5T 8.40 9.72

Free moisture 10.80 0.80

PEG 8000 is a liquid containing 50% water and at a temperature of approximately 55°F (12.8°C). CnAE6.5T is liquid and maintained at approximately 90°F (32.2°C). The two liquids were pumped through a 12-element static mixer to give a combined mass with an outlet temperature of about 75°F (23.9°C) and a viscosity of about 5000 cps. The ratio of PEG8000 and C _n AE6.5T passing through the static mixer is 72:28, respectively.

The Eirich R08 energy tumbler mixer operates in batch mode. First weigh 34.1 Kg of powdered zeolite A in the pan of the mixer. The mixer started by first rotating the disc at approximately 75 revolutions per minute (rpm) counterclockwise, and then the rotating blades were then rotated clockwise at 1800 rpm. The bound material was pumped directly from the static mixer into an Eirich R08 energy tumbler mixer containing zeolite A at a feed rate of about 2 minutes for the bound material. The mixer continued to mix for an additional 1 minute, for a total batch time of approximately 3 minutes. The batch is then unloaded and collected in fiber drums.

Each batch of steps was repeated until approximately 225 Kg of wet product was obtained. The discharge product is then dried in a fluidized bed at 240-270°F (116-132°C). The drying step removes most of the free moisture and modifies the above composition. The total energy input from the mixer to each batch of product formation was about 1.31 x ¹⁰¹² erg/Kg at a rate of about 2.18 x ¹⁰⁹ erg/Kg-s.

The following free flowing agglomerates were obtained having an average particle size of about 450-500 microns.

Example XV

For liquid laundry detergent compositions suitable for use in front-loading automatic washing machines, often used in high concentrations, especially in Europe, and over a wide temperature range, the composition is as follows:

Component Wt.%

Coconut Alkyl (C ₁₂ ) N Methyl Glucamide 14

C _14-15 EO (2.25) sulfate, Na salt 10.0

C _14-15 EO (7) 4.0

C _12-14 alkenyl succinic anhydride ¹ 4.0

C _12-14 Fatty Acids* 3.0

Citric acid (anhydrous) 4.6

Protease (enzyme) ² 0.37

Termamyl (enzyme) ³ 0.12

Lipolase (enzyme) ⁴ 0.36

Carezyme (enzyme) ⁵ 0.12

Dequest 2060S ⁶ 1.0

NaOH (pH to 7.6) 5.5

1,2 Propanediol 4.7

Ethanol 4.0

Sodium metaborate 4.0

CaCl ₂ 0.014

Ethoxylated tetraethylenepentamine ⁷ 0.4

Brightener ⁸ 0.13

Silane ⁹ 0.04

Clay soil release polymer ¹⁰ 0.2

Silicone (foam suppressor) ¹¹ 0.4

Silicone dispersant ¹² 0.2

Water and minor substances Balance amount

¹ As SYNPRAX 3 from 1Cl or DTSA from Monsanto.

² As Protease B, described in EPO 0 34 2177 (1989.11.15), the ratio is 40g/1.

³ amylase, purchased from NOVO, the rate is 300KNU/g.

⁴ lipase, purchased from NOVO, the rate is 100KLU/g.

⁵ Cellulase was purchased from NOVO at a rate of 5000CEVU/L.

⁶ obtained by Monsanto.

⁷ Commercially available as LUTENSOL P6105 from BASF.

⁸ BLANKOPHOR CPG766, Bayer.

⁹ Silane corrosion inhibitor, A11 30 from Union Carbide or DYNASYLAN TRIAMINO from Hiils.

¹⁰ polyester, see USP 4711730.

¹¹ Silicone suds suppressor available from Dow Corning as Q2-3302.

¹² Dispersant for silicone suds suppressor available from Dow Corning as DC-3225C.

*The preferred fatty acid is topped palm kernel oil, comprising 12% oleic acid and 2% each of stearic and linoleic acids.

Example XVI

For a granular laundry detergent composition suitable for front-loading automatic washing machines, often used in high concentrations, especially in Europe, and used over a wide temperature range, the composition is as follows:

Component Wt.%

SOKALAN CP5 (100% active, as sodium salt) ¹ 3.52

DEQUEST 2066 (100% as acid) ² 0.45

TINOPAL DMS ³ 0.28

MgSO ₄ 0.49

Zeolite A (anhydrous) 17.92

CMC (100% activity) ⁴ 0.47

Na ₂ CO ₃ 9.44

Citric acid 3.5

Laminated silicate SKS-6 12.9

Tallow Alkyl Sulfate (100% active, sodium salt) 2.82

C ₁₄ -C ₁₅ alkyl sulfate (100% active, sodium salt) 3.5

C ₁₂ -C ₁₅ Alkyl EO(3) Sulfate 1.76

C ₁₆ -C ₁₈ N-Methyl Glucamide 4.1

DOBANOL C ₁₂ -C ₁₅ EO (3) 3.54

LIPOLASE (100,000LU/g) ⁵ 0.42

SAVINASE (4.0KNPU) ⁶ 1.65

Spice 0.53

X2-3419 ⁷ 0.22

Starch 1.08

Stearyl alcohol 0.35

Sodium percarbonate (coating) 22.3

Tetraacetylethylenediamine (TAED) 5.9

Zinc phthalocyanine 0.02

Water (from zeolite) Balance

¹ SOKALAN is polyacrylic acid/sodium maleate obtained from Hoechst.

² Monsanto trademark pentaphosphonomethyldiethylenetriamine.

³ Optical brightener, obtained from Ciba Geigy.

⁴ Trade name FINNFIX. Obtained from Metasaliton.

⁵ LIPOLASE lipolytic enzyme, obtained from NOVO.

⁶ SAVINASE protease obtained from NOVO.

^7X2-3419 is a silicone suds suppressor available ^from Dow Corning.

Methods of preparing particles include various tower drying, agglomeration, dry-addition, etc., as described below. Percentages are based on the final composition.

A. Supported with a tower and blown

The following components were fork dried using standard methods.

SOKALAN CP5 3.52%

DEQUEST 2066 0.45%

TINOPAL DMS 0.28%

Magnesium Sulfate 0.49%

Anhydrous Zeolite A 7.1%

CMC 0.47%

B. Surfactant aggregates

_B1 . Agglomeration of sodium salt of tallow alkyl sulfate and sodium salt of _C12-15 EO(3) sulfate paste

A 50% active paste of tallow alkyl sulfate and a paste of 70% _C₁₂ - _C₁₅EO (3) sulfate was assembled with Zeolite A and sodium carbonate according to the following formula (aggregate dried to facilitate detergent preparation).

Tallow Alkyl Sulfate 2.82%

C _12-15 EO(3) sulfate 1.18%

Zeolite A 5.3%

Sodium carbonate 4.5%

B2. Agglomerates of C ₁₄ -C ₁₅ alkyl sulfates, C ₁₂ -C ₁₅ alkyl ethoxy sulfates, DOBANOL C ₁₂ -C ₁₅ EO (3) and C ₁₆ -C ₁₈ N-methylglucamide -C ₁₆ -C ₁₈ Glucamide nonionics are synthesized by adding DOBANOLC _12-15 EO (3) during the reaction of methyl esters and N-methylglucamine. C _12-15 EO (3) acts as a melting point depressant so that the reaction proceeds without formation of the undesired cyclic glucamide.

A surfactant mixture consisting of 20% DOBANOL C _12-15 EO (3) and 80% C ₁₆ -C ₁₈ N-methylglucamide was obtained and co-assembled with 10% sodium carbonate.

Second, the above particles were then co-agglomerated with highly active pasty (70%) sodium salts of _C₁₄ - _C₁⁵ alkyl sulfate and C₁₂ _-₁⁵ EO(3) sulfate with zeolite A and excess sodium carbonate. The particles have good dispersibility in cold water of C ₁₆ -C ₁₈ N-methylglucamides.

The whole formula of this granule (aggregate dried to help make detergent) is:

C ₁₆ -C ₁₈ N-Methyl Glucamide 4.1%

DOBANOL C _12-15 EO (3) 0.94%

Sodium carbonate 4.94%

Zeolite A 5.3%

Sodium C ₁₄ -C ₁₅ Alkyl Sulfate 3.5%

C _12-15 EO (3) sodium sulfate 0.59%

C. Dry Additives

Add the following components

Percarbonate 22.3%

TAED (Tetraacetylethylenediamine) 5.9%

Phyllosilicate SKS 6 12.90% purchased from Hoechst

Citric acid 3.5%

Lipolase 0.42%

100,000LU/g

SAVINASE 4.0 KNPU 1.65%

Zinc phthalocyanine (actinic bleach) 0.02

D. Atomization

DOBANOL C _12-15 EO (3) 2.60%

Spices 0.53%

E. Foam inhibitor

Silicone suds suppressor X2-3419 (95-97% high molecular weight linear siloxane; 3%-5% hydrophobic silica gel) available from Dow Corning with Zeolite A (2-5μ size), starch and hard Lipid alcohol binders co-assemble. The granules have the following composition:

Zeolite A 0.22%

Starch 1.08%

X2-3419 0.22%

Stearyl Alcohol 0.35%

The detergent formulation has good solubility, superior performance and excellent foam suppression when using European washing machines, for example, 85 grams of detergent in an AEG trademark washing machine at 30°C, 40°C, 60°C and 90°C cycle.

Example XVII

In the preceding examples, the fatty acid glucamide surfactant can be replaced by the same amount of maltamide surfactant, or a mixture of glucamide and maltamide surfactant produced from a plant sugar source. The use of ethanolamide in these compositions is believed to contribute to the stability of the final product at low temperatures. Additionally, the use of sulfobetaine and/or amine oxide surfactants provides superfoam.

For compositions where high suds is desired, less than about 5%, preferably less than about 2%, and most preferably substantially no _C14 or higher fatty acids are present because these materials suppress suds. Formulators of high sudsing compositions should therefore preferably avoid introducing suds suppressing amounts of such fatty acids in high sudsing compositions of polyhydroxy fatty acid amides and/or avoid the formation of C ₁₄ and higher during the shelf life of the final composition. of fatty acids. A simple approach is to use _C12 ester reactants to prepare the polyhydroxy fatty acid amides herein. Fortunately, the use of amine oxide or sulfobetaine surfactants can overcome the adverse foaming effect caused by fatty acids.

Formulators wishing to add anionic optical brighteners to liquid detergents containing higher concentrations (10% higher) of anionic or polyanionic substituents such as polycarboxylate builders will find the following approach useful. That is, the whitening agent is premixed with water and polyhydroxy fatty acid amide, and then the premix is added to the final composition.

Polyglutamic acid or polyaspartic acid dispersants can be used with zeolite built detergents. AE fluid or block and DC-544 (Dow Corning) are other examples of foam control useful with this invention.

Those skilled in the chemical arts will recognize that the use of di- or higher saccharides such as maltose to prepare the polyhydroxy fatty acid amides herein will result in the formation of polyhydroxy fatty acid amides in which the linear substituent Z is "capped" by a polyhydroxy ring structure. Such materials are fully contemplated for use herein without departing from the spirit and scope of the invention disclosed and claimed.

Claims (34)

1. In an improved detergent composition, comprising one or more anionic surfactants, nonionic surfactants, or mixtures thereof, and detergent enzymes, characterized in that it is included in said composition Added a structural formula that improves the energy of the enzyme The polyhydroxy fatty acid amide substance, wherein R ¹ is H, C ₁ -C ₄ hydrocarbyl, 2-hydroxyethyl, 2-hydroxypropyl, or a combination of these groups, R ² is C ₅ -C ₃₁ hydrocarbyl, and Z is a polyhydroxyhydrocarbyl having a linear hydrocarbyl chain with at least 3 hydroxyl groups attached directly to the chain, or an alkoxylated derivative thereof. 2. A composition according to claim 1, wherein said enzyme comprises alkaline protease, amylase, lipase, cellulase, or peroxidase, or a mixture thereof. 3. A composition according to claim 2, wherein said enzyme comprises alkaline protease. 4. The composition of claim 1 comprising at least about 3% polyhydroxy fatty acid amide. 5. A composition according to claim 4, wherein Z is derived from a reducing sugar. 6. _A detergent composition according to claim 5 wherein ^R1 is methyl, ^R2 is _C11 - _C17 alkyl or alkenyl and Z is _-CH2 (CHOH) _4CH2OH . 7. A composition according to claim 1, for polyhydroxy fatty acid amides, wherein Z is derived from glucose or maltose or mixtures thereof. 8. A composition according to claim 1 wherein Z is derived from a mixture of monosaccharides, disaccharides and polysaccharides (optionally) comprising at least about 1% by weight of disaccharides, said mixture being of vegetable origin. 9. The composition of claim 1 comprising from about 0.0001% to about 2% by weight of active enzyme and at least about 1% by weight of said polyhydroxy fatty acid amide. 10. A laundry detergent composition according to Claim 1 wherein the anionic surfactant is other than an alkylbenzene sulphonate surfactant. 11. A liquid detergent composition comprising: (a) from about 1% to about 50% anionic surfactant; (b) from about 0.0001% to about 2% active detergent enzymes; (c) The structural formula for improving enzyme energy is

The polyhydroxy fatty acid amide substance, wherein R ¹ is H, C ₁ -C ₄ hydrocarbyl, 2-hydroxyethyl, 2-hydroxypropyl, or a combination of these groups, R ² is C ₅ -C ₃₁ hydrocarbyl, and Z is a polyhydroxyhydrocarbyl having a linear hydrocarbyl chain (at least 3 hydroxyl groups directly attached to the chain), or an alkoxylated derivative thereof; And the compositions described therein are substantially free of alkylbenzene sulfonates. 12. A composition according to claim 11, wherein said anionic surfactant comprises: RO(A) _m SO ₃ M wherein R is an unsubstituted C ₁₀ -C ₂₄ alkyl or hydroxyalkyl (C ₁₀ -C ₂₄ ) group, A is an ethoxy or propoxy unit, m is greater than 0, and M is hydrogen or a cation. 13. A composition according to claim 12, wherein said detersive enzyme is selected from the group consisting of proteases, lipases, amylases, cellulases, peroxidases and mixtures thereof. 14. A composition according to claim 13 wherein R is unsubstituted _C12 - _C18 alkyl, A is an ethoxy unit, m is from about 0.5 to about 6, and M is a cation. 15. A composition according to claim 14 comprising from about 4% to about 40% of said anionic surfactant. 16. A composition according to Claim 15 wherein the ratio of said anionic surfactant to said polyhydroxy fatty acid amide is from about 1:2 to about 8:1. 17. A composition according to claim 14, wherein said detersive enzyme comprises protease and one other detersive enzyme. 18. A composition according to claim 17 comprising from about 0.0001% to about 1% of both protease and lipase on an active substrate. 19. The composition of claim 18 further comprising about 0.5% to about 5% of the condensation product of a _C8 - _C22 linear alcohol with about 1 to about 25 moles of ethylene oxide per mole of alcohol. 20. A composition according to claim 18 wherein said lipase is derived from Humicola Lanuginosa. 21. The composition of claim 15 comprising from about 0.5% to about 12% of said polyhydroxy fatty acid amide. 22. A composition according to claim 21, wherein in the case of polyhydroxy fatty acid amides, Z is derived from glucose or maltose or mixtures thereof. 23. A composition according to claim 21 wherein Z is derived from a mixture of monosaccharides, disaccharides and polysaccharides (optionally) comprising at least about 1% by weight of disaccharides, said mixture being of vegetable origin. 24. The composition of claim 21 further comprising from about 1% to about 10% of a water-soluble alkyl sulfate. 25. The composition of claim 11 comprising from about 0.0001% to about 1% cellulase on active substrate. 26. A heavy duty liquid laundry detergent composition according to Claim 11 which has a pH of about 6.5 to about 11.0 as a 10% solution in water at 20°C. 27. The composition according to claim 26, wherein the ratio of said anionic surfactant to said polyhydroxy fatty acid amide is from about 3:1 to about 4:1. 28. A composition according to Claim 26 wherein said composition further comprises from about 0.1% to about 50% of a detergency builder. 29. The composition according to claim 28, wherein said composition comprises about 0.1% to about 20% citric acid, about 0.1% to about 20% sodium tartrate succinate, about 0.1% to about 20% oxydisuccinate salt, about 0.1% to about 50% alkenyl succinate, or mixtures thereof. 30. A composition according to claim 29, wherein in the case of polyhydroxy fatty acid amides, Z is derived from glucose or maltose or mixtures thereof. 31. A composition according to claim 29 wherein Z is derived from a mixture of monosaccharides, disaccharides and polysaccharides (optionally) comprising at least about 1% by weight of disaccharides, said mixture being of vegetable origin. 32. A method for improving the performance of detergent enzymes in a detergent composition containing detergent enzymes in the presence of an aqueous medium, comprising: The polyhydroxy fatty acid amide compound is added to the composition, wherein R ¹ is H, C ₁ -C ₄ hydrocarbon group, 2-hydroxyethyl, 2-hydroxypropyl, or a combination of these groups, R ² is C ₅ - _{C31hydrocarbyl} , and Z is a polyhydroxyhydrocarbyl having a linear hydrocarbyl chain (at least 3 hydroxyl groups directly attached to the chain), or an alkoxylated derivative thereof. 33. A process as claimed in claim 32, wherein R ² in the polyhydroxy fatty acid amide is C ₁₁ -C ₁₇ alkyl or alkenyl and wherein Z is derived from glucose, maltose or mixtures thereof derived from plants. 34. A process according to Claim 32 wherein the aqueous medium is substantially free of alkylbenzene sulfonate surfactants.