RU2105791C1 - Liquid detergent composition and granulated detergent composition - Google Patents

Abstract

FIELD: detergents. SUBSTANCE: improved detergent compositions are provided containing one or more anionic surfactants, nonionic surfactants, or their mixtures, and also scouring enzymes. Improvement consists in adding enzyme-enhancing amounts of fatty acid polyhydroxyamides with general formula R₂-CO-NR₁-Z where R₁ is C₁-C₄- hydrocarbyl, 2-hydroxyethyl, 2-hydroxypropyl, or their mixture; R₂ is C₅-C₃₁- hydrocarbyl; and z straight-chain polyhydroxyhydrocarbyl with at least 3 OH groups directly linked to hydrocarbyl chain or its alkoxylated derivative. EFFECT: improved detergent properties. 18 cl, 6 tbl

Description

 The invention relates to detergent (washing) compositions containing enzymes. More importantly, this invention relates to detergent compositions containing a fatty acid enzyme and polyhydroxy amide as a surfactant.

 It is generally accepted in commercial practice to include various enzymes in liquid and granular detergents to enhance the cleansing effect. Proteolytic enzymes are well known for such use, however, other enzymes, such as amylases, celluloses, lipases, peroxidases and combinations thereof, have also been proposed for these purposes. Literature and standard documents are full of messages on the use of enzymes in fabric detergents.

 Since enzymes are biological materials, they undergo denaturation and deactivation, especially after prolonged contact with other ingredients present in fully formulated detergent compositions. Therefore, a freshly formulated detergent composition containing enzymes will often exhibit a significantly stronger cleansing effect than an older product stored in a warehouse or on a shelf. The storage stability of enzyme-containing detergent compositions, especially liquid detergents, was a significant incentive in the development of various enzyme stabilizers. For example, various boron compounds, formate salts, ethanolamines, and / or various short chain fatty acids are typically added to detergent compositions to ensure enzyme stability. Such stabilizers are often added to liquid detergent compositions containing enzymes.

 In addition, enzymes are relatively expensive and their inclusion in detergent compositions creates additional cost for the compiler and, ultimately, for the user. Therefore, it would be beneficial for the enzyme to be improved with less expensive additives.

 Theoretically, it is possible not only to stabilize enzymes, preventing their decomposition, but also to enhance their action with the help of various boosters. However, if the activity of a long-acting enzyme is stabilized or enhanced, it should be understood that the ultimate goal in the market (where the duration of enzyme activity is taken into account) is the same to ensure the best effect of the detergent composition for the user.

 Currently, searches are continuing for materials stabilizing or enhancing the action of enzymes in detergent compositions of the whole composition, since almost all enzymes are expensive and almost all enzymes lose at least part of their activity during storage.

 The surface active polyhydroxy fatty acid amides, such as those described below, provide stabilization and / or booster functions for enzymes. It is very likely that fatty acid polyhydroxy amides act by removing molecular "fragments" obtained by the action of enzymes on dirt and paint, which allows enzymes to act more efficiently. Whatever the mechanism of action, the invention achieves its ultimate goal, providing maximum removal of enzyme-labile dirt and stains, and thus improving all the characteristics of enzyme-containing detergent compositions of the whole.

 In addition to maintaining the properties of the enzyme, the polyhydroxy fatty acid amide is in itself an excellent detergent surfactant. Moreover, this type of surfactant can be obtained mainly or exclusively from natural, reducing raw materials and can replace fully or partially surfactants based on oil without loss of detergent ability.

 Various polyhydroxy fatty acid amides are already described in the art. N-acyl, N-methyl glucamides, for example, are described in M.A. Goodby, M. A. Marcus, E. Chin, P.Z. Finn "Thermotropic liquid crystal properties of some straight chain amphiphiles." Liquid Cristals, 1988, Volume 3, No. 11, pp. 1569-1581, and A. Muller-Fahrnow, V. Label, M. Steifa, R. Hilgenfeld "Molecular and Crystal Structure of Nonionic Detergents: Nonanoyl-N-Methylglucamide ", J. Chem. Soc. Chem. Commun. 1986, p. 1573-1574. The use of N-alkyl polyhydroxyamide surfactants has recently become of significant interest for use in biochemistry, for example, in the dissociation of biological membranes (see, for example, Hildreth JEK's article "ND-Gluco-N-methyl-alkanamide compounds, a new class of nonionic detergents for membrane biochemistry ", Biochem.

 The use of N-alkyl glucamides in detergent compositions has also been discussed. U.S. Patent No. 2,965,576, issued December 20, 1960 E.R. Wilson, and UK Patent N 809,060, published February 18, 1959, Thomas Hedley I Co. Ltd. relate to detergent compositions containing anionic surfactants and some amide surfactants, which may include N-methylglucamide, added as an agent that increases foaming at low temperatures. Such compounds include a straight chain N-acyl radical of a higher fatty acid containing 10-14 carbon atoms. These compositions may also contain additional materials, such as alkali metal phosphates, alkali metal silicates, sulfates and carbonates. It is usually indicated that additional constituents that impart the desired properties of the composition can also be included in these formulations: such as fluorescent dyes, bleaching agents, perfumes, etc.

US Pat. No. 2,703,798, issued March 8, 1955 to AM Schivartz, relates to aqueous detergent compositions containing a condensation product of N-alkylglucamine and an aliphatic fatty acid ester. The product of this reaction, as you know, can be used in aqueous detergent compositions without further purification. It is also known to obtain an acylated glucamine sulfoester (see US Pat. No. 2,717,894, 09/13/1955.)
PCT International Application WO 83/04412, published December 22, 1983, J. Hildreth, relates to amphiphilic compounds containing polyhydroxyaliphatic groups, which are known to be useful for various purposes, including the use as surfactants in cosmetics, medicines, shampoos lotions and ointments for the eyes; as emulsifiers and dispersants for medicine; as well as in biochemistry for the solubilization of membranes, complete cells or other tissue samples, and for the preparation of liposomes. Compounds included in this series are of the formula R′CON (R) CH ₂ R ″ and R ″ CON (R) R ′, where R is hydrogen or an organic moiety; R 'is an aliphatic hydrocarbon group consisting of at least three carbon atoms; R ″ is an aldose residue.

It is known to use fatty acid N-polyhydroxyalkylamides as thickening agents in aqueous detergent systems [1] These include amides of the formula R ₁ C (O) N (X) R ₂ , where R ₁ is C ₁ -C ₁₇ (preferably C ₇ - C ₁₇ ) alkyl, R ₂ is hydrogen, C ₁ -C ₁₈ (preferably C ₁ -C ₆ ) alkyl or alkylene oxide, and X is polyhydroxy alkyl containing from four to seven carbon atoms, for example, coconut fatty acid N-methylglucamide . The predominant properties of these amides are especially evident when used in liquid surfactant systems containing paraffin sulfonate, although aqueous surfactant systems may contain other anionic surfactants, such as alkylaryl sulfonates, olefin sulfonates, salts of sulfosuccinic acid half esters, ether sulfonates fatty alcohols, and non-ionic surfactants such as polyglycol ether of fatty alcohol, polyglycol ether of alkyl phenol, polyglycol fir fatty acids, mixed polypropylene oxide -.. polyethylene oxide polymers, etc. As an example, with shampoo compositions are paraffin sulfonate (N- methylglucamide coconut fatty acid) nonionic surfactant. In addition to the thickening ability, it is known that N-polyhydroxyalkyl fatty acid amides have excellent skin tolerance properties.

 U.S. Patent No. 2,982,737, issued May 2, 1961, to Boetter et al. Relates to urea soap bars, sodium lauryl sulfate anionic (surfactant surfactant), and N-alkyl glucamide nonionic surfactant selected from N-methyl, N-sorbityl β-lauramide and N-methyl, N-sorbityl-myristamide.

Other glucamide surfactants are described, for example, DT 2 226 872, published December 20, 1973, HWEckert et al., Regarding detergent compositions containing one or more (surfactants), as well as (structure-forming) salts selected from polymer phosphates, passivators and washing alkalis improved by the addition of an N-acyl-polyhydroxy-alkyl-amine of the formula R ₁ C (O) N (R ₂ ) CH ₂ (CHOH) _n CH ₂ OH, where R ₁ is C ₁ -C ₃ alkyl; R ₂ is C ₁₀ -C ₂₂ alkyl; n 3 or 4. N-acylpolyhydroxyalkyl amine is added as a mud suspending agent.

US patent 3,654,166, issued April 4, 1972, HWEckert et al., Relates to detergent compositions containing at least one surfactant selected from the group of anionic, zwitterionic, nonionic surfactants, and N-acyl as a fabric softener. The N-alkyl polyhydroxyalkyl compound of the formula R ₁ N (Z) • C (O) R ₂ , where R ₁ is C ₁₀ -C ₂₂ alkyl, R ₂ is C ₇ -C ₂₁ alkyl, R ₁ and R ₂ are from 23 up to 39 carbon atoms, and Z is polyhydroxyalkyl, which may be —CH ₂ (CHOH) _m CH ₂ OH, where m 3 or 4.

Known cosmetic compositions for skin care containing N-polyhydroxyalkyl amines, which include compounds of the formula R ₁ N (R) CH (CHOH) _m R ₂ where R ₁ is H, lower alkyl, lower hydroxyalkyl, or aminoalkyl, and heterocyclic aminoalkyl, R has the same meaning as R ₁ , but both cannot be H, and R ₂ is CH ₂ OH or COOH [2]
French patent 1 360 018 of April 26, 1963, owned by Commercial Solvent Corp. contemplates formaldehyde-stabilized solutions by the addition of amides of the formula RC (O) N (R ₁ ) G, where R is a carboxylic acid having at least seven carbon atoms; R ₁ is hydrogen or a lower alkyl group; G represents a glycitol radical with at least five carbon atoms.

German patent 1 261 861 of February 29, 1968, A. Heins, relates to glucamine derivatives useful as wetting and dispersing agents of the formula N (R) (R ₁ ) (R ₂ ), where R is a sugar residue of glucamine; R ₁ represents a C ₁₀ -C ₂₀ alkyl radical, and R ₂ represents a C ₁ -C ₅ acyl radical.

UK patent N 745 036 dated February 15, 1956, owned by the Atlas Powder Company, relates to heterocyclic amides and carboxylic esters, which are known to be useful as chemical intermediates, emulsifiers, wetting and dispersing agents, detergents, fabric softeners, etc. These compounds correspond to the formula N (R) (R ₁ ) C (O) R ₂ , where R is the residue of anhydrous hexanopentol or a carboxylic acid ester thereof; R ₁ represents a monovalent hydrocarbon radical; —C (O) R ₂ is an acyl radical of a carboxylic acid containing 2 25 carbon atoms.

US Patent No. 3,322,627, issued April 4, 1967 to DTHooker, describes solid toilet soaps that are virtually free of anionic detergents and alkaline (structure-forming components) and contain lithium soaps of certain fatty acids, non-ionic surfactants selected from certain propylene oxide capacitors ethylenediamine-ethylene oxide-propylene oxide propilenglikoletilenoksida and polymerized ethylene glycol, and also contains a nonionic soap component, which may include polyhydroxyamide of the formula RC (O) NR ₁ (R _2), r e RC (O) contains from about 0 to about 14 carbon atoms, and R ₁ and R ₂ each represents H or C ₁ -C ₆ alkyl groups, said alkyl groups contain the total number of carbon atoms of from 2 to about 7 and a total the number of substituted hydroxyl groups is from 2 to about 6. A very similar invention is described in US Pat. No. 3,212,626 also issued April 4, 1967 by DTHooker.

где
R₁ является H₁, C₁-C₄ углеводородом 2-гидроксиэтилом, 2-гидроксипропилом или их смесью, R₂ является C₅-C₃₁ углеводородом; Z представляет собой полигидроксиуглеводород линейной углеводородной цепью с по крайней мере 3 гидроксильными группами, непосредственно связанными с цепью, или его алкоксилированное производное.The invention provides an improved detergent composition containing one or more of anionic surfactants, nonionic surfactants, or mixtures thereof, as well as washing enzymes, the improvement being the addition of amounts of polyhydroxyamide fatty acids of the formula enhancing the action of enzymes to the formula

Where
R ₁ is H ₁ , a C ₁ -C ₄ hydrocarbon, 2-hydroxyethyl, 2-hydroxypropyl or a mixture thereof, R ₂ is a C ₅ -C ₃₁ hydrocarbon; Z is a polyhydroxy hydrocarbon linear hydrocarbon chain with at least 3 hydroxyl groups directly attached to the chain, or an alkoxylated derivative thereof.

 In addition, the invention provides a method for improving the cleaning effect of detergent compositions with detergent surfactants, such as anionic, nonionic or cationic surfactants, especially anionic surfactants, in an aqueous medium by adding enzyme-enhancing amounts of the above-described polyhydroxyamide fatty acid to said detergent composition.

 The invention also provides a method for cleaning substrates, such as fibers, fabrics, hard surfaces, leather, etc. by reacting said substrates with a detergent composition consisting of one or more anionic, nonionic or cationic surfactants, as well as a washing enzyme moreover, this composition contains a polyhydroxy fatty acid amide in an amount enhancing the action of the enzyme.

 Polyhydroxy fatty acid amide as a surfactant.

 The detergent compositions of the invention contain an “enhancing enzyme action amount” of a polyhydroxy fatty acid amide. By “enhancing enzyme" is meant that the compiler can select the amount of polyhydroxy fatty acid amide to be introduced into the composition so as to improve the cleansing property of the enzyme in the detergent composition. Typically, for a detergent containing conventional enzyme levels, administration of about 1 wt. polyhydroxyamide fatty acid will enhance the action of the enzyme.

 The detergent compositions of the invention will usually contain at least about 1 wt. polyhydroxy fatty acid amide as a surfactant, preferably at least about 3% will even more preferably contain 3 to 50% but more preferably 3 to 30% polyhydroxy fatty acid amide.

где
R₁ является H, C₁-C₄ углеводородом, 2-гидроксиэтилом, 2-гидроксипропилом или их смесью, предпочтительно, C₁-C₄ алкилом, лучше C₁ или C₂ алкилом, лучше всего C₁ алкилом (т. е. метилом); R₂ является C₅-C₃₁ углеводородом, предпочтительно линейным C₉-C₁₇ алкилом или алкенилом, более предпочтительно линейным C₁₁-C₁₅ алкилом или алкенилом, или их смесью; Z - полигидроксиуглеводород с линейной углеводородной цепью с по крайней мере тремя гидроксилами, напрямую связанными с цепью, или алкоксилированное производное (предпочтительно этоксилированное или пропоксилированное). Z предпочтительнее получать из восстанавливающего сахара в реакции восстановительного аминирования, предпочтительно, чтобы Z был глицитилом. Подходящие восстанавливающие сахара включают глюкозу, фруктозу, мальтозу, лактозу, галактозу, маннозу и ксилозу. Что касается сырьевых материалов, то можно использовать кукурузный сироп с высоким содержанием декстрозы, фруктозы или мальтозы, также, как индивидуальные сахара перечисленные выше. Эти сиропы кукурузы могут давать смесь сахарных компонентов. Следует понять, что это никоим образом не исключает возможности других подходящих сырьевых материалов. Z предпочтительно следует выбрать из группы, содержащей -CH₂(CHOH)_n-CH₂OH, -CH(CH₂OH)-(CHOH)_n-1-CH₂OH, -CH₂-(CHOH)₂(CHOR₁)•(CHOH)-CH₂OH, их алкоксилированные производные, где n варьируется от 3 до 5 включительно; R₁ является H или циклическим или алифатическим моносахаридом. Самыми предпочтительными являются глицитилы с n равным 4, в частности -CH₂-(CHOH)₄-CH₂OH.The surfactant component of the polyhydroxyamide fatty acid in the invention contains compounds with the structural formula I

Where
R ₁ is H, C ₁ -C ₄ hydrocarbon, 2-hydroxyethyl, 2-hydroxypropyl or a mixture thereof, preferably C ₁ -C ₄ alkyl, preferably C ₁ or C ₂ alkyl, most preferably C ₁ alkyl (i.e. methyl); R ₂ is a C ₅ -C ₃₁ hydrocarbon, preferably a linear C ₉ -C ₁₇ alkyl or alkenyl, more preferably a linear C ₁₁ -C ₁₅ alkyl or alkenyl, or a mixture thereof; Z is a linear hydrocarbon chain polyhydroxy hydrocarbon with at least three hydroxyls directly attached to the chain, or an alkoxylated derivative (preferably ethoxylated or propoxylated). Z is preferably derived from reducing sugar in a reductive amination reaction, preferably Z is glycityl. Suitable reducing sugars include glucose, fructose, maltose, lactose, galactose, mannose and xylose. As for raw materials, corn syrup with a high content of dextrose, fructose or maltose can be used, as well as individual sugars listed above. These corn syrups may produce a mixture of sugar constituents. It should be understood that this in no way precludes the possibility of other suitable raw materials. Z preferably should be selected from the group consisting of -CH ₂ (CHOH) _n -CH ₂ OH, -CH (CH ₂ OH) - (CHOH) _n-1 -CH ₂ OH, -CH ₂ - (CHOH) ₂ (CHOR ₁ ) • (CHOH) -CH ₂ OH, their alkoxylated derivatives, where n varies from 3 to 5 inclusive; R ₁ is H or a cyclic or aliphatic monosaccharide. Most preferred are glycityls with n equal to 4, in particular —CH ₂ - (CHOH) ₄ —CH ₂ OH.

In the formula, IR ₁ may be, for example, N-methyl, N-ethyl, N-propyl, N-isopropyl, N-butyl, N-2-hydroxyethyl, or N-2-hydroxypropyl.

может быть, например, кокамидом, стеарамидом, олеамидом, лаурамидом, миристамидом, каприкамидом, пальмитамидом, талловамидом и т.д. Z может быть 1-деоксиглицитилом, 2-деоксифруктитилом, 1-деоксимальтитилом, 1-деоксилактитилом, 1-деоксидалактитилом, 1-деоксиманнитилом, 1-деоксимальтотриотитилом и т.д.

may be, for example, cocamide, stearamide, oleamide, lauramide, myristamide, capricamide, palmitamide, tallamamide, etc. Z may be 1-deoxyglycityl, 2-deoxyfructityl, 1-deoxymaltithyl, 1-deoxylactityl, 1-deoxydalactityl, 1-deoxymannithyl, 1-deoxymaltotriotityl, etc.

 Techniques for producing polyhydroxyamide fatty acids are known in the art. Typically, they can be prepared by reacting an alkylamine with a reducing sugar in a reductive amination reaction to form the corresponding N-alkyl polyhydroxyamide and then reacting the N-alkyl polyhydroxyamine with an aliphatic fatty ether or triglyceride in the amination condensation step to form an N-alkyl, N-polyhydroxyamide fatty acid. Methods for creating compositions containing polyhydroxy fatty acid amides are known (see, for example, British Patent N 809 060, 02/18/59, Thomas Hedley Co. Ltd. US Pat. No. 2,965,576, 12.20.60, ERWilson, US Pat. No. 2,703,798. , March 8, 2005, Anthony M. Schwartz and U.S. Patent No. 1,985,424, December 25, 344, Piggot).

In one method for producing N-alkyl, N-deoxyglycytylamide fatty acids, in which the glycityl component is derived from glucose and the N-alkyl or N-hydroxylalkyl functionalities are N-methyl, N-ethyl, N-propyl, N-butyl, N- hydroxyethyl or N-hydroxypropyl, the product is obtained by reacting N-alkyl or N-hydroxyalkyl-glucamine with a fatty ester selected from fatty methyl esters, fatty ethyl ethers or triglycerides, in the presence of a catalyst selected from the group consisting of trilithium phosphate, trisodium sulphate, tripotassium phosphate, tetrasodium pyrophosphate, pentacalitripolyphosphate, lithium hydroxide, sodium hydroxide, potassium hydroxide, calcium hydroxide, lithium carbonate, sodium carbonate, potassium carbonate, disodium tartrate, dipotassium tartrate, potassium sodium tartrate, sodium trisodium citrate, basic sodium trisodium citrate, basic basic sodium aluminosilicates; basic potassium aluminosilicates or mixtures thereof. The amount of catalyst is preferably from about 0.5 mol. up to 50 mol. more preferably 2 to 10 mol. based on moles of N-alkyl or N-hydroxyalkylglucamine. It is preferable to carry out the reaction at a temperature of 138-170 ^° C and usually for from about 20 to about 90 minutes. When triglycerides are used as the source of fatty esters, it is also desirable to carry out the reaction using 10 wt. phase transfer agent based on the total weight of the entire reaction mixture selected from polyethoxylates of saturated fatty alcohols of alkyl polyglycosides, linear glucamides of surfactants, or mixtures thereof.

It is preferable to carry out this process as follows:
a) pre-heat the fatty ester to 138-170 ^o C;
b) add N-alkyl or N-hydroxyalkylglucamine to the heated fatty acid ester and mix for the time required to form a two-phase liquid / liquid mixture;
c) add catalyst to the reaction mixture;
d) mix the time necessary for the reaction.

 It is also desirable to add to the reaction mixture from about 2% to about 20% of the pre-prepared linear N-alkyl / N-hydroxyalkyl, N-linear amide, glucosyl fatty acid are added to the reaction mixture by weight of the reactants as a phase transfer agent if the fatty ester is triglyceride. This will poison the reaction, due to which the reaction rate will increase. The experimental procedure is described in detail below.

 The “fatty acid” polyhydroxyamides used here provide benefits to detergent builders because they can be prepared entirely or mainly from natural, renewable raw materials, non-petrochemical in origin, and are degradable. They also exhibit low toxicity to living in water.

 You must also indicate that along with the amides of polyhydroxy fatty acids of the formula I, the methods used to obtain them usually lead to the production of certain amounts of by-products of non-volatility, such as ethers and cyclic amides of polyhydroxy fatty acids. The level of these by-products will largely depend on the specific reagents and process conditions. Preferably, the polyhydroxy fatty acid amides incorporated into the detergent compositions of the invention are in the form where the polyhydroxyamide-containing fatty acid composition added to the detergent contains less than about 10% and preferably less than about 4% cyclic polyhydroxy fatty acid amide. The preferred processes described above are advantageous in that they give a sufficiently low level of by-products.

 Enzymes

 Detergent enzymes can be included in detergent formulations for a wide variety of applications, including stain removal based on proteins, hydrocarbons or triglycerides, and to prevent carrier migration briefly. Enzymes to be included include proteases, amylases, lipases, cellulases and peroxidases, as well as mixtures thereof. Other types of enzymes can also be incorporated. They can be from any suitable source of vegetable, animal, bacterial, fungal and yeast origin.

 However, the choice of enzymes is determined by several factors, such as optimal pH activity and / or stability, thermal stability, stability depending on the active detergents, builders, etc. From this point of view, bacterial or fungal enzymes, such as bacterial amylases and proteases, as well as fungal cellulases, are preferred.

 Enzymes are usually included in amounts sufficient to provide up to 5 mg per weight, more often from about 0.05 to about 3 mg of active enzyme per gram of composition.

 Suitable examples of proteases are Subtilisins, which are obtained from specific strains of B. Subtilis and B.licheniforms. Other suitable proteases are derived from the Bacillus strain, they have a maximum activity in the pH range of 8-12, are developed and marketed by Novo Industries A / S under the registered trademark ESPERASE. The preparation of these and similar enzymes is described in British Patent Specification No. 1,243,784 Novo. Proteolytic enzymes for removing contaminants based on proteins are also commercially available; they are sold under the trade names ALCALASE and SAVINASE Novo Industries A / S (Lenmark), MAXATASE by International Bio-Synth, Inc. (Netherlands).

 Of interest in the category of proteolytic enzymes, especially for liquid detergent compositions, are the enzymes presented here as protease A and protease B. Protease A and methods for its preparation are described in European Patent Application No. 130,756 of January 9, 1985. Protease B is a proteolytic enzyme that differs from prosthesis A in that it contains leucine instead of tyrosine at position 217 of its amino acid sequence. Protease B is described in European Patent Application No. 87303761.8, filed April 28, 1987. Methods for the preparation of Protease B are also described in European Patent Application No. 130,756, Bott et all, published January 9, 1985.

 Amylases include, for example, α-amylases derived from a special B.licheniform strain are described in more detail in British Patent Specification No. 1,296,839 (Novo). Amylolytic enzymes include, for example, RAPIDASE, International Bio-Syntheties, Inc, and EIRMAMYL, Novo Industries.

 The cellulases used in the invention include both bacterial and fungal cellulases. Preferably, they should have an optimum pH in the range of 5 to 9.5. Suitable cellulases are described in US Pat. No. 4,435,307 to Barbesgoardetal, issued March 6, 1984, which discloses fungal cellulase derived 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 obtained from a strain of Humicola insolens (Humicola grisea var. Thermoidea), especially Humicola strain DSM 1800, and cellulases produced by Bacillus N fungi or 212 cellulases produced by fungi belonging to the genus Aeromonsa, as well as cellulose extracellulose pancreas of a marine mollusk (Dolabella Auricula Solander).

 Lipases suitable for detergent use include enzymes produced by Pseudomonas microorganisms, such as Pseudomonas Stutzeri ATCC 19.154 (see UK Patent No. 1,372,034).

 Suitable lipases are those that give a positive immunological cross-reaction with antibodies of the lipase produced by the microorganism Pseudomonas fluorescens IAM 1057. This lipase and its purification method were described in Japanese Patent Application 53-20487, which was opened for examination on February 24, 1978. Such lipase is available from Amano Pharmaceutical Co. Ltd, Japan, under the trademark Lipase P "Amano", hereinafter referred to as "Amano-P". Such lipases of the invention should produce a positive immunological cross-reaction with the Amano-P antibody using the standard well-known Ouchterlony immunodiffusion procedure (Acta. Med. Sean. 133, pp. 76-79, 1950). These lipases and methods for their immunological cross-reaction with Amano-P are also described in US Pat. No. 4,707,291 to Thometal, issued November 17, 1987. Typical examples are Amano-P lipase, ex Pseudomanas fragi FERM 1339 lipase (available under the trade name Amano-B), ex Pseudomonas nitroreducens var. lipolyticum FERM P 1338), available under the trademark Amano-ces lipase ex chromobacter viscasum, chromobacter viscosum var. lipolyticum NRRLB 3673, commercially available from Toyo Jozo Co. Tagata, Japan, chromobacter viscosum lipase from Biochemical Corp. United States, Disoynth Co. Netherlands, lipase ex Pseudomonas Gladioli.

 Peroxidase enzymes are used in combination with oxygen sources, such as percarbonate, perborate, persulfate, hydrogen peroxide, etc. They are used for “bleaching solutions”, that is, they prevent the transfer of paints and pigments removed from the substrates during the washing operation to other substrates in the washing solution. Pyroxidase enzymes are also known in the art and include, for example, horseradish peroxidase, ligninase and haloperexidase, such as chloro and bromoperoxidase. Peroxidase-containing detergent compositions are described, for example, in PCT (International Application WO 89 N 099813, published October 19, 1989, O. Kirk owned by Novo Industries A / S.

 A wide variety of enzyme materials and agents for their incorporation into synthetic detergent granules are also disclosed in US Pat. N 3,553 39 issued January 5, 1971, Mc. Carty et. al. Enzymes are disclosed in US patent N 4 101 457, Place et. al. issued July 18, 1978, and U.S. Patent No. 4,507-19, to Hughes, issued March 26, 1985. Enzymatic materials suitable for liquid detergent compositions and their incorporation into such compositions are described in US Pat. No. 4,261,868 by Hora et al. issued April 14, 1981.

 For granular detergents, the enzymes are preferably coated or molded with additives that are inert to the enzymes to reduce dust formation and improve storage stability. The technique of this preparation is well known. The stabilizing enzyme system is mainly used in liquid formulations. Techniques for stabilizing aqueous detergent compositions are well known in the art. For example, one of the methods for stabilizing enzymes in aqueous detergent solutions involves the use of free calcium ions, the sources of which are calcium acetate, calcium formate and calcium propionate. Calcium ions can be used in combination with salts of short chain carboxylic acids, preferred with formates (see, for example, US Pat. No. 4,318,818, Letton, March 9, 1982). It has also been proposed to use such polyols as glycerol and sorbitol, alkoxy alcohols, dialkyl glycoesters, mixtures of polyvalent alcohols with polyfunctional aliphatic amines, for example, diethinelamine, triethanolamine, diisopropanolamine, and boric acid or alkali metal borate. Enzyme stabilization techniques are further discussed and illustrated in US Pat. No. 4,261,868, issued April 14, 1981, Horn in US Pat. No. 3,600,319, issued August 17, 1971, Gedge, and in European Patent Publication No. 0 199,405 of Application No. 86200586. published October 29, 1986, Venegas. Boric acid-free borate stabilizers are preferred. Enzyme-stabilizing systems are also described, for example, in US Pat. Nos. 4,261,868 and 3,551,570.

 In addition to the polyhydroxy fatty acid amide, these compositions may contain other detergent surfactants to enhance the cleansing ability. The particular surfactants used can vary widely using any surfactants suitable for the intended use. Enzyme-containing detergents are usually more widely used for cleaning clothes, fibers, fabrics, hard surfaces, etc. Suitable surfactants include anionic, nonionic, cationic and other surfactants, examples of which are given below. It is desirable that the compositions contain one or more of anionic surfactants, or a combination thereof. The advantages of the invention are particularly pronounced in compositions that contain surfactants or other ingredients that do not adversely affect enzymes. These mainly include (but are not limited to) anionic surfactants such as alkyl ester sulfonates, linear alkyl benzene sulfonates, alkyl sulfates, etc. Typically, the amount of added detergent surfactant is from about 3 wt. up to about 40 wt. detergent composition, preferably from about 5 wt. up to about 30 wt. Suitable surfactants are described below.

 Anionic surfactants.

One type of anionic surfactants that can be used includes alkyl sulfonate esters. They are desirable since they can be obtained from renewable non-petroleum feedstocks. Obtaining a surface-active component of the ester alkyl sulfonate can be carried out by known methods disclosed in the technical literature. So, for example, linear esters of C ₈ -C ₂₀ carboxylic acids can be sulfonated with gaseous SO ₃ according to the method of The Journal of American Oil Chemists Society. 52, 1975, p. 323-329. Suitable starting materials will include natural fatty substances derived from tall oil, palm oil, coconut oil, etc.

где
R₃ является C₈-C₂₀ углеводородом, предпочтительно алкилом, или их сочетанием; R₄ является C₁-C₆ углеводородом, предпочтительно алкилом, или их сочетанием; M является растворимым солеобразующим катионом. Подходящие соли металлов включают соли натрия, калия, лития, а также замещенные или незамещенные соли аммония, такие как метильные, диметильные, триметильные и четвертичные аммониевые катионы, например тетраметиламмоний, диметилпипердиний, а также катионы, полученные из алканоламинов, например моноэтаноламин, диэтаноламин и триэтаноламин. Предпочтительно R₃ является C₁₀-C₁₆ алкилом; R₄ является метилом, этилом или изопропилом. Особенно предпочтительны метиловые сложные эфиры сульфонатов, где R₃ является C₁₄-C₁₆ алкилом.Preferred surfactant alkyl sulfonates, especially for use in washing clothes, include alkyl sulfonate esters of the structural formula

Where
R ₃ is a C ₈ -C ₂₀ hydrocarbon, preferably alkyl, or a combination thereof; R ₄ is a C ₁ -C ₆ hydrocarbon, preferably alkyl, or a combination thereof; M is a soluble salt-forming cation. Suitable metal salts include sodium, potassium, lithium salts, as well as substituted or unsubstituted ammonium salts such as methyl, dimethyl, trimethyl and quaternary ammonium cations, for example tetramethylammonium, dimethylpiperdinium, as well as cations derived from alkanolamines, for example monoethanolamine, diethanol and . Preferably R ₃ is C ₁₀ -C ₁₆ alkyl; R ₄ is methyl, ethyl or isopropyl. Particularly preferred are methyl sulfonate esters, where R ₃ is C ₁₄ -C ₁₆ alkyl.

Alkyl sulfate surfactants are another type of anionic surfactant that is important for use here. In addition to providing excellent overall cleaning ability when used in conjunction with fatty acid polyhydroxy amides, including good mass removal at a wide range of temperatures, detergent concentrations and washing times, dissolution of alkyl sulfates can be achieved, as well as improving overall activity in liquid detergent compositions are water soluble salts or acids of the formula ROSO ₃ M, where R is preferably a C ₁₀ -C ₂₄ hydrocarbon, preferably an alkyl or hydroxyalkyl containing C ₁₀ -C ₂₀ alkyl flaxen components, more preferably C ₁₂ -C ₁₈ alkyl or hydroxyalkyl; M is H or a cation, for example, an alkali metal cation (sodium, potassium, lithium), substituted or unsubstituted ammonium cations, such as methyl, dimethyl, trimethylammonium and a quaternary ammonium cation, for example tetramethylammonium and dimethylpiperdinium, as well as cations derived from alkanolamines for example, ethanolamine, diethanolamine, triethanolamine and mixtures thereof, etc. Typically, C ₁₂ -C ₁₆ alkyl chains are preferred for low washing temperatures (below 50 ^° C) and C _16-18 alkyl chains are preferred for high washing temperatures (above 50 ^° C).

Another category of useful anionic surfactants are alkyl alkoxylated sulfates. These surfactants are water-soluble salts or acids, usually of the formula RO (A) _m SO ₃ M, where R is an unsubstituted C ₁₀ -C ₂₄ alkyl or hydroxyalkyl group with a C ₁₀ -C ₂₄ alkyl component, preferably a C ₁₂ -C _{20 by} alkyl or hydroxyalkyl, more preferably C ₁₂ -C ₁₈ alkyl or hydroxyalkyl; A is an ethoxy or propoxy moiety m greater than 0, usually between 0, 5 and 6, more preferably between about 0.5 and about 3; M is H or a cation, which may be, for example, a metal cation (e.g. sodium, potassium, lithium, calcium, magnesium, etc.), an ammonium or substituted ammonium cation. Alkyl ethoxylated sulfates as well as alkyl propoxylated sulfates are discussed herein. Specific examples of substituted ammonium cations include methyl, dimethyl, trimethyl ammonium and quaternary ammonium cations, such as tetramethyl ammonium cation, dimethyl piperdinium, as well as cations derived from alkanolamines, for example monoethanolamine, diethanolamine, and mixtures thereof. Examples of surfactants are C ₁₂ -C ₁₈ alkyl polyethoxylate (1,0) sulfate, C ₁₂ -C ₁₈ alkalpolyethoxylate sulfate (2.25), C ₁₂ -C ₁₈ alkyl polyethoxylate (3.0) sulfate, and C ₁₂ -C ₁₈ alkylpolyethoxylate (4.0) sulfate, where M is usually selected from sodium or potassium.

 Other anionic surfactants.

Other anionic surfactants suitable for purification purposes may also be included in these compositions. They may include salts (including, for example, sodium, potassium, ammonium, and substituted ammonium salts, such as salts of mono-, di-, and triethanolamine) soaps, C ₉ -C ₂₀ linear alkylbenzenesulfonates, C ₈ -C ₂₂ primary or secondary alkanesulfonates, C ₈ -C ₂₄ olefinsulfonates, sulfonated polycarboxylic acids prepared by sulfonation products of pyrolysis alkaline earth metal citrates, e.g., as described in British patent specification N 1,082,179, alkyl glitserinsulfonatov, oleinglitserin fatty acid sulfonates, sulfates ether alkilfena ethylene, paraffin sulfonates, alkyl phosphates, izotianatov such as the acyl isethionates, N-acyl taurates, fatty acid amides of methyl Taurito, alkyl succinamates and sulfosuccinates, monoesters of sulfosuccinate, especially saturated and unsaturated C ₁₂ -C ₁₈ monoesters, diesters of sulfosuccinate, especially unsaturated and unsaturated C ₆ -C ₁₄ diesters, N -atsilsarkozinaty, sulfates of alkylpolysaccharides such sulfates of alkylpolyglucoside (neon nonsulfated substance will be described below), branched primary alkyl sulfates, alkilpolietoksikarboksila s, such as the formula RO (CH ₂ CH ₂ O) _k • CH ₂ COO ^- M ^+, wherein R is a C ₈ -C ₂₂ alkyl; k is an integer 0 10; M is a soluble salt-forming cation, as well as fatty acids esterified with isothionic acid and neutralized with sodium hydroxide. Resin acids and hydrogenated resin acids such as rosin, hydrogenated rosin and hydrogenated resin acids present in or isolated from tall oil are also suitable. Additional examples are described in "Surface Active Agents and Detergents" (volumes -1 and 2, Schwartz, Perry and Berch). A variety of such surfactants are also disclosed in detail in US Pat. No. 3,929,678, issued December 30, 1975, Lauglilin et.al.

Non-ionic, detergent surfactants
Suitable neon detergent surfactants are fully described in US Pat. No. 3,929,678 to Laughlin, issued December 30, 1975. Examples of non-limiting classes of useful non-ionic surfactants are given below.

 1. Polyethylene, polypropylene and polybutylene oxide condensates of alkyl phenols. Mostly preferred are polyethylene oxide condensates. Such compounds include condensation products of alkyl phenols with alkyl groups containing 6 to 12 carbon atoms in both branched and unbranched chains, with alkylene oxide. In a preferred embodiment, ethylene oxide is present in an amount of about 5 to about 25 moles of ethylene oxide per mole of alkyl phenol. Commercially available non-ionic surfactants of this type include IGEPAL CO-630 sold by GAP Corporation; IRITON X-45, X-114, X-100 and X-102, all sold by Rohm Haas Company. These compounds are usually defined as alkyl phenol alkoxylates. (For example, alkyl phenol ethoxylates).

2. Condensation products of aliphatic alcohols with from about 1 to about 25 mol of ethylene oxide. The alkyl chain of an aliphatic alcohol can be either branched or unbranched, primary or secondary, and usually it contains 8 to 22 carbon atoms, alcohols can be either primary or secondary. Particularly preferred are condensation products of alcohols containing alkyl groups containing from about 10 to about 20 carbon atoms, with ethylene oxide in an amount of 2 to 18 mol per 1 mol 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 alcohol with 9 mol of ethylene oxide), TERGITOL 24-L-6 NMW (condensation product of C ₁₂ -C ₁₄ primary alcohol with 6 mol of ethylene oxide, with a narrow molecular weight distribution), both sold by Union Carbide Corporation, Neodol 45-9 (condensation product of C ₁₄ -C ₁₅ linear alcohol with 9 mol of ethylene oxide NEODOL 23-6.5 (condensation product of C ₁₂ -C ₁₃ linear alcohol, with 6.5 mol of ethylene oxide), NEODOL 45-7 (condensation product of C ₁₄ -C ₁₅ linear alcohol with 7 mol of ethylene oxide), NEODOL 45-4 (a condensation product of a C ₁₄ -C ₁₅ linear alcohol with 4 mol of ethylene oxide) sold by Shell Chem. Comp. and KYROEOB (a condensation product of a C ₁₃ -C ₁₅ alcohol with 9 mol of ethylene oxide) sold by The Procter Gamble Comp. This category of nonionic surfactants is commonly referred to as "alkyl ethoxylates."

 3. Condensation products of ethylene oxide with a hydrophobic base obtained by condensation of propylene oxide with propylene glycol. The hydrophobic part of these compounds preferably has a molecular weight of from about 1500 to about 1800 and they are not soluble in water. The addition of polyethylene oxide fragments to these hydrophobic parts leads to an increase in the water solubility of the molecule as a whole, and the liquid character of the product remains until the point where the polyoxyethylene content is about 50% of the total mass of the condensation product, which corresponds to condensation up to about 40 mol of ethylene oxide. Examples of compounds of this type include certain commercially available PLURONIC surfactants sold by BASF.

 4. Condensation products of ethylene oxide with the product resulting from the interaction of propylene oxide with ethylene diamine. The hydrophobic fragment of these products consists of the reaction product of ethylene diamine and an excess of propylene oxide and usually has a molecular weight of from about 2500 to about 3000. The hydrophobic fragment is condensed with ethylene oxide to the extent that the condensation product contains from about 40 wt. up to 80 wt. polyoxyethylene, and has a molecular weight of from about 5,000 to about 11,000. Examples of this type of nonionic surfactant include some of the commercially available TETRONIC compounds sold by BASF.

 5. Semi-polar non-ionic surfactants is a special category of non-ionic surfactants that include water-soluble amine oxides containing one alkyl fragment of 10-18 carbon atoms and 2 fragments selected from the group consisting of alkyl and hydroxyalkyl groups containing 1-3 atoms carbon, water-soluble phosphine oxides containing one alkyl fragment containing from about 10 to about 18 carbon atoms, and 2 fragments selected from the group consisting of alkyl hydroxyalkyl groups with 1-3 carbon atoms And water-soluble sulfoxides containing one alkyl moiety of from about 10 to 18 carbon atoms and a moiety selected from the group consisting of alkyl and hydroxyalkyl moieties containing from about 1 to 3 carbon atoms.

где
R₃ является алкилом гидроксиалкилом, или алкилфенильной группой, или их смесями, содержащими от около 8 до 22 углеродных атомов; R₄ является алкиленовой или гидроксиалкиленовой группой, содержащей 2 3 углеродных атомов, или их смесями; X имеет значения от 0 до 3; каждый из R₅ является алкильной или гидроксиалкильной группой, содержащей от около 1 до около 3 углеродных атомов, или является полиэтиленоксидной группой, содержащей от 1 до 3 этиленоксидных групп. R₅ группы могут быть связаны друг с другом, например через атомы кислорода иди азота, образуя кольцевую структуру.Semi-polar non-ionic detergent surfactants include amine oxide surfactants of the formula

Where
R ₃ is alkyl hydroxyalkyl, or an alkyl phenyl group, or mixtures thereof, containing from about 8 to 22 carbon atoms; R ₄ is an alkylene or hydroxyalkylene group containing 2 to 3 carbon atoms, or mixtures thereof; X has values from 0 to 3; each of R ₅ is an alkyl or hydroxyalkyl group containing from about 1 to about 3 carbon atoms, or is a polyethylene oxide group containing from 1 to 3 ethylene oxide groups. R ₅ groups can be bonded to each other, for example through oxygen atoms or nitrogen, forming a ring structure.

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

 6. Alkyl polysaccharides disclosed in US Pat. No. 4,565,647, issued January 21, 1986, Ilenado containing a hydrophobic group containing from about 6 to about 30 carbon atoms, and preferably from about 10 to about 16 carbon atoms and a polysaccharide, for example polyglycoside, the hydrophilic group of which contains from about 1.3 to 10, preferably from about 1.3 to 3, most preferably from 1.3 to 2.7 saccharide moieties. Any reducing saccharide containing 5 or 6 carbon atoms can be used, for example, glucose, galactose and glycosyl fragments can be replaced by galactosyl (optionally hydrophobic group attached at positions 2-, 3-, 4-, etc. which gives glucose or galactose as opposed to glucoside or galactoside). Inter-saccharide bonds can be, for example, between one position of additional saccharide fragments at 2-, 3-, 4- and / or 6 positions of precursors of saccharide fragments.

 Optionally and less desirable, there may be a polyalkylene oxide chain connecting the hydrophobic moiety and the polysaccharide moiety. A preferred alkylene oxide is ethylene oxide. Typical hydrophobic groups include alkyl groups, both saturated and unsaturated, branched or unbranched, containing from about 8 to about 18, preferably from about 10 to about 16 carbon atoms. Preferably, the alkyl group is an unbranched saturated alkyl group. An alkyl group may contain up to about 3 hydroxyl groups and / or a polyalkylene oxide chain containing up to 10, preferably less than 5 alkylene oxide fragments. Suitable alkyl polysaccharides are octyl, nonyldecyl, undecyldodecyl, tridecyl, tetradecyl, pentadecyl, hexadedyl, heptadecyl and octadecyl, di-, tri-, tetra-, penta-, and hexaglucosides, galactosides, fructosides, lactose, fructosides, lactose, fructosides, lactose, fructosides, lactose, fructosides, lactose, fructosides, lactose, fructosides, lactose, fructosides, lactososides, lactososides, fructosides, lactososides, lactososides, lactososides, lactososides, fructosides, lactososides, lactosides, lactososides, lactososides, lactososides, lactososides, fructosides, lactososides, lactososides, lactososides, lactosides, Suitable mixtures include coconut alkyl, di-, tri-, tetra-, and pentaglucosides and tall alkyl, tetra-, penta-, and hexaglucosides.

Preferred alkyl polyglucosides have the formula
R ₂ O (C _n H _2n O) _t (glycosyl) _x
Where
R _{2 is} selected from the group consisting of alkyl, alkylphenyl, hydroxyalkyl, hydroxyalkylphenyl, and mixtures thereof, in which the alkyl groups contain 10 18, preferably 12 14 carbon atoms; n 2 or 3, preferably 2; t is 0 10, preferably 0; x has a value of from 1.3 to 10, preferably from 1.3 to 3, most preferably from 1.3 to 2.7. Glycosyl is preferably derived from glucose. To obtain these compounds, alcohol or an alkylpolyethoxy alcohol is first prepared and then reacted with glucose or a glucose source to produce a glucoside attached at the 1-position. Additional glycosyl moieties can then be attached between their 1-position and the preceding glycosyl moieties at the 2-, 3-, 4- and / or 6-positions, preferably at the 2-position.

где
R₆ является алкильной группой, содержащей от около 7 до около 21, предпочтительно от 9 до 17, углеродных атомов и каждый; R₇ выбирают из группы, состоящей из водорода C₁-C₄ алкила, C₁-C₄ гидроксиалкила и -(C₂H₄O)_xH, где x меняется от 1 до 3.7. Surfactants fatty acid amides of the formula

Where
R ₆ is an alkyl group containing from about 7 to about 21, preferably from 9 to 17, carbon atoms and each; R _{7 is} selected from the group consisting of hydrogen C ₁ -C ₄ alkyl, C ₁ -C ₄ hydroxyalkyl and - (C ₂ H ₄ O) _x H, where x varies from 1 to 3.

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

 Cationic surfactants.

Cationic detergent surfactants may also be included in the detergent compositions of the invention. Cationic surfactants include ammonium surfactants, such as alkyl dimethyl ammonium halides, and these surfactants are of the formula
[R ₂ (OR ₃ ) _y ] [R ₄ (OR ₃ ) _y ] ₂ R ₃ N ⁺ X ^- ,
Where
R ₂ is an alkyl or alkylbenzyl group containing 8 to 18 carbon atoms in the alkyl chain; each R _{3 is} selected from the group consisting of —CH ₂ CH ₂ -, —CH ₂ CH (CH ₃ ) -, —CH ₂ CH (CH ₂ OH) -, —CH ₂ CH ₂ CH ₂ -, and mixtures thereof; each R _{4 is} selected from the group consisting of C ₁ -C ₄ alkyl, C ₁ -C ₄ hydroxyalkyl, benzyl, ring structures formed by the addition of two R ₄ groups, —CH ₂ CHOH-CHOHCOR ₆ —CHOHCH ₂ OH, where R ₆ is hexose or hexose polymer with a molecular weight of less than about 1000, and hydrogen, if y is not 0; R _{5 is the} same as R ₄ or is an alkyl chain, where the total number of carbon atoms R ₂ plus R _{5 is} not more than 18; each y takes values from 0 to 10 and the total value of y from 0 to 15; x is a compatible anion.

 Other cationic surfactants useful herein are also described in US Pat. No. 4,228,044, Cambre, issued October 14, 1980.

 Other surfactants.

 Ampholytic surfactants can be incorporated into the detergent compositions of this invention. These surfactants are widely described as aliphatic derivatives of secondary or tertiary amines, or aliphatic derivatives of heterocyclic secondary and tertiary amines, in which the aliphatic radical may be a branched or unbranched chain. One of the aliphatic substituents contains at least 8 carbon atoms, usually 8 to 18 carbon atoms, and at least one contains an anionic water-solubilizing group, for example, a carboxyl, sulfonate, sulfate group (see U.S. Patent No. 3,929,667, Laughlin et al. Issued 30 December 1975 (included herein for examples (ampholytic surfactants).

 Zwitterionic surfactants can also be incorporated into the detergent compositions of the invention. These surfactants can be broadly described as derivatives of secondary or tertiary amines, derivatives of heterocyclic secondary and tertiary amines, or derivatives of quaternary ammonium, quaternary phosphonium or tertiary sulfonium compounds (see U.S. Patent No. 3,929,678, Laughlin et al, issued December 30 1975, for examples of zwitterionic surfactants).

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

 In addition to enzymes, fatty acid polyoxyamide, and other optional detergent surfactants, the detergents herein may include one or more other detergent auxiliaries, or other materials to facilitate and / or enhance the cleansing effect so that the substrate is processed perfectly or modify the detergent aesthetics compositions or modify, for example perfumes, paints, dyes, etc.).

 Structural materials.

 Detergent structure-forming materials may optionally be included in these compositions and serve to control mineral hardness. Both organic and inorganic structure-forming materials can be used.

 The level of structure-forming material can largely depend on the end use of the composition and its target physical form. In this composition will typically contain at least 1% builder. Liquid formulations typically contain from about 5 wt. up to about 50 wt. more preferably from 5 wt. up to 30 wt. detergent builder. Granular formulations typically contain from about 10 wt. up to about 80 wt. more typically from about 15 wt. up to about 50 wt. detergent builder. However, this does not mean that higher or lower levels of the structure-forming substance are excluded.

Inorganic detergent builders include (but are not limited to) alkali metal, ammonium and alkanolammonium salts of polyphosphates (e.g. tripolyphosphates, pyrophosphates and glassy polymer metaphosphates), phosphonates, phytic acid, silicates, carbonates (including bicarbonates and sesquicarbonates and aluminates). Borate builders, as well as builders containing borate-forming materials that can release boron during storage of the detergent or under washing conditions, hereinafter, together “borate builders” can also be used. It is preferable to use non-borate builders in the compositions of the invention, which are intended to be used at washing temperatures of less than about 50 ^° C., especially less than 40 ^° C.

Examples of silicate builders are alkali metal silicates, especially those having a SiO ₂ • Na ₂ O ratio in the range of 1.6: 1 to 3.2: 1, and layered silicates, such as layered sodium silicates, described in US Pat. No. 4,664,839 issued May 12, 1987, HPRieck. However, other silicates can also be used, for example magnesium silicate, which can serve as an agent to impart granularity to granular formulations, as a stabilizing agent for oxygen bleaches, and as a component for systems with controlled foaming.

 Examples of carbonate builders are alkali and alkaline earth metal carbonates, including sodium carbonate and sesquicarbonate, as well as mixtures thereof with ultrafine calcium carbonate (see German Patent Application No. 2,321,001, published November 15, 1973).

Aluminosilicate builders are particularly useful for the present invention. Aluminosilicate structurants are important in the most common, highly effective granular detergent compositions, and can also be an important structure-forming ingredient in liquid detergent compositions. Empirical formula products are aluminosilicate builders.
M ₂ (zAlO _z • YSiO ₂ ),
Where
M is sodium, potassium, ammonium or substituted ammonium; Z varies from 0.5 to 2; Y is 1; such a material with a magnesium ion exchange capacity of at least about 50 mg equivalents of CaCO ₃ hardness per gram of anhydrous aluminosilicate. Preferred aluminosilicates are zeolite builders of the formula
Na ₂ [(Al) ₂ (SiO ₂ ) _y ] • xH ₂ O,
Where
Z and Y are integers of at least 6; the molar ratio of Z to Y lies in the range from 1.0 to about 0.5; X is an integer from about 15 to about 264.

Suitable aluminosilicate ion exchange materials are commercially available. These aluminosilicates can be crystalline or amorphous in structure and can be either natural or synthetically prepared. A method for producing aluminosilicate ion-exchange materials is disclosed in US patent N 3 985 669, Krummel et. al. October 12, 1976. The preferred synthetic crystalline aluminosilicate ion exchange materials used herein are available under the names Zeolite A, Zeolite P (B), and Zeolite X. In a particularly preferred embodiment, crystalline aluminosilicate ion exchange materials have the formula
Na ₁₂ [(AlO ₂ ) ₁₂ (SiO ₂ ) ₁₂ ] • xH ₂ O,
Where
X varies from 20 to 30, especially about 27. Such a material is known as Zeolite A. It is desirable that the aluminosilicates have a particle size of from about 0.1 to 10 microns in diameter.

 Specific examples of polyphosphates are alkali metal tripolyphosphates, sodium, potassium and ammonium pyrophosphates, sodium and potassium orthophosphate, sodium polymethosphate, in which the degree of polymerization varies from about 6 to about 21, and phytic acid salt.

 Examples of salts with a phosphonate builder are water-soluble salts, ethane-1-hydroxy-1,1-diphosphonate, in particular sodium and potassium salts, water-soluble salts of methylenediphosphonic acid, for example trisodium, and tri-potassium salts, and water-soluble salts of substituted methylenediphosphonic acids, such as tri , tripotassium ethylidene, isopropylidene, benzylmethylidene and halomethylidene phosphonates. Phosphonate structure-forming salts of the above types are disclosed in US Pat. Nos. 3,159,851 and 3,213,030 issued December 1, 1964 and October 19, 1965 by Diehl; U.S. Patent Nos. 3,422,021 issued January 14, 1969 to Roy; US Pat. Nos. 3,400,148 and 3,422,137, issued September 3, 1968 and January 14, 1969, by Quimby.

 Organic detergent builders suitable for the purposes of the invention include, but are not limited to, a wide range of polycarboxylate compounds. As used herein, the term "polycarboxylate" refers to compounds having multiple carboxylate groups, preferably at least 3 carboxylates.

 The polycarboxylate builder can usually be added to the composition in the form of an acid, but can also be added in the form of a neutral salt. When used in salt form, alkali metal salts such as sodium, potassium, lithium or alkanolammonium salts are preferred.

 Polycarboxylate builders include a number of categories of useful materials. Each class of polycarboxylate builders includes polycarboxylate esters. A number of ether polycarboxylates have been found to be used as detergent builders. Examples of suitable ester polycarboxylates include oxide disuccinate as disclosed by Berg in US Pat. No. 3,128,287 issued April 7, 1964 and Lambesti et. al. U.S. Patent No. 3,635,830, issued January 18, 1972.

A particular type of ester polycarboxylates suitable as builders in the invention also includes compounds of 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) —CH ₂ (COOX); X is H or a salt forming cation. For example, if in the above basic formula A and B are both H, then the compound is oxysucic acid and its water-soluble salts.

If A is OH and B is H, then the compound is tartrate monosuccinic acid (TMS) and its water-soluble salts. If A is H and B is —O — CH (COOX) —CH ₂ (COOX), then the compound is tartrate disuccinic acid (TDS) and its water soluble salts. Mixtures of these builders are particularly preferred for use herein. Particularly preferred are mixtures of TMS and TDS with a weight ratio of TMS and TDS from about 97: 3 to about 20:80. These builders are described in US Pat. No. 4,663,071 to Bush et. al May 5, 1987.

 Suitable ester polycarboxylates also include cyclic compounds, especially alicyclic compounds, such as those described in US Pat. Nos. 3,923,679,3,835,163,410,903.

Other suitable detergent builders include ether hydroxypolycarboxylates represented by the structural formula
HO- [C (R) (COOM) -C (R) (COOM) -O] _n -H
Where
M is hydrogen or a cation, wherein the salt formed is water soluble; these are preferably cations of an alkali metal, ammonium or substituted ammonium; n varies from 2 to 15 (preferably from 2 to 10, more preferably when the values of n lie in the range from 2 to 4); each R is the same or different, selected from hydrogen, C _1-4 alkyl or C _1-4 substituted alkyl, preferably R is hydrogen.

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

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

 Also included are polycarboxylates such as the polycarboxylates of mellitic, succinic, oxidisuccinic, polymaleic acid, benzene-1,3,5-tricarboxylic acid, and carboxymethyloxy-succinic acid, as well as their soluble salts.

 Citrate builders, for example citric acid and its soluble salts (especially sodium salt), are polycarboxylate builders, especially important for highly effective liquid detergent compositions, but can also be used in granular compositions.

 Other carboxylate builders include carboxylated hydrocarbons disclosed in US Pat. No. 3,723,322, Diehl, issued March 28, 1973.

Also useful in the detergent compositions of the invention are 3,3-dicarboxy-4-oxa-1,6-hexanedioates and related compounds disclosed in US Pat. No. 4,566,984, Bush, issued January 28, 1986. Suitable succinic acid builders include C ₅ -C ₂₀ alkyl succinic acids and their salts. A particularly preferred compound of this type is dodecenyl succinic acid. Alkyl succinic acids usually have the basic formula R CH (COOH) CH ₂ (COOH), that is, they are derivatives of succinic acid, where R is a hydrocarbon, for example C ₁₀ -C ₂₀ alkyl or alkenyl, preferably C ₁₂ -C ₁₆ , or, if R may be substituted by hydroxyl, sulfo, sulfoxy or sulfonic substituents, all of which are described in the aforementioned patents.

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

 Representative examples of succinate builders include lauryl succinate, myristyl succinate, palmityl succinate, 2-dodecyl succinate (preferred), 2-pentadecyl succinate, and the like. Lauryl succinates are the preferred builders of this group (see European patent application N 86200690 5 / 0,200,263, published November 5, 1986).

 Examples of suitable builders include sodium and potassium carboxymethyloximalonate, carboxymethyloxysuccinate, cis-cyclohexane-hexacarboxylate, cis-cyclopentane-tetracarboxylate, water-soluble polyacrylates (these polyacrylates have molecular weights higher than about 2,000, and can also be used effectively) anhydride with vinyl methyl ether or ethylene.

 Other suitable polycarboxylates are polyacetal carboxylates described in US Pat. No. 4,144,226, Crutchfield et. al. issued March 13, 1979. These polyacetal carboxylates can be prepared by placing together under polymerization conditions a polymerization initiator and a glyoxylic acid ester. The resulting polyacetal carboxylate ester is then coupled to chemically stable end groups to stabilize the polyacetal carboxylate from rapid depolymerization in alkaline solutions, transferred to the corresponding salt and added to the surfactant.

 Polycarboxylate builders are also described in US Pat. No. 3,308,067 to Diehl, issued March 7, 1967.

 Such materials include water-soluble salts of homo- and copolymers of aliphatic carboxylic acids, such as maleic acid, itaconic acid, mesaconic acid, fumaric acid, aconitic acid, citraconic acid and methylene malonic acid.

 Other organic builders known in the art can also be used. For example, monocarboxylic acids and their soluble salts containing long hydrocarbon chains. These include materials commonly referred to as "soaps."

Typically, chains of length C ₁₀ -C _{20 are used} . Hydrocarbons can be saturated and unsaturated.

 Whitening compounds whitening agents and whitening activators.

 The detergent compositions of the invention may contain whitening agents or compositions containing a whitening agent and one or more whitening activators. When conducting bleaching, the compounds should usually be maintained at levels of from about 1% to about 20%, more preferably from about 1% to about 10% of the detergent composition. Bleaching compounds are optional components in non-liquid formulations, such as granular detergents. If present, the amount of bleach activators should generally be maintained from about 0.1% to about 60%, more typically from about 0.5% to about 40%, of the whitening composition.

The bleaching agents used herein may be any bleaching agents useful for detergent compositions in cleaning fabrics, cleaning a hard surface, or for other cleaning purposes that are known or will be known. They include both oxygen and other whitening agents. Under washing conditions below 50 ^° C, especially below 40 ^° C, it is preferred that the compositions do not contain borate or material that can form borate in situ (i.e., borate forming material) under detergent storage conditions or under washing conditions. Thus, it is preferable that non-borate and non-borate non-borate bleaching agents are used under these conditions. It is preferred that the detergents used at these temperatures are substantially free of borates and borate-forming materials. Used here, the term "practically free of borate and borate-forming material" should mean that the composition contains no more than 2 wt. borate-containing and borate-forming material of any type, preferably not more than 1% and even more preferably 0%
The first category of whitening agents that can be used here encompasses percarboxylic acid whitening agents and their salts. Suitable examples of this class of agents include magnesium monoperoxyphthalate hexahydrate, magnesium salt of metachloroperbenzoic acid, 4-nonylamino-4-oxo-peroxybutyric acid, and diperoxide-decanedioic acid. Such whitening agents are disclosed in US Patent No. 4,483,781 to Hastman, November 20, 1984, US Patent Application No. 740, 446, Burus, filed June 3, 1985, European Patent Application 0 133 354, Banks, published February 20, 1985. U.S. Patent No. 4,412,934, Chng et. al. issued November 1, 1983. The most preferred whitening agents also include 6-nonylamino-6-oxoperoxycaproic acid, as described in US Pat. No. 4,634,551, issued January 6, 1987, Burns et al.

 Another category of whitening agents that can be used includes halide whitening agents. Examples of hypogalitic whitening agents, for example, include trichloroisocyanuronic acid, and also sodium and potassium dichloroisocyanurates, N-chloro and N-bromo alkanesulfonamides. Typically, such compounds are added in an amount of 0.5-10 wt. the final product, preferably 1-5 wt.

 Peroxide whitening agents can also be used. Suitable peroxide whitening compounds include sodium carbonate peroxyhydrate, sodium pyrophosphate peroxyhydrate, urea peroxyhydrate and sodium peroxide.

 Peroxide whitening agents are preferably combined with whitening activators, which lead to the formation in situ in an aqueous solution (i.e., during washing) of peroxy acid corresponding to the whitening activator.

где
R является алкильной группой, содержащей 1 18 углеродных атомов, причем самая длинная линейная цепь, простирающаяся от и включающая углерод карбонила, содержит 6 10 атомов углерода; Z является отщепляемой группой, сопряженная кислота которой имеет pK_a в интервале от около 4 до около 13. Эти активаторы отбеливания описаны в патенте США N 4 915 854, выданном 10 апреля 1990 года. Mao et.al. и в патенте США 4 412 934.Preferred whitening activators incorporated into the compositions of this invention have the general formula

Where
R is an alkyl group containing 1 to 18 carbon atoms, the longest linear chain extending from and including carbon carbonyl, contains 6 to 10 carbon atoms; Z is a leaving group, the conjugate acid of which has pK _a in the range of about 4 to about 13. These whitening activators are described in US Pat. No. 4,915,854, issued April 10, 1990. Mao et.al. and in US patent 4,412,934.

 Bleaching agents other than oxygen bleaching agents are also known, and they can be used here. One of the types of non-oxygen whitening agents of greatest interest includes photoactivated whitening agents such as zinc sulfonates and / or aluminum phthalocyanines. These materials may be deposited on the substrate during the washing process.

 When irradiated with light in the presence of oxygen, sulfonated zinc phthalocyanine is activated and the substrate is bleached, which happens when hanging clothes for drying in daylight. Preferred zinc phthalocyanines and photoactivated whitening processes are described in US Pat. No. 4,033,718, issued July 5, 1977, Holcombe et.al.

 Typically, detergent compositions should contain from about 0 025 wt. up to about 1.25 wt. sulfonated zinc phthalocyanine.

 Polymeric agent for removing dirt.

 Some polymeric dirt removing agents known to those skilled in the art can be used in the practice of this invention. Polymeric dirt-removing agents are characterized by the presence of both hydrophilic segments to impart hydrophilicity to the surface of hydrophobic fibers, such as polyester or nylon, and hydrophobic segments for deposition on hydrophobic fibers, and which remain attached to them until washing and rinsing cycles are completed and thus serve as a place fixation for hydrophilic segments. This makes it possible to more easily remove stains remaining after treatment with a stain removing agent in further washing processes. Whereas it may be beneficial to use polymeric dirt-removing agents in any detergent compositions, especially those used in laundries or other applications where the removal of fat and oil from hydrophobic surfaces is necessary, the presence of polyhydroxyamide fatty acids in detergent compositions also containing Anionic surfactants can enhance the action of many of the commonly used types of polymer agents to remove dirt. Anionic surfactants interfere with the ability of some dirt removing agents to deposit and adhere to hydrophobic surfaces. Such polymeric dirt-removing agents have non-ionic hydrophilic segments or hydrophobic segments that are capable of interacting with an anionic surfactant.

Compositions of the invention for which an improved action of a polymeric dirt-removing agent can be achieved by using a polyhydroxy fatty acid amide are compounds that contain an anionic surfactant system, an anionic surfactant, interacting with a dirt-removing agent, and an amount of amide enhancing the effect of the dirt-removing agent polyhydroxy fatty acid (PFA), where
The I anionic surfactant interaction between the dirt removing agent and the anionic surfactant detergent composition system can be shown by comparing the retention rate of the dirt removing agent (SRA) on hydrophobic fibers (eg polyester) in an aqueous solution between the (A) “Control” cycle during SRA deposition a detergent composition in an aqueous solution in the absence of other detergent ingredients, and (B) a "SRA anionic surfactant" test cycle is measured where a similar type and amount of anionic surfactant system used in the detergent composition is combined in an aqueous solution with SRA at the same mass ratio of SRA to anionic surfactant system of the detergent composition, and a decrease in deposition in (B) relative to (A) indicates anionic surfactant interaction;
II whether the detergent composition contains the enhancing effect of the dirt-removing agent the amount of polyhydroxy fatty acid amide can be determined by comparing the SRA deposition of the SRA (anionic surfactant) of the test cycle (B) with the deposition of the dirt-removing agent in (C) "SRA (anionic surfactant) PFA test cycle" where the same type and level of the polyhydroxy fatty acid amide of the detergent composition is combined with a dirt removing agent and an anionic surfactant system corresponding to the SRA (anionic surfactant) test cycle, with increased deposition of the dirt removing age that a test cycle (C) relative to test cycle B indicates the presence of the dirt-removing agent-enhancing amount of polyhydroxy fatty acid amide. For these purposes, tests should be carried out at concentrations of anionic surfactants in an aqueous solution above the critical micelle concentration (CMC) of the anionic surfactant and preferably above 100 ppm. The concentration of the polymer dirt-removing agent should be at least 15 ppm. Sample polyester fabric should be used as a source of hydrophobic fiber. Identical samples are immersed and stirred at 35 ^° C. in aqueous solutions for the respective test cycles for 12 minutes, then removed and analyzed. The level of deposition of the polymeric dirt-removing agent can be determined by treating the dirt-removing agent with radiolabels prior to processing by further radiochemical analysis in accordance with a technique known to those skilled in the art.

 As an alternative to the radiochemical analytical procedure discussed above, the deposition of the dirt-removing agent can be determined in the above test cycles (i.e. test cycles A, B, C) by determining the ultraviolet absorption of the test solutions in accordance with well-known techniques. The decrease in UV absorption in the test solution after removal of the hydrophobic fiber material corresponds to increased SRA deposition. As obvious to those skilled in the art, UV analysis should not be used to test solutions containing the types and levels of materials that cause excessive interference of UV absorption, such as solutions with high levels of surfactants containing aromatic groups (e.g., alkylbenzenesulfonates, etc.). )

 Thus, the term "efficiency enhancing amount of a dirt removing agent" of polyhydroxy fatty acid amides is understood to mean such an amount of a given surfactant that will enhance the deposition of the dirt removing agent on hydrophobic fibers, as described above, or the amount at which an enhanced cleansing fat / oil for fabrics washed in the detergent composition of the invention in a subsequent cleaning operation.

 The amount of polyhydroxy fatty acid amide needed to enhance deposition will vary depending on the selected anionic surfactant, its amount, the particular dirt removing agent selected, as well as the particular polyhydroxy fatty acid amide selected. Typically, the composition will contain from 0.1 wt. up to 10 wt. polymeric dirt-removing agent, typically 0.1 to 5 wt. and 4 to 50 wt. more typically 5 to 30 wt. anionic surfactant. Such compositions should generally contain at least 1 wt. preferably 3 wt. polyhydroxy fatty acid amide, although this is not a limitation.

Polymeric dirt-removing agents whose effect is enhanced by a polyhydroxy fatty acid amide in the presence of an anionic surfactant containing such dirt-removing agents that have: a) one or more non-ionic hydrophilic agents containing mainly (i) polyoxyethylene segments with a degree of polymerization at least 2, or (ii) oxypropylene or polyoxypropylene segments with a degree of polymerization of 2 to 10, wherein said hydrophilic segment does not include any oxypropylene fragments, if only it is not associated with adjacent fragments, ether bonds at each end, or (iii) a mixture of oxyalkylene fragments containing oxyethylene and 1 30 oxypropylene fragments, where the mixture contains a sufficient amount of oxyethylene fragments such that the hydrophilic component has a hydrophilicity high enough to increase the hydrophilicity of the surfaces of conventional polyester synthetic fibers when a dirt-removing agent is deposited on such a surface, said hydrophilic segments being preferably contain at least about 25% oxyethylene units, more preferably, especially for components having 20 to 30 oxypropylene units, at least about 50% oxyethylene units; or b) one or more of the hydrophobic components containing (i) segments of C ₃ oxyalkylene terephthalate, where if the hydrophobic components also contain oxyethylene terephthalate, the ratio of oxyethylene terephthalate and C ₃ oxyethylene terephthalate units is 2: 1 or lower; (i) C ₄ -C ₆ alkylene or oxy-C ₄ -C ₆ alkylene segments, or mixtures thereof; (iii) poly (vinyl ester) segments, preferably poly (vinyl acetate), with a degree of polymerization of at least 2, or (ii) C ₁ -C ₄ alkyl ether or C ₄ hydroxyalkyl ether substituents, or mixtures thereof, wherein said substituents are present as C ₁ -C ₄ alkyl ether or C ₄ hydroxyalkyl ether cellulose derivatives or mixtures thereof; such cellulosic derivatives are amphiphilic, whereby they have a sufficient level of C ₁ -C ₄ alkyl ether and / or hydroxyalkyl ether units to deposit on ordinary surfaces of the polyester synthetic fiber and retain a sufficient level of hydroxyls once adhered to such a normal surface of the synthetic fiber to increase surface hydrophilicity fiber; or a combination of (a) and (c).

Typically, the polyoxyethylene segments (a) (i) will have a degree of polymerization of from 2 to about 200, although higher degrees can be used, preferably from 2 to about 150, more preferably from 6 to about 100. Suitable hydroxy C ₄ -C ₆ alkylene hydrophobic segments include, but are not limited to, end groups in the form of polymeric dirt-removing agents, such as MO ₃ S (CH ₂ ) _n OCH ₂ CH ₂ O-, where M is sodium; n varies from 4 to 6, (see U.S. Patent No. 4,721,580, issued January 26, 1988, Crorselink).

 Polymeric dirt-removing agents useful in the invention include cellulosic derivatives such as hydroxyether cellulose polymers, copolymer blocks of ethylene terephthalate or propylene terephthalate with polypropylene or polyethylene oxide terephthalate and the like.

Cellulosic derivatives that function as dirt removing agents are commercially available and include cellulose hydroxyesters such as Methoceo ^R (DOW).

Cellulosic dirt-removing agents for use in the method of the invention also include those selected from the group consisting of C ₁ -C ₄ alkyl and C ₄ hydroxyanyl cellulose, for example methyl cellulose, ethyl cellulose, hydroxypropyl methyl cellulose and hydroxybutyl methyl cellulose. Various cellulose derivatives suitable as dirt removing polymers are disclosed in US Pat. No. 4,000,093, issued December 28, 1976 to Nicol. et.al.).

Mud removing agents characterized by hydrophobic segments of poly (vinyl ester) include grafted copolymers of poly (vinyl ester), for example C ₁ -C ₆ vinyl esters, preferably poly (vinyl acetate), grafted onto a polyalkylene oxide backbone, such as a polyethylene oxide backbone. Such materials are known in the art and are described in European Patent Application No. 0 219,048, published April 22, 1987, Kud et al.

 Suitable, commercially available dirt-removing agents of this type include a material such as SOKALAN, for example SOKALAN HP-22, manufactured by BASF (West Germany).

 One type of contaminant removing agent considered is a copolymer with statistical units of ethylene terephthalate and polyethylene oxide terephthalate (PEO) terephthalate at a molar ratio of ethylene terephthalate units and PEO terephthalate units of from about 25:75 to about 35:65, said PEO terephthalate units having a molecular weight of from 300 to about 250 up to about 2000. The molecular weight of such a polymeric dirt-removing agent lies in the region of 25,000 55,000 (see US Pat. No. 3,959,230, Hays, issued May 25, 1976, US Patent No. 3,893,929, Basadur, issued th July 8, 1975).

 Another preferred dirt removing agent is a polyester with repeating units of ethylene terephthalate containing 10 to 15 wt. ethylene terephthalate units with 90 80 wt. polyoxyethylene terephthalate units derived from polyethylene glycol with an average molecular weight in the region of 300-5,000, and the molar ratio of ethylene terephthalate units and polyoxyethylene terephthalate units in the polymer compound is between 2: 1 and 6: 1. Examples of such a polymer include the commercially available ZELCON 5126 material (Dupont ) and MILEASET (Yci). These polymers and methods for their preparation are most fully described in US patent N 4 702 857, published October 27, 1987, Gosselink.

 Another preferred polymeric dirt-removing agent is a sulfonated product of a substantially linear ether oligomer consisting of an oligomeric ester backbone of terephthaloyl and oxyalkyleneoxy repeating units, with terminal fragments being covalently linked to the main chain, and said dirt-removing agents are derived from allyl alcohol, ethoxylate, 1 2-propylene diol, and after sulfonation, the terminal fragments of each oligomer have an average total amount of sulfonate groups 4. These claim 1 dirt removing agents are described fully in U.S. Patent N 4,968,451, issued 6 November 1990 and goda J.J.cheibel E.P.Gosselink.

The following suitable polymeric dirt-removing agents include ethyl or methyl-terminated 1,2-propylene terephthalate-polyoxyethylene terephthalate polymers in US Pat. No. 4,711,730, issued December 8, 1987, Crosselind et.al. oligomeric esters with anionic ends (see U.S. Patent No. 4,721,580, issued January 26, 1988, Crosselink), the anionic ends containing sulfo-polyethoxy groups derived from polyethylene glycol (PEC), block polyester oligomeric compounds (see patent U.S. No. 4,702,857, issued October 27, 1987, Crosselink), with the polyethoxy ends of the formula X- (OCH ₂ CH ₂ ) _n -, where n varies from 12 to about 43; X is C ₁ -C ₄ alkyl or preferably methyl.

 Additional polymeric dirt-removing agents include dirt-removing agents of US Pat. No. 4,877,896, issued October 31, 1989, to Maldonado et al. which discloses terephthalate esters with anionic, especially sulfoaryl, ends.

Terephthalate esters contain asymmetrically substituted hydroxy-1,2-alkeneoxy units. Among the dirt removing polymers included in U.S. Patent No. 4,877,896 are polyoxyethylene hydrophilic components or C ₃ hydroxyalkylene terephthalate propylene terephthalate repeating fragments that fall within the scope of the above hydrophobic components (c) (i). It is these polymeric dirt-removing agents, characterized separately or together by such criteria, that significantly benefit from the inclusion of polyhydroxyamide fatty acids in the presence of anionic surfactants.

 When used, dirt-removing agents will typically be from about 0.01 wt. up to about 10 wt. detergent composition, typically from about 0.1 to about 5 wt. preferably from about 0.2 to about 3.0 wt.

 Chelating agents.

 The detergent compositions of the invention may also (optionally) contain one or more of agents that chelate iron or manganese as a structure-forming auxiliary material. Such chelating agents can be selected from the group consisting of aminocarboxylates, aminophosphonates, multifunctionally substituted aromatically chelating agents in their mixture, defined below, without claiming to limit the roots, it is believed that the advantage of these materials is partially due to their exceptional ability to remove iron and magnesium ions from washing solutions due to the formation of soluble chelates.

где
M является водородом, щелочным металлом, аммонием или замещенным аммонием, например этаноламином; X меняется от 1 до около 3, и предпочтительно равен 1. Предпочтительно, чтобы эти аминокарбоксилаты не содержали алкильных или алкенильных групп с более чем 6 атомами углерода. Подходящие аминкарбоксилаты включают этилендиаминтетраацетаты, N-гидроксиэтилэтилендиамитриацетаты, нитрилотриацетаты, этилендиаминтетрапропианаты, триэтилентетраамингексаацетаты, диэтилентриамипентаацетаты и этанолдиглицины, щелочные металлы, аммоний и их замещенные аммониевые соли и их смеси.Amino carboxylates useful as optional chelating agents in the compositions of the invention may have one or more, preferably at least 2 substructure fragments

Where
M is hydrogen, an alkali metal, ammonium, or substituted ammonium, for example ethanolamine; X varies from 1 to about 3, and is preferably equal to 1. Preferably, these aminocarboxylates do not contain alkyl or alkenyl groups with more than 6 carbon atoms. Suitable amine carboxylates include ethylenediaminetetraacetates, N-hydroxyethylethylenediamitriacetates, nitrilotriacetates, ethylenediaminetetrapropyanates, triethylenetetraaminehexacetates, diethylene triamipentaacetates and ethanolic diglycines, ammonium alkali metals and mixtures thereof, ammonium and ammonium salts thereof.

где
M является водородом, щелочным металлом, аммонием или замещенным аммонием; X равен 1 -3, предпочтительно 1, используются и включают этилендиаминтетракис(метиленфосфонаты), нитрилотрис(метиленфосфонаты) и диэтилентриаминпентакис(метиленфосфонаты). Предпочтительно, чтобы эти аминофосфонаты не содержали алкильных или алкенильных групп с более чем 6 углеродными атомами (алкиленовые группы могут быть заменены субструктурами).Amino phosphonates are also suitable for use as chelating agents in the compositions of the invention if at least low levels of total phosphorus are allowed in the detergent compositions. Compounds with one or more, preferably at least 2 substructure fragments

Where
M is hydrogen, alkali metal, ammonium or substituted ammonium; X is 1-3, preferably 1, are used and include ethylene diamine tetrakis (methylene phosphonates), nitrilotris (methylene phosphonates) and diethylene triamine pentakis (methylene phosphonates). Preferably, these aminophosphonates do not contain alkyl or alkenyl groups with more than 6 carbon atoms (alkylene groups may be replaced by substructures).

где по крайней мере один R является SO₃H или -COOH, или их растворимыми солями, и их смесями. Патент США N 3 812 044, выданный 21 мая 1974 года, Connor et al. раскрывает полифункционально замещенные ароматические хелатирующие и пассивирующие агенты. Предпочтительные соединения такого типа в форме кислот являются такими дигидроксидисульфобензолами, как 1,2-дигидрокси- 3,5-дисульфобензол. Щелочные детергентные композиции могут содержать эти материалы в форме солей щелочных металлов, аммония или замещенного аммония, например моно- или триэтаноламина.Multifunctionally substituted aromatic chelating agents are also useful in such compositions. These materials may contain compounds of the general formula

where at least one R is SO ₃ H or —COOH, or their soluble salts, and mixtures thereof. U.S. Patent No. 3,812,044, issued May 21, 1974, Connor et al. discloses multifunctionally substituted aromatic chelating and passivating agents. Preferred compounds of this type in the form of acids are dihydroxy disulfobenzenes such as 1,2-dihydroxy-3,5-disulfobenzene. Alkaline detergent compositions may contain these materials in the form of salts of alkali metals, ammonium or substituted ammonium, for example mono- or triethanolamine.

 If they are used such chelating agents, they contain mainly from about 0.1% to about 10 wt. detergent composition. More preferably, the chelating agents comprise from about 0.1 to about 3 wt. such compositions.

 Agents that remove dirt and prevent its re-deposition.

или
(X-L-)₂-N-R₁-N-(R₂)₂;
(3) этоксилированные полиамины, имеющие формулу

(4) этоксилированные полиамины, имеющие основную формулу

и (5) их смеси, где A₁ являются

или -O-; R является H или C₁-C₄ алкилом или гидроксиалкилом; R₁ является C₂-C₁₂ алкиленом, гидроксиалкиленом, алкениленом, ариленом или алкилариленом, или C₂-C₃ оксиалкиленовый фрагмент, содержащий от 2 до около 20 оксиалкиленовых звеньев, при условии, что не образуются O-N связи; каждый R₂ это C₁-C₄ или гидроксиалкил, фрагмент -L-X, или два R₂ вместе образуют фрагмент -(CH₂)_r, -A₂-(CH₂)_s-, где A₂ есть -O- или -CH₂; r равен 1 или 2; s равно 1 или 2, и r + s равно 3 или 4; X является неионной группой, анионной группой, или их смесью; R₃ является замещенным C₃-C₁₂ алкилом, гидроксиалкилом, алкенилом, арилом, или алкиларильной группой, содержащей заместители; R₄ является C₁-C₁₂ алкиленом, гидроксиалкиленом, алкениленом, ариленом или алкариленом, или C₂-C₃ оксиалкиленовым фрагментом, содержащим от 2 до около 20 оксиалкиленовых звеньев, при условии, что не образуются O-O или O-N связи; Z является гидрофильной цепью, которая содержит полиоксиалкиленовый фрагмент -[(R₅O)_m(CH₂CH₂O)_n] -, где R₅ является C₃-C₄ алкиленом или гидроксиалкиленом, а m и n принимают такие значения, что фрагмент -(CH₂CH₂O)_n- содержит по крайней мере 50 мас. указанного полиоксиалкиленового фрагмента; для названных моноаминов m принимает значения 0 4, а n как минимум равно 12; для названных диаминов m принимает значения 0 3, n как минимум равно 6, когда R₁ является C₂-C₃ алкиленом гидроксиалкиленом или алкениленом и по крайней мере равно 3, когда R₁ отлично от C₂-C₃ алкилена, гидроксиалкилена или алкенилена; для названных полиаминов и полиаминов m принимает значения от 0 до 10, а n как минимум равно 3; R принимает значения от 3 до 8; q 1 или 0; t 1 или 0 при условии, что t равно 1, когда q равно 1; w равно 1 или 0; X + Y + Z равно как минимум 2; а Y + Z равно как минимум 2. Самым предпочтительным удаляющим грязь агентом, препятствующим переосаждению, является этоксилированный тетраэтиленпентамин. Примеры этоксилированных аминов далее описаны в патенте США N 4 597 898, Vander Weer, выданном 1 июля 1986 года. Другой группой предпочтительных агентов, удаляющих грязь и препятствующих переосаждению, являются катионные соединения, раскрытые в Европейской патентной заявке N 111965 Oh и Gosselink, опубликованной 27 июня 1984 года.The compositions of the invention may also contain water-soluble ethoxylated amines having the properties of removing earth dirt and preventing its re-deposition. Granular detergent compositions that contain these substances typically include from about 0.01 to about 10 wt. water-soluble ethoxylated amines, liquid detergent compositions usually contain from about 0.01 to about 5%. These substances are preferably selected from the group consisting of:
(1) ethoxylated monoamines having the formula
(XL -) - N- (R ₂ ) ₂ ;
(2) ethoxylated diamines having the formula

or
(XL-) ₂ -NR ₁ -N- (R ₂ ) ₂ ;
(3) ethoxylated polyamines having the formula

(4) ethoxylated polyamines having the basic formula

and (5) mixtures thereof, where A ₁ are

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 alkylarylene, or a C ₂ -C ₃ oxyalkylene moiety containing from 2 to about 20 oxyalkylene units, provided that ON bonds are not formed; each R ₂ is C ₁ -C ₄ or hydroxyalkyl, a —LX fragment, or two R ₂ together form a - (CH ₂ ) _r , -A ₂ - (CH ₂ ) _s - fragment, where A ₂ is —O— or - CH ₂ ; r is 1 or 2; s is 1 or 2, and r + s is 3 or 4; X is a nonionic group, an anionic group, or a mixture thereof; R ₃ is substituted C ₃ -C ₁₂ alkyl, hydroxyalkyl, alkenyl, aryl, or an alkylaryl group containing substituents; R ₄ is a C ₁ -C ₁₂ alkylene, hydroxyalkylene, alkenylene, arylene or alkarylene, or a C ₂ -C ₃ oxyalkylene moiety containing from 2 to about 20 oxyalkylene units, provided that no OO or ON bonds are formed; Z is a hydrophilic chain that contains a polyoxyalkylene fragment - [(R ₅ O) _m (CH ₂ CH ₂ O) _n ] -, where R ₅ is C ₃ -C ₄ alkylene or hydroxyalkylene, and m and n take such values that the fragment - (CH ₂ CH ₂ O) _n - contains at least 50 wt. said polyoxyalkylene moiety; for the named monoamines m takes the values 0 4, and n is at least 12; for these diamines, m takes the values 0 3, n is at least 6 when R ₁ is C ₂ -C ₃ alkylene hydroxyalkylene or alkenylene and at least 3 when R _{1 is} different from C ₂ -C ₃ alkylene, hydroxyalkylene or alkenylene ; for the named polyamines and polyamines m takes values from 0 to 10, and n is at least 3; R takes values from 3 to 8; q 1 or 0; t 1 or 0, provided that 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. Ethoxylated tetraethylene pentamine is the most preferred anti-reprecipitation agent. Examples of ethoxylated amines are further described in US Pat. No. 4,597,898 to Vander Weer, issued July 1, 1986. Another group of preferred dirt removing and reprecipitation agents are cationic compounds disclosed in European Patent Application No. 111965 Oh and Gosselink, published June 27, 1984.

 Other dirt removing and reprecipitation inhibitors that may be used include the ethoxylated polyamines described in Gosselink European Patent No. 111,984, published June 27, 1984; Zwitterionic polymers are disclosed in US Pat. No. 4,548,744 to Connor, issued October 22, 1985.

 Other dirt removing and / or anti-reprecipitation agents known in the art can also be used in the compositions of this invention. Another type of preferred anti-reprecipitation agents includes carboxymethyl cellulose materials (SMS). These materials are well known in science.

 Polymeric dispersing agents.

 Polymeric dispersing agents can be advantageously used in the compositions of this invention. These materials can help control water hardness through calcium and manganese. Suitable polymeric dispersing agents include polymeric polycarboxylates and polyethylene glycols, although other agents known in the art may also be used. It is suggested, although this does not imply a theory limitation, that polymer dispersants enhance the overall effect of the detergent structure-forming component when used in combination with other structure-forming components (including low molecular weight polycarboxylates) by inhibiting crystal growth, peptization of released dirt particles and preventing reprecipitation.

где
X, Y и Z каждый выбран из группы, содержащей водород, метил, карбоксил, карбоксиметил, гидрокси и гидроксиметил; солеобразующий катион и n принимают значения от около 30 до около 400. Предпочтительно, чтобы X был водородом или гидроксилом, Y является водородом пли карбоксилом, X представляет водород, а M представляет водород, щелочной металл, аммоний или замещенный аммоний.Polycarboxylate materials that can be used here as polymeric dispersing agents are polymers or copolymers that contain at least about 60 wt. segments of the general formula

Where
X, Y and Z are each selected from the group consisting of hydrogen, methyl, carboxyl, carboxymethyl, hydroxy and hydroxymethyl; the salt forming cation and n are from about 30 to about 400. Preferably, X is hydrogen or hydroxyl, Y is hydrogen or carboxyl, X is hydrogen, and M is hydrogen, alkali metal, ammonium or substituted ammonium.

 Polymeric polycarboxylate materials of this type can be obtained by polymerization or copolymerization of the corresponding unsaturated monomers, preferably in the form of acids. Unsaturated monomeric acids that can be polymerized to form the desired polymer polycarboxylate include acrylic, maleic (or maleic anhydride), fumaric, itaconic, aconitic, mesaconic, citraconic and methylene malonic acids. The presence in the polymeric polycarboxylates of monomer segments not containing carboxylate radicals, such as vinyl methyl ether, styrene, ethylene, etc. suitable provided that such segments do not constitute more than 4 wt.

 Particularly suitable polymeric polycarboxylates can be obtained from acrylic acid. Such acrylic acid-based polymers that can be used here are water-soluble salts of polymerized acrylic acid. The average molecular weight of such polymers in the form of acids is preferably from about 2,000 to about 10,000, more preferably from 4,000 to about 7,000, and most preferably from about 4,000 to about 5,000. Water-soluble salts of such acrylic acid polymers may include, for example , alkali metal salts of ammonium and substituted ammonium. Soluble polymers of this type are known. The use of such polyacrylates in detergent compositions has been described, for example, by Diehl in US Pat. No. 3,308,067, issued March 7, 1967.

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

 Another polymeric material that may be included is polyethylene glycol (PEG). PEG can act as a dispersing agent, as well as an agent that removes earth dirt and prevents reprecipitation. A typical molecular weight is in the range of from 500 to about 100,000, preferably from about 1,000 to about 50,000, more preferably from 1,500 to about 10,000.

 Optical brightener.

 Any optical brighteners or other brightening or whitening agents known in the art can be incorporated into the detergent compositions of the invention.

 The choice of optical brightener for use in detergent compositions will depend on a number of factors, such as the type of detergent, the nature of the other components present in the detergent composition, the temperature of the washing water, the degree of mixing, and the ratio of material that is washed to the size of the chamber.

 The choice of optical brightener also depends on the type of material being cleaned, such as cotton, synthetics, etc. Since most detergent washing products are used to clean various fabrics, detergent compositions should contain a mixture of brighteners that will be effective for various fabrics. The individual components of such a clarifier mixture must be compatible.

 From a commercial point of view, the brighteners that can be used in the invention can be classified into subgroups that include (but are not necessarily limited to) derivatives of stilbene, pyrazoline, coumarin, carboxylic acid, methincyanines, dibenzothiophene-5,5-dioxide, azoles, 5 -, and 6-membered heterocycles and other mixed agents. Examples of such brighteners are disclosed in the monograph "Preparation and Use of Fluorescent Brightening Agents", M.ahradnic, published by John Wiley Sons, New York (1982), which is incorporated herein by reference.

 Stilbene derivatives that may be used in the invention include (but are not necessarily limited to) bis (triazinyl) amino-stilbene derivatives; bisacylamino derivatives of stilbene; triazole, oxadiazole, oxazole and styryl derivatives of stilbene.

 Some derivatives of bis (triazinyl) aminostilbene that can be used in the invention can be obtained from 4,4'-diamine-stilbene-2,2'-disulfonic acid.

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

 Derivatives of carboxylic acids that can be used in the invention include (but are not necessarily limited to) derivatives of fumaric acid; benzoic acid; para-phenylene-bis-acrylic acid; naphthalenedicarboxylic acid; heterocyclic acid derivatives; cinnamic acid.

 The cinnamic acid derivatives that can be used in the invention can further be classified into groups that include (but are not necessarily limited to) cinnamic acid derivatives, sterilazole derivatives, styrylbenzofurans, styryloxydiazoles, styryl triazoles, and styrylpolyphenyls, as described on page 77 of the Zahradnic monograph .

 Styralazoles can be further classified into sterilbenzoxazoles, styrylimidazoles and styrylthiazoles, as described on page 78 of the Zahradnic monograph. It should be noted that these three indicated subclasses cannot fully reflect the exhaustive list of subgroups into which styrylazoles can be divided.

 Another class of optical brighteners that can be used in the invention are dibenzothiophene-5,5-dioxide derivatives (see Kirk-Othmer. Encyclopedia of Chemical Technology, vol. 3, pp. 737-750, John Wiley Sons, Inc. 1962), which include 5,5-dioxide 3,7-diaminodibenzothiophen-2,8-disulfonic acid.

 The next class of optical brighteners that can be used in the invention includes azoles, which are derivatives of 5-membered heterocycles. Further, they can be divided into monoazoles and bisazoles. Examples of monoazoles and bisazoles are disclosed in the Kirk Othmes Encyclopedia.

 The next class of clarifiers that can be used in the invention are derivatives of 6-membered heterocycles described in the Kirk Othmer encyclopedia. Examples of such compounds include clarifiers derived from pyrazine and from 4-aminonaphthalamide.

 Mixed agents may also be used in addition to the clarifiers already described. Examples of such mixed agents are described on p. 93-95 Zahradnic monographs and include 1-hydroxy-3,6,8-pirentrisulfonic acid, 2,4-dimethoxy-1,3,5-tyrazin-6-yl-pyrene, 4,5-diphenylmidazoldisulfonic acid and pyrazoline-quinoline derivatives.

 Other specific examples of optical brighteners useful for the invention are indicated in US Pat. No. 4,790 856, issued to Wixon on December 13, 1988. These bleaches include the PHORWHITE series of clarifiers from Verona. Other brighteners described in this work include Tinopal, UNPA, Tinopal and Tinopal 5 BM, available from Ciba-Geigy; Arctic White CC and Artic White CWD, available from Aklton-Davis, Italy; 2- (4-styryl-phenyl) -2H-naphthol [1,2-d] triazoles; 4,4 '- (1,2,3-triazol-2-yl) -stilbenes; 4,4'-bis (styryl) bis-phenyls; and Y-aminocoumarins. Representative examples of these brighteners include 4-methyl-7-diethylaminocoumarin; 1,2-bis- (benzimidazol-2-yl) ethylene; 1,3-diphenylprazolines; 2,5-bis (benzoxazol-2-yl) thiophene; 2-styryl-naphtha [1,2-d] -d] oxazole; and 2- / stilben-4-yl / -2H-naphtho- [1,2-d] triazole.

 Other optical brighteners that can be used in the invention include those described in US Pat. No. 3,646,015, issued February 29, 1972, to Hamilton.

 Foam suppressants.

 Compounds known or known to reduce and inhibit foaming can be incorporated into the compositions of the invention. The introduction of such materials, or otherwise “suppressors” of foaming, may be useful, since polyhydroxyamide fatty acids are surfactants that can enhance the stability of foaming of detergent compositions. Foam suppression can be very important when detergent compositions include a sufficiently strong foaming surfactant in combination with polyhydroxyamide fatty acids surfactants. Foam suppression is highly desirable for compositions intended for use in front-loading automatic washing machines. Such machines are usually characterized by the presence of drums in which laundry and washing solution are placed and which have a horizontal axis and rotate around this axis.

 This type of mixing leads to strong foaming and, accordingly, to a decrease in the cleansing effect. Also, the use of foaming suppressors can be very important when washing in hot water and in conditions of a high concentration of surfactant.

 A wide variety of materials can be used as foam suppressors in the compositions of the invention. Foam suppressors are well known in the art. They are widely described, for example, in the encyclopedia of chemical technology Kirk-Othmes, third edition, v. 7, pp. 230-447 (John Wiley Sons, Inc. 1979). One category of particularly interesting foam suppressors contains monocarboxylic fatty acids and their soluble salts (see US Pat. No. 2,954,347, September 27, 1960, Waynl, St John).

 Monocarboxylic fatty acids and their salts, used as foam suppressors, mainly have hydrocarbon chains with 10-24 carbon atoms, preferably from 12 to about 18 carbon atoms. Suitable salts include alkali metal salts such as sodium, potassium and lithium, and ammonium and alkenolammonium salts. These materials are in the preferred category of foam suppressors for detergent compositions.

Detergent compositions may also contain foaming suppressors other than surfactants. These include, for example, the following: high molecular weight hydrocarbons paraffins, fatty acid esters (e.g. fatty acid triglycerides), monovalent alcohol fatty acid esters, aliphatic C ₁₈ -C ₄₀ ketones (e.g. stearones), etc. Other foaming inhibitors include N-alkylated aminotriazines such as tri- to hexa-alkyl-melamines or di- to tetra-alkyl-diamine-chlorotriazines, formed as cyanurin chloride products with 2 or 3 mol of a primary or secondary amine containing from 1 to 24 carbon atoms, propylene oxide and monostearyl phosphates, such as monostearyl alcohol phosphate ester and alkali metal monostearyl diphosphates (potassium, sodium, lithium) and phosphate esters.

Paraffin hydrocarbons and halide paraffins can be used in liquid form. Liquid hydrocarbons must be liquid at room temperature and atmospheric pressure and must have a pour point in the range of about -40 ^° C to about 5 ^° C and a minimum boiling point of at least 110 ^° C (atmospheric pressure). Paraffin hydrocarbons are also known, preferably having a melting point lower than about 100 ^° C. Hydrocarbons are the preferred category of foam suppressors for detergent compositions. Hydrocarbon foaming suppressors are described, for example, in US Pat. No. 4,265,779, issued May 5, 1981, to Gandolfo et al.

 Thus, hydrocarbons include aliphatic, aliacyclic, aromatic and heterocyclic saturated or unsaturated hydrocarbons having from about 12 to about 70 carbon atoms. The term “paraffin,” as used in this discussion of foam suppressors, is intended to include mixtures of true paraffins and cyclic hydrocarbons.

 Another preferred category of non-surface active foam suppressors includes silicone foam suppressors. This category includes the use of polyorganosiloxane oils, such as polydimethylsiloxane, dispersions or emulsions of polyorganosiloxane oils or resins, and combinations of polyorganosiloxane with silica particles, where the polyorganosiloxane is chemisorbed or fused to silica.

 Silicone foam suppressors are well known and used in the art, for example, they are described in US Pat. No. 4,265,779, issued May 5, 1981, to Gandolfo, and in European Patent Application No. 89307851. 9, published February 7, 1990, Starch, M.S.

 Other silicone foam suppressors are disclosed in US Pat. No. 3,455,839, which relates to compositions and methods for stopping foaming in aqueous solutions by incorporating small amounts of polydimethylsiloxane liquids therein.

 Mixtures of silicone and silanized silica are described, for example, in German patent application DOSN 2 124 526. Silicone antifoam agents and foaming control agents in granular detergent compositions are described in US Pat. No. 3,933,672, Bartolotta et.al. and U.S. Patent No. 4,652,392, Baginski et al. issued March 24, 1987.

An exemplary silicone-based foam suppressor for use herein is an inhibitory foaming amount of a foaming control agent, consisting essentially of
(i) a polydimethylsiloxane fluid with a viscosity of from 20 to about 1500 cSt at 25 ^° C;
(ii) from about 5 to about 50 parts per 100 parts by weight of (i) a siloxane resin consisting of (CH ₃ ) ₃ SiO _1/2 fragments of SiO ₂ fragments in relation to (CH ₃ ) ₃ SiO _1/2 fragments to SiO ₂ fragments from 0.6: 1 to about 1.2: 1, and
(iii) from about 1 to about 20 parts by weight per 100 parts by weight (i) to solid silica gel.

 For any detergent compositions that are intended to be used in automatic machines for washing clothes, foam should not form to the degree of overfilling of the washing machine. When using foam suppressors, they are preferably present in amounts that inhibit pricing. By “foam inhibitory” amounts, it is meant that the formulator can select such an amount of a foam control agent that it successfully controls foam formation, and as a result, a low foam washing detergent used in automatic washing machines is obtained. The amount of foam control agent will vary depending on the detergent surfactant selected. For example, with a highly foaming surfactant, more foam control agent is used to achieve the necessary foam control than with a less foaming surfactant. In general, a sufficient amount of a foaming suppressor should be incorporated into detergent compositions with low pricing so that the foam that forms during the cycle of the automatic washing machine (i.e., when the detergent is mixed in an aqueous solution under the conditions of the temperature and concentration assumed for washing) does not exceed % of the free volume of the drum of the washing machine, it is preferable that the foam does not exceed about 50% of the specified volume, and the free volume is defined as the difference between the total volume m tub with a drum and the volume of the water plus the volume of the laundry.

 The compositions herein typically contain from 0 to about 5% foam suppressor. When monocarboxylic fatty acids and their salts are used as suppressors, amounts up to 5 wt. detergent composition. It is preferable to use from 0.5 to about 3% fatty monocarboxylate foam suppressors. Silicone foam suppressors are typically used in amounts up to about 2.0 wt. from a detergent composition, although large amounts can be used. This upper limit is of practical importance, which is mainly associated with maintaining a minimum cost and the problem of the effectiveness of small quantities that provide effective control of foaming. It is preferable to use 0.01 to 1% silicone foaming suppressor, more preferably 0.25 to 0.5%. As used herein, these percentages by weight include some silica gel, which can be used in combination with polyorganosiloxanes, as well as some additional materials which can also be used. Monostearyl phosphates are usually used in amounts of from 0.1 to about 2 wt. composition.

 Hydrocarbon foaming suppressors are typically used in amounts of from about 0.01 to about 5.0%, although large amounts can be used.

 Other ingredients

 A wide range of other constituents useful in detergent compositions may be included in the compositions of the invention, including other active ingredients, for example, carriers, hydrotrons, auxiliary agents, dyes or pigments, solvents for liquid compositions, etc.

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

 Detergent compositions should preferably be formulated so that during use in water washing operations, the wash water has a pH between 6.5 and about 11, preferably between 7.5 and about 10.5. Liquid formulations should preferably have a pH between 7.5 and about 9.5, more preferably between 7.5 and about 9. Methods for controlling pH at recommended levels of use include the use of buffers, alkalis, acids, etc. they are well known to specialists.

 The invention provides a method for improving the action of detergents containing anionic, nonionic, and / or cationic surfactants, as well as a washing enzyme, by using enzyme-enhancing amounts of the surfactant of a polyhydroxylamide fatty acid described above, usually it is at least about 1% of such a surfactant.

 The invention further provides a method for cleaning substrates such as fibers, fabrics, hard surfaces, leather, etc. upon contacting said substrate with a detergent composition containing a washing enzyme and one or more of anionic, nonionic or cationic surfactants, said detergent composition containing an enhancing effect of the enzyme amount of polyhydroxyamide fatty acid, which usually is at least about 1 wt. compositions in the presence of a solvent such as water or a water miscible solvent (e.g., primary or secondary alcohols). To enhance the cleansing effect, it is preferable to carry out mixing. By mixing is meant a hand wash, or preferably with a brush, sponge, mop or other washing device, automatic washing machine, dishwasher, etc.

 Experimental part.

 Here are examples of the preparation of the N-methyl, 1-deoxyglucityllauramide surfactant used here. Although an experienced chemist can vary the configuration of the apparatus, a suitable apparatus for use is a three-liter four-necked flask equipped with a paddle stirrer connected to a controlled motor and a thermometer of such a length that is sufficient to contact the reaction medium. The other two necks are equipped with a nitrogen inlet and a wide diameter side outlet that connects the efficient condensate collector and the vacuum outlet. The latter is connected with the descent of nitrogen and a vacuum gauge, then with an aspirator and a trap. The 500 watt heater ("Variac") used to heat the reaction is so located on a laboratory rack that it can be easily raised or lowered, which gives additional control of the reaction temperature.

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 liquid / solid mixture is heated with stirring in a stream of nitrogen until a melt is formed (about 25 minutes). When the melt temperature reaches 145 ^° C., a catalyst is added (anhydrous sodium carbonate powder, 10.5 g, 0.1 mol, JT Baker). The nitrogen supply is stopped and the aspirator and nitrogen supply are adjusted until a pressure of 5 inches (5/31 atm) of the mercury column is established. From this point on, the reaction temperature is maintained at 150 ^° C. by adjusting Variac and / or raising or lowering the shirt.

 After 7 minutes, the first methanol bubbles will appear on the surface of the reaction mixture. Then a violent reaction follows. Methanol is distilled off until its speed drops. Vacuum is set to 10 inches of mercury (10/31 atm). The vacuum increases approximately as follows, (inch Hg per minute): 10 to 3; 20 in 7; 25 at 10 (25 cm at 3; 50 at 7 and 62.5 at 10 minutes). At the 11th minute from the start of methanol evolution, heating and stirring were stopped, which coincides with some foaming. The product is cooled and it hardens.

 The following examples are examples of compositions of the invention, but they do not necessarily limit or otherwise define the scope of the invention.

 Examples I-III. (These examples show highly effective granular detergent compositions containing polyhydroxyamide fatty acids and protease enzymes, and are shown in table 1.

Samples I-III are compositions for preferred use at 1,400 ppm. based on the weight of the washing solution for temperatures below 50 ^o C. The above examples were carried out by combining the main granular ingredients in suspensions, which are dried by spraying to a residual moisture content of 4-8% The remaining dry ingredients are mixed in granular or powder form with granules dried in a drum rotary mixer, and inject liquid ingredients (non-ionic surfactants and perfume).

 Examples IV-IX. The following examples demonstrate highly effective liquid compositions containing polyhydroxyamide fatty acids and protease and amylase enzymes, and are shown in tables 2 and 3.

Examples IV-IX preferably use about 2000 ppm. based on the weight of the washing solution for a washing temperature below 50 ^o C.

 Samples IV-IX were prepared by combining non-aqueous solvents, aqueous pastes or surfactant solutions, molten fatty acids, aqueous solutions of polycarboxylate builders and other salts, aqueous ethoxylated tetraethylene ethylene, buffering agents, caustic soda (the rest is water). The pH is adjusted using both an aqueous solution of citric acid and a solution of sodium hydroxide to a pH of 8.5. After reaching pH, final ingredients, such as dirt-removing agents, enzymes, dyes, and perfumes, are added and the mixture is stirred until a uniform phase is obtained.

 Example X. An alternative and highly preferred method for producing the polyhydroxyamide fatty acids used herein is as follows. Use a reaction mixture containing 84.87 g of a fatty acid methyl ester (source: CE1270 methyl ester, Proct. Gamble), 75 g of N-methyl-D-glucamine (source: Aldrich Chem. Comp. M4700-0), 1.04 g of sodium methoxide (source: 16, 49942, Aldrich Chem. Comp.) and 68.51 g of methyl alcohol.

 The reaction vessel is equipped with a standard vertical refrigerator with a drying tube, condenser and stirrer. In this procedure, N-methylglucamine is combined with methanol under stirring in an argon atmosphere, and heating is started with good stirring, after 15-20 minutes, when the solution has reached the required temperature, ether and sodium methoxide catalyst are added. Samples were taken periodically to track the progress of the reaction, but it was noted that the solution became completely transparent after 63.5 minutes. It is believed that the reaction is almost complete at this point. The reaction mixture is kept at reflux for 4 hours. After removal of methanol, the isolated crude product weighs 156.16 g. After vacuum drying and purification, the total yield of the purified product is 106.92 g. However, the percentage yield is not calculated on this basis because that regular sampling during the course of the reaction makes the value of the overall percentage yield inadequate. The reaction can be carried out at 80 and 90% concentrations of the reagents for a period of up to 6 hours before the formation of products with extremely low formation of by-products.

 Modern condensed detergent granules for washing clothes are discussed below.

 Example XI The composition is presented in table.4.

 The most preferred granules of the aforementioned type are those that comprise from 0.0001 to 2 wt. active enzyme, at least about 1 wt. polyhydroxyamide fatty acid and more preferably, if the anionic surfactant is not an alkylbenzenesulfonate surfactant.

 The following relates to the preparation of a preferred liquid high-performance detergent for the invention. It should be recognized that the stability of enzymes in such compositions is significantly lower than in granular detergents.

 However, through the use of conventional enzyme stabilizers, such as formate and boric acid, lipase and cellulase enzymes can be protected from degradation by protease enzymes. However, lipase stability is still relatively low in the presence of alkylbenzenesulfonate surfactants (LAS). LAS seems to partially denature the lipase and further it appears that the denatured lipase is more vulnerable to protease attack.

 Considering the considerations discussed above, which can be significant obstacles in liquid compositions, it becomes necessary to create liquid detergent compositions containing together lipase, protease and cellulase enzymes. In particular, the creation of such triple enzyme systems in stable liquid detergents together with an effective mixture of detergent surfactants is particularly desirable.

 In addition, it is quite difficult to incorporate peroxidase and / or amylase enzymes stably into such compositions.

 It has been determined that various mixtures of lipases, proteases, cellulases, amylases and peroxidases are sufficiently stable in the presence of certain non-alkylbenzyl sulfonate surfactant systems, so that effective, highly effective solid and even liquid detergents can be formulated. Indeed, the creation of stable, liquid enzyme-containing detergent compositions is a very advantageous preferred option, possible by the method of the invention.

In particular, the prior art liquid detergent compositions typically included LAS or a mixture of LAS with a surfactant of the RO (A) _m SO ₃ M type ("AES") noted above, i.e. LAS / AES mixes. In contrast, the liquid detergents of the invention preferably constitute a binary mixture of AES and polyhydroxyamide fatty acids of the type described herein. Although a minimal amount of LAS may be present, it should be recognized that enzyme stability will decrease because of this. Accordingly, it is preferred that the liquid compositions are substantially free of LAS (i.e., contain less than 10%, preferably less than 5%, even better less than 1%).

где
R₁ является водородом, C₁-C₄ углеводородом, 2-гидроксиэтилом, 2-гидроксипропилом или их смесью; R₂ является C₅-C₃₁ углеводородом; Z полигидроксиуглеводород с линейной углеводородной цепью, содержащей как минимум 3 гидроксила, напрямую связанных с ней, или его алкоксилированное производное.The invention provides liquid detergent compositions composed of
a) from about 1 to about 50%, preferably from about 4 to about 40%, of an anionic surfactant;
b) from about 0.0001 to about 2% of the active washing enzyme;
c) an enzyme-enhancing amount (preferably from about 0.5 to about 12%) of a polyhydroxyamide fatty acid material of the formula

Where
R ₁ is hydrogen, C ₁ -C ₄ hydrocarbon, 2-hydroxyethyl, 2-hydroxypropyl or a mixture thereof; R ₂ is a C ₅ -C ₃₁ hydrocarbon; Z a polyhydroxyhydrocarbon with a linear hydrocarbon chain containing at least 3 hydroxyls directly bonded to it, or an alkoxylated derivative thereof.

 And where the composition is virtually free of alkylbenzenesulfonate.

The water soluble anionic surfactant preferably contains ("AES")
RO (A) _m SO ₃ M
Where
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 an integer greater than zero; M is hydrogen or a cation. Preferably, R is an unsubstituted C ₁₂ -C ₁₈ alkyl group, A is an ethoxy fragment, m is 0.5 to 6; M is a cation. As the cation, metal cations (sodium preferred, potassium, lithium, calcium, magnesium, etc.) or ammonium or a substituted ammonium cation are preferred.

 Preferably, the ratio between the above surfactant ("AES") and polyhydroxyamide fatty acid is from about 1: 2 to about 5: 1, most preferably from about 1: 1 to about 4: 1.

Alternative liquid compositions may contain polyhydroxyamide fatty acid, AES and from about 0.5 to about 5% of a condensation product of C ₈ -C ₂₂ (preferably C ₁₀ -C ₂₀ ) linear 1 25, preferably 2 18 mol ethylene oxide per mole of alcohol.

As described above, the liquid compositions of the invention preferably have a pH in a 10% aqueous solution at 20 ^° C. of from about 6.5 to about 11.0, preferably from 7.0 to about 8.5.

 The instant compositions preferably contain from 0.1 to 50% detergent builders. These compositions preferably contain from about 0.1 to about 20% citric acid or a water-soluble salt thereof and from about 0.1 to about 20% water-soluble succinate tartrate, especially its sodium salt, and mixtures thereof, or from about 0.1 to about 20 wt. . oxydisuccinate or its mixtures with the above structure-forming agent. 0.1 5% alkenyl succinate can also be used.

 Preferred liquid compositions of the invention contain from 0.0001 to about 2%, preferably from about 0.0001% to about 1%, more preferably from 0.0001 to about 0.5%, based on the active ingredient of the washing enzymes. These enzymes are preferably selected from the group consisting of protease (preferred), lipase (preferred), amylase, cellulase, peroxidase, and mixtures thereof. It is preferable to use compositions with one or more classes of enzymes, preferably only with a protease.

 Although the differences are descriptions of detergent proteases, cellulases, etc. available in the literature, detergent lipases are the lesser known part. Therefore, lipases of interest to compilers include Amano ARG and Bacillis Sp. lipases, for example Solvay enzymes (also see the description of lipases in EP A N 0 399 681, published November 28, 1990, EP A N 0 218 272, published April 15, 1987 and PCT / DC 88/00177, published May 18, 1989).

 Suitable fungal lipases include lipases produced by Humicola lanuginosa and Thermomyces lanuginosus, preferably lipases obtained by cloning the Aspergillus oryzae gene as described in European Patent Application No. 0,258,068, commercially available under the ZIPOZASE trademark.

From about 2 to about 20,000, preferably from about 10 to about 6,000 lipase lipase units per gram of product (Lu / g) can be used in these compositions. A lipase unit is such a quantity of lipase that produces 1 μmol of titrated butyric acid per minute, where the pH is 7.0, a temperature of 30 ^° C., and the substrate is an emulsion of tributyrin and gum arabic in the presence of Ca ⁺⁺ and NaCl in phosphate buffer.

The following examples illustrate preferred highly effective liquid detergent compositions containing
a) an enzyme selected from proteases, cellulases and lipases, or preferably mixtures thereof, usually comprising from about 0.01 to about 2 wt. from the entire composition, although the amounts used can be set in accordance with the necessary compiler to achieve an “effective” amount (ie, a dirt-removing amount) of the named enzyme or mixture of enzymes;
b) a polyhydroxylamide fatty acid surfactant of the type described herein, typically comprising at least 2% by weight of the composition, more typically 3 to 15%, preferably from about 7 to about 14%
c) a surfactant of the type RO (A) _m SO ₃ M described herein, preferably RO (CH ₂ CH ₂ O) _m SO ₃ M, where R is C ₁₄ -C ₁₅ (average); m 2-3 (average); M is H or a water-soluble salt-forming cation, for example Na ⁺ , and said surfactant usually comprises from about 5% to about 20% by weight of the composition;
d) optional surfactants of the type ROSO ₃ M, as described here, preferably, where R is C ₁₂ -C ₁₄ (average), said surfactant is usually 1 10% by weight of the composition;
e) a liquid carrier, especially water or water-alcohol mixtures;
f) optionally, but more preferably, effective amounts of enzyme stabilizers, typically 1 10% by weight of the composition;
g) optionally, but preferably water-soluble builders, especially polycarboxylate builders, usually from about 4 to about 25% by weight of the composition;
h) optionally various washing auxiliary agents, brighteners, etc. noted above, usually (if used) comprise from about 1 to about 10% by weight of the composition;
i) the composition is substantially free of LAS.

Example XII. Composition Composition:
Ingredients
C ₁₄ -C ₁₅ alkyl polyethoxylate (2.25) sulfonic acid 21
N-methylglucamide C ₁₂ -C ₁₄ fatty acid 7.0
Sodium tartrate mono- and di-succinate (80:20 mixture) 4.00
Citric acid 3.80
C ₁₂ -C ₁₄ fatty acid 3.00
Tetraethylene pentaamine ethoxylate (15-18) 1.50
Ethoxylated copolymer of polyethylene polypropylene terephthalate polysulfonic acid 0.20
Protease P (34 g / L) 0.68
Lipase (100 KLU / g) 0.47
Cellulase (500 CE (g) 0.14
Lighter 36 0.15
Ethanol 5.20
Monoethanolamine 2.0
Sodium Formate 0.32
1,2 propanediol 8.0
Sodium hydroxide 3.10
Silicone Foam Suppressor 0.0375
Boric acid 2.00
Water / impurities 100
Protease P is a modified bacterial serine protease described in European Patent Application No. 87 E03761, filed April 28, 1987, pp. 17, 24, 98.

 The lipase used here is a lipase obtained by cloning a Humicola lanuginosa gene and expressing a gene in Aspergillus oryzae as described in European Patent Application No. 0 258 068, commercially available under the trademark ZIPOZASE (ex Novo Nordisk A / S, Copenhagen Denmark).

 Cellulase used here is sold under the trademark CAREZYME (Novo Nordisk, A / S, Copenhagen Denmark).

 A clarifier 36 is commercially available as TINOPAZTAS 36. A clarifier is added to the composition as a separately prepared preliminary mixture of a brightening agent (4.5%), monoethanolamine (60%) and water (35, 5%).

 The following is not intended to limit the invention, but merely points to additional aspects of the technology that may be considered by the compiler in the manufacture of a wide range of detergent compositions using polyhydroxy amides of fatty acids.

 It is easy to see that polyhydroxyamides of fatty acids, due to their amide bond, are subject to some instability under very alkaline or strongly acidic conditions. Although some decomposition can be allowed, it is preferable that these substances are not exposed to pH values above 11, better than 10 and lower than 3, for unreasonably long periods. The pH of the final product (liquid) is usually 7.0-9.0.

 In the preparation of fatty acid polyhydroxyamides, it is usually necessary to at least partially neutralize the alkaline catalyst used to form the amide bond. Although any acid can be used for this purpose, it will be clear to the detergent compiler that this is a simple and convenient way to use an acid that will produce an anion that is useful and desirable in the final detergent composition. For example, citric acid can be used for neutralization purposes, and the resulting ion citrate (about 1%) will remain in a suspension of 40% polyhydroxyamide fatty acid and will be pumped to subsequent production steps of the general detergent production process. Similarly, acidic forms of substances such as oxidisuccinate, nitrilotriacetate, ethylenediaminetetraacetate, tartrate / succinate, etc. can be used.

Fatty acid polyhydroxyamides derived from coconut alkyl fatty acids (preferably C ₁₂ -C ₁₄ ) are more soluble than their tall alkyl (preferably C ₁₆ -C ₁₈ ) counterparts. Accordingly, C ₁₂ -C ₁₄ substances are somewhat easier to formulate in liquid compositions and they are more soluble in cold water bathtubs. However, C ₁₆ -C ₁₈ substances are also quite suitable, especially in cases where water from warm to hot is used for washing. C ₁₆ -C ₁₈ substances may be better detergent surfactants than their C ₁₂ -C ₁₄ counterparts. Accordingly, the compiler may wish to balance ease of production with efficiency by selecting a particular fatty acid polyhydroxyamide for use in a given composition.

 It should also be recognized that the solubility of polyhydroxyamide fatty acids can be increased by the presence of unsaturation points and / or chain branches in fatty acid fragments. Therefore, materials such as polyhydroxy fatty acid amides derived from oleic acid and isostearic acid are more soluble than their N-alkyl counterparts.

 Similarly, the solubility of polyhydroxyamide fatty acids derived from disaccharides, trisaccharides, etc. usually there will be more than the solubility of their analogues derived from monosaccharides. Such higher solubility may, in particular, help in the preparation of liquid compositions. Moreover, it turns out that fatty acid polyhydroxyamides in which the polyhydroxy group is derived from maltose serve particularly well as detergents when used in combination with conventional alkylbenzene sulfonate “ZAS” surfactants. Without intending to limit ourselves to theory, it turns out that the combination of ZAS with polyhydroxyamide fatty acids derived from higher saccharides, such as maltose, leads to a significant and unexpected decrease in interfacial surface tension in an aqueous medium, thereby increasing the actual detergency characteristic (production of polyhydroxyamide fatty acids derived from maltose is described below).

 Fatty acid polyhydroxyamides can be obtained not only from refined sugars, but also from hydrolyzed starches, for example corn starch, potato starch, or any other suitable starch obtained from plants that contains mono-, di-, etc. saccharide desired by the originator. This is extremely important from an economic point of view. Thus, high glucose corn syrup, high maltose corn syrup, etc. can be conveniently and economically used. Delignified, hydrolyzed cellulosic pulp can also serve as a raw material source for polyhydroxy fatty acid amides.

 As noted above, fatty acid polyhydroxyamides derived from higher saccharides such as maltose, lactose, etc. are more soluble than their glucose counterparts. Moreover, it turns out that more soluble polyhydroxyamide fatty acids can contribute to the dissolution of their less soluble analogues to varying degrees. Accordingly, the compiler may choose to use a raw material comprising high glucose corn syrup, for example, choose a syrup that contains a very small fraction of maltose (for example 1% or more). The resulting mixture of fatty acid polyhydroxyamides will generally exhibit more preferred solubility characteristics over a wider range of temperatures and concentrations than the fatty acid polyhydroxyamide obtained from "pure" glucose would exhibit. Thus, in addition to any economic benefits of using sugar mixtures rather than pure sugar reagents, fatty acid polyhydroxyamides derived from mixed sugars can offer very significant advantages in terms of performance and / or ease of formulation. In some cases, however, there may be some loss in the characteristic of removing fat (washing dishes) at concentrations of maltamide fatty acid above 25% and some loss in foaming above 33% (the indicated percentages are the percentage of polyhydroxyamide fatty acid obtained from maltamide, from polyhydroxyamide fatty acid derived from glucose in a mixture). This may vary slightly depending on the chain length of the fatty acid fragment. Typically, then, the originator who chooses to use such mixtures may find advantages in the choice of mixtures of polyhydroxyamide fatty acids that contain ratios of monosaccharides (e.g. glucose) and di- and higher saccharides (e.g. maltose from about 4: 1 to about 99: 1.

The production of preferred, non-cyclized polyhydroxyamide fatty acids from fatty esters and N-alkyl polyols can be carried out in alcohol solvents at temperatures of 30-90 ^o C, preferably 50-80 ^o C. It has now been found that it may be convenient for the compiler, for example, liquid detergents to carry out such processes in the solvent 1,2-propylene glycol, since there is no need to completely remove the glycol solvent from the reaction product before use in the final detergent composition. Similarly, the originator of, for example, solid, typically granular, detergent compositions may find it convenient to carry out the process at 30-90 ^° C. in solvents that include ethoxylated alcohols, for example, ethoxylated (EO 3-8) C ₁₂ -C ₁₄ alcohols from known like NEODOZ 23 E06.5 (Shell). When using such ethoxylates, it is preferable that they do not contain significant amounts of unethoxylated alcohol and more preferably that they do not contain significant amounts of monoethoxylated alcohol ("T" designation).

 Although methods for producing polyhydroxyamide fatty acids are not part of this invention, the compiler may refer to other syntheses of polyhydroxyamide fatty acids, as described below.

 Typically, an industrial scale reaction sequence for preparing preferred acyclic polyhydroxyamide fatty acids involves the following steps.

 Step 1: Preparation of an N-alkyl polyhydroxyamide derivative from a desired sugar or sugar mixture by forming an adduct of N-alkylamine and sugar, followed by reaction with hydrogen in the presence of a catalyst.

 Stage 2 the interaction of the above polyhydroxyamide, preferably with a fatty ether to form an amide bond.

 Despite the fact that many N-alkyl polyhydroxyamides used in stage 2 of the reaction sequence can be obtained by various methods known in the art, the following process is convenient and uses economical sugar syrup as a raw material. It should be understood that for the best results when using such a syrup as a raw material, the manufacturer should choose syrups that are completely light in color or preferably almost colorless ("white as water").

 Obtaining N-alkylpolyhydroxy amine from sugar syrup of plant origin.

I. The formation of the adduct. The following is a standard process in which approximately 420 g of a 550% glucose solution (corn syrup 231 g glucose, about 1.28 mol), having a Gardner color of less than 1, is reacted with 119 g of a 50% methylamine solution (59, 5 g of methylamine - 1.92 mol). The methylamine solution (MMA) is purged and maintained under N ₂ and cooled to 10 ^° C. or less. Corn syrup is purged and maintained in an N ₂ atmosphere at a temperature of 10-20 ^° C. Corn syrup was slowly added to the MMA solution at the reaction temperature, as indicated. Gardner color was measured at the indicated approximate time (min).

As can be seen from the above data, the Gardner color for the adduct becomes much worse as the temperature rises above 30 ^o C and at 50 ^o C, and the time during which the adduct has a Gardner color below 7 is only 30 minutes . For longer reactions and / or retention times, the temperature should be less than 20 ^° C. The Gardner color should be less than 7 and preferably less than 4 to achieve a good glucamine color.

When lower temperatures are used to form the adduct, the time to reach the real equilibrium concentration of the adduct is shortened by using higher ratios of amine and sugar. With a molar ratio of amine and sugar of 1.5: 1, equilibrium is reached within about two hours at a reaction temperature of 30 ^° C. With a molar ratio of 1.2: 1, under the same conditions, the time is at least three hours. For a good color, a combination of the ratio of amine and sugar, reaction temperature and reaction time is chosen to achieve equilibrium conversion, for example, more than 90%, preferably more than 99%, based on sugar, and a color that is less than about 7, preferably less than about 4, more preferably less than about 1 for the adduct.

Using the above process at a reaction temperature of less than 20 ^o C and corn syrups with different colors according to Gardner, as indicated, get the color of the adduct MMA (after the actual equilibrium is reached for at least two hours), corresponding to the data in table.6.

 As can be seen from the foregoing, the starting sugar material must be very close to colorless in order to then have an acceptable adduct. If sugar has a Gardner 1 color, the adduct is sometimes acceptable, and sometimes unacceptable. When the Gardner color is above 1, the resulting adduct is unacceptable. The better the initial color of sugar, the better the color of the adduct.

 II. Hydrogenation Reaction. The above adduct having a Gardner color of 1 or less is hydrogenated in accordance with the following procedure.

539 g of the adduct in water and 23.1 g of the combined G498Ni catalyst are added to a one-liter autoclave and purged twice with hydrogen at a pressure of 200 psi (14 kg / cm ² ) and a temperature of 20 ^o C. The pressure of H _{2 was} raised to 1400psi (98 kg / cm ² ), and the temperature was raised to 50 ^o C. Then the pressure was raised to 1600psi (112 kg / cm ² ) and the temperature was maintained at 50-55 ^o C for about three hours. At this point, the product is hydrogenated at 95%. Then the temperature is raised to 85 ^o C for 30 minutes, and the reaction mixture was decanted, the catalyst was filtered off. The product after removal of water and MMA by evaporation is 95% N-methylglucamine, a white powder.

The above procedure is repeated with about 23.1 g of Raney nickel catalyst with the following changes. The catalyst was washed three times and the reactor with the catalyst was purged twice with hydrogen at 200, an increased hydrogen pressure of 1660psi (112 kg / cm ² ) was created in the reactor for two hours, the pressure was reduced by 1 h and pressure was again created 1600 (112 kg / cm ² ) Then the adduct was pumped to a reactor which was at a pressure of 200 psi (14 kg / cm ² ) at 20 ^° C, then the reactor was purged with hydrogen at 200 psi (14 kg / cm ² ), etc. as described above.

 In each case, the resulting product is more than 95% N-methyl glucamine, has less than 10 ppm. nickel per N-methyl glucamine and has a Gardner solution color of less than 2.

The crude N-methyl glucamine is color stable up to 140 ^° C. for a short exposure time.

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

In another reaction, the adduct begins to be obtained from 159 g of a 50% solution of methylamine in water, which is purged and protected with nitrogen at 10-20 ^o C. About 330 g of 70% corn syrup (almost "white as water") are degassed with nitrogen at 50 ^o C and slowly added to a solution of methylamine at a temperature below 20 ^o C. The solution is stirred for about 30 minutes to obtain a 95% adduct, which is a very light yellow solution.

190 g of adduct in water and 9 g of United Catalysy G49B Ni Ni catalyst was added to a 200 ml autoclave and purged three times with hydrogen at 20 ^o C. The hydrogen pressure raised to 200 psi lbs / ⁱⁿ² (14 kg / ^cm2) and the temperature was raised to 50 ^o C. The pressure was increased to 250 lb / ⁱⁿ² (17 kg / ^cm2) and the temperature was maintained at 50-55 ^o C for three hours. The product, which was 95% hydrogenated at this point, was then heated to 85 ^° C. for 30 minutes, and after removal of water and evaporation, the product was approximately 95% N-methylglucamine as a white powder.

It is also important to minimize contact between adduct and catalyst when the hydrogen pressure is less than about (70 kg / cm ²⁾ 1000 psi lbs / ⁱⁿ² to minimize Ni content in the glucamine. The nickel content of N-methylglucamine in this reaction is 100 ppm. compared to less than 10 ppm in the previous reaction.

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

 A 200 ml autoclave was used, performing typical procedures similar to those described above for the adduct and reaction with hydrogen at different temperatures.

 For use in the preparation of glucamine, the adduct was obtained by reacting 420 g of a 55% glucose solution (corn syrup) (231 g glucose, 1.28 mol) (the solution was prepared using 99 DE CarGill corn syrup, the solution was less than 1 Gardner) ) and about 119 g of 50% methylamine (59.5 g of MMA, 1.92 mol) (from Air Products).

 The reaction procedure is as follows.

1. Add 119 g of a 50% solution of methylamine in a nitrogen-flushed reactor (in a nitrogen atmosphere and cooled to a temperature below 10 ^o C).

2. Degassed and / or purged with a 55% solution of corn syrup at 10-20 ^o C with nitrogen to remove oxygen in the solution.

3. Slowly add a solution of corn syrup to a solution of methylamine and maintain the temperature below 20 ^o C.

 4. Once the whole corn syrup solution has been added, mix another 1-2 hours.

 The adduct is used to interact with hydrogen immediately after preparation or store it at a low temperature to prevent further decomposition.

 The reactions of glucamine adduct with hydrogen are as follows.

 1. Add about 134 g of the adduct (color below 1 according to Gardner) and 5.8 g of G49B Ni in a 200 ml autoclave.

2. Purge the reaction mixture with hydrogen at a pressure of 200 psi (14 kg / cm ² ) and a temperature of 20-30 ^o C.

3. A hydrogen pressure of 400 lb / ⁱⁿ² (28 kg / cm ²⁾ and the temperature was raised to 50 ^o C.

4. Raise pressure to about 500 lb / ⁱⁿ² (35 kg / cm ²⁾ exposed for 3 hours. The temperature was maintained at 50-55 ^o C. Take Sample 1.

5. Increase the temperature to 85 ^o C for 30 minutes

6. The Ni catalyst is decanted and filtered. Sample 2 is taken. Conditions for a constant temperature reaction:
1) introduce 134 g of the adduct and 5.8 g of G49B nickel into a 200 ml autoclave;
2) purge with hydrogen at 200 lb / in ² (14 kg / cm ² ) twice at low temperature;
3) a hydrogen pressure of 400 lb / ⁱⁿ² (28 kg / cm ²⁾ and raise the temperature to 50 ^o C;
4) increase pressure to 500 lb / ⁱⁿ² (35 kg / cm ^2), to act for 3.5 hours.

5) decant and filter the Ni catalyst. Take sample 3 at 50-55 ^o C; sample 4 at 75 ^o C; and sample 5 at 85 ^° C. (reaction time 45 minutes at a temperature of 85 ^° C.).

All cycles give the same purity N-methylglucamine (94%); Gardner colors of the samples after the reaction are exactly the same, but only two-stage heat treatment gives good color stability; and the 85 ^° C. row gives an extreme color immediately after the reaction.

 Example XIII Obtaining tall amide of fatty acid N-methylmaltamine for use in detergent compositions in accordance with this invention is as follows.

 Step 1. Reagents: Maltose monohydrate (Aldrich, lot 01318 KW methylamine (40 wt. In water) (Aldrich, lot 03325 TM); Raney Nickel, 50% suspension (VAD 52-73D, Aldrich, lot 12921 ZW).

The reagents were added to glass bottles (250 g maltose, 428 g methylamine solution, 100 g of a suspension of 50 g of Raney nickel catalyst) and placed in a 3-liter rocking autoclave which is purged with nitrogen (3 • 500 psi lbs / ⁱⁿ²⁾ to 35 kg / cm ² and hydrogen (2 • 500 lb / in ² ) 35 kg / cm ² and pumped under hydrogen at room temperature for the weekend at temperatures of 28-50 ^° C. The untreated reaction mixture was filtered under vacuum twice through a glass microfiber filter with a layer of silica gel. The filtrate is concentrated to a viscous material. The remaining traces of water are azeotropically distilled off, dissolving the substance in methanol and then removing the methanol / water mixture on a rotary evaporator. Finally, dried under high vacuum. The crude product is dissolved in methanol, refluxing, filtered, crystallized after cooling, filtered and the precipitate is dried under vacuum at 35 ^o C. This is fraction 1. The filtrate is concentrated until precipitation appears in the refrigerator overnight. The solid is filtered off and dried in vacuo. This is fraction 2. The filtrate is again concentrated to half its volume and recrystallization is carried out. Very little precipitate is formed. A small amount of ethanol is added and the solution is left in the freezer for the weekend. The solid is filtered off and dried in vacuo.

 The combined solids contain N-methyl maltamine, which is used in step 2 of the complete synthesis.

 Step 2. Reagents: N-methylmaltamine (from Step 1); cured tall oil methyl esters; sodium methoxide (25% in methanol), absolute methanol (solvent); the molar ratio of amine: ether is 1: 1; initial level of catalyst 10 mol. (w / r maltamine), increase to 20 mol. solvent level 50 wt.

20.36 g of tall methyl ether was heated to its melting point in a closed vessel (water bath) and a three-necked flask equipped with a mechanical stirrer was charged into a 250 ml. The flask was heated to 70 ^° C. to prevent the solidification of the ether. Separately, 25 g of N-methylmaltamine are combined with 45.36 g of methanol and the resulting suspension is added to the tall ether with good stirring. 1.51 g of 25% sodium methoxide in methanol are added. After four hours, the reaction mixture did not become transparent, so add another 10 mol. catalyst (up to a total of 20 mol.) and the reaction is carried out all night (68 ^o C), after which the mixture became transparent.

The reaction flask was then modified for distillation. The temperature was increased to 110 ^o C. Distilled for 60 min at atmospheric pressure. Then it was distilled in vacuo for 14 min, after which the product became very thick. The product was left in a reaction flask at 110 ^° C (external temperature) for 60 minutes. The product is scraped from the flask and thoroughly triturated in ethyl ether over the weekend. The ether is removed on a rotary evaporator and the product is left overnight, then triturated. Residues of N-methylamine are removed from the product using silica gel. A suspension of silica gel in 100% methanol is placed in a funnel and washed several times with 100% methanol. Concentrated product samples (20 g in 100 ml of 100% methanol) were placed on silica gel and eluted several times using vacuum and several methanol washes. The collected eluate is evaporated to dryness (rotary evaporator). Residues of tall ester are removed by precipitation in ethyl acetate overnight, then by filtration. The filter cake was dried in vacuo overnight. The resulting product is tall alkyl N-methylmaltamide.

 In an alternative method, step 1 of the described reaction sequence can be carried out using corn syrup containing glucose or a mixture of glucose, and usually 5% or higher of maltose. The resulting fatty acid polyhydroxyamides or mixtures can be used in some detergent compositions in the method of the invention.

 In another method, step 2 of the presented reaction sequence can be carried out in 1,2-propylene glycol or NEODOZ. If desired, propylene glycol or NEODOZ may not be removed from the reaction product until it is used in detergent compositions. Also, as desired by the compiler, the methoxide catalyst can be neutralized with citric acid to form sodium citrate, which can remain in the polyhydroxyamide fatty acid.

 Depending on the desires of the originator, the compositions may contain more or less foaming control agents. Typically, high foaming is suitable for washing dishes, and therefore foaming control agents should not be used. For washing laundry from a fabric in washing machines loaded from above, some control over foaming may be useful, and for front-loading, a greater degree of control over foam may be preferable. A wide range of foam control agents is known in the art and can be selected for use in the method of the invention. Indeed, the choice of a foaming control agent or mixture of agents for any specific detergent composition will depend not only on the presence of the polyhydroxyamide fatty acid and its amount used here, but also on other surfactants present in the composition. However, it has been observed that for use with polyhydroxyamide fatty acids, silicone-based foam control agents of various types based on silicone are more effective than other various types of foam control agents. Silicone foam control agents known as X2-3419 and 2-3302 (Dow Corning) are especially useful here.

где
R₁ является низшим алкилом C₁-C₄, особенно метилом; X и Y каждый меняются от около 6 до около 100; M может принимать значения 0,75 30; n принимает значения 0,25 20; R₂ является смесью как H, так и CH₃, до получения молярного соотношения оксиэтиленокси:оксиизопропиленокси как минимум около 0,5:1.The compiler of fabric laundry compositions that may advantageously contain a dirt removing agent has a wide range of known materials to choose from (see, for example, US Pat. N 3,962,152; N 4,116,885; N 4,238,531; N 4,702,857; N 4 72 580 and N 4 877 896). Additional dirt removing agents useful herein include a nonionic oligomeric esterification product of a reaction mixture containing a source of polyethoxy units with C ₁ -C ₄ alkoxy end groups (eg, CH ₃ [OCH ₂ CH ₂ ] ₁₆ OH), a source of terephthaloyl units (eg dimethyl terephthalate); a source of poly (oxyethylene) oxy units (e.g., polyethylene glycol 1500); a source of hydroxyisopropyleneoxy units (e.g., 1,2-propylene glycol); and a source of oxyethylene ethylene units (e.g. ethylene glycol), especially if the molar ratio of oxyethylene ethylene units to oxyisopropyleneoxy units is at least 0.5: 1. Such neon dirt-removing agents have the general formula

Where
R ₁ is lower alkyl C ₁ -C ₄ , especially methyl; X and Y each vary from about 6 to about 100; M can take values of 0.75 30; n takes values of 0.25 to 20; R ₂ is a mixture of both H and CH ₃ , to obtain a molar ratio of oxyethyleneoxy: oxyisopropyleneoxy of at least about 0.5: 1.

 Another preferred type of dirt removing agent useful here is the basic anionic type described in US Pat. No. 4,877,896, but provided that such agents are substantially free of HOROH type monomers, where R is propylene or higher alkyl. Thus, dirt-removing agents of US Pat. No. 4,877,896 may contain, for example, a reaction product of dimethyl terephthalate, ethylene glycol, 1,2-propylene glycol and 3-sodium sulfobenzoic acid, where these additional dirt-removing agents may contain, for example, a reaction product of dimethyl terephthalate, ethylene glycol, 5-sodium sulfoisophthalate and 3-sodium sulfobenzoic acid. Such agents are preferred for use in granular laundry detergents.

 The compiler may also determine that it is advantageous to include non-borate bleaches, especially in high-performance granular laundry detergents. A variety of peroxide bleaches are commercially available and can be used here, but percarbonate is convenient and economical. Thus, the compositions here may contain solid percarbonate bleach, usually in the form of sodium salt, introduced at a level of 3 to 20 wt. more preferably 5 to 18 wt. and most preferably 8 to 15 wt. by weight of the composition.

Sodium percarbonate is an additional compound having the formula corresponding to 2Na ₂ CO ₃ • 3H ₂ O ₂ and is commercially available as a crystalline solid. Most commercially available materials contain low levels of heavy metal passivators, such as EDTA, 1-hydroxyethylidene-1,1-diphosphonic acid (NEDR) or aminophosphonate, which are introduced during the manufacturing process. For use herein, percarbonates can be incorporated into detergent compositions without further protection, but preferred embodiments of the invention utilize stable material forms (FMC). Although various coatings may be used, the most economical is sodium silicate with a SiO ₂ : N ₂ O ratio of 1.6: 1 to 2.8: 1, preferably 2.0: 1, used as an aqueous solution, and when dried, give a level of 2 10% (usually 3 5%) of silicate solids by weight of percarbonate. Magnesium silicate may also be used, and one of the chelates discussed above may also be included in the coating.

 The particle radius of crystalline percarbonate is 350 to 450 microns, an average of approximately 400 microns. The coated crystals have a radius of 400 to 600 microns.

 Although the presence of heavy metals in the sodium carbonate used to produce percarbonate can be controlled by the inclusion of passivators in the reaction mixture, percarbonates still require protection from heavy metals present as impurities in other ingredients of the product. It was found that the total level of iron, copper and manganese ions in the product should not exceed 25 ppm. and preferably should be less than 20 ppm. in order to exclude unacceptable harmful effects on the stability of percarbonate.

 Example. Xiv. The following illustrates a perborate detergent composition consisting of a perborate bleach and a bleach activator of the invention, which is prepared by mixing the listed ingredients in a mixer drum.

In an example, zeolite A refers to a hydrated crystalline zeolite A containing about 20% water and having an average particle size of 1 10 μm, preferably 2 5 μm; LAS refers to a C ₁₂ -C ₁₃ linear sodium alkyl benzenesulfonate; AS refers to C ₁₄ -C ₁₅ sodium alkyl sulfate; non-ionic component refers to coconut alcohol, compensated with 6.5 mol of ethylene oxide per mole of alcohol and distilled from unethoxylated and monoethoxylated alcohol, also designated CnAE6.5T; DTPA refers to sodium diethylene triamine pentaacetate. The data according to example XIV are given in table.7.

 Note to table 7.

¹ The basis of the granules obtained by drying with spraying an aqueous vertically mixed mixture of these ingredients.

^{2 A} freshly prepared wet sample of NAPAAA is obtained, which typically contains about 60% water, about 2% of the available oxygen (AVO) peroxyacid (corresponding to about 36% of NAPAA), and the remainder (about 4%) of the unreacted starting material.

 This wet cake is the crude product of the reaction of NAAA (aditic acid monononylamide), sulfuric acid and hydrogen peroxide, which is substantially quenched by adding water, followed by filtration, washing with distilled water, washing with phosphate buffer and final filtration with suction to obtain a wet filter cake. A portion of the wet cake is dried in air at room temperature until a dry sample is obtained that typically contains about 5% AVO (corresponding to about 90% NAPAA) and about 10% unreacted starting material. After drying, the sample has a pH of about 4.5.

NAPAA granules were prepared by mixing 51.7 parts of dried NAPAA wet cake (containing about 10% unreacted), about 11.1 hours. C _12.3 linear sodium alkylbenzenesulfonate (LAS) as a paste (45% activity), about 43.3 parts of sulfate sodium and about 30 parts water in a CUISINART mixer.

 After drying, the granules (which contain about 47% NAPAA) are fractionated in size by sieving through an N 14 Tyler sieve and holding all particles that have not passed through an N 65 sieve.

 The average particle size of the amide peroxy acid (agglaurate) is about 5-40 microns, and the average particle size is about 10-20 microns, as determined by Malvern particle size analysis.

³ NOBS granules (nonanoyloxybenzenesulfonate) are prepared in accordance with US Pat. No. 4,997,596 Bowlingctal, issued March 5, 1991.

⁴ Zeolite granules are prepared by mixing Zeolite A with PEG 800 and CnAE6.5T in a high performance Eirich RO8 mixer.

 The composition of the zeolite granules is presented in table.8.

PEG 8000 is presented in aqueous form containing 50% water and at a temperature of approximately 55% ^o F (12.8 ^o C). CnAE6.5T is present in liquid form and is stored at approximately 90 ^° F (32.2 ^° C). The two liquids are connected by pumping through a 12-element static mixer. The resulting binder material has an outlet temperature of about 75 ^° F. (23.9 ^° C.) and a viscosity of about 5000 chyag. The ratio of PEG 8000 and CnAE6.5T passed through the mixer is 72:28, respectively.

 The highly efficient Eirich R08 mixer operates in batch mode. Initially, 34.1 kg of powdered zeolite A is weighed on a mixer cup. The mixer is first turned on by turning the cup counterclockwise in a direction at about 75 rpm, and then rotates the rotor blades clockwise at 1800 rpm. The binder material is then passed from the static mixer directly into the eirich R08 high energy mixer, which contains zeolite A. The feed rate of the binder is 2 minutes. The mixture was further stirred for an additional 1 minute until a total time of about 3 minutes. The batch is then unloaded and collected in a fiber drum.

Periodic loading is repeated until about 225 kg of wet product is collected. Then, the discharged product is dried in a fluidized bed at 240-270 ^o F (116-132 ^o C). The drying step removes most of the free water and changes the composition as described above. The total energy applied by the mixer to the product in one load is approximately 1.3 • 10 ¹² erg / kg at a speed of approximately 2.18 • 19 ⁹ erg / kg • s.

 The resulting free smooth agglomerates have an average particle size of about 450-500 microns.

 Example XV. A liquid detergent composition for washing, suitable for use at relatively high concentrations, typical for front-loading automatic washing machines, especially in Europe, and over a wide temperature range, has the composition shown in Table 9.

 Example XVI. Granular detergent composition for washing, suitable for use at relatively high concentrations, usually for front-loading automatic washing machines, especially in Europe, and over a wide temperature range, has the composition shown in Table 10.

 The pellet preparation procedure includes various tower draining, segregation, additional dehumidifiers, etc. as follows below. Percentages based on the final composition.

 A. Vertically mixed and blown through a tower.

Using a standard technique, the following components are vertically mixed and dried in a tower:
SOKOZAN CP5 3.52
DEQEST 2066 0.45
TINOPAL DMS 0.28
Magnesium Sulphate 0.49
Zeolite A, anhydrous 7.1
SMS 0.47
B. Agglomerates of surfactants.

B1. Agglomeration of the sodium salt of tall alkyl sulfate and the sodium salt of C _12-15 EO (3) sulfate pastes. 50% active paste of tall alkyl sulfate and 70% paste of C ₁₂ -C ₁₅ EO (3) sulfate are agglomerated with zeolite A and sodium carbonate in accordance with the following formula (contribution of the detergent composition after drying of the agglomerate),
Tall alkyl sulfate 2.82%
C _12-15 EO (3) Sulfate 1.18%
Zeolite A 5.3%
Sodium Carbonate 4.5%
B2. Agglomerate of C ₁₄ -C ₁₅ alkyl sulfate, C ₁₂ -C ₁₅ alkyl ethoxysulfate, DOBANOZ C ₁₂ -C ₁₅ EO (3) and C ₁₆ -C ₁₈ N-methylglucosamide. A non-ionic material based on C ₁₆ -C ₁₈ glucose amide was synthesized from DOBANOZ C ₁₂ -C ₁₅ EO (3) present during the reaction of methyl ether and N-methylglucamine. C ₁₂ -C ₁₅ EO (3) acts as a melting point depressor so that the above reaction proceeds without the formation of cyclic glucodamides, which are undesirable.

A mixture of surfactants 20% DOBANOZ, C ₁₂ -C ₁₅ EO (3) and 80% C ₁₆ -C ₁₈ N-methylglucosamide was obtained co-agglomerated with 10% sodium carbonate.

Then, this part is agglomerated together with a highly active paste (70%) of the sodium salt of C ₁₄ -C ₁₅ alkyl sulfate and C _12-15 EO (3) sulfate and zeolite A and additionally sodium carbonate. This part shows good dispersion capacity in cold water of C ₁₆ -C ₁₈ N-methylglucosamide.

The full composition of this part (contribution to the detergent composition after drying and agglomeration) consists,
C ₁₆ -C ₁₈ N-methyl glucosamide 4.1
DOBANOZ C _12-15 EO (3) 0.94
Sodium Carbonate 4.94
Zeolite A 5.3
Sodium C ₁₄ -C ₁₅ alkyl sulfate 3.5
Sodium C _12-15 EO (3) Sulfate 0.59
C. Dry additives.

The following ingredients are added,
Percarbonate 22.3
Tetraacetylethylenediamine (TAED) 5.9
Hoechst 12.9 Laminated Silicate SKS 6
Citric Acid 3.5
Lipolase 0.42 100,000 LU / g
SAVINASE 4.0 KNPV 1.65
Zinc phthalocyanine (photobleach) 0.02
D. Spray applied
DOBANOZ C _12-15 EO (3) 2.60
Fragrance 0.53
E. Foam suppressors.

Silicone foam suppressor X2-3419 (95-97% high molecular weight linear silicone, 3-5% hydrophobic silica gel) ex Dow. Corning was coagulated with zeolite A (size 2-5 μm), starch and stearyl alcohol binder. This part has the following composition,
Zeolite A 0.22
Starch 1.08
X2-3419 0.22
Stearyl alcohol 0.35
The detergent preparation shows excellent solubility, high efficiency and good foaming control when used in European washing machines, for example, using 85 g of detergent in an AEG washing machine at 30 ^o C, 40 ^o C, 60 ^o C and 90 ^o C in cycles .

 In any of the above examples, the surfactant glucamide fatty acid can be replaced with an equivalent amount of maltamide surfactant or glucamide / maltamide surfactant mixtures obtained from plant sources of sugars. It turns out that the use of ethanolamides in the compositions gives stability to the final compositions at low temperatures. Moreover, the use of sulfobetainic and / or amine oxide surfactants provides excellent foaming.

For compositions where high foaming is desired, it is preferred that less than about 5% is present, preferably less than about 2%, and preferably no C ₁₄ or higher fatty acids are present since they can inhibit foaming.

Accordingly, the high foaming agent should desirably avoid introducing suppressive foaming amounts of such fatty acids into these high foaming polyhydroxyamide fatty acid compositions and / or avoid the formation of C ₁₄ or higher higher fatty acids during storage of the final compositions. This simply means the use of C ₁₂ ester reagents for the preparation of polyhydroxyamide fatty acids in the method of the invention.

 The use of amine oxide or sulfobetainic surfactants can overcome some of the negative effects of foaming caused by fatty acids.

 A compiler desiring to add anionic optical brighteners to liquid detergents containing relatively high concentrations (e.g., 10% or higher) of anionic or polyanionic substituents, such as polycarboxylate structure-forming components, may find it useful to first mix the bleach with water and a polyhydroxy fatty acid amide, and then add this pre-mix to the final composition.

 Dispersants polyglutamic acid or polyaspartic acid - can be successfully used with detergents based on zeolites. AE liquid or flocculent DS-544 (Dow lorning) are other examples of useful foaming control agents in the method of the present invention.

 Professionals should be aware that the preparation of fatty acid polyhydroxyamides using di- and higher saccharides such as maltose will result in the formation of fatty acid polyhydroxyamides, where the linear substituent Z is “hidden” by the polyhydroxy ring structure. Such materials are fully suitable for use here without departing from the spirit and scope of the invention.

 Example XVII. Testing the composition for lipolase stability.

 A liquid detergent composition containing a mixture of tartrate / succinate (4%) and citrate (8%) as a binding agent is used as a base.

The residual activity of lipolase at 32.2 ^o C are presented in table.11.

Titrometric data on lipolase activity in a mixture with individual surfactants not containing a binding agent during titration with a 1 mM Ca ⁺ solution are presented in Table 12.

 Studies have shown that lipolase is more stable when stored in liquid washing compositions containing APGFA mixed with anionic surfactants than in compositions containing only anionic surfactants.

 Example XVIII. A comparative study of the effectiveness of detergent compositions containing BS / NPP and BS / NPP / APHFA.

 Test Procedure

Tissue samples with technical impurities were washed using the test composition and their removal rate was visually evaluated on a 0-4 scale. The results are presented based on a comparison of paired samples. The quantitative value of LOE (LOE is a linear evaluation unit that shows the degree of stain removal, is determined visually by an expert and evaluated on a special calibration scale.) Is determined by the following scale:
0 there are no differences between the pair;
1 the first sample seems cleaner than the second;
2 the first sample is clearly cleaner than the second;
3 the first sample is much cleaner than the second;
4 the first sample is much cleaner than the second.

The test samples are placed in a washing solution in which non-surfactant ingredients are previously dissolved (especially in the case of granular compositions) by stirring for 2 minutes, then 20% surfactant solutions in water pre-heated to a washing temperature and having a certain hardness are added . To fully obtain the necessary liquid composition, the components are pre-dissolved for 2 minutes. The hardness of the water was adjusted by adding a solution of CaCl ₂ / MgCl ₂ in a molar ratio of 3: 1 in soft water. The ratio of tissue to water is 1:25. A washing machine with top loading and stirring, manufactured by York Manufacturing, is used.

 The degree of removal of contaminants was compared after drying of either the sample as a whole or, in cases where the spots are not identical, of individual parts of the sample.

 Test 1. The basis of the composition, as shown in example XVII.

 Comparison data of BS / NPP with BS / NPP / APHLC.

 Spend two washing cycles (see table 13).

 Test 2. The basis of the composition, as shown in example XVIII.

 Comparison of NPP / NPP with NPP / NPP / APHLC.

 Spend 2 washing cycles (see table 14).

Pre-processing is presented in table.15
Test 3. The basis of the composition, as shown in example XVII.

 Comparison of BS / NPP and APGZhK / NPP.

 Spend 2 washing cycles (see table 16).

Notes: BS industrial surfactant: benzenesulfonate
NPP industrial surfactant: ethoxysulfonate
AS industrial surfactant: alkyl sulfonate
APHLC surfactant: polyhydroxy fatty acid amide according to the invention.

Studies show:
1) the cleansing effect of the lipolase enzyme in relation to the removal of fatty contaminants in compositions containing APGFA is equivalent to the action of the enzyme in compositions containing anionic surfactants;
2) the compositions disclosed in the invention, containing APGFA, have increased stability of the enzyme and detergent properties not inferior to known compositions.

 Example XIX. The study of the cleansing effect of compositions containing APGFA, mixed with nuclear power plants and AS in the presence or absence of the enzyme. The test procedure described in Example XVIII was used.

 The compositions of the investigated compositions are presented in table 17, 18.

The data obtained are shown in the presented summary table.19. The washing was carried out at 35 ^° C. and a water hardness of 6 g / g.

 The data obtained show that compositions containing AGPFA and protease exhibit an improved cleansing effect with respect to the removal of enzyme-labile impurities compared with compositions containing only protease without APFA.

Example XX. In the tests below, the efficacy of washing detergents containing a protease (commercially available savinase) and either C _12-14 methylglucamide or coconut monoethanolamide (CnMEA) or coconut diethanolamide (CnDEA) with respect to the removal of two different types of contaminants was investigated. some of which are grease / oil, while others are sensitive to the action of enzymes.

 Test Procedure

 Contaminated samples are washed in the tested compositions and visually evaluated on a comparative scale of 0-4. Analyze the statistical results obtained by the method of pairwise comparisons. A linear unit of measurement is quantified by the scale indicated in Example XVIII.

Samples with technical impurities are placed in a washing solution, previously prepared by mixing the ingredients of the composition for 2 minutes before loading the samples, in water previously heated to a washing temperature of 32 ^o C and having a hardness of 7 g / g, which is achieved by adding a solution of CaCl ₂ / MgCl ₂ at a molar ratio of 3: 1 and soft water. The ratio of water to fabric is 30: 1 and 250 ppm of artificial solid is added as an additional solid in the wash. Use cycle: 12 min wash followed by a 3-minute rinse. Use a top loading and stirring washing machine manufactured by York Manufacturing. The LOE value is determined after drying of the samples.

 The following is a detailed description of the tests performed.

Test 1. The compositions are presented in table 20
Test the washing efficiency of C _12-14 methylglucamide + enzyme are presented in table.21
Test 2. The composition is presented in table.22.

The obtained data on the washing efficiency are presented in table.23
Test 3. The composition is presented in table.24.

The obtained data on the washing efficiency are presented in table.25
The generalized results are presented in the summary table.26.

 The above data show that all three formulations have comparable efficacy against enzyme-sensitive contaminants, however, the composition containing glucamide exhibits better cleaning properties against grease / oil contamination compared with the composition containing monoethanolamide or coconut diethanolamide. The use of methyl glucamide in a detergent composition is preferred. Moreover, the use of methylglucamide in the composition instead of CnМЭА and CnДЭА, which makes it possible to increase its effectiveness against grease / oil contamination, does not negatively affect the cleansing efficiency of the enzyme.

Claims (16)

1. A liquid detergent composition with improved enzymatic stability and improved enzymatic cleaning properties, containing one or more anionic surfactants, nonionic surfactants or mixtures thereof, structure-forming components, additional detergent components, solvents and water, active detergent enzymes and polyhydroxyamide fatty acids of the general formula I

characterized in that it contains the specified polyhydroxyamide fatty acid of General formula I, where R ₁ H, (C ₁ - C ₄ ) hydrocarbon radical, 2-hydroxyethyl, 2-hydroxypropyl or a mixture thereof; R ₂ (C ₅ C _{3 1} ) hydrocarbon radical; Z a polyhydroxyhydrocarbon with a linear hydrocarbon chain with at least three hydroxyl groups directly linked to the specified chain, or its alkoxy derivative in the following ratio of components, wt. One or more anionic surfactants, nonionic surfactants, or mixtures thereof 3.0 40.0
Structural components 0.1 50.0
Fatty acid polyhydroxyamide of the general formula I 1.0 50.0
Active washing enzyme 0.0001 2
Additional detergent components, solvents and water Up to 100
2. The composition according to claim 1, characterized in that these enzymes contain an alkaline protease, amylase, lipase, cellulase or peroxidase, or mixtures thereof.  3. The composition according to claim 2, characterized in that these enzymes contain lipase enzymes and the composition contains at least 3 wt. the above polyhydroxyamide fatty acid. 4. The composition according to claim 3, characterized in that it contains a polyhydroxyamide of the specified formula I, where R ₁ CH ₃ ; R ₂ - (C _{1 1} C _{1 7} ) alkyl or alkenyl; Z group derived from glucose, maltose, fructose or mixtures thereof.  5. The composition according to claim 1, characterized in that the anionic surfactant is not an alkylbenzenesulfonate. 6. The composition according to claim 1, characterized in that it contains an anionic surfactant of the formula RO (A) _m SO ₃ M, where R is unsubstituted (C _{1 0} C _{2 4} ) alkyl or hydroxy (C _{1 0} C _{2 4} ) alkyl; A ethoxy or propoxy group; m greater than 0 and M N or cation.  7. The composition according to claim 6, characterized in that it contains a lipase, preferably obtained from Humicola lanuqinosa.  8. The composition according to claim 7, characterized in that it contains 4 to 40 wt. anionic surfactant.  9. The composition according to p. 1, characterized in that it contains as an anionic surfactant a water-soluble alkyl sulfate. 10. Granular detergent composition with improved enzymatic cleaning properties, containing one or more anionic surfactants, nonionic surfactants or mixtures thereof, structure-forming components, additional detergent components, solvents and water, active detergent enzymes and fatty acid polyhydroxyamide of the general formula I

characterized in that it contains the specified polyhydroxyamide fatty acid of General formula I, where R ₁ H, (C ₁ - C ₄ ) hydrocarbon radical, 2 hydroxyethyl, 2 hydroxypropyl or a mixture thereof; R ₁ (C ₅ C _{3 1} ) hydrocarbon radical; Z
polyhydroxyhydrocarbon with a linear hydrocarbon chain with at least three hydroxyl groups directly associated with the specified chain, or its alkoxy derivative in the following ratio of components, wt. One or more anionic surfactants, nonionic surfactants, or mixtures thereof 3.0 40.0
Structural components 0.1 50.0
Fatty acid polyhydroxyamide of the general formula I 1.0 50.0
Active washing enzyme 0.0001 2
Additional detergent components, solvents and water Up to 100
11. The composition of claim 10, wherein said detergent enzyme contains an alkaline protease, amylase, lipase, cellulose or peroxidase, or mixtures thereof.  12. The composition according to claim 11, characterized in that said enzyme contains a lipase enzyme and the composition contains at least 3 wt. the above polyhydroxyamide fatty acid. 13. The composition according to p. 12, characterized in that it contains a polyhydroxyamide of the specified formula I, where R ₁ CH ₃ ; R ₂ - (C _{1 1} C _{1 7} ) alkyl or alkenyl; Z group derived from glucose, maltose, fructose or mixtures thereof.  14. The composition of claim 10, wherein the anionic surfactant is not an alkylbenzenesulfonate.  15. The composition of claim 10, characterized in that it contains a lipase derived from Humicola lanuginosa.  16. The composition of claim 10, characterized in that it contains 4 to 40 wt. anionic surfactant.  17. The composition according to p. 16, characterized in that as an apionic surfactant, it contains a water-soluble alkyl sulfate.  18. The composition of claim 10, characterized in that as a structure-forming component, it contains zeolite or layered silicate or a mixture thereof. Priority by signs:
09/28/09 pp. 1 4, 7 11 and 13 18;
06/14/91 p. 5 6, 12.

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