JP2854136B2 - Polyhydroxy fatty acid amide surfactants for enhancing enzyme performance - Google Patents

Abstract

Disclosed is an improved detergent composition comprising one or more anionic surfactants, nonionic surfactants, or mixtures thereof, and detersive enzymes, the improvement which comprises incorporating into said composition an enzyme performance-enhancing amount of a polyhydroxy fatty acid amide material of formula (I), wherein R<1> is H1, C1-C4 hydrocarbyl, 2-hydroxy ethyl, 2-hydroxy propyl, or a mixture thereof, R2 is C5-C31 hydrocarbyl, and Z is a polyhydroxyhydrocarbyl having a linear hydrocarbyl chain with at least three hydroxyls directly connected to said chain, or an alkoxylated derivative thereof.

Description

Description: TECHNICAL FIELD The present invention relates to a detergent composition containing an enzyme. More particularly, the present invention relates to detergent compositions containing an enzyme and a polyhydroxy fatty acid amide surfactant.

BACKGROUND ART It is common commercial practice to incorporate various enzymes into liquid and granular laundry detergents to enhance cleaning performance. Proteolytic enzymes are well known for this use, but other enzymes such as amylase,
Cellulases, lipases, peroxidases, and combinations thereof have also been suggested for such uses. Literature and standard recipes make good references regarding the use of enzymes in fabric laundry compositions.

Because enzymes are biological substances, they are susceptible to denaturation and inactivation, especially after prolonged contact with other components present in a fully formulated detergent composition. Thus, freshly formulated detergent compositions containing enzymes will often exhibit substantially higher cleaning performance than older products stored or stored on shelves. The storage stability of enzyme-containing detergent compositions, especially liquid detergents, is of considerable importance to formulators and various enzyme stabilizers have been devised. For example, various boron compounds, formate, ethanolamine, and / or
Alternatively, various short-chain fatty acids are commonly added to detergent compositions to provide enzyme stability. Such stabilizers are often used in liquid detergent compositions containing enzymes.

Furthermore, enzymes are relatively expensive and their incorporation into detergent compositions ultimately results in increased costs for the formulator to the user. Therefore, it would be advantageous if enzyme performance could be improved with less expensive additives.

It is theoretically possible to enhance the performance of various enhancers as well as stabilize the enzyme against degradation. However, the net purpose in market situations where long term enzyme activity, whether stabilized or enhanced, must be considered is similar, providing better performance of the detergent composition to the user. That is.

Because almost all enzymes are expensive and almost all enzymes will lose at least some of their activity upon storage, they should be stabilized or otherwise enhance the performance of the enzyme in fully formulated detergent compositions There is ongoing research on materials.

Without being limited by theory, the types of polyhydroxy fatty acid amide surfactants disclosed below include:
It appears to provide a stabilizing and / or performance enhancing function to the enzyme. Quite possibly, polyhydroxyfatty acid amides work by removing molecular "fragments" that form when enzymes attack soils and stains, thereby making the enzyme perform more efficiently. Whatever the mechanism of action,
The present invention achieves the ultimate goal of providing enhanced removal of enzyme-labile soils and stains and thus improves the overall performance in fully formulated enzyme-containing detergent compositions.

In addition to enhancing enzyme performance, polyhydroxy fatty acids themselves are excellent detergent surfactants. Furthermore, surfactants of this kind can be obtained for the most or all from natural renewable raw materials and can be used in place of all or part of a petroleum-based surfactant without loss of detergency. .

Various polyhydroxy fatty acid amides have been described in the art. For example, N-acyl-N-methylglucamide is available from JW Goodbye, MA Marcus, E. Tin, and PL
Finn, "Thermotropic Liquid Crystallinity of Some Linear Carbohydrate Amphiphiles", Liquid Crystals, 1988, 3rd.
Vol. 11, pp. 1569-1581, and A. Muller
"Nonionic detergents: nonanoyl-N-" by Farnau, V. Zabel, M. Stafa and R. Hilgenfeld.
Molecular and Crystal Structure of Methylglucamide "J. Chem.S
oc. Chem. Commun., 1986, pp. 1573-1574. The use of N-alkyl polyhydroxyamide surfactants has recently become of substantial interest in biochemistry, for example, for use in biofilm degradation. For example, the journal article "ND-gluco-N-methyl-alkaneamide compounds for membrane biochemistry, a new class of nonionic detergents" by JEK Hildress, Bi
See ochem. J. (1982), 207, 363-366.

The use of N-alkylglucamides in detergent compositions has also been discussed. U.S. Pat. No. 2,965,576 issued to ER Wilson on Dec. 20, 1960 and Feb. 1, 1959
British Patent No. 809,060, published on August 8 and assigned to Thomas Hedley End Company Limited, describes an amide surfactant which is an anionic surfactant, which comprises N-methyl added as a low temperature foaming agent. Glucamide can be included). These compounds include the N-chain of higher linear fatty acids having 10 to 14 carbon atoms.
Acyl groups are mentioned. These compositions may also contain auxiliary substances, such as alkali metal phosphates, alkali metal silicates, sulfates, carbonates and the like. It is also generally pointed out that additional components that impart desirable properties to the composition, such as fluorescent dyes, bleaches, fragrances and the like, can be incorporated into the composition.

U.S. Patent No. 2, issued March 8, 1955 to AM Schwartz
No. 703,798 relates to an aqueous detergent composition containing a condensation reaction product of an N-alkylglucamine and an aliphatic ester of a fatty acid. The product of this reaction is said to be usable in aqueous detergent compositions without further purification. AM
U.S. Patent No. 2,717,89 issued to Schwartz on September 13, 1955
It is also known to prepare sulfated acylated glucamines as disclosed in US Pat.

PCT International Application No. WO 83/04412, published December 22, 1983 by J. Hildress, describes cosmetics, medicines, shampoos,
Lotions and eye ointments as surfactants, as medical emulsifiers and dispensers, and in various applications including solubilization of membranes, whole cells or other tissue samples and biochemistry to produce liposomes. To amphiphilic compounds containing polyhydroxyl aliphatic groups which are said to be useful for the purpose of This disclosure includes the formula R'CON
(R) CH ₂ R ″ and R ″ CON (R) R ′ (where R is hydrogen or an organic atomic group, and R ′ has at least 3 carbon atoms)
Wherein R ″ is the residue of an aldose).

EP 0 285 768, issued October 12, 1988 to H. Kelkenberg, relates to the use of N-polyhydroxyalkyl fatty acid amides as thickeners in aqueous detergent systems. Formula R ₁ C (O) N (X) R ₂ [wherein R ₁ is C ₁ -C
₁₇ (preferably C ₇ -C ₁₇ ) alkyl, wherein R ₂ is hydrogen, C
₁ -C ₁₈ (preferably C ₁ -C ₆₎ alkyl or alkylene oxide, X is an amide of a) polyhydroxy alkyl of 4-7 carbon atoms, for example, N- methyl coconut fatty acid glucamide and the like. Aqueous surfactant systems include other anionic surfactants such as alkyl aryl sulfonates, olefin sulfonates, sulfosuccinic acid half ester salts, and fatty alcohol ether sulfonates, and nonionic surfactants such as fatty alcohol polyglycol ethers, alkyl phenols It can contain polyglycol ether, fatty acid polyglycol ester, polypropylene oxide-polyethylene oxide mixed polymer, etc., but the thickening of amides has been pointed out to have particular application in liquid surfactant systems containing paraffin sulfonate. . Paraffin sulfonate / N
-A methyl coconut fatty acid glucamide / nonionic surfactant shampoo formulation is exemplified. In addition to the thickening properties, N-polyhydroxyalkyl fatty acid amides
It is said to have excellent skin tolerance properties.

US Patent No. 2, issued May 2, 1961 to Boettner et al.
No. 982,737 discloses urea, sodium lauryl sulfate anionic surfactant, and N-alkylglucamide selected from N-methyl-N-sorbicyllaurinamide and N-methyl-N-sorbicylmyristamide. Detergent solid containing an ionic surfactant.

Other glucamide surfactants are, for example, 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; ₂ is C ₁₀ -C ₂₂ alkyl and n is 3 or 4)
Announced on December 20, 1973 for a detersive composition comprising a builder salt selected from one or more surfactants and polymeric phosphates, a sequestering agent and a detersive alkali.
HW Eckert et al., DT 2,226,872. N-acyl polyhydroxyalkylamines are
Add as a stain settling inhibitor.

U.S. Patent issued on April 4, 1972 to HW Eckert
No. 3,654,166 describes at least one surfactant selected from the group of anionic surfactants, zwitterionic surfactants and nonionic surfactants and a formula as a fabric softener.
R ₁ N (Z) C (O) R _{2 wherein} R ₁ is C ₁₀ -C ₂₂ alkyl, R ₂ is C ₇ -C ₂₁ alkyl, and R ₁ and R ₂ are 23- has 39 carbon atoms, Z is _{-CH 2 (CHOH) m CH 2} O
H (where m is 3 or 4 is a polyhydroxyalkyl)].

U.S. Patent No. 4,021, issued May 3, 1977 to H. Meller et al.
No. 539 describes the formula R ₁ N (R) CH (CHOH) _m R ₂ (wherein R
₁ is H, lower alkyl, hydroxy-lower alkyl, or aminoalkyl, as well as heterocyclic aminoalkyl; R is the same as R ₁ but both cannot be H; R ₂ is CH ₂ OH Or COOH), comprising a N-polyhydroxyalkylamine comprising a compound of the formula:

French Patent No. 1,360,018 assigned to Commercial Solvents Corporation (April 26, 1963)
Day) has the formula RC (O) N (R ₁ ) G, where R is a carboxylic acid functionality having at least 7 carbon atoms, R ₁ is hydrogen or a lower alkyl group, and G is at least 5 carbon atoms. Glycidyl group) is added to the solution of formaldehyde stabilized against polymerization.

German Patent 1,261,861 (February 29, 1968, A.
Hines) has the formula _{N (R) (R 1)} (R 2) ( wherein, R is a sugar residue of glucamine, R ₁ is C ₁₀ -C ₂₀ alkyl group, R ₂ is C ₁ ~ C about ₅ useful glucamine derivative as a wetting agent / dispersant acyl group is).

UK Patent No. 745,036, issued February 15, 1956 and assigned to Atlas Powder Company, is useful as a chemical intermediate, emulsifier, wetting / dispersing agent, detergent, fabric softener, and the like. Heterocyclic amides and their carboxylic esters. The compound is
Formula N (R) (R ₁ ) C (O) R _{2 wherein} R is the residue of anhydrous hexanepentol or a carboxylic acid ester thereof, R ₁ is a monovalent hydrocarbon group, (O) R ₂ is an acyl group of a carboxylic acid having 2 to 25 carbon atoms).

US Patent No. 3,31 issued to DT Hooker on April 4, 1967
U.S. Pat. And a non-ionic surfactant selected from the group consisting of: RC (O) NR ¹ (R ² ) wherein RC (O) is about 1
It has 0 to about 14 carbon atoms, and R ¹ and R ² are each H or a C ₁ -C ₆ alkyl group, wherein the alkyl group has a total number of 2 to about 7 carbon atoms and a substituent hydroxyl group. (Having a total number of from about 2 to about 6) is disclosed. A substantially similar disclosure is found in U.S. Patent No. 3,312,626, issued April 4, 1967 to DT Hooker.

SUMMARY OF THE INVENTION The present invention is a detergent composition comprising one or more anionic surfactants, nonionic surfactants or mixtures thereof, and a detergent enzyme, wherein the composition comprises Wherein R ¹ is H ₁ , C ₁ -C ₄ hydrocarbyl, 2-hydroxyethyl, 2-hydroxypropyl, or a mixture thereof, R ₂ is C ₅ -C ₃₁ hydrocarbyl, and Z is A polyhydroxyhydrocarbyl having a linear hydrocarbyl chain having at least three hydroxyls directly linked thereto, or an alkoxylated derivative thereof). Offer things.

Further, the present invention provides a detergent composition comprising an enzyme-enhancing amount of said polyhydroxyfatty acid amide in a detergent composition in the presence of an aqueous medium, such as an anionic surfactant, a nonionic surfactant, Alternatively, there is provided a method for improving the cleaning performance of a detergent composition containing a cationic surfactant, particularly an anionic surfactant.

Further, the present invention provides a detergent composition comprising one or more anionic, non-ionic or cationic surfactants and a detergent enzyme comprising a substrate such as fibers, fabrics, hard surfaces, skin, etc. The article provides a method for cleaning a substrate by contacting it with an enzyme performance enhancing amount of a polyhydroxyfatty acid amide surfactant.

BEST MODE FOR CARRYING OUT THE INVENTION Polyhydroxy Fatty Acid Amide Surfactant The detergent compositions herein contain an "enzyme performance enhancing amount" of polyhydroxy fatty acid amide. By "enzyme enhancement" is meant that the formulator of the composition can select the amount of polyhydroxy fatty acid amide in the composition that will improve the enzyme cleaning performance of the detergent composition. In general, for detergents containing conventional amounts of enzyme, the incorporation of about 1% by weight of polyhydroxy fatty acid amide will enhance enzyme performance.

The compositions typically comprise at least about 1% (by weight) of a polyhydroxyfatty acid amide surfactant, preferably at least about 3%, and more preferably about 3% to about 50% of a polyhydroxyfatty acid amide, most preferably Preferably about 3%
~ 30%.

The polyhydroxy fatty acid amide surfactant component of the present invention has a structural formula Wherein R ¹ is H, C ₁ -C ₄ hydrocarbyl, 2-hydroxyethyl, 2-hydroxypropyl, or a mixture thereof, preferably C ₁ -C ₄ alkyl, more preferably C ₁ or C ₂ alkyl, Most preferably, it is C ₁ alkyl (ie, methyl); R ² is C ₅ -C ₃₁ hydrocarbyl, preferably linear C ₇ -C ₁₉ alkyl or alkenyl, more preferably linear C ₉ -C ₁₇ alkyl or alkenyl. , and most preferably lies in linear C ₁₁ -C ₁₅ alkyl or alkenyl, or mixtures thereof,; Z is polyhydroxy hydrocarbyl or alkoxylated with a linear hydrocarbyl chain with at least 3 hydroxyls directly connected to the chain Derivatives (preferably ethoxylated or propoxylated)]. Z will preferably be derived from a reducing sugar in a reductive amination reaction; more preferably Z is glycityl. Suitable reducing sugars include glucose, fructose, maltose, lactose, galactose, mannose, and xylose. As raw materials, high dextrose corn syrup, high fructose corn syrup, and high maltose corn syrup can be utilized as well as the individual sugars described above. These corn syrups may prepare a mix of Z sugar components. It should be understood that no other suitable raw materials are ever excluded. Z is preferably _{-CH 2 - (CHOH) n -CH} 2 OH, -CH (CH 2 OH) - (CHOH) n-1 CH 2 OH, -CH 2 - (CHOH) 2 (CHOR ') (CHOH ) —CH ₂ OH, and their alkoxylated derivatives, wherein n is 3-5.
Where R 'is H or a cyclic or aliphatic monosaccharide). glycityls wherein n is 4, particularly -CH ₂ - is _(CHOH) 4 -CH ₂ OH, most preferred.

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

R ² —CO—N <is, for example, cocoamide, stearamide, oleamide, laurinamide, myristamide,
It can be caprinamide, palmitoamide, tallowamide and the like.

Z is 1-deoxyglucityl, 2-deoxyfrucchityl, 1-deoxymultityl, 1-deoxylactyl, 1-deoxygalacticyl, 1-deoxymannityl, 1-deoxymaltotriotyl and the like Can be

The preparation of polyhydroxy fatty acid amides is known in the art. Generally, they react an alkylamine with a reducing sugar in a reductive amination reaction to produce the corresponding N-alkyl polyhydroxyamine, which is then reacted in a condensation / amidation step with a fatty aliphatic ester or React with triglyceride to give N-
It can be made by producing an alkyl-N-polyhydroxy fatty acid amide product. The method for producing a composition containing a polyhydroxyfatty acid amide is, for example, Thomas
19 by Hedley End Company Limited
British Patent No. 809,060 published February 18, 59, ER
U.S. Patent No. 2,965, issued on December 20, 1960 to Wilson
No. 576 and Antony M. Schwartz U.S. Pat.
No. 424, each of which is incorporated herein by reference.

The glycityl moiety is derived from glucose and the N-alkyl or N-hydroxyalkyl functionality is N-methyl;
In one process for the preparation of N-alkyl or N-hydroxyalkyl-N-deoxyglycityl fatty acid amides which are N-ethyl, N-propyl, N-butyl, N-hydroxyethyl, or N-hydroxypropyl, the product is , N-alkyl- or N-hydroxyalkyl-glucamine with trilithium phosphate, trisodium phosphate, tripotassium phosphate, tetrasodium pyrophosphate, pentapotassium tripolyphosphate, lithium hydroxide, sodium hydroxide,
Potassium hydroxide, calcium hydroxide, lithium carbonate, sodium carbonate, potassium carbonate, disodium tartrate, dipotassium tartrate, potassium sodium tartrate, trisodium citrate, tripotassium citrate, basic sodium silicate, basic potassium silicate Formed by reacting with a fatty acid ester selected from fatty methyl esters, fatty ethyl esters and fatty triglycerides in the presence of a catalyst selected from the group consisting of basic sodium aluminosilicate, and basic potassium aluminosilicate, and mixtures thereof. I do. The amount of catalyst is preferably N
About 0.5 mole% to about 50 mole%, more preferably about 2.0 mole% to about 10 mole%, based on moles of -alkyl or N-hydroxyalkyl-glucamine. The reaction is preferably performed at about 138 ° C to about 170 ° C, typically for about 20 to about 90 minutes. When triglycerides are used as the fatty acid ester source, the reaction is preferably from about 1 to about 10% by weight, calculated on the weight percent of the total reaction mixture, of saturated fatty alcohol polyethoxylates, alkyl polyglycosides, linear glucamide surfactants. The reaction is performed using a phase transfer agent selected from agents and mixtures thereof.

Preferably, the method is performed as follows: (a) preheating the fatty acid ester to about 138 ° C. to about 170 ° C .; (b) adding the N-alkyl or N-hydroxyalkyl glucamine to the heated fatty acid ester Mixing to the extent required to prepare a two-phase liquid-liquid mixture; (c) incorporating the catalyst into the reaction mixture;

Also preferably, if the fatty acid ester is a triglyceride, from about 2 to about 20% by weight of the reactants of the preformed linear N-alkyl / N-hydroxyalkyl-N-linear glucosyl fatty acid amide product is: It is added to the reaction mixture as a phase transfer agent. This facilitates the reaction, thereby increasing the rate of the reaction. Detailed experimental procedures are given below.

The polyhydroxy "fatty acid" amide materials used herein also provide the detergent formulator with the advantage that they can be made from all or predominantly natural renewable non-petrochemical feedstocks and are degradable. Also, they show low toxicity to aquatic organisms.

Together with the polyhydroxy fatty acid amides of the formula (I), the methods used to prepare them also typically produce certain amounts of non-volatile by-products such as ester amides, cyclic polyhydroxy fatty acid amides. It should be recognized that The amounts of these by-products will vary depending on the particular reactants and process conditions. Preferably, the polyhydroxyfatty acid amide incorporated into the detergent composition herein is such that the polyhydroxyfatty acid amide-containing composition added to the detergent contains less than about 10%, preferably less than about 4%, cyclic polyhydroxyfatty acid amide. Will be provided in the form. The above preferred method is advantageous because it produces rather small amounts of by-products.

Enzymes Detergent enzymes can be incorporated into detergent formulations for a variety of purposes, including, for example, removal of protein-based stains, carbohydrate-based stains, or triglyceride-based stains and prevention of escape dye transfer. Enzymes to be included include proteases, amylases, lipases, cellulases, and peroxidases, and mixtures thereof. Other types of enzymes may also be included. They may have any suitable origin, for example, plant, animal, bacterial, fungal and yeast origin. However, their choice depends on several factors, such as pH activity and / or stability optima, thermal stability,
Governed by stability to active detergents, builders and the like. In this regard, bacterial or fungal enzymes such as bacterial amylase and protease, and fungal cellulase are preferred.

The enzyme is usually formulated in an amount sufficient to provide up to about 5 mg (by weight) of active yeast per gram of composition, more typically from about 0.05 mg to about 3 mg.

Suitable examples of proteases are Bacillus subtilis and Bacillus
Subtilisin obtained from a specific strain of B. Licheniforms. Another suitable protease is obtained from a strain of Bacillus that has maximum activity over a pH range of 8 to 12, developed by Novo Industries A / S and sold under the registered trademark ESPERASE. The preparation of this and similar enzymes is described in Novo GB 1,243,784. Commercially available proteolytic enzymes suitable for removing protein-based stains include those marketed under the trade names ALCALASE and SAVINASE by Novo Industries A / S (Denmark) and International • those sold under the trade name MAXATASE by Bio-Synthetics, Inc. (Netherlands).

Enzymes designated herein as Protease A and Protease B are of particular interest in the category of proteolytic enzymes for liquid detergent compositions. Protease A and its preparation are described in European Patent Application No. 130,756 published Jan. 9, 1985.
The description is incorporated herein by reference (incorporated herein by reference). Protease B is a proteolytic enzyme that differs from protease A in that it has leucine instead of tyrosine at position 217 in the amino acid sequence. Protease B contains 19
It is described in European Patent Application No. 87303761.8, filed April 28, 1987, which is incorporated herein by reference. Further, the method for producing protease B is disclosed in European Patent Application No. 130,756, Bot et al., Published on January 9, 1985, which is incorporated herein by reference.

Amylases include, for example, α-amylases obtained from a special strain of Bacillus licheniformus, described in more detail in GB 1,296,839 (Novo) previously incorporated herein by reference. Starch degrading proteins include, for example, RAPIDASE from International Bio-Synthetics, Inc. and TERMAMYL from Novo Industries.

Cellulases that can be used in the present invention include both bacterial and fungal cellulases. Preferably, they will have a pH optimum of 5 to 9.5. Suitable cellulases are incorporated by reference in U.S. Pat. No. 4,435,307 to Barvesgoad et al., Issued Mar. 6, 1984, which discloses a fungal cellulase produced from Humicola insolens. Is disclosed. Suitable cellulases are also described in GB 2.075.028, GB 2.095.2.
No. 75 and DE-OS 2.247.832.

Examples of such cellulases include Humicola insolens [Humicola grisea bal thermo idea (Hu
micola grisea var. thermoidea)], in particular, a cellulase produced by a Humicola strain DSM1800, a cellulase produced by a fungus of Bacillus N belonging to the genus Aeromonas or a cellulase 212-producing fungus, and a seawater mollusk [Drabella auricular solander] (Dolabella Auricula Solander)] from the hepatopancreas.

A lipase enzyme suitable for detergent use is disclosed in British Patent No.
No. 1,372,034 (herein incorporated by reference) as disclosed in Pseudomonas st.
utzeri) produced by microorganisms of the Pseudomonas group, such as ATCC 19.154. Suitable lipases include the microorganism Pseudomonas fluorescens (Pseu
domonas Fluorescens) which show a positive immune cross-reactivity with antibodies to lipase produced by IAM1057. This lipase and its purification method are described in Japanese Patent Application No. 53-20487 published on Feb. 24, 1978 for the convenience of the public. This lipase is available from Amano Pharmaceutical Co., Ltd., Nagoya, Japan, under the trade name Ribase P "Amano" (hereinafter referred to as "Amano-P"). Such rivases according to the invention can be used in a standard well-known immunodiffusion method for octalony (Acta. Med. Sca).
n., 133, 76-79 (1950)) should be used to demonstrate positive immune cross-reactivity with Amano-P antibodies. Methods for these lipases and their immune cross-reactivity with Amano-P are also described in Tom et al., US Pat.
No. 7,291, incorporated herein by reference. Typical examples thereof are Amano-P lipase, lipase ex Pseudomonas fragi FERM P1339 (available under the trade name Amano-B), lipase ex Pseudomonas nitrore
ducens var.lipolyticum FERM P1338 (trade name Amano-C
ES), lipase ex Chromobacter viscosum,
For example, Chromobacter viscosum var.lipo, which is commercially available from Toyo Joeso Company of Takata, Japan
lyticum NRRLB3673; and US biochemicals
Yet another chromobacter viscosum lipase from the Corporation and the Dutch Disoint Company, and the lipase ex Pseudomonas gladioli.

The peroxidase enzyme is used in combination with an oxygen source, for example, percarbonate, perborate, persulfate, hydrogen peroxide and the like. They are used in "solution bleaching", i.e. to prevent the transfer of dyes or pigments removed from the base during the washing operation to other substrates in the washing liquor. Peroxidase enzymes are known in the art and include, for example, horseradish peroxidase, ligninase, and haloperoxidase, such as chloroperoxidase and bromoperoxidase. Peroxidase-containing detergent compositions are described, for example, in PCT International Application WO 89/099 by O. Kirk, assigned to Novo Industries A / S, published October 19, 1989.
No. 813, incorporated herein by reference.

A wide range of enzymatic substances and means of incorporation into synthetic detergent granules are also disclosed in McCarty et al., US Pat.
No. 3,553,139, which is incorporated herein by reference. Enzymes are further described in U.S. Pat. No. 4,101,457 issued to Place et al., Jul. 18, 1978, and U.S. Pat. No. 4,507,219 issued to Hughes Mar. 26, 1985, both incorporated herein by reference. ). Enzyme substances useful in liquid detergent formulations and methods of incorporation into such formulations are disclosed in Hora et al., U.S. Pat. No. 4,261,868, issued Apr. 14, 1981, incorporated herein by reference. .

In the case of particulate detergents, the enzyme is preferably coated or prilled with additives inert to the enzyme to minimize dust formation and improve storage stability. Techniques for accomplishing this are well known in the art. In liquid formulations, an enzyme stable system is preferably utilized. Enzyme stabilization techniques for aqueous detergent compositions are well known in the art. For example, one enzyme stabilization technique in aqueous solution involves the use of free calcium ions from sources such as calcium acetate, calcium formate, calcium propionate, and the like. Calcium ions can be used in combination with short-chain carboxylate, preferably formate. See, for example, U.S. Patent No. 4,318,818, issued March 9, 1982 to Retton et al., Which is incorporated herein by reference. It has also been proposed to use polyols such as glycerol and sorbitol. Alkoxy-alcohols, dialkyl glycoethers, mixtures of polyhydric alcohols with polyfunctional aliphatic amines (e.g. alkanolamines such as diethanolamine, triethanolamine, diisopropanolamine), and boric acid or alkali metal borates. Enzyme stabilization techniques are additionally disclosed in Horn et al., U.S. Pat. No. 4,261,868, issued Apr. 14, 1981, and Gedge et al., U.S. Pat. Which is incorporated herein by reference), and Venezuean European Patent Application Publication No. 0 199 405 published Oct. 29, 1986, application no.
It is disclosed and exemplified in 6200586.5. Stabilizers that are not boric acid and borates are preferred. Also, enzyme stable systems are described, for example, in U.S. Pat. Nos. 4,261,868, 3,600,319 and 3,519,570.

In addition to the polyhydroxy fatty acid amide, the compositions herein can contain other detergent surfactants to facilitate cleaning performance. The particular surfactant utilized may also vary widely utilizing detergent surfactants useful for the particular end use entailed. Enzyme-containing detergents are most commonly used for cleaning laundry, fabrics, fabrics, fibers, hard surfaces, and the like. Suitable surfactants include:
Anionic surfactants, nonionic surfactants, cationic surfactants and other surfactants are mentioned and are exemplified below. Preferably, the composition will include one or more anionic surfactants, one or more other nonionic surfactants, or a combination thereof. The benefits of the present invention are particularly evident in compositions containing enzymes with harsh surfactants or other ingredients. These generally include (but are not limited to) anionic surfactants such as alkyl ester sulfonates, linear alkyl benzene sulfonates, alkyl sulfates, and the like. Typically, the amount of additional detergent surfactant present will be from about 3 to about 40 of the detergent composition.
%, Preferably about 5 to about 30% by weight. Suitable surfactants are described below.

Anionic Surfactants One type of anionic surfactant that can be utilized includes alkyl ester sulfonates. These are desirable because they can be prepared from renewable non-petroleum resources. The production of the alkyl ester sulfonate surfactant component can be performed according to a known method disclosed in technical literature. For example, linear esters of C ₈ -C ₂₀ carboxylic acids, "The Journal of the American Oil Kemisutsu -
Society ", 52 (1975), can be sulfonated with gaseous SO ₃ according Pp.323-329. Suitable starting materials include
Natural fatty substances such as those derived from tallow, palm oil, coconut oil and the like may be mentioned.

Alkyl ester sulfonate surfactants particularly preferred for laundry applications have the structural formula Wherein R ³ is C ₈ -C ₂₀ hydrocarbyl, preferably alkyl, or a combination thereof, R ⁴ is C ₁ -C ₆ hydrocarbyl, preferably alkyl, or a combination thereof, and M is a soluble salt. (Which is a forming cation) of an alkyl ester sulfonate surfactant.
Suitable salts include metal salts, for example, sodium, potassium and lithium salts, and substituted or unsubstituted ammonium salts, for example, methyl-, dimethyl-, trimethyl-, and quaternary ammonium cations, for example, tetramethyl -Cations derived from ammonium and dimethylpiperidinium, and alkanolamines, for example monoethanolamine, diethanolamine and triethanolamine. Preferably, R ³ is C ₁₀ -C ₁₆ alkyl and R ⁴ is methyl, ethyl or isopropyl. Methyl ester sulfonates wherein R ³ is C ₁₄ -C ₁₆ alkyl is especially preferred.

Alkyl sulfate surfactants are another class of anionic surfactants of interest for use herein. When combined with polyhydroxy fatty acid amides, dissolution of alkyl sulfate can be obtained in addition to providing excellent overall overall cleaning capability including good grease / oil cleaning over a wide range of temperatures, wash concentrations and wash times. and improved formulation of liquid detergent formulations is that wherein ROSO ₃ M [wherein, R is preferably C ₁₀ -C ₂₄ hydrocarbyl, preferably an alkyl or hydroxyalkyl having a C ₁₀ -C ₂₀ alkyl component, more preferably C ₁₂ -C ₁₈ alkyl or hydroxyalkyl, where M is H or a cation, such as an alkali metal cation (eg, sodium, potassium, lithium), a substituted or unsubstituted ammonium cation, eg, methyl-, dimethyl- , And trimethylammonium and quaternary ammonium Cations such as tetramethyl-ammonium and dimethylpiperidinium, and cations derived from alkanolamines such as ethanolamine, diethanolamine, triethanolamine, and the like, and mixtures thereof). is there. Typically, C ₁₂ -C ₁₆ alkyl chains are preferred for lower wash temperatures (eg, less than about 50 ° C.) and C ₁₆ -C ₁₈ alkyl chains are preferred for higher wash temperatures (eg, less than about 50 ° C.). Is also preferable at high temperatures).

Alkyl alkoxylated sulfate surfactants are another category of useful anionic surfactants. These surfactants typically have the formula RO (A) _m SO ₃ M
[Wherein, R is an unsubstituted C ₁₀ with C ₁₀ -C ₂₄ alkyl component
-C ₂₄ alkyl or hydroxyalkyl group, preferably a C ₁₂ -C ₂₀ alkyl or hydroxyalkyl, more preferably C ₁₂ -C ₁₈ alkyl or hydroxyalkyl, A is an ethoxy or propoxy unit, m is than 0 Large, typically from about 0.5 to about 6, more preferably from about 0.5 to about 3, wherein M is H or, for example, a metal cation (eg, sodium, potassium, lithium,
Calcium, magnesium, etc.), ammonium or substituted ammonium cations]. Alkyl ethoxylated sulfates as well as alkyl propoxylated sulfates are contemplated herein. Specific examples of substituted ammonium cations include methyl-, dimethyl-, trimethyl-
Ammonium and quaternary ammonium cations, such as cations derived from tetramethyl-ammonium and dimethylpiperidinium and alkanolamines, such as monoethanolamine, diethanolamine, and triethanolamine, and mixtures thereof . Exemplary surfactants include C ₁₂ -C ₁₈ alkyl polyethoxylate (1.0) sulfate, C ₁₂ -C
₁₈ alkyl polyethoxylate (2.25) sulfate,
C ₁₂ -C ₁₈ alkyl polyethoxylate (3.0) sulfate, and C ₁₂ -C ₁₈ alkyl polyethoxylate (4.
0) sulfate, where M is conveniently selected from sodium and potassium.

Other Anionic Surfactants Other anionic surfactants useful for cleaning purposes can also be incorporated into the composition. These include soap salts (eg,
Sodium, potassium, ammonium and substituted ammonium salts, such as the monoethanolamine salt,
Including diethanolamine and triethanolamine salts), C ₉ -C ₂₀ linear alkylbenzene sulfonates, C ₈ -C ₂₂ primary or secondary alkane sulfonates, C ₈ -C ₂₄ olefin sulfonates, for example, British Patent No. Sulfonated polycarboxylic acids, alkyl glycerol sulfonates, fatty acyl glycerol sulfonates, fatty oleyl glycerol sulfates, alkyl phenol ethylene oxides prepared by sulfonation of the pyrolysis products of alkaline earth metal citrates as described in 1,082,179 Ether sulfates, paraffin sulfonates, alkyl phosphates, isethionates such as acyl isethionates, N-acyl taurates, fatty acid amides of methyl tauride, alkyl succinates and sulfos Shineto, monoesters of sulfosuccinates (especially saturated and unsaturated C ₁₂ -C
₁₈ monoesters), sulfosulfuron diester succinate (especially saturated and unsaturated C ₆ -C ₁₄ diesters), N- acyl sarcosinates, alkyl polysaccharides sulfate,
For example, sulfates of alkylpolyglucoside (the nonionic nonsulfated compounds described below), branched primary alkyl sulfates, and alkyl polyethoxy carboxylates such formula _{RO (CH 2 CH 2 O)} k -CH 2 COO ^- M
⁺ Wherein R is C ₈ -C ₂₂ alkyl, k is an integer from 0 to 10 and M is a soluble salt-forming cation;
And fatty acids esterified with isethionic acid and neutralized with sodium hydroxide. Resin acids and hydrogenated resin acids such as rosin, hydrogenated rosin, and resin acids present in or derived from tall oil are also suitable. Still other examples are described in "Surfactants and Detergents" (Volumes I and II by Schwartz, Perry and Birch). Various such surfactants are generally available from Rollin et al. In December 1975.
Also disclosed in U.S. Pat. No. 3,929,678, issued on the 30th, column 23, line 58 to column 29, line 23, incorporated herein by reference.

Nonionic Detergent Surfactants Suitable nonionic detergent surfactants are generally described in 1975
U.S. Pat. No. 3,929,678 to Rowlin et al., Issued on Jan. 30, at column 13, line 14 to column 16, line 6 (hereby incorporated by reference). Illustrative, non-limiting classes of useful nonionic surfactants are described below.

1. Polyethylene oxide condensate, polypropylene oxide condensate and polybutylene oxide condensate of alkylphenol. Generally, polyethylene oxide condensates are preferred. These compounds include condensates of alkylphenols with alkylphenols having alkyl groups having from about 6 to about 12 carbon atoms in either a straight or branched configuration. In a preferred embodiment, the ethylene oxide is present in an amount equal to about 5 to about 25 moles per mole of alkylphenol. Commercially available nonionic surfactants of this type include IGEPAL CO-63, commercially available from GAF Corporation.
0, TRITON X-45, X-114, X-1 marketed by Rohm and Haas Company
00, and X-102. These compounds are
Usually, an alkylphenol alkoxylate (for example,
(Alkylphenol ethoxylate).

2. Condensates of aliphatic alcohols with about 1 to about 25 moles of ethylene oxide. The alkyl chain of the aliphatic alcohol can be straight or branched, primary or secondary, and generally has from about 8 to about 22 carbon atoms. About 10 to about carbon atoms
Condensates of alcohols having 20 alkyl groups with about 2 to about 18 moles of ethylene oxide per mole of alcohol are particularly preferred. Examples of commercially available nonionic surfactants of this type include TERGITOL 15 sold by Union Carbide Corporation.
-S-9 (C ₁₁ ~C ₁₅ linear condensation product of secondary alcohols with ethylene oxide of about 9 moles), Tergitol 24-L-6N
MW (narrow C ₁₂ -C ₁₄ condensation product of primary alcohols with ethylene oxide 6 mol with a molecular weight distribution); Neodol marketed by Shell Chemical Company _{(NEODOL) 45-9 (C 14 ~C} 15 wire Condensate of 9 mol of ethylene oxide with ethylene alcohol), Neodol 23-6.5 (C ₁₂
-C ₁₃ linear alcohol with condensation products of ethylene oxide 6.5 moles), Neodol 45-7 (C ₁₄ ~C ₁₅ linear alcohols with ethylene oxide 7 condensates of moles), Neodol 45-
4 (C ₁₄ -C ₁₅ linear alcohol condensation products of ethylene oxide 4 mol), and kilometers marketed by The Procter end Gamble Company (KYRO)
EOB (C ₁₃ ~C ₁₅ condensates of alcohols with 9 moles ethylene oxide) and the like. Non-ionic surfactants in this category are commonly referred to as "alkyl ethoxylates".

3. Condensate of ethylene oxide with a hydrophobic base formed by condensation of propylene oxide and propylene glycol. The hydrophobic portion of these compounds preferably has a molecular weight of about 1500 to about 1800 and is water-insoluble. The addition of a polyoxyethylene moiety to this hydrophobic moiety tends to increase the water solubility of the molecule as a whole, and the liquid properties of the product are such that the polyoxyethylene content is about 50% of the total weight of the condensate (about (Corresponding to condensation with up to 40 moles of ethylene oxide). Examples of such compounds include certain of the PLURONIC surfactants marketed by BASF.

4. Condensates of ethylene oxide with products resulting from the reaction of propylene oxide with ethylenediamine. The hydrophobic portion of these products consists of the reaction product of ethylene diamine with an excess of propylene oxide and generally has a molecular weight of about 2500 to about 3000. The hydrophobic moiety condenses with ethylene oxide to the extent that the condensate contains about 40 to about 80% by weight polyoxyethylene and has a molecular weight of about 5,000 to about 11,000. Examples of this type of non-ionic surfactant include TETRON (commercially available from BASF).
IC) Certain of the compounds.

5. Semi-polar nonionic surfactants are a special category of nonionic surfactants, such as those with about 10 carbon atoms.
A water-soluble amine oxide containing from 1 to about 18 alkyl moieties and 2 moieties selected from the group consisting of alkyl and hydroxyalkyl groups having from about 1 to about 3 carbon atoms; alkyl moieties having from about 10 to about 18 carbon atoms A water-soluble phosphine oxide containing one and two moieties selected from the group consisting of alkyl and hydroxyalkyl groups of about 1 to about 3 carbon atoms; and one alkyl moiety of about 10 to about 18 carbon atoms and carbon number Water-soluble sulfoxides containing one moiety selected from the group consisting of about 1 to about 3 alkyl and hydroxyalkyl moieties.

As a semipolar nonionic detergent surfactant, the formula Wherein R ³ is an alkyl, hydroxyalkyl, or alkylphenyl group having from about 8 to about 22 carbon atoms or a mixture thereof; R ⁴ is an alkylene or hydroxyalkylene group having from about 2 to about 3 carbon atoms, or a mixture thereof. A mixture; x
Is from 0 to about 3; each R ⁵ is an alkyl or hydroxyalkyl group having about 1 to about 3 carbon atoms or a polyethylene oxide group containing about 1 to about 3 ethylene oxide groups. Agents. R ⁵ groups can, for example, can be bonded together to form a ring structure through an oxygen or nitrogen atom.

These amine oxide surfactants include, in particular, C
₁₀ -C ₁₈ alkyl dimethyl amine oxides and C ₈ -C ₁₂
Alkoxyethyl dihydroxyethylamine oxide is exemplified.

6. Hydrophobic groups of about 6 to about 30, preferably about 10 to about 16, carbon atoms and about 1.3 to about 10, preferably about 1.3 to about 3, most preferably about 1.3 to about 2.7 sugar units. Containing polysaccharides (eg, polyglycosides) with hydrophilic groups, January 1986
Alkyl polysaccharides disclosed in U.S. Pat. No. 4,565,647 to Lenado, issued on the 21st. Any reducing sugar having 5 or 6 carbon atoms can be used, for example, glucose, galactose and galactosyl moieties can be used in place of the glucosyl moieties (optionally, the hydrophobic group can be attached at the 2-, 3-, 4-, etc. To give glucose or galactose as opposed to glucoside or galactoside). The intersugar linkage can be, for example, between position 1 of the additional sugar unit and positions 2, 3, 4, and / or 6 on the previous sugar unit.

In some cases, although less desirable, there may be a polyalkylene oxide chain linking the hydrophobic and polysaccharide moieties. The preferred alkylene oxide is ethylene oxide. Typical hydrophobic groups include from about 8 to about
18, preferably from about 10 to about 16 saturated or unsaturated branched or unbranched alkyl groups. Preferably, the alkyl group is a straight-chain saturated alkyl group. The alkyl group can contain up to about 3 hydroxy groups and / or the polyalkylene oxide chain can contain up to about 10, preferably less than 5, alkylene oxide moieties. Suitable alkyl polysaccharides are octyl, nonyldecyl, undecyldodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, and octadecyl, di-, tri-, tetra-, penta-,
And hexaglucoside, galactoside, lactoside,
Glucose, fructoside, fructose and / or galactose. Suitable mixtures include coconut alkyl, di-, tri-, tetra-, and pentaglucoside and tallowalkyl tetra-, penta-,
And hexaglucoside.

Preferred alkyl polyglycosides are those wherein ^{_{R 2 O (C n H 2n}} O) t ( glycosyl) _{x (formula,} R ² is selected alkyl, alkylphenyl, hydroxyalkyl, hydroxyl alkyl phenyl, and mixtures thereof And the alkyl group has about 10 to about 18, preferably about 12 to about 14, carbon atoms; n is 2 or 3, preferably 2, and t is 0 to about 1
0, preferably 0; x is about 1.3 to about 10, preferably about
1.3 to about 3, most preferably about 1.3 to about 2.7). Glycosyl is preferably derived from glucose. To produce these compounds, first, an alcohol or alkyl polyethoxy alcohol is produced,
Then reacting with glucose or a glucose source,
Produces glucoside (linked at position 1). Additional glycosyl units can then be linked between their 1-position and the 2-, 3-, 4- and / or 6-position of the previous glycosyl unit, preferably mainly 2.

7. Fatty acid amide surfactant having the following formula [In the formula, R ⁶ has about 7 to about 21 carbon atoms (preferably about 9 to about 1 carbon atoms)
7) wherein each R ⁷ is hydrogen, C ₁ -C ₄ alkyl, C ₁ -C ₄ hydroxyalkyl, and — (C ₂ H ₄ O) _x H
] Preferred amides selected from the group consisting of (wherein, x is from about 1 to about 3), C ₈ -C ₂₀ ammonia amides, monoethanolamides, diethanolamides, and isopropanol amides.

Cationic surfactants Cationic detergent surfactants can also be included in the detergent compositions of the present invention. Examples of the cationic surfactant include an ammonium surfactant such as an alkyldimethylammonium halide and a compound represented by the formula [R ² (OR ³ ) _y ] [R ⁴ (OR ³ ) _y ] ₂ R ⁵ N ⁺ X ⁻ [formula Wherein R ² is an alkyl or alkyl benzyl group having about 8 to about 18 carbon atoms in the alkyl chain;
R ³ is _{-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 a C ₁ -C ₄ alkyl, C ₁ -C ₄ hydroxyalkyl, benzyl, linking two R ⁴ groups A ring structure formed by: —CH ₂ CHOH—CHOHCOR ⁶ CHOHCH ₂ OH (where R ⁶ is hexose or a hexose polymer having a molecular weight of less than about 1000) and hydrogen (when y is not 0)
Selected from the group consisting of; R ⁵ is either an alkyl chain is the same as R ^4, the total number of carbon atoms of R ² + R ⁵ is from about 18 or less; each y is from 0 to about 10, y The sum of the values is from 0 to about 15; and X is a compatible anion.

Other cationic surfactants useful here are also available from October 1980
No. 4,228,044, issued May 14, issued to Cambre, incorporated herein by reference.

Other Surfactants Amphoteric surfactants can be included in the present detergent compositions. These surfactants are aliphatic derivatives of secondary or tertiary amines in which the aliphatic groups can be straight-chain or branched, or aliphatic derivatives of complex secondary and tertiary amines. It can be widely described as a derivative. One of the aliphatic substituents has at least 8 carbon atoms, typically from about 8 to about 18 carbon atoms, and at least one has an anionic water solubilizing group, for example, carboxy, sulfonate, sulfate. It contains. For examples of amphoteric surfactants, see December 30, 1975.
See U.S. Pat. No. 3,929,678 to Rollin et al., Column 19, lines 18-35, incorporated by reference herein.

Zwitterionic surfactants can also be incorporated into the detergent compositions herein.
These surfactants include derivatives of secondary and tertiary amines, derivatives of heterocyclic secondary and tertiary amines, or derivatives of quaternary ammonium, quaternary phosphonium or tertiary sulfonium compounds. Can be widely described. For examples of amphoteric surfactants, see U.S. Pat. No. 3,929,678, issued Dec. 30, 1975, column 19, line 38 to column 22, line 48 (incorporated herein by reference). reference.

Amphoteric and amphoteric surfactants generally comprise 1
Used in combination with one or more anionic surfactants and / or nonionic surfactants.

In addition to enzymes, polyhydroxy fatty acid amides, and optional detergent surfactants, the present invention relates to one or more other detergent auxiliary substances or cleaning performance, detergent complexes that facilitate or enhance the treatment of the substrate to be cleaned. Other materials for modifying the aesthetics of the material or modifying the materials (eg, fragrances, colorants, dyes, etc.) can be included.

Builders Detergent builders can optionally be incorporated into the present compositions to help control mineral hardness. Inorganic and organic builders can be used.

The amount of builder can vary widely depending on the end use of the composition and the desired physical form. When present, the composition typically comprises at least about 1% builder
Will be included. Liquid formulations typically comprise from about 5 to about 50% by weight of the detersive builder, more typically from about 5 to about 30% by weight. Granular formulations are typically based on detersive builders.
10 to about 80% by weight, more typically about 15 to about 50% by weight. However, less but more builders
Does not mean to exclude.

Inorganic detergency builders include, but are not limited to, polyphosphoric acid (exemplified by tripolyphosphate, pyrophosphate, and glassy polymeric metaphosphate), phosphonic acid, phytic acid, silicic acid, carbonic acid (including bicarbonate and sesquicarbonate) ), Sulfuric acid, and alkali metal, annium and alkanolammonium salts of aluminosilicates. Borate builders as well as builders containing borate-forming substances capable of forming borate under detergent storage or washing conditions (hereinafter collectively "borate builders") can also be used. Preferably, non-borate builders are used in the compositions of the present invention that are to be used under wash conditions of less than about 50 ° C, especially less than about 40 ° C.

Examples of silicate builders are alkali metal silicates,
In particular those having an SiO ₂ : Na ₂ O ratio of 1.6: 1 to 3.2: 1 and layered silicates, for example, US Pat. No. 4,664,839 issued May 12, 1987 to HP Ricke, incorporated herein by reference. And the layered sodium silicate described in 1. above. However, other silicates, such as magnesium silicates, may also be used, which can serve as a crispness agent in granular formulations, as a fixative for oxygen bleaches, and as a component of the foam control system.

Examples of carbonate builders include sodium carbonate and sodium sesquicarbonate and those disclosed in German Patent Application No. 2,321,001, published Nov. 15, 1973, the disclosure of which is incorporated herein by reference. Alkaline earth metal and alkali metal carbonates, including mixtures with fine calcium carbonate.

Aluminosilicate builders are particularly useful in the present invention. Aluminosilicate builders are of great importance in most currently marketed heavy duty granular detergent compositions and can be a significant builder component in liquid detergent compositions. As an aluminosilicate builder, the empirical formula M _z (zAlO ₂ .y SiO ₂ ) wherein M is sodium, potassium, ammonium or substituted ammonium, z is from about 0.5 to about 2;
Is 1), which has a magnesium ion exchange capacity of at least 50 mg equivalent of CaCO ₃ hardness per gram of anhydrous aluminosilicate. Preferred aluminosilicates have the formula Na _z [(AlO ₂ ) _z (SiO ₂ ) _y ] xH ₂ O, where z and y are integers of at least 6, and the molar ratio of z to y is from 1.0 to about 0.5. Where x is from about 15 to about
Which is an integer of 264).

Useful aluminosilicate ion exchange materials are commercially available. These aluminosilicates can be crystalline or amorphous in structure and can be naturally occurring aluminosilicates or synthetically derived.
The method for producing aluminosilicate ion-exchange materials was October 1976.
No. 3,985,669 issued to Krumel et al. On May 12, which is incorporated herein by reference. Preferred synthetic crystalline aluminosilicate ion exchange materials useful herein are designated Zeolite A, Zeolite P
(B), and zeolite X. In a particularly preferred embodiment, the crystalline aluminosilicate ion exchange material has the formula Na _{12 [(AlO 2) 12 (SiO 2} ) 12 ] · xH ₂ O (wherein, x is from about 20 to about 30, especially about 27 There is). This material is known as zeolite A. Preferably, the aluminosilicate has a diameter of about 0.1
It has a particle size of ~ 10μ.

Specific examples of polyphosphates include alkali metal tripolyphosphates, sodium, potassium and ammonium pyrophosphates, sodium, potassium and ammonium pyrophosphates, sodium and potassium orthophosphates, having a degree of polymerization of about 6 to about 21. Certain sodium polymetaphosphate and salts of phytic acid.

Examples of phosphonate builder salts are the water-soluble salts of ethane-1-hydroxy-1,1-diphosphonic acid, especially the sodium and potassium salts, the water-soluble salts of methylene diphosphonic acid, such as the trisodium and tripotassium salts and Water-soluble salts of substituted methylene diphosphonic acids, such as trisodium and tripotassium ethylidene, isopropylidenebenzylmethylidene and halomethylidene diphosphonates. Phosphonate builder salts of the foregoing type are disclosed in U.S. Pat.Nos. 3,159,581 and 3,213,030 issued to Deal on December 1, 1964 and October 19, 1965; U.S. Pat. Patent 3,422,021
Issue No. 3 and 1969 to Quinnby, September 3, 1968
No. 3,400,148 and U.S. Pat. No. 3,422,137, issued Jan. 14, 1998, the disclosure of which is incorporated herein by reference.

Suitable organic detergency builders for the purpose of the present invention include:
Without limitation, various polycarboxylate compounds are included. The "polycarboxylate" used here is
A compound having a plurality of carboxylate groups, preferably at least three carboxylate is meant.

The polycarboxylate builder can generally be added to the composition in acid form, but can also be added in the form of a neutralized salt. When used in a salt form, an alkali metal salt such as a sodium salt, a potassium salt, and a lithium salt, or an alkanolammonium salt is preferable.

Polycarboxylate builders include various categories of useful substances. One important category of polycarboxylate builders includes ether polycarboxylates. A number of ether polycarboxylates for use as detergency builders have been disclosed.
Examples of useful ether polycarboxylates include 19
Oxydiscudinates as disclosed in Berg U.S. Pat. No. 3,128,287 issued Apr. 7, 644 and Lamberke et al. U.S. Pat. No. 3,635,830 issued Jan. 18, 1972 (both). And incorporated herein as a reference).

Specific types of ether polycarboxylates useful as builders in the present invention include those of the general formula CH (A) (COOX) -CH (COOX) -O-CH (COOX) -CH (COOX) (B) , A is H or OH; B is H or -O-CH
(COOX) a -CH ₂ (COOX), X can be mentioned those having a a a) H or a salt-forming cation. For example, in the above general formula, A
If and B are both H, the compound is oxydisuccinic acid and its water-soluble salts. A is OH, B is H
If is, the compound is tartrate monosuccinic acid (TMS) and its water-soluble salts. A is H, B is -O
If a _{-CH (COOX) -CH 2 (COOX} ), the compound,
Tartrate disuccinic acid (TDS) and its water-soluble salts. Mixtures of these builders are particularly preferred for use herein. TMS to TDS weight ratio of about 97: 3 to about 20:80
Particularly preferred is a mixture of TMS and TDS. These builders are disclosed in U.S. Pat. No. 4,663,071, issued May 5, 1987 to Bush et al.

Suitable ether polycarboxylates include cyclic compounds, especially alicyclic compounds, for example, U.S. Pat.Nos. 3,923,679, 3,835,163, 4,158,
No. 635, No. 4,120,874 and No. 4,102,903
And those described in the above specification (all of which are incorporated herein by reference).

Other useful detergency builders include the structure HO- [C (R) (COOM) -C (R) (COOM) -O] _n- H _where M is hydrogen or a cation (the resulting salt or Water soluble), preferably an alkali metal, ammonium or substituted ammonium cation, wherein n is from about 2 to about 15 (preferably, n is from about 2 to about 10, more preferably n is an average of from about 2 to about 4 ), Each R is the same or different, hydrogen,
Selected from C _1-4 alkyl or C _1-4 substituted alkyl (preferably, R is hydrogen)].

As other ether polycarboxylates, a copolymer of maleic anhydride and ethylene or vinyl methyl ether, 1,3,5-trihydroxybenzene-2,4,6-
Trisulfonic acid, and carboxymethyloxysuccinic acid.

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

Also included are polycarboxylates such as melitic acid, succinic acid, oxydisuccinic acid, polymaleic acid, benzene-1,3,5-tricarboxylic acid, carboxymethyloxysuccinic acid, and soluble salts thereof.

Citric acid-based builders, such as citric acid and its soluble salts (particularly the sodium salt), are polycarboxylate builders of particular importance to heavy duty liquid detergent formulations, but can also be used in particulate compositions.

Another carboxylate builder, March 1973
Carboxylated carbohydrates are disclosed in Deal US Pat. No. 3,723,322, issued on the 28th, incorporated herein by reference.

Also, U.S. Pat.
3,3-Dicarboxy-4-oxa-1,6-hexanediate and related compounds disclosed in US Pat. No. 566,984 (hereby incorporated by reference) are suitable in the detergent compositions of the present invention. Useful succinic acid builders include C ₅ -C ₂₀ alkyl succinic acids and salts thereof. A particularly preferred compound of this type is dodecenyl succinic acid.
Alkyl succinic acids typically have the general formula R-CH (CO
OH) CH ₂ (COOH), that is, a derivative of succinic acid, wherein R is a hydrocarbon, such as C ₁₀ -C ₂₀ alkyl or alkenyl, preferably C ₁₂ -C ₁₆ , or R
May be substituted with hydroxyl, sulfo, sulfoxy or sulfone substituents as described in said patent).

The succinate builder is preferably used in the form of a water-soluble salt, including sodium, potassium, ammonium and alkanolammonium salts.

Specific examples of succinate builders include lauryl succinate, myristyl succinate, palmityl succinate, 2-dodecenyl succinate (preferred), 2-pentadecenyl succinate, and the like. Lauryl succinate is a preferred builder of this group and is described in European Patent Application No. 86200690.5 / 0,200,263 published Nov. 5, 1986.

Examples of useful builders include sodium and potassium carboxymethyloxymalonates, carboxymethyloxysuccinates, cis-cyclohexanehexacarboxylate, cis-cyclopentanetetracarboxylate, water-soluble polyacrylic acid Salts (these polyacrylates having a molecular weight of greater than about 2,000 can also be usefully employed as dispersants), and salts of maleic anhydride and vinyl methyl ether or ethylene copolymers.

Other suitable polycarboxylates are the polyacetal carboxylates disclosed in U.S. Pat. No. 4,144,226 issued March 13, 1979 to Curtchfield et al., Which is incorporated herein by reference. These polyacetal carboxylates can be produced as described below.
The ester of glyoxylic acid and the polymerization initiator are placed together under polymerization conditions. The resulting polyacetal carboxylate is then attached to chemically stable end groups to stabilize the polyacetal carboxylate against rapid depolymerization in alkaline solution, convert it to the corresponding salt, Add to the agent.

Polycarboxylate builders are also disclosed in Deal U.S. Pat. No. 3,308,067, issued Mar. 7, 1967, incorporated herein by reference. Examples of such a substance include water-soluble salts of homopolymers and copolymers of aliphatic carboxylic acids such as maleic acid, itaconic acid, mesaconic acid, fumaric acid, aconitic acid, citraconic acid, and methylenemalonic acid.

Other organic builders known in the art can also be used. For example, monocarboxylic acids having long chain hydrocarbyl and their soluble salts can be utilized. These include substances commonly referred to as "soaps". Chain length of C ₁₀ -C ₂₀ are typically utilized. Hydrocarbyls can be saturated or unsaturated.

Bleaching Compounds-Bleaching Agents and Bleaching Activators The detergent compositions herein may contain bleaching agents or bleaching compositions containing a bleaching agent and one or more bleaching activators. When present, the bleaching compound typically comprises from about 1% to about 20% of the detergent composition, more typically from about 1% to about 20%.
% Will be present. Generally, the bleaching compound is an optional ingredient in non-liquid formulations, such as granular detergents. If present, the amount of bleach activator will typically be from about 0.1% to about 60% of the bleaching composition, more typically from about 0.5% to about 40%.
%Will.

The bleaches used herein can be any bleaches useful in detergent compositions for fabric cleaning, hard surface cleaning, or other cleaning now known or known. These include oxygen bleaches as well as other bleaches. Less than about 50 ° C, especially about 40 ° C
For less washing conditions, the composition preferably does not contain borates or substances capable of forming borates in situ under detergent storage or washing conditions (ie, borate-forming substances). Thus, under these conditions, it is preferred to use a non-borate, non-borate forming bleach. Preferably, the detergents to be used at these temperatures are substantially free of borate and borate producing substances. As used herein, "substantially free of borate and borate-forming substances" means that the composition contains no more than about 2%, preferably no more than 1%, more preferably no more than 0% by weight of borate-containing and borate-forming substances of any kind. Would mean containing.

One category of bleaches that can be used includes percarboxylic acid bleaches and their salts. Preferred examples of this type of bleach include magnesium monoperoxyphthalate hexahydrate, magnesium salt of m-chloroperbenzoic acid,
4-nonylamino-4-oxoperoxybutyric acid and diperoxidedecanedioic acid. Such bleaches are disclosed in Hartman, U.S. Pat.
No. 483,781, U.S. Patent Application No. 740,446 to Barnes et al. Filed on Jun. 3, 1985, European Patent Application No. 0,133,354 to Banks et al.
U.S. Patent No. 4,412,934 issued to Chung et al. On Nov. 1, 1991, all of which are incorporated herein by reference.
Is disclosed. Highly preferred bleaches include US Pat. No. 4,634,551 issued Jan. 6, 1987 to Vans et al.
Also mentioned are 6-nonyl-amino-6-oxoperoxycaproic acid described in the specification (herein incorporated by reference).

Another category of bleaches that can be used includes halogen bleaches. Examples of hypohalite bleaches include, for example, trichloroisocyanuric acid and sodium dichloroisocyanurate and potassium dichloroisocyanurate and N-chloro and N-bromoalkanesulfonamides. Such materials are usually
It is added at 0.5 to 10% by weight, preferably 1 to 5% by weight.

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

The peroxygen bleach is preferably combined with a bleach activator, which results in in-situ formation in an aqueous solution of the peroxyacid corresponding to the bleach activator (ie, during the washing process).

Preferred bleaching activators incorporated in the compositions of the present invention have the general formula Wherein R is an alkyl group having about 1 to about 18 carbon atoms and the longest linear alkyl chain extending from and including the carbonyl carbon has about 6 to about 10 carbon atoms. , L is a leaving group, the conjugate acid pK _a about 4
(With about 13). These bleach activators were supplied to Mao et al. In April 1990.
It is described in U.S. Pat. No. 4,915,854, issued on Dec. 10, which is hereby incorporated by reference, and in U.S. Pat. No. 4,412,934, hereby incorporated by reference herein.

Bleaches other than oxygen bleaches are known in the art and can be used herein. One type of non-oxygen bleach of particular interest includes light activated bleach, such as sulfonated zinc phthalocyanine and / or aluminum phthalocyanine. These substances can be deposited on the substrate during the cleaning process. Upon irradiation with light in the presence of oxygen by hanging the cloth to dry in sunlight, the sulfonated zinc phthalocyanine is activated and thus the substrate is bleached. Preferred zinc phthalocyanine and light activated bleaching methods are described in U.S. Pat. No. 4,033,718, issued Jul. 5, 1977, to Holcombe et al., Incorporated herein by reference. Typically,
The detergent composition contains about 0.025 of a sulfonated zinc phthalocyanine.
~ 1.25% by weight.

Polymeric Soil Release Agent Any polymeric soil release agent known to those skilled in the art can be used in the practice of the present invention. The polymeric soil release agent adheres to the hydrophobic fibers with hydrophilic segments to hydrophilize the surface of the hydrophobic fibers, such as polyester, nylon, etc., and remains adhered throughout the washing and rinsing cycles, thus. And a hydrophobic segment to serve as an anchor for the hydrophilic segment. This can make it easier to clean up stains that occur after treatment with the soil release agent in a later cleaning procedure.

It would be beneficial to utilize a polymeric soil release agent in any of these detergent compositions, especially in laundry or other applications where removal of grease / oil from hydrophobic surfaces is required. However, the presence of polyhydroxyfatty acid amides in detergent compositions that also contain anionic surfactants can enhance the performance of many of the more commonly utilized polymeric soil release agents. Anionic surfactants interfere with the ability of certain soil release agents to adhere and adhere on hydrophobic surfaces. These polymeric soil release agents have nonionic hydrophilic or hydrophobic segments that are anionic surfactant interacting.

Improved polymeric soil release agent performance can be obtained by the use of polyhydroxy fatty acid amides, the compositions herein include anionic surfactant systems, anionic surfactant interactive soil release agents and soil release agent enhancements Containing an amount of polyhydroxyfatty acid amide (PFA) [(I) the anionic surfactant interaction between the soil release agent of the detergent composition and the anionic surfactant system comprises (A) A "control" run measuring the adhesion of a soil release agent (SRA) of a detergent composition in an aqueous solution in the absence of detergent components and (B) the same type and amount of anionic surfactant used in the detergent composition Hydrophobic fibers (e.g., polyester) in an aqueous solution during the "SRA / anionic surfactant" test where the agent system is combined with the SRA in an aqueous solution at the same weight ratio of the SRA to the anionic surfactant system of the detergent composition ) On the soil release agent ( SRA) can be shown by comparison of the amount of deposition, whereby the reduced deposition of (B) compared to (A) indicates anionic surfactant interaction; and (II) the detergent composition Whether or not the soil release agent-enhancing amount of polyhydroxy fatty acid amide is contained is determined by comparing the (B) SRA adhesion of the SRA / anionic surfactant test and (C) the same type and amount of the polyhydroxy fatty acid amide of the detergent composition. It can be determined by comparing the soil release agent corresponding to the SRA / anionic surfactant test run and the soil release agent deposition in the `` SRA / anionic surfactant / PFA test run '' combined with the anionic surfactant system. The improved adhesion of the soil release agent in test run (C) as compared to test run (B) thereby indicates that soil release agent enhancing amounts of polyhydroxy fatty acid amide are present]. For the purposes herein, the tests herein are performed at an anionic surfactant concentration in an aqueous solution higher than the critical micelle concentration (CMC) of the anionic surfactant, preferably at an anionic surfactant concentration higher than about 100 ppm. Should. The polymeric soil releaser concentration should be at least 15 ppm. A sample of a polyester fabric should be used for the source of hydrophobic fibers. The same swatch is immersed in a 35 ° C. aqueous solution for each test run for 12 minutes, stirred, then removed and analyzed. The polymeric soil release agent coverage can be measured by radiolabeling the soil release agent prior to treatment and then performing a radiochemical analysis according to techniques known in the art.

Instead of the radiochemical analysis method, the soil release agent deposition is
According to techniques well known in the art, the test run (ie, test run A,
B and C) or can be measured. Reduced UV absorbance in test solution after removal of hydrophobic fiber material was increased
Corresponds to SRA adhesion. As will be appreciated by those skilled in the art, UV analysis involves the use of large amounts of surfactants (e.g., alkylbenzenesulfonate, etc.) with types and amounts of substances that cause excessive UV absorbance interference, e.g., aromatic groups. It should not be used for included test solutions. Thus, a "soil release agent-enhancing amount" of polyhydroxyfatty acid amide is defined as an amount of such a surfactant, or an increased amount of grease / Oil cleaning performance refers to the amount that can be obtained in the subsequent cleaning operation of a fabric that has been washed with the detergent composition herein.

The amount of polyhydroxy fatty acid amide required to enhance adhesion will depend on the anionic surfactant selected, the amount of anionic surfactant, the particular soil release agent selected, and the particular polyhydroxy fatty acid amide. Will change. Generally, the composition will have a polymeric soil release agent of about 0.01 to
About 10% by weight, typically about 0.1 to about 5% by weight, and about 4 to about 50% by weight of the anionic surfactant, more typically about 5% by weight.
About 30% by weight. Although not required to be limiting, such compositions should generally contain at least 1%, preferably at least about 3%, by weight of the polyhydroxy fatty acid amide.

Polymeric soil release agents whose performance is enhanced by polyhydroxy fatty acid amides in the presence of anionic surfactants include (a) essentially (i) polyoxyethylene segments having a degree of polymerization of at least 2 or (ii) oxypropylene Or a polyoxypropylene segment having a degree of polymerization of 2 to 10 (the hydrophilic segment does not include oxypropylene unless attached at each end to an adjacent moiety by an ether linkage) or (iii) oxyethylene and 1 to about 30 A mixture of oxyalkylene units consisting of two oxypropylene units, the mixture being sufficient for the hydrophilic component to increase the hydrophilicity of the normal polyester synthetic fiber surface upon deposition of the soil release agent on the normal polyester synthetic fiber surface Contains a sufficient amount of oxyethylene units to have And, the hydrophilic segments are preferably oxyethylene units at least 25%, in the case of such a component having a more preferably particularly about 20-30 oxy propyne alkylene units oxyethylene units of at least about
One or more non-ionic hydrophilic components;
Or (b) (i) C ₃ oxyalkylene terephthalate segments (if the hydrophobic component also comprises oxyethylene terephthalate, the ratio of oxyethylene terephthalate pair C ₃ oxyalkylene terephthalate units is about 2: 1 or less), (ii) C ₄ -C ₆ alkylene or oxy C ₄ -C ₆ alkylene segments, or mixtures thereof, (iii) degree of polymerization of poly (vinyl ester) having at least two segments, preferably poly (vinyl acetate), or (iv C) C ₁ -C ₄ alkyl ether or C ₄ hydroxyalkyl ether substituents or mixtures thereof, said substituents being present in the form of C ₁ -C ₄ alkyl ether or C ₄ hydroxyalkyl ether cellulose derivatives or mixtures thereof; Such cellulose derivatives are amphiphilic, whereby Have a minute amount of C ₁ -C ₄ alkyl ether and / or C ₄ hydroxyalkyl ether units attached onto conventional polyester synthetic fiber surfaces and retain a sufficient amount of hydroxyl, once such conventional synthetic (A) increases the hydrophilicity of the fiber surface when adhered to the fiber surface), or (a)
And a soil release agent having a combination of (b).

Typically, standards higher than 200 can be used,
(A) The polyoxyethylene segment of (i) has a degree of polymerization of 2 to about 200, preferably 3 to about 150, and more preferably 6 to about 150.
Will have about 100. Preferred examples of oxy C ₄ -C ₆ alkylene hydrophobic segments, without limitation, Gosse link 1988 January 26 issued U.S. Pat. No. 4,721,580 as disclosed in (incorporated by reference herein) MO ₃ S
(CH ₂ ) _n OCH ₂ CH ₂ O— (where M is sodium and n
Is an integer of 4 to 6).

Polymeric soil release agents useful in the present invention include cellulosic derivatives such as hydroxyethercellulose polymers, copolymer blocks of ethylene terephthalate or propylene terephthalate and polyethylene oxide terephthalate or polypropylene oxide terephthalate, and the like.

Cellulosic derivatives that function as soil release agents are commercially available, and examples thereof Methocel (Methocel ^R)
(Dow) and the like.

Cellulosic soil release agents for use herein, methyl cellulose, ethyl cellulose, hydroxypropyl methyl cellulose, may be mentioned those selected from C ₁ -C ₄ alkyl and C ₄ group consisting of hydroxy alkyl celluloses such as hydroxypropyl methylcellulose. Various cellulose derivatives useful as soil release polymers are described in U.S. Pat.
No. 000,093, incorporated herein by reference.

Soil release agents characterized by poly (vinyl ester) hydrophobic segments include poly (vinyl esters), for example, graft copolymers of C ₁ -C ₆ vinyl esters, preferably polyalkylene oxides such as polyethylene oxide backbones Poly (vinyl acetate) grafted on the main chain is mentioned. Such materials are known in the art and are disclosed in European Patent Application No.
No. 0 219 048. Suitable commercially available soil release agents of this type include materials of the SOKALAN type, such as Sokalan HP available from BASF (West Germany).
-22.

One type of preferred soil release agent is a copolymer having random blocks of ethylene terephthalate and polyethylene oxide (PEO) terephthalate. More specifically, these polymers have a molar ratio of ethylene terephthalate units to PEO terephthalate units of from about 25:75 to about 3
It consists of a 5:65 repeating unit of ethylene terephthalate and PEO terephthalate, said PEO terephthalate unit containing polyethylene oxide having a molecular weight of about 300 to about 2000. The molecular weight of this polymeric soil release agent is about 25,000
In the range of ~ 55,000. See Haze, U.S. Pat. No. 3,959,230, issued May 25, 1976, incorporated herein by reference. See also U.S. Pat. No. 3,893,929 to Busder, issued Jul. 8, 1975, which discloses a similar copolymer, incorporated by reference.

Another preferred polymeric soil release agent has an average molecular weight of 300-300.
A polyester having repeating units of ethylene terephthalate units containing 10 to 15% by weight of ethylene terephthalate units together with 90 to 80% by weight of polyoxyethylene terephthalate units derived from 5,000 polyoxyethylene glycol, and The molar ratio of ethylene terephthalate units to polyoxyethylene terephthalate units is from 2: 1 to 6: 1. Examples of this polymer include the commercially available materials ZELCON 5126 (Dupont) and MILEASE T (ICI). These polymers and their manufacturing methods are available from Gosselink.
The details are described in U.S. Pat. No. 4,702,857, issued Oct. 27, 1987, which is incorporated herein by reference.

Another preferred polymeric soil release agent is the sulfonation product of a substantially linear ester oligomer consisting of an oligomeric ester backbone of terephthaloyl and oxyalkyleneoxy repeat units and a terminal moiety covalently bonded to the backbone (as described above. The release agent is derived from allyl alcohol ethoxylate, dimethyl terephthalate, and 1,2-propylene diol, and after sulfonation, the terminal portion of each oligomer has an average of about 1 to about 4 sulfonate groups in total). These soil release agents are disclosed in U.S. Pat.
4,968,451, U.S. Patent Application No. 07 / 474,709, filed January 29, 1990, incorporated herein by reference.
In detail.

Other suitable polymeric soil release agents include ethyl- or methyl-blocked 1,2-propylene terephthalate-polyoxyethylene terephthalate polyesters of U.S. Patent No. 4,711,730 issued December 8, 1987 to Gosselink et al. U.S. Pat. No. 4,721,580, issued Jan. 26, 1988 to Gosselink et al., Wherein the anionic endblocking oligomeric ester comprises a sulfo-polyethoxy group derived from polyethylene glycol (PEG); _{X- (OCH 2 CH 2) n} - ( wherein, n is 12 to about 43, X is C ₁ -C ₄ alkyl or, preferably, methyl) 19 Gosse link having polyethoxy end blockade
No. 4,702,857 issued Oct. 27, 1987, all of which are incorporated herein by reference.

Additional polymeric soil release agents include, for example, U.S. Patent No.
No. 4,877,896, which is incorporated herein by reference. Terephthalate esters contain asymmetrically substituted oxy-1,2-alkyleneoxy units. Material soil release polymers of U.S. Patent No. 4,877,896 is to have a C ₃ oxyalkylene terephthalate (propylene terephthalate) repeat units within the scope of the hydrophobic component of the polyoxyethylene hydrophilic component or wherein (b) (i) Is mentioned. Of particular benefit from the incorporation of the polyhydroxy fatty acid amides herein in the presence of an anionic surfactant are polymeric soil release agents characterized by one or both of these criteria.

If utilized, soil release agents generally comprise from about 0.01 to about 10.0% by weight of the detergent compositions of the present invention, typically from about 0.1 to about 0.1%.
It will comprise about 5% by weight, preferably about 0.2 to about 3.0% by weight.

Chelating Agents The detergent compositions of the present invention may also optionally contain one or more iron / manganese chelating agents as builder auxiliary substances. Such chelators can be selected from the group consisting of aminocarboxylates, aminophosphonates, polyfunctionally substituted aromatic chelators, and mixtures thereof, as defined below. Without wishing to be limited by theory, it is believed that the benefits of these materials are due, in part, to the exceptional ability to remove iron and manganese ions from the wash liquor by the formation of soluble chelates.

Aminocarboxylates useful as optional chelating agents in the compositions of the present invention comprise one or more (preferably at least two) units of substructure. Wherein M is hydrogen, alkali metal, ammonium or substituted ammonium (eg, ethanolamine) and x is 1 to about 3, preferably 1. Preferably, these aminocarboxylates do not contain alkyl or alkenyl groups having more than about 6 carbon atoms. Examples of usable amine carboxylate include ethylenediaminetetraacetate, N-hydroxyethylethylenediaminetriacetate, nitrilotriacetate, ethylenediaminetetrapropionate, triethylenetetraaminehexaacetate, diethylenetriaminepentaacetate and ethanoldiglycine, and alkali metal salts thereof. Ammonium salts, and substituted ammonium salts and mixtures thereof.

Aminophosphonates are also suitable for use as chelating agents in the compositions of the present invention when at least a small amount of total phosphorus is allowed in the detergent composition. Substructure of one or more (preferably at least two) units Wherein M is hydrogen, alkali metal, ammonium or substituted ammonium and x is from 1 to about 3, preferably 1
Are useful, examples include ethylenediaminetetrakis (methylene phosphonate), nitrilotris (methylene phosphonate) and diethylenetriamine pentakis (methylene phosphonate). Preferably, these aminophosphonates are
It does not contain alkyl or alkenyl groups having more than about 6 carbon atoms. Alkylene groups can be shared by substructures.

Also, polyfunctionally substituted aromatic chelators are useful in the present compositions. These substances have the general formula (Wherein at least one R a is -SO ₃ H or -COOH) may be a compound or their soluble salts, and mixtures thereof having. May 21, 1974 to Conner
U.S. Pat. No. 3,812,044, issued to Japan, incorporated herein by reference, discloses polyfunctionally substituted aromatic chelating / sequestering agents. A preferred compound of this type in the acid form is dihydroxydisulfobenzene, such as 1,2-dihydroxy-3,5-disulfobenzene. Alkaline detergent compositions use these materials as alkali metal salts, ammonium salts or substituted ammonium salts (eg, mono-
Or triethanolamine salt).

If utilized, these chelators are generally
It will comprise from about 0.1 to about 10% by weight of the detergent composition of the present invention. More preferably, the chelating agent will make up from about 0.1% to about 3.0% by weight of such compositions.

Clay soil removal / anti-redeposition agent The composition of the present invention can optionally also include a water-soluble ethoxylated amine having clay soil removal and anti-redeposition properties. Particulate detergent compositions containing these compounds typically contain from about 0.01 to about 10 water-soluble ethoxylated amines.
% By weight. Liquid detergent compositions typically contain from about 0.01 to about 5% by weight of a water-soluble ethoxylated amine.
These compounds are preferably selected from the group consisting of:

(1) Ethoxylated monoamine having the formula (XL-)-N- (R ² ) ₂ (2) Ethoxylated diamine having the formula (3) Ethoxylated polyamines having the general formula (4) An ethoxylated amine polymer having the formula: (5) a mixture thereof, wherein A ¹ is Or -O- and it is; R is H or C ₁ -C ₄ alkyl or hydroxyalkyl; R ¹ is C ₂ -C ₁₂ alkylene, hydroxyalkylene, alkenylene, arylene or alkarylene, or from 2 to about 20, A C ₂ -C ₃ oxyalkylene moiety having an oxyalkylene unit, with the proviso that no O—N bond is formed; each R ² is a C ₁ -C ₄ or hydroxyalkyl, moiety -LX or 2 R ² together have the moiety — (CH ₂ ) _r , —A ² — (CH ₂ ) _s — (where A ² is —O—
Or —CH ₂ —, r is 1 or 2, s is 1 or 2, r
+ S forms 3 or 4); X is a non-ionic group, an anionic group or a mixture thereof; R ³ is a substituted C ₃ -C ₁₂ alkyl group having a substitution site, a hydroxyalkylene group,
An alkenylene group, an aryl group, or an alkaryl group; R ⁴ is C ₁ -C ₁₂ alkylene, hydroxyalkylene,
Alkenylene, a C ₂ -C ₃ oxyalkylene moiety having arylene or alkarylene, or from 2 to about 20 oxyalkylene units, with the proviso O-O bond or O-
No N bond is formed; L is a polyoxyalkylene moiety-
_{^{[(R 5 O) m (CH}} 2 CH 2 O) n ] - (wherein, R ⁵ is C ₃ -C ₄ alkylene or hydroxyalkylene, m and n
Moiety _{- (CH 2 CH 2 O)} n - is a number such to occupy at least about 50% by weight of said polyoxyalkylene moiety)
And m is from 0 to about 4 and n is at least about 12;
In the case of the diamine, m is 0 to about 3 and n is R ¹
There C ₂ -C ₃ alkylene, hydroxyalkylene, or at least about 6, R ¹ is C ₂ -C ₃ alkylene when alkenylene,, at least about 3 when is other than hydroxy alkylene or alkenylene; said polyamines and amine polymers In the case of m is from 0 to about 10,
n is at least about 3; p is 3-8; q is 1 or 0; t is 1 or 0, where t is 1 when q is 1; Or 0; x + y + z is at least 2; y + z is at least 2] The most preferred soil release / anti-redeposition agent is ethoxylated tetraethylenepentamine. Exemplary ethoxylated amines are further described in Vandermeal U.S. Pat. No. 4,597,898, issued Jul. 1, 1986, which is incorporated herein by reference. Another group of preferred clay soil removal /
The anti-redeposition agent is a cationic compound disclosed in Oh and Gosselink European Patent Application No. 111,965, published June 27, 1984, which is incorporated herein by reference. Other clay stain removal / anti-redeposition agents that can be used include 19
Gosselink European Patent Application No. 111, published June 27, 1984
Ethoxylated amine polymer disclosed in specification 984; July 1984
And the amine oxide disclosed in Conner U.S. Pat. No. 4,548,744 issued Oct. 22, 1985. (All of them are incorporated herein by reference).

Other clay soil removers and / or anti-redeposition agents known in the art may also be utilized in the compositions herein. Another type of preferred anti-redeposition agent includes carboxymethyl cellulose (CMC) material. These materials are well known in the art.

Polymeric Dispersants Polymeric dispersants can advantageously be utilized in the compositions herein. These substances can help control calcium and magnesium hardness. Suitable polymeric dispersants include polymeric polycarboxylates and polyethylene glycols, although others known in the art can be used. Without being limited by theory, polymeric dispersants, when used in combination with other builders (including low molecular weight polycarboxylates), are thoroughly washed by crystal growth suppression, particulate soil release peptization, and anti-redeposition. Believed to enhance sex builder performance.

A polycarboxylate substance that can be used as a polymer dispersant has a general formula Wherein X, Y and Z are each selected from the group consisting of hydrogen, methyl, carboxy, carboxymethyl, hydroxy and hydroxymethyl; a salt-forming cation and n is from about 30 to about 400. These polymers or copolymers contain about 60% by weight. Preferably, X is hydrogen or hydroxy, Y is hydrogen or carboxy, Z
Is hydrogen and M is hydrogen, alkali metal, ammonia or substituted ammonium.

Such polymeric polycarboxylate materials can be prepared by polymerizing or copolymerizing a suitable unsaturated monomer, preferably in the acid form. Unsaturated monomeric acids that can be polymerized to produce suitable polymeric polycarboxylates include acrylic acid, maleic acid (or maleic anhydride), fumaric acid, itaconic acid, aconitic acid, mesaconic acid, citraconic acid and Methylene malonic acid. The presence of monomeric segments containing non-carboxylate groups, such as vinyl methyl ether, styrene, ethylene, etc., in the polymeric polycarboxylates of the present invention indicates that such segments do not constitute more than about 40% by weight If so, it is preferable.

Particularly suitable polymeric polycarboxylates can be derived from acrylic acid. Such acrylic acid based polymers useful herein are water soluble salts of polymerized acrylic acid. The average molecular weight of such an acid form polymer is about 2,
From 000 to 10,000, more preferably from about 4,000 to 7,000, most preferably from about 4,000 to 5,000. Examples of the water-soluble salt of the acrylic acid polymer include an alkali metal salt, an ammonium salt and a substituted ammonium salt. Such soluble polymers are known substances. The use of this type of polyacrylate in detergent compositions is described, for example, in Deal U.S. Pat. No. 3,308, March 7, 1967.
No. 067. This patent is incorporated herein by reference.

Acrylic / maleic acid based copolymers are also
It may be used as a preferred component of a dispersant / anti-redeposition agent. Examples of such a substance include a water-soluble salt of a copolymer of acrylic acid and maleic acid. The average molecular weight of such copolymers in the acid form is preferably from about 2,000 to 100,000, more preferably from about 5,000 to 75,000, and most preferably about 7,000
~ 65,000. The ratio of acrylate to maleate segments in such copolymers is generally about 3
It will be from 0: 1 to about 1: 1, more preferably from about 10: 1 to about 2: 1. Examples of the water-soluble salt of the acrylic acid / maleic acid copolymer include an alkali metal salt, an ammonium salt and a substituted ammonium salt. Such soluble acrylate / maleate copolymers are known substances described in European Patent Application No. 66915 published December 15, 1982, which is hereby incorporated by reference.

Another polymeric material that can be included is polyethylene glycol (PEG). PEG exhibits dispersant performance and can act as a clay soil remover / anti-redeposition agent. Typical molecular weight ranges for these purposes are from about 500 to about 100,000, preferably from about 1,000 to about 50,000, more preferably from about 1,500 to about
10,000.

Brightener Any optical or other brightener or whitening agent known in the art can be incorporated into the detergent compositions herein.

The choice of whitening agent for use in the detergent composition can be based on a number of factors including the type of detergent, the nature of the other components present in the detergent composition, the temperature of the wash water, the degree of agitation, and the ratio of the tub to the tub size. Will depend on the factors of

Brightener selection also depends on the type of material to be cleaned, for example, cotton, synthetics, and the like. As most selective detergent products are used to clean various fabrics, the detergent composition should contain a mixture of brighteners that would be effective for various fabrics. Of course, the individual components of such brightener mixtures need to be compatible.

Commercially available optical brighteners that may be useful in the present invention include:
The subgroups can be classified, and the subgroups are not necessarily limited, but include stilbene, pyrazoline, coumarin, carboxylic acid,
Examples include methine cyanine, dibenzothiphene-5,5-dioxide, azoles, derivatives of 5- and 6-membered heterocyclic compounds, and other miscellaneous drugs. Examples of such brighteners are "Production and Application of Optical Brighteners", M. Zaradnik, John Willy End, New York.
Sands (1982), the disclosure of which is incorporated herein by reference.

Stilbene derivatives useful in the present invention include, but are not necessarily limited to, bis (triazinyl) amino-stilbene derivatives; stilbene bisacylamino derivatives; stilbene triazole derivatives; stilbene oxadiazole derivatives; Oxazole derivatives; and styryl derivatives of stilbene.

Bis (triazinyl) that may be useful in the present invention
One derivative of aminostilbene is 4,4'-diamine-
It may be prepared from stilbene-2,2'-disulfonic acid.

Coumarin derivatives that may be useful in the present invention include, but are not necessarily limited to, 3-position, 7-position, and 3-position and 7-position.
Derivatives substituted at the position.

Carboxylic acid derivatives that may be useful in the present invention include, but are not necessarily limited to, fumaric acid derivatives; benzoic acid derivatives; p-phenylene-bis-acrylic acid derivatives; naphthalenedicarboxylic acid derivatives; heterocyclic acid derivatives; And cinnamic acid derivatives.

Cinnamic acid derivatives that may be useful in the present invention can be further subdivided into a plurality of groups, and these groups are not necessarily limited, as disclosed on page 77 of the Zaradonic literature. , Styrylazole, styrylbenzofuran, styryloxadiazole, styryltriazole, and styrylpolyphenyl.

Styrylazoles can be further subdivided into styrylbenzoxazoles, styrylimidazoles and styrylthiazoles as disclosed on page 78 of the Zaradonic literature. It will be appreciated that these three subclasses may not necessarily reflect an exhaustive list of subgroups that may subclass styrylazole.

Another type of optical brightener that may be useful in the present invention is the Kirk-Othmer Encyclopedia of Chemical Tech.
nology , vol. 3, pp. 737-750 (John Willy End Sun, Inc., 1962), the disclosures of which are incorporated by reference herein, pages 741-749. A derivative of thiophene-5,5-dioxide and 3,7-diaminodibenzothiophene-2,8-
5,5 Dioxide of disulfonic acid.

Another class of optical brighteners that may be useful in the present invention is azoles, which are derivatives of 5-membered heterocyclic compounds. These can be further subdivided into monoazoles and diazoles. Examples of monoazoles and diazoles are
It is disclosed in Kirk-Othmer's literature.

Another type of brightener that may be useful in the present invention is
Derivatives of the 6-membered heterocyclic compounds disclosed in Kirk-Osmer's literature. Examples of such compounds include brighteners derived from pyrazine and derivatives derived from 4-aminonaphthalamide.

In addition to the brighteners already described, miscellaneous drugs may also be useful as brighteners. Examples of such miscellaneous agents are disclosed in the Zaradonic literature at pages 93-95 and include 1-hydroxy-3,6,8-pyrenetrisulfonic acid; 2,4
-Dimethoxy-1,3,5-triazin-6-yl-pyrene;
4,5-di-phenylimidazolone disulfonic acid; and pyrazoline-quinoline derivatives.

Another specific example of an optical brightener that may be useful in the present invention is described in U.S. Pat.
No. 4,790,856, the disclosure of which is incorporated herein by reference. As these brighteners,
PHORWHITE series brighteners from Verona. Other brighteners disclosed in this document include:
Tinopal U available from Ciba Geigy
NPA, Tinopearl CBS and Tinopearl 5BM; Arctic White CC and Arctic White CWD available from Hilton-Davis, Italy; 2- (4-styrylphenyl) -2H-naphthol [1, 2-d] triazole; 4,4'-bis- (1,
2,3-triazol-2-yl) -stilbene; 4,4'-
Bis (styryl) bisphenyl; and y-aminocoumarin. Specific examples of these brighteners include:
4-methyl-7-diethylaminocoumarin; 1,2-bis (benzimidazol-2-yl) -ethylene; 1,3-diphenylfurazoline; 2,5-bis (benzoxazole-
2-yl) -thiophene; 2-styryl-naphtho- [1,2
-D] -oxazole; and 2- (stilbene-4-
Yl) -2H-naphtho [1,2-d] triazole.

Other optical brighteners that may be useful in the present invention include US Pat. No. 3,642, issued Feb. 29, 1972 to Hamilton.
No. 6,015, the disclosure of which is incorporated herein by reference.

Foam Inhibitors Known or becoming known compounds for reducing or inhibiting foam formation can be incorporated into the compositions of the present invention. The incorporation of such substances (hereinafter "foam inhibitors") may be desirable because the polyhydroxy fatty acid amide surfactants here can increase the foam stability of the detergent composition. Foam control may be of particular importance when the detergent composition includes a comparatively high foaming surfactant in combination with a polyhydroxy fatty acid amide surfactant. Foam control is particularly desirable for compositions intended to be used in front-loading automatic washing machines. These washing machines are typically characterized by having a horizontal axis and a drum for containing the wash / wash water having a rotating action about this axis. This type of agitation can result in high foam formation and therefore reduced cleaning performance. The use of inhibitors can also be of particular importance under hot water washing conditions and under high surfactant concentration conditions.

Various materials may be used as inhibitors in the compositions herein. Foam suppressants are well known to those skilled in the art. They are generally, for example, Kirk-Othmer Encyclopedia of Chemica
Technology, Third Edition, Volume 7, pp. 430-447 (John Wiley End Sons, Inc., 1979). One category of foam inhibitors of particular interest includes monocarboxylic fatty acids and their soluble salts. These substances are
US Patent No. 2,954, issued September 27, 1960 to St. John
No. 347, which patent is hereby incorporated by reference. Monocarboxylic fatty acids and their salts for use as foam suppressors typically have 10 carbon atoms.
It has a hydrocarbyl chain of up to about 24, preferably 12 to 18 carbon atoms. Suitable salts include alkali metal salts, for example,
Sodium, potassium, and lithium salts, and ammonium and alkanolammonium salts. These substances are a preferred category of inhibitors for detergent compositions.

The detergent composition may also contain a non-surfactant inhibitor. These include, for example, high molecular weight hydrocarbons,
For example, paraffins, fatty acid esters (eg, fatty acid triglycerides), fatty acid esters of monohydric alcohols,
Aliphatic C ₁₈ -C ₄₀ ketones (e.g., stearone), and the like. Other suds suppressors include N-alkylated aminotriazines, such as trialkylmelamines formed as the product of 2 or 3 moles of a primary or secondary amine having 1 to 24 carbon atoms and cyanuric chloride. Up to hexaalkylmelamine, or from dialkyldiaminechlorotriazine to tetraalkyldiaminechlorotriazine, propylene oxide, and monostearyl phosphates such as monostearyl alcohol phosphate and monostearyl dialkali metal (e.g.,
K, Na, Li) phosphates and phosphate esters. Hydrocarbons such as paraffins and haloparaffins are available in liquid form. The liquid hydrocarbon will be liquid at room temperature and atmospheric pressure and will have a pour point of about -40 ° C to about 5 ° C and a minimum boiling point of about 110 ° C or higher (atmospheric pressure). It is also known to utilize wax hydrocarbons, preferably those having a melting point below about 100 ° C. Hydrocarbons constitute a preferred category of inhibitors for detergent compositions. Hydrocarbon inhibitors are described, for example, in U.S. Pat. No. 4,265,779, issued May 5, 1981 to Gandolho et al., Incorporated herein by reference. Hydrocarbons thus include aliphatic, cycloaliphatic, aromatic and heterocyclic saturated or unsaturated hydrocarbons having about 12 to about 70 carbon atoms. The term "paraffin" as used in this defoamer discussion is intended to encompass a mixture of true paraffins and cyclic hydrocarbons.

Another preferred category of non-surfactant inhibitors consists of silicone inhibitors. This category includes polyorganosiloxane oils such as polydimethylsiloxane, dispersions or emulsions of polyorganosiloxane oils or resins,
And the use of a combination of a polyorganosiloxane oil and silica particles, where the polyorganosiloxane chemisorbs or melts on the silica. Silicone inhibitors are well known in the art and are described, for example, in Gandolho et al.
U.S. Pat. No. 4,265,779, issued in the United States, and European Patent Application No. 893078 issued February 7, 1990 by MS Starch.
No. 51.9, both of which are incorporated herein by reference.

Other silicone inhibitors are disclosed in U.S. Patent No. 3,455, which relates to a method for defoaming an aqueous solution by incorporating the composition and a small amount of a polydimethylsiloxane fluid into the aqueous solution.
No. 839.

Mixtures of silicone and silanized silica, for example,
It is described in German patent application DOS 2,124,526. Silicone defoamers and antifoams in granular detergent compositions are disclosed in U.S. Pat. No. 3,933,672 to Bartrotta et al. And U.S. Pat. No. 4,652,392 to Bangginsky et al. Issued Mar. 24, 1987. .

Exemplary silicone-based suds suppressors for use herein are essentially: (i) a polydimethylsiloxane fluid having a viscosity at 25 ° C. of about 20 cs to about 1500 cs; (ii) (i) per 100 parts by weight about 5 to about 50 parts, (CH _3)
3 The ratio of SiO _1/2 units to SiO ₂ units from about 0.6: 1 to about 1.2: 1 (C
A and (iii) (i) anti-foaming amount of suds control agent comprising from about 1 to about 20 parts of a solid silica gel per 100 parts by weight; H _{3) 3} SiO _1/2 units and consisting of SiO ₂ Metropolitan siloxane resin.

In the case of detergent compositions to be used in automatic washing machines, the foam should not form to the extent that it overflows the washing machine. Inhibitors, when utilized, are preferably present in a "foam inhibiting amount". "Foam control" means that the formulator of the composition can select the amount of this foam control agent that will provide sufficient control of the foam to produce a low foaming laundry detergent for use in automatic washing machines. Means The degree of foam control will vary depending on the detergent surfactant chosen. For example, in the case of high foaming surfactants, a relatively large amount of foam control agent is used to achieve the desired foam control than in the case of low foaming surfactants. In general, a sufficient amount of foam inhibitor is sufficient to form bubbles during the washing cycle of an automatic washing machine (i.e., during agitation of the detergent in an aqueous solution under the desired washing temperature and concentration conditions). The low foaming detergent composition should be incorporated into the low foaming detergent composition such that no more than about 75% of the deposition, preferably no more than about 50% of the void volume (void volume is the total volume of the storage drum plus water plus Determined as the difference between the volume of the laundry).

The compositions herein will generally contain from 0% to about 5% of a foam inhibitor. When utilized as suds suppressors, the monocarboxylic fatty acids and their salts will typically be present in amounts up to about 5% by weight of the detergent composition. Preferably,
About 0.5% to about 3% of the fat monocarboxylate foam inhibitor
Used. Although large amounts may be used, silicone suds suppressors are typically utilized in amounts up to about 2.0% by weight of the detergent composition. This upper limit is practical in nature mainly due to concerns about small amounts of effectiveness to keep costs to a minimum and to effectively control foam. Preferably, from about 0.01% to about 1% of the silicone foam inhibitor, more preferably from about 0.25% to
About 0.5% is used. These weight percent values used herein are silica, which may be used in conjunction with the polyorganosiloxane,
As well as auxiliary substances that may be utilized. Monostearyl phosphate is generally utilized in an amount of about 0.1 to about 2% by weight of the composition.

Although large amounts can be used, hydrocarbon suds suppressors are typically utilized in amounts of about 0.01% to about 5.0%.

Other Ingredients Various other ingredients useful in detergent compositions, such as other active ingredients, carriers, hydrotropes, processing aids, dyes or pigments, liquid formulation solvents, and the like, can be incorporated into the compositions herein. .

Liquid detergent compositions can contain water and other solvents as carriers. Preferred are low molecular weight primary or secondary alcohols exemplified by methanol, ethanol, propanol, and isopropanol. Monohydric alcohols are preferred for solubilizing surfactants, but polyols, such as those containing about 2 to about 6 carbon atoms and about 2 to about 6 hydroxy groups (eg, propylene glycol, ethylene Glycol, glycerin, and 1,2-propanediol) can also be used.

The detergent compositions herein will preferably be formulated such that when used in an aqueous cleaning operation, the wash water has a pH of about 6.5 to about 11, preferably about 7.5 to about 10.5. Liquid product formulations preferably have a pH of about 7.5 to about 9.5, more preferably about 7.5 to about 9.0. Techniques for controlling pH to recommended use levels include the use of buffers, alkalis, acids and the like and are well known to those skilled in the art.

In addition, the present invention provides for the use of anionic performance enhancing polyhydroxyfatty acid amide surfactants, typically at least about 1% of such surfactants, to provide anionic, nonionic surfactants. Activator and / or
Alternatively, there is provided a method for improving the performance of a detergent containing a cationic surfactant and a detergent enzyme.

Further, the present invention provides a method for treating a substrate, such as a fiber, fabric, hard surface, skin, etc., in the presence of a solvent, such as water, a water-miscible solvent (eg, primary and secondary alcohols), with one or more detergent enzymes. A detergent composition comprising an anionic surfactant, a nonionic surfactant or a cationic surfactant, wherein the detergent composition comprises an enzyme-enhancing amount of a polyhydroxyfatty acid amide, typically at least 1% by weight of the composition. (Containing a polyhydroxyfatty acid amide) by cleaning the substrate. Agitation is preferably provided to enhance cleaning. Suitable means for providing agitation include hand rubbing, or preferably using a brush, sponge, cloth, mop or other cleaning device, automatic washing machines, automatic dishwashers, etc. Is mentioned.

Experiment This illustrates the preparation of N-methyl-1-deoxyglucityl lauramide surfactant for use herein. Although skilled chemists can vary the device geometry, one device suitable for use herein is one equipped with a thermometer long enough to contact the reaction medium and a motor driven paddle stirrer. Consists of a four-necked flask. The other two ports of the flask were equipped with a nitrogen sweep and a wide bore arm (Note:
The wide bore arm is important in the case of very rapid methanol generation), which is connected to an efficient collection cooler and vacuum outlet. The latter is connected to a nitrogen bleed / vacuum gauge and then to an aspirator and trap. Variable transformer temperature controller used to heat the reaction mixture [Variac]
A heating mantle of 500 W with the following is placed on the lab-jack so that it can be easily raised and lowered to further control the temperature of the reaction mixture.

N-methylglucamine (195 g, 1.0 mol, Aldrich, M4700-0) and methyl laurate (Procter & Gamble CE1270, 220.9 g, 1.0 mol) are placed in a flask. The solid / liquid mixture is heated under stirring and a nitrogen sweep to prepare a melt (about 25 minutes). Melting temperature
When 145 ° C. is reached, the catalyst (anhydrous sodium carbonate in powder form, 10.5 g, 0.1 mol, JT Baker) is added. Stop the nitrogen sweep and adjust the aspirator and nitrogen bleed to give a vacuum of 5 inches (5/31 atm) Hg. From this point, the reaction temperature is raised to 150 ° C. by adjusting the variac and / or by raising or lowering the mantle.
To hold.

Within 7 minutes, primary methanol bubbles are visible at the meniscus of the reaction mixture. A vigorous reaction is immediately associated.
The methanol is distilled until the rate decreases. Adjust the vacuum to give a vacuum of about 10 inches Hg (10/31 atm).
Increase the vacuum approximately as follows (inches Hg at a given minute): 3
At 10; 7 at 20; 10 at 25. Heating and stirring are discontinued 11 minutes after the onset of methanol evolution (simultaneous foaming occurs). The product cools and solidifies.

The following examples are intended to illustrate the compositions of the present invention, but do not necessarily limit or otherwise define the scope of the present invention, which is determined according to the following claims. ).

Examples I-III These examples illustrate heavy duty granular detergent compositions containing polyhydroxy fatty acid amides and protease enzymes.

Examples I-III show about 1400 ppm for temperatures below about 50 ° C.
Formulation for preferred use (based on wash water weight). The above example is prepared by combining the base particulate components as a slurry and spray drying to a residual moisture of about 4-8%. The remaining dry ingredients are mixed with the spray-dried granules in granular or powder form in a rotating mixing drum and the liquid ingredients (nonionic surfactants and fragrances) are sprayed on.

Examples IV-IX are prepared as follows. Combine the non-aqueous solvent, aqueous surfactant paste or solution, aqueous solutions of molten fatty acids, polycarboxylate builders and other salts, aqueous ethoxylated tetraethylenepentamine, buffers, caustic, and the remaining water. The pH is adjusted to about pH 8.5 using either aqueous citric acid or aqueous sodium hydroxide. After pH adjustment, final ingredients such as soil release agents, enzymes, colorants, fragrances, etc. are added and the mixture is stirred until a single phase is achieved.

Example X Another highly preferred preparation of the polyhydroxy fatty acid amide used herein is as follows. 84.87 g of fatty acid methyl ester (source: Procter & Gamble methyl ester CE 1270) and N-methyl-D-glucamine (source: Aldrich Chemical Company M4700-)
0) 75 g and sodium methoxide (source: Aldrich
Chemical Company 16,499-2) A reaction mixture consisting of 1.04 g and 68.51 g of methyl alcohol is used. The reaction vessel is equipped with standard reflux equipment equipped with a dry grind, condenser and stir bar. In this method, N-methylglucamine is combined with methanol under argon under stirring and heating is started with good mixing (stir bar; reflux). 15-20
After a minute, when the solution has reached the desired temperature, the ester and sodium methoxide catalyst are added. Samples are taken periodically to monitor the course of the reaction and the solution is found to be completely clear at 63.5 minutes. The reaction is in fact judged almost complete at this point. The reaction mixture is kept under reflux for 4 hours. After removing the methanol, the recovered crude product is 156.16 g. After vacuum drying and purification,
A total yield of 106.92 g of purified product is recovered. However, yields are not calculated on this basis since regular sampling over the course of the reaction renders the overall yield value meaningless. The reaction can be performed at 80% and 90% reactant concentrations for up to 6 hours to produce product (with very little by-product formation).

 Modern concentrated laundry detergent granules are as follows.

Example XI Component Weight% C ₁₄ -C ₁₅ alkyl alcohol sulfonic acid 13 C ₁₄ -C ₁₅ alkyl polyethoxylate (2.25) sulfonium phosphate 5.60 C ₁₂ -C ₁₃ alkyl polyethoxylate (6.5) 1.45 C ₁₂ ~C ₁₄ fatty acid N -Methylglucamide 2.50 Sodium aluminosilicate (as hydrated zeolite A) 25.2 Crystalline layered silicate builder ¹ 23.3 Citric acid 10.0 Sodium carbonate Wash water pH = 9.90 Sodium polyacrylate (Molecular weight 2000-4500) 3.2 Diethylenetriaminepentaacetic acid 0.45 Savinase ² 0.70 6-Nonanoylamino-6-oxo-pentoxycaproic acid 7.40 Sodium perborate monohydrate 2.10 Nonanonyloxybenzenesulfonic acid 5.00 Brightener 0.10 ^One- layer silicate builders are known in the art. Layered sodium silicate is preferred. For example, 1987
See Layered Sodium Silicate Builder in U.S. Pat. No. 4,664,859, issued May 12, 1998, incorporated herein by reference. Suitable layered silicate builders are from Hoechst
Available as SKS-6. ² Available from Novo Nordisk A / S in Copengagen.

Highly preferred particulates of the type described above have an active enzyme of about 0.00
From about 0.01 to about 2% by weight and at least about 1% by weight of the polyhydroxy fatty acid amide (most preferably, the anionic surfactant is not an alkylbenzene sulfonate surfactant).

The following relates to the preparation of a preferred liquid heavy duty laundry detergent according to the present invention. It will be appreciated that the stability of the enzyme in such compositions is much lower than in granular detergents. However, by using typical enzyme stabilizers such as formate, boric acid, lipase and cellulase enzymes can be protected from degradation by protease enzymes. However, lipase stability does not depend on alkylbenzene sulfonate ("LAS")
Still relatively poor in the presence of surfactants. Apparently, LAS partially denatures lipase, and more denatured lipase appears to be more susceptible to attack by proteases.

In view of the above considerations, which can be particularly cumbersome with liquid compositions as described above, it is an object to provide a liquid detergent composition that contains a lipase, a protease and a cellulase enzyme together. It is a particular challenge to provide such a ternary enzyme system in a stable liquid detergent with an effective blend of detergent surfactants. Additionally, it is difficult to stably incorporate peroxidase and / or amylase enzymes into such compositions.

Various mixtures of lipases, proteases, cellulases, amylases, and peroxidases are suitably stable in the presence of certain non-alkylbenzene sulfonate surfactant systems, and therefore can formulate even effective heavy duty solid and liquid detergents. Now confirmed. In fact, the formulation of a stable liquid enzyme-containing detergent composition constitutes a highly advantageous preferred embodiment provided by the technology of the present invention.

In particular, prior art liquid detergent compositions typically include LA
Mixture of surfactant of the the S or _{LAS RO (A) m SO 3} M type ( "AES"), i.e., containing LAS / AES mixtures. In contrast, the liquid detergents of the present invention preferably comprise a binary mixture of AES and a polyhydroxy fatty acid amide of the type disclosed herein. It will be appreciated that a minimal amount of LAS can be present, but the stability of the enzyme will be reduced thereby. Thus, it is preferred that the liquid composition be substantially free of LAS (ie, contain less than about 10%, preferably less than about 5%, more preferably less than about 1%, and most preferably 0%).

The present invention provides: (a) about 1% to about 50%, preferably about 4% to about 40%, of an anionic surfactant; (b) about 0.001% to about 2% of an active detergent enzyme; Wherein R ¹ is H ₁ , C ₁ -C ₄ hydrocarbyl, 2-hydroxyethyl, 2-hydroxypropyl, or a mixture thereof, R ₂ is C ₅ -C ₃₁ hydrocarbyl, and Z is An enzymatic performance-enhancing amount (preferably from about 0.5% to about 12%) of a polyhydroxyfatty acid amide material having a linearly linked hydrocarbyl chain having at least three hydroxyls, or an alkoxylated derivative thereof, , Wherein the composition is substantially free of alkylbenzene sulfonate.

Water-soluble anionic surfactants of the present invention is preferably _{RO (A) m SO 3 M} ( wherein, R is an unsubstituted C ₁₀ -C ₂₄ alkyl or hydroxyalkyl (C ₁₀ ~C ₂₄₎ group, A is an ethoxy or propoxy unit, m is an integer greater than 0,
M is hydrogen or a cation) ("AES"). Preferably, R is an unsubstituted C ₁₂ -C
₁₈ alkyl groups, A is an ethoxy unit, m is about 0.5 to about 6,
M is a cation. The cation is preferably a metal cation [eg, sodium (preferred), potassium,
Lithium, calcium, magnesium, etc.] or ammonium or substituted ammonium cations.

The ratio of the surfactant ("AES") to the polyhydroxyfatty acid amide of the present invention is from about 1: 2 to about 8: 1, preferably from about 1: 1 to about 5: 1, most preferably about 1: 1. And preferably about 4: 1.

The liquid compositions of the present invention, or polyhydroxy fatty acid amide, AES, and C ₈ -C ₂₂ (preferably C ₁₀ -C ₂₀₎
About 1 to about 25 per mole of linear alcohol and alcohol,
Preferably, it may contain about 0.5% to about 5% of a condensate with about 2 to about 18 moles of ethylene oxide.

As described above, the liquid composition of the present invention preferably comprises
It has a pH of about 6.5 to about 11.0, preferably about 7.0 to about 8.5 in a 10% solution in water at 20 ° C.

The composition preferably comprises from about 0.1% of a detersive builder.
Further includes about 50%. These compositions preferably comprise from about 0.1% to about 20% of citric acid or a water-soluble salt thereof, and from about 0.1% to about 20% of a water-soluble succinate tartrate, especially its sodium salt and mixtures thereof, or Oxydisuccinate or a mixture thereof with the builder
0.1 to about 20% by weight. Alkenyl succinate 0.1%
~ 50% can be used.

Preferred liquid compositions of the present invention have, on an active basis, about 0.00
It contains from 01% to about 2%, preferably from about 0.0001% to about 1%, most preferably from about 0.001% to about 0.5% of detergent enzyme. These enzymes are preferably selected from the group consisting of proteases (preferred), lipases (preferred), amylase, cellulase, peroxidase, and mixtures thereof. Compositions having two or more enzymes are preferred, most preferably one in which one is a protease.

Various descriptions of detergent proteases, cellulases and the like are available in the literature, but detergent lipases are somewhat unknown. Thus, to assist the formulator, lipases of interest include Amano AKG and Bacillis Sp lipase (eg, Solvay enzyme).
Also, EP A 0 399 681 published on November 28, 1990, EP A 0 218 272 published on April 15, 1987, and PCT / DK No. published on May 18, 1989 See lipase in 88/00177, all incorporated herein by reference.

Suitable fungal lipases include Humicola lanuginosa
And those that can be produced by Thermomyces lanuginosus. Humicola as described in European Patent Application No. 0 258 068, incorporated herein by reference.
Clone the gene from lanuginosa and replace the gene with Asp
Lipases obtained by expression in ergillus oryzae (commercially available under the trade name LIPOLASE) are most preferred.

From about 2 to about 20,000 per gram of product, preferably from about 10 to about 20,000
6,000 lipase units of lipase (LU / g) can be used in these compositions. Lipase units are pH stats (pH is
7.0, temperature 30 ° C, substrate is emulsion tributyrin and gum arabic) Ca ⁺⁺ and Na in phosphate
The amount of lipase that produces 1 μmol of titratable butyric acid per minute in the presence of Cl.

The following examples include: (a) an enzyme selected from proteases, cellulases and lipases or a mixture thereof (the amount used is an "effective" amount (i.e., the amount of soil removal) of the enzyme or enzyme mixture to provide the enzyme or enzyme mixture; (B) a polyhydroxy fatty acid amine surfactant of the type disclosed herein (typically comprising from about 0.01 to about 20% by weight of the total composition, but can be adjusted as desired); At least about 2%, more typically about 3 to about 15%, preferably about 7% by weight of
Accounts for about 14 wt%); (c) where the disclosure of such RO (A) _m SO _{3 M} type, in preferably _{RO (CH 2 CH 2 O)} m SO 3 M [wherein, R is C ₁₄ CC ₁₅ (average), m is 2-3 (average), and M is H or a water-soluble salt-forming cation, such as Na ^+. Contains from about 5 to about 25% by weight of the composition
Occupy); optionally (d), wherein the ROSO ₃ M [preferably, wherein, R C ₁₂ -C ₁₄ (average) and is] as disclosed surfactants (surfactant preferably Represents from about 1 to about 10% by weight of the composition); (e) a liquid carrier, especially water or a water-alcohol mixture; (f) an optionally but most preferably effective amount of an enzyme stabilizer (typically (G) optionally but preferably a water-soluble builder, especially a polycarboxylate builder (typically about 4 to about 25% by weight of the composition); Optionally, various detergent adjuvants, brighteners and the like described above (typically, if used, from about 1 to about 10
%) And (i) the composition exemplifies a preferred heavy duty liquid detergent composition substantially free of LAS.

Example XII Ingredient % by Weight _C14-15 alkyl polyethoxylate (2.25) Sulfonic acid 21.0 _C12-14 fatty acid N-methylglucamide ¹ 7.0 Tartrate mono- and sodium disuccinate (80:20 mixture) 4.00 Citric acid 3.80 C _12-14 fatty acids 3.00 Tetraethylene pentaamine ethoxylate (15-18) 1.50 Ethoxylation of polyethylene-polypropylene terephthalate sulfonic acid Copolymer 0.20 Protease B (34 g /) ² 0.68 Lipase (100 KLU / g) ³ 0.47 Cellulase (500 cevu / g) ⁴ 0.14 Brightener 36 ⁵ 0.15 Ethanol 5.20 Monoethanolamine 2.00 Sodium formate 0.32 1,2-Propanediol 8.00 Sodium hydroxide 3.10 Silicone foam suppressor 0.0375 Boric acid 2.00 Water / miscellaneous components Remaining (100) ¹ Preparation ² Protease B as described above is described in European Patent Application No. 87 303761 filed on April 28, 1987, in particular Pages 17, 24 and 98
The denatured bacterial serine protease described on page 4. ³ The lipase used here is described in European Patent Application No. 0 258 068
Lipase obtained by cloning the gene from Humicola lanuginosa and expressing the gene in Aspergillus oryzae [commercially available under the trade name Lipolase (LIPOLASE) (Novo Nordisk, Copenhagen, Denmark) A / S)). ⁴ The cellulase used here is trade name KAREZYME.
ME) (Novo Nordisk A / S, Copenhagen, Denmark). ⁵ Brightener 36 is commercially available as Tinopearl TAS36.

The brightener is added to the composition as a separately prepared premix of brightener (4.5%), monoethanolamine (60%) and water (35.5%).

The following are not intended to limit the invention, but merely to further illustrate additional aspects of the technology that can be considered by formulators in preparing various detergent compositions using polyhydroxy fatty acid amides. .

It will be readily recognized that polyhydroxy fatty acid amides are susceptible to some instability under highly basic or high productivity conditions due to amide bonds. Although some degradation is acceptable, these substances can
It is preferred not to be subjected to a pH above 11, preferably above pH 10, below about 3. Final product pH (liquid)
Is typically between 7.0 and 9.0.

During the production of the polyhydroxy fatty acid amide, it will typically be necessary to at least partially neutralize the base catalyst used to form the amide bond. Although any acid can be used for this purpose, detergent formulators will recognize that it is a simple and convenient matter to use an acid that would otherwise be useful and give the desired anion in the finished detergent composition. There will be. For example, citric acid can be used for neutralization purposes and allows the resulting citrate ions (about 1%) to remain with the about 40% polyhydroxyfatty acid amide slurry and is pumped to a manufacturing stage after the entire detergent process. Let it be supplied. Acid form substances such as oxydisuccinate, nitrilotriacetate, ethylenediaminetetraacetate, tartrate / succinate and the like can likewise be used.

Polyhydroxy fatty acid amides derived from coconut alkyl fatty acids (predominantly C ₁₂ -C ₁₄₎ are more soluble than tallow alkyl (predominantly C ₁₆ -C ₁₈₎ equivalents. Thus, C ₁₂ -C ₁₄ materials are soluble in easy and and cold water washing bath to be formulated is slightly more to the liquid composition. However, C ₁₆ -C ₁₈ materials are also quite useful, especially in situations where warm to hot wash water is used. In fact, C ₁₆
-C ₁₈ materials may be better detergent surfactants than C ₁₂ -C ₁₄ equivalents. Thus, formulators may want to balance manufacturability vs. performance when selecting a particular polyhydroxy fatty acid amide for use in a given formulation.

It will also be appreciated that the solubility of the polyhydroxy fatty acid amide can be increased by having unsaturation and / or chain branching points in the fatty acid moiety. Thus, materials such as polyhydroxy fatty acid amides derived from oleic and isostearic acids are more soluble than their n-alkyl equivalents.

Similarly, the solubility of polyhydroxy fatty acid amides made from disaccharides, trisaccharides, etc. will generally be greater than the solubility of monosaccharide-derived equivalents. This high solubility can have particular help in formulating liquid compositions. In addition, polyhydroxy fatty acid amides in which the polyhydroxy groups are derived from maltose appear to perform particularly well as detergents when used in conjunction with conventional alkylbenzene sulfonate ("LAS") surfactants. Without wishing to be limited by theory, the combination of polyhydroxyfatty acid amides derived from higher sugars such as maltose with LAS results in a substantially unexpected decrease in interfacial tension in aqueous media, thereby resulting in a net wash. It seems to improve performance (the production of polyhydroxy fatty acid amide derived from maltose will be described later).

Polyhydroxyfatty acid amides can be produced not only from purified sugars, but also from starches derived from hydrolyzed starches, such as corn starch, potato starch, or other convenient plants containing monosaccharides, disaccharides, etc. as desired by the formulator. Can also be manufactured. This has particular importance from an economic point of view. Thus, "high glucose" corn syrup, "high maltose" corn syrup and the like can be used conveniently and economically. Delignified hydrolyzed cellulose pulp can also provide a stock solution for polyhydroxy fatty acid amides.

As mentioned above, polyhydroxy fatty acid amides derived from higher sugars such as maltose and lactose are more soluble than their glucose equivalents. In addition, more soluble polyhydroxy fatty acid amides may help solubilize less soluble equivalents to varying degrees. Thus, the prescriber may, for example, decide to use a raw material comprising high glucose corn syrup,
A syrup containing a small amount of maltose (eg, 1% or more) may be selected. The resulting mixture of polyhydroxy fatty acids will generally exhibit more favorable solubility over a wide range of temperatures and concentrations than "pure" glucose-derived polyhydroxy fatty acid amides. Thus, in addition to the economic advantages of using a sugar mixture rather than a pure sugar reactant, polyhydroxy fatty acid amides made from mixed sugars have very substantial performance and / or ease of formulation. Benefits can be provided. However, in some cases, some loss of grease removal performance (dishwashing) may be observed at fatty acid maltamide levels greater than about 25% and some loss of foaming properties is greater than about 33% It may be found in an amount (the percentage is the percentage of maltamide-derived polyhydroxy fatty acid amide VS glucose-derived polyhydroxy fatty acid amide in the mixture). This can vary slightly depending on the chain length of the fatty acid moiety. Typically, and formulators who decide to use such mixtures, the ratio of a monosaccharide (eg, glucose) to a disaccharide / higher sugar (eg, maltose) will include a ratio of about 4: 1 to about 99: 1. It can be found to be advantageous to choose a polyhydroxy fatty acid amide mixture which is:

The preparation of a preferred acyclic polyhydroxy fatty acid amide from a fatty ester and an N-alkyl polyol is carried out in an alcoholic solvent at about 30C to 90C, preferably about 50C to 80C
Temperature. For example, it is advantageous for liquid detergent formulators to perform such a process in 1,2-propylene glycol solvent because the glycol solvent does not need to be completely removed from the reaction product prior to use in the finished detergent formulation. Is now confirmed. Similarly, for example, solid detergent compositions, the formulator will typically granular detergent composition, ethoxylated process (EO3~8) C ₁₂ ~C ₁₄
It can be found to be convenient to work at 30 ° C. to 90 ° C. in a solvent consisting of an ethoxylated alcohol such as an alcohol, for example, neodol 23EO6.5 (shell). When such ethoxylates are used, they preferably do not contain substantial amounts of non-ethoxylated alcohols, and most preferably do not contain substantial amounts of monoethoxylated alcohols (designation "T").

Although the preparation of the polyhydroxyfatty acid amide itself does not form part of the present invention, the formulator may recognize other methods of synthesizing the polyhydroxyfatty acid amide as described below.

Typically, an industrial scale reaction sequence to produce the preferred acyclic polyhydroxy fatty acid amide comprises a step 1: N
An N-alkyl polyhydroxyamine derivative is produced from the desired saccharide or saccharide mixture by reacting with hydrogen in the presence of a catalyst after forming an adduct of the alkylamine and the saccharide, A source of xyethylene ethylene units (eg, ethylene glycol)
A nonionic oligomeric esterification product of a reaction mixture containing (particularly, the molar ratio of oxyethyleneoxy units to oxyisopropyleneoxy units is at least about 0.5: 1)
Is mentioned. Such nonionic soil release agents have the general formula Wherein R ¹ is lower (eg, C ₁ -C ₄ ) alkyl, especially methyl; x and y are each an integer from about 6 to about 100;
m is from about 0.75 to about 30 integer; n is about 0.25 to from about 20 integer; R ² is an oxyethylene oxy pair oxyisopropylene propyleneoxy mole ratio of at least about 0.5: H and CH to give 1 ₃ is a mixture of both).

Another preferred class of soil release agents useful herein is U.S. Pat. No. 4,877,896, except that such agents are substantially free of monomers of the HOROH type, where R is propylene or higher alkyl. It has the general anionic type described in the specification. Thus, the soil release agent of U.S. Pat.No. 4,877,896 can comprise, for example, the reaction product of dimethyl terephthalate, ethylene glycol, 1,2-propylene glycol, and 3-sodeiosulfobenzoic acid, while these Additional soil release agents are, for example, dimethyl terephthalate, ethylene glycol and 5
-Sodiosulfoisophthalate and 3-sodeiosulfobenzoic acid. Such agents are preferred for use in granular laundry detergents.

Also, formulators may find it advantageous to include non-perborate bleaches, especially in heavy duty granular laundry detergents. Various peroxygen bleach,
Although commercially available and can be used here, of these, percarbonate is convenient and economical. Thus, the composition comprises from 3 to 20%, more preferably from 5 to 18%, most preferably from 8 to 15% by weight of the composition.
Of solid percarbonate (usually in the form of a sodium salt).

Sodium percarbonate is an adduct having the formula corresponding to 2Na ₂ CO ₃ .3H ₂ O ₂ and is commercially available as a crystalline solid. Most commercially available substances include small amounts of EDTA, 1-hydroxyethylidene 1,1-
Heavy metal ion sequestering agents such as diphosphonic acid (HEDP) and aminophosphonate. For use herein, percarbonate can be incorporated into the detergent composition without additional protection, but a preferred embodiment of the present invention utilizes a stable form of the material (FMC). A variety of coatings can be used, but with an SiO ₂ : Na ₂ O ratio of 1.6 applied as an aqueous solution and dried to give an amount of silicate solids of 2-10% (usually 3-5%) by weight of percarbonate. :from 1 to 2.
8: 1, preferably 2.0: 1, sodium silicate is the most economical. Magnesium silicate can also be used and chelating agents, such as one of the foregoing, can be incorporated into the coating.

The particle size range of the crystalline percarbonate is from 350 μm to 450
μm (about 400 μm on average). When coated, the crystals have a size in the range of 400-600 μm.

While the heavy metals present in the sodium carbonate used to make percarbonate can be controlled by the incorporation of the sequestering agent into the reaction mixture, the percarbonate is derived from heavy metals present as impurities in other components of the product. You still need protection. The total amount of iron, copper and manganese ions in the product is 25 to avoid unacceptable adverse effects on percarbonate stability.
It has been found that it should not be above ppm, and preferably below 20 ppm.

Example XIV The following illustrates a perborate bleach / bleach activator detergent composition of the present invention prepared by mixing the indicated ingredients in a mixing drum.

In the examples, zeolite A refers to hydrated crystalline zeolite A containing about 20% water and having an average particle size of 1-10, preferably 2-5μ; LAS is a sodium C _12.3 linear alkylbenzene sulfonate. Means AS; means C ₁₄ -C ₁₅ sodium alkyl sulfate; non-ionic compounds mean coconut alcohol condensed with about 6.5 moles of ethylene oxide per mole of alcohol and free of unethoxylated and monoethoxylated alcohols. (DTn means sodium diethylenetriaminepentaacetate).

^One base granules are prepared by spray drying an aqueous clutcher mixture of the indicated ingredients. ² Freshly prepared sample of PAPAA wet cake (typically water
60%, peroxyacid available oxygen (AvO) about 2% (NAPAA about 36
%) And the balance (approximately 4%) of unreacted starting material]. The wet cake is a crude reaction product of NAAA (monononylamide of adipic acid), sulfuric acid and hydrogen peroxide, which is subsequently quenched by addition to water, then filtered and distilled. Wash with water, wash with phosphate buffer and perform a final suction filtration to collect the wet cake. A portion of the wet cake is air dried at room temperature to obtain a dry sample, typically consisting of about 5% AvO (corresponding to about 90% NAPAA) and about 10% unreacted starting material. When dry, the sample pH is about 4.5.

The NAPAA granules are about 51.7 parts of a dried NAPAA wet cake (containing about 10% unreacted material) and a C _12.3 linear sodium alkylbenzene sulfonate (LAS) paste (45% active).
Prepared by mixing about 11.1 parts, about 43.3 parts of sodium sulfate, and about 30 parts of water in a CUISINART mixer. After drying, the granules (containing about 47% NAPAA) are sized by passing through a No. 14 Tyler mesh sieve and retaining all particles that do not pass through a No. 65 Tyler mesh. The average amidoperoxy acid particle size (aggregates) is about 5 to 40μ and the median particle size is about 10 to 20μ as determined by Malvern particle size analysis. ³ NOBS (nonanoyloxybenzenesulfonate) granules were obtained from Boring U.S. Pat.
Prepared according to US Pat. No. 7,596, incorporated herein by reference. ^{4 The} zeolite granules having the following composition are zeolite A
PEG8000 in Erich R08 energy intensive mixer
And mixed with CnAE6.5T.

PEG 8000 is an aqueous form containing 50% water and contains about 55
It is a temperature of ℃ F (12.8 ° C). CnAE6.5T is in a liquid state and is maintained at about 90 ° F (32.2 ° C). The two liquids are 1
Combine by pumping through a two-element static mixer. The resulting binder material is approximately 75 ° F
It has an outlet temperature of (23.9 ° C.) and a viscosity of about 5000 cps. The ratio of PEG8000 and CnAE6.5T through a static mixer is 72:28, respectively.

Operate the Eirich R08 energy intensive mixer in batch form. Be sure to weigh 34.1 kg of powdered zeolite A into a mixer pan. The mixer first rotates the pan counterclockwise at about 75 revolutions per minute (rpm), and then
Start by rotating the rotor blade clockwise at 1800 rpm. The binder material is then pumped directly from the static mixer to an Erich R08 energy intensive mixer containing zeolite A. The feed rate of the binder material is about 2 minutes. The mixer continues mixing for an additional minute (total batch time about 3 minutes). The batch is then discharged and collected in a fiber drum.

The batch process is repeated until about 225 kg of the wet product has been collected. The discharged product is then passed through a fluidized bed for 240-2.
Dry at 70 ° F (116-132 ° C). The drying process is
Most of the free water is removed and the composition is changed as described above. The total energy input by the mixer to the product in batch form is about 1.18 × 10 ⁹ ergs / kg-s.
31 × 10 ¹² ergs / kg.

The resulting free-flowing aggregate has an average particle size of about 450-500μ
Having.

Example XV Liquid laundry detergent compositions suitable for use in relatively high concentrations common to flotted automatic washing machines over a wide range of temperatures, especially in Europe, are as follows. Ingredient Weight% Coconut alkyl (C ₁₂₎ N-Mechiruguruka bromide ₁₄ C 14~15 EO (2.25) sulfate, Na salt 10.0 _C 14~15 EO (7) 4.0 anhydride C _{12 to 14} alkenylsuccinic acid ¹ 4.0 C _{12 to 14} Fatty acid ^★ 3.0 Citric acid (anhydrous) 4.6 Protease (enzyme) ² 0.37 Termamyl (enzyme) ³ 0.12 Lipolase (enzyme) ⁴ 0.36 Kalezyme (enzyme) ⁵ 0.12 Duquest 2060S ⁶ 1.0 NaOH (pH 7.6) 5.5 1,2- Propanediol 4.7 Ethanol 4.0 Sodium metaborate 4.0 CaCl ₂ 0.014 Ethoxylated tetraethylenepentamine ⁷ 0.4 Brightener ⁸ 0.13 Silane ⁹ 0.04 Soil release polymer ¹⁰ 0.2 Silicone (antifoam) ¹¹ 0.4 Silicone dispersant ¹² 0.2 Water and trace components Rest ^{1 as} SYNPRAX 3 from ICI or DTSA from Monsanto. ^{2 As} Protease B as described in EPO 0342177 of November 15, 1989;% at 40 g /. Amylase from ³ Novo;% at 300 KNU / g. Lipase from ⁴ Novo;% at 100 KLU / g. Cellulase from ⁵ Novo;% at 5000 CEVU /. Available from ⁶ Monsanto. ^{7 As} Lutensol P6105 from BASF. ⁸ Bayer swing hall CPG766. ⁹ Silane corrosion inhibitor available as A1130 from Union Carbide or DYNASYLAN TRIAMINO from Hills. ¹⁰ Polyester of U.S. Pat. No. 4,711,730. ¹¹ Silicone foam control available from Dow Corning as Q2-3302 ¹² Dispersant for silicone foam control available from Dow Corning as DC-3225C. ^The preferred fatty acid is a topped park core containing 12% oleic acid and 2% each of stearic and linoleic acids.

Example XVI Granular laundry detergent compositions suitable for use in relatively high concentrations common to front-loading automatic washing machines over a wide range of temperatures, especially in Europe, are as follows: Ingredient weight% Sokalan CP5 (active component 100% as Na salt) ¹ 3.52 Duquest 2066 (100% acid) ² 0.45 Tinopearl DMS ³ 0.28 MgSO ₄ 0.49 Zeolite A (anhydrous) 17.92 CMC (active component 100%) ⁴ 0.47 Na ₂ CO ₃ 9.44 Citric acid 3.5 Layered silicate SKS-6 12.9 Tallow alkyl sulfate 2.82 (active content 100%; Na salt) C ₁₄ -C ₁₅ alkyl sulfate 3.5 (active content 100%; Na salt) C ₁₂ -C ₁₅ alkyl EO (3) Sulfate 1.76 C ₁₆ -C ₁₈ N-methylglucamide 4.1 Dovanol C ₁₂ -C ₁₅ EO (3) 3.54 Lipolase (100,000 LU / g) ⁵ 0.42 Savinase (4.0 KNPU) ⁶ 1.65 Fragrance 0.53 X2-3419 ⁷ 0.22 starch 1.08 stearyl alcohol 0.35 sodium percarbonate (coated) 22.3 tetra acetylene diamine (TAED) (zeolite) 5.9 zinc phthalocyanine 0.02 water balance ¹ Sokalan are available from Hoechst polyacrylamide Acid /
It is sodium maleate. ² penta-phosphonomethyl diethylenetriamine of Monsanto's brand. ³ Optical brightener available from Ciba Geigy. ⁴ Finnfix (trade name) available from Metasariton. Lipolase lipolytic enzyme from ⁵ Novo. Savinase protease enzyme from ⁶ Novo. ⁷ X2-3419 is a silicone foam inhibitor available from Dow Corning.

The method for producing the granular material comprises various types of tower drying, coagulation, cyclic addition, and the like, as follows. The percentages are based on the finished composition.

A. Clutching and blowing through towers Using standard techniques, the following components are
ch) Dry the tower.

Sokalan CP5 3.52% du Quest 2066 0.45% Tinopal DMS 0.28% Zeolite A 7.1% CMC 0.47% as magnesium sulfate 0.49% anhydride B. Surfactant agglomerate B1. Paste and C ₁₂ -C of the sodium salt of tallow alkyl sulfate ₁₅ EO (3) aggregation of the paste of the sodium salt of sulfuric acid - 50% active paste of tallow alkyl sulfate and C ₁₂ ~C ₁₅ EO (3) 70% paste sulfate agglomerate zeolite a and sodium carbonate according to the following formulation ( Contributes to detergent formulation after drying of aggregates).

Tallow alkyl sulphate _{2.82% C 12~15 EO (3)} 1.18% sulphate Zeolite A 5.3% Sodium carbonate 4.5% B2. C ₁₄ ~C ₁₅ alkyl sulfates, C ₁₂ -C ₁₅ alkyl ethoxysulfate, Dobanol C ₁₂ -C ₁₅ EO (3)
And C ₁₆ -C ₁₈ N-methyl glucose amide aggregates -C ₁₆
-C ₁₈ synthesized in glucose Dobanol _C 12~15 EO (3) amide nonionic material is present in the reaction of methyl ester and N- methylglucamine. _C12-15 EO (3)
Acts as a melting point depressant that allows the reaction to take place without producing undesirable cyclic glucose amides.

A surfactant mixture of 20% dovanol C _12-15 EO (3) and 80% C ₁₆ -C ₁₈ N-methylglucoseamide is obtained and co-aggregates with 10% sodium carbonate.

Secondly, then the particles C ₁₄ -C ₁₅ sodium salt and C _{12 to 15} alkyl sulfate EO (3) sulfate and Zeolite A and extra high activity paste and sodium carbonate (70
%). The particles exhibit good dispersibility in cold water of C ₁₆ -C ₁₈ N-methyl glucose amide.

The total formulation of the particles (contributing to the detergent formulation after drying of the agglomerates) is as follows.

C ₁₆ -C ₁₈ N-methylglucose amide 4.1% Dovanol C _12-15 EO (3) 0.94% Sodium carbonate 4.94% Zeolite A 5.3% C ₁₄ -C ₁₅ Sodium alkyl sulfate 3.5% C _12-15 EO (3) Sulfuric acid Sodium 0.59% C. Drying additives Add the following ingredients:

Percarbonate 22.3% TAED (tetraacetylethylenediamine) 5.9% Hoechst layered silicate SKS-6 12.90% Citric acid 3.5% Lipolase 0.42% 100,000 LU / g Savinase 4.0KNPU 1.65% Zinc phthalocyanine (photobleach) 0.02% D. Spray-on Dovanol C _12-15 EO (3) 2.60% Fragrance 0.53% E. Foam Inhibitor Silicone foam inhibitor X2-3419 from Dow Corning
(High molecular weight linear silicone 95% to 97%; hydrophobic silica 3
% To 5%) with zeolite A (2-5 μm in size), starch and stearyl alcohol binder. The particles have the following formulation.

Zeolite A 0.22% Starch 1.08% X2-3419 0.22% Stearyl alcohol 0.35% The detergent formulation is, for example, a European washing machine using 85 g of detergent in an AEG brand washing machine at 30 ° C, 40 ° C, 60 ° C and 90 ° C cycles. Shows excellent solubility, excellent performance and excellent foam control when used in

Example XVII In any of the above examples, the fatty acid glucamide surfactant can be replaced by an equivalent amount of a maltamide surfactant or a glucamide / maltamide surfactant derived from a plant sugar source. In compositions, the use of ethanolamide appears to promote cold stability of the finished formulation.
Furthermore, the use of sulfobetaines and / or amine oxide surfactants gives excellent foaming properties.

In the case of a composition in which a high foaming property is desired, a fatty acid having ₁₄ or more fatty acids may suppress the foaming property. Therefore, the fatty acid having ₁₄ or more fatty acids should have less than about 5%, more preferably less than about 2%. Preferably, it is present, most preferably substantially absent.
Accordingly, formulators of high foaming compositions desirably avoid introducing low foaming amounts of such fatty acids into high foaming compositions having polyhydroxy fatty acid amides and / or store the finished composition. It would avoid the production of C ₁₄ or more fatty acids when. One simple means is to use C ₁₂ ester reactants to produce the polyhydroxy fatty acid amides of the present invention. Fortunately, the use of amine oxide or sulfobetaine surfactants can overcome some of the negative foaming effects caused by fatty acids.

Formulators who wish to add anionic optical brighteners to liquid detergents containing relatively high concentrations (eg, 10% or more) of anionic or polyanionic surfactants, such as polycarboxylate builders, It may be useful to premix the brightener with water and the polyhydroxy fatty acid amide, and then add the premix to the final composition.

The polyglutamic acid or polyaspartic acid dispersant can be usefully used together with the detergent containing zeolite builder.
AEE fluids or flakes and DC-544 (Dow Corning) are other examples of other foam control agents useful herein.

Preparation of polyhydroxy fatty acid amides using disaccharides and higher sugars, such as maltose, will result in the production of polyhydroxy fatty acid amides in which the linear substituent Z is "blocked" by a polyhydroxy ring structure. Will be recognized by those skilled in the art. Such materials are fully contemplated for use herein and do not depart from the spirit and scope of the invention as disclosed and claimed.

────────────────────────────────────────────────── ─── Continued on the front page (31) Priority number 755,904 (32) Priority date September 6, 1991 (33) Priority country United States (US) (72) Inventor Panandika, Rajan Keshaf Ohio, United States of America State, Cincinnati, Williamsburg, Rd., 1321 (72) Inventor Wolf, Ann Margaret, Cincinnati, Boomer, Rd., Ohio, USA 4570 (56) References JP-A-61-252300 (JP, A) Hei 1-501154 (JP, A) (58) Fields investigated (Int. Cl. ⁶ , DB name) C11D 1/52 C11D 3/386

Claims (10)

(57) [Claims] 1. A detergent composition comprising one or more anionic detergent surfactants, nonionic detergent surfactants, or mixtures thereof, and a detergent enzyme, wherein the composition comprises a formula Wherein R ¹ is H ₁ , C ₁ -C ₄ hydrocarbyl, 2-hydroxyethyl, 2-hydroxypropyl, or a mixture thereof, R ₂ is C ₅ -C ₃₁ hydrocarbyl, and Z is (A polyhydroxyhydrocarbyl having a linear hydrocarbyl chain having at least three hydroxyls directly linked thereto or an alkoxylated derivative thereof). Detergent composition. 2. The composition according to claim 1, wherein said enzyme comprises an alkaline protease, amylase, lipase, cellulase, or peroxidase, or a mixture thereof. 3. The composition according to claim 2, wherein Z is derived from a reducing sugar. 4. The detergent composition according to claim 3, wherein R ¹ is methyl, R ² is C ₁₁ -C ₁₇ alkyl or alkenyl, and Z is derived from glucose, maltose or a mixture thereof. 5. With respect to said polyhydroxy fatty acid amide, Z is derived from a mixture of monosaccharides, disaccharides and optionally higher saccharides, said mixture comprising at least one disaccharide, preferably at least 1% maltose. , Claim 1
A composition according to claim 1. (6) anionic detergent enzyme 1% to 50%; (b) active detergent enzyme 0.0001% to 2%; (c) formula Wherein R ¹ is H ₁ , C ₁ -C ₄ hydrocarbyl, 2-hydroxyethyl, 2-hydroxypropyl, or a mixture thereof, R ₂ is C ₅ -C ₃₁ hydrocarbyl, and Z is A polyhydroxyhydrocarbyl having at least three hydroxyl-linked linear hydrocarbyl chains, or an alkoxylated derivative thereof), wherein the enzymatic performance-enhancing amount of the polyhydroxyfatty acid amide material is substantially free of alkylbenzene sulfonate. A liquid detergent composition comprising: 7. The method according to claim 1, wherein the anionic surfactant is RO (A) _m SO ₃ M wherein R is an unsubstituted C ₁₀ -C ₂₄ alkyl or hydroxyalkyl (C ₁₀ -C ₂₄ ) group; Is an ethoxy or propoxy unit, m is greater than 0, and M is hydrogen or a cation. 8. The composition of claim 6, wherein said detergent enzyme is selected from the group consisting of proteases, lipases, amylases, cellulases, peroxidases, and mixtures thereof. 9. The composition of claim 6, wherein the ratio of said anionic surfactant to said polyhydroxy fatty acid amide is from 1: 2 to 8: 1. 10. The polyhydroxy fatty acid amide 0.5%
7. The composition of claim 6, comprising -12%.