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EP0670884A1 - Compositions detergentes comprenant un melange d'ions de calcium et de tensioactifs/savons non ioniques/anioniques selectionnes contenant des amides d'acide gras polyhydroxy - Google Patents

Compositions detergentes comprenant un melange d'ions de calcium et de tensioactifs/savons non ioniques/anioniques selectionnes contenant des amides d'acide gras polyhydroxy

Info

Publication number
EP0670884A1
EP0670884A1 EP94901680A EP94901680A EP0670884A1 EP 0670884 A1 EP0670884 A1 EP 0670884A1 EP 94901680 A EP94901680 A EP 94901680A EP 94901680 A EP94901680 A EP 94901680A EP 0670884 A1 EP0670884 A1 EP 0670884A1
Authority
EP
European Patent Office
Prior art keywords
alkyl
anionic
compositions
weight
fatty acid
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP94901680A
Other languages
German (de)
English (en)
Inventor
Yi-Chang Fu
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Procter and Gamble Co
Original Assignee
Procter and Gamble Co
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Procter and Gamble Co filed Critical Procter and Gamble Co
Publication of EP0670884A1 publication Critical patent/EP0670884A1/fr
Withdrawn legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D10/00—Compositions of detergents, not provided for by one single preceding group
    • C11D10/04—Compositions of detergents, not provided for by one single preceding group based on mixtures of surface-active non-soap compounds and soap
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02—Anionic compounds
    • C11D1/04—Carboxylic acids or salts thereof
    • C11D1/06—Ether- or thioether carboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02—Anionic compounds
    • C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
    • C11D1/14—Sulfonic acids or sulfuric acid esters; Salts thereof derived from aliphatic hydrocarbons or mono-alcohols
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02—Anionic compounds
    • C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
    • C11D1/16—Sulfonic acids or sulfuric acid esters; Salts thereof derived from divalent or polyvalent alcohols
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02—Anionic compounds
    • C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
    • C11D1/28—Sulfonation products derived from fatty acids or their derivatives, e.g. esters, amides
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02—Anionic compounds
    • C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
    • C11D1/29—Sulfates of polyoxyalkylene ethers
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/38—Cationic compounds
    • C11D1/52—Carboxylic amides, alkylolamides or imides or their condensation products with alkylene oxides
    • C11D1/525—Carboxylic amides (R1-CO-NR2R3), where R1, R2 or R3 contain two or more hydroxy groups per alkyl group, e.g. R3 being a reducing sugar rest

Definitions

  • the present invention relates to fully-formulated detergent compositions containing a polyhydroxy fatty acid amide surfactant, a member of a specially selected class of anionic surfactants, together with a soap.
  • the resulting compositions yield extremely low interfacial tensions in aqueous media, especially in the presence of calcium ions, and are thus useful for cleaning operations.
  • Most conventional detergent compositions contain mixtures of various detersive surfactants in order to remove a wide variety of soils and stains from surfaces.
  • various anionic surfactants especially the alkyl benzene sulfonates, are useful for removing particulate soils
  • various nonionic surfactants such as the alkyl ethoxylates and alkylphenol ethoxylates are useful for removing greasy soils.
  • mixtures of anionic and nonionic surfactants are used in many modern detergent compositions.
  • Soaps i.e., the salts of fatty acids
  • Soaps have the advantage that they are available via the hydrolysis of renewable resources such as plant and animal oils and fats.
  • soaps are quite susceptible to the formation of "curd" in the presence of water hardness.
  • soaps are not as effective for lowering solution interfacial tensions across conditions of pH and water hardness as are their counterpart synthetic surfactants, and are less effective cleaners, especially for grease and oil deposits.
  • nonionic surfactants which can be prepared using mainly renewable resources, such as fatty acid esters and sugars.
  • One such class of surfactants includes the pol hydroxy fatty acid amides.
  • nonionic surfactants with conventional anionic surfactants such as the alkyl sulfates, alkyl benzene sulfonates, alkyl ether sulfates, and the like. Attention is now being given to the improvement of such combinations of nonionic/anionic surfactants, especially with regard to their ability to reduce interfacial tensions and to provide improved grease/oil removal from a variety of substances. To achieve this goal, especially in the absence of phosphate builders, is a substantial challenge to the detergent formulator.
  • the present invention encompasses detergent compositions which provide an extremely low interfacial tension, comprising a mixed nonionic/anionic/soap surfactant system which comprises: (a) a polyhydroxy fatty acid amide of the formula 0 Rl
  • R2 - C - N - Z wherein Rl is H, C1-C3 hydrocarbyl, 2-hydroxyethyl ,
  • R2 is C5-C32 hydrocarbyl
  • Z is a polyhydroxyhydrocarbyl moiety having a linear hydrocarbyl chain with at least two (in the case of glyceraldehyde), preferably at least three (in the case of other reducing sugars) hydroxyls directly connected to the chain;
  • an anionic surfactant which is a member selected from the group consisting of alpha-sulfonated fatty acid esters (also known as alkyl ester sulfonates), especially methyl esters (“MES”), alkyl alkoxylated sulfates, especially alkyl ethoxylated sulfates (“AES”), alkyl ethoxylated carboxylates (“AEC”), alkyl and alkenyl sulfates (“AS”), and sulfated alkyl polyglucosides (“SAP”); at a weight ratio of (a):(b)
  • the "anionic surfactants" employed herein are all well-known to detergent formulators.
  • the C12-I8 alpha-sulfonated fatty acid methyl esters, the C12-I8 alkyl ethoxylated (E01-7, preferably 3) sulfates, the C12-I8 alkyl ethoxylated (E0 1-7, preferably 3-4) carboxylates, the C12-I8 primary and secondary alkyl and alkenyl (e.g., oleyl) sulfates and the sulfated C12-I8 alkyl polyglyco- sides are all fully described in the extensive patent and general literature on surfactants.
  • soaps herein is intended to encompass the classic, conventional water-soluble salts of C o-Cis linear saturated and unsaturated fatty acids.
  • Compositions according to the present invention containing such soaps exhibit quite low interfacial tensions and good grease removal properties, even at pH's near neutrality, i.e., in the range of ca. 6.5-11.0, and are thus quite useful for fabric laundering.
  • the improved qualities of the compositions herein appear to peak with soaps of about Cj2. and to decrease somewhat with soaps which are longer than about C13 and shorter than about C ⁇ , especially with respect to spontaneous e ulsification of greasy soils. Accord ⁇ ingly, the C12 soaps are preferred herein.
  • the "soaps" can be employed in any water-soluble salt form, e.g., alkali metal, alkaline earth metals, ammonium, alkanolammonium, di- or tri- alkanolammonium, C1-.5 alkyl ammonium, basic amino acid groups, and the like, all of which are well-known to manufacturers.
  • the sodium salt form is convenient, cheap and effective.
  • the fatty acid form can also be used, but will usually be converted into the ionic form by pH adjustments which are made during processing of the compositions. Since water-soluble soaps are generally easier to work with, it is preferred that they be used, rather than the fatty acid form.
  • Nonlimiting examples of soaps useful herein include: deca- noate; undecanoate; laurate; undecyleneate; tridecanoate; 2-dodecenoate; and mixtures thereof.
  • the soaps typically comprise at least about 1% by weight of the compositions herein and preferably comprise from about 4% to about 10% by weight of the total compositions herein. Stated otherwise, the weight ratio of soap (c) to the combined mixture nonionic/anionic (a + b) is in the range c:(a + b) from about 1:20 to about 1:2, preferably about 1:9 to about 1:3.
  • compositions herein contain at least about 10%, preferably from about 25% to about 65%, by weight of said mixed nonionic/anionic/soap surfactant system.
  • Such compositions typically comprise from about 5% to about 50% of the nonionic surfactant and from about 5% to about 50% of the anionic surfact ⁇ ant.
  • Highly preferred are compositions which additionally contain from about 2% to about 40% by weight of an additional detersive surfactant, as well as other optional detersive adjuncts as disclosed hereinafter.
  • compositions which comprise from about 10% to about 65% by weight of said mixed nonionic/ani ⁇ onic/soap surfactant system, from about 1% to about 15% by weight of an ethoxylated C8-C24 alcohol, and optional builders and detersive enzymes. Such compositions exhibit especially good removal of cosmetic stains from fabrics.
  • the compositions herein will also contain from about 0.5% to about 2%, preferably from about 1% to about 1.5%, by weight, of calcium ions.
  • High sudsing compositions will also contain from about 0.5% to about 2%, preferably about 1%, by weight of magnesium ions.
  • Sources of calcium and magnesium can be any convenient water-soluble and toxicologically acceptable salt, including but not limited to, calcium formate, CaCl2» MgCl2 > Ca(0H)2, Mg(0H)2, CaBr2, MgBr2, Ca jnalate, Mg malate; Ca maleate, Mg maleate, or the calcium and/or magnesium salts of anionic surfactants or hydrotropes.
  • C Cl2 and MgCl2 are convenient and preferred herein.
  • builders are used in the compositions, it is preferred that they be non-phosphate builders such as citrate, zeolite or layered silicate. This allows a residuum of calcium ions to advantageously co-act with the surfactant system to help lower interfacial tension.
  • the invention also encompasses a method for reducing the interfacial tension (IFT; oil/water interface) in a system comprising water (e.g., a washing liquor) and oil (e.g., a stain or soil on solid surfaces, fabrics, dishware, and the. like) to a level of about 0.15 dynes/cm at the oil/water interface, whereby spontaneous emulsification can occur, thereby cleansing said solid surface.
  • IFT interfacial tension
  • oil/water interface oil/water interface
  • usage levels of at least about 200 ppm, typically from about 300 ppm to about 3,000 ppm, of the composi ⁇ tions of this invention in water achieve this desirable result.
  • the invention also encompasses an improved method for removing greasy stains such as cosmetic stains from fabrics, comprising contacting the fabrics thus stained with an aqueous bath containing at least about 0.02% by weight of a composition which comprises said mixed nonionic/anionic surfactant system and said C8-C24 alkoxylated (preferably ethoxylated) alcohol or alkoxylated C8-C24 alkyl phenol (preferably ethoxylated).
  • polyhydroxy fatty acid amides used herein can be prepared, for example, by the methods disclosed in the Schwartz references above, this invention most preferably employs high quality polyhydroxy fatty acid amide surfactants which are substantially free of cyclized by-products.
  • the methods comprise reacting N-alkylamino polyols with, preferably, fatty acid methyl esters in a solvent using an alkoxide catalyst at temperatures of about 85 * C to provide high yields (90-98%) of polyhydroxy fatty acid amides having desirable low levels (typically, less than about 1.0%) of sub-optimally degradable cyclized by-products and also with improved color and improved color stability, e.g., Gardner Colors below about 4, preferably between 0 and 2.
  • the N-methyl and N-hydroxyalkyl amine compounds are preferred.
  • the C2-C3 alkyl preferably the N-C3 alkyl amine compounds
  • the methanol introduced via the catalyst or generated during the reaction provides sufficient fluidization that the use of additional reaction solvent may be optional.
  • any unreacted N-alkylamino polyol remaining in the product can be acylated with an acid anhydride, e.g., acetic anhydride, maleic anhydride, or the like, to minimize the overall level of amines in the product.
  • cyclized by-products herein is meant the undesirable reaction by-products of the primary reaction wherein it appears that the multiple hydroxyl groups in the polyhydroxy fatty acid amides can form ring structures which may not be readily biodegradable. It will be appreciated by those skilled in the chemical arts that the preparation of the polyhydroxy fatty acid amides herein using the di- and higher saccharides such as maltose will result in the formation of polyhydroxy fatty acid amides wherein linear substituent Z (which contains multiple hydroxy substituents) is naturally "capped” by a polyhydroxy ring structure. Such materials are not cyclized by-products, as defined herein.
  • compositions herein employ polyhydroxy fatty acid amide surfactants of the formula:
  • Rl is H, C1-C3 hydrocarbyl (C1-C2 is preferred for dishwashing; C3 is preferred for fabric laundering), 2-hydroxy- ethyl, 2-hydroxypropyl , or a mixture thereof, preferably C1-C4 alkyl, more preferably Ci or C2 alkyl, most preferably Cj alkyl (i.e., methyl); and R2 is a C5-C31 hydrocarbyl moiety, preferably straight chain C7-C19 alkyl or alkenyl, more preferably straight chain C9-C17 alkyl or alkenyl, most preferably straight chain Cn-Cig alkyl or alkenyl, or mixture thereof; and Z is a poly- hydroxyhydrocarbyl moiety having a linear hydrocarbyl chain with at least 2 (in the case of glyceraldehyde) or 3 hydroxyls (in the case of other reducing sugars) directly connected to the chain, or an alkoxylated derivative (preferably
  • Z preferably will be derived from a reducing sugar in a reductive amination reaction; more preferably Z is a glycityl moiety.
  • Suitable reducing sugars include glucose, fructose, maltose, lactose, galactose, mannose, and xylose, as well as glyceraldehyde.
  • high dextrose corn syrup, high fructose corn syrup, and high maltose corn syrup can -be utilized as well as the individual sugars listed above. These corn syrups may yield a mix of sugar components for Z. It should be under ⁇ stood that it is by no means intended to exclude other suitable raw materials.
  • Z preferably will be selected from the group consisting of -CH2-(CH0H) n -CH20H, -CH(CH2 ⁇ H)-(CHOH) n -i-CH2 ⁇ H, -CH2-(CHOH)2(CHOR')(CHOH)-CH2 ⁇ H, where n is an integer from 1 to 5, inclusive, and R' is H or a cyclic mono- or poly- saccharide, and alkoxylated derivatives thereof. Most preferred are glycityls wherein n is 4, particularly -CH2-(CHOH)4-CH2 ⁇ H.
  • R 1 can be, for example, N-methyl, N-ethyl, N-propyl and N-2-hydroxy ethyl.
  • R2-C0-N ⁇ can be, for example, coca ide, stearamide, oleamide, laura ide, myristamide, capricamide, palmita ide, tallowamide, etc.
  • Z can be 1-deoxyglucityl, 2-deoxyfructityl, 1-deoxyxylityl, 1-deoxymaltityl, 1-deoxylactityl, 1-deoxygalactityl, 1-deoxyman- nityl, 1-deoxymaltotriotityl, 2,3-dihydroxypropyl (from glyceral ⁇ dehyde), etc.
  • the polyhydroxy fatty acid amide surfactants used herein as the nonionic surfactant component can be mixtures of materials having various substituents R 1 and R 2 .
  • enzymes may also be included. They may be of any suitable origin, such as vegetable, animal, bacterial, fungal and yeast origin. However, their choice is governed by several factors such as pH-activity and/or stability optima, thermostability, stability versus active detergents, builders and so on. In this respect bacterial or fungal enzymes are preferred, such as bacterial amylases and proteases, and fungal cellulases. Enzymes are normally incorporated at levels sufficient to provide up to about 5 mg by weight, more typically about 0.05 mg to about 3 mg, of active enzyme per gram of the composition.
  • proteases are the subtilisins which are obtained from particular strains of B.subtilis and B.licheniforms. Another suitable protease is obtained from a strain of Bacillus, having maximum activity throughout the pH range of 8-12, developed and sold by Novo Industries A S under the registered trade name ESPERASE. The preparation of this enzyme and analogous enzymes is described in British Patent Specification No. 1,243,784 of Novo.
  • protealytic enzymes suitable for removing protein-based stains that are commercially available include those sold under the tradena es ALCALASE and SAVINASE by Novo Industries A/S (Denmark) and MAXATASE by International Bio-Synthetics, Inc. (The Netherlands).
  • proteases include Protease A (see European Patent Application 130,756, published January 9, 1985) and Protease B (see European Patent Application Serial No. 87303761.8, filed April 28, 1987, and European Patent Application 130,756, Bott et al, published January 9, 1985).
  • Amylases include, for example, ⁇ -amylases described in British Patent Specification No. 1,296,839 (Novo), RAPIDASE, International Bio-Synthetics, Inc. and TERMAMYL, Novo Industries.
  • the cellulases usable in the present invention include both bacterial or fungal cellulase. Preferably, they will have a pH optimum of between 5 and 9.5. Suitable cellulases are disclosed in U.S. Patent 4,435,307, Barbesgoard et al, issued March 6, 1984, which discloses fungal cellulase produced from Humicola insolens and Humicola strain DSM1800 or a cellulase 212-producing fungus belonging to the genus Aeromonas, and cellulase extracted from the hepatopancreas of a marine mollusk (Dolabella Auricula Solander). Suitable cellulases are also disclosed in GB-A-2.075.028; GB-A-2.095.275 and DE-0S-2.247.832.
  • Suitable lipase enzymes for detergent usage include those produced by microorganisms of the Pseudomonas group, such as Pseudomonas stutzeri ATCC 19.154, as disclosed in British Patent 1,372,034. See also Upases in Japanese Patent Application 53-20487, laid open to public inspection on February 24, 1978. This lipase is available from Amano Pharmaceutical Co. Ltd., Nagoya, Japan, under the trade name Lipase P "Amano,” hereinafter referred to as "Amano-P.” Other commercial Upases Include Amano-CES, Upases ex Chromobacter viscosum, e.g. Chromobacter viscosum var.
  • lipolyticum NRRLB 3673 commercially available from Toyo Jozo Co., Tagata, Japan; and further Chromobacter viscosum Upases from U.S. Biochemical Corp., U.S.A. and Disoynth Co., The Netherlands, and Upases ex Pseudomonas gladioli .
  • Peroxidase enzymes are used in combination with oxygen sources, e.g., percarbonate, perborate, persulfate, hydrogen peroxide, etc. They are used for "solution bleaching," i.e. to prevent transfer of dyes or pigments removed from substrates during wash operations to other substrates in the wash solution.
  • Peroxidase enzymes are known in the art, and include, for example, horseradish peroxidase, ligninase, and haloperoxidase such as chloro- and bromo-peroxidase.
  • Peroxidase-containing detergent compositions are disclosed, for example, in PCT International Application W089/099813, published October 19, 1989, by 0. Kirk, assigned to Novo Industries A/S.
  • Enzyme stabilization systems are also described, for example, in U.S. Patents 4,261,868, 3,600,319, and 3,519,570.
  • compositions herein xan option ⁇ ally include one or more other detergent adjunct materials or other materials for assisting or enhancing cleaning performance, treatment of the substrate to be cleaned, or to modify the aesthetics of the detergent composition (e.g., perfumes, color ⁇ ants, dyes, etc.).
  • other detergent adjunct materials or other materials for assisting or enhancing cleaning performance, treatment of the substrate to be cleaned, or to modify the aesthetics of the detergent composition (e.g., perfumes, color ⁇ ants, dyes, etc.).
  • Builders - Detergent builders can optionally be included in the compositions herein to assist in controlling mineral hardness.
  • Inorganic as well as organic builders can be used. Builders are typically used in fabric laundering compositions to assist in the removal of particulate soils.
  • the level of builder can vary widely depending upon the end use of the composition and its desired physical form.
  • the compositions will typically comprise at least about 1% builder.
  • Liquid formulations typically comprise from about 5% to about 50%, more typically about 5% to about 30%, by weight, of detergent builder.
  • Granular formulations typically comprise from about 10% to about 80%, more typically from about 15% to about 50% by weight, of the detergent builder.
  • Lower or higher levels of builder are not meant to be excluded.
  • silicate builders are the alkali metal silicates, particularly those having a Si ⁇ 2: a2 ⁇ ratio in the range 1.6:1 to 3.2:1 and layered silicates, such as the layered sodium silicates described in U.S. Patent 4,664,839, issued May 12, 1987 to H. P. Rieck.
  • layered silicates such as the layered sodium silicates described in U.S. Patent 4,664,839, issued May 12, 1987 to H. P. Rieck.
  • other silicates may also be useful such as for example magnesium silicate, which can serve as a crispening agent in granular formulations, as a stabilizing agent for oxygen bleaches, and as a component of suds control systems. .
  • Preferred aluminosilicates are zeolite builders which have the formula:
  • aluminosilicate ion exchange materials are commer ⁇ cially available. These aluminosilicates can be crystalline or amorphous in structure and can be naturally-occurring aluminosili- cates or synthetically derived.
  • a method for producing alumino ⁇ silicate ion exchange materials is disclosed in U.S. Patent 3,985,669, Krummel, et al, issued October 12, 1976.
  • Preferred synthetic crystalline aluminosilicate ion exchange materials useful herein are available under the designations Zeolite A, Zeolite P (B), and Zeolite X.
  • the crystalline aluminosilicate ion exchange material has the formula:
  • Organic detergent builders suitable for the purposes of the present invention include, but are not restricted to, a wide variety of polycarboxylate compounds.
  • polycar- boxylate refers to compounds having a plurality of carboxylate groups, preferably at least 3 carboxylates.
  • 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 utilized in salt form, alkali metals, such as sodium, potassium, and lithium, or alkanolammonium salts are preferred.
  • polycarboxylate builders include a variety of categories of useful materials.
  • One important category of poly ⁇ carboxylate builders encompasses the ether polycarboxylates, including oxydisuccinate, as disclosed in Berg, U.S. Patent 3,128,287, issued April 7, 1964, and Lamberti et al, U.S. Patent 3,635,830, issued January 18, 1972. See also "TMS/TDS" builders of U.S. Patent 4,663,071, issued to Bush et al, on May 5, 1987.
  • Suitable ether polycarboxylates also include cyclic compounds, particularly alicyclic compounds, such as those described in U.S.
  • ether hydroxy- polycarboxylates copolymers of maleic anhydride with ethylene or vinyl methyl ether, 1, 3, 5-trihydroxy benzene-2, 4, 6-trisul- phonic acid, and carboxymethyloxysuccinic acid
  • various alkali metal, ammonium and substituted ammonium salts of polyacetic acids such as ethylenediamine tetraacetic acid and nitrilotriacetic acid
  • polycarboxylates such as mellitic acid, succinic acid, oxydisuccinic acid, polymaleic acid, benzene 1,3,5-tricar- boxylic acid, carboxymethyloxysuccinic acid, and soluble salts thereof.
  • succinic acid builders include the C5-C20 alkyl and alkenyl succinic acids and salts thereof.
  • a particularly preferred compound of this type is dodecenylsuccinic acid.
  • succinate builders include: laurylsuc- cinate, myristylsuccinate, palmitylsuccinate, 2-dodecenylsuccinate (preferred), 2-pentadecenylsuccinate, and the like.
  • Laurylsuccin- ates are the preferred builders of this group, and are described in European Patent Application 86200690.5/0,200,263, published November 5, 1986.
  • Other suitable polycarboxylates are disclosed in U.S. Patent 4,144,226, Crutchfield et al, issued March 13, 1979 and in U.S. Patent 3,308,067, Diehl, issued March 7, 1967. See also Diehl U.S. Patent 3,723,322.
  • phosphorus builders can be used, the various alkali metal phosphates such as the well-known sodium tripolyphosphates, sodium pyrophosphates and sodium orthophosphates can be used.
  • Phosphate builders such as ethane-1- hydroxy-1,1-diphosphonate and other known phosphonates (see, for example, U.S. Patents 3,159,581; 3,213,090; 3,442,021; 3,400,148; and 3,422,137) can also be used.
  • bleaching agents will typically be at levels of from about 1% to about 20%, more typically from about 1% to about 10%, of the detergent composition, especially for fabric laundering. If present, the amount of bleach activators will typically be from about 0.1% to about 60%, more typically from about 0.5% to about 40% of the bleaching composition comprising the bleaching agent-plus-bleach activator.
  • bleaching agent that can be used without restriction encompasses percarboxylic (“percarbonate”) acid bleaching agents and salts therein. Suitable examples of this class of agents include magnesium monoperoxyphthalate hexahydrate, the magnesium salt of meta-chloro perbenzoic acid, 4-nonylamino-4- oxoperoxybutyric acid and diperoxydodecanedioic acid.
  • percarboxylic acid bleaching agents include magnesium monoperoxyphthalate hexahydrate, the magnesium salt of meta-chloro perbenzoic acid, 4-nonylamino-4- oxoperoxybutyric acid and diperoxydodecanedioic acid.
  • Such bleaching agents are disclosed in U.S. Patent 4,483,781, Hartman, issued November 20, 1984, U.S. Patent Application 740,446, Burns et al, filed June 3, 1985, European Patent Application 0,133,354,
  • Highly preferred bleaching agents also include 6-nonylamino-6-oxoperoxycaproic acid as described in U.S. Patent 4,634,551, issued January 6, 1987 to Burns et al .
  • Peroxygen bleaching agents can also be used. Suitable peroxygen bleaching compounds include sodium carbonate peroxy- hydrate, sodium pyrophosphate peroxyhydrate, urea peroxyhydrate, and sodium peroxide. Persulfate bleach (e.g., 0X0NE, manufactured commercially by DuPont) can also be used.
  • Mixtures of bleaching agents can also be used.
  • Peroxygen bleaching agents and the perborates are preferably combined with bleach activators, which lead to the in situ produc ⁇ tion in aqueous solution (i.e., during the washing process) of the peroxy acid corresponding to the bleach activator.
  • bleach activators Various nonlimiting examples of activators are disclosed in U.S. Patent 4,915,854, issued April 10, 1990 to Mao et al, and U.S. Patent 4,412,934.
  • NOBS nonanoyloxybenzene sulfonate
  • TAED tetraacetyl ethylene diamine
  • Bleaching agents other than oxygen bleaching agents are also known in the art and can be utilized herein.
  • One type of non- oxygen bleaching agent of particular interest includes photo- activated bleaching agents such as the sulfonated zinc and/or aluminum phthalocyanines. See U.S. Patent 4,033,718, issued July 5, 1977 to Holco be et al.
  • detergent compositions will contain about 0.025% to about 1.25%, by weight, of sulfonated zinc phthalocyanine.
  • Polymeric Soil Release Agent Any polymeric soil release agent known to those skilled in the art can optionally be employed in the compositions and processes of this invention.
  • Polymeric soil release agents are characterized by having both hydrophilic segments, to hydrophilize the surface of hydrophobic fibers, such as polyester and nylon, and hydrophobic segments, to deposit upon hydrophobic fibers and remain adhered thereto through completion of washing and rinsing cycles and, thus, serve as an anchor for the hydrophilic segments. This can enable stains occurring subsequent to treatment with the soil release agent to be more easily cleaned in later washing procedures.
  • the polymeric soil release agents for which performance is enhanced herein especially include those soil release agents having: (a) one or more nonionic hydrophile components consisting essentially of (i) polyoxyethylene segments with a degree of polymerization of at least 2, or (ii) oxypropylene or polyoxy- propylene segments with a degree of polymerization of from 2 to 10, wherein said hydrophile segment does not encompass any oxypropylene unit unless it is bonded to adjacent moieties at each end by ether linkages, or (iii) a mixture of oxyalkylene units comprising oxyethylene and from 1 to about 30 oxypropylene units wherein said mixture contains a sufficient amount of oxyethylene units such that the hydrophile component has hydrophilicity great enough to increase the hydrophilicity of conventional polyester synthetic fiber surfaces upon deposit of the soil release agent on such surface, said hydrophile segments preferably comprising at least about 25% oxyethylene units and more preferably, especially for such components having about 20 to 30 oxypropylene units, at least about 50%
  • the polyoxyethylene segments of (a)(i) will have a degree of polymerization of from 2 to about 200, although higher levels can be used, preferably from 3 to about 150-, more prefer ⁇ ably from 6 to about 100.
  • Suitable oxy C4-C6 alkylene hydrophobe segments include, but are not limited to, end-caps of polymeric soil release agents such as M ⁇ 3S(CH2)nOCH2CH2 ⁇ -, where M is sodium and n is an integer from 4-6, as disclosed in U.S. Patent 4,721,580, issued January 26, 1988 to Gosselink.
  • Polymeric soil release agents useful in the present invention also include cellulosic derivatives such as hydroxyether cellu- losic polymers, copolymeric blocks of ethylene terephthalate or propylene terephthalate with polyethylene oxide or polypropylene oxide terephthalate, and the like. Such agents are commercially available and include hydroxyethers of cellulose such as METHOCEL (Dow). Cellulosic soil release agents for use herein also include those selected from the group consisting of C1-C4 alkyl and C4 hydroxyalkyl cellulose; see U.S. Patent 4,000,093, issued December 28, 1976 to Nicol, et al .
  • Soil release agents characterized by poly(vinyl ester) hydrophobe segments include graft copolymers of poly(vinyl ester), e.g., Ci-C ⁇ vinyl esters, preferably poly(vinyl acetate) grafted onto polyalkylene oxide backbones, such as polyethylene oxide backbones.
  • poly(vinyl ester) e.g., Ci-C ⁇ vinyl esters
  • poly(vinyl acetate) grafted onto polyalkylene oxide backbones such as polyethylene oxide backbones.
  • Commercially available soil release agents of this kind include the SOKALAN type of material, e.g., SOKALAN HP-22, available from BASF (West Germany).
  • One type of preferred soil release agent is a copolymer having random blocks of ethylene terephthalate and polyethylene oxide (PEO) terephthalate.
  • the molecular weight of this polymeric soil release agent is in the range of from about 25,000 to about 55,000. See U.S. Patent 3,959,230 to Hays, issued May 25, 1976 and U.S. Patent 3,893,929 to Basadur issued July 8, 1975.
  • Another preferred polymeric soil release agent is a polyester with repeat units of ethylene terephthalate units containing 10-15% by weight of ethylene terephthalate units together with 90-80% by weight of polyoxyethylene terephthalate units, derived from a polyoxyethylene glycol of average molecular weight 300-5,000. Examples of this polymer include the commercially available material ZELCON 5126 (from Dupont) and MILEASE T (from ICI). See also U.S. Patent 4,702,857, issued October 27, 1987 to Gosselink.
  • Another preferred polymeric soil release agent is a sulfonated product of a substantially linear ester oligomer comprised of an oligomeric ester backbone of terephthaloyl and oxyalkyleneoxy repeat units and terminal moieties covalently attached to the backbone.
  • Suitable polymeric soil release agents include the terephthalate polyesters of U.S. Patent 4,711,730, issued December 8, 1987 to Gosselink et al, the anionic end-capped oligomeric esters of U.S. Patent 4,721,580, issued January 26, 1988 to Gosselink, and the block polyester oligomeric compounds of U.S. Patent 4,702,857, issued October 27, 1987 to Gosselink.
  • Preferred polymeric soil release agents also include the soil release agents of U.S. Patent 4,877,896, issued October 31, 1989 to Maldonado et al, which discloses anionic, especially sulfo- aroyl, end-capped terephthalate esters.
  • soil release agents will generally comprise from about 0.01% to about 10.0%, by weight, of the detergent composi- tions herein, typically from about 0.1% to about 5%, preferably from about 0.2% to about 3.0%.
  • the detergent compositions herein may also optionally contain one or more iron and/or manganese chelating agents.
  • chelating agents can be selected from the group consisting of amino carboxylates, amino phosphonates, polyfunctionally-substituted aromatic chelating agents and mixtures therein, all as hereinafter defined. Without intending to be bound by theory, it is believed that the benefit of these materials is due in part to their exceptional ability to remove iron and manganese ions from washing solutions by formation of soluble chelates.
  • Amino carboxylates useful as optional chelating agents include ethylenediaminetetraacetates, N-hydrox eth lethylenedi- aminetriacetates, nitrilotriacetates, ethylenediamine tetrapropri- onates, triethylenetetraaminehexaacetates, diethylenetriamine- pentaacetates, and ethanoldiglycines, alkali metal, ammonium, and substituted ammonium salts therein and mixtures therein.
  • Amino phosphonates are also suitable for use as chelating agents in the compositions of the invention when at least low levels of total phosphorus are permitted in detergent compositions, and include ethylenediaminetetrakis (methylenephos- phonates), nitrilotris (methylenephosphonates) and diethylenetri- aminepentakis (methylenephosphonates).
  • these amino phosphonates do not contain alkyl or alkenyl groups with more than about 6 carbon atoms.
  • Polyfunctionally-substituted aromatic chelating agents are also useful in the compositions herein. See U.S. Patent 3,812,044, issued May 21, 1974, to Connor et al .
  • Preferred compounds of this type in acid form are dihydroxydisulfobenzenes such as 1,2-dihydroxy -3,5-disulfobenzene.
  • a preferred biodegradable chelator for use herein is ethyl- enediamine disuccinate ("EDDS"), as described in U.S. Patent 4,704,233, November 3, 1987, to Hartman and Perkins. If utilized, these chelating agents will generally comprise from about 0.1% to about 10% by weight of the detergent composi ⁇ tions herein. More preferably, if utilized, the chelating agents will comprise from about 0.1% to about 3.0% by weight of such compositions.
  • EDDS ethyl- enediamine disuccinate
  • compositions of the present invention can also optionally contain water-soluble ethoxylated amines having clay soil removal and anti-redeposition properties.
  • Granular detergent compositions which contain these compounds typically contain from about 0.01% to about 10.0% by weight of the water-soluble ethoxylated amines; liquixi detergent compositions typically contain about 0.01% to about 5%.
  • the most preferred soil release and anti-redeposition agent is ethoxylated tetraethylenepentamine. Exemplary ethoxylated amines are further described in U.S. Patent 4,597,898, VanderMeer, issued July 1, 1986.
  • Another group of preferred clay soil removal/antiredeposition agents are the cationic compounds dis ⁇ closed in European Patent Application 111,965, Oh and Gosselink, published June 27, 1984.
  • Other clay soil removal/antiredeposition agents which can be used include the ethoxylated amine polymers disclosed in European Patent Application 111,984, Gosselink, published June 27, 1984; the zwitterionic polymers disclosed in European Patent Application 112,592, Gosselink, published July 4, 1984; and the amine oxides disclosed in U.S.
  • Patent 4,548,744, Connor, issued October 22, 1985 Other clay soil removal and/or anti redeposition agents known in the art can also be utilized in the compositions herein.
  • Another type of preferred anti- redeposition agent includes the carboxy methyl cellulose (CMC) materials. These materials are well known in the art.
  • CMC carboxy methyl cellulose
  • Polymeric Dispersing Agents can advantageously be utilized at levels from about 0.1% to about 7%, by weight, in the compositions herein. These materials can also aid in calcium and magnesium hardness control.
  • Suitable polymeric dispersing agents include polymeric polycarboxylates and polyethylene glycols, although others known in the art can also be used.
  • polymeric dispersing agents enhance overall detergent builder performance, when used in combination with other builders (including lower molecular weight polycarboxylates) by crystal growth inhibition, particulate soil release peptization, and anti-redeposition.
  • Polymeric polycarboxylate materials can be prepared by polymerizing or copolymerizing suitable unsaturated monomers, preferably in their acid form.
  • Unsaturated onomeric acids that can be polymerized to form suitable polymeric polycarboxylates include acrylic acid, maleic acid (or maleic anhydride), fumaric acid, itaconic acid, aconitic acid, mesaconic acid, citraconic acid and methylenemalonic acid.
  • the presence in the polymeric polycarboxylates herein of monomeric segments, containing no carboxylate radicals such as vinylmethyl ether, styrene, ethylene, etc. is suitable provided that such segments do not constitute more than about 40% by weight.
  • Particularly suitable polymeric polycarboxylates can be derived from acrylic acid.
  • acrylic acid-based polymers which are useful herein are the water-soluble salts of polymerized acrylic acid.
  • the average molecular weight of such polymers in the acid form preferably ranges from about 2,000 to 10,000, more preferably from about 4,000 to 7,000 and most preferably from about 4,000 to 5,000.
  • Water-soluble salts of such acrylic acid polymers can include, for example, the alkali metal, ammonium and substituted ammonium salts. Soluble polymers of this type are known materials. Use of polyacrylates of this type in detergent compositions has been disclosed, for example, in Diehl, U.S. Patent 3,308,067, issued March 7, 1967.
  • Acrylic/maleic-based copolymers may also be used as a preferred component of the dispersing/anti-redeposition agent.
  • Such materials include the water-soluble salts of copolymers of acrylic acid and maleic acid.
  • the average molecular weight of such copolymers in the acid form preferably ranges from about 2,000 to 100,000, more preferably from about 5,000 to 75,000, most preferably from about 7,000 to 65,000.
  • the ratio of acrylate to maleate segments in such copolymers will generally range from about 30:1 to about 1:1, more preferably from about 10:1 to 2:1.
  • Water-soluble salts of such acrylic acid/maleic acid copolymers can include, for example, the alkali metal, ammonium and substituted ammonium salts. Soluble acrylate/maleate copolymers of this type are known materials which are described in European Patent Application No. 66915, published December 15, 1982.
  • PEG poly ⁇ ethylene glycol
  • PEG can exhibit dispersing agent perform- ance as well as act as a clay soil removal/antiredeposition agent.
  • Typical molecular weight ranges for these purposes range 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.
  • Polyaspartate and polyglutamate dispersing agents may also be used, especially in conjunction with zeolite builders.
  • Briohtener Any optical brighteners or other brightening or whitening agents known in the art can be incorporated at levels typically from about 0.05% to about 1.2%, by weight, into the detergent compositions herein.
  • Commercial optical brighteners which may be useful in the present invention can be classified into subgroups which include, but are not necessarily limited to, derivatives of stilbene, pyrazoline, coumarin, carboxylic acid, methinecyanines, dibenzothiphene-5,5-dioxide, azoles, 5- and 6-membered-ring heterocycles, and other miscellaneous agents. Examples of such brighteners are disclosed in "The Production and Application of Fluorescent Brightening Agents", M. Zahradnik, Published by John Wiley & Sons, New York (1982).
  • optical brighteners which are useful in the present compositions are those identified in U.S. Patent 4,790,856, issued to Wixon on December 13, 1988. These brighteners include the PHORWHITE series of brighteners from Verona. Other brighteners disclosed in this reference include: Tinopal UNPA, Tinopal CBS and Tinopal 5BM; available from Ciba- Geigy; Arctic White CC and Artie White CWD, available from Hilton- Davis, located in Italy; the 2-(4-styryl-phenyl)-2H- naphthol[l,2- d]triazoles; 4,4'-bis- (l,2,3-triazol-2-yl)-stil- benes; 4,4'-bis- (styryl)bisphenyls; and the y-aminocoumarins.
  • these brighteners include 4-methyl-7-diethyl- amino coumarin; l,2-bis(-benzimidazol-2-yl)ethylene; 1,3-diphenylphrazolines; 2,5-bis(benzoxazol-2-yl)thiophene; 2-styryl-naphth-[l,2-d]oxazole; and 2-(stilbene-4-yl)-2H-naphtho- [l,2-d]triazole. See also U.S. Patent 3,646,015, issued February 29, 1972 to Hamilton. Suds Suppressors - Compounds for reducing or suppressing the formation of suds can be incorporated into the compositions of the present invention.
  • suds suppressors A wide variety of materials may be used as suds suppressors, and suds suppressors are well known to those skilled in the art. See, for example, Kirk Othmer Encyclopedia of Chemical Technology, Third Edition, Volume 7, pages 430-447 (John Wiley & Sons, Inc., 1979).
  • One category of suds suppressor of particular interest encompasses monocarboxylic fatty acids and soluble salts therein. See U.S. Patent 2,954,347, issued September 27, 1960 to Wayne St. John.
  • the monocarboxylic fatty acids and salts thereof used as suds suppressor typically have hydrocarbyl chains of 10 to about 24 carbon atoms, preferably 12 to 18 carbon atoms.
  • Suitable salts include the alkali metal salts such as sodium, potassium, and lithium salts, and ammonium and alkanolammonium salts.
  • the detergent compositions herein may also contain non- surfactant suds suppressors.
  • non- surfactant suds suppressors include, for example: high molecular weight hydrocarbons such as paraffin, fatty acid esters (e.g., fatty acid triglycerides), fatty acid esters of monovalent alcohols, aliphatic C18-C40 ketones (e.g. stearone), etc.
  • suds inhibitors include N-alkylated amino triazines such as tri- to hexa-alkylmelamines or di- to tetra-alkyldiamine chlortriazines formed as products of cyanuric chloride with two or three moles of a primary or secondary amine containing 1 to 24 carbon atoms, propylene oxide, and monostearyl phosphates such as monostearyl alcohol phosphate ester and monostearyl di-alkali metal (e.g. K, Na, and Li) phosphates and phosphate esters.
  • the hydrocarbons such as paraffin and haloparaffin can be utilized in liquid form.
  • the liquid hydrocarbons will be liquid at room temperature and atmospheric pressure, and will have a pour point in the range of about -40 * C and about 5 * C, and a minimum boiling point not less than about 110 * C (atmospheric pressure). It is also known to utilize waxy hydrocarbons, preferrably having a melting point below about 100 * C.
  • the hydrocarbons constitute a preferred category of suds suppressor for detergent compositions. Hydrocar- bon suds suppressors are described, for example, in U.S. Patent 4,265,779, issued May 5, 1981 to Gandolfo et al .
  • the hydrocar ⁇ bons thus, include aliphatic, alicyclic, aromatic, and hetero- cyclic saturated or unsaturated hydrocarbons having from about 12 to about 70 carbon atoms.
  • the term "paraffin,” as used in this suds suppressor discussion, is intended to include mixtures of true paraffins and cyclic hydrocarbons.
  • Non-surfactant suds comprises silicone suds suppressors.
  • This category includes the use of polyorganosiloxane oils, such as polydimethylsiloxane, dispersions or emulsions of polyorganosiloxane oils or resins, and combina ⁇ tions of polyorganosiloxane with silica particles wherein the polyorganosiloxane is chemisorbed of fused onto the silica.
  • Silicone suds suppressors are well known in the art and are, for example, disclosed in U.S. Patent 4,265,779, issued May 5, 1981 to Gandolfo et al and European Patent Application No. 89307851.9, published February 7, 1990, by Starch, M. S.
  • silicone and silanated silica are described, for instance, in German Patent Application DOS 2,124,526.
  • Silicone defoamers and suds controlling agents in granular detergent compositions are disclosed in U.S. Patent 3,933,672, Bartolotta et al, and in U.S. Patent 4,652,392, Baginski et al, issued March 24, 1987.
  • An exemplary silicone based suds suppressor for use herein is a suds suppressing amount of a suds controlling agent consisting essentially of: (i) polydimethylsiloxane fluid having a viscosity of from about 20 cs. to about 1500 cs.
  • the solvent for a continuous phase is made up of certain polyethylene glycols or polyethylene-polypropylene glycol copolymers or mixtures thereof (preferred), and not polypropylene glycol.
  • the primary silicone suds suppressor is branched/crosslinked and not linear.
  • typical liquid laundry detergent compositions with controlled suds will optionally comprise from about 0.001 to about 1, preferably from about 0.01 to about 0.7, most preferably from abut 0.05 to about 0.5, weight % of said silicone suds suppressor, which comprises (1) a nonaqueous emulsion of a primary antifoam agent which is a mixture of (a) a polyorganosiloxane, (b) a resinous siloxane or a silicone resin-producing silicone compound, (c) a finely divided filler material, and (d) a catalyst to promote the reaction of mixture components (a), (b) and (c), to form silanolates; (2) at least one nonionic silicone surfactant; and (3) polyethylene glycol or a copolymer of polyethylene-polypropylene glycol having a solubility in water at room temperature of more than about 2 weight %; and without polypropylene glycol.
  • a primary antifoam agent which is a mixture of (a) a polyorgano
  • the silicone suds suppressor herein preferably comprises polyethylene glycol and a copolymer of polyethylene glycol/poly- propylene glycol, all having an average molecular weight of less than about 1,000, preferably between about 100 and 800.
  • the polyethylene glycol and polyethylene/polypropylene copolymers herein have a solubility in water at room temperature of more than about 2 weight %, preferably more than about 5 weight %.
  • the preferred solvent herein is polyethylene glycol having an average molecular weight of less than about 1,000, more preferably between about 100 and 800, most preferably between 200 and 400, and a copolymer of polyethylene glycol/polypropylene glycol, preferably PPG 200/PEG 300. Preferred is a weight ratio of between about 1:1 and 1:10, most preferably between 1:3 and 1:6, of polyethylene glycol:copolymer of polyethylene-polypropylene glycol .
  • the preferred silicone suds suppressors used herein do not contain polypropylene glycol, particularly of 4,000 molecular weight. They also preferably do not contain block copolymers of ethylene oxide and propylene oxide, like PLUR0NIC L101.
  • suds suppressors useful herein comprise the secondary alcohols (e.g., 2-alkyl alkanols) and mixtures of such alcohols with silicone oils, such as the silicones disclosed in U.S. 4,798,679, 4,075,118 and EP 150,872.
  • the secondary alcohols include the C6-Ci6 alkyl alcohols having a C1-C16 chain.
  • a preferred alcohol is 2-butyl octanol, which is available from Condea under the trademark IS0F0L 12.
  • Mixtures of secondary alcohols are available under the trademark ISALCHEM 123 from Enichem.
  • Mixed suds suppressors typically comprise mixtures of alcohol + silicone at a weight ratio of 1:5 to 5:1.
  • Suds suppressors when utilized, are preferably present in a "suds suppressing amount.”
  • Suds suppressing amount is meant that the formulator of the composition can select an amount of this suds controlling agent that will sufficiently control the suds to result in a low-sudsing laundry detergent for use in automatic laundry washing machines.
  • the low-sudsing compositions herein will generally comprise from 0% to about 5% of suds suppressor.
  • monocarboxylic fatty acids, and salts therein will be present typically in amounts up to about 5%, by weight, of the detergent composition.
  • Silicone suds suppressors are typically utilized in amounts up to about 2.0%, by weight, of the detergent composition, although higher amounts may be used. This upper limit is practical in nature, due primarly to concern with keeping costs minimized and effectiveness of lower amounts for effectively controlling sudsing.
  • silicone suds suppressor is used, more preferably from about 0.25% to about 0.5%.
  • these weight percentage values include any silica that may be utilized in combination with polyorganosiloxane, as well as any adjunct materials that may be utilized.
  • Monostearyl phosphate suds suppressors are generally utilized in amounts ranging from about 0.1% to about 2%, by weight, of the composition.
  • Hydrocarbon suds suppressors are typically utilized in amounts ranging from about 0.01% to about 5.0%, although higher levels can be used.
  • the surfactant compositions herein can also be used with a variety of other adjunct ingredi- ents which provide still other benefits in various compositions within the scope of this invention.
  • the following illustrates a variety of such adjunct ingredients, but is not intended to be limiting therein.
  • Various through-the-wash fabric softeners especially the impalpable smectite clays of U.S. Patent 4,062,647, Storm and Nirschl, issued December 13, 1977, as well as other softener clays known in the art, can be used typically at levels of from about 0.5% to about 10% by weight in the present composi ⁇ tions to provide fabric softener benefits concurrently with fabric cleaning.
  • the polyhydroxy fatty acid amides of the present invention cause less interference with the softening performance of the clay than do the common polyethylene oxide nonionic sur ⁇ factants of the art.
  • Clay softeners can be used in combination with amine and cationic softeners, as disclosed, for example, in U.S. Patent 4,375,416, Crisp et al, March 1, 1983 and U.S. Patent 4,291,071, Harris et al, issued September 22, 1981.
  • Hair Care Ingredients - Shampoo compositions formulated in the manner of this invention can contain from about 0.05% to about 10% by weight of various agents such as: conditioners, e.g., silicones (see, for example, U.S. Patents 4,152,416 and 4,364,847); antidandruff agents such as the pyridinethiones, especially zinc pyridinethione (see U.S. Patents 4,379,753 and 4,345,080), selenium compounds such as selenium sulfide and OCTOPIROX; hair styling polymers (see U.S.
  • conditioners e.g., silicones
  • antidandruff agents such as the pyridinethiones, especially zinc pyridinethione (see U.S. Patents 4,379,753 and 4,345,080), selenium compounds such as selenium sulfide and OCTOPIROX
  • hair styling polymers see U.S.
  • Various detersive ingredients employed in the present compo ⁇ sitions advantageously can be stabilized by absorbing said ingredients onto a porous hydrophobic substrate, then coating said substrate with a hydrophobic coating.
  • the detersive ingredient is admixed with a surfactant before being absorbed into the porous substrate.
  • the detersive ingredient is released from the substrate into the aqueous washing liquor, where it performs its intended detersive function.
  • a porous hydro ⁇ phobic silica (trademark SIPERNAT D10, DeGussa) is admixed with a proteolytic enzyme solution containing 3%-5% of C ⁇ 3_i5 ethoxylated alcohol E0(7) nonionic surfactant.
  • the enzyme/surfact ⁇ ant solution is 2.5 X the weight of silica.
  • the resulting powder is dispersed with stirring in silicone oil (various silicone oil viscosities in the range of 500-12,500 can be used).
  • silicone oil various silicone oil viscosities in the range of 500-12,500 can be used.
  • the result- ing silicone oil dispersion is emulsified or otherwise added to the final detergent matrix.
  • ingredients such as the aforementioned enzymes, bleaches, bleach activators, bleach catalysts, photoactivators, dyes, fluorescers, fabric conditioners and hydrolyzable surfactants can be "protected” for use in deter- gents, including liquid laundry detergent compositions.
  • Liquid detergent compositions can contain water and other solvents as carriers.
  • Low molecular weight primary or secondary alcohols exemplified by methanol, ethanol, propanol, and isopropanol are suitable.
  • Monohydric alcohols are preferred for solubilizing surfactant, but polyols such as those containing from 2 to about 6 carbon atoms and from 2 to about 6 hydroxy groups (e.g., 1,3-propanediol, ethylene glycol, glycerine, and 1,2- propanediol) can also be used.
  • Formulations - The formulation of effective, modern detergent compositions poses a considerable challenge, especially in the absence of phosphate builders.
  • the formu ⁇ lator is required to address the removal of a wide variety of soils and stains, many of which are termed "greasy/oily" soils, such as foods, cosmetics, motor oil, and the like, from a wide variety of fabric surfaces and under a spectrum of usage condi ⁇ tions, ranging from boil wash temperatures preferred by some users to laundering temperatures as cold as 5*C preferred by others.
  • Local factors especially water hardness levels and the presence or absence of metal cations such as iron in local.wash water supplies, can dramatically impact detergency performance.
  • the formulator of hand dishwashing compositions must provide compositions which remove high loads of greasy food residues, but which do so under conditions which are not irritating to the user's skin nor damaging to the articles being washed. It is especially difficult to provide good grease removal at near- neutral pH's.
  • spontaneous emulsifica ⁇ tion may be achievable with some specialized surfactants only at relatively high pH's in the range of 10-11, whereas this desirable result is also achievable with the present compositions even in the near-neutral pH range of about 6.5-8. This is particularly important for hand-washing operations, for example, hand dishwash ⁇ ing, where skin mildness is of concern to the user.
  • polyhydroxy fatty . acid amides employed in the practice of this invention are, structurally, nonionic-type surfactants and are referred to herein as "nonionics". It now also appears that the conformation of the polyhydroxy fatty acid amides may be changed due to interaction between water hardness ions, especially calcium cations, and the soap or anionic surfact- ant. This may increase the molecular packing of the polyhydroxy fatty acid amides at the air/water interface. Whatever the explanation at the molecular level, the net result is the lower interfacial tensions and improved cleaning benefits associated with the compositions of this invention, especially with respect to greasy/oily stains.
  • IFT interfacial tension
  • Cayias, Schechter and Wade "The Measurement of Low Interfacial Tension via the Spinning Drop Technique", ACS Symposium Series No. 8 (1975) ADSORPTION AT INTERFACES, beginning at page 234.
  • Equipment for running IFT measurements is currently available from W. H. Wade, Depts. of Chemistry and Chemical Engineering, The University of Texas at Austin, Austin, Texas 78712.
  • low interfacial tension herein is meant an IFT which is sufficiently low that "spontaneous emulsification", i.e., rapid emulsification with little or no mechanical agitation, can occur.
  • a typical fatty acid N-methyl glucamide nonionic surfactant at concentrations in water ranging from about 300 ppm to about 600 ppm and at water hardness (Ca++) concentra ⁇ tions of 2 grains/gallon (14 ppm), 7 gr/gal (48 ppm) and 15 gr/gal (103 ppm) one notes a range of IFT from about 0.25 dynes/cm to about 0.4 dynes/cm. Under such conditions, “spontaneous emulsifi- cation" of grease/oil soil, if any, is minimal.
  • the IFT is reduced to 0.15 dynes/cm, or less, and spontaneous oil emulsification is noted.
  • a consumer relevant test soil is dyed with 0.5% Oil Red EGN.
  • a 100 ml sample of the detergent composition being tested is prepared at the desired concentration (typically, about 500 ppm) and temperature in water which is "pre-hardened” to any desired concentration of calcium ions (typically, about 48 ppm), and contained in an 8 oz. capped jar.
  • the sample pH is adjusted to the intended end-use pH (typically in the range of 6.5 to 8) and 0.2 g of the test soil is added.
  • the jar is shaken 4 times and the sample graded. Alternatively, the sample is placed in a beaker and stirred with a stir bar for 15 seconds.
  • the sample is graded as follows:
  • 0 Clear solution with large red oil droplets in it (0.1-5 mm diameter), i.e., no emulsification;
  • the formulator may determine that it is acceptable prac ⁇ tice to rely on natural water hardness to provide such ions to the compositions under in-use situations. This may be a reasonable expedient, since as little as 2 gr/gal calcium hardness can provide substantial benefits. However, the formulator will most likely decide to add the calcium and/or optional magnesium ions directly to the compositions, thereby assuring their presence in the in-use situation.
  • the calcium and/or magnesium to the compositions in the form of a lightly co plexed chelate, such as calcium malate or maleate, magnesium malate or maleate, or the like.
  • the detergent compositions herein will preferably be formu ⁇ lated such that during use in aqueous cleaning operations, the wash water will have a pH of between about 6.5 and about 11, preferably between about 7.5 and about 10.5.
  • Liquid product formulations preferably have a pH between about 7.5 and about 9.5, more preferably between about 7.5 and about 9.0.
  • Techniques for controlling pH at recommended usage levels include the use of buffers, alkalis, acids, etc., and are well known to those skilled in the art.
  • a liquid detergent composition herein comprises the following.
  • Nonionic/anionic* 15.0 Sodium citrate 1.0
  • a granular detergent herein comprises the following. Ingredient % (wt.)
  • compositions of Example I and II are modified by including 0.5% of a commercial proteolytic enzyme preparation (ESPERASE) therein.
  • ESPERASE a commercial proteolytic enzyme preparation
  • TERMAMYL a commercial a ylase preparation
  • LIPOLASE a commercial lipolytic enzyme preparation
  • EXAMPLE V A shampoo composition is prepared according to Example IV by deleting the magnesium ions.
  • compositions according to the present invention which additionally comprise from about 1% to about 20% by weight of an ethoxylated (EO 1-7; preferably 2-3) C12-C18 alcohol or alkyl phenol are preferably used in such formulations to further boost performance.
  • EO 1-7 ethoxylated
  • C12-C18 alcohol or alkyl phenol ethoxylated phenol
  • compositions herein will typically be used in aqueous media at concentrations of at least about 200 ppm, e.g., for lightly-soiled fabrics and/or hand dishwashing. Higher usage concentrations in the range of 1,000 ppm to 8,000 ppm, and higher, are used for heavily-soiled fabrics. However, usage levels can vary, depending on the desires of the user, soil loads, soil types, and the like. Wash temperatures can range from 5'C to the boil. It will be further appreciated that the invention encompasses a method for lowering IFT's of oil/grease (especially triglyceride fats and oils) in the presence of water, comprising admixing in said water at least about 200 ppm of the compositions herein.
  • oil/grease especially triglyceride fats and oils
  • Such lowering of IFT also provides a means for achieving spontane ⁇ ous emulsification which is useful not only in fabric and hard surface cleaning, but also in any circumstance where it is import ⁇ ant to render oily materials more fluid, e.g., petroleum recovery and transmission, cosmetic formulations, and the like.

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Detergent Compositions (AREA)
  • Cosmetics (AREA)

Abstract

Des tensioactifs non ioniques/anioniques mélangés comprenant des amides d'acide gras polyhydroxy et des tensioactifs anioniques d'esters d'acide gras α-sulfonatés, de sulfate d'alkyle éthoxylé, de carboxylate d'alkyle éthoxylé, de classes de polyglycosides de sulfate d'alkyle ou d'alkyle sulfaté sont utilisés dans divers types de nettoyage. Ainsi, des glucamides N-alkyle d'acide gras sont combinés à ces tensioactifs anioniques, à un savon, et à une source d'ions de calcium. Les mélanges obtenus présentent une tension interfaciale exceptionnellement faible, notamment en présence d'ions de calcium. Les mélanges de ces systèmes de tensioactifs non ioniques/anioniques/savon/calcium avec des tensioactifs d'alcool éthoxylé classiques permettent d'enlever parfaitement les taches de cosmétiques des tissus.
EP94901680A 1992-11-30 1993-11-24 Compositions detergentes comprenant un melange d'ions de calcium et de tensioactifs/savons non ioniques/anioniques selectionnes contenant des amides d'acide gras polyhydroxy Withdrawn EP0670884A1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
US98407392A 1992-11-30 1992-11-30
US984073 1992-11-30
PCT/US1993/011453 WO1994012609A1 (fr) 1992-11-30 1993-11-24 Compositions detergentes comprenant un melange d'ions de calcium et de tensioactifs/savons non ioniques/anioniques selectionnes contenant des amides d'acide gras polyhydroxy

Publications (1)

Publication Number Publication Date
EP0670884A1 true EP0670884A1 (fr) 1995-09-13

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EP94901680A Withdrawn EP0670884A1 (fr) 1992-11-30 1993-11-24 Compositions detergentes comprenant un melange d'ions de calcium et de tensioactifs/savons non ioniques/anioniques selectionnes contenant des amides d'acide gras polyhydroxy

Country Status (7)

Country Link
EP (1) EP0670884A1 (fr)
JP (1) JPH08503733A (fr)
CN (1) CN1090886A (fr)
AU (1) AU5618294A (fr)
CA (1) CA2148099A1 (fr)
MX (1) MX9307501A (fr)
WO (1) WO1994012609A1 (fr)

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US5760199A (en) * 1995-07-13 1998-06-02 Akzo Nobel Nv Polysaccharide acid amide comprising fatty alkyl group in amide
US5990066A (en) * 1995-12-29 1999-11-23 The Procter & Gamble Company Liquid hard surface cleaning compositions based on carboxylate-containing polymer and divalent counterion, and processes of using same
US8172953B2 (en) 2009-11-06 2012-05-08 Ecolab Usa Inc. Alkyl polyglucosides and a propoxylated-ethoxylated extended chain surfactant
US8071520B2 (en) 2009-11-06 2011-12-06 Ecolab Usa Inc. Sulfonated alkyl polyglucoside use for enhanced food soil removal
US8216994B2 (en) 2009-11-09 2012-07-10 Ecolab Usa Inc. Phosphate functionalized alkyl polyglucosides used for enhanced food soil removal
US8389463B2 (en) 2009-11-09 2013-03-05 Ecolab Usa Inc. Enhanced dispensing of solid compositions
US10813862B2 (en) 2012-05-30 2020-10-27 Clariant International Ltd. Use of N-methyl-N-acylglucamines as solubilizers
IN2014DN09937A (fr) 2012-05-30 2015-08-14 Clariant Int Ltd
US10844322B2 (en) * 2012-08-07 2020-11-24 Ecolab Usa Inc. High flashpoint alcohol-based cleaning, sanitizing and disinfecting composition and method of use on food contact surfaces
DE102012021647A1 (de) 2012-11-03 2014-05-08 Clariant International Ltd. Wässrige Adjuvant-Zusammensetzungen
US9353335B2 (en) * 2013-11-11 2016-05-31 Ecolab Usa Inc. High alkaline warewash detergent with enhanced scale control and soil dispersion
DE102014003367B4 (de) 2014-03-06 2017-05-04 Clariant International Ltd. Verwendung von N-Methyl-N-acylglucamin als Korrosionsinhibitor
DE102014003215A1 (de) 2014-03-06 2015-05-28 Clariant International Ltd. Korrosionsinhibierende Zusammensetzungen
US20150252310A1 (en) 2014-03-07 2015-09-10 Ecolab Usa Inc. Alkyl amides for enhanced food soil removal and asphalt dissolution
DE102014005771A1 (de) 2014-04-23 2015-10-29 Clariant International Ltd. Verwendung von wässrigen driftreduzierenden Zusammensetzungen
DE102014016763A1 (de) 2014-11-13 2015-06-25 Clariant International Ltd. VOC-arme Koaleszensmittel für wässrige Dispersionen
DE202014010366U1 (de) 2014-11-24 2015-05-15 Clariant International Ltd. Verwendung von Polyhydroxyfettsäureamiden zur Verbesserung der Nassabriebbeständigkeit von wässrigen Dispersionen
DE102014017368A1 (de) 2014-11-24 2015-05-28 Clariant International Ltd. Verwendung von Polyhydroxyfettsäureamiden zur Verbesserung der Nassabriebbeständigkeit von wässrigen Dispersionsfarben
DE202015008045U1 (de) 2015-10-09 2015-12-09 Clariant International Ltd. Universelle Pigmentdispersionen auf Basis von N-Alkylglukaminen
DE102015219651A1 (de) 2015-10-09 2017-04-13 Clariant International Ltd. Zusammensetzungen enthaltend Zuckeramin und Fettsäure
DE202016003070U1 (de) 2016-05-09 2016-06-07 Clariant International Ltd. Stabilisatoren für Silikatfarben
DE202019000202U1 (de) 2018-01-17 2019-04-23 Horst Hercher Fluidisches Temperiermittel

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EP0557426B1 (fr) * 1990-11-16 1997-03-05 The Procter & Gamble Company Composition detergente douce pour vaisselle contenant un tensioactif d'ethoxycarboxylate d'alkyle et des ions de calcium ou de magnesium
CA2116955C (fr) * 1991-09-06 1998-06-23 Kofi Ofosu-Asante Compositions detergentes renfermant du calcium et un amide d'acide gras polyhydroxyle

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Also Published As

Publication number Publication date
MX9307501A (es) 1994-05-31
AU5618294A (en) 1994-06-22
CA2148099A1 (fr) 1994-06-09
WO1994012609A1 (fr) 1994-06-09
CN1090886A (zh) 1994-08-17
JPH08503733A (ja) 1996-04-23

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