EP0693113A1 - Agents tensioactifs a base de sulfate d'alkyle (2,3) secondaire utilises dans des compositions detersives avec des amides d'acide gras polyhydroxy - Google Patents

Agents tensioactifs a base de sulfate d'alkyle (2,3) secondaire utilises dans des compositions detersives avec des amides d'acide gras polyhydroxy

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Publication number
EP0693113A1
EP0693113A1 EP94913364A EP94913364A EP0693113A1 EP 0693113 A1 EP0693113 A1 EP 0693113A1 EP 94913364 A EP94913364 A EP 94913364A EP 94913364 A EP94913364 A EP 94913364A EP 0693113 A1 EP0693113 A1 EP 0693113A1
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EP
European Patent Office
Prior art keywords
surfactants
alkyl
alkyl sulfate
fatty acid
compositions
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.)
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Application number
EP94913364A
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German (de)
English (en)
Inventor
Jean-Pol Boutique
Yi-Chang Fu
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Procter and Gamble Co
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Procter and Gamble Co
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Publication of EP0693113A1 publication Critical patent/EP0693113A1/fr
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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
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/38—Cationic compounds
    • C11D1/65—Mixtures of anionic with cationic compounds
    • C11D1/652—Mixtures of anionic compounds with carboxylic amides or alkylol 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
    • C11D1/14—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
    • C11D1/38—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 cleaning compositions and methods which employ secondary (2,3) alkyl sulfate surfactants in admixture with polyhydroxy fatty acid amide surfactants.
  • 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.
  • secondary alkyl sulfates offers considerable advantages to the formulator and user of detergent compositions.
  • the secondary alkyl (2,3) sulfates are more soluble in aqueous media than their counterpart primary alkyl sulfates of comparable chain lengths. Accordingly, they can be formulated as readily- soluble, high-surfactant (i.e., "high-active") particles for use in granular laundry detergents. Moreover, they can be formulated as stable, homogeneous liquid detergents.
  • the solubility of the secondary (2,3) alkyl sulfates allows them to be formulated in the concentrated form now coming into vogue with both granular and liquid laundry detergents. Since the secondary (2,3) alkyl sulfates can be made available in solid, particulate form, they can be dry-mixed into granular detergent compositions without the need for passage through spray drying towers.
  • Nonionic surfactants typically used in multi-action detergent compositions comprise a polyethylene oxide adduct of an aliphatic alcohol or alkyl phenol. While useful for their intended purpose, very little in the way of improvement has been made with such materials. In addition to the foregoing considerations, the formulator of modern detergents has been confronted with the fact that the highly effective phosphate builders are no longer usable in many areas of the world. Moreover, there would be substantial advantages if an alternative to petrochemical-based alkyl benzene sulfonate surfactants were to be identified.
  • the secondary (2,3) alkyl sulfate anionic surfactants can be advantageously used in combination with polyhydroxy fatty acid amide nonionic surfactants to provide mixed anionic/nonionic surfactants which have substantial advantages over anionic/noni ⁇ onic mixtures known in the art.
  • the surfactant mixtures herein exhibit cleaning performance equivalent to, or better than, the alkyl benzene sulfonates.
  • the surfactant mixtures herein are milder to the skin than the alkyl benzene sulfonates, and are more compatible with detersive enzymes.
  • the surfactant mixtures herein provide extremely low interfacial tensions and, hence, excellent grease/oil cleaning even in the absence of phosphate builders.
  • the surfactant mixtures herein also provide excellent cleaning of mixed soils and stains.
  • the polyhydroxy fatty acid amides are available mainly from nonpetrochemical resources such as fats and sugars.
  • the surfactant mixtures herein are quite biodegradable.
  • SAS secondary (2,3) alkyl sulfates
  • PFAS polyhydroxy fatty acid amide surfactants
  • AE alkyl ethoxylate surfactants
  • AS primary alkyl sulfate surfactants
  • the improved solubility is of substantial benefit under cold water conditions (e.g., at temperatures in the range of 5 * C to about 30 * C) where the rate of solubility of detergent granules in an aqueous washing liquor can be problematic.
  • the improved solubility achieved herein is also of substantial benefit when preparing the modern compact or dense detergent granules where solubility can be problematic.
  • the present invention relates to the use of secondary (2,3) alkyl sulfate surfactants in combination with polyhydroxy fatty acid amide surfactants to provide low (typically below 1 dyne/cm) interfacial tensions in aqueous media. Such low interfacial tensions promote the removal of oily soils from fabrics by mecjianisms such as "roll-up" or, preferably, spontaneous emulsification.
  • the invention thus also relates to the use of secondary (2,3) alkyl sulfate surfactants in combination with polyhydroxy fatty acid amide surfactants to provide cleaning action in a fabric laundering process which comprises agitating fabrics in an aqueous laundry containing said surfactants.
  • the invention herein provides liquid, granular, bar, gel, and the like detergent compositions, comprising: (a) at least about 2%, typically from about 5% to about 50%, by weight of a secondary (2,3) alkyl sulfate surfactant; (b) at least about 2% by weight of a polyhydroxy fatty acid amide surfactant; and
  • compositions and methods herein can also optionally employ various adjunct materials (c) such as detersive enzymes which are members selected from the group consisting of proteases, amylases, upases, cellulases, peroxidases and mixtures thereof.
  • adjunct materials such as detersive enzymes which are members selected from the group consisting of proteases, amylases, upases, cellulases, peroxidases and mixtures thereof.
  • detersive adjuncts useful herein include the conventional non-secondary (2,3) alkylsulfate, non-polyhydroxy fatty acid amide adjunct surfactant.
  • the invention herein makes it possible to lower interfacial tensions and to clean surfaces effectively without using alkylbenzene sulfonate surfactants.
  • detersive adjuncts useful herein include the detergency builders.
  • the invention herein makes it possible to use non-phosphate builders to lower interfacial tensions and to clean surfaces effectively. Accordingly, preferred builders herein are the polycarboxylate builders, especially the citrates and oxydisuccinates. Such builders (especially citrate) are preferred for use in liquid compositions.
  • the invention also provides granular or bar detergent compositions wherein the detergency builder is a member selected froj the group consisting of zeolite builders, layered silicate builders, polycarboxylate builders, and mixtures thereof.
  • compositions herein can be in bar form, wherein the builder is a phosphate builder.
  • the invention also provides a method for cleaning surfaces, comprising contacting (preferably, with agitation) said surfaces with an aqueous medium containing an effective amount (typically 100 ppm to 3000 ppm in solution) of the aforesaid compositions. Fabric laundering methods, dishwashing methods and methods for cleaning other hard surfaces are thus provided. All percentages, ratios and proportions herein are by weight, unless otherwise specified. All documents cited are incorporated herein by reference.
  • R0S03-M+ wherein R is typically a linear C10-C20 hydrocarbyl group and M is a water-solubilizing cation.
  • Branched-chain primary alkyl sulfate surfactants i.e., branched-chain "PAS" having 10-20 carbon atoms are also known; see, for example, European Patent Application 439,316, Smith et al, filed 21.01.91.
  • Secondary alkyl sulfate surfactants are those materials which have the sulfate moiety distributed randomly along the hydrocarbyl "backbone" of the molecule. Such materials may be depicted by the structure
  • the secondary (2,3) alkyl sulfates have now been found to be preferred for use in the presence of calcium ions and under conditions of high water hardness, or in the so-called "under-built” situation which can occur when nonphosphate builders are employed.
  • the primary alkyl sulfates can be problematic due to such interactions with calcium or magnesium cations.
  • the solubility of the primary alkyl sulfates is not as great as the secondary (2,3) alkyl sulfates.
  • the formulation of high-active surfactant particles and high-concentrate liquid detergents has now been found to be simpler and more effective with the secondary (2,3) alkyl sulfates than with the primary alkyl sulfates.
  • the secondary (2,3) alkyl sulfates are exceptionally easy to formjjte as heavy-duty liquid laundry detergents, especially in combination with short-chain adjunct surfactants.
  • the random secondary alkyl sulfates i.e., secondary alkyl sulfates with the sulfate group at positions such as the 4, 5, 6, 7, etc. secondary carbon atoms
  • such materials tend to be tacky solids or, more generally, pastes.
  • the random alkyl sulfates do not afford the processing advantages associated with the solid secondary (2,3) alkyl sulfates when formulating detergent granules, bars, or tablets.
  • the secondary (2,3) alkyl sulfates provide better sudsing than the random mixtures. It is preferred that the secondary (2,3) alkyl sulfates be substantially free (i.e., contain less than about 20%, more preferably less than about 10%, most preferably less than about 5%) of such random secondary alkyl sulfates.
  • the secondary (2,3) alkyl sulfates used herein are quite different in several important properties from the secondary olefin sulfonates (e.g., U.S. Patent 4,064,076, Klisch et al, 12/20/77); accordingly, the secondary sulfonates are not the focus of the present invention.
  • the preparation of the secondary (2,3) alkyl sulfates of the type useful herein can be carried out by the addition of H2SO4 to olefins.
  • a typical synthesis using ⁇ -olefins and sulfuric acid is disclosed in U.S. Patent 3,234,258, Morris, or in U.S. Patent 5,075,041, Lutz, granted December 24, 1991.
  • Such crystallinity-interrupting materials are typically effective at levels of 20%, or less, of the secondary (2,3) alkyl sulfate.
  • the secondary (2,3) alkyl sulfate surfactants contain less than about 3% sodium sulfate, preferably less than about 1% sodium sulfate.
  • sodium sulfate is an innocuous material. However, it dissolves and adds to the ionic "load" in aqueous media, and this can contribute to phase separation in the liquid compositions and to gel breaking in the gel compositions.
  • Various means can be used to lower the sodium sulfate content of the secondary (2,3) alkyl sulfates.
  • Krafft temperature is a term of art which is well-known to workers in the field of surfactant sciences.
  • Krafft temperature is described by K. Shinoda in the text “Principles of Solution and Solubility", translation in collaboration with Paul Becher, published by Marcel Dekker, Inc. 1978 at pages 160-161.
  • the solubility of a surface active agent in water increases rather slowly with temperature up to that point, i.e., the Krafft temperature, at which the solubility evidences an extremely rapid rise.
  • the Krafft temperature At a temperature approximately 4'C above the Krafft temperature a solution of almost any composition becomes a homogeneous phase.
  • the Krafft temperature of any given type of surfactant such as the secondary (2,3) alkyl sulfates herein wh h comprise an anionic hydrophilic sulfate group and a hydrophobic hydrocarbyl group, will vary with the chain length of the hydrocarbyl group. This is due to the change in water solubility with the variation in the hydrophobic portion of the surfactant molecule.
  • the secondary (2,3) alkyl sulfate surfactant herein comprises a mixture of alkyl chain lengths
  • the Krafft temperature will not be a single point but, rather, will be denoted as a "Krafft boundary”.
  • the optional sodium sulfate removal operation it is preferred to conduct the optional sodium sulfate removal operation at a temperature which is below the Krafft boundary, and preferably below the Krafft temperature of the shortest chain-length surfactant present in such mixtures, since this avoids excessive losses of secondary (2,3) alkyl sulfate to the wash solution.
  • the washing process can be conducted batchwise by suspending wet or dry secondary (2,3) alkyl sulfates in sufficient water to provide 10-50% solids, typically for a mixing time of at least 10 minutes at about 22'C (for a C ⁇ 6 secondary [2,3] alkyl sulfate), followed by pressure filtration.
  • the slurry will comprise somewhat less than 35% solids, inasmuch as such slmxigs are free-flowing and amenable to agitation during the washing process.
  • the washing process also reduces the levels of organic contaminants which comprise the random secondary alkyl sulfates noted above.
  • Polyhydroxy Fatty Acid Amide Surfactants -
  • the polyhydroxy fatty acid amides used herein are of the formula:
  • R 1 is H, Ci -C ⁇ hydrocarbyl , 2-hydroxyethyl , 2-hydroxy- propyl , or a mixture thereof, preferably C1-C4 al kyl , more prefer ⁇ ably Ci or C2 al kyl , most preferably Ci al kyl (i .e.
  • 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 understood 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(CH20H)-(CH0H) n -i- CH2OH, -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 alkoxy!ated derivatives thereof. Most preferred are glycityls wherein n is 4, particularly -CH2-(CH0H)4-CH20H.
  • R can be, for example, N-methyl, N-ethyl, N-propyl, N-isopropyl, N-butyl, N-isobutyl, N-2-hydroxy ethyl, or N-2-hydroxy propyl.
  • Rl is preferably methyl .
  • Rl is preferably C2-C8 alkyl, especially n-propyl, iso-propyl, n-butyl, iso-butyl, pentyl, hexyl and 2-ethyl hexyl .
  • R2-C0-N ⁇ can be, for example, cocamide, stearamide, oleamide, lauramide, myristamide, capricamide, palmitamide, tallowamide, etc.
  • 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.
  • 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 such residual amines in the product.
  • an acid anhydride e.g., acetic anhydride, maleic anhydride, or the like.
  • Resi- dual sources of classical fatty acids, which can suppress suds can be depleted by reaction with, for example, triethanolamine.
  • 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 are, in the main, not 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 strypatur p .. Such materials are not cyclized by-products, as defined herein.
  • the amount of polyhydroxy fatty acid amide surfactants herein can range from about 2% to about 60%, typically from about 5% to about 30%, by weight of the total compositions herein.
  • Interfacial Tension By “interfacial Tension” (“IFT”) herein is meant the tension measured at the oil/water interface. IFT measurements using the spinning drop technique, are disclosed by 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 oily soil removal mechanisms like “roll-up” or, preferably, “spontaneous emulsification”, i.e., rapid emu!sification 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, soil removal may occur by roll-up.
  • compositions herein can be simply, but convincingly, demonstrated by admixing a detergent composition in accordance with the invention containing the specially selected soap with water. After dissolution of the detergent, a few drops of oil to which a colored oil-soluble dye has been added are added to the detergent solution. With minimal agitation, the entire system appears to take on the color of the dye, due to the dyed oil having been finely dispersed by the spontaneous emulsification effect. This dispersion remains for a considerable length of time, typically 30 minutes to several hours, even when agitation has stopped. By contrast, with surfactant systems which fail to provide spontaneous emulsification, the dyed oil droplets produced during agitation rapidly coalesce to form one or more relatively large oil globules at the air/water interface.
  • 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:
  • 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 0.01 mg to about 3 mg, of active enzyme per gram of the composition. Stated otherwise, the compositions herein will typically comprise from about 0.001% to about 5%, preferably 0.01%-1%, by weight of a commercial enzyme preparation. Protease enzymes are usually present in such commercial preparations at levels sufficient to provide from 0.005 to 0.1 Anson units (AU) of activity per gram of composition.
  • AU Anson units
  • 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, BolJ. et al, published January 9, 1985).
  • 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 ollusk (Dolabella Auricula Solander). Suitable cellulases are also disclosed in GB-A-2.075.028; GB-A-2.095.275 and DE-OS-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.
  • 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 WO 89/099813, 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.
  • Enzv e Stabilizers The enzymes employed herein are stabilized by the presence of water-soluble sources of calcium ions in the finished compositions which provide calcium ions to the enzymes. Additional stability can be provided by the presence of various other art-disclosed stabilizers, especially borate species: see Severson, U.S. 4,537,706, cited above.
  • Typical detergents, especially liquids will comprise from about 1 to about 30, preferably from about 2 to about 20, more preferably from about 5 to about 15, and most preferably from about 8 to about 12, millimoles of calcium ion per liter of finished composition. This can vary somewhat, depending on the amount of enzyme present and its response to the calcium ions.
  • the level of calcium ion should be selected so that there is always some minimum level available for the enzyme, after allowing for complexation with builders, fatty acids, etc., in the composition.
  • Any water-soluble calcium salt can be used as the source of calcium ion, including, but not limited to, calcium chloride, calcium sulfate, calcium alate, calcium hydroxide, calcium fnrfliat . and calcium acetate.
  • a small amount of calcium ion generally from about 0.05 to about 0.4 millimoles per liter, is often also present in the composition due to calcium in the enzyme slurry and formula water.
  • the formulation may include a sufficient quantity of a water-soluble calcium ion source to provide such amounts in the laundry liquor. In the alternative, natural water hardness may suffice.
  • compositions herein will typically comprise from about 0.05% to about 2% by weight of a water-soluble source of calcium ions.
  • the amount can vary, of course, with the amount and type of enzyme employed in the composition.
  • compositions herein may also optionally, but preferably, contain various additional stabilizers, especially borate-type stabilizers.
  • additional stabilizers especially borate-type stabilizers.
  • such stabilizers will be used at levels in the compositions from about 0.25% to about 10%, preferably from about 0.5% to about 5%, more preferably from about 0.75% to about 3%, by weight of boric acid or other borate compound capable of forming boric acid in the composition (calculated on the basis of boric acid).
  • Boric acid is preferred, although other compounds such as boric oxide, borax and other alkali metal borates (e.g., sodium ortho-, meta- and pyroborate, and sodium pentaborate) are suitable.
  • Substituted boric acids e.g., phenylboronic acid, butane boronic acid, and p-bromo phenylboronic acid
  • compositions herein can 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, colorants, dyes, etc.).
  • other detergent adjunct materials e.g., perfumes, colorants, dyes, etc.
  • the following are illustrative examples of such adjunct materials.
  • 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 tvp callv 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.
  • Inorganic detergent builders include, but are not limited to, the alkali metal, ammonium and alkanolammonium salts of polyphos- phates (exemplified by the tripolyphosphates, pyrophosphates, and glassy polymeric meta-phosphates), phosphonates, phytic acid, silicates, carbonates (including bicarbonates " and sesquicarbon- ates), sulphates, and aluminosilicates.
  • non-phosphate builders are required in some locales.
  • SKS-6 is a highly preferred layered silicate for us ⁇ isrein, but other such layered silicates, such as those having the general formula Na Si ⁇ ⁇ +ryH2 ⁇ wherein M is sodium or hydrogen, x is a number from 1.9 to 4, preferably 2, and y is a number from 0 to 20, preferably 0 can be used herein.
  • Various other layered silicates from Hoechst include NaSKS-5, NaSKS-7 and NaSKS-11, as the alpha, beta and gamma forms.
  • delta-Na2Si ⁇ 5 (NaSKS-6 form) is most preferred for use herein.
  • 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.
  • 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.
  • Examples of carbonate builders are the alkaline earth and alkali metal carbonates as disclosed in German Patent Application No. 2,321,001 published on November 15, 1973.
  • 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 syotJifitic 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:
  • This material is known as Zeolite A.
  • the aluminosilicate has a particle size of about 0.1-10 microns in diameter.
  • 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 polycarboxylate 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. Patents 3,923,679; 3,835,163; 4,158,635; 4,120,874 and 4,102,903.
  • ether hydroxy- polycarboxylates include the ether hydroxy- polycarboxylates, copoly ers of maleic anhydride with ethylene or vinyl methyl ether, 1, 3, 5-trihydroxy benzene-2, 4, 6-trisul- phonic acid, and carboxy ethyloxysuccinic acid, the various alkali metal, ammonium and substituted ammonium salts of polyacetic acids such as ethylenediamine tetraacetic acid and nitrilotriacetic acid, as well as polycarboxylates such as mellitic acid, succinic acid, oxydisuccinic acid, polymaleic acid, benzene 1,3,5-tricar- boxylic acid, carboxymethyloxysuccinic acid, and soluble salts thejeof.
  • polyacetic acids such as ethylenediamine tetraacetic acid and nitrilotriacetic acid
  • polycarboxylates such as mellitic acid, succinic acid
  • Citrate builders e.g., citric acid and soluble salts thereof (particularly sodium salt), are polycarboxylate builders of particular importance for heavy duty liquid detergent formulations due to their availability from renewable resources and their biodegradability. Citrates can also be used in granular composi ⁇ tions, especially in combination with zeolite and/or layered silicate builders. Oxydisuccinates are also especially useful in such compositions and combinations.
  • Fatty acids e.g., i2 _c 18 monocarboxylic acids
  • i2 _c 18 monocarboxylic acids can also be incorporated into the compositions alone, or in combination with the aforesaid builders, especially citrate and/or the succinate builders, to provide additional builder activity.
  • Such use of fatty acids will generally result in a diminution of sudsing, which should be taken into account by the formulator.
  • the various alkali metal phosphates such as the well-known sodium tripolyphosphates, sodium pyrophosphate and sodium orthophosphate can be used.
  • Phosphonate builders such as ethane-1-hydroxy-1,1-diphosphonate and other known phosphonates (see, for example, U.S. Patents 3,159,581; 3,213,030; 3,422,021; 3,4QJ 148 and 3,422,137) can also be used.
  • the detergent compositions herein may optionally contain bleaching agents or bleaching compositions containing a bleaching agent and one or more bleach activators.
  • bleaching agents will typically be at levels of from about 1% to about 30%, more typically from about 5% to about 20%, of the detergent composition, especially for fabric laundering.
  • 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.
  • the bleaching agents used herein can be any of the bleaching agents useful for detergent compositions in textile cleaning, hard surface cleaning, or other cleaning purposes that are now known or become known. These include oxygen bleaches as well as other bleaching agents.
  • Perborate bleaches e.g., sodium perborate (e.g., mono- or tetra-hydrate) can be used herein.
  • bleaching agents can also be used.
  • Peroxygen bleaching agents, the perborates, the percarbon- ates, etc. are preferably combined with bleach activators, which lead to the in situ production 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.
  • the nonanoyloxybenzene sulfonate (NOBS) and tetraacetyl ethylene diamine (TAED) activators are typical, and mixtures thereof can also be used. See also U.S.
  • 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 Holcombe et al . If used, detergent compositions will typically contain from about 0.025% to about 1.25%, by weight, of such bleaches, especially sulfonated zinc phthalocyanine.
  • Polymeric soil release agents useful in the present invention also include cellulosic derivatives such as hydroxyether cellu- losic polymers, copoly eric blocks of ethylene terephthalate or proj Lene 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 .
  • Suitable polymeric soil release agents include the t p rfipht.halat p 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.
  • 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 composi ⁇ tions, and include ethylenediaminetetrakis (methylenephosphon- ates), nitrilotris (methylenephosphonates) and diethylenetriamine- pentakis (methylenephosphonates), as DEQUEST.
  • these am ufl_ )hosphonates do not contain alkyl or alkenyl groups with more than about 6 carbon atoms.
  • a preferred biodegradable chelator for use herein is ethy - 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 ethy - enediamine disuccinate
  • 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.
  • Brightener 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-me bered-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).
  • 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.
  • 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 lOO'C.
  • the hydrocarbons constitute a preferred category of suds suppressor for detergent compositions. Hydrocarbon suds suppressors are described, for example, in U.S. Patent 4,265,779, issued May 5, 1981 to Gandolfo et al .
  • the hydrocarbons thus, include aliphatic, alicyclic, aromatic, and heterocyclic saturated or unsaturated hydrocarbons having from about 12 to about 70 carbon atoms.
  • paraffin as used in this suds suppressor discussion, is intended to include mixtures of true paraffins and cyclic hydrocarbons.
  • Another preferred category of non-surfactant suds suppressors comprises silicone suds suppressors. This category includes the use of polyorganosiloxane oils, such as polydimethylsiloxane, dispersions or emulsions of polyorganosiloxane oils or resins, and combinations of polyorganosiloxane with silica particles 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.
  • 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:
  • 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
  • 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 C ⁇ -Ci6 alkyl alcohols having a C ⁇ -C ⁇ 6 chain.
  • a preferred alcohol is 2-butyl octanol, which is available from Condea under the trademark ISOFOL 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.
  • 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.
  • from about 0.5% to about 3% of fatty monocarboxylate suds suppressor is utilized.
  • 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.
  • from about 0.01% to about 1% of 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 alcohol suds suppressors are typically used at 0.2%-3% by weight of the finished compositions.
  • 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.
  • Fabric Softeners 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 optionally be used typically at levels of from about 0.5% to about 10% by weight in the present compositions to provide fabric softener benefits concurrently with fabric cleaning.
  • 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.
  • compositions herein can optionally contain various anionic, nonionic, zwitterionic, etc. surfactants. If used, such adjunct surfactants are typically present at levels of from about 5% to about 35% of the compositions. However, it is to be understood that the incorporation of adjunct anionic sur ⁇ factants is entirely optional herein, inasmuch as the cleaning performance of the secondary (2,3) alkyl sulfates in combination with the polyhydroxy fatty acid amides is excellent and these materials can be used to entirely replace such surfactants as the alkyl benzene sulfonates in fully-formulated detergent compositions.
  • Nonli iting examples of optional surfactants useful herein include the conventional Cn-Ci ⁇ alkyl benzene sulfonates and primary and random alkyl sulfates, the Cio-Ci ⁇ alkyl alkoxy sulfates (especially EO 1-5 ethoxy sulfates), Cio-Ci ⁇ alkyl alkoxy carboxylates (especially the EO 1-5 ethoxycarboxylates), the C10-C18 alkyl polyglycosides and their corresponding sulfated polyglycosides, 12-C18 alpha-sulfonated fatty acid esters, C12-C18 alkyl and alkyl phenol alkoxy!ates (especially ethoxylates and mixed ethoxy/propoxy), C12-C18 betaines and sulfobetaines ("sultaines”), C10-C18 amine oxides, and the like.
  • Other conven ⁇ tional useful surfactants are listed in
  • ingredients useful in detergent compositions can be included in the composi ⁇ tions herein, including other active ingredients, carriers, hydrotropes, processing aids, dyes or pigments, solvents for liquid formulations, etc.
  • suds boosters such as the C10-C16 alkanolamides can be incorporated into the compositions, typically at 1%-10% levels.
  • the C10-C14 monoethanol and diethanol amides illustrate a typical class of such suds boosters.
  • Use of such suds boosters with high sudsing adjunct surfactants such as the amine oxides, betaines and sultaines noted above is also advantageous.
  • soluble magnesium salts such as MgCl2, MgS ⁇ 4, and the like, can be added at levels of, typically, 0.1%-2%, to provide additional sudsing.
  • Various detersive ingredients employed in the present compo ⁇ sitions optionally can be further 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 DlO, DeGussa) is admixed with a proteolytic enzyme solution containing 3%-5% of C13-15 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.
  • the compositions may contain from 5% to 90%, typically 10% to 50% of such carriers.
  • the detergent compositions herein will preferably be formulated 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 dishwashing formulations preferably have a pH between about 6.8 and about 9.
  • Laundry products are typically between pH 9-11. 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 heavy duty liquid detergent matrix of the following formula is prepared: Ingredient %
  • Ci2-14 alcohol 7 ethoxylate 6 Diethylene triamine pentamethylene phosphonic acid 0.95 Boric acid 2.4
  • Solutions containing 0.67% of this composition are prepared in water of hardness equal to 5 millimolar.
  • compositions and uses of the secondary (2,3) alkyl sulfates according to this invention contain no phosphates.
  • liquid detergents of Examples I-II are prepared by dissolving or dispersing the indicated ingredients in an aqueous carrier and adjusting the pH in the range of 7.D-10.5.
  • a liquid laundry detergent composition herein comprises the following.
  • a dishwashing composition with high grease removal properties is as follows.
  • particulate detergent compositions herein comprising the secondary (2,3) alkyl sulfate surfactants can be prepared using a variety of well-known processes. For example, particles can be formed by agglomeration, wherein solids (including the secondary (2,3) alkyl sulfates) are forced/hurled together by physical mixing and held together by a binder. Suitable apparatus for agglomeration includes dry powder mixers, fluid beds and turbilizers, available from manufacturers such as L ⁇ dige, Eric, Bepex and Aeromatic.
  • particles can be formed by extrusion.
  • solids such as the secondary (2,3) alkyl sulfates are forced together by pumping a damp powder at relatively high pressures and high energy inputs through small holes in a die plate.
  • This process results in rod like particles which can be divided into any desired particle size.
  • Apparatus includes axial or radial extruders such as those available from Fuji, Bepex and Teledyne/Readco.
  • particles can be formed by prilling.
  • a liquid mixture containing the desired ingredients i.e., one of them being secondary (2,3) alkyl sulfate particles
  • the desired ingredients i.e., one of them being secondary (2,3) alkyl sulfate particles
  • the liquid droplets cool they become more solid and thus the particles are formed.
  • the solidification can occur due to the phase change of a molten binder to a solid or through hydration of free mois ⁇ ture into crystalline bound moisture by some hydratable material in the original liquid mixture.
  • particles can be formed by compaction. This method is similar to tablet formation processes, wherein solids (i.e., secondary [2,3] alkyl sulfate particles) are forced together by compressing the powder feed into a die/mold on rollers or flat sheets.
  • solids i.e., secondary [2,3] alkyl sulfate particles
  • particles can be formed by melt/solidifica ⁇ tion.
  • particles are formed by melting the second- ary (2,3) alkyl sulfate with any desired additional ingredient and allowing the melt to cool, e.g., in a mold or as droplets.
  • Binders can optionally be used in the foregoing methods to enhance particle integrity and strength.
  • Water alone, is an operative binder with secondary (2,3) alkyl sulfates, since it will dissolve some of the secondary (2,3) alkyl sulfate to provide a binding function.
  • Other binders include, for example, starches, polyacrylates, carboxymethylcellulose and the like. Binders are well-known in the particle making literature. If used, binders are typically employed at levels of 0.1%-5% by weight of the finished particles.
  • fillers such as hydratable and nonhydratable salts, crystalline and glassy solids, various detersive ingredi- ents such as zeolites and the like, can be incorporated in the particles. If used, such fillers typically comprise up to about
  • Particles prepared in the foregoing manner can be subse ⁇ quently dried or cooled to adjust their strength, physical properties and final moisture content, according to the desires of the formulator.
  • the preferred overall making process for particulate products herein involves three distinct Steps: (1) agglomeration of the ingredients to form the base formula, followed by; (2) admixing various ingredients with the agglomerates formed in Step (1) (e.g., percarbonate bleach, bleach activators, and the like); and optionally, but preferably, (3) spraying materials such as perfume onto the final mix.
  • Step (1) agglomeration of the ingredients to form the base formula, followed by; (2) admixing various ingredients with the agglomerates formed in Step (1) (e.g., percarbonate bleach, bleach activators, and the like); and optionally, but preferably, (3) spraying materials such as perfume onto the final mix.
  • the base formula is agglomerated as opposed to spray dried in order to prevent degradation of some of the heat sensitive surfactants.
  • the resulting product is a high density (ranging from 600 g/l ter - 800 g/liter) free flowing detergent mix that can be used in place of current spray dried laundry detergents.
  • Aeromatic fluidized bed or a continuous type static or vibrating fluidized bed (NIR0, Bepex or Carrier
  • Step A Preparation of Surfactant Paste -
  • the objective is to combine the surfactants and liquids in the compositions into a common mix in order to aid in surfactant solubilization and agglomeration.
  • the surfactants and other liquid components in the composition are mixed together in a Sigma Mixer at 140'F (60'C) at about 40 rpm to about 75 rpm for a period of from 15 minutes to about 30 minutes to provide a paste having the general consistency of 20,000-40,000 centipoise.
  • the paste is stored at 140 * F (60'C) until agglomeration Step (B) is ready to be conducted.
  • the ingredients used in this Step include surfactants acrylate/maleic polymer (m.w. 70,000) and polyethylene glycol "PEG" 4000-8000.
  • Step B Agglomeration of Powders with Surfactant Paste -
  • the purpose of this Step is to transform the base formula ingredients into flowable detergent particles having a medium particle size range of from about 300 microns to about 600 microns.
  • the powders including materials such as zeolite, citrate, citric acid builder, layered silicate builder (as SKS-6), sodium carbonate, ethylenediaminedisuccinate, magnesium sulfate and optical brightener
  • the Eirich Mixer R-Series
  • mixed briefly ca. 5 seconds - 10 seconds
  • the surfactant paste from Step A is then charged into the mixer and the mixing is continued at about 1500 rpm to about 3000 rpm for a period from about 1 minute to about 10 minutes, preferably 1-3 minutes, at ambient temperature.
  • the mixing is stopped when coarse agglomerates (average particle size 800-1600 microns) are formed.
  • Step C The purpose of this Step is to reduce the agglomer- ates' stickiness by removing/drying moisture and to aid in particle size reduction to the target particle size (in the median particle size range from about 300 to about 600 microns, as measured by sieve analysis).
  • the wet agglomerates are charged into a fluidized bed at an air stream temperature of from about 41 * C to about 60 * C and dried to a final moisture content of the particles from about 4% to about 10%.
  • Step D Coat Agglomerates and Add Free-Flow Aids -
  • the objective in this Step is to achieve the final target particle size range of from about 300 microns to about 600 microns, and to admix materials which coat the agglomerates, reduce the caking/ lumping tendency of the particles and help maintain acceptable flowability.
  • the dried agglomerates from Step C are charged into the Eirich Mixer (R-Series) and mixed at a rate of about 1500 rpm to about 3000 rpm while adding 2-6% Zeolite A (median particle size 2-5 ⁇ m) during the mixing.
  • the mixing is continued until the desired median particle size of from about 1200 to about 400 microns is achieved (typically from about 5 seconds to about 45 seconds).
  • from about 0.1% to about 1.5% by weight of precipitated silica average particle size 1-3 microns
  • the following illustrates a laundry detergent composition prepared in the foregoing manner.
  • Citric acid/SKS-6l 11.5 13.5 Sodium carbonate 12.2 14.4
  • a laundry bar suitable for hand-washing soiled fabrics is prepared by standard extrusion processes and comprises the following:
  • compositions can also optionally contain various adjunct cationic surfactants and mixtures of cationic and nonionic adjunct surfactants.
  • Useful cationics include the C ⁇ o _c 18 lkyl trimethylammonium halides, the C10-C18 alkyl dimethyl (Ci-C ⁇ ) hydroxyalkylammonium halides, 10-C18 choline esters, and the like. If used, such cationic surfactants can typically comprise from 1% to 15% by weight of the co ⁇ QBflsitions herein.

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Abstract

Des compositions détersives contenant des agents tensioactifs à base de sulfate d'alkyle (2,3) secondaire et des amides d'acide gras polyhydroxy, produisent des tensions interfaciales extrêmement faibles dans des milieux aqueux. Ainsi, on obtient d'excellentes performances de nettoyage avec de telles compositions, même en l'absence d'adjuvants phosphatés et d'agents tensioactifs à base de sulfonate de benzène d'alkyle. Des compositions détersives biodégradables pour la lessive, comprenant un sulfate d'alkyle (2,3) secondaire et des amides d'acide gras polyhydroxy sont ainsi décrites.
EP94913364A 1993-04-08 1994-04-05 Agents tensioactifs a base de sulfate d'alkyle (2,3) secondaire utilises dans des compositions detersives avec des amides d'acide gras polyhydroxy Withdrawn EP0693113A1 (fr)

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US5318728A (en) * 1992-11-30 1994-06-07 The Procter & Gamble Company Low sudsing polyhydroxy fatty acid amide detergents
JPH08503986A (ja) * 1992-11-30 1996-04-30 ザ、プロクター、エンド、ギャンブル、カンパニー 低起泡性混合ポリヒドロキシ脂肪酸アミド非イオン界面活性剤／陰イオン界面活性剤によるクリーニング

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