EP0693107A1 - Tensioactifs a base de sulfates secondaires d'alkyle (2,3) incorpores dans des compositions detergentes granulaires de masse volumique elevee - Google Patents

Tensioactifs a base de sulfates secondaires d'alkyle (2,3) incorpores dans des compositions detergentes granulaires de masse volumique elevee

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Publication number
EP0693107A1
EP0693107A1 EP94912953A EP94912953A EP0693107A1 EP 0693107 A1 EP0693107 A1 EP 0693107A1 EP 94912953 A EP94912953 A EP 94912953A EP 94912953 A EP94912953 A EP 94912953A EP 0693107 A1 EP0693107 A1 EP 0693107A1
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EP
European Patent Office
Prior art keywords
alkyl
surfactants
alkyl sulfate
detergent
particles
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.)
Ceased
Application number
EP94912953A
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German (de)
English (en)
Inventor
Robert Gary Welch
Lester John Hollihan
David Robert Nassano
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
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Procter and Gamble Co
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Filing date
Publication date
Application filed by Procter and Gamble Co filed Critical Procter and Gamble Co
Publication of EP0693107A1 publication Critical patent/EP0693107A1/fr
Ceased legal-status Critical Current

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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
    • C11D1/02—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
    • C11D1/146—Sulfuric acid esters
    • 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
    • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/06—Powder; Flakes; Free-flowing mixtures; Sheets
    • C11D17/065—High-density particulate detergent compositions

Definitions

  • the present invention relates to detergent granules which employ secondary (2,3) alkyl sulfate surfactants, and means for preparing such granules having a bulk density of at least about 550 grams per liter, preferably at least about 650 g/1.
  • One class of surfactants which has found limited use in various compositions where emulsification is desired comprises the secondary alkyl sulfates.
  • the conventional secondary alkyl sulfates are available as generally pasty, random mixtures of sulfated linear and/or partially branched alkanes. Such materials have not come Into widespread use in laundry detergents, since they offer no particular advantages over the alkyl benzene sulfon ⁇ ates.
  • condensed formulations will typically comprise substantially less porous, high density detergent particles which are less amenable to solubilization.
  • the condensed form of granular detergents typically comprises particles which contain high levels of detersive ingredients with little room for solubilizing agents, and since such particles are intentionally manufactured at high bulk densities, the net result can be a substantial problem with regard to in-use solubility.
  • secondary alkyl sulfates referred to herein as secondary (2,3) alkyl sulfates (“SAS”)
  • SAS secondary alkyl sulfates
  • the secondary alkyl (2,3) sulfates are available as dry, particu ⁇ late solids which 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.
  • the solubility of the particulate secondary (2,3) alkyl sulfates allows them to be formulated in the concentrated, high density form now coming into vogue with granular laundry detergents. Since, with proper care in manufacturing, the secondary (2,3) alkyl sulfates are available in solid, particulate form, they can be dry-mixed into granular detergent compositions without the need for passage through spray drying towers. In addition to the foregoing advantages seen for the secondary (2,3) alkyl sulfates, it has now been determined that they are both aerobically and anaerobically degradable, which assists in their disposal in the environment. Desirably, the secondary (2,3) alkyl sulfates are quite compatible with detersive enzymes, especially in the presence of calcium ions.
  • the present invention relates to the use of secondary (2,3) alkyl sulfate surfactants to provide granular detergent composi ⁇ tions, especially laundry detergents, having a bulk density of at least 550 grams/liter, preferably at least about 650 grams/liter, and ranging as high as about 900 grams/liter.
  • the invention herein provides dry, free-flowing granular detergent compositions, especially fabric laundry compositions, having a bulk density of at least 550 grams/liter, preferably at least about 650 grams/liter, and characterized by a decreased tendency to cake or clump, especially under humid conditions (relative humidity of 60%, and greater) comprising:
  • adjunct ingredients optionally, from about 1% to about 50% by weight of adjunct ingredients, said granular detergent composition being preferably in the form of particles having a
  • the water-soluble secondary (2,3) alkyl sulfate preferably has an alkyl chain length in the range from about 10 to about 20, preferably from about 14 to about 18, 5 and mixtures thereof.
  • compositions herein comprise a nonphosphate detergency builder (b) which is a member selected from the group consisting of zeolite builders, layered silicate builders, polycarboxylate builders, and mixtures thereof.
  • the compositions herein comprise adjunct ingredients (c) including, but not limited to: detersive enzymes, especially members selected from the group consisting of proteases, amylases, Upases, cellulases and mixtures thereof; non-alkyl benzene sulfonate, non-secondary (2,3) alkyl sulfate 5 adjunct surfactants; bleach systems; soil release agents; suds suppressors; fabric softeners; and the like.
  • 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.
  • Mixtures of the 2- and 3-sulfate can be used herein.
  • x and (y+1) are, respectively, integers of at least about 6, and can range from about 7 to about 20, preferably about 10 to about 16.
  • M is a cation, such as an alkali metal, ammonium, alkanolammonium, alkaline earth metal, or the like.
  • Sodium is typical for use as M to prepare the water-soluble (2,3) alkyl sulfates, but ethanolam- monium, diethanolammonium, triethanolammonium, potassium, ammonium, and the like, can also be used.
  • the physical/chemical properties of the foregoing types of alkyl sulfate surfactants are unexpectedly different, one from another, in several aspects which are important to formulators of densified granular detergent compositions.
  • the primary alkyl sulfates can disadvantageously interact with, and even be precipi ⁇ tated by, metal cations such as calcium and magnesium.
  • metal cations such as calcium and magnesium.
  • water hardness can negatively affect the primary alkyl sulfates to a greater extent than the secondary (2,3) alkyl sulfates herein.
  • the solubility of the primary alkyl sulfates is not as great as the secondary (2,3) alkyl sulfates.
  • the formulation of high-density, high-active, yet water-soluble surfactant particles and has now been found to be simpler and more effective with the secondary (2,3) alkyl sulfates than with the primary alkyl sulfates.
  • 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 in the manner of this invention.
  • the secondary (2,3) alkyl sulfates be sub ⁇ stantially free (i.e., contain less than about 20%, 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 o-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.
  • solubility of the "crystalline" secondary (2,3) alkyl sulfate surfactants is desired, the formulator may wish to employ mixtures of such surfactants having a mixture of alkyl chain lengths.
  • a mixture of C14-C18 alkyl chains will provide an increase in solubility over a secondary (2,3) alkyl sulfate wherein the alkyl chain is, say, entirely C ⁇ ,.
  • the solubility of the secondary (2,3) alkyl sulfates can also be enhanced by the addition thereto of other surfactants such as the alkyl ethoxylates or other nonionic surfactants, or by any other material which decreases the crystallinity of the secondary (2,3) alkyl sulfates.
  • Such crystal!inity-interrupting materials are typically effective at levels of 20%, or less, of the secondary (2,3) alkyl sulfate.
  • the secondary (2,3) alkyl sulfates can be further purified to remove unwanted sodium sulfate.
  • Various means can be used to lower the sodium sulfate content of the secondary (2,3) alkyl sulfates. For example, when the H SO4 addition to the olefin is completed, care can be taken to remove unreacted H2SO4 before the acid form of the secondary (2,3) alkyl sulfate is neutralized.
  • the sodium salt form of the secondary (2,3) alkyl sulfate which contains sodium sulfate can be rinsed with water at a temperature near or below the Krafft temperature of the sodium secondary (2,3) alkyl sulfate.
  • 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 which 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 formulator may optionally wash the secondary (2,3) alkyl sulfate surfactant which is contaminated with sodium sulfate with water at a temperature that is no higher than the Krafft temperature, and which is preferably lower than the Krafft temperature, for the particular secondary (2,3) alkyl sulfate being washed. This allows the sodium sulfate to be dissolved and removed with the wash water, while keeping losses of the secondary (2,3) alkyl sulfate into the wash water to a minimum.
  • 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 operation 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 Ci6 secondary [2,3] alkyl sulfate), followed by pressure filtration.
  • the slurry will comprise somewhat less than 35% solids, inasmuch as such slurries 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.
  • the secondary (2,3) alkyl sulfates can be used to provide dense, yet readily water-soluble, fully-formulated detergent granules in various ways.
  • the secondary (2,3) alkyl sulfates can be provided in high active surfactant pastes formulated with co-surfactants to disrupt crystallinity of the components, and utilized as a "binder" in an overall agglomeration process.
  • the secondary (2,3) alkyl sulfates can be used as an admixable powder, along with other powder detergent components such as carbonate, zeolite or silicate builders, and the like, and agglomerated to a finished product using various liquid components, including adjunct surfactants, optional binders and the like.
  • the secondary (2,3) alkyl sulfates may also be used as high-surfactant particles, containing primarily SAS powder, using various liquid or pasty binders, for inclusion as an admix in an agglomera- tion/mixing process for making dense, heavy duty granular detergents.
  • the secondary (2,3) alkyl sulfates can be used in the present process in the form of particles, or as mixed particles.
  • the mixed particles which are provided herein comprise the secondary (2,3) alkyl sulfates herein and one or more co-surfactants. While not intending to be limited by theory, it is believed that the presence of the co-surfactant interrupts the crystallinity of the secondary (2,3) alkyl sulfate, and thereby substantially enhances its solubility.
  • the excellent free-flow properties and water solubility of the secondary (2,3) alkyl sulfates which are substantially free from materials such as unreacted alcohols, etc. allow the formulator to prepare readily- soluble, low-moisture (typically, 15% or less, which enhances free-flow properties), high-active content detergent particles which comprise a mixture of the secondary (2,3) alkyl sulfates and one.,or more co-surfactants.
  • Such "high-active content” particles can comprise 60% by weight of particles and greater, preferably 80% and greater, most preferably 90% and greater, of the mixture of secondary (2,3) alkyl sulfate surfactant plus co-surfactant.
  • Such mixtures used in said particles will typically comprise at least about 40%, more preferably at least about 50%, most prefer ⁇ ably at least about 80%, by weight, of the secondary (2,3) alkyl sulfate, the balance comprising the co-surfactant or mixtures of co-surfactants.
  • certain types of surfactants tend to be tacky. Other surfactants tend to be hygroscopic, and can thus become tacky when exposed to high humidity.
  • the resulting mixed, high- active particles may exhibit sub-optimal flowability.
  • the formulator may choose to coat the surfaces of the mixed particles with a free-flow promoter, such as finely- divided zeolite powder, or even, as now discovered, with a fine powder of the secondary (2,3) alkyl sulfate.
  • the formulator will also recognize that even with certain co-surfactants the overall solubility of the mixed high-active particles can be sub-optimal, especially in cold water. Under such circumstances, various additional solubilizing agents can be incorporated into the particles, typically at levels in the range of 5%-20% or higher, by weight of particles. For example, any highly soluble material can be used for this purpose, and innocuous inorganic salts such as sodium sulfate, sodium carbonate, sodium bicarbonate and the like are typical.
  • co-surfactants can be used as the "crystallinity-disrupting" material which enhances the solubility of the mixed particles herein.
  • various ethoxylated 12-CI8 alcohols such as C]4E0(5), Ci6(E0)3 and the like can be used.
  • such materials are generally liquids and may tend to cause the mixed particles to be undesirably tacky. If used, such liquid nonionics preferably comprise no more than 20% by weight of the particles.
  • One class of especially suitable nonionic co-surfactants herein comprises the polyhydroxy fatty acid amide surfactant (PFAS) such as the C1 -C18 NCj-C ⁇ alkyl glucamides disclosed more fully hereinafter.
  • PFAS polyhydroxy fatty acid amide surfactant
  • This class of nonionic surfactants has the advantage that they exist as slightly waxy solids at room temperature. Hence, when blended with the solid secondary (2,3) alkyl sulfates herein, the PFAS materials do not tend to increase the tackiness of the final mixed particles.
  • co-surfactants useful herein for solubil izing purposes include C12-C18 primary alkyl sulfates, but it will be appreciated by the formulator that a variety of acceptable co-surfactants may be chosen from standard formularies. Binary, ternary, quaternary, etc. mixtures of the secondary (2,3) alkyl sulfate/co-surfactants may al o be used.
  • mixed particles herein comprise, for example: secondary (2,3) alkyl sulfates plus primary Cio-Cj ⁇ alkyl sul ⁇ fates; secondary (2,3) alkyl sulfates plus polyhydroxy fatty acid amide surfactants; secondary (2,3) alkyl sulfates plus alkyl ethoxy sulfates; secondary (2,3) alkyl sulfates plus alkyl ethoxy carboxylates; secondary (2,3) alkyl sulfates plus primary alkyl sulfates plus polyhydroxy fatty acid amides; secondary (2,3) alkyl sulfates plus alkyl ethoxy sulfates plus polyhydroxy fatty acid amides; secondary (2,3) alkyl sulfates plus primary alkyl sulfates plus alkyl ethoxy sulfates plus alkyl amides; secondary (2,3) alkyl sulfates plus primary alkyl sulfates plus alkyl sulf
  • Particles comprising the secondary (2,3) alkyl sulfates plus conventional Cio-Cis soaps can also be prepared.
  • the foregoing are intended to be nonlimiting examples of such mixed particles, others of which will readily come to mind with the skilled formu ⁇ lator.
  • Cjo-Ci8 alkyl benzene sulfonates (LAS) can be used in such particles, but it is preferred that the particles be substantially free of LAS. Indeed, one advantage of the present invention is that it provides LAS-free laundry detergents.
  • particles used herein comprising the secondary (2,3) alkyl sulfate surfactants can be prepared using a variety of well-known processes.
  • 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 turbiliz- ers , 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, crystal ⁇ line and glassy solids, various detersive ingredients such as zeolites and the like, can be incorporated in the particles. If used, such fillers typically comprise up to about 20% by weight of the particles.
  • Particles prepared in the foregoing manner can be subse ⁇ quently dried or cooled to adjust their strength, physical proper ⁇ ties and final moisture content, according to the desires of the formulator.
  • One mode for preparing particles comprising either solely the secondary (2,3) alkyl sulfates or mixtures of the secondary (2,3) alkyl sulfate surfactant and the co-surfactants comprises mixing molten secondary (2,3) alkyl sulfate with one or more molten co-surfactants and forming the resulting solidified melt into particles or prills of any desired size.
  • the desired particle size can be achieved, for example, in blenders, such as that marketed under the trademark OSTER or in large-scale mills, such as that available under the trademark WILEY mill.
  • the melt comprising the mixed surfactant can be sprayed through a nozzle to form droplets which, when cooled, provide particles of the desired size.
  • a rotating disc can be used to form droplets of a melt comprising the secondary (2,3) alkyl sulfate and any desired co-surfactants.
  • the droplets are then solidified by cooling and may be passed through appropriate sieves to secure particles of any desired size.
  • tower prilling can be used to provide particles having a distribution of sizes around a given mean size range.
  • a homogeneous melt of the secondary (2,3) alkyl sulfate plus co-surfactants is solidified, and comminuted to provide particles.
  • High energy comminution processes such as hammer, rod and ball mills can be used.
  • low energy comminution processes such as grating through sieves of any desired pore size can be employed.
  • the particles When used as the bulk surfactant ingredient in the detergent compositions herein, the particles (“base granules”) will typically range in size from about 400 to about 1,200 microns (median size). When used to coat larger particles comprising surfactant, the secondary alkyl sulfate coating particles will typically be in a substantially finer size range, typically from about 0.01 to about 5 microns. In any event, size ranges herein can be established using standard sieves. A sieve size in the range of 600 to 1,000 microns is typical for base granules. A sieve size in the range of 0.05 to 1 micron is typical for coating particles. Densification Equipment
  • the device marketed under the trademark "L ⁇ dige CB30" Recycler comprises a static cylindrical mixing drum having a central rotating shaft with mixing/cutting blades mounted thereon.
  • the ingredients for the detergent composition are introduced into the drum and the shaft/blade assembly is rotated at speeds in the range of 100-2500 rpm to provide thorough mixing/densification.
  • Other such apparatus includes the devices marketed under the trademark “Shugi Granulator” and under the trademark “Drais K-TTP 80).
  • a processing step involving further densification can be conducted.
  • Equipment such as that marketed under the trademark "L ⁇ dige KM600 Mixer", also known as the “L ⁇ dige Ploughshare” can be used. Such equipment is typically operated at 40-160 rpm. Other useful equipment includes the device which is available under the trademark "Drais K-T 160".
  • the L ⁇ dige CB or KM type equipment can be used by itself or sequentially, e.g., by using the CB for paste dispersion and the KM for agglomeration. Batch or continuous feed can be employed.
  • the method of this invention can be conducted using a fluidized bed mixer.
  • the various ingredients of the finished composition are combined in an aqueous slurry and sprayed into a fluidized bed of particles comprising the secondary (2,3) alkyl sulfate to provide the finished detergent granules.
  • the slurry can be sprayed into a fluidized bed of zeolite or layered silicate particles, or into a mixture of secondary (2,3) alkyl sulfate particles plus zeolite and/or layered silicate particles.
  • the first step may optionally include mixing of the slurry using a "L ⁇ dige CB30" or "Flexomix 160", available from Shugi. Fluidized bed or moving beds of the type available under the trademark "Escher Wyss can be used in such processes.
  • the compositions herein can be prepared by a combination of a spray-drying step, followed by an admixing/densi- fication step.
  • an aqueous slurry of various heat-stable ingredients in the final detergent composition are formed into homogeneous granules by passage through a spray-dry tower, using conventional techniques, at temperatures of about 175 * C to about 225 * C.
  • the resulting granules are then admixed with granules of the secondary (2,3) alkyl sulfate in a rotary or screw-type mixer/densifier, using a residence time of typically 1-5 minutes at an operating speed of 500-1500 rpm to provide the finished, densified product.
  • heat-labile ingredients such as detersive enzymes and bleach activators are added to the composition in the mixer/densifier apparatus.
  • compositions are prepared and densified by passage through two mixer and densifier machines operating in sequence.
  • the desired compositional ingredients can be admixed and passed through a L ⁇ dige mixture using residence times of 0.1 to 1.0 minute then passed through a second L ⁇ dige mixer using residence times of 1 minute to 5 minutes.
  • compositions can be prepared in densified granular form using any of the foregoing methods, followed by admixture with finely-powdered (typically 0.1-10 micrometer) secondary (2,3) alkyl sulfate.
  • finely-powdered (typically 0.1-10 micrometer) secondary (2,3) alkyl sulfate This provides a coating of particulate secondary (2,3) alkyl sulfate on the exterior surfaces of the densified granules, which enhances their flowability and reduces caking.
  • an aqueous slurry typically 80% solids content
  • particulate secondary (2,3) alkyl sulfate typically 0.1-200 micrometer size.
  • the resulting particles can be further densified by passage through a L ⁇ dige apparatus, as noted above.
  • the final density of the particles herein can be measured by a variety of simple techniques, which typically involve dispensing a quantity of the granular detergent into a container of known volume, measuring the weight of detergent and reporting the density as grams/liter. Methods used herein allow the detergent to flow into the measuring container under gravity, and without pressure or other compaction of the granules in the measuring container.
  • the density measurements should be run at room tem ⁇ perature.
  • the granular detergent whose density is being measured should be at least 24 hours old and should be held at room tem ⁇ perature for 24 hours prior to testing.
  • the relative humidity is not particularly critical, but should not be so high that the granules stick together. A relative humidity of 50% or less is convenient.
  • any clumps in the detergent should be gently broken up prior to running the test.
  • the sample of detergent granules is allowed to flow through a funnel mounted on a filling hopper and stand (#150; Seedburo Equipment Company, Chicago, Illinois) into an Ohaus cup of known volume and weight (#104; Seedburo).
  • the top of the cup is positioned about 50 mm from the bottom of the funnel, and the cup is filled to overflowing.
  • a spatula or other straight edge is then scraped over the top of the cup, without vibration or tap- ping, to level the detergent granules, thereby exactly and entirely filling the cup.
  • the weight of granules in the cup is then measured. Density can be reported as g/1 or ounces/cubic inch. Repeat runs are made and reported as an average. Relative error is about 0.4%.
  • the detergent compositions herein will typically comprise various detersive and aesthetic adjunct ingredients.
  • Nonlimiting examples of such ingredients are as follows.
  • Enzymes - Enzymes can be included in the formulations herein for a wide variety of fabric laundering purposes, including removal of protein-based, carbohydrate-based, or triglyceride- based stains, for example, for the prevention of refugee dye transfer, and fabric restoration.
  • the enzymes to be incorporated include proteases, amylases, Upases, cellulases, and peroxidases, as well as mixtures thereof. Other types of enzymes may also be included. They may be of any suitable origin, such as vegetable, animal, bacterial, fungal and yeast origin.
  • 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. Suitable examples of proteases are the subtilisins which are obtained from particular strains of B.subtilis and B.licheniforms.
  • 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.
  • Proteolytic enzymes suitable for removing protein-based stains include those sold under the tradenames ALCALASE and SAVINASE by Novo Industries A/S (Denmark) and MAXATASE by International Bio-Synthetics, Inc. (The Netherlands).
  • Other 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-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 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 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 malate, calcium hydroxide, calcium formate, 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.
  • Solid detergent compositions according to the present invention 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 may 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 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. When present, the compositions will typically comprise at least about 1% 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, however, 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 eta-phosphates) , phosphonates, phytic acid, silicates, carbonates (including bicarbonates and sesquicarbon- ates), sulphates, and aluminosilicates.
  • non-phosphate builders are required in some locales.
  • the co posi- tions herein function surprisingly well even in the presence of the so-called “weak” builders (as compared with phosphates) such as citrate, or in the so-called “underbuilt” situation that may occur with zeolite or layered silicate builders.
  • the secondary (2,3) alkyl sulfate plus enzyme components perform best in the presence of weak, nonphosphate builders which allow free calcium ions to be present.
  • silicate builders are the alkali metal silicates, particularly those having a Si ⁇ 2:Na2 ⁇ 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.
  • NaSKS-6 is the trademark for a crystalline layered silicate marketed by Hoechst (commonly abbreviated herein as "SKS-6").
  • Hoechst commonly abbreviated herein as "SKS-6”
  • the Na SKS-6 silicate builder does not contain aluminum.
  • NaSKS-6 has the delta-Na2Si0s morphology form of layered silicate.
  • SKS-6 is a highly preferred layered silicate for use herein, but other such layered silicates, such as those having the general formula Na Si x ⁇ 2 ⁇ + ⁇ - H2 ⁇ 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- a2Si ⁇ 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.
  • 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 builders are also useful in the present invention. Aluminosilicate builders are of great importance in most currently marketed heavy duty granular detergent composi ⁇ tions. Aluminosilicate builders include those having the empirical formula:
  • 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:
  • 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.
  • polycarboxylate 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 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.
  • Citrate builders e.g., citric acid and soluble salts thereof (particularly sodium salt), are polycarboxylate builders of particular importance for heavy duty detergent formulations due to their availability from renewable resources and their biodegrad- ability. Citrates can also be used in combination with zeolite and/or layered silicate builders. Oxydisuccinates are also especially useful in such compositions and combinations.
  • 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.
  • Fatty acids e.g., C12-C18 monocarboxylic acids
  • 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; 3,400,148 and 3,422,137) can also be used.
  • the detergent compositions herein may optionally contain a bleach system which can comprise one or more 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 typic ⁇ ally from about 5% to about 20%, of the detergent composition, espe-cially 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 ) 10 (e-9-» mono- or tetra-hydrate) can be used herein.
  • bleaching agent that can be used without restriction encompasses percarboxylic acid bleaching agents and salts thereof. Suitable examples of this class of agents include magnesium monoperoxyphthalate hexahydrate, the magnesium salt of 15 meta-chloro perbenzoic acid, 4-nonylamino-4-oxoperoxybutyric acid and diperoxydodecanedioic acid. Such bleaching agents are dis ⁇ closed in U.S. Patent 4,483,781, Hartman, issued November 20,
  • 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
  • 25 peroxygen bleaching compounds include sodium carbonate peroxy ⁇ hydrate and equivalent "percarbonate” bleaches, sodium pyrophosphate peroxyhydrate, urea peroxyhydrate, and sodium peroxide.
  • Persulfate bleach e.g., 0X0NE, manufactured commercially by DuPont
  • 0X0NE manufactured commercially by DuPont
  • Peroxygen bleaching agents, the perborates, the percarbonates, 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
  • 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 diam-ine
  • 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 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 useful 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 polyoxypropylene 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 con ⁇ tains 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 compon ⁇ ents having about 20 to 30 oxypropylene units, at
  • 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) n OCH2CH ⁇ -, 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 METH0CEL (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 ZELC0N 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-hydroxyethylethylenedi- 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) as DEQUEST.
  • these amino phosphonates do not contain alkyl or alkenyl groups with more than about 6 carbon atoms.
  • 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.
  • 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.
  • 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, especially in the presence of zeolite and/or layered silicate builders.
  • Suitable polymeric dispersing agents include polymeric polycarboxylates and poly ⁇ ethylene glycols, although others known in the art can also be used. It is believed, though it is not intended to be limited by theory, that 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 monomeric 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 vinyl ethyl 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.
  • Briqhtener 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 brighten ⁇ ers include the PH0RWHITE series of brighteners from Verona.
  • Tinopal UNPA Tinopal CBS and Tinopal 5BM
  • Ciba-Geigy available from Ciba-Geigy
  • Arctic White CC available from Hilton-Davis, located in Italy
  • 2-(4-styryl-phenyl)-2H- naphthol [1,2-d]- triazoles 4,4'-bis- (l,2,3-triazol-2-yl)-stil- benes
  • 4,4'-bis- (styryl)bisphenyls and the 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 suppression can be of particular importance under conditions such as those found in European-style front loading laundry washing machines, or in the concentrated detergency process of U.S. Patents 4,489,455 and 4,489,574, or when the detergent compositions herein optionally include a relatively high sudsing adjunct surfactant.
  • 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 lOO'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.
  • 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. 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.
  • Other silicone suds suppressors are disclosed in U.S. Patent 3,455,839 which relates to compositions and processes for defoaming aqueous solutions by incorporating therein small amounts of polydimethylsiloxane fluids.
  • 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:
  • 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/crossl inked and not linear.
  • typical 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 polyorganos
  • 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 PLURONIC 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-C]6 alkyl alcohols having a C]-Ci6 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 should not form to the extent that they overflow the washing machine.
  • 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 compositions herein will generally comprise from 0% to about 5% of suds suppressor. When utilized as suds suppressors, monocarboxylic fatty acids, and salts therein, will be present typically in amounts up to about 5%, by weight, of the detergent composition.
  • 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 ingredients 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.
  • Adjunct Surfactants -
  • the 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.
  • adjunct anionic surfactants is entirely optional herein, inasmuch as the cleaning performance of the secondary (2,3) alkyl sulfates is excellent and these materials can be used to entirely replace such surfactants as the alkyl benzene sulfonates in fully-formulated detergent compositions.
  • Nonlimiting examples of optional surfactants useful herein include the conventional C ⁇ -Cis alkyl benzene sulfonates and primary and random alkyl sulfates (having due regard for the enzyme stability issues noted above), the Cio-Ci ⁇ alkyl alkoxy sulfates (especially EO 1-5 ethoxy sulfates), the Cio-Ci ⁇ alkyl alkoxy carboxylates (especially the EO 1-5 ethoxy carboxylates), the C10-C18 alkyl polyglycosides and their corresponding sulfated polyglycosides, C12-C18 alpha-sulfonated fatty acid esters, 12- 18 alk l and alkyl phenol alkoxylates (especially ethoxylates and mixed ethoxy/propoxy) , C12- 18 betaines and sulfobetaines ("sultaines”), Cio-Cjs amine oxides, and the like.
  • adjunct nonionic surfactants especially useful herein comprises the polyhydroxy fatty acid amides of the formula:
  • Rl is H, Cj-C ⁇ hydrocarbyl, 2-hydroxyethyl , 2-hydroxy- propyl , or a mixture thereof, preferably C1-C4 alkyl, more prefer ⁇ ably C ⁇ or C2 alkyl, most preferably Ci alkyl (i.e., methyl); and R2 is a C5-C32 hydrocarbyl moiety, preferably straight chain C7-C19 alkyl or alkenyl, more preferably straight chain C9-C17 alkyl or alkenyl, most preferably straight chain C11-C19 alkyl or alkenyl, or mixture thereof; and Z is a polyhydroxyhydrocarbyl moiety having a linear hydrocarbyl chain with at least 2 (in the case of glyceraldehyde) or at least 3 hydroxyls (in the case of other reducing sugars) directly connected to the chain, or an alkoxyl
  • 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-(CHOH) n -CH2 ⁇ H, -CH(CH2 ⁇ H)-(CHOH) n _ ⁇ - 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 alkoxylated derivatives thereof. Most preferred are glycityls wherein n is 4, particularly -CH2-(CHOH)4-CH2 ⁇ H.
  • 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 or hydroxyalkyl.
  • Rl is preferably C2-C8 alkyl, especially n-propyl, iso-propyl, n-butyl, iso-butyl, pentyl , hexyl and 2-ethyl hexyl .
  • R2-CO-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 structure. Such materials are not cyclized by-products, as defined herein.
  • polyhydroxy fatty acid amides can also be sulfated, e.g., by reaction with S ⁇ 3/pyridine, and the resulting sulfated material used as an adjunct anionic surfactant herein.
  • adjunct surfactants can be added separately to the compositions herein or, as noted above, can be combined with the secondary (2,3) alkyl sulfates to provide dense, high-active, mixed detergent particles.
  • Other Ingredients A wide variety of other ingredients useful in detergent compositions can be included in the composi ⁇ tions herein, including other active ingredients, carriers, hydrotropes, processing aids, dyes or pigments. If high sudsing is desired, suds boosters such as the C ⁇ o _c 16 alkanolamides can be incorporated into the compositions, typically at 1%-10% levels. The C]o-Ci4 monoethanol and diethanol amides illustrate a typical class of such suds boosters.
  • 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 D10, 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 detergents.
  • 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.
  • 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.
  • the laundry detergents of Examples I-11 are prepared by mixing/densifying the indicated ingredients as noted above.
  • Preferred compositions are free of phosphate builders.
  • the preferred overall making process for particulate products herein involves three distinct Steps: (1) agglomeration of the ingredients to form the common 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 common base formula
  • various ingredients e.g., percarbonate bleach, bleach activators, and the like
  • 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/liter - 800 g/liter) free flowing detergent mix that can be used in place of current spray dried laundry detergents.
  • Step 1 this procedure is comprised of four Steps: (A) preparing a surfactant paste using mixers such as the Readco Standard Sigma Mixer, T-Series;
  • Aeromatic fluidized bed or a continuous type static or vibrating fluidized bed (NIRO, 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.
  • 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 at about 1500 rpm to about 3000 rpm in order to mix the various dry powders fully.
  • 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). At this point, from about 0.1% to about 1.5% by weight of precipitated silica (average particle size 1-3 microns) is added as a flow aid and the mixing is stopped.
  • a granular detergent herein comprises the following.
  • compositions can also optionally contain various adjunct cationic surfactants and mixtures of cationic and nonionic adjunct surfactants.
  • Useful cationics include the Cio-Cis alkyl trimethylammonium halides, the Cio-Ci ⁇ alkyl dimethyl (Ci-C ⁇ ) hydroxyalkylammonium halides, C10-C18 choline esters, and the like. If used, such cationic surfactants can typically comprise from 1% to 15% by weight of the compositions herein.

Abstract

Des tensioactifs à base de sulfates secondaires d'alkyle (2,3) peuvent être fabriqués sous une forme particulaire sèche qui est utilisée pour préparer des détergents granulaires, notamment des détergents pour le linge, ayant une masse volumique d'au moins 550 grammes/litres. Les sulfates secondaires d'alkyle (2,3) remplacent le benzènesulfonate d'alkyle dans ces détergents. L'invention concerne des compositions entièrement formulées contenant des ingrédients complémentaires tels que des enzymes détersives, des adjuvants, des agents de blanchiment et des agents éliminant les taches.
EP94912953A 1993-04-08 1994-04-05 Tensioactifs a base de sulfates secondaires d'alkyle (2,3) incorpores dans des compositions detergentes granulaires de masse volumique elevee Ceased EP0693107A1 (fr)

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US4574593A 1993-04-08 1993-04-08
US45745 1993-04-08
PCT/US1994/003702 WO1994024244A1 (fr) 1993-04-08 1994-04-05 Tensioactifs a base de sulfates secondaires d'alkyle (2,3) incorpores dans des compositions detergentes granulaires de masse volumique elevee

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JP3164826B2 (ja) * 1996-03-08 2001-05-14 ザ、プロクター、エンド、ギャンブル、カンパニー 混練／押出法による改善された溶解度を有する第二級アルキルサルフェート界面活性剤
WO1997032952A1 (fr) * 1996-03-08 1997-09-12 The Procter & Gamble Company Preparation de particules de sulfate alkyle secondaire possedant une meilleure solubilite
US5955418A (en) * 1997-02-26 1999-09-21 The Procter & Gamble Company Secondary alkyl sulfate surfactant with improved solubility by kneading/extruding process

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GB1585030A (en) * 1978-05-22 1981-02-18 Shell Int Research Preparation of salts of secondary monoalkyl sulphuric acids
US5075041A (en) * 1990-06-28 1991-12-24 Shell Oil Company Process for the preparation of secondary alcohol sulfate-containing surfactant compositions
SK25093A3 (en) * 1990-09-28 1993-07-07 Procter & Gamble Detergent containing alkyl sulfate and polyhydroxy fatty acid amide surfactants

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