CN1124494A - Secondary (2,3) alkyl sulfate surfactants to coat free-flowing granular detergent compositions - Google Patents

Abstract

The present invention relates to granular detergent compositions which have a tendency to clump or cake are coated with finely-divided secondary (2,3) alkyl sulfate surfactant to improve free-flow properties. Thus, a typical granular laundry detergent comprising one or more conventional detersive surfactants, a builder, such as zeolite or layered silicate, and various detersive adjuncts such as enzymes, bleaches, and the like, is coated with a fine dust of dry secondary (2,3) alkyl sulfate. The resulting coated granules are especially useful as fabric laundry compositions.

Description

Free-flowing granular detergent compositions coated with secondary (2,3) alkyl sulfate surfactants

Field of the invention

The present invention relates to detergent particles coated with secondary (2,3) alkyl sulfate surfactant particles to reduce caking and enhance free flow.

Background of the Invention

Most conventional detergent compositions contain a mixture of various detersive surfactants in order to remove various soils and stains from surfaces. For example, various anionic surfactants, especially alkylbenzene sulfonates, are used to remove dirt particles, and various nonionic surfactants such as alkyl ethoxylates and alkylphenol ethoxylates are used to remove greasy sex dirt. One class of surfactants which has been found to be of limited use in compositions requiring emulsification includes secondary alkyl sulfates. Conventional secondary alkyl sulfates are commercially available as pasty random mixtures of sulfated linear and/or partially branched alkanes. Such materials are not widely used in laundry detergents because they do not provide specific benefits over alkylbenzene sulfonates.

Today's granular laundry detergents are formulated as "concentrates" which offer great benefits to both consumers and manufacturers. For consumers, the concentrated product packages are smaller and easier to use and store. For the manufacturer, unit storage costs, shipping costs, and packaging costs are reduced.

The preparation of acceptable concentrated granular detergents presents its own difficulties. In typical concentrated formulations, so-called "inert" ingredients such as sodium sulfate are excluded, yet such ingredients act to enhance the solubility of the detergent granules; thus concentrated detergents often suffer from solubility problems. In addition, conventional low density detergent granules are usually prepared by spray drying, which results in porous detergent granules which are quite soluble in aqueous laundry solutions. Concentrated formulations in contrast generally contain substantially non-porous high-density detergent particles which do not readily dissolve. In conclusion, since concentrated granular detergents generally comprise granules containing high levels of decontamination ingredients with little solubilizer, and since such granules are intentionally made to have a high Basic questions about sex.

Additionally, there are problems associated with "sticking" or "agglomeration" with both conventional spray-dried detergent granules and the newer concentrated granules. Various so-called free-flow agents have been developed, but crisp granular detergents with free-flow properties remain a challenge for formulators.

It has now been discovered that a particularly subordinate class of secondary alkyl sulfates, referred to herein as secondary (2,3) alkyl sulfates ("SAS"), offers considerable benefits to formulators and users of detergent compositions. . The secondary alkyl (2,3) sulfates are commercially available as dry particulate solids which are more soluble in aqueous media than their primary alkyl counterparts. Accordingly, granular laundry detergents have been coated with secondary alkyl (2,3) sulfate in granular form to enhance their flow properties. In addition to the above, it has been determined that secondary (2,3) alkyl sulfates are degradable both aerobically and anaerobically, which facilitates their decomposition in the environment.

Background technique

Various methods and equipment suitable for the preparation of high density granules have been disclosed in the literature and some have been used in detergent technology. See, for example: U.S. 5,133,924; EP-A-367,339; EP-A-390,251; EP-A-340,013; EP-A-327,963; -A-6,106,990; EP-A-342,043; GB-B-2,221,695; EP-B-240,356; EP-B-242,138; -264,049; U.S. 4,238,199; DE 4,021,476.

Detergent compositions containing various "secondary" and branched chain alkyl sulfates are disclosed in various patents, see: U.S. 2,900,346, Fowkes et al., August 18, 1959; U.S. 3,468,805, Grifo et al., 1969 Sep. 23; U.S. 3,480,556, DeWitt et al., Nov. 25, 1969; U.S. 3,681,424, Bloch et al., Aug. 1, 1972; U.S. 4,052,342, Fernley et al., Oct. 4, 1977; U.S. 4,079,020, Mills et al., March 14, 1978; U.S. 4,235,752, Rossall et al., November 25, 1980; U.S. 4,529,541, Wilms et al., July 16, 1985; U.S. 4,614,612, Reilly et al., September 1986 30; U.S. 4,880,569, Leng et al., Nov. 14, 1989; U.S. 5,075,041, Lutz, Dec. 24, 1991; U.K. 818,367, Bataafsche Petroleum, Aug. 12, 1959; U.K. 1,585,030, Shell, 1981 February 18, 1987; GB2,179,054A, Leng et al., February 25, 1987 (see GB2,155,031). Morris, US Patent 3,234,258, issued February 8, 1966, relates to sulfated alpha-olefins using H2SO4, an olefinic reactant and a low boiling nonionic organic crystallization medium.

Summary of the invention

The present invention involves the use of fine (typically about 0.01 to about 20 micron) particulate secondary (2,3) alkyl sulfate surfactants as coatings for detergent granules to reduce the cohesion of the granules, thereby obtaining Improved free movement.

The present invention provides granular detergent compositions comprising granules comprising one or more detersive surfactants and optionally additional components, said granules being substantially dry, finely divided (generally as described above) about 0.01 to about 20 microns) of secondary (2,3) alkyl sulfate surfactant coating. In preferred embodiments, the compositions of the present invention further comprise one or more of the additional ingredients described, such as detergent builders, detergent enzymes, bleaches, fabric softeners, and the like.

The present invention also includes a process for preparing a free-flowing granular detergent comprising the steps of: (a) preparing a mixture of one or more detersive surfactants and optional additional components to obtain a granular detergent composition (i.e. "primary particles") having an average particle size in the range of about 400 to about 1,200 microns; and (b) substantially coating step (a) with finely powdered dry secondary (2,3) alkyl sulfate surfactant Composition particles, (ie "coated particles").

All percentages, ratios and proportions herein are by weight unless otherwise indicated. All documents cited are hereby incorporated by reference.

            Detailed Description of the Invention

    Secondary (2,3) Alkyl Sulfate Surfactants

For the convenience of the formulator, the differences between the sulfated surfactants used herein and other conventional alkyl sulfate surfactants are demonstrated and described below.

Conventional primary alkyl sulfate surfactants have the general formula:

ROSO ₃ ^- M ⁺ wherein R is generally a linear C ₁₀ -C ₂₀ hydrocarbon group, and M is a water-soluble cation. Branched primary alkyl sulfate surfactants having 10 to 20 carbon atoms (i.e. branched "PAS") are also known; see for example European Patent Application 439,316 filed January 21, 1991 by Smith et al. .

Conventional secondary alkyl sulfate surfactants are those having sulfate moieties irregularly distributed along the hydrocarbyl "backbone" of the molecule. These substances can be described by the following structures:

CH ₃ (CH ₂ ) _n (CHOSO ₃ ^- M ⁺ )(CH ₂ ) _m CH ₃ wherein m and n are integers of 2 or greater, the sum of m+n is generally about 9 to 17, and M is a water-soluble cation.

In contrast to the above, the secondary (2,3) alkyl sulfate surfactants selected herein include those having the formulas A and B structures:

(A) CH ₃ (CH ₂ ) _x (CHOSO ₃ ^- M ⁺ ) CH ₃ and

(B) CH ₃ (CH ₂ ) _y (CHOSO ₃ ⁻ M ⁺ ) CH ₂ CH ₃ They are 2-sulfate and 3-sulfate, respectively. Mixtures of 2-sulfate and 3-sulfate salts may be used herein. In formulas A and B, x and (y+1) are integers of at least about 6, respectively, and may range from about 7 to about 20, preferably from about 10 to about 16. M is a cation, such as alkali metal, ammonium, alkanolammonium, alkaline earth metal and the like. M is generally sodium to make a water-soluble (2,3) alkyl sulfate, but ethanolammonium, diethanolammonium, triethanolammonium, potassium, ammonium, etc. can also be used. _C10 - _C20 secondary (2,3) alkyl sulfates are suitable for use herein, the _C14 - _C18 compounds being preferred in laundry cleaning operations.

It has been established by the present invention that the physical/chemical properties of the aforementioned types of alkyl sulfate surfactants differ unexpectedly from one another in several respects, which are important to the formulator of granular detergent compositions. For example, primary alkyl sulfates interact negatively with, and can even be precipitated by, metal cations such as calcium and magnesium. Therefore, water hardness negatively affects primary alkyl sulfates to a greater extent than secondary (2,3) alkyl sulfates herein. Accordingly, it has now been found that secondary (2,3) alkyl sulfates are produced in the presence of calcium ions and under conditions of high water hardness, or in so-called "low build" environments (when non-phosphate builders are used). environment) is preferred.

In addition, primary alkyl sulfates are not as soluble as secondary (2,3) alkyl sulfates. Accordingly, it has now been found that formulating and coating high active surfactant particles with secondary (2,3) alkyl sulfates is simpler and more effective than primary alkyl sulfates.

With respect to random secondary alkyl sulfates (i.e. secondary alkyl sulfates with the sulfate group at the secondary carbon atom positions such as 4, 5, 6, 7, etc.), this material tends to be a viscous solid, or more usually a slurry paste. Thus, such random alkyl sulfates do not provide the processing advantages afforded by solid secondary (2,3) alkyl sulfates when formulated and coated on detergent granules in accordance with the present invention. In addition, the secondary (2,3) alkyl sulfates herein have better foaming properties than the corresponding random mixtures. It is preferred that secondary (2,3) alkyl sulfates are 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 .

Another advantage of the secondary (2,3) alkyl sulfate surfactants herein over other positional or "random" alkyl sulfate isomers is that in the case of fabric laundering operations, the (2,3) The improved benefit provided by alkyl sulfates on soil redeposition. Laundry detergents are well known to remove soil from fabrics being laundered and to suspend the soil in an aqueous laundry solution. However, a portion of the soil can redeposit onto the fabric, as is well known to detergent formulators. Some soil redistribution and redeposition to all fabrics in the load being washed may thus occur. This is of course undesirable and can lead to the known "graying" of the fabric. (A simple test of redeposition properties with any given laundry detergent formulation, a clean white "tracer" cloth can be mixed with the soiled fabric to be washed. At the end of the laundry operation, a technical observer uses photometric Measure or visually estimate the extent to which the white tracer cloth deviates from its original whiteness. The better the whiteness of the tracer cloth is maintained, the less dirt redeposition occurs.)

It has now been determined that secondary (2,3) alkyl sulfates are more effective in soil redeposition performance than other positional secondary alkyl sulfate isomers in laundry detergents, as determined by the cloth tracer method described above. Significant advantages. Thus selection of secondary (2,3) alkyl sulfate surfactants, preferably substantially free of secondary isomers at other positions, in accordance with the practice of the present invention unexpectedly contributes to soil resolution in a previously unrecognized manner. redeposition problem.

It should be noted that the secondary (2,3) alkyl sulfates used in the present invention differ significantly from secondary olefin sulfonates in certain important properties (e.g. Klisch et al., U.S. Patent 4,064,076, 12/20/77), Such secondary sulfonates are therefore not central to the present invention.

The preparation of secondary (2,3) alkyl sulfates used _herein can be carried out by adding _H2SO4 to alkenes. General syntheses using alpha-olefins and sulfuric acid are disclosed in US Patent 3,234,258 to Morris or US Patent 5,075,041 to Lutz on December 24,1991. The synthesis reaction is carried out in a solvent, and the secondary (2,3) alkyl sulfate is obtained after cooling, and the obtained product is refined to remove unreacted substances, random sulfated substances, unsulfated by-products such as Typically a mixture of 2-sulfated and 3-sulfated species of 90+% purity (typically about 10% sodium sulfate present) for C ₁₀ or higher alcohols, secondary olefin sulfonates, etc., and is white, non-sticky transparent crystalline body. Some 2,3-disulfate may also be present, but usually not more than 5% of the mixture of secondary (2,3) alkyl sulfates. Such materials are commercially available under the "DAN" tradename, for example "DAN 200" from Shell Oil Company.

If a "crystalline" secondary (2,3) alkyl sulfate surfactant with enhanced solubility is desired, the formulator may wish to use a mixture of such surfactants with mixed length alkyl chains. Thus, mixtures with C ₁₂ -C ₁₈ alkyl chains are better in solubility than secondary (2,3) alkyl sulfates with a C 12 -C 18 alkyl chain, that is to say all C ₁₆ . By adding other surfactants such as alkyl ethoxylates or other nonionic surfactants to secondary (2,3) alkyl sulfates, or using substances that can reduce the crystallinity of secondary (2,3) alkyl sulfates Any other substance may also increase the solubility of the secondary (2,3) alkyl sulfate. Such crystallinity interfering species are generally effective at levels of 20% or less of the secondary (2,3) alkyl sulfate.

The secondary (2,3) alkyl sulfate may optionally be further refined to remove unwanted sodium sulfate, if desired. Various methods can be used to reduce the sodium sulfate content in secondary (2,3) alkyl sulfates. For _example , when the addition of _H2SO4 to the olefin is complete, _{unreacted H2SO4} is carefully removed before the acid form of the secondary (2,3) alkyl sulfate is neutralized. In another method, a secondary (2,3) alkyl sulfate containing sodium sulfate in the form of its sodium salt is rinsed with water at a temperature close to or below the Krafft temperature of sodium secondary (2,3) alkyl sulfate . This will remove _Na2SO4 with only a small loss of _the desired refined sodium secondary (2,3) alkyl sulfate. Of course, both steps can be used, the first is the pre-neutralization step, and the second is the post-neutralization step.

The term "Krafft temperature" as used herein is a technical term known to those working in the field of surfactant science. The Krafft temperature is described by K. Shinoda in the article "Principles of Solution and Solubility", translated in collaboration with Paul Becher, published by Marcel Dekker Inc., 1978, pp. 160-161. Briefly stated, the solubility of surfactants in water increases rather slowly with increasing temperature up to the point at which the Krafft temperature is reached, whereas at the Krafft temperature the solubility exhibits a sharply rapid increase. At temperatures about 4°C above the Krafft temperature, almost any solution of the composition becomes a homogeneous phase. Generally for any given type of surfactant such as secondary (2,3) alkyl sulfates herein, which contain anionic hydrophilic sulfate groups and hydrophobic hydrocarbyl groups, the Krafft temperature will vary with the hydrocarbyl chain length. This is due to the fact that the solubility of surfactants in water changes with the hydrophobic portion of the surfactant.

In the implementation of the present invention, the formulator can selectively wash the secondary (2,3) alkyl sulfate surfactant polluted by sodium sulfate with water at a temperature not higher than the Krafft temperature, especially for the washed secondary (2 , 3) sodium alkyl sulfate, preferably carried out below the Krafft temperature. This allows the sodium sulfate to be dissolved by the wash water and removed together with the wash water while keeping the loss of secondary (2,3) alkyl sulfate to the wash water to a minimum.

In cases where the secondary (2,3) alkyl sulfate surfactants in the present invention comprise mixed length alkyl chains, it will be recognized that the Krafft temperature is not a single point, but is expressed as a "Krafft range". This situation is well known to those skilled in the art of surfactant/solution assay technology. For such secondary (2,3) alkyl sulfate mixtures, it is preferred in any case that the selective sodium sulfate component be removed at temperatures below the Krafft range, preferably below the temperature present in such mixtures. The Krafft temperature of the surfactant with the shortest chain length, as this avoids excessive loss of secondary (2,3) alkyl sulfate to the wash solution. For example for C ₁₆ secondary alkyl (2,3) sodium sulfate surfactants, it is preferred to carry out the wash operation at a temperature below about 30°C, more preferably below about 20°C. Of course, the Krafft temperature and this preferred wash temperature can vary with the nature of the cation associated with the secondary (2,3) alkyl sulfate.

The washing process can be carried out intermittently, that is, by suspending the wet or dry secondary (2,3) alkyl sulfate in enough water to obtain 10-50% solids, generally at about 22 ° C for a mixing time of at least 10 minutes (for C ₁₆ secondary (2,3) alkyl sulfates), followed by pressure filtration. In a preferred embodiment, the slurry will contain slightly less than about 35% solids, since such a slurry is flowable and easily agitated during the washing process.

Another advantage is that the washing process also reduces the level of organic contaminants including the aforementioned random secondary alkyl sulfates.

The secondary (2,3) alkyl sulfate is used in the process of the invention in the form of granules or mixed granules as disclosed below.

                                         

In addition to comprising only pure secondary (2,3) alkyl sulfate particles, secondary (2,3) alkyl sulfates substantially free of the above-mentioned unreacted alcohols etc. also have excellent Free-flowing properties, which allow formulators to prepare high active detergent granules comprising a mixture of secondary (2,3) alkyl sulfate and one or more co-surfactants. Such "high active content" granules may comprise 35% (by weight) and higher, preferably 50% and higher, most preferably 90% and higher, of secondary (2,3) alkyl sulfate surfactants Mixture granules with co-surfactants. Such mixtures used in the particles generally include at least about 40% by weight, more preferably at least about 50% by weight, of secondary (2,3) alkyl sulfates, and include cosurfactants or cosurfacing The balance of the mixture of active agents.

Additionally, it has now been found that secondary (2,3) alkyl sulfates (SAS) herein are associated with polyhydroxy fatty acid amide cosurfactants (PFAS), alkyl ethoxylate cosurfactants (AE) and primary alkanes The incorporation and agglomeration of mixtures of sulphate-based cosurfactants (AS) resulted in mixed SAS/PFAS/AE/AS particles with greatly and significantly improved solubility in cold water. Without being bound by theory, it appears that the increase in solubility is due to disruption of SAS crystallinity. Whatever the reason, improved solubility is of great benefit under cold water conditions (eg, temperatures in the range of 5°C to about 30°C) where the rate of dissolution of the detergent granules in the aqueous wash solution can be problematic. Of course, the improved solubility obtained herein is also of great benefit when making today's concentrated or dense detergent granules where solubility can be an issue.

Formulators will recognize that for some cosurfactants, the overall solubility of the blended high active granules may be slightly impaired, especially in cold water. In this case, various solubilizers may be incorporated into the granules, generally in the range of 5% to 20% by weight of the granules. For example, any highly soluble substance is used for this purpose, and harmless inorganic salts such as sodium sulfate, sodium bicarbonate, etc. are commonly used.

The mixed particles herein can be used as the base particle or the coated particle of the present invention, or both. Such mixed particles may include, for example: secondary (2,3) alkyl sulfate with primary C ₁₀ -C ₁₈ alkyl sulfate; secondary (2,3) alkyl sulfate with polyhydroxy Fatty acid amide surfactants; secondary (2,3) alkyl sulfates and alkyl ethoxy sulfates; secondary (2,3) alkyl sulfates and alkyl ethoxy carboxylates; secondary (2,3) ) alkyl sulfate and primary alkyl sulfate and polyhydroxy fatty acid amides; secondary (2,3) alkyl sulfate and alkyl ethoxy sulfate and polyhydroxy fatty acid amides; secondary (2,3) alkyl sulfate Salts and primary alkyl sulfates and alkyl ethoxy sulfates and polyhydroxy fatty acid amides; secondary (2,3) alkyl sulfates and alpha-sulfonated fatty acid methyl esters; secondary (2,3) alkyl sulfates salts with C ₁₀ -C ₁₈ alkyl polyglycosides; and secondary (2,3) alkyl sulfates with α-sulfonated fatty acid methyl esters and polyhydroxy fatty acid amides. Granules comprising secondary (2,3) alkyl sulfates with conventional _C10 - _C18 soaps can also be prepared. The above are not limitative examples of such mixed particles, and other examples can easily be thought of by formulators skilled in the art. For coating purposes herein, it is preferred to use secondary (2,3) alkyl sulfate alone, ie without co-surfactant. _C10 - _C18 alkylbenzene sulfonates (LAS) may be used in the base particles herein, but preferably the composition is substantially free of LAS. Indeed, it is an advantage of the present invention to provide LAS-free laundry detergents.

Formation of particles

In general, the particles comprising secondary (2,3) alkyl sulfate surfactants used herein can be prepared by various known methods. Particles can be formed, for example, by agglomeration, wherein solids (including secondary (2,3) alkyl sulfates) are squeezed/bumped together by mechanical mixing and held together with a binder. Suitable equipment for agglomeration includes dry powder mixers, fluidized beds and turbilizers, commercially available from the manufacturers Lodige, Eric, Bepex and Aeromatic.

In another embodiment, the particles can be formed by extrusion. In this method, solids such as secondary (2,3) alkyl sulfates are extruded together by feeding at relatively high pressure and high energy, pumping the conditioned powder through small holes in a die plate. This method yields rod-shaped granules which can be comminuted to any desired particle size. Equipment includes axial or radial extruders such as those available from Fuji, Bepex and Teledyne/Readco.

In another embodiment, particles may be formed by pelletization. In this process, a liquid mixture containing the desired components, ie one of them being secondary (2,3) alkyl sulfate particles, is pumped under high pressure and sprayed into cold air. As the droplets cool, they become stronger, forming particles. This solidification occurs as a result of a phase transition from molten binder to solid or by some hydratable species in the original liquid mixture converting free water to water of crystallization.

In another embodiment, the granules can be formed by compression. The process is similar to the tablet forming process in which the solids (ie secondary (2,3) alkyl sulfate particles) are compressed together by pressing the powder into a mold/molding on rolls or flat plates.

In another embodiment, particles may be formed by melting/solidification. In this method, a secondary (2,3) alkyl sulfate is formed by melting a secondary (2,3) alkyl sulfate together with any desired additional components and allowing the melt to cool, for example in a mold or in the form of droplets. particles.

Binders can optionally be used in the above process to enhance the integrity and strength of the granules. Water alone is an effective binder for secondary (2,3) alkyl sulfates because it can dissolve some of the secondary (2,3) alkyl sulfates to provide the binding function. Other binders include, for example, starches, polyacrylates, carboxymethylcellulose, and the like. Binders are known in the granulation process. Binders, if used, are generally used in amounts of 0.1% to 5% by weight of the final granulate.

Additives such as hydratable and nonhydratable salts, crystalline and glassy solids, various soil release components such as zeolites, and the like can be incorporated into the particles, if desired. Such additives generally comprise up to about 20% by weight of the granules, if desired.

The granules prepared as described above can then be dried or cooled to adjust their strength, physical properties and final moisture content according to the formulator's needs.

A preparation of granules comprising a single secondary (2,3) alkyl sulfate, or optionally but less preferably a mixture of secondary (2,3) alkyl sulfate surfactants and co-surfactants The protocol involves melting the secondary (2,3) alkyl sulfate, optionally together with one or more molten cosurfactants, and forming the resulting solidified melt into granules or pellets of any desired particle size. The desired particle size can be obtained, for example, with a mixer such as that commercially available under the trademark OSTER, or with a large mill such as that available under the trademark WILEY.

In another version, the melt including mixed surfactants is sprayed through a nozzle to form droplets which when cooled give particles of the desired size.

In another approach, a rotating disk can be used to form melt droplets comprising the secondary (2,3) alkyl sulfate and any desired co-surfactant. The droplets are then solidified by cooling and can be passed through a suitable screen to obtain particles of any desired size. In an alternative, a prilling tower can be used to obtain granules with a particle size distribution within the given mean particle size range.

In another approach, a homogeneous melt of secondary (2,3) alkyl sulfate and cosurfactant is solidified and comminuted to produce granules. High energy comminuting operations such as hammering, rod compaction and ball milling can be used. In a different approach, a low energy comminuting operation, such as grid filtering through a sieve of any desired pore size, may be used.

When the secondary alkyl sulfate is used to coat the final detergent particles herein having a size of 400 to 1200 microns, the secondary alkyl sulfate will be used in a very fine particle size range, typically from about 0.01 to about 5 microns. In each case, the particle size ranges herein can be determined using standard sieves.

                                  

A variety of methods and equipment can be used to prepare the granular detergent compositions according to the invention. It is common commercial practice in the art to use spray drying towers to produce granular laundry detergents with a bulk density of less than about 550 grams per liter. Therefore conventional spray drying can be used as the general method herein. Alternatively formulators can avoid spray drying by using commercially available mixing, densifying and granulating equipment. The following is a non-limiting description of such equipment suitable for use herein.

In the process of the present invention, a high speed mixer/densifier furnace may be used. For example, equipment marketed under the trademark "Lodige CB30" Recycler includes an axial cylindrical mixing drum with a central rotating shaft on which mixing/cutting blades are mounted. In use, the ingredients of the detergent composition are added to the drum and the shaft/blade assembly is rotated at a speed in the range of 100-2500 rpm for thorough mixing/densification. Other such devices include those marketed under the trademark "Shugi Granulator" and under the trademark "Drais K-TTP 80".

Depending on the desired degree of densification and/or agglomeration, processing steps including further densification may be performed. A device marketed under the trademark "Lodige KM300 Mixer", also known as "Lodige Ploughshare" may be used. Such equipment typically operates at 40-160 rpm. Other useful equipment includes that commercially available under the trademark "Drais K-T 160".

In another version, the granulation process can be performed using a fluidized bed mixer. In this process, the various components of the final composition are mixed in an aqueous slurry and sprayed into a fluidized bed containing secondary (2,3) alkyl sulphate particles to obtain the final detergent granules. Alternatively, the slurry can be sprayed into a fluidized bed of zeolite or layered silicate particles, or into secondary (2,3) alkyl sulfate particles mixed with zeolite and/or layered silicate in a mixture of particles. In this method, the first step optionally involves the use of "Lodige CB30" or "Flexomix 160" mixed slips available from Shugi. Fluidized bed or moving bed equipment commercially available under the trade name "Escher Wyss" may be used in these processes.

Other types of granulation equipment useful herein include the equipment disclosed in G.L. Heller, US Patent 2,306,898, 1942, 12,29.

  Densification operating conditions

It should be appreciated that the present invention provides a unique advantage in that the granular nature of the secondary (2,3) alkyl sulfates allows the formulator to select from a variety of manufacturing equipment and operating conditions to produce the desired high density, high solubility , Free-flowing detergent granules.

In one approach, the compositions herein may be prepared by a combination of steps comprising a spray drying step followed by a mixing/densifying step followed by a coating step wherein the detergent particles are coated with fine particle secondary (2 , 3) Alkyl sulfate coated. In this step, an aqueous slurry with the various thermally stable components present in the final detergent composition is passed through a spray drying tower to form uniform granules at a temperature of from about 175°C to about 225°C using conventional techniques. The resulting granules are then mixed with secondary (2,3) alkyl sulfate granules in a rotary or helical mixer/densifier furnace at an operating speed of 500-1500 rpm, typically with a residence time of 1-5 minutes, to obtain Densified particles. A modification of this process is the addition of heat labile components such as detergent enzymes and bleach activators to the composition in the mixer/densifier apparatus.

In another version, the granules are prepared and densified by two mixer and densifier machines operating in sequence. For example, the desired composition components are mixed and passed through a Lodige mixer with a residence time of 0.1 to 1.0 minutes, followed by a second Lodige mixer with a residence time of 1 minute to 5 minutes.

In another approach, an aqueous slurry (typically 80% solids) containing the desired formulation components is sprayed into a fluidized bed of secondary (2,3) alkyl sulfate particles (typically 50 to 200 microns in size). in bed. The resulting granules can be further densified by a Lodige apparatus as described above.

Final Coating Step

Regardless of the method used to prepare the primary detergent granules or mixed primary granules, the final step in all methods involves the use of finely divided secondary (2,3) alkyl sulfates or, in less preferred versions, the A finely mixed powder of secondary (2,3) alkyl sulfate surfactant and co-surfactant coats the primary particles. This is simply accomplished by adding the finely divided secondary (2,3) alkyl sulfate to the larger detergent particle near the end of any of the aforementioned mixing steps. Typically the ratio of fines to granules is in the range of about 1:25 to about 1:5. This ensures that all larger particles are fully coated with secondary (2,3) alkyl sulfate fine particles.

Additional Components

In addition to the secondary (2,3) alkyl sulfate coating, the detergent composition granules herein optionally, but generally include various other detersive and aesthetically enhancing ingredients. Non-limiting examples of these components are as follows.

Surfactants - As noted above, the compositions of the present invention may contain a variety of anionic, nonionic, zwitterionic, etc. surfactants. Such additional surfactants are generally present at from about 5% to about 35% of the composition. It is to be noted that the composition may contain secondary (2,3) alkyl sulfate as the primary detersive surfactant in the base particle as well as in the coated particle. Other optional surfactants can also be used as the primary surfactant in the secondary (2,3) alkyl sulfate coated detergent granules.

Non-limiting examples of optional surfactants used herein include conventional C ₁₁ -C ₁₈ alkylbenzene sulfonates, C ₁₀ -C ₁₈ primary and random alkyl sulfates, C ₁₀ -C ₁₈ alkyl alkanes Oxysulfate (especially EO 1~5 ethoxysulfate), C ₁₀ ～C ₁₈ alkyl alkoxy carboxylate (especially EO 1~5 ethoxy carboxylate), C ₁₀ ～C ₁₈ Alkyl polyglycosides and their corresponding sulfated polyglycosides, C ₁₂ -C ₁₈ α-sulfonated fatty acid esters, C ₁₂ -C ₁₈ alkyl and alkylphenol alkoxylates (especially ethoxylated and mixed ethoxy/propoxylates), C ₁₂ -C ₁₈ betaines and sulfobetaines ("sultaines"), C ₁₀ -C ₁₈ amine oxides, and the like. Other conventionally useful surfactants are listed in standard textbooks.

其中R¹为H、C₁～C₈烃基、2-羟乙基、2-羟丙基、或其混合物，优选C₁～C₄烷基、较优选C₁或C₂烷基、最优选C₁烷基(即甲基)；R²为C₅～C₃₂烃基部分，优选直链C₇～C₁₉烷基或链烯基、较优选直链C₉～C₁₇烷基或链烯基，最优选直链C₁₁～C₁₉烷基或链烯基或其混合物；Z为具有至少2个羟基(在甘油醛的情况中)或至少3个羟基(在其它还原糖的情况中)直接连在直链烃基链上的多羟基烃基部分，或其乙氧基化衍生物(优选乙氧基化或丙氧基化)。Z优选衍生自在还原性胺化反应中的还原糖；较优选Z为糖基部分。适宜的还原糖包括葡萄糖、果糖、麦芽糖、乳糖、半乳糖、甘露糖和木糖、以及甘油醛。可以使用为原料的高葡萄糖玉米糖浆、高果糖玉米糖浆和高麦芽糖玉米糖浆以及以上所列的单个糖，由这些玉米糖浆可得到糖成分Z的混合物。应当认识到并没有排除其它适宜的原料的意思。Z优选选自于-CH₂-(CHOH)_n-CH₂OH、-CH(CH₂OH)-(CHOH)_n－1CH₂OH、-CH₂(CHOH)₂(CHOR¹)(CHOH)-CH₂OH，其中n为1至5的整数，包括1和5本身， R¹为H或环状的单一或多糖化物和其烷氧基化衍生物。最优选的是糖基，其中n为4，特别是-CH₂-(CHOH)₄-CH₂OH。A particular class of additional nonionic surfactants especially useful in the present invention includes the polyhydroxy fatty acid amides of the formula:

Wherein R ¹ is H, C ₁ -C ₈ hydrocarbon group, 2-hydroxyethyl, 2-hydroxypropyl, or a mixture thereof, preferably C ₁ -C ₄ alkyl, more preferably C ₁ or C ₂ alkyl, most preferably C ₁ alkyl (i.e. methyl); R ² is C ₅ ~ C ₃₂ hydrocarbon moiety, preferably straight chain C ₇ ~ C ₁₉ alkyl or alkenyl, more preferably straight chain C ₉ ~ C ₁₇ alkyl or alkenyl A group, most preferably straight chain C ₁₁ ~ C ₁₉ alkyl or alkenyl or a mixture thereof; Z has at least 2 hydroxyl groups (in the case of glyceraldehyde) or at least 3 hydroxyl groups (in the case of other reducing sugars) A polyhydroxyhydrocarbyl moiety attached directly to a linear hydrocarbyl chain, or an ethoxylated derivative thereof (preferably ethoxylated or propoxylated). Z is preferably derived from a reducing sugar in a reductive amination reaction; more preferably Z is a glycosyl moiety. Suitable reducing sugars include glucose, fructose, maltose, lactose, galactose, mannose and xylose, and glyceraldehyde. High dextrose corn syrup, high fructose corn syrup and high maltose corn syrup as well as the individual sugars listed above can be used as raw materials from which the mixture of sugar components Z can be obtained. It should be appreciated that it is not meant to exclude other suitable starting materials. Z is preferably selected from -CH ₂ -(CHOH) _n -CH ₂ OH, -CH(CH ₂ OH)-(CHOH) _n-1 CH ₂ OH, -CH ₂ (CHOH) ₂ (CHOR ¹ )(CHOH) -CH ₂ OH, wherein n is an integer from 1 to 5, including 1 and 5 itself, R ¹ is H or cyclic mono- or polysaccharides and their alkoxylated derivatives. Most preferred are glycityls where n is 4, especially _-CH2- (CHOH) ₄ - _CH2OH .

In formula (I), ^R can be, for example, N-methyl, N-ethyl, N-propyl, N-isopropyl, N-butyl, N-isobutyl, N-2-hydroxyethyl group or N-2-hydroxypropyl group. For best sudsability, ^R1 is preferably methyl or hydroxyalkyl. If low foaming is desired, R ¹ is preferably C ₂ -C ₈ alkyl, especially n-propyl, isopropyl, n-butyl, isobutyl, pentyl, hexyl and 2-ethylhexyl.

R ² -CO-N< can be, for example, cocamide, stearylamide, oleamide, laurylamide, myristamide, capricamide, palmitamide, tallowamide, and the like.

Although polyhydroxy fatty acid amides can be prepared by the method of Schwartz, US Patent 2,703,798, there may be contamination problems with cyclized by-products and other colored materials. As a comprehensive process, the preparation methods described in WO-9,206,154 and WO-9,206,984 will result in high quality polyhydroxy fatty acid amides. The process involves reacting N-alkylamino polyols with, preferably fatty acid methyl esters, in a solvent at a temperature of about 85° C. using an alkoxide catalyst to obtain high yields (90% to 98%) of polyhydroxy fatty acid amides containing all Desired low levels (generally less than about 1.0%) of suboptimal degradable cyclization by-products, and also have improved chroma and improved color stability, e.g. Gardner Colors below about 4, preferably between 0 and 2 within range. (For compounds such as butyl, isobutyl and n-hexyl, methanol introduced by the catalyst or generated in the reaction provides sufficient fluidization, and additional reaction solvents may optionally be used). If desired, any N-alkylamino polyol remaining unreacted in the product can be acylated with an anhydride such as acetic anhydride, maleic anhydride, etc. to reduce the total amount of such residual amines in the product. Classical residual sources of fatty acids, which suppress foam, can be consumed by reaction with, for example, triethanolamine.

Herein "by-products of cyclization" means unwanted reaction by-products of the main reaction where it is apparent that multiple hydroxyl groups in polyhydroxy fatty acid amides can form ring structures which are generally not readily biodegradable . Those skilled in the chemical arts will be aware that the use of di- and higher saccharides such as maltose to prepare the polyhydroxy fatty acid amides herein will result in the formation of linear substituents Z (which contain polyhydroxy substituents) that are naturally replaced by polyhydroxy ring structures. "Sealed" polyhydroxy fatty acid amides. Such species are not cyclization by-products as defined herein.

The aforementioned polyhydroxy fatty acid amides can also be sulfated, such as reacted with _SO3 /pyridine, to give the sulfated species used herein as the additional anionic surfactant.

Enzymes - Detergents may be included in detergent formulations for a variety of fabric washing purposes, including the removal of protein-based, carbohydrate-based or triglyceride-based stains and, for example, to inhibit leached dye migration and for fabric restoration. dirty enzymes. Enzymes to be incorporated include proteases, amylases, lipases, cellulases and peroxidases, and 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. Their choice is however determined by several factors such as pH-activity and/or stability optimum, thermostability, stability to active detergents, builders, etc. Bacterial or fungal enzymes are preferred in this respect, such as bacterial amylases and proteases, and fungal cellulases.

Enzymes are generally incorporated in sufficient amounts to provide up to about 5 mg (by weight), typically about 0.01 mg to about 3 mg, of active enzyme per gram of composition. In addition, the compositions herein generally comprise from about 0.001% to about 5%, preferably from 0.1% to 1% by weight of commercial enzyme preparations. Proteases are usually present in such commercial preparations in amounts sufficient to provide an activity of 0.005 to 0.1 Anson units (AV) per gram of composition.

Examples of suitable proteases are subtilisins, which are obtained from special strains of Bacillus subtilis and Bacillus licheniformis. Another suitable protease is obtained from a Bacillus strain having maximum activity in the pH range of 8-12, developed and sold by Novo Industries A/S under the registered tradename ESPERASE. The preparation of this and similar enzymes is described in British Patent Specification 1,243,784 to Novo. Commercially available proteolytic enzymes suitable for the removal of protein-based stains include those sold under the tradenames ALCALASE and SAVINASE by Novo Industries A/S (Denmark), and by InternationalBio-Synthetics, Inc. (Netherlands). Sold by MAXATASE. 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 Bott et al. Published European Patent Application 130,756).

Amylases include, for example, α-amylases described in British Patent Specification 1,296,839 (Novo), RAPIDASE (sold by International Bio-Synthetics, Inc.) and TERMAMYL (sold by Novo Industries).

Cellulases useful in the present invention include bacterial and fungal cellulases. Preferably they have an optimum pH range of 5 to 9.5. Suitable cellulases are disclosed in U.S. Patent 4,435,307 issued March 6, 1984 to Barbesgoard et al., which discloses fungal cellulases produced by Humicola insolens and Humicola strain DSM1800 or by fungal cellulases belonging to the genus Aeromonas The cellulase 212 prepared by the fungus of , and the cellulase extracted from the hepatopancreas of the 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 lipases for detergent use 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 lipases in Japanese Patent Application 53-20487 published February 24,1978. This lipase is commercially available from Amano Pharmaceutical Co. Ltd., Nagoya (Japan) under the trade name Lipase P "Amano", hereinafter referred to as "Amano-P". Other commercial lipases include Amano-CES, lipase ex Chromobacter viscosum, such as Chromobacter viscosum var. Lipolyticum NRRLB 3673, commercially available from Toyo Jozo Corporation, Tagata, (Japan); and other Chromobacter viscosum lipids Enzyme, commercially available from U.S., Biochemical Corp. (USA) and Disoynth Co. (Netherlands), and lipase ex Pseudomonas gladioli. The LIPOLASE enzyme from Humicola lanuginosa and commercially available from Novo (see also EPO 341,947) is a preferred enzyme for use herein.

Peroxidase is used in combination with an oxygen source such as percarbonate, perborate, persulfate, hydrogen peroxide, and the like. They are used for "solution bleaching", ie to inhibit the migration of dyes or pigments that have been released from a substrate during a wash operation to other substrates in the wash solution. Peroxidases are known in the art and include, for example, horseradish peroxidase, ligninase, and haloperoxidases such as chloro- and bromo-peroxidases. Peroxidase-containing detergent compositions are disclosed, for example, in PCT International Application WO 89/099813, published October 19, 1989, invented by O. Kirk, and assigned to Novo Industries A/S.

A wide range of enzyme materials and methods for their incorporation into synthetic detergent granules are also disclosed in US Patent 3,553,139, issued January 5,1971 to McCarty et al. Some enzymes are disclosed in both US Patent 4,101,457 to Place et al., issued July 18, 1978, and US Patent 4,507,219 to Hughes et al., issued March 26, 1985. Enzyme materials useful in detergent formulations and methods of their incorporation into such formulations are disclosed in US Patent 4,261,868, Hora et al., issued April 14,1981. Enzymes for use in detergents can be stabilized by various techniques. Enzyme stabilization techniques are disclosed and exemplified in U.S. Patent 4,261,868 issued April 14, 1981 to Horn et al., U.S. Patent 3,600,319 issued August 17, 1971 to Gedge et al., and European Patent Application Publication No. 0,199,405, Application No. 86200586.5, published October 29, 1986, Venegas. Enzyme stabilization systems are also described, for example, in US Patent Nos. 4,261,868, 3,600,319, and 3,519,570.

Enzyme Stabilizers - Enzymes used herein can be stabilized by the presence of a water-soluble source of calcium ions that provides calcium ions to the enzyme in the final composition. Additional stability may be obtained by the presence of various other prior art disclosed stabilizers, especially borate species (see Severson US Patent 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, most preferably from about 8 to about 12 millimoles of calcium ion per liter of final composition. It can vary depending on the amount of enzyme present and the responsiveness of the enzyme to calcium ions. The amount of calcium ions should be chosen such that after complexation with auxiliaries, fatty acids etc. in the composition, there is always a minimum amount available for the enzyme. Any water-soluble calcium salt can be used as the source of calcium ions, including, but not limited to, calcium chloride, calcium sulfate, calcium malate, calcium hydroxide, calcium formate, and calcium acetate. Small amounts of calcium ions, typically from about 0.05 to about 0.4 mmol/L, are also often present in the composition due to the presence of calcium ions in the enzyme slurry and formulated water. The solid detergent compositions of the present invention may include a sufficient amount of a water-soluble source of calcium ions to provide the required amount in an aqueous laundry solution. On the other hand, natural water hardness may be sufficient.

It should be appreciated that the aforementioned amounts of calcium ions are sufficient to ensure enzyme stability. Further calcium ions can be added to the composition to provide an additional means of achieving grease removal. Accordingly, the compositions of the present invention may comprise from about 0.05% to about 2% by weight of a water-soluble source of calcium ions. The amount will of course vary with the amount and type of enzyme used in the composition.

The compositions of the present invention may also optionally, but preferably contain various other stabilizers, especially borate-type stabilizers. Typically, such stabilizers are present in the composition in an amount of from about 0.25% to 10%, preferably from about 0.5% to about 5%, more preferably from about 0.75% to about 3% by weight. Boric acid is preferred, although other compounds such as boron oxide, borax, and other alkali metal borates (eg, sodium orthoborate, sodium metaborate, and sodium pyroborate, and pentaborate) are suitable. Substituted boronic acids (eg, phenylboronic acid, butaneboronic acid, and p-bromophenylboronic acid) can also be used in place of boric acid.

In addition to enzymes, the compositions of the present invention may optionally include an agent that contributes to or enhances cleaning performance, care of the substrate being washed, or improves the aesthetics of the detergent composition (e.g., perfumes, colorants, dyes, etc.). One or more other detergent add-on substances or other substances. The following are illustrative examples of such additional substances.

Builders - Detergent builders can optionally be included in the compositions herein to assist in controlling mineral hardness. Inorganic and organic builders can be used. Builders are generally used in fabric laundry compositions to aid in the removal of soil particles.

The amount of builder can vary widely depending upon the end use of the composition and its desired physical form. When present, the compositions will generally contain at least about 1% builder. Granular formulations generally include from about 10% to about 80%, more typically from about 15% to about 50%, by weight, of detergent builder. However this is not meant to preclude the use of lower or higher levels of builder.

Inorganic detergent builders include, but are not limited to, polyphosphates (exemplified by tripolyphosphates, pyrophosphates, and glassy polymeric metaphosphates), phosphates, phytic acid, silicates , alkali metal, ammonium, alkylammonium salts of carbonates (including bicarbonates and sesquicarbonates), sulfates and aluminosilicates. However, in some areas it is necessary to use non-phosphate builders. Importantly, the compositions of the present invention can be used even in the presence of so-called "weak" builders (compared to phosphates) such as citrates, or so-called "low builders" (zeolite or layered silicate builders). The resulting) also has unexpected effects. Additionally, secondary (2,3) alkyl sulfates plus enzyme components work best in the presence of weak non-phosphate builders that do not allow the presence of calcium ions.

Examples of silicate builders are alkali metal silicates, especially those having a _SiO2 : _Na2O ratio in the range of 1.6:1 to 3.2:1, and layered silicates, as described in Layered sodium silicates in US Patent 4,664,839, issued May 12, 1987 to HP Rieck. NaSKS-6 is a trademark for layered crystalline silicates sold by Hoechst (commonly abbreviated herein as "SKS-6"). Unlike zeolite builders, NaSKS-6 silicate builders do not contain aluminum. NaSKS-6 is a layered silicate with a δ-Na ₂ SiO ₅ morphological configuration. It can be prepared by methods such as those described in German DE-A-3,417,649 and DE-A-3,742,043. SKS-6 is the most preferred phyllosilicate for use herein, but other such phyllosilicates, such as those having the general formula _{NaMSixO2x + 1.yH2O} , where M is sodium or hydrogen, Sheet silicates in which x is a value from 1.9 to 4, preferably 2, and y is a value from 0 to 20, preferably 0, are also useful herein. Various other layered silicates commercially available from Hoechst include NaSKS-5, NaSKS-7 and NaSKS-11, each in the alpha, beta and gamma structure. As mentioned above, δ-Na ₂ SiO ₅ (NaSKS-6 type) is most preferably used herein. Other silicates are also useful, such as magnesium silicate, as a crisping agent in granulate formulations, as a stabilizer for oxygen bleaches and as a component of foam control systems.

Examples of carbonate builders are the alkaline earth and alkali metal carbonates disclosed in German Patent Application 2,321,001, published November 15,1973.

Aluminosilicate builders are especially useful herein. Aluminosilicate builders are of great importance in most commonly marketed heavy duty granular detergent compositions. Aluminosilicate builders include those having the following empirical formula:

M _z (zAlO ₂ ·ySiO ₂ ) wherein M is sodium, potassium, ammonium or substituted ammonium. z is from about 0.5 to about 2; y is 1; and the material has a magnesium ion exchange capacity of at least about 50 milliequivalents of _CaCO3 hardness per gram of anhydrous aluminosilicate. Preferred aluminosilicates are zeolite builders having the formula:

Na _z [(AlO ₂ ) _z (SiO ₂ ) _y ] xH ₂ O wherein z and y are integers of at least 6, the molar ratio of z to y is in the range of 1.0 to about 0.5, and x is from about 15 to about 264 integer.

Useful aluminosilicate ion exchange materials are commercially available. These aluminosilicates can be of crystalline or amorphous structure and can be naturally occurring aluminosilicates or synthetically derived. A method of preparing aluminosilicate ion exchange materials is disclosed in US Patent 3,985,669, issued October 12, 1976 to Krummel et al. Preferred synthetic crystalline aluminosilicate ion exchange materials for use herein are commercially available under the designations Zeolite A, Zeolite P(B) and Zeolite X. In a particularly preferred embodiment, the crystalline aluminosilicate ion exchange material has the formula:

Na ₁₂ [(AlO ₂ ) ₁₂ (SiO ₂ ) ₁₂ ]·xH ₂ O wherein x is about 20 to about 30, especially about 27. This substance is known publicly as Zeolite A. Preferably, the aluminosilicate has a particle size of about 0.1 to 10 microns in diameter.

Organic detergent builders suitable herein include, but are not limited to, a wide variety of polycarboxylate compounds. As used herein, "polycarboxylate" refers to a compound having a plurality of carboxylate groups, preferably at least 3 carboxylate groups. Polycarboxylate builders are usually incorporated into the compositions in acid form, but may also be included in neutralized salt form. When used in salt form, alkali metals such as sodium, potassium and lithium or alkanolammonium salts are preferred.

Included in polycarboxylate builders are many types of useful materials. An important class of polycarboxylate builders includes ether polycarboxylates, including oxydisuccinates, as disclosed in Berg. U.S. Patent 3,128,287, issued April 7, 1964, and U.S. Patent 3,635,830 to Lamberti et al. , granted on January 18, 1972. See also "TMS/TDS"builders in US Patent 4,663,071, Bush et al., issued May 5,1987. Suitable ether polycarboxylates also include cyclic compounds, especially cycloaliphatic compounds, such as those described in US Patents 3,923,679; 3,835,163; 4,158,635;

Other useful detergency builders include ether hydroxy polycarboxylates, copolymers of maleic anhydride and ethylene or vinyl methyl ether, 1,3,5-trihydroxybenzene-2,4,6-trisulfonic acid and Carboxymethyloxysuccinic acid, alkali metal, ammonium and substituted ammonium salts of various polyacetic acids such as ethylenediaminetetraacetic acid and nitrilotriacetic acid, and polycarboxylates such as mellitic acid, succinic acid, Succinic acid, polymaleic acid, benzene 1,3,5-tricarboxylic acid, carboxymethoxysuccinic acid and their water-soluble salts.

Citrate builders, such as citric acid and its soluble salts (especially the sodium salt), are particularly important polycarboxylate builders in heavy duty detergent formulations because of their availability from renewable resources and their Biodegradability. Citrates can also be used in combination with zeolite and/or layered silicate builders. Oxydisuccinates are also particularly useful in these compositions and mixtures.

Also suitable for use in the detergent compositions of the present invention are 3,3-dicarboxy-4-oxa-1,6-hexanediene disclosed in US Patent 4,566,984 issued January 28, 1986 to Bush et al. salts and related compounds. Useful succinic acid builders include _C5 to _C20 alkyl and alkenyl succinic acids and salts thereof. A particularly preferred compound of this type is dodecenylsuccinic acid. Specific examples of succinate builders include: lauryl succinate, myristyl succinate, palmityl succinate, 2-dodecenyl succinate (preferred), 2-pentadecanyl succinate alkenyl succinate, etc. Lauryl succinate is a preferred builder of this class and is described in European Patent Application 86200690.5/0,200,263, published November 5,1986.

Other suitable polycarboxylates are disclosed in US Patent 4,144,226, Crutchfield et al., issued March 13,1979 and in US Patent 3,308,067, Diehl et al., issued March 7,1967. See also US Patent 3,723,322 to Diehl et al.

Fatty acids, such as C ₁₂ to C ₁₈ monocarboxylic acids, may also be incorporated into the composition alone, or in combination with the aforementioned builders, especially citrate and/or succinate builders, to provide Additional builder activity. The use of fatty acids generally results in reduced lather, which should be considered by the formulator.

In the case of phosphorus-containing builders, the various alkali metal phosphates such as the well known sodium tripolyphosphate, sodium pyrophosphate and sodium orthophosphate can be used. Phosphate builders such as ethane-1-hydroxy-1,1-diphosphate and other known phosphates (see, eg, U.S. 3,159,581; 3,213,030; 3,422,021; 3,400,148 and 3,422,137) can also be used.

Bleaching Compounds - Bleaching Agents and Bleach Activators - The detergent compositions herein may optionally contain a bleaching agent or a bleaching composition comprising a bleaching agent and one or more bleach activators. Bleaching agents, when present, will generally be present in amounts of from about 1% to about 30%, more typically from about 5% to about 20%, of the detergent compositions, especially detergent compositions for laundering fabrics. Bleach activators, if present, will generally be present in amounts of from about 0.1% to about 60%, more typically from about 0.5% to about 40%, of the bleaching compositions containing the bleach and bleach activators.

A bleaching agent as used herein is any bleaching agent for use with detergent compositions in fabric cleaning, hard surface cleaning or other cleaning purposes which are or will become known to the public. These include oxygen bleaches as well as other bleaches. Perborate bleaches such as sodium perborate (eg, monohydrate or tetrahydrate) may be used herein.

One class of bleaches which may be used without limitation includes percarboxylic acid bleaches and salts thereof. Suitable examples of such bleaching agents include magnesium monoperoxyphthalate hexahydrate, magnesium m-chloroperbenzoate, magnesium 4-nonylchloro-4-oxoperoxybutyrate, and magnesium diperoxydodecane Magnesium acid. These bleaching agents are disclosed in U.S. Patent 4,483,781, Hartman, issued November 20, 1984; U.S. Patent Application 740,446, Burns et al., filed June 3, 1985; European Patent Application, Banks et al., published February 20, 1985. Application 0,133,354 and US Patent 4,412,934, Chung et al., issued November 1, 1983. Most preferred bleaching agents also include 6-nonylamino-6-oxo-peroxycaproic acid as described in US Patent 4,634,551, issued January 6,1987 to Burns et al.

Peroxygen bleach can also be used. Suitable peroxygen bleaching compounds include sodium carbonate peroxyhydrate ("percarbonate"bleach), sodium pyrophosphate peroxyhydrate, urea peroxyhydrate and sodium peroxide. Persulfate bleaches (eg, OXONE, commercially available from Du Pont) can also be used.

Mixtures of bleaches can also be used.

Peroxygen bleaches, perborates, percarbonates, etc. are preferably used in combination with a bleach activator, which results in the in situ generation of peroxyacids corresponding to the bleach activator in aqueous solution (ie during the wash). Various non-limiting examples of activators are disclosed in US Patent 4,915,854 and US Patent 4,412,934, issued April 10, 1990 to Mao et al. Nonanoyloxybenzenesulfonate (NOBS) and tetraethylenediamine (TAED) activators are commonly used, and mixtures thereof can also be used. See U.S. 4,634,551 for other representative bleaches and activators useful herein.

Bleaching agents other than oxygen type bleaching agents are also known in the art and can be used in the present invention. One class of non-oxygen bleaches of particular interest includes photoactivated bleaches such as sulfonated zinc and/or aluminum phthalocyanines. See U.S. 4,033,718 issued July 5, 1977 to Holcombe et al. If bleaching agents are used, the detergent compositions will generally contain from about 0.025% to about 1.25% by weight of such bleaching agents, especially sulfonated zinc phthalocyanine.

polymeric soil release agent

Any polymeric soil release agent known to those skilled in the art can optionally be used in the compositions and methods of the present invention. The polymeric soil release agent is characterized in that it contains both a hydrophilic part, which makes the surface of hydrophobic fibers such as polyester and nylon hydrophilized; After the rinse cycle is completed, it remains fixed on the surface of the fiber, thereby immobilizing the hydrophilic part. This makes it easier to remove stains in subsequent wash cycles after the soil release agent treatment.

Polymeric soil release agents for use in the present invention especially include those soil release agents having the following composition: (a) one or more nonionic hydrophilic ingredients consisting essentially of (i), (ii) or (iii), wherein ( i) is a polyoxyethylene moiety having a degree of polymerization of at least 2, (ii) is propylene oxide or a polyoxypropylene moiety having a degree of polymerization of at least ether linkages at both ends of adjacent moieties; (iii) a mixture of oxyalkylene units comprising ethylene oxide and 1 to about 30 propylene oxide units, wherein said mixture contains sufficient oxyethylene units so that The hydrophilic component is sufficiently hydrophilic to increase the hydrophilicity of the surface of conventional polyester synthetic fibers on which the soil release agent is deposited. The hydrophilic portion preferably contains at least about 25% oxyethylene units, with about 20 to 30 oxypropylene units and at least about 50% oxyethylene units being particularly preferred; or (b) from (i), (ii) ), (iii) or (iv) composed of one or more hydrophobic components, wherein (i) is a C ₃ alkylene oxide terephthalate moiety, wherein if the hydrophobic component also includes ethylene oxide phthalates, the ratio of ethylene oxide terephthalate to C ₃ alkylene oxide terephthalate units is about 2:1 or less, and (ii) is C ₄ to C ₆ alkenes or an oxidized _C4 - _C6 alkene moiety, or a mixture thereof, (iii) is a poly(vinyl ester) moiety, preferably a poly(vinyl acetate) having a degree of polymerization of at least 2, and (iv) is a _C1- C ₄ alkyl ether or C ₄ hydroxyalkyl ether substituent, or a mixture thereof, wherein the substituent is in the form of C ₁ to C ₄ alkyl ether or C ₄ hydroxyalkyl ether cellulose derivatives or a mixture thereof Existence, such cellulose derivatives are amphiphilic, thus they have sufficient C ₁ ~ C ₄ alkyl ether and/or C ₄ hydroxyalkyl ether units to fix on the surface of conventional polyester synthetic fibers , and maintain a sufficient amount of hydroxyl groups, once it is adsorbed on the surface of this conventional synthetic fiber, it can increase the hydrophilicity of the fiber surface; or (a) and (b) combination.

Generally, the degree of polymerization of the polyoxyethylene moiety in (a)(i) is from 2 to about 200, preferably from 3 to about 150; more preferably from 6 to about 100, although higher degrees of polymerization can also be used. Suitable oxidized C ₄ -C ₆ alkene hydrophobic moieties include, but are not limited to, polymeric soil release agent capping moieties such as MO ₃ S(CH ₂ ) _n OCH ₂ CH ₂ O-, where M is Sodium, n is an integer from 4 to 6, as disclosed in Gosselink, US Patent 4,721,580, issued January 26,1988.

Polymeric soil release agents useful in the present invention also include cellulose derivatives such as hydroxyether cellulose polymers, ethylene glycol terephthalate or propylene glycol terephthalate and polyoxyethylene terephthalic acid Copolymerized block of ester or polyoxypropylene terephthalate, etc. These reagents are commercially available and include hydroxyethers of cellulose such as METHOCEL (Dow). Cellulosic soil release agents useful herein also include _C1 to _C4 alkyl and _C4 hydroxyalkyl celluloses; see US Patent 4,000,093, issued December 28,1976 to Nicol et al.

Soil release agents characterized by poly(vinyl ester) hydrophobic moieties include graft copolymers of poly(vinyl ester), e.g., C ₁ -C ₆ vinyl esters, preferably grafted on a polyoxyalkylene backbone such as polyoxyalkylene Poly(vinyl acetate) on a vinyl backbone. See European Patent Application 0,219,048, published April and 22, 1987, by Kud et al. Commercially available soil release agents of this type include SOKALAN type materials, eg SOKALAN HP-22, ex BASF (West Germany).

One class of preferred soil release agents are copolymers having random blocks of ethylene terephthalate and polyoxyethylene (PEO) terephthalate. Such polymeric soil release agents have a molecular weight of from about 25,000 to about 55,000. See US Patent 3,959,230, issued May 25, 1976 to Hays and US Patent 3,893,929, issued July 8, 1975 to Basadur.

Another preferred polymeric soil release agent is a polyester with repeating ethylene terephthalate units containing 10-15% (wt) ethylene terephthalate units and 90% -80% (wt) of polyoxyethylene terephthalate units derived from polyoxyethylene glycol with an average molecular weight of 300-5000. Examples of such polymers include commercially available ZELCON 5126 (from Dupont) and MILEASE T (from ICI). See US Patent 4,702,857, issued October 27, 1987 to Gosselink.

Yet another preferred polymeric soil release agent is the sulfonation product of a substantially linear ester oligomer containing an oligoester backbone of terephthaloyl and oxyalkyleneoxy repeat units, and Covalently linked terminal moieties. These soil release agents are fully described in US Patent 4,968,451, issued November 6, 1990 to J.J. Scheibel and E.P. Gosselink.

Other suitable polymeric soil release agents include terephthalate polyesters in U.S. Patent 4,711,730 issued December 8, 1987 to Gosselink et al., anionically terminated polymers in U.S. Patent 4,721,580 issued January 26, 1988 to Gosselink. and block polyester oligomers in US Patent 4,702,857, issued October 27, 1987 to Gosselink.

Preferred polymeric soil release agents also include those of US Patent 4,877,896, Maldonado et al., issued October 31, 1989, which discloses anionic, especially sulfoaroyl, terminated terephthalates.

Soil release agents, if employed, can be used at levels of from about 0.01% to about 10.0%, typically from about 0.1% to about 5%, preferably from about 0.2% to about 30%, by weight of the detergent compositions herein.

Chelating agent

The detergent compositions of the present invention may optionally contain one or more iron and/or manganese chelating agents. Such chelating agents may be selected from amino carboxylates, amino phosphonates, polyfunctionally substituted aromatic chelating agents and mixtures thereof, all of which are defined hereinafter. Without being bound by theory, it is believed that the benefit of these materials is due in part to their superior ability to remove magnesium and iron from wash solutions by forming soluble chelates.

Amino carboxylates used as selective chelating agents include ethylenediaminetetraacetate, N-hydroxyethylethylenediaminetriacetate, nitrilotriacetate, ethylenediaminetetrapropionate, triethylenediamine Tetraamine hexaacetate, diethylenetriaminepentaacetate and ethanol diglycine, which are alkali metal, ammonium and substituted ammonium salts and mixtures thereof.

When at least a small amount of total phosphorus is allowed in the detergent composition, phosphoramidates are also suitable as chelating agents of the present invention, including: ethylenediaminetetra(methylene phosphate), nitrogen tri(methylene base phosphate) and diethylene triamine penta (methylene phosphate) (DEQUEST). Preferably these phosphoramidates do not contain alkyl or alkenyl groups with more than six carbon atoms.

Polyfunctionally substituted aromatic chelating agents can also be used in the compositions of the present invention. See US Patent 3,812,044, issued May 21, 1974 to Connor et al. Preferred compounds of this type in acid form are dihydroxydisulfobenzenes, eg 1,2-dihydroxy-3,5-disulfobenzene.

The most preferred biodegradable chelating agent for use in the present invention is ethylenediamine disuccinate ("EDDS"), see U.S. Patent 4,704,233, issued November 3, 1987 to Hartman and Perkins.

If utilized, chelating agents can be used at levels of from about 0.1% to about 10% by weight of the detergent compositions herein. More preferred levels of chelating agents are from about 0.1% to about 3.0% by weight of the composition.

Clay soil removal/anti-redeposition agent

The compositions of the present invention may also contain water-soluble ethoxylated amines having clay soil removal and anti-redeposition properties. Granular detergent compositions containing these compounds typically contain from about 0.01% to about 10.0% by weight of the water-soluble ethoxylated amines.

The most preferred soil removal and antiredeposition agent is ethoxylated tetraethylenepentamine. Examples of ethoxylated amines are described in US Patent 4,597,898, issued July 1,1986 to VanderMeer. Another preferred class of clay soil removal/antiredeposition agents are the cationic compounds reported in European Patent Application 111,965, published June 27,1984, Oh and Gosselink. Other clay soil removal/anti-redeposition agents that can be used in the present invention include the ethoxylated amine polymers reported in European Patent Application 111,984 of Gosselink, published June 27, 1984; Amphoteric polymers reported in European Patent Application 112,592 to Gosselink; and amine oxides in US Patent 4,548,744, issued October 22, 1985 to Connor. Other clay soil removal and/or antiredeposition agents known in the art may also be used in the compositions of the present invention. Another class of preferred anti-redeposition agents includes carboxymethylcellulose (CMC). Such substances are well known in the art.

polymeric dispersant

Polymeric dispersants are advantageously used at levels of from about 0.1% to about 7% by weight of the compositions herein, especially when zeolite and/or layered silicate builders are present. Suitable polymeric dispersing agents include polymeric polycarboxylates and polyethylene glycols, although others known in the art can also be used. While not wishing to be bound by theory, it is believed that polymeric dispersants, when used in conjunction with other builders, including low molecular weight polycarboxylates, through crystal formation inhibition, especially peptization of soil release and resistance to Redeposition improves the performance of all detergent builders.

The polymeric polycarboxylates are prepared by polymerizing or copolymerizing suitable unsaturated monomers, especially in the acid form. Unsaturated monomeric acids which can be polymerized to produce suitable polymeric polycarboxylates include: acrylic acid, maleic acid (or maleic anhydride), fumaric acid, itaconic acid, aconitic acid, mesaconic acid, citraconic acid and methylenemalonic acid. Monomeric moieties not bearing carboxylic acid groups, such as vinylmethyl ether, styrene, ethylene, are suitable in the polymeric polycarboxylates of the present invention so long as they do not constitute more than about 40% by weight.

The polymeric polycarboxylates obtainable from acrylic acid are especially suitable. Such acrylic acid-based polymers useful in the present invention are water-soluble salts of polymerized acrylic acid. The average molecular weight of such polymers in the acid form is preferably from about 2,000 to 10,000, more preferably from 4,000 to 7,000, and most preferably from 4,000 to 5,000. Examples of water-soluble salts of such acrylic polymers include, for example, alkali metal, ammonium and substituted ammonium salts. Such soluble polymers are known. The use of such polymeric acrylates in detergent compositions is disclosed in US Patent 3,308,067, Diehl, issued March 7,1967.

Acrylic/maleic acid based copolymers can 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 is preferably from about 2,000 to 10,000; 5,000 to 75,000 is more preferred, and 7,000 to 65,000 is most preferred. The ratio of acrylic acid moieties to maleic acid moieties in such copolymers generally ranges from about 30:1 to about 1:1, with about 10:1 to 2:1 being more preferred. Water-soluble salts of such acrylic acid/maleic acid copolymers may include, for example, alkali metal, ammonium and substituted ammonium salts. Acrylic/maleic acid copolymers of this type are known materials described in European Patent Application 66915, published December 15,1982.

Another class of polymeric substances included is polyethylene glycol (PEG). PEG has dispersant properties in addition to being a clay soil removal/anti-redeposition agent. The polyethylene glycols used for this purpose generally have a molecular weight of from about 500 to about 100,000, with about 1,000 to about 50,000 being preferred, and about 1,500 to about 10,000 being more preferred.

Polyaspartates and polyglutamates can also be used, especially with zeolite builders.

brightener

Any optical brighteners or other brighteners known in the art can be incorporated into the detergent compositions of the present invention, generally from about 0.05% to about 1.2% by weight. Commercially available optical brighteners that can be used in the present invention can be divided into the following groups, but not limited thereto: stilbenes, pyrazolines, coumarins, carboxylic acids, methinecyanines, thiofluorene-5,5- Dioxides, pyrroles, derivatives of 5- and 6-membered heterocycles, and other heterochromants. Examples of these brightening agents are disclosed in "The Production and Application of Fluorescent Brightening Agent", M. Zahradnik, published by John Wiley & Sons, New York (1982).

Specific examples of optical brighteners useful in the compositions of the present invention are those disclosed in US Patent 4,790,856, issued December 13,1988 to Wixon. These brighteners include the PHORWHITE range of brighteners from Verona. Other brighteners disclosed in this reference include: Tinopal UNPA, Tinopal CBS and Tinopal 5BM from Ciba-Geigy; Arctic White CC and Artic White CWD from Hilton-Davis (Italy); 2-(4-Styrene phenyl)-2H-naphthol[1,2-d]triazole; 4,4'-bis(1,2,3-triazol-2-yl)stilbene; 4,4'-bistyryl Biphenyl and aminocoumarin. Specific examples of these brighteners are: 4-methyl-7-diethylaminocoumarin; 1,2-bis(benzimidazol-2-yl)ethylene; 1,3-diphenylpyrazoline ; 2,5-bis(benzoxazol-2-yl)thiophene; 2-styryl-naphthalene-[1,2-d]oxazole and 2-(stilbene-4-yl)-2H-naphtho -[1,2-d]triazole. See also US Patent 3,646,015, issued February 29, 1972 to Hamilton.

Foam suppressor

Compounds which reduce or inhibit suds formation can be incorporated into the compositions of the present invention. Suds Inhibition Optional high sudsing co-surfactants are used in European style front-fill washing machines, or in the concentrated wash method of U.S. Patent Nos. 4,489,455 and 4,489,574, or in the detergent compositions of the present invention It is especially important when dosing.

A variety of substances can be used as suds suppressors, and suds suppressors are well known to those skilled in the art. See, e.g., Kirk Othmer Encyclopedia of Chemical Technology, Third Edition, Vol. 7, pp. 430-447 (John Wiley & Sons, Inc., 1979). A particularly important class of suds suppressors includes monocarboxylic fatty acids and soluble salts thereof. See US Patent 2,954,347, issued September 27, 1960 to Wavne St. John. The monocarboxylic fatty acids and salts thereof useful as suds suppressors generally have hydrocarbyl chains of 10 to about 24 carbon atoms, preferably 12 to 18 carbon atoms. Suitable salts include alkali metal salts such as sodium, potassium and lithium; ammonium and alkanolammonium salts.

The detergent compositions of the present invention may also contain non-surfactant suds suppressors. Examples of such suds suppressors are: high molecular weight hydrocarbons, such as paraffin, fatty acid esters (such as triglyceride fatty acid esters), fatty acid esters of monohydric alcohols, aliphatic _C18 - _C40 ketones (such as stearyl ketone) wait. Other suds suppressors include N-alkylated aminotriazines, such as tri- to hexa-alkylmelamines or di- to tetra-alkyldiamine chlorotriazines, which are cyanuric chloride with 2 or 3 Moles of primary or secondary amines with 1 to 24 carbon atoms, propylene oxide and monostearyl phosphate salts, such as monostearyl phosphate and monostearyl phosphate dialkali metal (such as K, Na And Li) salt and phosphate products. For example, paraffins and haloparaffins can be used in liquid form. The liquid hydrocarbon should be liquid at room temperature and atmospheric pressure and should have a pour point of from about -40°C to about 5°C, with a minimum boiling point of not less than about 110°C (atmospheric pressure). It is known to use waxy hydrocarbons, preferably having a melting point below about 100°C. Such hydrocarbons are a preferred class of suds suppressors for detergent compositions. Hydrocarbon suds suppressors are described, for example, in US Patent 4,265,779, issued May 5, 1981 to Gandolfo et al. The hydrocarbons include aliphatic, cycloaliphatic, aromatic and heterocyclic saturated or unsaturated hydrocarbons containing from about 12 to about 70 carbon atoms. The term "paraffin" as used in the discussion of this class of suds suppressors is meant to include mixtures of true paraffins and naphthenes.

Another preferred class of non-surfactant suds suppressors includes silicone suds suppressors. These include the use of polyorganosiloxane oils such as polydimethylsiloxane, dispersants or emulsifiers for polyorganosiloxane oils or resins, and mixtures of polyorganosiloxanes with silica particles, of which Polyorganosiloxanes are chemically fused to silica. Silicone suds suppressors are well known in the art and are disclosed, for example, in U.S. Patent 4,265,779, Gandolfo et al., issued May 5, 1981, and European Patent Application 89307851.9, published February 7, 1990, to Starch, M.S. .

Other silicone suds suppressors are disclosed in US Patent No. 3,455,839 which relates to compositions and methods for defoaming aqueous solutions by incorporating small amounts of polydimethylsiloxane fluids into the compositions.

Mixtures of polysiloxanes and silylated silicas are described, for example, in German patent application DOS 2,124,526. Silicone antifoams and suds suppressors in granular detergents are disclosed in US Patent Application No. 3,933,672 (Bartolotta et al.) and US Patent No. 4,652,392 (Baginski et al.), issued March 24,1987.

An example of a silicone-based suds suppressor useful in the present invention is a suds suppressor having a suds suppressing amount consisting essentially of:

(i) polydimethylsiloxane fluids having a viscosity of from about 20 cs to about 1500 cs at 25°C;

(ii) about 5 to about 50 parts (wt) polysiloxane resin/100 parts (wt) (i), the resin

From (CH ₃ ) ₃ SiO _1/2 units and SiO ₂ units, with a ratio of about 0.6:1 to about 1.2:1

proportional composition; and

(iii) about 1 to about 20 parts of solid silica gel (wt)/100 parts of (i) (wt);

In preferred silicone suds suppressors for use in the present invention, the solvent for the continuous phase consists of certain polyethylene glycols or polyethylene glycol-polypropylene glycol copolymers or mixtures thereof (preferred) (but not including poly propylene glycol) composition. Silicone based suds suppressors are branched/crosslinked rather than linear.

In order to further illustrate this point of view, for example, the laundry detergent with foam control effect can generally contain about 0.001% to about 1% (wt), preferably about 0.01% to 0.7% (wt), most preferably about 0.05% to about The polysiloxane antifoam agent of 0.5% (wt), this antifoam agent contains: (1) is the non-aqueous emulsion of main antifoam agent, and this antifoam agent is following (a), (b), ( Mixtures of c) and (d), (a) polyorganosiloxanes, (b) resinous polysiloxanes or polysiloxane compounds that yield polysiloxane resins, (c) finely divided fillers and (d) a catalyst that promotes the reaction of a mixture of components (a), (b) and (c) to form a silanolate; (2) at least one nonionic polysiloxane surfactant; and (3) a room temperature Polyethylene glycol or polyethylene glycol-polypropylene glycol copolymers having a solubility in water of more than 2% by weight; polypropylene glycol is not contained therein. Similar amounts may also be used in granular compositions, gels, and the like. See US Patent 4,978,471, Starch, December 18, 1990; US Patent 4,983,316, Starch, January 8, 1991, and US Patents 4,639,489 and 4,749,740, Aizawa et al., Col. 1, line 46-Column 4, line 35.

Preferred silicone suds suppressors herein include polyethylene glycol and polyethylene glycol/polypropylene glycol copolymers, which should have an average molecular weight of less than about 1,000, preferably between about 100 and 800. The polyethylene glycol and polyethylene glycol/polypropylene glycol copolymers of the present invention should have a solubility in water at room temperature of greater than 2% (wt), preferably greater than about 5% (wt).

Preferred solvents of the present invention are polyethylene glycols having an average molecular weight of less than about 1,000, more preferably about 100-800, most preferably 200-400, and polyethylene glycol/polypropylene glycol copolymers, preferably PPG 200/PEG 300. The weight ratio of polyethylene glycol to polyethylene glycol-polypropylene glycol copolymer is preferably 1:1 to 1:10; most preferably 1:3 to 1:6.

The silicone suds suppressors preferably used herein are free of polypropylene glycol, especially polypropylene glycol having a molecular weight of 4,000. Block copolymers that also do not contain ethylene oxide and propylene oxide, such as PLURONIC L101, are preferred.

Other suds suppressors useful in the present invention include secondary alcohols such as 2-alkyl alkanols and mixtures of these alcohols with silicone oils such as US 4,798,679, 4,075,118 and EP 150,872 Polysiloxanes disclosed in . Secondary alcohols include C ₆ -C ₁₆ alkyl alcohols with C ₆ -C ₁₆ chains. A preferred alcohol is 2-butyloctanol, which is commercially available from Condea under the trademark ISOFOL 12. A mixture of secondary alcohols is commercially available from Enichem under the trademark ISALCHEM 123. Mixed suds suppressors generally contain a mixture of alcohol and polysiloxane in a weight ratio of 1:5 to 5:1.

For any detergent composition to be used in an automatic washing machine, the suds formed should not overflow the washing machine. When a suds suppressor is used it is preferably present in a "suds suppressing amount". By "suds suppressing level" is meant the amount of suds suppressor selected by the formulator of the composition which provides sufficient suds control to provide a low sudsing laundry detergent useful in automatic washing machines.

The compositions of the present invention generally contain from 0% to about 5% suds suppressor. When used as suds suppressors, monocarboxylic fatty acids and their salts are generally used at levels up to about 5% by weight of the detergent compositions. Preferably from about 0.5% to about 3% fatty monocarboxylate suds suppressor is used. Silicone suds suppressors are generally used at levels up to about 2.0% by weight of the detergent composition, although higher levels can also be used. This upper limit is practical by its nature, due to the primary considerations of keeping costs to a minimum and the efficiency of lower levels for effective suds control. Preferably from about 0.01% to about 1% silicone suds suppressor is used, more preferably from about 0.25% to about 0.5%. In the present invention, these weight percent values include all silica that may be used with the polyorganosiloxane as well as any additive materials that may be used. Monostearyl phosphate suds suppressors are generally used at levels of from about 0.1% to about 2% by weight of the composition. Hydrocarbon suds suppressors are generally used at levels from about 0.01% to about 5.0%, although higher levels can be used. The amount of alcohol suds suppressor is generally 0.2% to 3% by weight of the finished composition.

In addition to the components described above, the compositions of the present invention may also be combined with a variety of other additive components that impart other benefits to the various compositions within the scope of the present invention. Various examples of such additive components are given below, but are not limited thereto.

fabric softener

Various full-wash fabric softeners may also optionally be used in the compositions of the present invention, particularly the particulate smectite clays disclosed in U.S. Patent 4,062,647 issued to Storm and Nirschl on December 13, 1977, as well as existing Other softening agents known in the art, so as to achieve the effect of softening the fabric while cleaning the fabric, the amount of the softening agent is generally about 0.5% to 10% (wt). Clay softeners can also be used with amine and cationic softeners as disclosed in US Patent 4,375,416 issued March 1, 1983 to Crisp et al. and US Patent 4,291,071 issued September 22, 1981 to Harris et al.

other components

A variety of other ingredients useful in detergent compositions may also be present in the compositions of the present invention, including other active ingredients, carriers, processing aids, dyes or pigments. If high foaming is required, a foam booster such as C ₁₀ -C ₁₆ alkanolamides can be added to the composition, generally in an amount of 1% - 10%. C ₁₀ -C ₁₄ monoethanols and diethanolamides are typical examples of such suds boosters. It is also advantageous to use such suds boosters with high sudsing co-surfactants such as the amine oxides, betaines, sultaines mentioned above. If necessary, soluble magnesium salts such as MgCl ₂ and MgSO ₄ can also be added to obtain more foam, and the dosage of the magnesium salt is generally 0.1% to 2%.

The various detersive components employed in the compositions of the present invention can be further stabilized by absorbing the components onto a porous hydrophobic substrate and then coating the substrate with a hydrophobic coating. The detersive component is preferably mixed with the surfactant prior to adsorption with the porous substrate. During use, the soil release component is released from the substrate into the aqueous wash solution where it performs its intended detergency function.

The following example illustrates this technology in more detail: Porous hydrophobic silica (trademark SIPERNAT D10, DeGussa) was mixed with nonionic _surface -active Mix the proteolytic enzyme solution of the agent. The amount of the enzyme/surfactant solution is typically 2.5 times the weight of silica. The obtained powder is dispersed in polysiloxane oil by stirring (various polysiloxane oils with a viscosity of 500 to 12,500 can be used). The resulting silicone oil dispersion is emulsified or added to the final detergent base. In this way, enzymes, bleaches, bleach activators, bleach catalysts, photosensitizers, dyes, optical brighteners, fabric conditioners and hydrolyzable surfactants such as the aforementioned can be used in "protected form" in the wash in the dose.

The detergent compositions of the present invention are preferably formulated for use in aqueous wash operations having a wash water pH of from about 6.5 to about 11, preferably from about 7.5 to about 10.5. Methods of controlling the pH to desired usage values include the use of buffers, bases, acids, etc., and all methods known to those skilled in the art.

The following are typical, but non-limiting, examples illustrating the detergent compositions of the invention and the coated use of the secondary (2,3) alkyl sulfates of the invention.

The overall manufacturing process of the granular product of the present invention preferably includes three distinct steps: (1) agglomeration of the components to form a base, and then; (2) bleaching of the agglomerates formed in step (1), such as percarbonate agent, bleach activator, etc.) mixed with the various components; and may additionally include, but is also preferred (3) spraying materials such as perfume into the final mixture.

The base is agglomerated rather than spray dried to prevent degradation of certain heat sensitive surfactants. The resulting product is a high density (600g/l-800g/l) free-flowing detergent mixture that can replace current spray-dried laundry detergents.

For the agglomeration of the base material (step 1 above), this process includes the following 4 steps: (A) use a mixer such as Readco Standard Sigma Mixer, T-series to prepare the surfactant paste; (B) use Such as Eirich Mixer, R-series mixers agglomerate surfactant paste and powder components; (C) such as in batch Aeromatic fluidized bed or continuous fixed or vibrating fluidized bed (NIRO, Bepex or Carrier Comp ), and (D) coat the agglomerate using, for example, an Eirich Mixer, R-series mixer.

The agglomeration step is specifically described below.

Step A: Preparation of Surfactant Paste

The purpose of this step is to mix the surfactant and liquid in the composition to form a blend to facilitate the solubilization and agglomeration of the surfactant. In this step, the surfactants and other liquid components of the composition are mixed together in a Sigma Mixer at 140°F (60°C) at about 40 rpm to about 75 rpm for about 15 minutes to about 30 minutes to produce A paste with a viscosity of 20,000 to 40,000 centipoise. After thorough mixing, store the paste at 140F (60°C) until ready for agglomeration in step (B). Components used in this step included surfactant, acrylic/maleic polymer (m.w, 70,000) and polyethylene glycol "PEG" 4000-8000.

Step B: Agglomeration of Powder and Surfactant Paste

The purpose of this step is to transfer the base components to flowable detergent particles having an average particle size of from about 300 microns to about 600 microns. In this step, powders (including builders such as zeolite, citrate, citric acid, layered silica builders (such as SKS-6), sodium carbonate, ethylenediamine disuccinate, magnesium sulfate and fluorescent whitening agent) into the Einich Mixer (R-series), and briefly stir (about 5 to 10 seconds) at about 1500 rpm to about 3000 rpm to fully mix various dry powders. Then feed the surfactant paste of step A into the mixer; and mix continuously at about 1500 rpm to about 3000 rpm and room temperature for about 1 minute to about 10 minutes, preferably 1 to 3 minutes. Mixing was terminated when coarse agglomerates (average particle size 800-1600 μm) were formed.

Step C:

The purpose of this step is to reduce the viscosity of the agglomerates by removing/drying the water and to facilitate particle size reduction to the target size (average particle size from about 300 to about 600 μm as determined by sieve analysis). In this step, the wet agglomerate feed is dried in a fluidized bed with an air flow temperature of about 41°C to about 60°C to a final moisture content of the granules of about 4% to about 10%.

Step D: Coat the agglomerate and add free flow aid

The purpose of this step is to achieve a final target particle size of about 300 [mu]m to about 600 [mu]m, mix the material to coat the agglomerates, reduce the particle's tendency to agglomerate and help maintain acceptable flowability. In this step, the dry agglomerate obtained in step C is fed into an Eirich Mixer (R-series), mixed at a speed of about 1500 to about 3000 rpm, and 2 to 6% of zeolite A (average particle size diameter 2 ~ 5μm). Mixing is continued until the desired average particle size of about 1200 to about 400 microns is obtained (typically about 5 seconds to about 45 seconds). At this point, about 0.1% to about 1.5% (wt) of secondary (23) alkyl sulfate (average particle size 1-3 μm) is added as a flow aid and mixing is terminated. In another embodiment, fine secondary (2,3) alkyl sulfates may be used in combination with other autoflow agents such as 1-3 micron silica.

The laundry detergent prepared by the aforementioned method is exemplified below.

Example 1

Agglomerates

%(wt) %(wt)

In final product Sodium C _14-15 alkyl sulfate in agglomerates 5.8 6.8 C ₁₆ Sodium secondary (2,3) alkyl sulfate 17.3 20.4 C ₁₂ -C ₁₃ ethoxylated alcohol (EO3) 4.7 5.5C _12～14 N-methylglucamide 4.7 5.5 Acrylate/maleate copolymer 6.2 7.3 Polyethylene glycol 1.4 1.7 Aluminosilicate (zeolite) 8.8 10.3 Sodium citrate 1.9 2.2 Citric acid/SKS-6 ¹ 11.5 13.5 Sodium carbonate 12.2 14.4EDDS ² 0.4 0.5 Magnesium sulfate 0.4 0.5 Fluorescent whitening agent 0.1 0.1 Moisture 7.6 8.9 Secondary (2,3) alkyl sulfate (fine powder) ³ 0.4 0.5 Balance (unreacted and Na ₂ SO ₄ ) 1.6 1.9

Total Agglomerates 85.0 100.0

Dry mixed sodium percarbonate (400-600 microns) 7.8NORS ⁴ 5.9 Siloxane/PEG defoamer 0.3 Lipase 0.3Savinase 0.3

Spray fragrance 0.4

Total final product 100.0 ¹ Blended particles of citric acid and layered silicate (ratio 2.0) ² Ethylenediamine disuccinate ³ Particle size 1-3 microns ⁴ Sodium nonanoyloxybenzenesulfonate

The granular laundry detergents of Examples II-III below were prepared using the conventional spray drying and/or mixing/densifying techniques described above. According to their formulation, the granules were thoroughly mixed with about 2 micron particles of secondary (2,3) alkyl sulfate to produce free-flowing granules with a coating (about 1% of the total composition) thereon .

Example II

The granular detergent of the present invention comprises the following components:

Component % (weight) secondary (2,3) alkyl sulfate * 10.0 zeolite A (1 ~ 10 microns) 26.0C _{12 ~ 14} primary alkyl sulfate sodium salt 5.0 sodium citrate 5.0 sodium carbonate 20.0 optical brightener 0.1 Detergent Enzyme** 1.0 Sodium Sulfate 15.0 Water and Minor Component Balance *C ₁₄ ~ C ₁₈ Average Chain Length; Sodium Salt ** 1:1 Mixture LIPOLASE/ESPERASE

Example II

Surfactant A B C

% (weight) % (weight) % (weight) C ₁₆ secondary (2,3) alkyl sulfate sodium 6.92 9.00 7.60C _16/18 primary alkyl sulfate 2.05 3.00 1.30C ₁₂ ~ C ₁₅ alkyl ethoxy ( 1-3) Sulfuric acid 0.17 0.40 0.10 salt C ₁₄ ～C ₁₅ alkyl ethoxylate (EO7) 4.02 5.00 1.30C ₁₆ ～C ₁₈ AE11 alkyl ethoxylate 1.10 1.40 1.10(EO11)C ₁₆ ～C ₁₈ AE25 Alkyl ethoxylate 0.85 -- 0.66 (EO25) dimethyl monoethoxy C _{12 ~ 14} alkyl ammonium -- -- 1.40 chloride

Builder Citrate 5.20 10.00 5.00 Zeolite 4A 20.50 37.20 17.90 Carbonate (Na) 15.00 5.50 12.10 Amorphous Silicate 2.0 3.00 2.00 3.10 SOKALAN CP5 ¹ 4.00 4.90 3.20 Carboxymethyl Cellulose 0.30 0.2039

Bleach perborate monohydrate 8.77 -- 5.80 perborate tetrahydrate 11.64 -- 7.40 CO ₃ /SO ₄ coated percarbonate -- 12.0 --TAED ² 5.00 -- 3.40 zinc phthalocyanine 20ppm -- 20ppmDEQUEST 2060(Monsanto) 0.36 0.60 0.38MgSO ₄ 0.40 0.40 0.40LIPOLASE(100,000LU/g) 0.36 0.25 0.15Savinase(4.0 KNPU) 1.40 1.60 1.40纤维素酶(1000CEVU/g) 0.13 0.13 0.26污垢解脱剂聚合物³ 0.20 0.20 0.15 Anionic fluorescent whitening agent 0.19 -- 0.15 Polyvinylpyrrolidone -- 0.15 -- Bentonite -- -- 12.50 Polyethylene ^glycol4 -- -- 0.30 Glycerin -- -- 0.62 Fragrance 0.43 0.43 0.43 Silicone Alkane + dispersant (defoamer) 0.49 0.60 0.49 Moisture, trace components ---- balance ---- ¹ acrylic acid/maleic acid copolymer; molecular weight 70,000; sodium salt ² tetraacetylethylenediamine ³ sulfonate Anionic polyester reaction product of benzoic acid, terephthalic acid, 1,2-propanediol, ethylene glycol, sulfoisophthalic acid, Maldonado, the place of origin is the same as above. ⁴ Molecular weight range 4,000,000

In the foregoing, examples of the invention using secondary (2,3) alkyl sulfate surfactants and other, mainly anionic, additional surfactants have been exemplified. The composition may also optionally contain various additional cationic surfactants and A mixture of cationic and nonionic additional surfactants. Useful cationic surfactants include C ₁₀ -C ₁₈ alkyl trimethyl ammonium halides, C ₁₀ -C ₁₈ alkyl dimethyl (C ₁ -C ₆ ) hydroxyalkyl ammonium halides, C ₁₀ -C ₁₈ Choline esters and more. If a cationic surfactant is used, its content is 1% to 15% by weight of the composition of the present invention.

Claims (6)

1. A granular detergent composition comprising granules comprising one or more detersive surfactants and optionally granulated additional components, said granules being dry powdered secondary (2,3 ) basic coating with alkyl sulfate surfactant. 2. A composition according to claim 1, wherein the detergent composition comprises as an additional ingredient one or more detergency builders. 3. A composition according to claim 1 or 2, which additionally comprises, as an additional component, one or more detersive enzymes. 4. A composition according to any one of claims 1 to 3 which additionally comprises one or more bleaching agents as an additional component. 5. A composition according to any one of claims 1 to 4 which additionally comprises, as an additional component, one or more fabric softening agents. 6. A method of preparing a free-flowing granular detergent comprising the steps of: (a) preparing a mixture containing one or more detersive surfactants and optional additional components to provide a granular detergent composition having an average particle size in the range of 400 to 1200 microns; and (b) substantially coating particles of the composition of step (a) with a finely powdered dry secondary (2,3) alkyl sulfate surfactant.