Classifications

• • C—CHEMISTRY; METALLURGY
  • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
  • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
  • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
  • C11D17/0039—Coated compositions or coated components in the compositions, (micro)capsules
• • C—CHEMISTRY; METALLURGY
  • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
  • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
  • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
  • C11D3/02—Inorganic compounds ; Elemental compounds
  • C11D3/12—Water-insoluble compounds
  • C11D3/124—Silicon containing, e.g. silica, silex, quartz or glass beads
  • C11D3/1246—Silicates, e.g. diatomaceous earth
  • C11D3/128—Aluminium silicates, e.g. zeolites
• • C—CHEMISTRY; METALLURGY
  • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
  • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
  • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
  • C11D3/16—Organic compounds
  • C11D3/38—Products with no well-defined composition, e.g. natural products
  • C11D3/386—Preparations containing enzymes, e.g. protease or amylase
  • C11D3/38672—Granulated or coated enzymes
• • C—CHEMISTRY; METALLURGY
  • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
  • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
  • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
  • C11D3/39—Organic or inorganic per-compounds
• • C—CHEMISTRY; METALLURGY
  • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
  • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
  • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
  • C11D3/50—Perfumes
  • C11D3/502—Protected perfumes
  • C11D3/505—Protected perfumes encapsulated or adsorbed on a carrier, e.g. zeolite or clay
• • C—CHEMISTRY; METALLURGY
  • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
  • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
  • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
  • C11D1/02—Anionic compounds

Definitions

• the present invention relates to detergent particles having coating or partial coating.
• the present invention also relates to detergent composition of both the conventional non-compact type or low dosage compact detergent products.
• Granular detergent products are typically produced from one of two manufacturing methods. The first involves the spray-drying of a aqueous detergent slurry in a spray drying tower to produce detergent granules while the second involves dry mixing va ⁇ ous components after which they are agglomerated with a binder such as surfactant. The resultant detergent particles are then dried to achieve an acceptable moisture content such that the finished product is flowable and non-caking in the package once delivered to the consumer.
• the factors which impact these flow characte ⁇ stics include chemical composition and type and length in the drying process.
• a detergent particle that has improved surface, appearance and flow properties is provided.
• the particles of the present invention have improved surface properties m that they are smoother and have a generally more uniform surface and appearance than p ⁇ or art detergent particles. Further, the appearance of the particles have been improved m that they appear b ⁇ ghter and whiter than currently available detergent particles and have improved flow properties where the particles have reduced lumping and caking profiles.
• a detergent particle having a coating layer of a water-soluble mate ⁇ al is provided.
• the detergent particle comprises a particle core of a detergent active mate ⁇ al such as conventional detergent particles of surfactant and carbonate blends or individual detergent ingredients such as enzymes, bleaching agents, etc.
• This particle core is then at least partially covered by a particle coating layer of a water soluble matenal which imparts the aforementioned improved properties an a reduction in the surface area of the particle.
• a particle coating layer of a water soluble matenal which imparts the aforementioned improved properties an a reduction in the surface area of the particle.
• Particularly preferred are non-hydratable inorganic coating materials including double salt combinations of alkali metal carbonates and sulfates.
• the particle coating layer may also include detergent adjunct ingredients such as b ⁇ ghteners, chelants, nonionic surfactants, co-builders, etc. Accordingly, it is an object of the present invention to provide a detergent particle having improved appearance and flow characte ⁇ sttcs by coating a detergent core mate ⁇ al with a layer of water soluble inorganic mate ⁇ als.
• the word "particles” means the entire size range of a detergent final product or component or the entire size range of discrete particles, agglomerates, or granules in a final detergent product or component admixture. It specifically does not refer to a size fraction (i.e., representing less than 100% of the entire size range) of any of these types of particles unless the size fraction represents 100% of a discrete particle m an admixture of particles.
• the entire size range of discrete particles of that type have the same or substantially similar composition regardless of whether the particles are in contact with other particles.
• the agglomerates themselves are considered as discrete particles and each discrete particle may be comp ⁇ sed of a composite of smaller p ⁇ mary particles and binder compositions.
• the phrase “geomet ⁇ c mean particle diameter” means the geomet ⁇ c mass median diameter of a set of discrete particles as measured by any standard mass-based particle size measurement technique, preferably by dry sieving.
• the phrase “geomet ⁇ c standard deviation” or “span” of a particle size distribution means the geomet ⁇ c breadth of the best-fitted log-normal function to the above-mentioned particle size data which can be accomplished by the ratio of the diameter of the 84 13 percentile divided by the diameter of the 50 th percentile of the cumulative dist ⁇ bution (D S4 ⁇ 3 /D 50 ), See Gotoh et al, Powder Technology Handbook, pp. 6-11, Marcel Dekker 1997.
• the phrase “builder” means any inorganic material having “builder” performance in the detergency context, and specifically, organic or inorganic material capable of removing water hardness from washing solutions.
• the term “bulk density” refers to the uncompressed, untapped powder bulk density, as measured by pouring an excess of powder sample through a funnel into a smooth metal vessel (e.g., a 500 ml volume cylinder), scraping off the excess from the heap above the rim of the vessel, measuring the remaining mass of powder and dividing the mass by the volume of the vessel.
• compositions and “granular detergent composition” are intended to include both final products and additives/components of a detergent composition. That is, the compositions produced by the processes claimed herein may be complete laundry detergent compositions or they may be additives that are used along with other detergent ingredients for laundering fabrics and the like.
• surface area mean the total amount of surface of a powder available for gas adso ⁇ tion and thus includes both internal (i.e. that within cracks and crevices) and external surface area. Surface area is measured using BET multi point surface area analysis.
• the novel detergent particles of the present invention comprise a particle core which is at least partially coated with a water soluble coating material.
• the particle core may comprise a detergent particle, agglomerate, flake etc.
• the particle core will preferably comprise a blend of surfactant ingredients, particularly anionic surfactants with dry detergent ingredients such as carbonates, aluminosilicate builders, silicate builder materials, alkali metal sulfates, chelants and various other dry detergent ingredients in minor amounts.
• the particle core may comprise an individual detergent ingredient such as an enzyme, bleaching agents, perfume or mixtures thereof.
• Particularly preferred particle cores include detergent agglomerates formed by an agglomeration of a highly viscous surfactant paste or a liquid acid precursor of a surfactant and the aforementioned dry detergent ingredients.
• the agglomeration of the surfactant material and dry detergent material may be carried out in a high or moderate speed mixer after which an optional low or moderate speed mixer may be employed for further agglomeration, if necessary.
• the agglomeration may be earned out in a single mixer that can be low, moderate or high speed.
• the particular mixer used in the present process should include pulverizing or grinding and agglomeration tools so that both techniques can be carried forth simultaneously in a single mixer.
• the first processing step can be successfully completed, under the process parameters desc ⁇ bed herein, in a Lodige KMTM (Ploughshare) 600 moderate speed mixer, Lodige CBTM high speed mixer, or mixers made by Fukae, Drais, Schugi or similar brand mixer.
• the Lodige KMTM (Ploughshare) 600 moderate speed mixer which is a preferred mixer for use in the present invention, comp ⁇ ses a ho ⁇ zontal, hollow static cylinder having a centrally mounted rotating shaft around which several plough- shaped blades are attached.
• the shaft rotates at a speed of from about 15 ⁇ m to about 140 ⁇ m, more preferably from about 80 ⁇ m to about 120 ⁇ m.
• the g ⁇ ndmg or pulvenzing is accomplished by cutters, generally smaller in size than the rotating shaft, which preferably operate at about 3600 ⁇ m
• Other mixers similar in nature which are suitable for use in the process include the Lodige PloughshareTM mixer and the Drais® K-T 160 mixer
• the mean residence time of the va ⁇ ous starting detergent ingredients m the low, moderate or high speed mixer is preferably m range from about 0.05 minutes to about 15 minutes, most preferably the residence time is about 0.5 to about 5 minutes.
• This agglomeration is typically followed by a drying step.
• This drying step may be earned out in a wide va ⁇ ety of equipment including, but not limited to a fluid bed drying apparatus.
• dryer characte ⁇ stics include fixed or vibrating; rectangular bed or round bed; and straight or se ⁇ entme dryers. Manufacturers of such dryers include Niro, Bepex, Spray Systems and Glatt.
• apparatus such as a fluidized bed can be used for drying while an airlift can be used for cooling should it be necessary.
• the air lift can also be used to force out the "fine" particles so that they can be recycled to the particle agglomeration process
• the particles of the present invention compnse at least about 50% by weight of particles having a geomet ⁇ c mean particle diameter of from about 500 microns to about 1500 microns and preferably have a geomet ⁇ c standard deviation of from about 1 to about 2.
• the geomet ⁇ c standard deviation is from about 1.0 to about 1 7, preferably from about 1 0 to about 1.4.
• the granular detergent composition resulting from the processes may comprise fine particles, wherein "fine particles” are defined as particles that have a geomet ⁇ c mean particle diameter that is less than about 1.65 standard deviations below the chosen geomet ⁇ c mean particle diameter of the granular detergent composition Large particles may also exist wherein "large particles” are defined as particles that have a geomet ⁇ c mean particle diameter that is greater than about 1 65 standard deviations above the chosen geomet ⁇ c mean particle diameter of the granular detergent composition.
• the fine particles are preferably separated from the granular detergent composition and returned to the process by adding them to at least one of the mixers and/or the fluid bed dryer as desc ⁇ bed in detail below
• the large particles are preferably separated from the granular detergent composition and then fed to a g ⁇ nder where their geomet ⁇ c mean particle diameter is reduced. After the geomet ⁇ c mean particle diameter of the large particles is reduced, the large particles are returned to the process by adding them to at least one of the mixers and/or the fluid bed dryer.
• the agglomeration may comprise the step of spraying an additional binder in the mixers to facilitate production of the desired detergent particles.
• a binder is added for pu ⁇ oses of enhancing agglomeration by providing a "binding" or "sticking" agent for the detergent components.
• the binder is preferably selected from the group consisting of water, anionic surfactants, nonionic surfactants, polyethylene glycol, polyvinyl pyrrohdone polyacrylates, cit ⁇ c acid and mixtures thereof.
• Other suitable binder mate ⁇ als including those listed herein are desc ⁇ bed in Beerse et al, U.S. Patent No. 5,108,646 (Procter & Gamble Co.), the disclosure of which is inco ⁇ orated herein by reference.
• Another optional processing step to form the particle core of the present invention includes continuously adding a coating agent such as zeolites, recycled "fines" as described above and fumed silica to the mixer to improve the particle color, increase the particle "whiteness or facilitate free flowabihty of the resulting detergent particles and to prevent over agglomeration
• a coating agent such as zeolites, recycled "fines" as described above and fumed silica
• the fines are preferably m the approximate size range of 0.1 to 0.5 times the mean particle size of the larger particles.
• the particle coating layer will also improve the integrity of the fines layering and provide abrasion and att ⁇ tion resistance du ⁇ ng handling.
• the detergent starting matenals can be fed into a pre-mixer, such as a Lodige CB mixer or a twm-screw extruder, p ⁇ or to ente ⁇ ng m the mixer.
• a pre-mixer such as a Lodige CB mixer or a twm-screw extruder, p ⁇ or to ente ⁇ ng m the mixer. This step, although optional, does indeed facilitate agglomeration.
• particle cores which comprise tower blown particles.
• the core particle is formed by the preparation of a slurry of surfactant mate ⁇ als, water and dry starting detergent materials.
• the resultant slurry is then passed to a tower where the slurry is sprayed into a stream of air at a temperature typically ranging from about 175°C to about 225°C to dry the detergent slurry and form detergent particles Typically, resultant densities of these particles range from about 200 to about 500 g/L.
• the particle coating layer of the present invention is a water soluble coating mate ⁇ al.
• the particle coating layer imparts dramatically new surface and appearance properties on the detergent particles of the present invention.
• the coated particles of the present invention have an appearance which is b ⁇ ghter and/or whiter than current detergent particles. This provides a more favorable response from consumers who prefer white detergent products.
• the particle coating layer of the present invention imparts a dramatically improved feel to the particles of the present invention.
• the coated particles of the present invention have a glassy, smoother feel than prior art detergent products. This again provides a more favorable response from consumers who prefer a rounded, uniform product. Additionally, the coated particles of the present invention provide improved sound to a detergent product containing the particles of the present invention.
• the coated particles have a c ⁇ sper sound than current detergent products, thereby leaving the consumer with a more favorable overall impression of the product.
• the coated particles of the present invention provide improved clumping and flowabihty profiles to detergent products containing the particles of the present invention.
• the particle coating layer provides a coating which is c ⁇ sper and non-tacky.
• LAS linear alkyl benzene sulfonates
• surfactant actives i.e. greater than about 25 wt % surfactant active
• the particle coating layer of the present invention at least partially coats the particle core While the desired state is for particles which are completely coated by the particle coating, it is, of course, anticipated that complete coverage will not be possible m all cases in a continuous, high speed manufactu ⁇ ng process. While it is rather difficult to quantify the extent of the coating layer coverage, it is observed that increasing the amount of coating solids, either by increasing the solids concentration in the solution or by spraying on more of the solution, results in improved benefits and the appearance of a more uniform coverage. The benefits of increased coverage is balanced with the cost of drying excess water in the process. Accordingly, in preferred embodiments of the present invention, adequate coverage is achieved by applying coating solids at more than about 3 wt.% and most preferably more than about 5 wt.% of the particle core mass.
• the particle coating layer of the present invention comp ⁇ ses a water soluble coating mate ⁇ al.
• the coating mate ⁇ al is not an alkali metal silicate as presents stability problems in the detergent composition and has a tendency to form insoluble residues in the processing of the detergent.
• the water soluble coating mate ⁇ al is applied to provide a smoother more uniform appearance to the resultant detergent particles.
• the coating mate ⁇ al may be selected from a wide va ⁇ ety of mate ⁇ als provided the coating imparts the appearance, flowabihty and surface properties described herein.
• Preferred mate ⁇ als include inorganic salts and organic salts, polymers and combinations thereof. Suitable organic salts include alkali metal carboxylates such as citrates and acetates.
• Inorganic salts may include silicates, boron salts, phosphate salts, magnesium salts and va ⁇ ous other glass forming or crystalline inorganic salts. Most preferred are non-hydratmg materials. By non-hydrating it is intended that the mate ⁇ al does not have a strong tendency to react with environmental water such as moisture present in composition or humidity in the air to form higher hydrate phases.
• a non-hydrating coating means a coating layer in which at least 40 wt.% of the coating consists of a non-hydrating inorganic mate ⁇ al, preferably more than about 60 wt.% and most preferably more than about 80 wt.% non-hydrating.
• the non-hydratmg mate ⁇ al is preferably selected from alkali and/or alkaline earth metal sulfate and carbonate salts or mixtures of the two.
• a highly preferred mate ⁇ als are double salts of sulfate and carbonate having the formula M n X n :MS0 4 :MC0 3 , where MX can a salt compound such as a metal halide, and the molar fractions of MS0 4 and MC0 3 are both at least 10 mol% of the formula.
• the molar ratio of MS0 4 :MC0 3 is from about 90: 10 to about 10:90 and more preferably from about 75:25 to about 60:40 where M independently represents an alkali or alkaline earth metal and n is an integer or fraction thereof from 0 to 5.
• M independently represents an alkali or alkaline earth metal
• n is an integer or fraction thereof from 0 to 5.
• these highly preferred mate ⁇ als are the water-free sulfates and water-free carbonate minerals that are formed naturally by evaporative deposition, such as Hanksite, KNa22(S04)9(C03)2Cl , and Tychite, Na6Mg2(C03)4(S04).
• An especially preferred mate ⁇ al is a 2: 1 molar ratio of the double salt Na 2 S0 4 :Na 2 C0 3 otherwise known as "Burkeite", Na6(C03)(S04)2.
• the particle coating layer may also include an detergent adjunct ingredient in addition to the particle coating mate ⁇ al.
• detergent adjunct ingredients may include a wide va ⁇ ety of ingredients, including but not limited to optical b ⁇ ghteners, pigments or dyes, chelants, nonionic surfactants, pH control agents, detergency co-builders and mixtures of these mate ⁇ als.
• pigments or dyes such as titanium dioxide, bluing agents such as copper sulfate, zinc thiosulfate and Ultrama ⁇ ne blue, Sparkle enhancers such as mica flake, and co- builders such as citrates and nonionic surfactants.
• the particles of the present invention are produced by coating the particle core as desc ⁇ bed hereinbefore with the particle coating mate ⁇ al in a coating mixer.
• the coating mixer may be any of a number of mixers including high, moderate, and low speed mixers such as a Lodige KMTM (Ploughshare) 600 moderate speed mixer, Lodige CBTM high speed mixer, or mixers made by Fukae, Drais, Schugi or similar brand mixer Particularly preferred for use in the present invention are low speed drum mixers and low shear fluidized bed mixers.
• the mixer is preferably followed m sequence by a drying apparatus, for example a fluid bed, wherein the coated particles are then dried to achieve the coated particles of the present invention.
• the coating mixer is an fluidized bed.
• the preferred particle core of detergent agglomerates, spray-d ⁇ ed particles or most preferably mixtures thereof is passed into a fluid bed dryer having multiple internal "stages" or "zones".
• a stage or zone is any discrete area within the dryer, and these terms are used interchangeably herein.
• the process conditions withm a stage may be different or similar to the other stages in the dryer. It is understood that two adjacent dryers are equivalent to a single dryer having multiple stages.
• the va ⁇ ous feed streams of particle core and coating material can be added at the different stages, depending on, for example, the particle size and moisture level of the feed stream. Feeding different streams to different stages can minimize the heat load on the dryer, and optimize the particle size and shape as defined herein
• the fluid bed mixer of the present invention comprises a first coating zone where the particle coating mate ⁇ al of the present invention is applied.
• the coating zone involves the spraying of the coating mate ⁇ al m aqueous or slurry form onto the fluidized particles.
• the bed is typically fluidized with heated air in order to dry or partially dry moisture from the spray coating as it is applied.
• the spraying is achieved via nozzles capable of de ve ⁇ ng a fine or atomized spray of the coating mixture to achieve complete coverage of the particles.
• the droplet size from the atomizer is less than about 100 um. This atomization can be achieved either through a conventional two-fluid nozzle with atomizing air, or alternatively by means of a conventional pressure nozzle.
• the solution or slurry rheology is typically characte ⁇ zed by a viscosity of less than about 500 centipoise, preferably less than about 200 centipoise.
• the nozzle location is placed at or above the fluidized height of the particles m the fluid bed.
• the fluidized height is typically determined by a weir or overflow gate height.
• the coating zone of the fluid bed is then typically followed by a drying zone and a cooling zone.
• An alternative embodiment uses an agitated fluid bed, which includes mechanical and/or pneumatic mixing elements in addition to the conventional bed that is fluidized air passing through holes in a distributor plate.
• the advantage of the agitated bed is that it can be used to apply additional shear as a means to control granular shape and smoothness while performing the coating operation.
• Typical conditions within a fluid bed or agitated fluid bed apparatus of the present invention include (i) from about 1 to about 20 minutes of mean residence time, (ii) from about 100 to about 600 mm of depth of unfluidized bed, (iii) preferably not more than about 100 micron of droplet spray size, (iv) from about 175 to about 250 mm of spray height, (v) from about 0.4 to about 2.0 m/s of fluidizing velocity and (vi) from about 12 to about 100 °C of bed temperature.
• the conditions in the fluid bed may vary depending on a number of factors.
• the coated particles exiting the coating mixer may comprise in and of themselves a fully formulated detergent composition or in preferred embodiments may be admixed with additional ingredients, such as bleaching agents, enzymes, perfumes, non-coated detergent particles, and various other ingredients to produce a fully formulated detergent composition.
• the coated particles of the present invention have improved surface properties in that the particles are more uniform in shape and smoother on the surface than the uncoated spray-dried or agglomerated detergent particles. These features are reflected in a reduction of the overall surface area of particles having the coating of the present invention as opposed to particles not having the coatings of the present invention.
• the coatings of the present invention reduce total surface area by smoothing irregularities and filling crevices on the surface of the particles.
• the coatings of the present invention provide a reduction in overall surface area as measured by the formula:
• the surface area of the particles of the present invention are measured according to the following procedure. Detergent Particles are placed into a Micromeritics VacPrep 061 , available from Micromeritics of Norcross, Georgia, for pre-test preparation. The particles are placed under a vacuum of approximately 500 millitorr and heated to a temperature of between 80 and 100 C C for approximately 16 hours.
• the BET multi-point surface area is then measured m a Micromeritics Gemini 2375 surface area analyzer using a mixture " of helium and nitrogen gases and the following general conditions: Evacuation rate - 500.0 mmHg/min: Analysis Mode - Equilibration: Evacuation Time - 1.0 min.; Saturation Pressure - 771.77 mml ⁇ g; Equilibration Time - 5 sec. Helium Nitrogen Pressure - 15 psig; Helium and Nitrogen purity 99.9%, free space is measured and P/Po points cover 0.05 to 0.3 with 5 data points taken.
• the coated particles of the present invention may be treated with a post coating gloss treatment to provide a gloss layer on the coated detergent particle.
• the gloss layer may comprise inorganic salt materials, chelating materials, polymeric materials and mixtures thereof.
• Preferred inorganic materials are sulfate salts such as magnesium sulfate
• preferred chelants are diamines such as ethylene diamine disuccinic acids (EDDS)
• preferred polymers include acrylic polymers and copolymers such as acrylic/maleic copolymers.
• the surfactant system of the detergent composition may include anionic, nonionic, zwitterionic, ampholytic and cationic classes and compatible mixtures thereof.
• Detergent surfactants are described in U.S. Patent 3,664,961, Norris, issued May 23, 1972, and in U.S. Patent 3,919,678, Laughlin et al., issued December 30, 1975, both of which are inco ⁇ orated herein by reference.
• Cationic surfactants include those described in U.S. Patent 4,222,905, Cockrell, issued September 16, 1980, and in U.S. Patent 4,239,659, Mu ⁇ hy, issued December 16, 1980, both of which are also inco ⁇ orated herein by reference.
• Nonlimiting examples of surfactant systems include the conventional Ci 1 -Ci g alkyl benzene sulfonates ("LAS") and primary, branched-chain and random C j Q-C20 alkyl sulfates ("AS"), the C10-C1 8 secondary (2,3) alkyl sulfates of the formula CH 3 (CH 2 ) x (CHOS0 3 ⁇ M + ) CH3 and CH3 (CH2) y (CHOS0 3 " M + ) CH 2 CH 3 where x and (y + 1) are integers of at least about 7, preferably at least about 9, and M is a water-solubilizing cation, especially sodium, unsaturated sulfates such as oleyl sulfate, the C I Q-CI g alkyl alkoxy sulfates (“AE X S”; especially EO 1-7 ethoxy sulfates), Ci Q-C I g alkyl alkoxy carboxylates (especially the EO 1
• the conventional nonionic and amphoteric surfactants such as the C 12" 18 alkyl ethoxylates ("AE") including the so-called narrow peaked alkyl ethoxylates and Cg-C ] ⁇ alkyl phenol alkoxylates (especially ethoxylates and mixed ethoxy/propoxy), C 1 2-C1 g betaines and sulfobetaines ("sultaines"), C ⁇ ⁇ -C ⁇ amine oxides, and the like, can also be included in the surfactant system.
• the Ci o-Cj g N-alkyl polyhydroxy fatty acid amides can also be used. Typical examples include the N-methylglucamides. See WO 9,206,154.
• sugar-de ⁇ ved surfactants include the N-alkoxy polyhydroxy fatty acid amides, such as Cjo-Cig N-(3-methoxypropyl) glucamide.
• the N-propyl through N-hexyl C ⁇ -C ⁇ g glucamides can be used for low sudsing.
• C 0-C20 conventional soaps may also be used. If high sudsing is desired, the branched-chain C ⁇ -C J g soaps may be used. Mixtures of anionic and nonionic surfactants are especially useful. Other conventional useful surfactants are listed in standard texts.
• the detergent composition can, and preferably does, include a detergent builder.
• Builders are generally selected from the va ⁇ ous water-soluble, alkali metal, ammonium or substituted ammonium phosphates, polyphosphates, phosphonates, polyphosphonates, carbonates, silicates, borates, polyhydroxy sulfonates, polyacetates, carboxylates, and polycarboxylates.
• the alkali metal especially sodium, salts of the above.
• Preferred for use herein are the phosphates, carbonates, silicates, C, seemingly , 0 fatty acids, polycarboxylates, and mixtures thereof. More preferred are sodium t ⁇ polyphosphate, tetrasodium pyrophosphate, citrate, tartrate mono- and di-succinates, sodium silicate, and mixtures thereof (see below).
• inorganic phosphate builders are sodium and potassium t ⁇ polyphosphate, pyrophosphate, polyme ⁇ c metaphosphate having a degree of polymenzation of from about 6 to 21, and orthophosphates.
• polyphosphonate builders are the sodium and potassium salts of ethylene diphosphonic acid, the sodium and potassium salts of ethane 1-hydroxy-l, 1 -diphosphonic acid and the sodium and potassium salts of ethane,
• nonphosphorus, inorganic builders are sodium and potassium carbonate, bicarbonate, sesquicarbonate, tetraborate decahydrate, and silicates having a weight ratio of S ⁇ O» to alkali metal oxide of from about 0.5 to about 4.0, preferably from about 1.0 to about 2.4.
• Water-soluble, nonphosphorus organic builders useful herein include the va ⁇ ous alkali metal, ammonium and substituted ammonium polyacetates, carboxylates, polycarboxylates and polyhydroxy sulfonates.
• polyacetate and polycarboxylate builders are the sodium, potassium, lithium, ammonium and substituted ammonium salts of ethylene diamme tetraacetic acid, nit ⁇ lot ⁇ acetic acid, oxydisuccimc acid, melhtic acid, benzene polycarboxyhc acids, and cit ⁇ c acid.
• Polyme ⁇ c polycarboxylate builders are set forth in U S. Patent 3,308,067, Diehl, issued March 7, 1967, the disclosure of which is inco ⁇ orated herein by reference.
• Such mate ⁇ als include the water-soluble salts of homo- and copolymers of aliphatic carboxylic acids such as maleic acid, itaconic acid, mesaconic acid, fuma ⁇ c acid, acomtic acid, citraconic acid and methylenemalonic acid. Some of these materials are useful as the water-soluble anionic polymer as hereinafter desc ⁇ bed, but only if m intimate admixture with the nonsoap anionic surfactant
• polycarboxylates for use herein are the polyacetal carboxylates described in U.S. Patent 4,144,226, issued March 13, 1979 to Crutchfield et al., and U.S. Patent 4,246,495, issued March 27, 1979 to Crutchfield et al., both of which are inco ⁇ orated herein by reference
• These polyacetal carboxylates can be prepared by bnngmg together under polyme ⁇ zation conditions an ester of glyoxyhc acid and a polyme ⁇ zation initiator.
• polyacetal carboxylate ester is then attached to chemically stable end groups to stabilize the polyacetal carboxylate against rapid depolyme ⁇ zation in alkaline solution, converted to the corresponding salt, and added to a detergent composition.
• Particularly preferred polycarboxylate builders are the ether carboxylate builder compositions compnsmg a combination of tartrate monosuccmate and tartrate disuccmate descnbed m U.S. Patent 4,663,071, Bush et al., issued May 5, 1987, the disclosure of which is inco ⁇ orated herein by reference
• Water-soluble silicate solids represented by the formula M being an alkali metal, and having a S ⁇ O»:M»0 weight ratio of from about 0 5 to about 4.0, are useful salts in the detergent granules of the invention at levels of from about 2% to about 15% on an anhydrous weight basis, preferably from about 3% to about 8% Anhydrous or hydrated particulate silicate can be utilized, as well.
• any number of additional ingredients can also be included as components in the granular detergent composition.
• these include other detergency builders, bleaches, bleach activators, suds boosters or suds suppressors, anti-tarnish and anti-corrosion agents, soil suspending agents, soil release agents, germicides, pH adjusting agents, nonbuilder alkalinity sources, chelatmg agents, smectite clays, enzymes, enzyme-stabilizing agents and perfumes. See U.S. Patent 3,936,537, issued February 3, 1976 to Baskerville, Jr. et al, inco ⁇ orated herein by reference.
• Bleaching agents and activators are desc ⁇ bed m U S. Patent 4,412,934, Chung et al, issued November 1, 1983, and in U.S Patent 4,483,781, Hartman, issued November 20, 1984, both of which are inco ⁇ orated herein by reference
• Chelatmg agents are also desc ⁇ bed in U S Patent 4,663,071, Bush et al., from Column 17, line 54 through Column 18, line 68, inco ⁇ orated herein by reference
• Suds modifiers are also optional ingredients and are desc ⁇ bed in U S Patents 3,933,672, issued January 20, 1976 to Bartoletta et al., and 4,136,045, issued January 23, 1979 to Gault et al., both inco ⁇ orated herein by reference.
• Suitable smectite clays for use herein are described in U.S. Patent 4,762,645, Tucker et al., issued August 9, 1988, Column 6, line 3 through Column 7, line 24, inco ⁇ orated herein by reference.
• Suitable additional detergency builders for use herein are enumerated in the Baskerville patent, Column 13, line 54 through Column 16, line 16, and in U.S. Patent 4,663,071, Bush et al., issued May 5, 1987, both inco ⁇ orated herein by reference.
• a detergent agglomerate composition was made using the following formula using dry neutralization of HLAS in a high- speed mixer, followed by paste agglomeration with a pre-neutralized NaLAS paste in a second medium speed mixer, followed by spray-on of a Burkeite solution (5% solids basis) in a fluid bed dryer.
• Coated Product 107% ⁇ Solution made up of 1.5 wt% Na2C03, 3.5 wt% Na2S04 and 12.5 wt% H20.
• the spray solution can be made from a burkeite starting material, dissolved in water at -28.5 wt % solids, or by dissolving a mixture of Sodium Carbonate and Sodium Sulfate salts in a ratio of -30:70 with a total salt solids loading of -28.5 wt % in water.
• the solution is atomized to form droplets which coat or partially coat the particle core agglomerates, then the water is evaporated at a bed temperature of about 40 to 80 °C. Upon evaporation, the salts co-precipitate to form the Burkeite coating.
• a granular detergent composition was made using the following formula using a spray-dried core granule, followed by spray-on of a Potassium Citrate solution (5% solids basis) in a fluid bed dryer.
• the spray solution was made by co-dissolving Potassium Carbonate and Citric Acid in water.
• the solution is atomized to form droplets which coat or partially coat the core agglomerates, then the water is evaporated at a bed temperature of about 40 to 80 degrees Centigrade.
• the organic salt, Potassium Citrate forms a coating or partial- coating layer on the surface of the spray-dried granules.

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