EP1159390A1 - Procede de production de particules de detergent enrobees - Google Patents

Procede de production de particules de detergent enrobees

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Publication number
EP1159390A1
EP1159390A1 EP00916147A EP00916147A EP1159390A1 EP 1159390 A1 EP1159390 A1 EP 1159390A1 EP 00916147 A EP00916147 A EP 00916147A EP 00916147 A EP00916147 A EP 00916147A EP 1159390 A1 EP1159390 A1 EP 1159390A1
Authority
EP
European Patent Office
Prior art keywords
detergent
mixer
particle
coating
particles
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
EP00916147A
Other languages
German (de)
English (en)
Other versions
EP1159390B2 (fr
EP1159390B1 (fr
Inventor
Paul R. Mort, Iii
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Procter and Gamble Co
Original Assignee
Procter and Gamble Co
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
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Application filed by Procter and Gamble Co filed Critical Procter and Gamble Co
Publication of EP1159390A1 publication Critical patent/EP1159390A1/fr
Application granted granted Critical
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/02—Inorganic compounds ; Elemental compounds
    • C11D3/04—Water-soluble compounds
    • C11D3/046—Salts
    • 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
    • C11D1/66—Non-ionic compounds
    • C11D1/83—Mixtures of non-ionic with anionic 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
    • C11D11/00—Special methods for preparing compositions containing mixtures of detergents
    • C11D11/0082—Special methods for preparing compositions containing mixtures of detergents one or more of the detergent ingredients being in a liquefied state, e.g. slurry, paste or melt, and the process resulting in solid detergent particles such as granules, powders or beads
    • C11D11/0088—Special methods for preparing compositions containing mixtures of detergents one or more of the detergent ingredients being in a liquefied state, e.g. slurry, paste or melt, and the process resulting in solid detergent particles such as granules, powders or beads the liquefied ingredients being sprayed or adsorbed onto solid particles
    • 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
    • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/06—Powder; Flakes; Free-flowing mixtures; Sheets
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02—Anionic compounds
    • C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
    • C11D1/14—Sulfonic acids or sulfuric acid esters; Salts thereof derived from aliphatic hydrocarbons or mono-alcohols
    • C11D1/146—Sulfuric acid esters
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02—Anionic compounds
    • C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
    • C11D1/22—Sulfonic acids or sulfuric acid esters; Salts thereof derived from aromatic 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
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02—Anionic compounds
    • C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
    • C11D1/29—Sulfates of polyoxyalkylene ethers
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66—Non-ionic compounds
    • C11D1/72—Ethers of polyoxyalkylene glycols

Definitions

  • the present invention relates to detergent particles and a process for producing the particles. More particularly, the present invention relates detergent particles having a non- hydratmg coating layer and a process for producing these particles from solutions of the inorganic material.
  • Granular detergent products are typically produced from one of two manufacturing methods. The first involves the spray-drymg 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 d ⁇ ed to achieve an acceptable moisture content such that the finished product is flowable and non-cakmg 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.
  • the particles of the present invention have improved surface properties in 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 process for prepa ⁇ ng detergent particles having a coating layer of a water-soluble mate ⁇ al is provided.
  • the detergent particle comp ⁇ ses a particle core of a detergent active mate ⁇ al such as conventional detergent particles of surfactant -3-
  • This particle core is then at least partially covered by a particle coating layer of a water soluble material which imparts the aforementioned improved properties.
  • a particle coating layer of a water soluble material which imparts the aforementioned improved properties.
  • 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.
  • the process includes the steps of passing the particle core as defined above through a coating mixer such as a low speed mixer or fluid bed mixer and coating the particle core with a coating solution or slurry of the water soluble, non-hydratmg inorganic mate ⁇ al.
  • a coating mixer such as a low speed mixer or fluid bed mixer
  • the resultant detergent particles Upon drying, the resultant detergent particles have improved appearance and flow properties and may be packaged and sold as a detergent material or mixed with various other detergent ingredients to provide a fully formulated detergent composition
  • 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 in 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 compnsed of a composite of smaller primary particles and binder compositions.
  • the phrase “geomet ⁇ c mean particle diameter” means the geometnc 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 “geometric standard deviation” or “span” of a particle size distribution means the geometric 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 distribution (D 8
  • 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 agent, 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 carried out in a single mixer that can be low, moderate or high speed
  • the particular mixer used in the present process should include pulve ⁇ zmg or g ⁇ ndmg 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 described 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 rpm to about 140 rpm, more preferably from about 80 ⁇ m to about 120 ⁇ m.
  • the g ⁇ ndmg or pulve ⁇ zing is accomplished by cutters, generally smaller m size than the rotating shaft, which preferably operate at about 3600 ⁇ m.
  • Other mixers similar in nature which are suitable for use m the process include the Lodige PloughshareTM mixer and the Drais® K-T 160 mixer.
  • the mean residence time of the various starting detergent ingredients in the low, moderate or high speed mixer is preferably in range from about 0.05 minutes to about 15 minutes, most preferably the residence time is about 0.5 to about 5 minutes. In this way, the density of the resulting detergent agglomerates is at the desired level.
  • This agglomeration is typically followed by a drying step.
  • This drying step may be earned out m 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 ⁇ entine 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 comprise 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 geometric mean particle diameter of the granular detergent composition Large particles may also exist wherem "large particles” are defined as particles that have a geometric 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 detail below Likewise, the large particles are preferably
  • the agglomeration may comprise the step of spraying an additional binder m 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
  • suitable binder materials 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 desc ⁇ bed above and fumed silica to the mixer to improve the particle color, increase the particle "whiteness or facilitate free flowability of the resulting detergent particles and to prevent over agglomeration.
  • a coating agent such as zeolites, recycled "fines” as desc ⁇ bed above and fumed silica
  • the fines are preferably in the approximate size range of 0.1 to 0 5 times the mean particle size of the larger particles
  • the particle coatmg layer will also improve the mteg ⁇ ty of the fines layering and provide abrasion and attrition resistance during handling.
  • the detergent starting mate ⁇ als can be fed into a pre-mixer, such as a Lodige CB mixer or a twin-screw extruder, p ⁇ or to ente ⁇ ng in the mixer.
  • a pre-mixer such as a Lodige CB mixer or a twin-screw extruder, p ⁇ or to ente ⁇ ng in the mixer. This step, although optional, does indeed facilitate agglomeration
  • the present invention are 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 temperatures typically ranging from about 175°C to about 225°C to dry the detergent slurry and formed detergent particles
  • resultant densities of these particles range from about 200 to about 500 g/1 -7-
  • 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 p ⁇ or art detergent products. This again provides a more favorable response from consumers who prefer a rounded, uniform product.
  • 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 flowability 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. While effective at improving flowability in all detergent products, it is particularly effective at preventing clumping in products containing surfactants which are more difficult to dry to a non- tacky state including nonionic surfactants, linear alkyl benzene sulfonates (“LAS”), and ethoxylated alkyl sulfates or m detergent products containing high amounts of surfactant actives (i.e. greater than about 25 wt % surfactant active).
  • LAS linear alkyl benzene sulfonates
  • ethoxylated alkyl sulfates or m detergent products containing high amounts of surfactant actives i.e. greater than about 25 wt % surfactant active.
  • Trie 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 in all cases m 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 m 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.
  • the particle coating layer of the present invention comprises a water soluble coating material.
  • the coating material 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 material is applied to provide a smoother more uniform appearance to the resultant detergent particles.
  • the coating material may be selected from a wide variety of materials provided the coating imparts the appearance, flowability and surface properties described herein. Preferred materials 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 various other glass forming or crystalline inorganic salts. Most preferred are non-hydrating materials. By non-hydrating it is intended that the material 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 material, preferably more than about 60 wt.% and most preferably more than about 80 wt.% non-hydrating.
  • the non-hydrating material is preferably selected from alkali and/or alkaline earth metal sulfate and carbonate salts or mixtures of the two.
  • a highly preferred materials are double salts of sulfate and carbonate having the formula M n X n :MS0 4 :MC ⁇ 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 materials 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 material 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 material.
  • detergent adjunct ingredients may include a wide variety of ingredients, including but not limited to optical brighteners, pigments or dyes, chelants, nonionic surfactants, pH control agents, detergency co-builders and mixtures of these materials. Particularly preferred are pigments or dyes such as titanium dioxide, bluing agents such as copper sulfate, zinc thiosulfate and Ultramarine blue, Sparkle enhancers such as mica flake, and co- builders such as citrates and nonionic surfactants. -9-
  • the particles of the present invention are produced by coatmg the particle core as described hereinbefore with the particle coating matenal 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 in 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 a 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 within a stage may be different or similar to the other stages m 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 mate ⁇ al 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 comp ⁇ ses a first coatmg zone where the particle coatmg mate ⁇ al of the present invention is applied.
  • the coatmg zone involves the spraying of the coatmg mate ⁇ al in aqueous or slurry form onto the fluidized particles.
  • the bed is typically fluidized with heated air m order to dry or partially dry moisture from the spray coating as it is applied.
  • the spraying is achieved via nozzles capable of dehve ⁇ 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 in the fluid bed may be in most any location, the preferred location is a positioning that allows a vertical down spray of the coating mixture such as a top spray configuration. To achieve best results, the nozzle location is placed at or above the -10-
  • 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 50 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:
  • a reduction in surface area as provided by the present invention leads to improved flow properties and to improved overall aesthetics by providing a more reflective surface.
  • the surface area of the particles of the present invention are measured according to the following procedure.
  • Detergent Particles are placed into a Micromcritics VacPrep 061. available from Micromcritics of Norcross, Georgia, for pre-lest preparation.
  • the particles arc placed under a vacuum of approximately 500 millitorr and heated to a temperature of between 80 and 100°C for approximately 16 hours.
  • the BET multi-point surface area is then measured in a Micromcritics 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 mm.; Saturation Pressure - 771.77 mmllg; 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 granular detergent compositions of this invention have a standard deviation of the number distribution of circularity less than about 20, that is preferably less than about 10, more preferably less than about 7 most preferably less than about 4.
  • the standard deviation of the number distribution of aspect ratios is preferably less than about 1 , more preferably less than about 0.5, even more preferably less than about 0.3, most preferably less than about 0.2.
  • granular detergent compositions are produced wherein the product of circularity and aspect ratio is less than about 100, preferably less than about 50, more preferably less than about 30, and most preferably less than about 20. Also preferred are granular detergent compositions with the standard deviation of the number distribution of the product of circularity and aspect ratio of less than about 45, preferably less than about 20, more preferably less than about 7 most preferably less than about 2.
  • 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, zwitte ⁇ onic, ampholytic and cationic classes and compatible mixtures thereof
  • Detergent surfactants are desc ⁇ bed m U S Patent 3,664,961, Nor ⁇ s, issued May 23, 1972, and in U.S Patent 3,919,678, Laughhn et al , issued December 30, 1975, both of which are mco ⁇ orated herein by reference.
  • Cationic surfactants include those desc ⁇ bed m 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 mco ⁇ orated herein by reference.
  • Nonhmitmg examples of surfactant systems include the conventional C 1 -Ci g alkyl benzene sulfonates ("LAS") and primary, branched-cham and random Ci 0-C20 alkyl sulfates (“AS”), the C 10 -C 18 secondary (2,3) alkyl sulfates of the formula CH3(CH 2 ) x (CHOS0 3 ' M + ) CH 3 and CH3 (CH 2 ) y (CHOS ⁇ 3 " M + ) CH2CH3 where x and (y + 1) are integers of at least about 7, preferably at least about 9, and M is a water-solubihzmg cation, especially sodium, unsaturated sulfates such as oleyl sulfate, the Cj -Cig alkyl alkoxy sulfates ("AE X S”; especially EO 1-7 ethoxy sulfates), CJQ-C j alkyl alkoxy carboxylates (
  • Ci 0-C 1 g amme oxides can also be included in the surfactant system.
  • the Cjn-Cig N-alkyl polyhydroxy fatty acid amides can also be used. Typical examples include the Ci 2-C1 g N-methylglucamides. See WO 9,206,154.
  • Other sugar-de ⁇ ved surfactants include the N-alkoxy polyhydroxy fatty acid amides, such as C ⁇ -C I g N-(3-methoxypropyl) glucamide.
  • the N-propyl through N-hexyl Ci 2-C ⁇ g glucamides can be used for low sudsmg.
  • C10-C20 conventional soaps may also be used. If high sudsmg is desired, the branched-cham Ci -Cig 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.
  • alkali metal especially sodium, salts of the above.
  • phosphates for use herein are the phosphates, carbonates, silicates, C. chief . chief 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 tripolyphosphate, pyrophosphate, polyme ⁇ c metaphosphate having a degree of polymerization of from about 6 to 21, and orthophosphates.
  • polyphosphonate builders are the sodium and potassium salts of ethylene diphosphomc acid, the sodium and potassium salts of ethane 1-hydroxy-l, 1 -diphosphomc acid and the sodium and potassium salts of ethane, 1 , 1 ,2-t ⁇ phosphon ⁇ c acid.
  • Other phosphorus builder compounds are disclosed m U.S. Patents 3,159,581; 3,213,030; 3,422,021; 3,422,137; 3,400,176 and 3,400,148, all of which are inco ⁇ orated herein by reference.
  • 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 various 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 m 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 tSe water-soluble salts of homo- and copolymers of aliphatic carboxyhc acids such as maleic acid, ltacomc 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 desc ⁇ bed 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 b ⁇ nging 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 m alkaline solution, converted to the corresponding salt, and added to a detergent composition.
  • Particularly preferred polycarboxylate builders are the ether carboxylate builder compositions compnsing a combination of tartrate monosuccmate and tartrate disuccinate desc ⁇ bed in 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 S ⁇ O ? »M ?
  • M being an alkali metal, and having a SiO-.M-O weight ratio of from about 0.5 to about 4.0, are useful salts 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.
  • Bleaching agents and activators are desc ⁇ bed in 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.
  • Chelating 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 described in U.S.
  • Suitable smectite clays for use herein are desc ⁇ bed 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
  • Example I In this example of coating by a non-hydrating inorganic salt, 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 -16-
  • the water is evaporated at a bed temperature of about 40 to 80 °C.
  • 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 Cit ⁇ c 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- coatmg layer on the surface of the spray-d ⁇ ed granules.

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  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Detergent Compositions (AREA)

Abstract

L'invention concerne un procédé permettant de préparer des particules de détergent enrobées d'une couche d'une matière inorganique soluble dans l'eau. La particule de détergent est constituée d'un noyau d'un matériau détergent actif. Ledit noyau est ensuite enrobé au moins partiellement d'un revêtement particulaire d'une matière inorganique soluble dans l'eau. On préfère en particulier des matières de revêtement inorganiques non hydratables comprenant des combinaisons de sels doubles de carbonates et de sulfates métalliques alcalins. Le revêtement particulaire comprend également des additifs détergents tels que azurants, chélateurs, tensio-actifs non ioniques, co-adjuvants, etc. Le procédé consiste à faire passer le noyau particulaire par un mélangeur, par exemple à faible vitesse ou en lit fluidisé, et à enrober le noyau particulaire d'une solution d'enrobage ou d'une boue de la matière inorganique soluble dans l'eau. Une fois séchées, les particules de détergent résultantes présentent une apparence et des caractéristiques de fluidité meilleures et peuvent être emballées et vendues comme matière détergente, ou mélangées à divers autres ingrédients détergents pour produire une composition détergente entièrement formulée.
EP00916147A 1999-03-09 2000-03-08 Procede de production de particules de detergent enrobees Expired - Lifetime EP1159390B2 (fr)

Applications Claiming Priority (5)

Application Number Priority Date Filing Date Title
US12344399P 1999-03-09 1999-03-09
US123443P 1999-03-09
US12777299P 1999-04-05 1999-04-05
US127772P 1999-04-05
PCT/US2000/005983 WO2000053714A1 (fr) 1999-03-09 2000-03-08 Procede de production de particules de detergent enrobees

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EP1159390A1 true EP1159390A1 (fr) 2001-12-05
EP1159390B1 EP1159390B1 (fr) 2006-05-03
EP1159390B2 EP1159390B2 (fr) 2009-08-12

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JP (1) JP2002538291A (fr)
CN (1) CN1343250A (fr)
AR (1) AR022885A1 (fr)
AT (1) ATE325183T1 (fr)
AU (1) AU3729600A (fr)
BR (1) BR0008852A (fr)
CA (1) CA2362413A1 (fr)
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WO (1) WO2000053714A1 (fr)

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DE10221742A1 (de) * 2002-05-16 2003-12-04 Henkel Kgaa Gerüststoffgranulate
PL2584028T3 (pl) * 2011-10-19 2017-10-31 Procter & Gamble Cząstka
EP2639291A1 (fr) * 2012-03-13 2013-09-18 Unilever PLC Composition de détergent particulaire conditionnée
WO2013139702A1 (fr) * 2012-03-21 2013-09-26 Unilever Plc Particules de détergent à lessive
EP3039113B1 (fr) * 2013-08-28 2019-12-04 Novozymes A/S Granulés enzymatiques avec agent de blanchiment fluorescent
WO2015154277A1 (fr) * 2014-04-10 2015-10-15 The Procter & Gamble Company Granulés de détergent composites et compositions de lavage du linge comprenant ces derniers
CN111893008B (zh) * 2020-08-10 2022-09-20 纳爱斯集团有限公司 一种洗涤制剂及其制备方法

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FR2226460B1 (fr) † 1973-04-20 1976-12-17 Interox
US4105827A (en) * 1973-04-20 1978-08-08 Interox Particulate peroxygen compounds coated with sodium sesquicarbonate or Na2 SO4 mNa2 CO3
DE2652776A1 (de) † 1975-05-13 1978-05-24 Interox Chemicals Ltd Verfahren zur herstellung von natriumpercarbonat
LU72575A1 (fr) † 1975-05-23 1977-02-10
US5707953A (en) † 1993-04-19 1998-01-13 Akzo Nobel N.V. Fluidized bed coated amidoperoxyacid bleach composition
US5462804A (en) † 1993-05-06 1995-10-31 Mitsubishi Gas Chemical Co., Ltd. Stabilized particle of sodium percarbonate
ATE185838T1 (de) † 1993-07-14 1999-11-15 Procter & Gamble Stabilisierte reinigungsmittelzusammensetzungen
US5576285A (en) * 1995-10-04 1996-11-19 The Procter & Gamble Company Process for making a low density detergent composition by agglomeration with an inorganic double salt
RU2182164C2 (ru) † 1996-03-27 2002-05-10 Солвей Интерокс (Сосьете Аноним) Перкарбонат натрия, способ выбора перкарбоната натрия, композиция моющего средства
DE19713328A1 (de) * 1997-03-29 1998-10-01 Henkel Kgaa Verfahren zur Herstellung von Granulaten
DE69911623T2 (de) † 1998-07-17 2004-07-01 The Procter & Gamble Company, Cincinnati Waschmitteltablette

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Title
See references of WO0053714A1 *

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BR0008852A (pt) 2002-01-08
JP2002538291A (ja) 2002-11-12
DE60027707D1 (de) 2006-06-08
ATE325183T1 (de) 2006-06-15
WO2000053714A1 (fr) 2000-09-14
CA2362413A1 (fr) 2000-09-14
EP1159390B2 (fr) 2009-08-12
DE60027707T2 (de) 2007-04-05
CN1343250A (zh) 2002-04-03
AU3729600A (en) 2000-09-28
AR022885A1 (es) 2002-09-04
EP1159390B1 (fr) 2006-05-03

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