WO2005058473A2 - Particulate materials - Google Patents
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- WO2005058473A2 WO2005058473A2 PCT/GB2004/005256 GB2004005256W WO2005058473A2 WO 2005058473 A2 WO2005058473 A2 WO 2005058473A2 GB 2004005256 W GB2004005256 W GB 2004005256W WO 2005058473 A2 WO2005058473 A2 WO 2005058473A2
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- particulate material
- particles
- range
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- material according
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2/00—Processes or devices for granulating materials, e.g. fertilisers in general; Rendering particulate materials free flowing in general, e.g. making them hydrophobic
- B01J2/02—Processes or devices for granulating materials, e.g. fertilisers in general; Rendering particulate materials free flowing in general, e.g. making them hydrophobic by dividing the liquid material into drops, e.g. by spraying, and solidifying the drops
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
- Y10T428/2982—Particulate matter [e.g., sphere, flake, etc.]
Definitions
- This invention relates to particulate materials and methods of producing particulate materials.
- Particulate materials have found utility in a wide range of applications.
- encapsulated fragrances and flavours organoleptics
- Other encapsulated actives such as biocides
- Encapsulated pharmaceutical preparations that permit slow or controlled release of the active ingredient have been widely used.
- New applications in electronics materials are also generating significant interest.
- Particulate materials in which active ingredients are encapsulated within carrier or matrix materials enables the actives to be handled easily and to be readily incorporated within other systems to be dispersed or released, in use, to permit the active ingredient to have its affect.
- effective protection of the actives until required, long shelf life, size and density and the controlled or phased release of the active are very important factors in whether such particulate materials are commercially attractive.
- a wide particle size range may result in a poor dispersion/dissolution of the particles and hence the active in use; or the separating out of the particulate material containing the active ingredient from other particulate materials in a mixture, eg in laundry powders, would be detrimental to the even dispersion of the active in use.
- Such particulate materials are generally produced from a liquid precursor by spraying the liquid precursor and, depending on the precursor, either drying it or cooling it to form the particulate materials.
- the liquid precursor may typically be a melt of a polymer matrix material in which is dispersed an active ingredient in which case the sprayed material is chilled to cause it to at least partially solidify during flight to form substantially spherical particles.
- the liquid precursor may be a solution or emulsion containing the matrix material and the active ingredient and it is subjected to conditions such as heat to dry it or cause some other phase change sufficient to form the particles during flight.
- Spray dryers or chillers are well known and typically consist of a tower into which the liquid precursor is sprayed by an atomiser and in which the liquid droplets are subjected to a gas flow, either co-current or counter-current, to effect at least a partial phase change in the droplets.
- Commonly used atomisers are single fluid nozzles, two-fluid pneumatic nozzles and high speed rotary disc atomisers. Examples of such spray dryers/atomisers can be found in US-B-5545360, US-B-564530, US-B- 6531444 and US-A1 -2002/0071871.
- Other forms of equipment use different techniques to produce particulate material in which the particle size range is relatively narrow, ie the particles are said to be substantially mono-dispersed.
- the techniques include applying fluctuating pressure to the liquid being atomised and mechanically or acoustically perturbing the jets of liquid to break them up into droplets. Examples of such equipment can be found in US-A-4585167, GB-A-1454597, EP-A-86704, EP-A-320153 and WO 94/20204.
- Such equipment has been primarily used to form relatively large prills from a molten precursor such as molten ammonium nitrate.
- Particulate materials having a relatively narrow particle size distribution may have advantages over particulate materials having relatively wide particle size distributions. For example, particulate materials having a relatively narrow particle size distribution tend to be less dusty, are free flowing and more easily metered and are safer to handle.
- the Applicant has been found that, even with particulate materials having a relatively narrow particle size distribution, significant difficulties may be experienced in dispersing the particles in liquids in use. Additionally, wetting of the particles by liquids in use and release of the active ingredient is frequently very variable. Those variables are disadvantageous in many applications as they may give rise to poor or incomplete release of the active ingredient in applications such as crop adjuvants, instant foods and laundry products or leave unattractive residues in deodorant/anti-perspirant applications. These issues do not appear to have previously been addressed.
- the morphologies are described in more detail below.
- the Applicant has found the density of the particles and the release of the active ingredients from the particles is dependent on the morphologies of the particles.
- the presence of significant amounts of differing morphologies in the particulate material results in non-uniform release of the active ingredient which situation is exacerbated by the presence of a relatively wide spread of particle sizes.
- Even in substantially homogeneous particulate materials, the dispersibility and dissolution of the material is non-uniform.
- the Applicant has found that, surprisingly, by the selection of the production method and the parameters under which the particles are generated, it is possible to make particulate material having a selected morphology when more than one morphology is capable of being produced.
- a particulate material made by a spray process has at least 80%, preferably at least 90% and more especially at least 95% of the particles of the same morphology, said particulate material having a mono-dispersivity index of not more than 1.2, preferably not more than 1.0 and more especially not more than 0.6.
- a particulate material made by a spray process has at least 80%, preferably at least 90% and more especially at least 95% of the particles of the same morphology, said particles having at least two components, a first component being at least one matrix material and a second component being at least one active ingredient retained by said first component, and said particulate material having a mono-dispersivity index of not more than 1.2, preferably not more than 1.0 and more especially not more than 0.6.
- particles have a morphology selected from hollow sphere, roughly spherical, cenospheres and packed porous network morphologies.
- MDI mono-dispersivity index
- particle size 90% is the size below which 90% by volume or weight of the particles lie: (particle size 10%) is the size below which 10% by volume or weight of the particles lie; and (particle size 50%) is the size below which 50% by volume or weight of the particles lie.
- the particulate material according to the invention has an MDI of greater than 0.05 and is more typically greater than 0.1, and is usually greater than 0.2.
- the particulate material according to the invention comprises particles that are substantially all of the same morphology, ie substantially 100% of the particles are of a particular morphology.
- the particulate material according to the invention comprises particles having a mean size in the range 50 ⁇ m to 3000 ⁇ m whether measured by volume or weight.
- the lower end of the mean size range is 50 ⁇ m and more preferably 100 ⁇ m.
- the upper end of the mean size range is 3000 ⁇ m and more preferably 2000 ⁇ m and more especially 1000 ⁇ m.
- the particulate material comprises particles having a mean size in the range 100 ⁇ m to 600 ⁇ , more especially 200 ⁇ m to 500 ⁇ m.
- the mean sizes refer to volume mean sizes.
- the mean size is essentially refers to the diameter of the particles.
- the mean size refers to the equivalent spherical diameter the particle would have if the material in it had a spherical morphology.
- the particulate material according to the invention is essentially dust free by which is meant it essentially does not contain any particles having a volume mean size less than 20 ⁇ m; more preferably it essentially does not contain any particles having sizes less than 50 ⁇ m and especially it essentially does not contain any particles having a volume mean size less than 80 ⁇ m.
- this reference to the particulate material being essentially dust free is to the particulate material as made. In other words, it is not necessary to subject the particulate material according to the invention to a subsequent processing step to remove fines.
- the particles if homogeneous, or the first component and second components of the particles, if heterogeneous, may be selected from a wide range of materials depending on the application in which the particulate material is to be used.
- the materials from which the first component is selected will enable the second component to be retained thereby, for example through encapsulation or binding together, to form discrete particles.
- the first component forms a material network that has interstices in which the second component is held.
- matrices may be inorganic or organic crystalline structures or may be amorphous or glassy-like structures.
- examples of such matrices include inorganic salts such as sulphates, nitrates, acetates, carbonates etc and organic materials such as lactose, starches, sugars and organic acids.
- the particles have to be biocompatible.
- the first component has to be biocompatible.
- biocompatible is meant that users of products containing the particulate material according to the invention experience no adverse af ects. Examples of such uses are the use of encapsulated organoleptics in food, personal care and home care applications.
- Suitable biocompatible materials for use as the first component may be selected from sugars, polysaccharides, starches and glycerides, especially di- and tri-glycerides. Such materials are also film forming.
- the material of the particles or when heterogeneous, the material of the first component to be film forming.
- examples of such materials are polyvinyl acetate and ethylene vinyl acetate copolymers including mixture thereof with each other or with other materials such as latex, waxes, fats, lipids, and biopolymers.
- the second component of the particles when the particles are heterogeneous, may be selected from a wide range of materials depending on the application in which the particulate material is to be used.
- the materials from which the second component are selected will be compatible with the first component in the sense of not being substantially detrimentally degraded by reaction with the first component, at least in the particles and the precursor formulations from which the particles are derived.
- the second component of the particles may be selected from organoleptics, nanoscale fillers such as inorganic fine oxides, catalysts, skin benefit agents, nutrients, responsive polymers such as hydrogels.
- the preferred organoleptic components are those that are most susceptible to attack without the protection offered by encapsulation e.g. highly volatile molecules, essential oils and fragrance chemicals which are susceptible to oxidative attack when used in bleach-containing detergents.
- Hydrogels are polymers that absorb liquids and swell.
- the polymer chains are tangled and form porous networks similar to micro-sponges.
- Hydrogel particles are used to absorb the active ingredient and are then dispersed in a matrix material and subjected to a spray process to form particulate material according to the present invention.
- Polymers that form hydrogels typically contain hydroxyl, amine, amide, ether, carboxylate or sulphate groups or combinations of such groups. Typical of such polymers is ⁇ , ⁇ -poly (N-2-hydroxyethyl)-DL-aspartamide.
- the second component of the particles when the particles are heterogeneous, may in itself be a binary or higher order particle.
- the second component may be an active material encapsulated by a matrix to form a core shell particle.
- matrix materials are maltodextrin, starches, sugars, polysaccharides and fats.
- matrix-forming materials are: starch, chemically and/or physically modified starch, starch systems containing other carbohydrates and/or polyols as described in EP 0 922 449 A2, US 5,185,176; 4,977,252; 3,971,852, EP 0550067 (also, Modified Starches: Properties and Uses, O.B.Wurzburg, editor, CRC Press, Boca Raton, Florida (1986).). Starch/oil composites (US 5,882,713 and 5,676,994); cellulose and cellulose derivatives (e.g.
- active ingredients are: adhesives, oils, , lubricants, fats, flavors, fragrances, colourants, vitamins, pharmaceuticals, inorganic or organic fillers, inks, sunscreens, moisturizers, biocidal substances or mixtures that accomplish a pest control or antifungal function, antibacterial materials, oil field additives, laundry additives such as fabric conditioners, enzymes, cosmetic materials, deodorants, hair conditioners and skin conditioners.
- the second component comprises between 25 wt% to 55 wt%, more preferably 30 wt% to 50 wt%, of the particles.
- a preferred embodiment of the present invention when the particles are heterogeneous, comprises the first component being at least one matrix material selected from sugars, polysaccharides, starches and glycerides, especially di- and tri-glycerides, and a second component being at least one active ingredient retained by said first component and being an organoleptics.
- Another preferred embodiment of the present invention when the particles are heterogeneous, comprises the first component being at least one film-forming polymeric matrix material.
- slow dissolution of the particles and/or dispersion of active ingredients therein may be achieved by selecting film-forming materials and morphologies, ie spherical, hollow spheres and cenospheres; medium dissolution of the particles and/or dispersion of active ingredients therein may be achieved by selecting particles having a morphology suited to erosion mechanisms, ie roughly spherical; and fast dissolution of the particles and/or dispersion of active ingredients therein may be achieved by selecting the packed porous network morphology.
- the particulate material according to the present invention is made by projecting from a body of liquid comprising a precursor formulation for said particulate material an array of mutually divergent jets, disturbing the jets to cause break up thereof into streams of droplets of narrow size distribution, contacting the array of resulting droplet streams with a gas flow to reduce coalescence of the droplets in each stream and causing or allowing the droplets to solidify at least partially in flight, wherein said precursor formulation has a density in the range 800 kg/m 3 to 1700 kg/m 3 , more preferably 1000 kg/m 3 to 1700 kg/m 3 , a viscosity in the range 0.01 Pa.s to 1 Pa.s, more preferably in the range 0.06 Pa.s to 1 Pa.s and a surface tension in the range 0.01 N/m to 0.72 N/m, more preferably 0.02 N/m to 0.72 N/m and an Ohnesorge Number (Ohn) in the range 0.005 to 2.5, more especially in the range 0.008 to
- the viscosity of the precursor formulation is normally determined at zero shear rate, but it may be determined at the wall shear rate of nozzles through which it passes to form the jets when it is higher than 0.1 Pa.s.
- the Weber number of the precursor formulation is in the range 300 to 3000.
- the process of the invention produces droplets having a volume mean droplet size in the range 50 ⁇ m to 3000 ⁇ m.
- the divergent jets may be disturbed to cause break up thereof by mechanical or acoustic vibration.
- the divergent jets are preferably disturbed to cause break up thereof by acoustic vibration.
- the Weber frequency (fw) used for droplet generation is in the range 0.5 kHz to 100 kHz.
- the flow in the jets is laminar.
- a preferred embodiment of the method of the present invention when the particles are heterogeneous and in which the first component is at least one matrix material selected from sugars, polysaccharides, starches and glycerides, especially di- and tri-glycerides comprises the liquid jets having a Rej in the range 10 to 5000 and the ' drops are generated using an fw in the range 2 kHz to 15 kHz.
- Another preferred embodiment of the method of the present invention when the particles are heterogeneous and in which the first component is at least one film- forming polymeric matrix material comprises the liquid jets having a Rej in the range 10 to 100 and the drops are generated using an fw in the range 10 kHz to 100 kHz.
- Yet another preferred embodiment of the method of the present invention when the particles are heterogeneous and wherein a material network is formed comprises the liquid jets having a Rej in the range 10 to 1000 and the drops are generated using an fw in the range 2 kHz to 50 kHz.
- Figure 1 is a schematic view of particle morphology formation
- Figure 2 is a schematic view of spraying apparatus;
- Figure 3 is a micrograph of the particulate material of sample 1 described in Example
- Figure 4 is a micrograph of the particulate material of sample 2 described in Example 1;
- Figure 5 is a micrograph of the particulate material of sample 4 described in Example 1;
- Figure 6 is a micrograph of the particulate material of sample 5 described in Example 1;
- Figure 7 is a micrograph of the particulate material of sample 6 described in Example 2.
- Figure 8 is a micrograph of the particulate material of sample 6 described in Example 2 taken at a higher magnification
- Figure 9 is a micrograph of the particulate material of sample 12 described in Example 2.
- Figures 10 and 11 are micrographs of the particulate material of sample 12 described in Example 2 taken at a higher magnification;
- Figures 12 and 14 are micrographs similar to Figures 9 to 11 but of the particulate material of sample 11 described in Example 2;
- Figures 15 to 19 are, respectively, micrographs of the particulate materials of samples 21, 23 to 25 and 27 described in Example 4.
- Figures 20 and 21 are, respectively, micrographs of the particulate materials of samples 31 and 32 described in Example 7.
- the morphologies are identified as: spherical hollow sphere roughly spherical cenospheres packed porous network.
- the particulate material of the present invention preferably comprises particles of one of the morphologies shown. As shown, as the droplet is subjected to the gas flow, a crust is formed and each particle is then able to adopt one of the morphologies shown or a spherical morphology (not shown).
- the particles In the hollow sphere morphology, the particles generally have a shape close to or actually spherical and are hollow.
- the roughly spherical morphology has particles that are generally round, ie spherelike, in shape but they do not have a smooth surface.
- the surface appearance can vary from slightly rough, almost scale-like in appearance to very rough, irregular and knobbly or protrusion-covered surfaces.
- the particles are solid apart from a very small irregular central cavity, which arises as a result of density differences between the precursor formulation and the particle.
- the particles In the cenospheres morphology, the particles generally have a shape close to a sphere but are more likely to be slightly elongate or elliptical in appearance as compared to a true sphere and have an opening through the shell into the hollow centre.
- the particle density varies across the morphologies as does the release mechanism of the active from the matrix.
- slow dissolution of the particles and/or dispersion of active ingredients therein may be achieved by selecting film-forming materials and morphologies, ie spherical, hollow spheres and cenospheres; medium dissolution of the particles and/or dispersion of active ingredients therein may be achieved by selecting particles having a morphology suited to erosion mechanisms, ie roughly spherical; and fast dissolution of the particles and/or dispersion of active ingredients therein may be achieved by selecting the packed porous network morphology.
- a spherical morphology would be similar to the hollow sphere morphology shown in Figure 1 except that it would be solid apart from a very small irregular central cavity, which arises as a result of density differences between the precursor formulation and the particle. In this instance, the particle would have high density and the release would be erosion controlled.
- spraying apparatus 10 has a spray tower 12 at the top of which is located a spray head (not shown).
- a feed line 14 supplies a precursor formulation to the spray head and a gas supply line 16 provides gas via a heater or cooler 18 to the tower 12 for the gas to impinge on droplet streams emitted from the spray head.
- An exhaust line 20 feeds the particles and exhaust gas to a separator 22 from which products off take 24 and a gas exhaust 26 exit.
- the gas flow is concurrent with the droplet streams.
- the gas flow may be counter-current with the gas entering the lower section of the spray tower 12 and being exhausted at its upper end above the spray head.
- the spray head (not shown) may be a nozzle or rotary atomiser in conventional spray drying; alternatively, in accordance with the present invention, it is an accoustic spray head of the type described in WO 94/20204.
- a measured amount of particulate material was poured into a beaker containing a 100g of demineralised water and its capacity to be completely dissolved or, on the contrary, to remain in particulate form or to aggregate into lumps was observed, together with the time needed to achieve the final condition.
- the water amount in a material can highly influence its physical and chemical properties, causing for example its plasticisation and consequently reducing its glass transition temperature.
- the test was carried out to measure the residual moisture in the particulate material to enable an appropriate correction to be made to the measured active ingredient retention, which is at least partly dependent on this variable.
- the moisture content of the particulate material was measured using a Karl-Fisher water measurement apparatus.
- a non-aqueous solvent for the particulate material ie ethanol
- 100 ⁇ litres of ethanol was injected into the apparatus and the moisture content of the solvent was measured.
- a measured amount, around 1 mg, of particulate material was dissolved in ethanol and 100 ⁇ litres of the solution was injected into the Karl-Fisher apparatus and the moisture content of the solvent was measured.
- the amount of water in the pure solvent and in the solution are known and the exact weight of the dissolved and injected particulate material is known, the residual moisture in the sample can be calculated.
- the (1.04) in the formula is a correction factor for residual moisture, in this instance 4%.
- the particulate material was made only using the HI-CAP 100.
- the HI-CAP 100 is formed into a dispersion which is then subjected to a spray process.
- the dispersion was prepared following the recommended procedure to prepare a dispersion of HI-CAP 100, namely:
- the resultant particulate samples were free flowing and non-dusty.
- the particles sizes are in the range from 250 to 500 microns depending on the nozzles used.
- the emulsion had a density of 1300 kg/m3, a viscosity of 0.15 Pa.s and a surface tension of 0.03 N/m.
- the resultant particulate samples were free flowing and non-dusty.
- Figures 7 to 11 the particulate material exhibits hollow spherical morphology, the voids left by the evaporation of encapsulated oil particles clearly being visible in the wall structure of the hollow spherical particle.
- Example 1 was repeated but using a modified starch sold under the trade name Tuk 2001 by National Starch & Chemical Co, USA was used to make particulate materials according to the invention.
- Tuk 2001 starch material The details of the dispersion samples made using Tuk 2001 starch material are given in Table 7 below.
- a comparative sample 20 was also prepared.
- the dispersion samples 18 and 19 were each then subjected to a spray process in accordance with the invention using the conditions shown in Table 8.
- Sample 20 was subjected to a rotary spray process using a rotary wheel atomiser from Niro in which the inlet temperature was 230°C, the outlet temperature was 111°C and the rotary wheel speed was 2000 rpm.
- sample 20 took a relatively long time, ie of the order of 45 minutes, to disperse, forming aggregates in the process.
- the particulate material of sample 18 was essentially completely of cenospherical morphology whereas the particulate material of sample 19 was essentially completely of a denser, roughly spherical morphology.
- the particulate material of sample 20 exhibited mixed morphologies.
- Example 2 was repeated using the Tuk 2001 starch material identified in Example 3 and an according fragrance available from Quest Fragrances, Ashford, Kent, GB. Emulsion samples were made as shown in Table 10. In contrast to the emulsions in Example 2, these emulsions were prepared by weighing the ingredients into a tank, recirculating the ingredients through an inline mixer to form a premix and then passing the premix through an APV Rannie 2-stage high pressure homogeniser. Table 10
- the emulsion samples 21 to 24 were each then subjected to a spray process in accordance with the invention using the conditions shown in Table 11.
- Samples 25 and 26 were subjected to a rotary spray process as described in Example 3.
- Sample 27 was subjected to a two-fluid nozzle spray process in which pressurised air is used to atomise the emulsion.
- the resultant particulate samples 21 to 24 were free flowing and non-dusty. In contrast, samples 25 to 27 were extremely dusty and not free flowing.
- the bulk density of the resultant particulate samples were measured as described above and the mono-dispersivity index (MDI) and the results are shown in Table 12.
- the weight mean size (WMS) was also determined and is also shown in Table 12.
- the WMS was determined by sieving 100g of particulate material using 6 sieves having mesh sizes in the range 710 to 125 ⁇ m for 30 minutes and plotting the resultant weight distribution of particles at each size to enable the weight mean size to be interpolated.
- samples 21 to 24 were tested for dispersibility as described above. In respect of samples 21 to 24, all of the particulate material dispersed well in the water within a few minutes, there being no discernible amounts of particulate material present whether as added or aggregating in clumps. In contrast, samples 25 to 27 took a relatively long time, ie of the order of 35 minutes, to disperse, forming aggregates in the process.
- Sample 24 ( Figure 17) exhibited essentially completely cenospherical morphology having a very narrow size distribution.
- Figures 18 (sample 25) and 19 (sample 27) show mixed morphologies and wide size distributions. Sample 26 was very similar to sample 25.
- Example 2 was repeated but using Capsul, an encapsulant obtained from Quest Foods, Naarden, Holland, maltodextrin, sugar and lemon oil obtained from Quest Foods.
- the emulsion compositions are shown in Table 13; the proportions are in parts by weight.
- the resultant emulsions had a 50% solids concentration and a viscosity of 0.15 PA.s.
- the emulsion samples 28 and 29 were each then subjected to a spray process in accordance with the invention using the conditions shown in Table 14.
- the resultant particulate samples 28 and 29 were free flowing and non-dusty
- the particulate samples 28 and 29 were tested for dispersibility as described above. All of the particulate material dispersed well in the water within a few minutes, there being no discernible amounts of particulate material present whether as added or aggregating in clumps.
- Sample 28 exhibited essentially complete cenospherical morphology whereas sample 29 exhibited essentially complete roughly spherical morphology, the particles having a shrivelled appearance; both samples exhibited a narrow size distribution.
- Example 1 was repeated but using magnesium sulphate obtained from British Drug Houses (BDH).
- BDH British Drug Houses
- the resultant particulate sample 30 was free flowing and non-dusty
- the particulate sample 30 was tested for dispersibility as described above. All of the particulate material dispersed well in the water within a few minutes, there being no discernible amounts of particulate material present whether as added or aggregating in clumps. Sample 30 exhibited essentially completely a roughly spherical morphology and had a narrow size distribution.
- Example 1 was repeated but using a polyvinylacetate (PVA) available under the trade name Elotex WRRP by Elotex, a division of National Starch & Chemical Co, USA.
- PVA polyvinylacetate
- the emulsion compositions were made up using the PVA and water and are shown in Table 18; the proportions are in parts by weight.
- Emulsion sample 31 was then subjected to a spray process in accordance with the invention using the conditions shown in Table 19.
- Emulsion sample 32 was subjected to a rotary spray process as described in Example 3.
- the resultant particulate sample 31 was free flowing and non-dusty in contrast to the resultant particulate sample 32 which was dusty and not free flowing.
- sample 31 is shown to have essentially a completely cenospherical morphology and a narrow size distribution in contrast to the mixed morphologies and sizes exhibited by comparative sample 32 as shown in Figure 21.
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Abstract
Description
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Priority Applications (5)
Application Number | Priority Date | Filing Date | Title |
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JP2006544546A JP2007515275A (en) | 2003-12-17 | 2004-12-15 | Particulate matter |
BRPI0417527-1A BRPI0417527A (en) | 2003-12-17 | 2004-12-15 | particulate matter, and, method of producing the same |
EP04806070A EP1694429A2 (en) | 2003-12-17 | 2004-12-15 | Particulate materials |
AU2004298897A AU2004298897A1 (en) | 2003-12-17 | 2004-12-15 | Particulate materials |
US10/583,086 US20080050592A1 (en) | 2003-12-17 | 2004-12-15 | Particulate Materials |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
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GB0329208.3 | 2003-12-17 | ||
GBGB0329208.3A GB0329208D0 (en) | 2003-12-17 | 2003-12-17 | Particulate materials |
Publications (2)
Publication Number | Publication Date |
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WO2005058473A2 true WO2005058473A2 (en) | 2005-06-30 |
WO2005058473A3 WO2005058473A3 (en) | 2005-08-04 |
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PCT/GB2004/005256 WO2005058473A2 (en) | 2003-12-17 | 2004-12-15 | Particulate materials |
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US (1) | US20080050592A1 (en) |
EP (1) | EP1694429A2 (en) |
JP (1) | JP2007515275A (en) |
CN (1) | CN100482335C (en) |
AU (1) | AU2004298897A1 (en) |
BR (1) | BRPI0417527A (en) |
GB (1) | GB0329208D0 (en) |
WO (1) | WO2005058473A2 (en) |
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US8865880B2 (en) * | 2002-05-31 | 2014-10-21 | The United States Of America As Represented By The Secretary Of The Department Of Health And Human Services | Identification of a novel BHD gene |
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GB0327723D0 (en) | 2003-09-15 | 2003-12-31 | Vectura Ltd | Pharmaceutical compositions |
US9316645B2 (en) | 2011-10-07 | 2016-04-19 | Brown University | Methods, compositions and kits for imaging cells and tissues using nanoparticles and spatial frequency heterodyne imaging |
CN107774204A (en) * | 2016-08-27 | 2018-03-09 | 中国林业科学研究院木材工业研究所 | A kind of hollow open lignin nanosphere and preparation method thereof |
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2003
- 2003-12-17 GB GBGB0329208.3A patent/GB0329208D0/en not_active Ceased
-
2004
- 2004-12-15 BR BRPI0417527-1A patent/BRPI0417527A/en not_active IP Right Cessation
- 2004-12-15 AU AU2004298897A patent/AU2004298897A1/en not_active Abandoned
- 2004-12-15 EP EP04806070A patent/EP1694429A2/en not_active Withdrawn
- 2004-12-15 WO PCT/GB2004/005256 patent/WO2005058473A2/en active Application Filing
- 2004-12-15 JP JP2006544546A patent/JP2007515275A/en active Pending
- 2004-12-15 CN CNB2004800377182A patent/CN100482335C/en not_active Expired - Fee Related
- 2004-12-15 US US10/583,086 patent/US20080050592A1/en not_active Abandoned
Patent Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0320153A1 (en) * | 1987-12-07 | 1989-06-14 | Imperial Chemical Industries Plc | Controlled break-up of liquid jets |
WO1994020204A1 (en) * | 1992-12-18 | 1994-09-15 | Imperial Chemical Industries Plc | Production of particulate materials |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US8865880B2 (en) * | 2002-05-31 | 2014-10-21 | The United States Of America As Represented By The Secretary Of The Department Of Health And Human Services | Identification of a novel BHD gene |
Also Published As
Publication number | Publication date |
---|---|
EP1694429A2 (en) | 2006-08-30 |
JP2007515275A (en) | 2007-06-14 |
US20080050592A1 (en) | 2008-02-28 |
GB0329208D0 (en) | 2004-01-21 |
AU2004298897A1 (en) | 2005-06-30 |
CN1894027A (en) | 2007-01-10 |
CN100482335C (en) | 2009-04-29 |
WO2005058473A3 (en) | 2005-08-04 |
BRPI0417527A (en) | 2007-03-13 |
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