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EP0382464A2 - Procédé d'enrobage - Google Patents

Procédé d'enrobage Download PDF

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Publication number
EP0382464A2
EP0382464A2 EP19900301208 EP90301208A EP0382464A2 EP 0382464 A2 EP0382464 A2 EP 0382464A2 EP 19900301208 EP19900301208 EP 19900301208 EP 90301208 A EP90301208 A EP 90301208A EP 0382464 A2 EP0382464 A2 EP 0382464A2
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EP
European Patent Office
Prior art keywords
coating
particles
coating material
process according
water
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.)
Withdrawn
Application number
EP19900301208
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German (de)
English (en)
Other versions
EP0382464A3 (fr
Inventor
Galip Akay
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.)
Unilever PLC
Original Assignee
Unilever PLC
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
Application filed by Unilever PLC filed Critical Unilever PLC
Publication of EP0382464A2 publication Critical patent/EP0382464A2/fr
Publication of EP0382464A3 publication Critical patent/EP0382464A3/fr
Withdrawn legal-status Critical Current

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    • 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

Definitions

  • This invention relates to a novel agglomeration, coating or encapsulation process.
  • the process has a wide range of applications. It can be applied to coating or encapsulating solid particles, liquid droplets or a mixture of the two.
  • the invention provides a process for coating or encapsulating solid particles and/or liquid droplets, the process comprising a first step of forming a melt of a coating material with the said particles and/or droplets as a disperse phase therein, and a second step of destabilizing the melt by addition of solid particles and/or by cooling, causing the melt to crumble to a particulate product whereof the particles comprise the coating material with the particles and/or droplets of the disperse phase embedded therein.
  • the coating process may serve as a means of agglomeration of disperse phase particles.
  • a second aspect of this invention is the particulate products of the process.
  • Certain forms of the present invention therefore do not include the combination of water-insoluble solid particles as the sole disperse phase and polyalkylene or alkylene copolymers with not more than 30% of other monomers containing a carboxylic acid or ester group as the organic polymeric material.
  • Essential to this invention is the finding that a melt containing a sufficient quantity of a disperse phase can be induced to crumble to a particulate state in which the disperse phase is embedded in particles of what was previously the continuous phase. Crumbling occurs when the amount of disperse phase present exceeds the amount which the continuous phase is able to support. It can be induced by cooling - which reduces the ability of the continuous phase to support disperse phase - or by direct addition of some material which adds to the total amount of disperse material. Combination of cooling and addition of solid disperse phase is most effective since the solid material causes crumbling locally and cooling fortifies this phase separation.
  • the coating material which forms a melt will generally be one or more organic compounds. It may especially be provided by an organic polymeric material which melts at a temperature above ambient. Another possibility is that the coating material is waxy, e.g. paraffin wax. A further possibility is that the coating material is an organic compound which contains alkyl groups of detergent chain length, i.e. 8 to 20 carbon atoms, as in a surfactant, soap or fatty acid.
  • An advantage of the present invention is that it is effective for coating or encapsulating small particles, and mixtures of particles displaying a range of particle sizes.
  • Some known coating processes, such as fluidized beds, are least effective with small particles.
  • the invention can be used to coat or encapsulate a range of materials and by doing so can serve a variety of useful purposes depending on the nature of the encapsulated material and the polymeric coating material.
  • a characteristic of the invention is that solvent is often not employed, so that the product does not contain traces of solvent.
  • This example consists in coating sodium chloride with polyethylene glycol having an average molecular weight of 20,000.
  • the final product contains, by weight: polyethylene glycol (PEG 20,000) 25% sodium chloride 65% silica, mean particle size 7 x 10 ⁇ 9m 10%
  • the polyethylene glycol is heated to somewhat above its melting point.
  • the sodium chloride as fine crystals, is mixed into the molten polymer forming a disperse phase in the melt.
  • the melt is now cooled to slightly above the melting point of the polymer.
  • the silica is mixed in and the mixture allowed to cool further.
  • the melt crumbles into particles. These particles are mostly agglomerates of sodium chloride crystals embedded in solidified polymer, with silica mainly at the exterior of these particles.
  • the materials in the above example are thus an organic polymeric coating material which in the above example was polyethylene glycol, a solid disperse phase which was sodium chloride and a "crumbling agent" which was silica.
  • crumbling agent is used because it causes the melt to crumble into particulate form.
  • surfactants may also be incorporated into the coating material, or used as coating material. When more than one coating is to be employed, surfactant can form a "bridge" to enhance the compatibility of the coating materials.
  • the disperse phase be solid.
  • a liquid disperse phase may be employed. This may be liquid at ambient temperature, or it may be a material which is solid at ambient temperature but is sufficiently low melting that it is liquid at the temperatures of processing.
  • liquid may be incorporated into the pores of a porous disperse phase, or liquid may be dispersed in coating material applied to a solid disperse phase. Indeed it would be possible for liquid to be present in both the coating material and a porous solid disperse phase.
  • Protective coating of a material protecting it from an adverse environment until the time of use. This could for instance serve to protect a chemically reactive material until it is used.
  • Delayed release of a material, or controlled slow release, due to the presence of a coating due to the presence of a coating.
  • a preliminary coating of a liquid may be applied to a solid disperse phase.
  • a preliminary coating may be coating of surfactant or of a liquid which includes a surfactant.
  • Such a preliminary coating may serve to provide a desired degree of compatibility with the polymeric coating material.
  • Another use for a preliminary coating on the solid disperse phase is to provide a barrier layer to isolate a potentially reactive solid disperse phase during mixing with polymer at elevated temperatures.
  • a preliminary coating of a high molecular weight polymer may be used before coating with a lower molecular weight coating material in order that the porous solid does not absorb excessive quantities of the coating material.
  • particles may be encapsulated with a first coating material by a procedure in accordance with the invention after which a second outer coating may be applied either by use of a further procedure in accordance with the invention or by means of some other coating technique such as fluidized bed coating.
  • the inner coating provides mechanical strength while the outer coating provides a barrier to protect the coated material from the surrounding environment.
  • the outer coating is a water-insoluble coating (or a poorly soluble outer coating) applied over particles which are water-soluble or water-swellable. Such an arrangement can serve to delay release of the encapsulated material when the particles are placed in water until such time as the water has penetrated the outer coating. Swelling of the inner particles when water does penetrate to them may at that point serve to rupture the outer coating so that after a delay caused by the outer coating the subsequent release is not restrained by the outer coating.
  • the inner particles that is to say the particles to which the second, outer coating is applied
  • these particles may contain as first coating material an organic polymeric material which is water-soluble or water-­swellable.
  • the second, outer coating can serve to delay release of any part of the encapsulated dispersed phase until the outer coating is penetrated, after which dissolution or swelling of the organic polymeric material within the particles controls the rate of release of the disperse phase.
  • the polymeric material needs to melt at a temperature which is suitable for incorporating the disperse phase.
  • the material may be a mixture of polymers.
  • a polymer of high melting point or which degrades before reaching its melting point then a polymer of low molecular weight may be used as a solvent for the polymer. Alternatively some organic solvent may be used to form a viscous concentrated solution of the polymer.
  • Use of high molecular weight polymer may be advantageous in that less crumbling agent tends to be required.
  • non-soap surfactant This may, or may not, be surfactant derived from a polymer such as fatty acyl and fatty diacyl derivatives of polyethyleneglycol.
  • Another useful possibility for the coating material is a mixture of soap and fatty acid.
  • Yet another possibility is waxy material such as paraffin wax with melting point above ambient temperature.
  • Blends of materials may be used in order to obtain desired properties of the coating material. These blends may in particular be blends of two or more polymers, or blends of polymer(s) with non soap surfactants or with soap and fatty acid. For instance, surfactant may serve as solvent for high molecular weight polymer.
  • the coating material is a blend of compatible materials
  • the melting and crystallisation behaviour of the components of the blend is modified.
  • Blends of materials may be chosen for release of the enclosed material to be brought about by any of: physical corrosion of coating, solution of coating on exposure to water, swelling of coating on exposure to water, permeation of water through insoluble porous coating, possibly followed by rupture on swelling of encapsulated material, exposure to specified temperature, exposure to specified pH.
  • coating materials which may be used alone or in blends are:
  • a wide variety of materials may be employed. Examples are sodium chloride, sodium carbonate, organic peroxy acids and their salts (bleaching agents), tetra-­acetyl ethylene diamine (TAED, a low temperature bleach precursor), sodium perborate (bleaching agent), sodium dichloro isocyanurate dihydrate (SDCCA, a bleaching agent) and distearyl dimethyl ammonium chloride (a cationic surface active agent solid under the Trade Mark AROSURF TA-100).
  • Solid disperse phase particles may be porous, organic or inorganic, and may contain a liquid entrapped in the inter- or intra-particle pores.
  • solid disperse phase particles are anhydrous sodium carbonate and porous silica.
  • Liquids which may be carried by a porous disperse phase include antifoam agents and perfumes.
  • silicone fluid serving as a fabric softener
  • silicone oil which serve as antifoam agent
  • the function of the crumbling agent is to enhance, locally or globally, the total amount of dispersed material beyond the point at which the molten system becomes unstable.
  • the crumbling agent has to be solid at the temperature at which crumbling occurs and should not dissolve in the coating material at the temperature of processing.
  • Crumbling agents may be inorganic particulate solids, or may be particles of high molecular weight polymer. Other organic or inorganic particulate solids are not ruled out, but will generally be less economical and therefore are not preferred unless they have a specific function in the final product as discussed later.
  • Crosslinked polymer powders and polymer latex particles may also be considered as crumbling agent. The effectiveness of a crumbling agent will be enhanced if its particle size is small.
  • crumbling agents are: Silica, anionic or cationic clays, zeolite, talc, sodium carbonate, sodium bicarbonate, calcite, polyethylene oxide (PEO), sodium carboxymethyl cellulose, starch, cellulose acetate, microcrystalline cellulose.
  • the crumbling agent may be provided by a further quantity of the material used as solid disperse phase (if any).
  • crumbling agent adheres to the surface of the particles formed by crumbling and it can therefore be used to modify the surface characteristics of these particles.
  • the crumbling agent may confer hydrophilic or hydrophobic character and/or reduce the permeability of the coating to gases and vapours.
  • Crumbling agent in particles with a double coating can provide some important functions.
  • most of the crumbling agent can be placed at the exterior of the particles with a single coating, which are formed before the application of the second coating.
  • a different crumbling agent inert can be used to induce crumbling in the second coating step, if this step is carried out in accordance with the invention (rather than by using conventional coating techniques such as fluidized bed coating).
  • surfactants may be used as or included in the coating material.
  • surfactants may be included in order to emulsify a liquid disperse phase, or to effect surface modification of a solid dispersed phase.
  • silicone glycol copolymer surfactants DC190, DC193 and DC198 supplied by Dow Corning were found to be a suitable surfactant.
  • the surfactants DC193 and DC198 were also then used in the polymer phase which was the coating material. Presence of a surfactant to effect surface modification of a solid phase may in particular be utilised if the solid is not compatible with the coating material.
  • an outer coating i.e. a second coating onto previously coated particles, it may be composed of any coating material which is immobile at ambient temperature (or whatever temperature the final particles are to be kept at).
  • Paraffin wax and poly(caprolactone)diol or poly(caprolactone)triol or their mixture are examples of materials which may be employed as an outer coating.
  • Water soluble polymers such as polyethylene glycol may also be used.
  • the central step of the processing is the crumbling to particles.
  • a melt of the organic polymeric material, containing disperse phase is induced to crumble by cooling, addition of crumbling agent or some combination of both, while mixing is continued.
  • a liquid disperse phase is used, this is preferably first emulsified in the coating material in a suitable mixing apparatus able to form an emulsion.
  • the temperature must remain above the melting point of the coating material and if desired the liquid disperse phase may be preheated to above this temperature before adding to the mixer.
  • the liquid disperse phase may be mixed with surfactant before being mixed with the coating material.
  • the coating material and additional surfactant are supplied to a suitable mixer and brought to a temperature above the melting point of the coating material.
  • solid disperse phase is used, this is next added to the mixer and mixed into the molten polymeric material to form a homogeneous melt. This again is carried out at a temperature above the melting point of the polymeric material and if desired the solid disperse phase is preheated before it is added to the mixer. (Since a homogeneous melt is formed, a reversed order of addition to the mixer will generally be possible, if desired).
  • the temperature of the mix is now reduced to just above the melting point of the coating agent: 5°C above the melting point is suitable.
  • the crumbling agent is next added and the mixture is cooled further. It has been found convenient to add around 65% of the crumbling agent while holding the temperature just above the melting point of the polymeric material and then start cooling while adding the balance of the crumbling agent. Crumbling of the melt will generally commence before all of the crumbling agent has been added but the further addition of crumbling agent will complete the process and may bring about some further crumbling to smaller sized particles. It is desirable to continue mixing until the temperature has cooled to 30°C less than the melting point of the coating agent.
  • the particulate material which is produced may be subjected to a size reduction process at this stage if smaller particles are desired.
  • the disperse phase is porous solid with liquid absorbed therein, it may be desirable to avoid the generation of severe stresses during mixing, because high stress could cause break up of the porous solid and release of the absorbed liquid. Low rotational speed mixing is then preferable.
  • the process of the invention can be carried out as a batch process, for instance using a Z-blade mixer, or as a continuous process, for instance using a twin screw extruder with more than one zone for introduction of material into the extruder.
  • crumbling could be brought about in different apparatus to that used for initial melt formation.
  • a process was carried out using a variety of materials for the solid disperse phase and a variety of organic coating materials. In most of these examples surfactant was unnecessary and was not used. The procedure was the same in each case, except in Examples 1.22 and 1.23.
  • the coating material was melted in a Z-blade mixer of 1Kg capacity equipped with heating and cooling facilities.
  • the solid disperse phase was added at a temperature about 10 to 15°C above the melting point of the coating material and after a homogeneous mix had been obtained, cooling of the mixture was started. When the temperature was within 5°C of the melting point of the coating material 65% of the crumbling agent was added and then the temperature was held constant while mixing was continued to allow full incorporation of the crumbling agent. At this stage the mixture formed large agglomerates, and the remainder of the crumbling agent was added.
  • Examples 1.22 and 1.23 used porous solid disperse phases with liquids absorbed by them.
  • the disperse phase was light soda ash carrying absorbed silicone antifoam.
  • the disperse phase was silica carrying absorbed perfume.
  • the processing procedure commenced with solid disperse phase placed in the Z-blade mixer at a temperature about 10°C above the melting point of the coating material.
  • the coating material was added progressively at a temperature 5°C above its melting point.
  • the crumbling agent was added and cooling of the mixer commenced. Again mixing was continued until the temperature had fallen to 30°C below the melting point of the coating material.
  • Example 1.1 to 1.23 The materials used in Examples 1.1 to 1.23 are set out in Table 1 below, which gives the amounts of the materials as percentages by weight of the final particulate composition.
  • the porous disperse phase used in Example 1.23 was prepared by a route in which the porous silica (Microsil GP) was initially coated with a methoxyl functional silane coupling agent which forms a monolayer with a hydrophobic surface.
  • the coupling agent was gamma-methacryloxypropyl trimethoxy-silane (A174, ex Union Carbide) with a monolayer surface coverage capacity of 314m2/gram. Since Microsil GP has a large surface area, full surface coverage requires large amounts of silane and it reduces the pore volume of silica. Therefore, only the surface and the outermost pores of Microsil GP were coated, following the procedure below:
  • the full water holding capacity of Microsil GP was determined to be 2.2 grams of water per gram of silica. (Further addition of water resulted in the loss of free-flow of the powder). Silica particles were filled with water to 80% of their capacity. A sufficient amount of A174 silane coupling agent was dissolved in n-pentane to make up a solution able to occupy the rest of the pores left by water (i.e. 20% of the full absorbing capacity of the silica). When the n-pentane solution was added to the silica already wetted with water, the powder stopped being free-flowing. Subsequently the n-pentane was evaporated at room temperature and silane A174 polymerised at 38°C and 70% relative humidity. The resulting surface-hydrophobed powder was then dried under vacuum at 60°C for 24 hours before being allowed to absorb the perfume.
  • the surface of the solid dispersed phase was given a preliminary coating.
  • the general procedure was that the solid dispersed phase was first mixed with a suitable preliminary coating material (i.e. surfactant or a liquid which may contain a surfactant) in a Z-blade mixer at an elevated temperature T s . After a sufficient period of mixing at temperature T s , the temperature of the mixer was reduced to some 10°C above the melting point of the main (polymeric) coating material and this molten polymer was added to obtain a homogeneous mix. The temperature of the mixture was then reduced to a temperature t c which is approximately 5°C above the melting point of the polymer and 65% of the crumbling agent was added.
  • a suitable preliminary coating material i.e. surfactant or a liquid which may contain a surfactant
  • Example 2.1 only a surfactant was used to provide compatibility between NaCl and polymeric coating.
  • Example 2.2 the solid dispersed phase was coated with a liquid mixture comprising a silicone fluid and a surfactant compatible with the solid dispersed phase and polymeric coating material.
  • the function of the silicone fluid is to provide full surface coverage of the disperse phase and also to isolate the potentially reactive solid disperse phase during mixing with polymer at elevated temperatures.
  • Particles were prepared having compositions in accordance with Table 3 which also includes the relevant temperatures attained in the Z-blade mixer during various stages of the process.
  • the process consisted of two stages. In the first coating stage solid dispersed phase and a polymeric coating material were melted together and mixed at a temperature T MAX-1 which was approximately 10°C above the melting point of the solid dispersed phase. When a homogeneous melt was obtained, the melt was cooled down to the temperature T C1 which was just above the melting point of the first coating material. Some crumbling agent was added to induce crumbling. Cooling and mixing was continued until temperature was reduced to T MIN which was below the melting point of the second coating material. The particulate product is now ready for the second stage of the coating process.
  • the temperature was raised to T MAX-2 which was about 5-10°C above the melting point of the second coating material which was added molten at the same temperature T MAX-2 while continuing to mix.
  • T MAX-2 which was about 5-10°C above the melting point of the second coating material which was added molten at the same temperature T MAX-2 while continuing to mix.
  • more crumbling agent was added at the same temperature, after which the temperature was allowed to fall to some 30°C below the melting point of the second coating material at a rate of approximately 1°C per minute.
  • the resulting particles consisted of solid dispersed phase particles encapsulated with a polymer coat over which another material formed an outer coat.
  • Particles were prepared having compositions in accordance with Table 4. These particles have two coatings in which the outer coat is water-insoluble and has lower melting point than the material in the first coat. In this respect these examples are similar to the Example 3.1 except that in the Example 3.1, the solid dispersed phase is melted with the first coat.
  • the first coating material was mixed with the solid dispersed phase at an elevated temperature T MAX-1 .
  • T MAX-1 the melt was cooled down to the temperature T C1 just above the melting point of the first coating material and a crumbling agent was added. Cooling was continued until the temperature of T MIN was reached.
  • T MAX-2 the temperature of the particles from the first stage was raised to T MAX-2 and the second coating material was added at this temperature. Mixing was continued until the agglomeration of the particles was observed. At this stage the temperature was lowered to a temperature T C2 just above the melting point of the second coating material and a small amount of crumbling agent was found to be sufficient to obtain crumbling. These double coated particles were then cooled to ambient temperature while continuing to mix.
  • the crumbling agents used in the first coating stage can create large amounts of heat and also act as water sink upon exposure to water.
  • Particles were prepared having compositions in accordance with Table 5 below. These include both solid and liquid disperse phases.
  • the polymeric material could contain a suitable surfactant while the silicone fluid or paraffin wax which constituted the liquid disperse phase could also contain surfactant.
  • the general procedure was that the polymeric material was first heated with its surfactant (if any) to obtain a mixture of the two.
  • the liquid phase was separately heated with its surfactant (if any) to obtain a mixture of the two.
  • the polymeric material and liquid disperse phase were heated together and mixed to form an emulsion.
  • the emulsification was carried out in a static mixer which consists of a series of short capillaries separated by flow dividers to prevent channelling of the fluid.
  • the capillary diameter (D), capillary length (L), capillary entry angle ( ⁇ 1), capillary exit angle ( ⁇ 2), total flow rate of the continuous and dispersed phases (Q) and the number of capillary units (N) are important factors in achieving small dispersed phase droplet particles ( ⁇ 10 ⁇ m) with a narrow size distribution. Since the viscosity of the silicone antifoams and silicone fluid used in the Examples 5.1 to 5.5 is extremely large compared with the continuous phase viscosity, it is necessary to use elongational flow fields to achieve emulsification.
  • Emulsion emerging from the last capillary unit is sprayed on to the solid dispersed phase which was heated in the Z-blade mixer to the temperature of the emulsion. Mixing was continued until a homogeneous mix had been achieved.
  • the melt was cooled to a temperature T C just above the melting point of the coating material, 65% of the crumbling agent was added and then when agglomeration was observed the remainder of the crumbling agent was added while cooling the melt to some 30°C below the melting point of the coating material.
  • ethylene acrylic acid copolymer AC 5120
  • this copolymer acted as a very efficient emulsifier in emulsifying the silicone antifoam.
  • this copolymer increases the viscosity of the continuous phase in the emulsion thus helping to reduce its tendency to form a double emulsion and also to reduce the size of the dispersed silicone antifoam.
  • it increases the hardness of the continuous phase once it has solidified.
  • the average size and size distribution of the coated particles were found to depend on a large number of factors. These are: (1) raw material characteristics such as size, concentration and surface chemistry of the solid dispersed phase particles and crumbling agent, and molecular weight and chemistry of the coating material(s), (2) process conditions such as rotational speed of the mixer blades, temperature of the mixer when the crumbling agent is added and the type of mixer.
  • process conditions such as rotational speed of the mixer blades, temperature of the mixer when the crumbling agent is added and the type of mixer.
  • Table 6 the average size and size distribution of the particles illustrated by various Examples are tabulated.
  • the release characteristics of various encapsulated particles placed in water were determined by monitoring the concentration of the dispersed phase material in water as a function of time. Final concentration of the dispersed phase material after a prolonged time was also determined.
  • the release profiles of the particles are expressed here as:- (1) delay time (t D ) (if any) before release commences; (2) initial rate of release (R o ; percent release per unit time) and (3) half life of the encapsulated dispersed phase (t H ). These values are tabulated in Table 7. As seen in this Table, considerable variations in delay time, initial release rate and half life of the dispersed phase can be obtained.
  • Coated particles were prepared generally in accordance with Example 1.22 but using different coating materials. In some instances the coated particles were coated again with a second coating material. In contrast to Example 4, both coating materials were water-soluble. The release of antifoam from the resulting particles was determined by monitoring change in surface tension at 25°C and/or by monitoring the foam controlling action of the particles.
  • Example 6.2 and 6.3 Particles in accordance with Examples 6.2 and 6.3 were also subjected to agitation in a powder mixer for 15 minutes to test the durability of the coating.
  • the release of antifoam was not altered for Example 6.3 particles, and increased only slightly for particles of Example 6.2, thus illustrating the durability of their coatings.

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Detergent Compositions (AREA)
  • Manufacturing Of Micro-Capsules (AREA)
  • Glanulating (AREA)
  • Paints Or Removers (AREA)
EP19900301208 1989-02-09 1990-02-06 Procédé d'enrobage Withdrawn EP0382464A3 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
GB898902909A GB8902909D0 (en) 1989-02-09 1989-02-09 Coating process
GB8902909 1989-02-09

Publications (2)

Publication Number Publication Date
EP0382464A2 true EP0382464A2 (fr) 1990-08-16
EP0382464A3 EP0382464A3 (fr) 1992-10-28

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EP19900301208 Withdrawn EP0382464A3 (fr) 1989-02-09 1990-02-06 Procédé d'enrobage

Country Status (7)

Country Link
EP (1) EP0382464A3 (fr)
JP (1) JPH02261535A (fr)
AU (1) AU633299B2 (fr)
BR (1) BR9000544A (fr)
CA (1) CA2009444A1 (fr)
GB (1) GB8902909D0 (fr)
ZA (1) ZA90987B (fr)

Cited By (32)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0495345A1 (fr) * 1991-01-16 1992-07-22 THE PROCTER & GAMBLE COMPANY Agents anti-mousse sous forme de granulés
EP0510761A1 (fr) * 1991-04-24 1992-10-28 Unilever N.V. Particules encapsulées avec de la cire et procédé pour leur fabrication
US5167854A (en) * 1985-08-21 1992-12-01 The Clorox Company Encapsulated enzyme in dry bleach composition
WO1993016161A1 (fr) * 1992-02-05 1993-08-19 Basf Aktiengesellschaft Composition granulaire d'activateurs de blanchiment a grains structures de maniere heterogene
US5254287A (en) * 1985-08-21 1993-10-19 The Clorox Company Encapsulated enzyme in dry bleach composition
US5259994A (en) * 1992-08-03 1993-11-09 The Procter & Gamble Company Particulate laundry detergent compositions with polyvinyl pyrollidone
EP0573731A1 (fr) * 1992-06-08 1993-12-15 Eka Nobel Ab Agent de blanchiment
EP0583512A1 (fr) * 1992-08-18 1994-02-23 The Procter & Gamble Company Additifs détergents
EP0622453A1 (fr) * 1993-04-26 1994-11-02 Setric International S.A. Procédé de protection particulaire d'un produit combustible contre l'action d'un produit chloré avec lequel il est mélangé
WO1995014077A1 (fr) * 1993-11-16 1995-05-26 Warwick International Group Limited Compositions d'activateur de blanchiment
TR27734A (tr) * 1992-08-01 1995-07-07 Procter & Gamble Peroksiasit agartici ön-madde bilesimleri.
EP0652848A4 (fr) * 1992-08-01 1995-07-26 Procter & Gamble Compositions de precurseurs de blanchiment a base de peroxyacide.
EP0652930A4 (fr) * 1992-08-01 1995-08-02 Procter & Gamble Compositions detersives a faible niveau de gelification et procede de preparation.
US5456855A (en) * 1991-01-16 1995-10-10 The Procter & Gamble Company Stable granular foam control agent comprising a silicone antifoam compound and glycerol
WO1996003046A1 (fr) * 1994-07-23 1996-02-08 Solvay Interox Limited Compositions microbicides
EP0675978A4 (fr) * 1992-12-22 1996-03-27 Procter & Gamble Composition de precurseurs de peroxyacide enrobes, servant d'agents de blanchiment.
FR2725456A1 (fr) * 1994-10-07 1996-04-12 Rhone Poulenc Chimie Composition solide, granulaire, comprenant un ingredient liquide emprisonne dans une matrice solide, procede de preparation et utilisation dans une composition detergente en poudre
US5767062A (en) * 1992-11-16 1998-06-16 The Procter & Gamble Company Fabric softening compositions with dye transfer inhibitors for improved fabric appearance
WO1999000476A1 (fr) * 1997-06-25 1999-01-07 Henkel Kommanditgesellschaft Auf Aktien Ingredients enrobes de produits de nettoyage
WO1999054431A1 (fr) * 1998-04-22 1999-10-28 Henkel Kommanditgesellschaft Auf Aktien Constituants detersifs enrobes
WO2001023513A1 (fr) * 1999-09-24 2001-04-05 Novozymes A/S Particules pour compositions liquides
GB2358871A (en) * 1999-12-28 2001-08-08 Reckitt Benckiser Nv Laundry compositions
US6407052B2 (en) * 1997-02-07 2002-06-18 Henkel Kommanditgesellschaft Auf Aktien pH-controlled release of detergent components
US6451753B2 (en) 1996-03-14 2002-09-17 Basf Aktiengesellschaft Solid composition consisting of heterocyclic compounds and/or oxime esters and inert porous carrier materials and the use thereof as stable bleach activator component in detergents, bleaches and cleaners
DE19938609C2 (de) * 1999-08-14 2002-11-14 Erhard Weber Kugelgel-Flächenlager
WO2003022979A1 (fr) 2001-09-06 2003-03-20 The Procter & Gamble Company Chandelles parfumees
WO2003087287A1 (fr) * 2002-04-10 2003-10-23 Salvona L.L.C. Compositions a liberation controlee ciblee activees par des modifications du ph ou de la concentration en sel
US6673763B1 (en) 1999-09-24 2004-01-06 Novozymes A/S Particles for liquid compositions
WO2004080585A1 (fr) * 2003-03-12 2004-09-23 Henkel Kommanditgesellschaft Auf Aktien Enduction de substances et melanges de substances fusibles
WO2006024415A1 (fr) * 2004-09-02 2006-03-09 Henkel Kommanditgesellschaft Auf Aktien Liquides fabriques sous forme solide, pour une utilisation dans des detergents et des nettoyants particulaires
US7534758B2 (en) 2000-05-11 2009-05-19 The Procter & Gamble Company Laundry system having unitized dosing
US8834934B2 (en) 2003-02-11 2014-09-16 Haviland Products Company Material encapsulation system

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JP4704672B2 (ja) * 2003-10-14 2011-06-15 花王株式会社 単分散固体微粒子の製造法
BR112013014811B1 (pt) * 2010-12-17 2020-10-06 Dow Global Technologies Llc Composição de tratamento de pano

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US5167854A (en) * 1985-08-21 1992-12-01 The Clorox Company Encapsulated enzyme in dry bleach composition
US5254287A (en) * 1985-08-21 1993-10-19 The Clorox Company Encapsulated enzyme in dry bleach composition
TR26052A (tr) * 1991-01-16 1994-12-15 Procter & Gamble GRANüL SEKLINDE KÖPüK KONTROL ETME VASITALARI
EP0495345A1 (fr) * 1991-01-16 1992-07-22 THE PROCTER & GAMBLE COMPANY Agents anti-mousse sous forme de granulés
US5456855A (en) * 1991-01-16 1995-10-10 The Procter & Gamble Company Stable granular foam control agent comprising a silicone antifoam compound and glycerol
EP0510761A1 (fr) * 1991-04-24 1992-10-28 Unilever N.V. Particules encapsulées avec de la cire et procédé pour leur fabrication
WO1993016161A1 (fr) * 1992-02-05 1993-08-19 Basf Aktiengesellschaft Composition granulaire d'activateurs de blanchiment a grains structures de maniere heterogene
EP0573731A1 (fr) * 1992-06-08 1993-12-15 Eka Nobel Ab Agent de blanchiment
US5336433A (en) * 1992-06-08 1994-08-09 Eka Nobel Ab Bleaching agent
EP0652930A4 (fr) * 1992-08-01 1995-08-02 Procter & Gamble Compositions detersives a faible niveau de gelification et procede de preparation.
TR27734A (tr) * 1992-08-01 1995-07-07 Procter & Gamble Peroksiasit agartici ön-madde bilesimleri.
EP0652848A4 (fr) * 1992-08-01 1995-07-26 Procter & Gamble Compositions de precurseurs de blanchiment a base de peroxyacide.
US5259994A (en) * 1992-08-03 1993-11-09 The Procter & Gamble Company Particulate laundry detergent compositions with polyvinyl pyrollidone
EP0583512A1 (fr) * 1992-08-18 1994-02-23 The Procter & Gamble Company Additifs détergents
TR27709A (tr) * 1992-08-18 1995-06-22 Procter & Gamble Hidrofil deterjan aktif bilesiklerini iceren deterjan ilave maddeleri.
US5932253A (en) * 1992-11-16 1999-08-03 The Procter & Gamble Company Fabric softening compositions with dye transfer inhibitors for improved fabric appearance
US5767062A (en) * 1992-11-16 1998-06-16 The Procter & Gamble Company Fabric softening compositions with dye transfer inhibitors for improved fabric appearance
US5804219A (en) * 1992-11-16 1998-09-08 The Procter & Gamble Company Fabric softening compositions with dye transfer inhibitors for improved fabric appearance
EP0675978A4 (fr) * 1992-12-22 1996-03-27 Procter & Gamble Composition de precurseurs de peroxyacide enrobes, servant d'agents de blanchiment.
EP0622453A1 (fr) * 1993-04-26 1994-11-02 Setric International S.A. Procédé de protection particulaire d'un produit combustible contre l'action d'un produit chloré avec lequel il est mélangé
US6080710A (en) * 1993-11-16 2000-06-27 Warwick International Group Limited Bleach activator compositions
WO1995014077A1 (fr) * 1993-11-16 1995-05-26 Warwick International Group Limited Compositions d'activateur de blanchiment
WO1996003046A1 (fr) * 1994-07-23 1996-02-08 Solvay Interox Limited Compositions microbicides
WO1996011255A1 (fr) * 1994-10-07 1996-04-18 Rhone-Poulenc Chimie Composition solide, granulaire, comprenant un ingredient liquide emprisonne dans une matrice solide, procede de preparation et utilisation dans une composition detergente en poudre
FR2725456A1 (fr) * 1994-10-07 1996-04-12 Rhone Poulenc Chimie Composition solide, granulaire, comprenant un ingredient liquide emprisonne dans une matrice solide, procede de preparation et utilisation dans une composition detergente en poudre
US6451753B2 (en) 1996-03-14 2002-09-17 Basf Aktiengesellschaft Solid composition consisting of heterocyclic compounds and/or oxime esters and inert porous carrier materials and the use thereof as stable bleach activator component in detergents, bleaches and cleaners
US6407052B2 (en) * 1997-02-07 2002-06-18 Henkel Kommanditgesellschaft Auf Aktien pH-controlled release of detergent components
WO1999000476A1 (fr) * 1997-06-25 1999-01-07 Henkel Kommanditgesellschaft Auf Aktien Ingredients enrobes de produits de nettoyage
WO1999054431A1 (fr) * 1998-04-22 1999-10-28 Henkel Kommanditgesellschaft Auf Aktien Constituants detersifs enrobes
DE19938609C2 (de) * 1999-08-14 2002-11-14 Erhard Weber Kugelgel-Flächenlager
US6673763B1 (en) 1999-09-24 2004-01-06 Novozymes A/S Particles for liquid compositions
WO2001023513A1 (fr) * 1999-09-24 2001-04-05 Novozymes A/S Particules pour compositions liquides
GB2358871A (en) * 1999-12-28 2001-08-08 Reckitt Benckiser Nv Laundry compositions
US6579838B2 (en) 1999-12-28 2003-06-17 Reckitt Benckiser N.V. Laundry compositions
US6653269B2 (en) 1999-12-28 2003-11-25 Reckitt Benckiser N.V. Laundry compositions
US7534758B2 (en) 2000-05-11 2009-05-19 The Procter & Gamble Company Laundry system having unitized dosing
WO2003022979A1 (fr) 2001-09-06 2003-03-20 The Procter & Gamble Company Chandelles parfumees
EP1992680A2 (fr) 2001-09-06 2008-11-19 The Procter and Gamble Company Bougies parfumées
WO2003087287A1 (fr) * 2002-04-10 2003-10-23 Salvona L.L.C. Compositions a liberation controlee ciblee activees par des modifications du ph ou de la concentration en sel
US7053034B2 (en) 2002-04-10 2006-05-30 Salvona, Llc Targeted controlled delivery compositions activated by changes in pH or salt concentration
US8834934B2 (en) 2003-02-11 2014-09-16 Haviland Products Company Material encapsulation system
WO2004080585A1 (fr) * 2003-03-12 2004-09-23 Henkel Kommanditgesellschaft Auf Aktien Enduction de substances et melanges de substances fusibles
WO2006024415A1 (fr) * 2004-09-02 2006-03-09 Henkel Kommanditgesellschaft Auf Aktien Liquides fabriques sous forme solide, pour une utilisation dans des detergents et des nettoyants particulaires

Also Published As

Publication number Publication date
BR9000544A (pt) 1991-01-15
GB8902909D0 (en) 1989-03-30
AU633299B2 (en) 1993-01-28
ZA90987B (en) 1991-10-30
CA2009444A1 (fr) 1990-08-09
JPH02261535A (ja) 1990-10-24
AU4920690A (en) 1990-08-16
EP0382464A3 (fr) 1992-10-28

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