Classifications

• • 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
  • B01J13/00—Colloid chemistry, e.g. the production of colloidal materials or their solutions, not otherwise provided for; Making microcapsules or microballoons
  • B01J13/02—Making microcapsules or microballoons
  • B01J13/06—Making microcapsules or microballoons by phase separation

Definitions

• the present invention relates to capsules comprising at least one mineral shell (E) and a core (N) which comprises at least one polyhydroxylated compound (P), each shell consisting essentially of a single mineral compound.
• compositions of the "core-shell” type consisting of a shell in which at least one material is immobilized or encapsulated.
• the active material (s) can be permanently or temporarily isolated from their surrounding medium, in particular for the purpose of protecting them and / or delaying and / or controlling their release.
• controlled release means a release which can be triggered by a factor external to the system which can also be called “trigger”, such as temperature, pH, pressure, regardless of time. ; in other words, we choose precisely when and under what conditions we want the release to take place;
• the term "delayed” release means release which takes place as a function of time with more or less slow kinetics and without the intervention of external factors; in other words, the release conditions are predetermined so that the release begins as soon as the "core-shell” composition is in the medium with more or less rapid kinetics, and this without any can a posteriori master it.
• These “core-shell” compositions are particularly advantageous when it is sought, for example, to mask the taste of a material, to delay and / or control the thickening and / or gelling action of a material, or to preserve the structural and functional integrity of a material.
• dietary fiber has nutritional properties and has a definite interest in the prevention of certain pathologies in particular abnormalities of intestinal transit, anomalies in the metabolism of lipids (hypocholesterolemic effect) and that of carbohydrates (case of diabetics).
• Dietary fibers which are polyhydroxylated compounds, can be chosen for example from celluloses, hemicelluloses, pectins, galactomannans, guars, beta-glucans, lignins, algae polysaccharides. Dietary fiber is found naturally in grains, fruits and vegetables.
• the parameters which will lead to the "destruction" of the bark and therefore to the "release” of said material in the medium are preferably determined prior to encapsulation. These parameters will essentially depend on the chemical nature of the material constituting the shell but may also depend on its homogeneity in terms of chemical composition.
• homogeneity in terms of chemical composition of the bark is meant a bark which consists essentially of a single chemical compound. Moreover the bark of each capsule consists essentially of the same unique chemical compound.
• the term "compound” designates a set formed by several elements.
• the bark consists essentially of a single mineral compound, that is to say that at least 90% of said bark consists of a single mineral compound.
• the object of the invention is to provide compositions of the “core-shell” type, also called capsules, for which the parameters of release and diffusion of the material can be determined and controlled with greater precision.
• Another object of the invention is to provide capsules whose bark is temporary in the sense that it allows controlled release of the nucleus under the action of a "trigger".
• capsules comprising at least one mineral bark (E) and a core (N) which comprises at least one polyhydroxylated compound (P), each bark essentially consisting of '' a unique mineral compound.
• the invention further relates to a process for the solid phase preparation of these capsules.
• the first aspect of the present invention is a capsule comprising at least one mineral shell (E) and a core (N) which comprises at least one polyhydroxy compound (P), each shell consisting of a single mineral compound.
• the mineral compound constituting the shell (E) is chosen from phosphates of alkaline earth metals, carbonate or hydroxycarbonate of alkaline earth metals, hydroxycarbonate of transition metals, sulfates of alkaline earth metals or of transition metals, alkaline earth metal borates, alkaline earth metal halides, precipitated silicas.
• the alkaline earth metals are advantageously chosen from magnesium and calcium.
• the transition metals are preferably chosen from aluminum and iron.
• the halogen atoms can be chosen from bromine, chlorine, and iodine.
• alkaline earth metal phosphates mention may in particular be made of pyrophosphates, triphosphates, mono-, di- or tri-calcium phosphates.
• precipitation silica is meant here a silica obtained by precipitation from the reaction of an alkali metal silicate with an acid, generally inorganic, at an adequate pH of the precipitation medium, in particular a basic, neutral or slightly acidic; the mode of preparation of the silica can be any (addition of acid on a silicate base stock, total or partial simultaneous addition of acid or silicate on a base stock of water or silicate solution, etc.
• a filter cake is thus collected, which is washed if necessary; this cake can be, optionally after disintegration, dried by any known means, in particular by atomization, then optionally ground and / or agglomerated.
• the particles of the mineral compound generally have a size of between 0.1 and 100 microns, advantageously between 0.1 and 50 microns.
• the particle size is conventionally determined by laser granulometry, for example using a Coulter® LS 230.
• the capsules consist essentially of a single layer of particles of single mineral compound. This characteristic contributes positively to the determination and control of the parameters of release and diffusion of the material. More particularly, it contributes to the good dispersibility of the capsules.
• the mineral bark (E) represents between 0 excluded and 50%, advantageously between 2 to 40%, and preferably between 5 and 30%, by weight relative to the total weight of the capsule.
• the capsules also consist of a core (N) which comprises at least one polyhydroxy compound (P).
• the polyhydroxy compound (P) is advantageously a polysaccharide which can be chosen from threose, erythrosis, arabinose, xylose, ribose, deoxyribose, rhamnose, fucose, glucosamine, galactosamine, N-acetyl-glucosamine, N-acetyl-galactosamine, starches, amylopectin, amylose, arabane, alginates, carrageenans, cellulose, chitosan, chondroitin sulfate, dextran, dextrin, fructosan, galactan, mannans such as galactomannans, gum arabic, pectins, ghatti gum, galactoside, glucan, glycan, glycogen, hemicellulose, hyaluronic, inulin, lamarinarine, levane, mucoitin sulfate, nigeran, pen
• polyhydroxy compound (P) is chosen from guars, pectins, celluloses, and beta-glucans.
• the polyhydroxy compounds (P) can be found alone or as a mixture in the nucleus (N).
• hydroxylated compound will be used to denote both a single and a mixture of polyhydroxy compounds.
• the particles of compound (P) preferably have a size between 1 to 500 microns, advantageously between 2 and 200 microns, preferably between 2 and 80 microns.
• the core (N) comprising at least one polyhydroxylated compound (P) represents between 50% and 100% excluded, advantageously between 60 and 98%, and preferably between 70 and 95% by weight relative to the total weight of the capsule.
• the polyhydroxylated compound (P) can be partially substituted by a substance (S) chosen from aromas, essential oils, dyes, film-forming substances such as depolymerized guar or arabinoxylan , substances preventing foaming such as polyethoxylated oils derived from palm oil, soybean oil, castor oil, rapeseed oil, corn oil, l 'sunflower oil.
• a substance (S) chosen from aromas, essential oils, dyes, film-forming substances such as depolymerized guar or arabinoxylan , substances preventing foaming such as polyethoxylated oils derived from palm oil, soybean oil, castor oil, rapeseed oil, corn oil, l 'sunflower oil.
• the content of the nucleus namely, the total amount of the polyhydroxy compound (P) and of substance (S) is between 50% and 100% excluded, advantageously between 60 and 98%, and preferably between 70 and 95% by weight relative to the total weight of the capsule.
• the controlled release of the contents of the nucleus into the environment can be accomplished by destroying the bark.
• the bark (E) has the advantage of being sensitive to pH.
• the variation in pH necessary for the destruction of the bark (E) will depend on the nature of the material constituting the bark and on the application which will be made of the capsules.
• the destruction pH is less than 7. It is preferably less than 5, and more preferably less than 4.
• the mineral shell (E) has the advantage of effectively protecting the content of the nucleus, that is to say the polyhydroxy compound (P) and, where appropriate, the substance (S), to transport them in a given medium, and finally to release them.
• This release phenomenon can be characterized, for example, by particle size measurements of the content of the released nucleus, of the viscosity of the medium, of the turbidity of the medium.
• the invention also relates to a process for the preparation in solid phase of capsules.
• the encapsulation of the material is conventionally done wet.
• This type of process consists of forming a mineral shell, after precipitation of the salts and chemical reaction at the interface of what will constitute the nucleus.
• the control of the degree of homogeneity in terms of chemical composition of the bark within the meaning of the invention can prove to be very difficult or in some cases impossible.
• the bark formed by precipitation consists of a mixture of salts.
• calcium chloride (CaCl 2 ) is generally reacted with sodium phosphate (sodium orthophosphate NaH 2 PO 4 , 2H 2 O).
• the expected salt is effectively obtained which is brushite (CaHPO 4 , 2H 2 O), but also mixed salts such as 2CaHPO 4 , 2Ca 3 (PO) 2 , 5H 2 O or 2CaHPO 4 , 5Ca 3 ( PO 4 ) 2 , Ca (OH) 2 . Therefore, the behavior of the bark, and more particularly its solubilization by lowering of pH, will be modified: the determination and the implementation of optimal conditions for an optimal solubilization of the bark will be more difficult.
• the capsules according to the present invention are prepared by a "dry process” process, that is to say in the absence of water, solvents, or any other liquid medium.
• the process of the present invention has the advantage of making it possible to start from the desired mineral compound, and to obtain a shell consisting essentially of said compound.
• the mineral compound constituting the shell (E) will have the same crystalline phase as that of the mineral compound initially used in the process.
• the solubilization (trigger of release) of the bark will be governed only by the chemistry of the mineral compound constituting it.
• This process also has the advantage of being simpler and more economical. Indeed, the step of drying the capsules, a step which is essential in a wet encapsulation, is eliminated in a process according to the invention.
• the raw materials used namely, the mineral compound constituting the shell (E), the compound (P), and where appropriate the substance (S), intervene in the solid state, which makes it possible to considerably limit the loss of raw materials.
• the raw materials used namely, the mineral compound constituting the shell (E), the compound (P), and where appropriate the substance (S), intervene in the solid state, which makes it possible to considerably limit the loss of raw materials.
• almost the entire quantity of raw material involved is transformed into capsules.
• the capsules according to the invention are prepared by a process in which: (i) a mixture of particles constituting the core (N) and that constituting the shell (E) is formed, said particles being in the solid state, ( ii) subjecting said mixture to impact forces with an impact speed of between 30 and 100 m / sec. for a time long enough for the particles constituting the shell (E) to cover the particles constituting the core (N), (iii) the capsules (C) thus obtained are then recovered.
• An important criterion of this process is to respect the particle size ratio between the size of the particles constituting the shell (E) and that of the particles constituting the core (N). This ratio is advantageously at least 1/5, preferably at least 1/10. More particularly, the particles of the mineral compound constituting the shell (E) have a size of between 0.1 and 50 microns, advantageously between 0.1 and 10 microns, and preferably between 0.1 and 5 microns.
• the particles of the compound (P), and if necessary of the substance (S), have a size of between 1 to 500 microns, advantageously between 2 and 200 microns, preferably 2 and 80 microns.
• each particle essentially retains its initial size.
• r is the average radius of the particles of the nucleus and that r 'is the average radius of the particles constituting the shell
• the average radius of the capsules will be equal to r + 2r'. Knowing that the value of r is much greater than that of r ′, it can then be considered that the size of the capsules corresponds substantially to that of the nucleus.
• the key parameters for successfully preparing capsules according to the invention are the time required for coating and temperature control.
• Temperature control is important to avoid local heating which may lead to undesirable side reactions (such as total dehydration of the polysaccharide). It can be done, for example, using a double jacket cooling device.
• the capsules obtained are finally recovered as they are, without the need for additional purification, drying, etc. steps.
• This process can be carried out in any reactor allowing encapsulation by the dry route.
• the method according to the invention can be implemented by any type of device which, under the effect of impact and / or shear forces, allows fine particles in the solid state to encapsulate large particles at solid state with sufficient impact velocity.
• it is important to respect a size ratio of large particles / fine particles varying from 10 to 100 or even more.
• systems consisting of a chamber inside which a rotor can be set in motion can be used from the moment when the energy provided by this rotor within said chamber is sufficient for the small particles to meet "effectively" the largest.
• apparatus there may be mentioned, for example, an apparatus of the "Nara" type.
• Hybridizer NHS-0 sold by the company Nara Machinery Co, LTD Zweign. Europa, or a device of the" Mechanofusion System “type sold by the company HOSOKAWA.
• Another aspect of the invention relates to the use of capsules according to the invention, in the field of food, cosmetics, detergency, pharmaceutical, building.
• the invention relates to the use of capsules in the food sector, in particular as an adjuvant, for example in energy drinks, diet drinks, meal replacements, etc.
• the compositions (C) of the invention have the advantage of being able to be used at concentrations greater than those of the prior art, and more particularly greater than 10 g / l.
• the invention finally relates to food formulations comprising capsules according to the invention.
• EXAMPLE 1 Preparation of capsules with a shell consisting of calcium phosphate and a core comprising guar.
• the capsules obtained are characterized by the methods described below.
• Transmission microscopy makes it possible to observe the presence of small mineral particles on the surface of the guar, uniformly covering the surface of the latter.
• the contrast obtained makes it possible to differentiate the phosphate compound which coats the guar.
• the objective of this coating is to be able to disperse the guar particles encapsulated by calcium triphosphate without viscosing the medium, the test consists in verifying that the guar is well protected from the surrounding medium and that it does not lead to an increase in the viscosity of the medium.
• the polysaccharide 1% of dry extract in deionized water
• the polysaccharide is poured into water with gentle stirring (55 mm deflocculating blade, stirring speed of 300 rpm for 15 min)).
• the pH of the dispersion is around 6.
• the viscosity is determined using a Brookfield rotational viscometer (LVT; 6 rpm).
• EXAMPLE 2 Preparation of capsules with a shell consisting of calcium phosphate and a core comprising starch.
• the capsules obtained are characterized by the methods described below.
• Transmission microscopy makes it possible to observe the presence of small mineral particles on the surface of the guar, uniformly covering the surface of the latter.
• the contrast obtained makes it possible to differentiate the phosphate compound which coats the starch.

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• Chemical & Material Sciences (AREA)
• Organic Chemistry (AREA)
• Dispersion Chemistry (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Manufacturing Of Micro-Capsules (AREA)
• Cosmetics (AREA)
• Medicinal Preparation (AREA)
• General Preparation And Processing Of Foods (AREA)

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• 1999
  • 1999-12-07 FR FR9915405A patent/FR2801810B1/fr not_active Expired - Fee Related
• 2000
  • 2000-12-06 AU AU23807/01A patent/AU2380701A/en not_active Abandoned
  • 2000-12-06 US US10/148,790 patent/US20030124242A1/en not_active Abandoned
  • 2000-12-06 WO PCT/FR2000/003405 patent/WO2001041914A1/fr not_active Application Discontinuation
  • 2000-12-06 EP EP00987556A patent/EP1239947A1/fr not_active Withdrawn
  • 2000-12-06 JP JP2001543251A patent/JP2003516222A/ja active Pending

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