EP2880061A1 - Method for the reactive extrusion of an amylaceous material in the presence of a polyphosphate serving as a cross-linking agent, resulting products, and uses thereof - Google Patents

Method for the reactive extrusion of an amylaceous material in the presence of a polyphosphate serving as a cross-linking agent, resulting products, and uses thereof

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Publication number
EP2880061A1
EP2880061A1 EP13756622.0A EP13756622A EP2880061A1 EP 2880061 A1 EP2880061 A1 EP 2880061A1 EP 13756622 A EP13756622 A EP 13756622A EP 2880061 A1 EP2880061 A1 EP 2880061A1
Authority
EP
European Patent Office
Prior art keywords
starch
polyphosphate
extruder
solvent
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Withdrawn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
EP13756622.0A
Other languages
German (de)
French (fr)
Inventor
Julien Parcq
René SAINT-LOUP
Vincent Wiatz
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.)
Roquette Freres SA
Original Assignee
Roquette Freres SA
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 Roquette Freres SA filed Critical Roquette Freres SA
Publication of EP2880061A1 publication Critical patent/EP2880061A1/en
Withdrawn legal-status Critical Current

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L3/00—Compositions of starch, amylose or amylopectin or of their derivatives or degradation products
    • C08L3/02—Starch; Degradation products thereof, e.g. dextrin
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
    • C08B31/00—Preparation of derivatives of starch
    • C08B31/003—Crosslinking of starch
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
    • A01N25/12—Powders or granules
    • A—HUMAN NECESSITIES
    • A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
    • A23L—FOODS, FOODSTUFFS, OR NON-ALCOHOLIC BEVERAGES, NOT COVERED BY SUBCLASSES A21D OR A23B-A23J; THEIR PREPARATION OR TREATMENT, e.g. COOKING, MODIFICATION OF NUTRITIVE QUALITIES, PHYSICAL TREATMENT; PRESERVATION OF FOODS OR FOODSTUFFS, IN GENERAL
    • A23L29/00—Foods or foodstuffs containing additives; Preparation or treatment thereof
    • A23L29/20—Foods or foodstuffs containing additives; Preparation or treatment thereof containing gelling or thickening agents
    • A23L29/206—Foods or foodstuffs containing additives; Preparation or treatment thereof containing gelling or thickening agents of vegetable origin
    • A23L29/212—Starch; Modified starch; Starch derivatives, e.g. esters or ethers
    • A—HUMAN NECESSITIES
    • A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
    • A23P—SHAPING OR WORKING OF FOODSTUFFS, NOT FULLY COVERED BY A SINGLE OTHER SUBCLASS
    • A23P30/00—Shaping or working of foodstuffs characterised by the process or apparatus
    • A23P30/20—Extruding
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K47/00—Medicinal preparations characterised by the non-active ingredients used, e.g. carriers or inert additives; Targeting or modifying agents chemically bound to the active ingredient
    • A61K47/30—Macromolecular organic or inorganic compounds, e.g. inorganic polyphosphates
    • A61K47/36—Polysaccharides; Derivatives thereof, e.g. gums, starch, alginate, dextrin, hyaluronic acid, chitosan, inulin, agar or pectin
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/02—Cosmetics or similar toiletry preparations characterised by special physical form
    • A61K8/0241—Containing particulates characterized by their shape and/or structure
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/72—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
    • A61K8/73—Polysaccharides
    • A61K8/732—Starch; Amylose; Amylopectin; Derivatives thereof
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K9/00—Medicinal preparations characterised by special physical form
    • A61K9/14—Particulate form, e.g. powders, Processes for size reducing of pure drugs or the resulting products, Pure drug nanoparticles
    • A61K9/141—Intimate drug-carrier mixtures characterised by the carrier, e.g. ordered mixtures, adsorbates, solid solutions, eutectica, co-dried, co-solubilised, co-kneaded, co-milled, co-ground products, co-precipitates, co-evaporates, co-extrudates, co-melts; Drug nanoparticles with adsorbed surface modifiers
    • A61K9/146—Intimate drug-carrier mixtures characterised by the carrier, e.g. ordered mixtures, adsorbates, solid solutions, eutectica, co-dried, co-solubilised, co-kneaded, co-milled, co-ground products, co-precipitates, co-evaporates, co-extrudates, co-melts; Drug nanoparticles with adsorbed surface modifiers with organic macromolecular compounds
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q19/00—Preparations for care of the skin
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
    • C08B31/00—Preparation of derivatives of starch
    • C08B31/003—Crosslinking of starch
    • C08B31/006—Crosslinking of derivatives of starch
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/12—Powdering or granulating
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/24—Crosslinking, e.g. vulcanising, of macromolecules
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L101/00—Compositions of unspecified macromolecular compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L3/00—Compositions of starch, amylose or amylopectin or of their derivatives or degradation products
    • C08L3/04—Starch derivatives, e.g. crosslinked derivatives
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D103/00—Coating compositions based on starch, amylose or amylopectin or on their derivatives or degradation products
    • C09D103/04—Starch derivatives
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
    • D21H17/20—Macromolecular organic compounds
    • D21H17/21—Macromolecular organic compounds of natural origin; Derivatives thereof
    • D21H17/24—Polysaccharides
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
    • D21H17/20—Macromolecular organic compounds
    • D21H17/21—Macromolecular organic compounds of natural origin; Derivatives thereof
    • D21H17/24—Polysaccharides
    • D21H17/28—Starch
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H19/00—Coated paper; Coating material
    • D21H19/36—Coatings with pigments
    • D21H19/44—Coatings with pigments characterised by the other ingredients, e.g. the binder or dispersing agent
    • D21H19/54—Starch
    • A—HUMAN NECESSITIES
    • A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
    • A23V—INDEXING SCHEME RELATING TO FOODS, FOODSTUFFS OR NON-ALCOHOLIC BEVERAGES AND LACTIC OR PROPIONIC ACID BACTERIA USED IN FOODSTUFFS OR FOOD PREPARATION
    • A23V2002/00—Food compositions, function of food ingredients or processes for food or foodstuffs
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K2800/00—Properties of cosmetic compositions or active ingredients thereof or formulation aids used therein and process related aspects
    • A61K2800/10—General cosmetic use
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K2800/00—Properties of cosmetic compositions or active ingredients thereof or formulation aids used therein and process related aspects
    • A61K2800/40—Chemical, physico-chemical or functional or structural properties of particular ingredients
    • A61K2800/41—Particular ingredients further characterized by their size
    • A61K2800/412—Microsized, i.e. having sizes between 0.1 and 100 microns
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K2800/00—Properties of cosmetic compositions or active ingredients thereof or formulation aids used therein and process related aspects
    • A61K2800/40—Chemical, physico-chemical or functional or structural properties of particular ingredients
    • A61K2800/60—Particulates further characterized by their structure or composition
    • A61K2800/65—Characterized by the composition of the particulate/core
    • A61K2800/654—The particulate/core comprising macromolecular material
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2303/00—Characterised by the use of starch, amylose or amylopectin or of their derivatives or degradation products
    • C08J2303/04—Starch derivatives
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/14—Polymer mixtures characterised by other features containing polymeric additives characterised by shape
    • C08L2205/18—Spheres

Definitions

  • the present invention relates to a process for the reactive extrusion of starchy material in the presence of a crosslinking agent which is a polyphosphate and more preferably sodium trimetaphosphate.
  • a crosslinking agent which is a polyphosphate and more preferably sodium trimetaphosphate.
  • Sodium trimetaphosphate behaves as an effective substitute for the glyoxal used and recommended by the prior art.
  • the process according to the invention makes it possible, in some of its variants, to control the competition between the destructuring and the crosslinking of the starch. This method therefore makes it possible to obtain crosslinked starches with adaptable residual crystalline phase levels in order to ideally meet the specific needs of the different end applications.
  • Reactive extrusion is a well-known technique for forming starchy materials in the form of nano-sized particles, which can then be dispersed in water or in a hydroalcoholic solvent.
  • This technology is based on a first step of extruding the starchy material in the presence of a crosslinking agent, followed by a granulation and grinding step.
  • water or a hydroalcoholic solvent By adding water or a hydroalcoholic solvent, it is finally possible to achieve dispersions with a dry matter content of at least 20% by dry weight of starchy material, stable over time, and having a size of particles between 100 and 500 nm as determined by laser particle size.
  • This crosslinking agent which is present in the extruder and will therefore react with the starchy material in the extruder, may be introduced, added to the starch just before being introduced into the extruder (pre- mixture) and / or introduced directly into the extruder, preferably directly into the extruder.
  • the crosslinking agent is reversible or not.
  • these documents mention the polyaldehydes and especially the dialdehydes, such as glutaraldehyde, glyoxal and carbohydrates, with glyoxal being the most preferred.
  • epichlorohydrin there may be mentioned epichlorohydrin. It is noted that only the glyoxal is illustrated in the examples, without any evidence that the other agents mentioned do indeed work in the process described.
  • glyoxal has disadvantages in many respects. Most of the time, it is delivered in the form of aqueous solutions that are very acidic and therefore corrosive (pH close to 2). In addition, it is an extremely reactive compound that can react violently with oxidants, acids and strong bases. In addition, like all aldehydes, it is highly irritating to the skin and mucous membranes. Finally, glyoxal is a product called "CMR": mutagenic and toxic for reproduction. It is labeled H341, which means that it is likely to induce genetic abnormalities.
  • a first object of the present invention consists in a process for producing particles consisting of at least one starchy material, said process comprising:
  • crosslinking agent is a polyphosphate
  • WO 2004/085481 discloses a process for producing particles of a starchy material by extrusion, said extrusion taking place on a previously crosslinked starchy material. Indeed, it is stipulated in particular on page 4 lines 24 to 28 that initially forms a paste by mixing between the starch, water, an alkali and a crosslinking agent and that said paste is then introduced into an extruder.
  • the process that is the subject of the present application consists, more particularly, in a process for producing particles made of at least one starchy material, said process comprising:
  • d) optionally a dispersion step in a solvent.
  • the crosslinking agent is a polyphosphate and in that the extrusion step a) is carried out by introducing the starchy material, the polyphosphate and a solvent into the extruder.
  • the polyphosphate is sodium trimetaphosphate.
  • the extrusion step a) of the process according to the invention is carried out in an extruder: this device is the site of important shearing forces that apply to the starch or the starchy material.
  • this step is carried out at a temperature at least equal to 40 ° C, preferably at least 50 ° C, very preferably at least 60 ° C, but in all cases at a temperature below the degradation temperature of starchy material; the choice of this temperature is within the normal skills of those skilled in the art, with regard to the physicochemical characteristics of the materials used.
  • the process generates a pressure of between 5 bar and 150 bar
  • the extrusion step a) is carried out by introducing the non-crosslinked starchy material and the polyphosphate into the extruder.
  • the starchy material or the starch is subjected to high shearing forces in the presence of the crosslinking agent in a extruder. Crosslinking of the starch therefore takes place within the extruder.
  • the process which is the subject of the invention therefore consists of a process for producing particles consisting of at least one crosslinked starchy material, said process comprising: a) at least one step of extruding at least one starchy material, in the presence of at least one crosslinking agent, b) a granulation step, the crosslinking agent being a polyphosphate and the extrusion step comprising:
  • the noncrosslinked starchy material is generally introduced into the first zones of the extruder, in zone 1 or at the bottom of the extruder, but may also be introduced into any zone other than the latter. This introduction can be achieved by gravimetric insertion from above the extruder or by the use of specific introduction systems known to those skilled in the art as "side-feeder" for example.
  • the starchy material may be introduced in admixture with another starchy material and / or in admixture with another constituent other than a starchy material.
  • constituent different from a starchy material include antimicrobial agents, plasticizers other than water such as polyols (eg ethylene glycol, propylene glycol, glycerol, maltose), urea, sodium lactate etc. .
  • This mixture is therefore generally introduced in zone 1, but can be introduced in any zone of the extruder other than the last one. As such, the mixture can be obtained by homogenization in a device of the "dry-blend" type.
  • the starchy material may also or according to another variant be introduced in combination with another starchy material and / or with another constituent different from a starchy material, not in the form of a mixture but separately.
  • the ingredients are introduced separately either in the same zone (in any zone with the exception of the last zone but preferably in the first zones of the extruder or in the foot), or in separate zones. .
  • Step a) of extruding at least one starchy material is carried out, further by introducing into the extruder the starchy material to be crosslinked and the crosslinking agent, in this case polyphosphate, by introduction into the extruder of at least one solvent, preferably a solvent.
  • the extrusion indeed takes place in a solvent medium.
  • the extrusion step a) is carried out by introduction into the extruder of at least one solvent, selected from water and hydroalcoholic solvents. Preferentially it is water.
  • This solvent or solvent mixture is used to destructure the starch fraction.
  • the solvent in particular can act, acts as a plasticizer.
  • the solvent or solvent mixture can be introduced into any zone of the extruder.
  • the solvent or solvent mixture can be introduced after the starchy material to be crosslinked and the crosslinking agent (the polyphosphate) have been introduced into the extruder.
  • the solvent and the starchy material are introduced simultaneously in the form of an aqueous dispersion of starchy material of the "slurry" type.
  • the crosslinking agent in this case the polyphosphate and more preferably the sodium trimetaphosphate, which is introduced into the extruder and which will react with the starchy material only within the extruder, may be either added the starch just before being introduced into the extruder (premix) is introduced directly into the extruder already comprising the starchy material to be crosslinked, optionally in the presence of a solvent.
  • the crosslinking agent is introduced directly into the extruder.
  • the crosslinking agent, in this case polyphosphate represents from 0.1% to 10% by dry weight relative to the dry weight of starch material used.
  • the zone of introduction of the polyphosphate and in particular its relative position with respect to the zone of introduction of the solvent (in particular the water) is a critical parameter in the optics of the control of the competition between the destructuration of the starchy matter. and the crosslinking reaction between the nucleophilic functions carried by the amylaceous material and at least one of the possible other ingredients.
  • the solvent especially water
  • particularly advantageous products were obtained. at the level of their application.
  • the extrudate designates all of the material present in the extruder, therefore at least the starchy material and the solvent, and possibly other ingredients (such as plasticizers, lubricants, antimicrobials). While not wishing to be bound by any theory, the Applicant believes that these results are related to the control of the phenomenon of destructuring of the starchy material and of its content in the crystalline phase, via the particular regulation of the solvent content. In another version of the invention, a particularly preferred variant, the competition between these two mechanisms (destructuration-crosslinking) is managed, controlled by the addition of a catalyst alkaline, which participates in the destructuring of starch. In this case, the extrusion step a) further comprises introducing into the extruder an alkaline catalyst.
  • the crosslinking agent in this case the polyphosphate
  • the polyphosphate before the said alkaline catalyst (the polyphosphate is thus in its non-activated form) in the reaction medium: this makes it possible to disperse the polyphosphate effectively in the material.
  • the alkaline catalyst is then chosen from alkali and alkaline earth oxides and hydroxides, especially sodium hydroxide.
  • the alkaline catalyst is preferably introduced into the extruder as an aqueous solution or dispersion.
  • the process according to the invention is a process for producing particles consisting of at least one crosslinked starchy material, comprising: a) at least one step of extruding at least one starchy material, in the presence of at least one less a crosslinking agent and
  • the crosslinking agent is a polyphosphate and in that the extrusion step a) comprises: i) a step of introduction into an extruder of the starchy material in a first zone introducing the extruder, the crosslinking agent into a second zone, at least one solvent into a third zone, and the alkaline catalyst into a fourth zone, the second zone and the fourth zone being different, ii) a step of kneading the starchy material under high shear in the presence in particular of the crosslinking agent.
  • the first zone and the second zone are identical.
  • the introduction of the starchy material and the crosslinking agent can then be carried out separately or in premix.
  • the first zone is located upstream of the third zone itself upstream of the fourth zone.
  • the second zone and the third zone are identical.
  • the introduction of the crosslinking agent and the solvent can then be carried out separately or in premix.
  • the first zone is located upstream of the second zone itself located upstream of the fourth zone.
  • the first, second and third zones are identical.
  • the introduction of the starchy material, the crosslinking agent and the solvent can then be carried out separately or in premix.
  • the first zone is located upstream of the fourth zone.
  • the first zone and the fourth zone are identical.
  • the introduction of the starchy material and the catalyst alkali can then be carried out separately or in premix.
  • the first zone is located upstream of the third zone itself located upstream of the second zone.
  • the starchy material may be chosen from “granular starches”.
  • granular starch is used herein to mean a starch which is native or physically modified, chemically or enzymatically, and which has retained, within the starch granules, a semicrystalline structure similar to that evidenced in starch grains. naturally occurring in reserve organs and tissues of higher plants, particularly in cereal grains, legume seeds, potato or cassava tubers, roots, bulbs, stems and fruits. This semi-crystalline state is essentially due to macromolecules of amylopectin, one of the two main constituents of starch.
  • the starch grains In the native state, the starch grains have a degree of crystallinity which varies from 15% to 45%, and which essentially depends on the botanical origin of the starch and the possible treatment that it has undergone.
  • the granular starch can come from all botanical origins, including a granular starch rich in amylose or conversely, rich in amylopectin (waxy). It may be native cereal starch such as wheat, corn, barley, amaranth, triticale, sorghum or rice, tubers such as potato or cassava, or legumes such as pea, mango bean and soy, and mixtures of such starches.
  • the granular starch is an acid hydrolyzed, oxidizing or enzymatic starch, or an oxidized starch. It can be a starch commonly called fluidized starch or a white dextrin.
  • it may also be a starch modified physico-chemically but having essentially retained the structure of the native starch starting, such as in particular esterified and / or etherified starches, in particular modified by acetylation , hydroxypropylation, cationization, crosslinking, phosphatation, or succinylation, or starches treated in aqueous medium at low temperature (in English "annealing").
  • the granular starch is a native, hydrolysed, oxidized or modified starch, in particular corn, wheat, peas or potato.
  • Granular starch generally has a degree of soluble at 20 ° C in demineralized water, less than 5% by weight. It is preferably almost insoluble in cold water.
  • the starchy material may be a water-soluble starch, which may also come from all botanical origins, including a water-soluble starch rich in amylose or, conversely, rich in amylopectin (waxy).
  • This water-soluble starch can be introduced as a partial or total replacement of the granular starch.
  • the term "water-soluble starch” means any starchy component which, at 20 ° C. and with mechanical stirring for 24 hours, has a soluble fraction in demineralized water of at least 5% by weight. This soluble fraction is preferably greater than 20% by weight and in particular greater than 50% by weight.
  • Such water-soluble starches can be obtained by pregelatinization on a drum, by pregelatinization on an extruder, by spraying a suspension or a starch solution, by precipitation with a non-solvent, by hydro-thermal cooking, by chemical functionalization or the like. It is in particular a pregelatinized, extruded or atomized starch, a highly converted dextrin (also called yellow dextrin), a maltodextrin, a functionalized starch or any mixture of these products.
  • the pregelatinized starches may be obtained by hydrothermal treatment of gelatinization of native starches or modified starches, in particular by steam cooking, jet-cooker cooking, drum cooking, cooking in kneader / extruder systems, then drying for example. in an oven, by hot air on a fluidized bed, on a rotating drum, by atomization, by extrusion or by lyophilization.
  • Such starches generally have a solubility in demineralised water at 20 ° C. of greater than 5% by weight and more generally of between 10% and 100% and a starch crystallinity level of less than 15% (in X-ray diffraction intensity). , generally less than 5% and most often less than 1%, or even zero.
  • dextrins are also part of the starchy materials that can be used in the context of the invention. They can be prepared from native or modified starches, by dextrinification in acid medium with little hydration. It may be in particular soluble white dextrins or yellow dextrins.
  • STABILYS® A 053 or TACKIDEX® C 072 products manufactured and marketed by the Applicant Such dextrins present in demineralized water at 20 ° C., a solubility generally of between 10% and 95% by weight and a starch crystallinity of less than 15%, generally less than 5%.
  • Maltodextrins and dehydrated glucose syrups are also suitable for the present invention. They can be obtained by acid, oxidative or enzymatic hydrolysis of starches in an aqueous medium. They may in particular have an equivalent dextrose (DE) of between 0.5 and 40, preferably between 0.5 and 20 and better still between 0.5 and 12.
  • DE dextrose
  • Such dehydrated maltodextrins or glucose syrups are for example manufactured and sold by the Applicant under the trade name GLUCIDEX® and have a solubility in demineralized water at 20 C generally greater than 90 ⁇ 6, or even close to 100%, and a starch crystallinity generally less than 5% and usually almost zero.
  • the functionalized starches can be obtained from a native or modified starch.
  • the functionalization can for example be carried out by esterification or etherification at a sufficiently high level to confer a solubility in water.
  • Such functionalized starches have a soluble fraction, as defined above, greater than 5%, preferably greater than 10%, more preferably greater than 50%.
  • the functionalization can be obtained in particular by acetylation in aqueous phase with acetic anhydride, by reaction with mixed anhydrides, by hydroxypropylation in the glue phase, by cationization in dry phase or glue phase, by anionization in dry phase or glue phase. by phosphatation or succinylation.
  • the water-soluble highly functionalized starches obtained may have a degree of substitution of between 0.01 and 3, and more preferably between 0.05 and 1.
  • the reagents for modification or functionalization of starch are of renewable origin. .
  • the water-soluble starch is a water-soluble starch of corn, wheat or peas, or a water-soluble derivative thereof.
  • it advantageously has a low water content, generally less than 10%, preferably less than 5%, in particular less than 2.5% by weight, and ideally less than 0.5%, or even less than 0%, 2% by weight.
  • the amylaceous component selected for the preparation of the composition is an organomodified starch, preferably organosoluble, which may also come from all botanical origins, including a organomodified starch, preferably organosoluble, rich in amylose or conversely, rich in amylopectin (waxy). This organosoluble starch may be introduced as partial or total replacement of the granular starch or of the water-soluble starch.
  • organomodified starch means any starchy component other than a granular starch or a water-soluble starch according to the definitions given above.
  • this organomodified starch is almost amorphous, that is to say having a starch crystallinity level of less than 5%, generally less than 1% and especially zero.
  • organosoluble that is to say having at 20 ° C, a fraction soluble in a solvent selected from ethanol, ethyl acetate, propyl acetate, butyl acetate , diethyl carbonate, propylene carbonate, dimethyl glutarate, triethyl citrate, dibasic esters, dimethylsulfoxide (DMSO), dimethylisosorbide, glycerol triacetate, isosorbide diacetate, isosorbide dioleate and methyl esters of vegetable oils, at least equal to 5% by weight.
  • This soluble fraction is preferably greater than 20% by weight and in particular greater than 50% by weight.
  • the organomodified starch may be used according to the invention in solid form, including having a low water content, ie less than 10% by weight. In particular, it may be less than 5%, in particular lower than at 2.5% by weight and ideally less than 0.5 ⁇ 6, or even less than 0.2% by weight.
  • the organomodified starch that can be used in the composition according to the invention can be prepared by functionalization of the native or modified starches such as those presented above.
  • This functionalization can for example be carried out by esterification or etherification at a sufficiently high level to make it essentially amorphous and to confer on it an insolubility in water and preferably a solubility in one of the organic solvents above.
  • Such functionalized starches have a soluble fraction as defined above, greater than 5%, preferably greater than 10%, more preferably greater than 50%.
  • the functionalization can be obtained in particular by acetylation in the solvent phase with acetic anhydride, grafting, for example in the solvent phase or by reactive extrusion of acid anhydrides, mixed anhydrides, fatty acid chlorides, oligomers of caprolactones or lactides, hydroxypropylation and crosslinking in the glue phase, cationization and crosslinking in the dry phase or in the glue phase, anionization by phosphatation or succinylation, and crosslinking in the dry phase or in the glue phase, silylation, butadiene telomerization.
  • organomodified, preferably organosoluble, highly functionalized starches can be, in particular, starch acetates, dextrins, maltodextrins of dehydrated glucose syrups or fatty esters of these starchy materials (starches, dextrins, maltodextrins from dehydrated glucose syrups). with fatty chains of 4 to 22 carbons, all of these products preferably having a degree of substitution (DS) of between 0.5 and 3.0, preferably of between 0.8 and 2.8 and in particular of between 1.0 and 2.7.
  • DS degree of substitution
  • the organomodified starch is an organomodified starch of corn, wheat or peas or an organomodified derivative thereof.
  • the dry matter content of starchy material in the extruder is at least 40%, preferably at least 50%, very preferably at least 60% by dry weight of the extruder contents.
  • the starchy material (s) used according to the invention can therefore be used with other ingredients.
  • the latter may especially be chosen from cellulose, lignin, carboxymethylcellulose (CMC), hemicellulose, polyesters based on polybutylene succinate, polylactic acid or polyhydroxyalkanoates, thermoplastic polyurethanes, gluten, proteins and especially pea proteins, polyamides, guar, xanthan, carrageenan, alginates f chitosan, cassia, tamarind, hemoglobin, gelatin, elastomers, lipids, triglycerides, unsaturated fatty acids or no, algae and microalgae.
  • the second step of the process according to the invention consists in granulating the extrudate at the extruder outlet. This operation is performed by all available means for granulating.
  • step c The granulation is then followed by an optional grinding step (step c), in particular a step of mechanical grinding on a solid, mechanical grinding after dispersion in a water or aqueous-alcoholic solvent, followed by a solid extraction step.
  • step c a step of mechanical grinding on a solid, mechanical grinding after dispersion in a water or aqueous-alcoholic solvent, followed by a solid extraction step.
  • step c a step of mechanical grinding on a solid, mechanical grinding after dispersion in a water or aqueous-alcoholic solvent, followed by a solid extraction step.
  • the granulation step within the meaning of the invention may also comprise, besides the granulation of the extrudate resulting from the extrusion step, a grinding step as described above.
  • the granulation in the sense of the invention may consist of a grinding step as described above.
  • the granules from step b) or the ground particles from step c) can be dispersed in water or a hydroalcoholic solvent, preferably in water.
  • particles having a size between about 100 nm and 500 nm are obtained, as determined by light scattering particle size, which can easily be aqueous dispersion in water or a hydroalcoholic solvent and this, with dry matter contents of at least 20% by dry weight of starch, the dispersion thus obtained being quite stable over time.
  • the invention also relates to the crosslinked starch particles obtained according to the method described above.
  • Another subject of the invention concerns the dispersion of the particles of crosslinked starchy material obtained according to the process described above as well as the dispersions in water or in a resulting solvent.
  • other objects of the present invention are constituted by the granules resulting from the implementation of steps a) and b) of the process of the invention, by the crushed or granulated particles resulting from the setting up steps a), b) and c) of the process of the invention, by the dispersions in water or in a hydroalcoholic solvent of granules or crushed or granulated particles, said dispersions resulting from the implementation of the steps a ), b) and d) or a), b), c) and d) of the process of the invention.
  • a last object resides in the use of dispersions in water or in a hydroalcoholic solvent of the granules or crushed particles resulting from the process according to the invention, in the manufacture of generally wet films, in the manufacture of paper. and in particular in the manufacture of coating coatings, in the field of drugs as a carrier of active principle, in cosmetology, in agriculture and horticulture, in human and animal nutrition, in the manufacture of blends with synthetic polymers.
  • different screw profiles can be used to control the specific mechanical energy transmitted to the material and thus control the competition between destructure of the starch and crosslinking reactions.
  • a screw profile is defined through the different zones that constitute said screw.
  • Each zone (Z) consists of a particular element (P) ensuring in particular the transport or the shearing at a certain angle of the material passing through it.
  • Each zone is also associated with a particular temperature (T).
  • C includes all elements with a high shear component, ie all shear elements at 30 45 60 and 90 ° in direct pitch, and also 45 60 ° in reverse pitch and transport elements or reverse mixing.
  • a mixture of native maize starch (113 parts by weight with a water content of 11.5%) and glycerol (17.9%) parts by weight) is introduced into an extruder at a rate of 8.22 kg / h by means of a volumetric feed. Said mixture is introduced into zone 1 of the extruder which has 15 zones, and has a screw and temperature profile shown in FIG. 1. The screw speed is set at 500 revolutions / minute.
  • Water (21 parts) is introduced at zone 2, at a flow rate of 0.6 kg / h, by means of a piston pump.
  • glyoxal (1.9 parts) and water are introduced at zone 5 at a rate of 1.07 kg / h.
  • the amount of water in the extrudate is less than 25% by weight and especially 13% by weight thereof were introduced before the addition of the crosslinking agent (glyoxal).
  • a mixture of native maize starch (113 parts by weight with a water content of 11.5%) and of glycerol (17.9 parts by weight) is introduced into an extruder at a rate of 6.46 kg. / h by means of a volumetric feed. Said mixture is introduced into zone 1 of the extruder which has 15 zones, and has a screw profile as shown in FIG. 2. The screw speed is set at 500 revolutions / minute.
  • Water (20 parts including the water contained in the native starch) is introduced at zone 2, at a flow rate of 0.5 kg / h, by means of a piston pump.
  • glyoxal (1 part) and water are introduced at zone 5, at a rate of 1.39. kg / h.
  • the amount of water in the extrudate is less than 31% by weight and especially 14% by weight thereof were introduced before the addition of the crosslinking agent (glyoxal).
  • Native maize starch (113 parts by weight with a water content of 12%) is introduced into an extruder at a rate of 4.94 kg / h using a volumetric feed. It is introduced into zone 1 of the extruder which has 15 zones, and has a screw profile as shown in FIG. 3. The screw speed is set at 500 revolutions / minute. Water (170.4 parts including water of the native starch) is introduced at zone 2 at a flow rate of 0.5 kg / h by means of a piston pump. Using the same device, sodium trimetaphosphate (2.3 parts) in solution at zone 5 is introduced at a rate of 0.1 kg / h.
  • a sodium hydroxide solution (0.74 part) is introduced at a rate of 0.032 kg / h.
  • the amount of water in the extrudate is equal to 65.5% by weight and especially 60% by weight thereof were introduced before the addition of the crosslinking agent (trimetaphosphate).
  • Native maize starch (113 parts by weight with a water content of 12%) is introduced into an extruder at a rate of 4.94 kg / h using a volumetric feed. It is introduced into zone 1 of the extruder which has 15 zones, and has a screw profile 1 as shown in FIG. 6. The screw speed is set at 500 revolutions / minute.
  • Water (170.4 parts including water of the native starch) is introduced at zone 2 at a flow rate of 0.5 kg / h by means of a piston pump.
  • sodium trimetaphosphate (2.3 parts in solution at zone 3, at a rate of 0.1 kg / h) is introduced at the level of zone 9.
  • sodium hydroxide (0.74 part) at a rate of 0.032 kg / hr
  • the amount of water in the extrudate is equal to 65.5% by weight and especially 60% by weight of that these were introduced before the addition of the crosslinking agent.
  • Example 7 This example illustrates the invention; it is identical to the previous one, with the difference that the extruder has a profile as shown in FIG.
  • Example 8 This example illustrates the invention; it is identical to the previous one, with the difference that the extruder has a profile as shown in FIG.
  • Example 8 This example illustrates the invention; it is identical to the previous one, with the difference that the extruder has a profile as shown in FIG.
  • Example 8
  • Example 9 This example also illustrates the invention; it is identical to the previous one, with the difference that the extruder has a profile as shown in FIG. 9.
  • Example 11 illustrates the invention; it is identical to example 3, but the screw speed is set at 250 rpm.
  • Example 11 illustrates the invention; it is identical to example 3, but the screw speed is set at 250 rpm.
  • Example 3 illustrates the invention; it is identical to Example 3, with the difference that sodium trimetaphosphate is premixed with starch and introduced in this form at zone 1, whereas the sodium hydroxide solution is introduced in zone 9 (see FIG. ).
  • Example 12 This example illustrates the invention; it is identical to Example 11, with the difference that the water is introduced before the mixture of starch and sodium trimetaphosphate (see FIG. 11).
  • Example 13 This example illustrates the invention; it is identical to Example 11, with the difference that the water is introduced before the mixture of starch and sodium trimetaphosphate (see FIG. 11).
  • This example illustrates the invention; it is identical to Example 3, with the difference that the starch is a potato starch.
  • This example illustrates the invention; it is identical to Example 3, with the difference that the starch is a rice starch.
  • Example 15 This example illustrates the invention; it is identical to Example 3, with the difference that the starch is a pea starch.
  • Example 17 This example illustrates the invention; it is identical to Example 3, with the difference that the starch is an anionic corn starch.
  • Example 17 This example illustrates the invention; it is identical to Example 3, with the difference that the starch is an anionic corn starch.
  • Example 18 This example illustrates the invention; it is identical to Example 3, with the difference that the starch is a cationic maize starch.
  • Example 18 This example illustrates the invention; it is identical to Example 3, with the difference that the starch is a cationic maize starch.
  • This example illustrates the invention; it is identical to Example 3, with the difference that the starch is a hydroxypropyl corn starch.
  • This example illustrates the invention; it is identical to Example 3, with the difference that the compound introduced is a mixture of waxy starch and starch.
  • the powders are introduced into the extruder using Schlenck solid gravimetric feeders of the Proflex type.
  • the liquids are introduced into the extruder by means of Brabender liquid gravimetric feeders when the flow rates are higher than 1 kg / h. When the flow rates of liquids are less than 1 kg / h, gravimetric microdosers are used.
  • the temperature profile used is given in Table 1 below.
  • the screw speed for all the tests listed in the table below is set at 400 rpm.
  • the reagents are introduced separately except for test 26 in which a premix containing 10 kg of potato starch, 13.9 kg of water and 543 g of sodium trimetaphosphate (STMP) and 10 gd 'Irgasan ®.
  • Irgasan ® is an antimicrobial agent.
  • Eurylon ® is a high amylose corn starch. Tests 2 to 30 are according to the invention. Test 1 is not in accordance with the invention.
  • the two magnifications X10 and X20 make it possible to assess the presence or absence of unstructured starch grains.
  • test 1 not in accordance with the invention, a continuous matrix of starch is observed in which the grains are no longer visible because they have been completely destructured.
  • tests 2 to 30 in accordance with the invention polarization crosses (cross-malt cross-polarization) are observed in a very distinct manner during the presence of uncooked grains (still crystalline phase). present) .

Abstract

The invention relates to a method for the reactive extrusion of an amylaceous substance in the presence of a polyphosphate serving as a cross-linking agent, to the resulting products, and to the uses thereof. The present invention relates to a method for the reactive extrusion of starch in the presence of a cross-linking agent which is a polyphosphate, in particular sodium trimetaphosphate, which behaves like an effective substitute for glyoxal. Said method makes it possible to manage the competition between the destructuring and cross-linking mechanisms of the amylaceous substance. The crystalline phase content of the cross-linked starches is thus controlled in accordance with the specific needs of the final use.

Description

Procédé d' extrusion réactive de matière amylacée en présence de polyphosphate comme agent réticulant, produits obtenus et leurs utilisations .  Process for the reactive extrusion of starchy material in the presence of polyphosphate as crosslinking agent, products obtained and their uses.
La présente invention se rapporte à un procédé d' extrusion réactive de matière amylacée en présence d'un agent réticulant qui est un polyphosphate et plus préférentiellement le trimétaphosphate de sodium. Le trimétaphosphate de sodium se comporte comme un substitut efficace du glyoxal utilisé et recommandé par l'art antérieur. Ainsi, de manière avantageuse, le procédé selon l'invention permet, dans certaines de ses variantes, de contrôler la compétition entre la déstructuration et la réticulation de l'amidon. Ce procédé permet donc d'obtenir des amidons réticulés avec des taux de phases cristallines résiduelles adaptables afin de répondre idéalement aux besoins spécifiques des différentes applications finales. L' extrusion réactive est une technique bien connue pour mettre en forme des matières amylacées sous forme de particules de taille nanométrique, qui peuvent ensuite être dispersées dans l'eau ou dans un solvant hydroalcoolique. Cette technologie repose sur une première étape d' extrusion de la matière amylacée en présence d'un agent réticulant, suivie d'une étape de granulation et de broyage. Par adjonction d'eau ou d'un solvant hydroalcoolique, on parvient au final à réaliser des dispersions d'une teneur en matière sèche au moins égale à 20 % en poids sec de matière amylacée, stables dans le temps, et présentant une taille de particules comprise entre 100 et 500 nm telle que déterminée par granulométrie laser. Cette technologie a été relatée dans les documents EP 1 159 301, puis reprise et affinée dans les documents EP 1 303 667, EP 1 303 670 et EP 2 251 484, ces 3 documents visant pour les produits obtenus des applications dans la fabrication du papier. Plus précisément, ces derniers documents sont orientés vers la fabrication des compositions destinées à recouvrir la feuille de papier pour lui conférer notamment des propriétés optiques améliorées, lesdites compositions étant connues par l'homme du métier sous l'expression « sauces de couchage ». The present invention relates to a process for the reactive extrusion of starchy material in the presence of a crosslinking agent which is a polyphosphate and more preferably sodium trimetaphosphate. Sodium trimetaphosphate behaves as an effective substitute for the glyoxal used and recommended by the prior art. Thus, advantageously, the process according to the invention makes it possible, in some of its variants, to control the competition between the destructuring and the crosslinking of the starch. This method therefore makes it possible to obtain crosslinked starches with adaptable residual crystalline phase levels in order to ideally meet the specific needs of the different end applications. Reactive extrusion is a well-known technique for forming starchy materials in the form of nano-sized particles, which can then be dispersed in water or in a hydroalcoholic solvent. This technology is based on a first step of extruding the starchy material in the presence of a crosslinking agent, followed by a granulation and grinding step. By adding water or a hydroalcoholic solvent, it is finally possible to achieve dispersions with a dry matter content of at least 20% by dry weight of starchy material, stable over time, and having a size of particles between 100 and 500 nm as determined by laser particle size. This technology has been reported in documents EP 1 159 301 and then incorporated and refined in documents EP 1 303 667, EP 1 303 670 and EP 2 251 484, these 3 documents aimed at products obtained from applications in the manufacture of paper. . More specifically, the latter documents are directed towards the manufacture of compositions intended to cover the paper sheet to confer in particular improved optical properties, said compositions being known by those skilled in the art under the term "coating colors".
Comme le montrent les 3 derniers documents cités, la mise en œuvre des particules fabriquées par extrusion réactive dans des sauces de couchage papetières, permet de substituer en partie les liants synthétiques couramment utilisés dans de telles applications et ce, tout en maintenant un niveau de propriétés équivalent : à la fois dans la sauce de couchage proprement dite, en terme de viscosité à haut et bas gradient de cisaillement (viscosité Brookfield et Haake) , mais aussi au niveau de la feuille de papier en termes de rétention d'eau et d' imprimabilité . As shown by the last 3 cited documents, the implementation of particles manufactured by reactive extrusion in paper coating coatings, allows to partially replace the synthetic binders commonly used in such applications and while maintaining a level of properties equivalent: both in the actual coating color, in terms of viscosity at high and low shear rate (Brookfield viscosity and Haake), but also at the paper sheet in terms of water retention and printability.
Ces documents portent un éclairage très appuyé sur l'agent de réticulation qui apparaît comme un élément essentiel de l'étape d' extrusion. Cet agent réticulant, qui est présent au sein de l'extrudeuse et va donc réagir avec la matière amylacée au sein de l'extrudeuse, peut être introduit, ajouté à l'amidon juste avant d'être introduit dans l'extrudeuse (pré-mélange) et / ou introduit directement dans l'extrudeuse, préférentiellement directement dans l'extrudeuse. L'agent réticulant est réversible ou non. Dans la catégorie des agents réticulants réversibles, ces documents citent les polyaldéhydes et notamment les dialdéhydes, tels que le glutaraldéhyde, le glyoxal et les carbohydrates , le glyoxal étant le plus préféré. Parmi les agents réticulants non réversibles, on peut citer 1 ' épichlorhydrine . On note que seul le glyoxal est illustré dans les exemples, sans aucune preuve que les autres agents cités fonctionnent bel et bien dans le procédé décrit. These documents bear a very strong light on the crosslinking agent which appears as an essential element of the extrusion stage. This crosslinking agent, which is present in the extruder and will therefore react with the starchy material in the extruder, may be introduced, added to the starch just before being introduced into the extruder (pre- mixture) and / or introduced directly into the extruder, preferably directly into the extruder. The crosslinking agent is reversible or not. In the category of reversible crosslinking agents, these documents mention the polyaldehydes and especially the dialdehydes, such as glutaraldehyde, glyoxal and carbohydrates, with glyoxal being the most preferred. Among the non-reversible crosslinking agents, there may be mentioned epichlorohydrin. It is noted that only the glyoxal is illustrated in the examples, without any evidence that the other agents mentioned do indeed work in the process described.
Or, le glyoxal présente des inconvénients à bon nombre d'égards. Il est la plupart du temps délivré sous forme de solutions aqueuses très acides donc corrosives (pH voisin de 2) . De plus, il s'agit d'un composé extrêmement réactif, pouvant réagir violemment avec les oxydants, les acides et les bases fortes. En outre, comme tous les aldéhydes, il est fortement irritant pour la peau et les muqueuses. Enfin, le glyoxal est un produit dit « CMR » : mutagène et toxique pour la reproduction. Il est étiqueté H341, ce qui signifie qu'il est susceptible d'induire des anomalies génétiques. However, glyoxal has disadvantages in many respects. Most of the time, it is delivered in the form of aqueous solutions that are very acidic and therefore corrosive (pH close to 2). In addition, it is an extremely reactive compound that can react violently with oxidants, acids and strong bases. In addition, like all aldehydes, it is highly irritating to the skin and mucous membranes. Finally, glyoxal is a product called "CMR": mutagenic and toxic for reproduction. It is labeled H341, which means that it is likely to induce genetic abnormalities.
Par conséquent, il existe un problème technique non résolu, consistant à trouver un agent réticulant pouvant se substituer efficacement au glyoxal dans un procédé d'extrusion réactive. Therefore, there is an unsolved technical problem of finding a crosslinking agent that can effectively substitute for glyoxal in a reactive extrusion process.
Travaillant dans ce sens, la Demanderesse est parvenue à démontrer que les polyphosphates et notamment le trimétaphosphate de sodium répondaient à ces exigences. Working in this direction, the Applicant has succeeded in demonstrating that polyphosphates and especially sodium trimetaphosphate meet these requirements.
Aussi, un premier objet de la présente invention consiste en un procédé de fabrication de particules constituées d' au moins une matière amylacée, ledit procédé comprenant : Also, a first object of the present invention consists in a process for producing particles consisting of at least one starchy material, said process comprising:
a) au moins une étape d'extrusion d'au moins une matière amylacée, en présence d'au moins un agent réticulant, b)une étape de granulation, c) éventuellement une étape de broyage, d) éventuellement une étape de mise en dispersion dans un solvant. a) at least one extrusion step of at least one starchy material, in the presence of at least one crosslinking agent, b) a granulation step, c) optionally a grinding step, d) optionally a dispersion step in a solvent.
caractérisé en ce que l'agent réticulant est un polyphosphate . characterized in that the crosslinking agent is a polyphosphate.
Le document WO 2004/085481 divulgue un procédé de fabrication de particules d'une matière amylacée par extrusion, la dite extrusion ayant lieu sur une matière amylacée réticulée au préalable. En effet, il est stipulé notamment en page 4 lignes 24 à 28 qu'on forme initialement une pâte par mélange entre l'amidon, l'eau, un alcalin et un agent réticulant et que la dite pâte est ensuite introduite dans une extrudeuse. WO 2004/085481 discloses a process for producing particles of a starchy material by extrusion, said extrusion taking place on a previously crosslinked starchy material. Indeed, it is stipulated in particular on page 4 lines 24 to 28 that initially forms a paste by mixing between the starch, water, an alkali and a crosslinking agent and that said paste is then introduced into an extruder.
L'article de Bi Zheng Li et collaborateurs, Journal of Food Engineering 92 (2009) 255-260, divulgue un procédé de fabrication de particules d'une matière amylacée réticulée par du trimétaphosphate de sodium. Cet articule divulgue nullement une étape d' extrusion ou un quelconque traitement ou malaxage de matière amylacée sous de fortes contraintes de cisaillement en présence de trimétaphosphate de sodium. The article by Bi Zheng Li et al., Journal of Food Engineering 92 (2009) 255-260, discloses a process for making particles of starchy material crosslinked with sodium trimetaphosphate. This articule does not disclose an extrusion step or any treatment or kneading of starchy material under high shear stresses in the presence of sodium trimetaphosphate.
Le procédé objet de la présente demande consiste, plus particulièrement, en un procédé de fabrication de particules constituées d'au moins une matière amylacée, ledit procédé comprenant : The process that is the subject of the present application consists, more particularly, in a process for producing particles made of at least one starchy material, said process comprising:
a) au moins une étape d' extrusion d'au moins une matière amylacée, en présence d'au moins un agent réticulant, b)une étape de granulation,  a) at least one step of extruding at least one starchy material, in the presence of at least one crosslinking agent, b) a granulation step,
c) éventuellement une étape de broyage,  c) optionally a grinding stage,
d) éventuellement une étape de mise en dispersion dans un solvant. caractérisé en ce que l'agent réticulant est un polyphosphate et en ce que l'étape a) d'extrusion est réalisée par introduction de la matière amylacée, du polyphosphate et d'un solvant dans 1 ' extrudeuse . d) optionally a dispersion step in a solvent. characterized in that the crosslinking agent is a polyphosphate and in that the extrusion step a) is carried out by introducing the starchy material, the polyphosphate and a solvent into the extruder.
Dans une variante préférée du procédé objet de la présente invention, le polyphosphate est le trimétaphosphate de sodium . In a preferred variant of the process that is the subject of the present invention, the polyphosphate is sodium trimetaphosphate.
L'étape a) d'extrusion du procédé selon l'invention est réalisée dans une extrudeuse : ce dispositif est le lieu de forces de cisaillement importantes qui s'appliquent à l'amidon ou à la matière amylacée. En outre, cette étape est réalisée à une température au moins égale à 40 °C, préférentiellement à au moins 50 °C, très préférentiellement à au moins 60 °C, mais dans tous les cas à une température inférieure à la température de dégradation de la matière amylacée ; le choix de cette température relève des compétences normales de l'homme du métier, au regard des caractéristiques physico-chimique des matières mises en œuvre. The extrusion step a) of the process according to the invention is carried out in an extruder: this device is the site of important shearing forces that apply to the starch or the starchy material. In addition, this step is carried out at a temperature at least equal to 40 ° C, preferably at least 50 ° C, very preferably at least 60 ° C, but in all cases at a temperature below the degradation temperature of starchy material; the choice of this temperature is within the normal skills of those skilled in the art, with regard to the physicochemical characteristics of the materials used.
Le procédé génère une pression comprise entre 5 bars et 150 bars  The process generates a pressure of between 5 bar and 150 bar
Plus particulièrement l'étape a) d'extrusion est réalisée par introduction de la matière amylacée non réticulée et du polyphosphate dans 1 ' extrudeuse . Selon le procédé objet de l'invention, la matière amylacée ou l'amidon est soumis à d'importantes forces de cisaillement en présence de l'agent réticulant dans une extrudeuse. La réticulation de l'amidon a donc lieu au sein de 1 ' extrudeuse . More particularly, the extrusion step a) is carried out by introducing the non-crosslinked starchy material and the polyphosphate into the extruder. According to the process which is the subject of the invention, the starchy material or the starch is subjected to high shearing forces in the presence of the crosslinking agent in a extruder. Crosslinking of the starch therefore takes place within the extruder.
Plus particulièrement, le procédé objet de l'invention consiste donc en un procédé de fabrication de particules constituées d'au moins une matière amylacée réticulée, ledit procédé comprenant : a) au moins une étape d'extrusion d'au moins une matière amylacée, en présence d'au moins un agent réticulant, b)une étape de granulation, l'agent réticulant étant un polyphosphate et l'étape d'extrusion comprenant : More particularly, the process which is the subject of the invention therefore consists of a process for producing particles consisting of at least one crosslinked starchy material, said process comprising: a) at least one step of extruding at least one starchy material, in the presence of at least one crosslinking agent, b) a granulation step, the crosslinking agent being a polyphosphate and the extrusion step comprising:
i) une étape d'introduction de la matière amylacée, de l'agent réticulant et d'un solvant dans une extrudeuse  i) a step of introducing the starchy material, the crosslinking agent and a solvent into an extruder
ii) une étape de malaxage de la matière amylacée sous fortes cisaillement en présence de l'agent réticulant .  ii) a step of kneading the high shear starchy material in the presence of the crosslinking agent.
La matière amylacée non réticulée est introduite en général dans les premières zones de l' extrudeuse, en zone 1 ou en pied d' extrudeuse, mais peut également être introduite dans n'importe quelle zone à l'exclusion de la dernière. Cette introduction peut être réalisée par insertion gravimétrique par le dessus de l' extrudeuse ou via l'emploi de systèmes d'introduction spécifiques connus de l'homme de l'art comme des « side-feeder » par exemple. The noncrosslinked starchy material is generally introduced into the first zones of the extruder, in zone 1 or at the bottom of the extruder, but may also be introduced into any zone other than the latter. This introduction can be achieved by gravimetric insertion from above the extruder or by the use of specific introduction systems known to those skilled in the art as "side-feeder" for example.
La matière amylacée peut être introduite en mélange avec une autre matière amylacée et/ou en mélange avec un autre constituant différent d'une matière amylacée. Comme exemple d'autre constituant différent d'une matière amylacée on peut citer les agents antimicrobiens, les plastifiants autres que l'eau tels que les polyols (e.g éthylène glycol, propylène glycol, glycérol, maltose) , l'urée, le lactate de sodium etc. Ce mélange est donc introduit en général en zone 1, mais peut l'être également dans toute zone de l'extrudeuse à l'exclusion de la dernière. A ce titre, le mélange peut être obtenu par homogénéisation dans un dispositif du type « dry-blend ». The starchy material may be introduced in admixture with another starchy material and / or in admixture with another constituent other than a starchy material. For example other constituent different from a starchy material include antimicrobial agents, plasticizers other than water such as polyols (eg ethylene glycol, propylene glycol, glycerol, maltose), urea, sodium lactate etc. . This mixture is therefore generally introduced in zone 1, but can be introduced in any zone of the extruder other than the last one. As such, the mixture can be obtained by homogenization in a device of the "dry-blend" type.
La matière amylacée peut également ou selon une autre variante être introduite en combinaison avec une autre matière amylacée et/ou avec un autre constituant différent d'une matière amylacée, non pas sous la forme d'un mélange mais séparément. Selon cette variante, les ingrédients sont introduits séparément soit dans la même zone (dans n'importe quelle zone à l'exception de la dernière zone mais de préférence dans les premières zones de l'extrudeuse ou en pied), soit dans des zones distinctes. The starchy material may also or according to another variant be introduced in combination with another starchy material and / or with another constituent different from a starchy material, not in the form of a mixture but separately. According to this variant, the ingredients are introduced separately either in the same zone (in any zone with the exception of the last zone but preferably in the first zones of the extruder or in the foot), or in separate zones. .
Dans tous les cas, lorsque les ingrédients sont introduits de manière séparée, ils le sont à partir de systèmes de dosages classiques bien connus de l'homme du métier. L'étape a) d'extrusion d'au moins une matière amylacée est réalisée, outre par introduction dans l'extrudeuse de la matière amylacée à réticuler et de l'agent de réticulation, en l'espèce le polyphosphate, par introduction dans l'extrudeuse d'au moins un solvant, de préférence d'un solvant. L'extrusion a en effet lieu dans un milieu solvant. In all cases, when the ingredients are introduced separately, they are introduced from conventional dosing systems well known to those skilled in the art. Step a) of extruding at least one starchy material is carried out, further by introducing into the extruder the starchy material to be crosslinked and the crosslinking agent, in this case polyphosphate, by introduction into the extruder of at least one solvent, preferably a solvent. The extrusion indeed takes place in a solvent medium.
Ainsi l'étape a) d'extrusion est réalisée par introduction dans l'extrudeuse d'au moins un solvant, choisi parmi l'eau et les solvants hydroalcooliques. Préférentiellement il s'agit de l'eau. Ce solvant ou mélange de solvants est employé pour déstructurer la fraction amylacée. En d'autres termes le solvant notamment peut agir, agit comme plastifiant. Le solvant ou mélange de solvants peut être introduit dans n'importe quelle zone de 1 ' extrudeuse . Thus the extrusion step a) is carried out by introduction into the extruder of at least one solvent, selected from water and hydroalcoholic solvents. Preferentially it is water. This solvent or solvent mixture is used to destructure the starch fraction. In other words, the solvent in particular can act, acts as a plasticizer. The solvent or solvent mixture can be introduced into any zone of the extruder.
Ainsi le solvant ou mélange de solvant peut être introduit après que la matière amylacée à réticuler et l'agent réticulant (le polyphosphate) aient été introduits dans l' extrudeuse Thus, the solvent or solvent mixture can be introduced after the starchy material to be crosslinked and the crosslinking agent (the polyphosphate) have been introduced into the extruder.
Plus le solvant ou mélange de solvants est ajouté vers la fin de l' extrudeuse, plus la durée de déstructuration de l'amidon sera réduite et donc le taux de déstructuration de la matière amylacée ou amidon sera faible.  The more the solvent or solvent mixture is added towards the end of the extruder, the shorter the destructuring time of the starch will be and therefore the rate of destructuring of the starchy material or starch will be low.
II est également possible d'envisager des systèmes où le solvant est injecté avant l'introduction de la matière amylacée dans 1 ' extrudeuse . It is also possible to envisage systems where the solvent is injected before the introduction of the starchy material into the extruder.
Toujours selon une autre variante du procédé objet de l'invention, le solvant et la matière amylacée sont introduits simultanément sous forme de dispersion aqueuse de matière amylacée de type « slurry ».  Still according to another variant of the method which is the subject of the invention, the solvent and the starchy material are introduced simultaneously in the form of an aqueous dispersion of starchy material of the "slurry" type.
Dans ce procédé, l'agent réticulant, en l'espèce le polyphosphate et plus préférentiellement le trimétaphosphate de sodium, qui est introduit dans l' extrudeuse et qui va réagir avec la matière amylacée uniquement au sein de l' extrudeuse, peut être soit ajouté à l'amidon juste avant d'être introduit dans l' extrudeuse (pré-mélange) soit introduit directement dans l' extrudeuse comprenant déjà la matière amylacée à réticuler, éventuellement en présence d'un solvant. De manière préférée, l'agent réticulant est introduit directement dans 1 ' extrudeuse . L'agent réticulant, en l'espèce le polyphosphate, représente de 0,1 % à 10 % en poids sec par rapport au poids sec de matière amylacée mise en œuvre. In this process, the crosslinking agent, in this case the polyphosphate and more preferably the sodium trimetaphosphate, which is introduced into the extruder and which will react with the starchy material only within the extruder, may be either added the starch just before being introduced into the extruder (premix) is introduced directly into the extruder already comprising the starchy material to be crosslinked, optionally in the presence of a solvent. Preferably, the crosslinking agent is introduced directly into the extruder. The crosslinking agent, in this case polyphosphate, represents from 0.1% to 10% by dry weight relative to the dry weight of starch material used.
La zone d' introduction du polyphosphate et en particulier sa position relative par rapport à la zone d' introduction du solvant (notamment l'eau) est un paramètre critique dans l'optique de la maîtrise de la compétition entre la déstructuration de la matière amylacée et de la réaction de réticulation entre les fonctions nucléophiles portées éventuellement par la matière amylacée et au moins un des éventuels autres ingrédients. II a notamment été remarqué que lorsque le solvant (notamment l'eau) était présent dans l'extrudât à raison d'au moins 40 % en poids de l'extrudât au moment où était introduit le polyphosphate, on parvenait à des produits particulièrement avantageux au niveau de leur application. L'extrudât désigne la totalité de la matière présente dans l' extrudeuse, donc au moins la matière amylacée et le solvant, voire d'éventuels autres ingrédients (tels que des plastifiants, lubrifiants, anti-microbiens) . Sans vouloir être tenue à une quelconque théorie, la Demanderesse estime que ces résultats sont liés au contrôle du phénomène de déstructuration de la matière amylacée et de sa teneur en phase cristalline, via la régulation particulière de la teneur en solvant. Dans une autre version de l'invention, variante particulièrement préférée, la compétition entre ces deux mécanismes (déstructuration-réticulation) est gérée, contrôlée par l'introduction en outre d'un catalyseur alcalin, qui participe à la déstructuration de l'amidon. Dans ce cas de figure, l'étape a) d'extrusion est comprend en outre l'introduction dans l'extrudeuse d'un catalyseur alcalin. On préférera alors introduire l'agent réticulant, en l'espèce le polyphosphate, avant ledit catalyseur alcalin (le polyphosphate est donc sous sa forme non activée) dans le milieu réactionnel : ceci permet de disperser efficacement le polyphosphate dans la matière. Le catalyseur alcalin est alors choisi parmi les oxydes et hydroxydes alcalins et alcalino-terreux, notamment l'hydroxyde de sodium. Le catalyseur alcalin est de préférence introduit dans l'extrudeuse sous la forme d'une solution ou dispersion aqueuse. De préférence, le procédé selon l'invention est un procédé de fabrication de particules constituées d' au moins une matière amylacée réticulée, comprenant : a) au moins une étape d'extrusion d'au moins une matière amylacée, en présence d'au moins un agent réticulant et The zone of introduction of the polyphosphate and in particular its relative position with respect to the zone of introduction of the solvent (in particular the water) is a critical parameter in the optics of the control of the competition between the destructuration of the starchy matter. and the crosslinking reaction between the nucleophilic functions carried by the amylaceous material and at least one of the possible other ingredients. In particular, it was noted that when the solvent (especially water) was present in the extrudate at a rate of at least 40% by weight of the extrudate at the moment when the polyphosphate was introduced, particularly advantageous products were obtained. at the level of their application. The extrudate designates all of the material present in the extruder, therefore at least the starchy material and the solvent, and possibly other ingredients (such as plasticizers, lubricants, antimicrobials). While not wishing to be bound by any theory, the Applicant believes that these results are related to the control of the phenomenon of destructuring of the starchy material and of its content in the crystalline phase, via the particular regulation of the solvent content. In another version of the invention, a particularly preferred variant, the competition between these two mechanisms (destructuration-crosslinking) is managed, controlled by the addition of a catalyst alkaline, which participates in the destructuring of starch. In this case, the extrusion step a) further comprises introducing into the extruder an alkaline catalyst. It will then be preferable to introduce the crosslinking agent, in this case the polyphosphate, before the said alkaline catalyst (the polyphosphate is thus in its non-activated form) in the reaction medium: this makes it possible to disperse the polyphosphate effectively in the material. The alkaline catalyst is then chosen from alkali and alkaline earth oxides and hydroxides, especially sodium hydroxide. The alkaline catalyst is preferably introduced into the extruder as an aqueous solution or dispersion. Preferably, the process according to the invention is a process for producing particles consisting of at least one crosslinked starchy material, comprising: a) at least one step of extruding at least one starchy material, in the presence of at least one less a crosslinking agent and
b) une étape de granulation, caractérisé en ce que l'agent réticulant est un polyphosphate et en ce que l'étape a) d'extrusion comprend : i) une étape d'introduction dans une extrudeuse de la matière amylacée dans une première zone d'introduction de l'extrudeuse, de l'agent réticulant dans une deuxième zone, d'au moins un solvant dans une troisième zone, et du catalyseur alcalin dans une quatrième zone, la deuxième zone et la quatrième zone étant différentes, ii) une étape de malaxage de la matière amylacée sous fortes cisaillement en présence notamment de l'agent réticulant. Selon une première variante du procédé selon l'invention, la première zone et la deuxième zone sont identiques. L'introduction de la matière amylacée et de l'agent réticulant peut alors être réalisée de manière séparée ou en pré-mélange. b) a granulation step, characterized in that the crosslinking agent is a polyphosphate and in that the extrusion step a) comprises: i) a step of introduction into an extruder of the starchy material in a first zone introducing the extruder, the crosslinking agent into a second zone, at least one solvent into a third zone, and the alkaline catalyst into a fourth zone, the second zone and the fourth zone being different, ii) a step of kneading the starchy material under high shear in the presence in particular of the crosslinking agent. According to a first variant of the method according to the invention, the first zone and the second zone are identical. The introduction of the starchy material and the crosslinking agent can then be carried out separately or in premix.
Dans cette variante, la première zone est située en amont de la troisième zone elle-même située en amont de la quatrième zone. In this variant, the first zone is located upstream of the third zone itself upstream of the fourth zone.
Selon une deuxième variante du procédé selon l'invention, la deuxième zone et la troisième zone sont identiques. L'introduction de l'agent réticulant et du solvant peut alors être réalisée de manière séparée ou en pré-mélange. Dans cette variante, la première zone est située en amont de la deuxième zone elle-même située en amont de la quatrième zone. According to a second variant of the method according to the invention, the second zone and the third zone are identical. The introduction of the crosslinking agent and the solvent can then be carried out separately or in premix. In this variant, the first zone is located upstream of the second zone itself located upstream of the fourth zone.
Selon une troisième variante du procédé selon l'invention, les première, deuxième et troisième zones sont identiques. L'introduction de la matière amylacée, de l'agent réticulant et du solvant peut alors être réalisée de manière séparée ou en pré-mélange. According to a third variant of the method according to the invention, the first, second and third zones are identical. The introduction of the starchy material, the crosslinking agent and the solvent can then be carried out separately or in premix.
Dans cette variante, la première zone est située en amont de la quatrième zone.  In this variant, the first zone is located upstream of the fourth zone.
Selon une quatrième variante du procédé selon l'invention, la première zone et la quatrième zone sont identiques. L' introduction de la matière amylacée et du catalyseur alcalin peut alors être réalisée de manière séparée ou en pré-mélange . According to a fourth variant of the method according to the invention, the first zone and the fourth zone are identical. The introduction of the starchy material and the catalyst alkali can then be carried out separately or in premix.
Dans cette variante, la première zone est située en amont de la troisième zone elle-même située en amont de la deuxième zone.  In this variant, the first zone is located upstream of the third zone itself located upstream of the second zone.
La matière amylacée peut être choisie parmi les « amidons granulaires ». On entend ici par « amidon granulaire », un amidon natif ou modifié physiquement, chimiquement ou par voie enzymatique, ayant conservé, au sein des granules d'amidon, une structure semi-cristalline similaire à celle mise en évidence dans les grains d'amidon présents naturellement dans les organes et tissus de réserve des végétaux supérieurs, en particulier dans les graines de céréales, les graines de légumineuses, les tubercules de pomme de terre ou de manioc, les racines, les bulbes, les tiges et les fruits. Cet état semi-cristallin est essentiellement dû aux macromolécules d' amylopectine, l'un des deux constituants principaux de l'amidon. A l'état natif, les grains d'amidon présentent un taux de cristallinité qui varie de 15 % à 45 %, et qui dépend essentiellement de l'origine botanique de l'amidon et du traitement éventuel qu'il a subi. L'amidon granulaire, placé sous lumière polarisée, présente une croix noire caractéristique, dite croix de Malte, typique de l'état granulaire . The starchy material may be chosen from "granular starches". The term "granular starch" is used herein to mean a starch which is native or physically modified, chemically or enzymatically, and which has retained, within the starch granules, a semicrystalline structure similar to that evidenced in starch grains. naturally occurring in reserve organs and tissues of higher plants, particularly in cereal grains, legume seeds, potato or cassava tubers, roots, bulbs, stems and fruits. This semi-crystalline state is essentially due to macromolecules of amylopectin, one of the two main constituents of starch. In the native state, the starch grains have a degree of crystallinity which varies from 15% to 45%, and which essentially depends on the botanical origin of the starch and the possible treatment that it has undergone. Granular starch, placed under polarized light, has a characteristic black cross, so-called Maltese cross, typical of the granular state.
Selon l'invention, l'amidon granulaire peut provenir de toutes origines botaniques, y compris un amidon granulaire riche en amylose ou, inversement, riche en amylopectine (waxy) . Il peut s'agir d'amidon natif de céréales telles que le blé, le maïs, l'orge, l'amarante, le triticale, le sorgo ou le riz, de tubercules tels que la pomme de terre ou le manioc, ou de légumineuses telles que le pois, le haricot mango et le soja, et de mélanges de tels amidons. According to the invention, the granular starch can come from all botanical origins, including a granular starch rich in amylose or conversely, rich in amylopectin (waxy). It may be native cereal starch such as wheat, corn, barley, amaranth, triticale, sorghum or rice, tubers such as potato or cassava, or legumes such as pea, mango bean and soy, and mixtures of such starches.
Selon une variante, l'amidon granulaire est un amidon hydrolysé par voie acide, oxydante ou enzymatique, ou un amidon oxydé. Il peut s'agir d'un amidon communément appelé amidon fluidifié ou d'une dextrine blanche. According to one variant, the granular starch is an acid hydrolyzed, oxidizing or enzymatic starch, or an oxidized starch. It can be a starch commonly called fluidized starch or a white dextrin.
Selon une autre variante, il peut s'agir également d'un amidon modifié par voie physico-chimique mais ayant essentiellement conservé la structure de l'amidon natif de départ, comme notamment les amidons estérifiés et/ou éthérifiés, en particulier modifiés par acétylation, hydroxypropylation, cationisation, réticulation, phosphatation, ou succinylation, ou les amidons traités en milieu aqueux à basse température (en anglais « annealing ») . De préférence, l'amidon granulaire est un amidon natif, hydrolysé, oxydé ou modifié, en particulier de maïs, de blé, de pois ou de pomme de terre. According to another variant, it may also be a starch modified physico-chemically but having essentially retained the structure of the native starch starting, such as in particular esterified and / or etherified starches, in particular modified by acetylation , hydroxypropylation, cationization, crosslinking, phosphatation, or succinylation, or starches treated in aqueous medium at low temperature (in English "annealing"). Preferably, the granular starch is a native, hydrolysed, oxidized or modified starch, in particular corn, wheat, peas or potato.
L'amidon granulaire présente généralement un taux de solubles à 20°C dans l'eau déminéralisée, inférieur à 5 % en masse. Il est de préférence quasiment insoluble dans l'eau froide. Granular starch generally has a degree of soluble at 20 ° C in demineralized water, less than 5% by weight. It is preferably almost insoluble in cold water.
Selon une seconde variante, la matière amylacée peut être un amidon hydrosoluble, pouvant provenir aussi de toutes origines botaniques, y compris un amidon hydrosoluble riche en amylose ou, inversement, riche en amylopectine (waxy) . Cet amidon hydrosoluble peut être introduit en remplacement partiel ou total de l'amidon granulaire. On entend au sens de l'invention par « amidon hydrosoluble», tout composant amylacé présentant à 20°C et sous agitation mécanique pendant 24 heures, une fraction soluble dans de l'eau déminéralisée au moins égale à 5 % en poids. Cette fraction soluble est de préférence supérieure à 20 % en poids et en particulier supérieure à 50 % en poids. Bien entendu, l'amidon hydrosoluble peut être totalement soluble dans l'eau déminéralisée (fraction soluble = 100 %) . De tels amidons hydrosolubles peuvent être obtenus par prégélatinisation sur tambour, par prégélatinisation sur extrudeuse, par atomisation d'une suspension ou d'une solution amylacée, par précipitation par un non-solvant, par cuisson hydro-thermique, par fonctionnalisation chimique ou autre. Il s'agit en particulier d'un amidon prégélatinisé, extrudé ou atomisé, d'une dextrine hautement transformée (appelée aussi dextrine jaune), d'une maltodextrine, d'un amidon fonctionnalisé ou d'un mélange quelconque de ces produits. According to a second variant, the starchy material may be a water-soluble starch, which may also come from all botanical origins, including a water-soluble starch rich in amylose or, conversely, rich in amylopectin (waxy). This water-soluble starch can be introduced as a partial or total replacement of the granular starch. For the purposes of the invention, the term "water-soluble starch" means any starchy component which, at 20 ° C. and with mechanical stirring for 24 hours, has a soluble fraction in demineralized water of at least 5% by weight. This soluble fraction is preferably greater than 20% by weight and in particular greater than 50% by weight. Of course, the water-soluble starch can be totally soluble in demineralized water (soluble fraction = 100%). Such water-soluble starches can be obtained by pregelatinization on a drum, by pregelatinization on an extruder, by spraying a suspension or a starch solution, by precipitation with a non-solvent, by hydro-thermal cooking, by chemical functionalization or the like. It is in particular a pregelatinized, extruded or atomized starch, a highly converted dextrin (also called yellow dextrin), a maltodextrin, a functionalized starch or any mixture of these products.
Les amidons prégélatinisés peuvent être obtenus par traitement hydro-thermique de gélatinisation d'amidons natifs ou d'amidons modifiés, en particulier par cuisson vapeur, cuisson jet-cooker, cuisson sur tambour, cuisson dans des systèmes de malaxeur / extrudeur puis séchage par exemple en étuve, par air chaud sur lit fluidisé, sur tambour rotatif, par atomisation, par extrusion ou par lyophilisation. De tels amidons présentent généralement une solubilité dans l'eau déminéralisée à 20 C supérieure a 5 ~6 en poids et plus généralement comprise entre 10 % et 100 % et un taux de cristallinité en amidon inférieur à 15 % (en intensité de diffraction RX) , généralement inférieur à 5 % et le plus souvent inférieur à 1 %, voire nul. A titre d'exemple, on peut citer les produits fabriqués et commercialisés par la Demanderesse sous le nom de marque PREGEFLO®. Les dextrines hautement transformées font également partie des matières amylacées qui peuvent être mises en œuvre dans le cadre de l'invention. Elles peuvent être préparées à partir d'amidons natifs ou modifiés, par dextrinification en milieu acide peu hydraté. Il peut s'agir en particulier de dextrines blanches solubles ou de dextrines jaunes. A titre d'exemple, on peut citer les produits STABILYS® A 053 ou TACKIDEX® C 072 fabriqués et commercialisés par la Demanderesse. De telles dextrines présentent dans l'eau déminéralisée à 20°C, une solubilité comprise généralement entre 10 % et 95 % en poids et une cristallinité en amidon inférieure à 15 %, généralement inférieure à 5 %. The pregelatinized starches may be obtained by hydrothermal treatment of gelatinization of native starches or modified starches, in particular by steam cooking, jet-cooker cooking, drum cooking, cooking in kneader / extruder systems, then drying for example. in an oven, by hot air on a fluidized bed, on a rotating drum, by atomization, by extrusion or by lyophilization. Such starches generally have a solubility in demineralised water at 20 ° C. of greater than 5% by weight and more generally of between 10% and 100% and a starch crystallinity level of less than 15% (in X-ray diffraction intensity). , generally less than 5% and most often less than 1%, or even zero. As for example, mention may be made of the products manufactured and marketed by the Applicant under the brand name PREGEFLO®. The highly converted dextrins are also part of the starchy materials that can be used in the context of the invention. They can be prepared from native or modified starches, by dextrinification in acid medium with little hydration. It may be in particular soluble white dextrins or yellow dextrins. By way of example, mention may be made of the STABILYS® A 053 or TACKIDEX® C 072 products manufactured and marketed by the Applicant. Such dextrins present in demineralized water at 20 ° C., a solubility generally of between 10% and 95% by weight and a starch crystallinity of less than 15%, generally less than 5%.
Les maltodextrines et sirops de glucose déshydratés conviennent aussi à la présente invention. Ils peuvent être obtenus par hydrolyse acide, oxydante ou enzymatique d'amidons en milieu aqueux. Ils peuvent présenter en particulier un dextrose équivalent (DE) compris entre 0,5 et 40, de préférence entre 0,5 et 20 et mieux encore entre 0,5 et 12. De telles maltodextrines ou sirops de glucose déshydratés sont par exemple fabriqués et commercialisés par la Demanderesse sous l'appellation commerciale GLUCIDEX® et présentent une solubilité dans l'eau déminéralisée à 20 C généralement supérieure à 90 ~6 , voire proche de 100 %, et une cristallinité en amidon généralement inférieure à 5 % et d'ordinaire quasiment nulle . Les amidons fonctionnalisés peuvent être obtenus à partir d'un amidon natif ou modifié. La fonctionnalisation peut par exemple être réalisée par estérification ou éthérification à un niveau suffisamment élevé pour lui conférer une solubilité dans l'eau. De tels amidons fonctionnalisés présentent une fraction soluble, telle que définie ci-dessus, supérieure à 5 %, de préférence supérieure à 10 %, mieux encore supérieure à 50%. La fonctionnalisation peut s'obtenir en particulier par acétylation en phase aqueuse avec de l'anhydride acétique, par réaction avec des anhydrides mixtes, par hydroxypropylation en phase colle, par cationisation en phase sèche ou phase colle, par anionisation en phase sèche ou phase colle par phosphatation ou succinylation . Les amidons hautement fonctionnalisés hydrosolubles obtenus peuvent présenter un degré de substitution compris entre 0,01 et 3, et mieux encore compris entre 0,05 et 1. De préférence, les réactifs de modification ou de fonctionnalisation de l'amidon sont d'origine renouvelable. Maltodextrins and dehydrated glucose syrups are also suitable for the present invention. They can be obtained by acid, oxidative or enzymatic hydrolysis of starches in an aqueous medium. They may in particular have an equivalent dextrose (DE) of between 0.5 and 40, preferably between 0.5 and 20 and better still between 0.5 and 12. Such dehydrated maltodextrins or glucose syrups are for example manufactured and sold by the Applicant under the trade name GLUCIDEX® and have a solubility in demineralized water at 20 C generally greater than 90 ~ 6, or even close to 100%, and a starch crystallinity generally less than 5% and usually almost zero. The functionalized starches can be obtained from a native or modified starch. The functionalization can for example be carried out by esterification or etherification at a sufficiently high level to confer a solubility in water. Such functionalized starches have a soluble fraction, as defined above, greater than 5%, preferably greater than 10%, more preferably greater than 50%. The functionalization can be obtained in particular by acetylation in aqueous phase with acetic anhydride, by reaction with mixed anhydrides, by hydroxypropylation in the glue phase, by cationization in dry phase or glue phase, by anionization in dry phase or glue phase. by phosphatation or succinylation. The water-soluble highly functionalized starches obtained may have a degree of substitution of between 0.01 and 3, and more preferably between 0.05 and 1. Preferably, the reagents for modification or functionalization of starch are of renewable origin. .
Selon une autre variante avantageuse, l'amidon hydrosoluble est un amidon hydrosoluble de maïs, de blé ou de pois, ou un dérivé hydrosoluble de ceux-ci. De plus, il présente avantageusement une faible teneur en eau, généralement inférieure à 10 %, de préférence inférieure à 5 % , en particulier inférieure à 2,5 % en poids, et idéalement inférieure à 0,5 %, voire inférieure à 0,2 % en poids. Selon une troisième variante, le composant amylacé sélectionné pour la préparation de la composition est un amidon organomodifié, de préférence organosoluble, pouvant provenir aussi de toutes origines botaniques, y compris un amidon organomodifié, de préférence organosoluble, riche en amylose ou, inversement, riche en amylopectine (waxy) . Cet amidon organosoluble peut être introduit en remplacement partiel ou total de l'amidon granulaire ou de l'amidon hydrosoluble . According to another advantageous variant, the water-soluble starch is a water-soluble starch of corn, wheat or peas, or a water-soluble derivative thereof. In addition, it advantageously has a low water content, generally less than 10%, preferably less than 5%, in particular less than 2.5% by weight, and ideally less than 0.5%, or even less than 0%, 2% by weight. According to a third variant, the amylaceous component selected for the preparation of the composition is an organomodified starch, preferably organosoluble, which may also come from all botanical origins, including a organomodified starch, preferably organosoluble, rich in amylose or conversely, rich in amylopectin (waxy). This organosoluble starch may be introduced as partial or total replacement of the granular starch or of the water-soluble starch.
On entend au sens de l'invention par « amidon organomodifié», tout composant amylacé autre qu'un amidon granulaire ou un amidon hydrosoluble selon les définitions données ci-avant. De préférence, cet amidon organomodifié est quasiment amorphe, c'est à dire présentant un taux de cristallinité en amidon inférieur à 5 %, généralement inférieur à 1% et notamment nul. Il est aussi de préférence « organosoluble », c'est à dire présentant à 20°C, une fraction soluble dans un solvant choisi parmi l'éthanol, l'acétate d'éthyle, l'acétate de propyle, l'acétate de butyle, le carbonate de diéthyle, le carbonate de propylène, le glutarate de diméthyle, le citrate de triéthyle, les esters dibasiques, le diméthylsulfoxide (DMSO) , le diméthylisosorbide, le triacétate de glycérol, le diacétate d' isosorbide, le dioléate d' isosorbide et les esters méthyliques d'huiles végétales, au moins égale à 5 % en poids. Cette fraction soluble est de préférence supérieure à 20 % en poids et en particulier supérieure à 50 % en poids. Bien entendu, l'amidon organosoluble peut être totalement soluble dans l'un ou plusieurs des solvants indiqués ci-dessus (fraction soluble = 100%) . For the purposes of the invention, the term "organomodified starch" means any starchy component other than a granular starch or a water-soluble starch according to the definitions given above. Preferably, this organomodified starch is almost amorphous, that is to say having a starch crystallinity level of less than 5%, generally less than 1% and especially zero. It is also preferably "organosoluble", that is to say having at 20 ° C, a fraction soluble in a solvent selected from ethanol, ethyl acetate, propyl acetate, butyl acetate , diethyl carbonate, propylene carbonate, dimethyl glutarate, triethyl citrate, dibasic esters, dimethylsulfoxide (DMSO), dimethylisosorbide, glycerol triacetate, isosorbide diacetate, isosorbide dioleate and methyl esters of vegetable oils, at least equal to 5% by weight. This soluble fraction is preferably greater than 20% by weight and in particular greater than 50% by weight. Of course, the organosoluble starch may be totally soluble in one or more of the solvents indicated above (soluble fraction = 100%).
L'amidon organomodifié peut être utilisé selon l'invention sous forme solide, y compris présentant une teneur en eau peu élevée, à savoir inférieure à 10 % en poids. Elle peut notamment être inférieure à 5 %, en particulier inférieure à 2,5 % en poids et idéalement inférieure à 0,5 ~6 , voire inférieure à 0,2 % en poids. The organomodified starch may be used according to the invention in solid form, including having a low water content, ie less than 10% by weight. In particular, it may be less than 5%, in particular lower than at 2.5% by weight and ideally less than 0.5 ~ 6, or even less than 0.2% by weight.
L'amidon organomodifié utilisable dans la composition selon l'invention peut être préparé par une fonctionnalisation des amidons natifs ou modifiés tels que ceux présentés ci- avant. Cette fonctionnalisation peut par exemple être réalisée par estérification ou éthérification à un niveau suffisamment élevé pour le rendre essentiellement amorphe et pour lui conférer une insolubilité dans l'eau et de préférence une solubilité dans l'un des solvants organiques ci-dessus. De tels amidons fonctionnalisés présentent une fraction soluble telle que définie ci-dessus, supérieure à 5 %, de préférence supérieure à 10 %, mieux encore supérieure à 50 %. The organomodified starch that can be used in the composition according to the invention can be prepared by functionalization of the native or modified starches such as those presented above. This functionalization can for example be carried out by esterification or etherification at a sufficiently high level to make it essentially amorphous and to confer on it an insolubility in water and preferably a solubility in one of the organic solvents above. Such functionalized starches have a soluble fraction as defined above, greater than 5%, preferably greater than 10%, more preferably greater than 50%.
La fonctionnalisation peut s'obtenir en particulier par acétylation en phase solvant par l'anhydride acétique, greffage, par exemple en phase solvant ou par extrusion réactive d'anhydrides d'acides, d'anhydrides mixtes, de chlorures d'acides gras, d' oligomères de caprolactones ou de lactides, hydroxypropylation et réticulation en phase colle, cationisation et réticulation en phase sèche ou en phase colle, anionisation par phosphatation ou succinylation, et réticulation en phase sèche ou en phase colle, silylation, télomérisation au butadiène. The functionalization can be obtained in particular by acetylation in the solvent phase with acetic anhydride, grafting, for example in the solvent phase or by reactive extrusion of acid anhydrides, mixed anhydrides, fatty acid chlorides, oligomers of caprolactones or lactides, hydroxypropylation and crosslinking in the glue phase, cationization and crosslinking in the dry phase or in the glue phase, anionization by phosphatation or succinylation, and crosslinking in the dry phase or in the glue phase, silylation, butadiene telomerization.
Ces amidons hautement fonctionnalisés organomodifiés , de préférence organosolubles , peuvent être en particulier des acétates d'amidons, des dextrines, des maltodextrines des sirops de glucose déshydratés ou des esters gras de ces matières amylacées (amidons, dextrines, maltodextrines des sirops de glucose déshydratés) avec des chaînes grasses de 4 à 22 carbones, l'ensemble de ces produits présentant de préférence un degré de substitution (DS) compris entre 0,5 et 3,0, de préférence compris entre 0,8 et 2,8 et notamment compris entre 1,0 et 2,7. These organomodified, preferably organosoluble, highly functionalized starches can be, in particular, starch acetates, dextrins, maltodextrins of dehydrated glucose syrups or fatty esters of these starchy materials (starches, dextrins, maltodextrins from dehydrated glucose syrups). with fatty chains of 4 to 22 carbons, all of these products preferably having a degree of substitution (DS) of between 0.5 and 3.0, preferably of between 0.8 and 2.8 and in particular of between 1.0 and 2.7.
Il peut s'agir, par exemple, d' hexanoates , d' octanoates , de décanoates, de laurates, de palmitates, d' oléates et de stéarates d'amidon, de dextrines, de maltodextrines des sirops de glucose déshydratés, en particulier présentant un DS compris entre 0,8 et 2,8. Selon une autre variante avantageuse, l'amidon organomodifié est un amidon organomodifié de maïs, de blé ou de pois ou un dérivé organomodifié de ceux-ci. Dans tous les cas, la teneur en matière sèche de matière amylacée dans l'extrudeuse est au moins égale à 40 %, préférentiellement à au moins 50 %, très préférentiellement à au moins 60 % en poids sec du contenu de l'extrudeuse. La ou les matières amylacées utilisées selon l'invention (seule, en mélange ou en combinaison comme déjà indiqué) peuvent donc être mises en œuvre avec d'autres ingrédients. Ces derniers peuvent notamment être choisis parmi la cellulose, la lignine, la carboxyméthylcellulose (CMC) , l' hémicellulose, les polyesters à base de polybutylène succinate, d'acide polylactique ou de polyhydroxyalkanoates, les polyuréthannes thermoplastiques, le gluten, les protéines et notamment les protéines de pois, les polyamides, le guar, le xanthane, la carraghénane, les alginatesf le chitosane, le cassia, la tamarin, l'hémoglobine, la gélatine, les élastomères, les lipides, les triglycérides, les acides gras insaturés ou non, les algues et les micro-algues. La deuxième étape du procédé selon l'invention consiste à granuler l'extrudât en sortie d'extrudeuse. Cette opération est réalisée par tous les moyens disponibles permettant de granuler. It may be, for example, hexanoates, octanoates, decanoates, laurates, palmitates, oleates and stearates of starch, dextrins, maltodextrins, dehydrated glucose syrups, in particular having a DS between 0.8 and 2.8. According to another advantageous variant, the organomodified starch is an organomodified starch of corn, wheat or peas or an organomodified derivative thereof. In all cases, the dry matter content of starchy material in the extruder is at least 40%, preferably at least 50%, very preferably at least 60% by dry weight of the extruder contents. The starchy material (s) used according to the invention (alone, as a mixture or in combination as already indicated) can therefore be used with other ingredients. The latter may especially be chosen from cellulose, lignin, carboxymethylcellulose (CMC), hemicellulose, polyesters based on polybutylene succinate, polylactic acid or polyhydroxyalkanoates, thermoplastic polyurethanes, gluten, proteins and especially pea proteins, polyamides, guar, xanthan, carrageenan, alginates f chitosan, cassia, tamarind, hemoglobin, gelatin, elastomers, lipids, triglycerides, unsaturated fatty acids or no, algae and microalgae. The second step of the process according to the invention consists in granulating the extrudate at the extruder outlet. This operation is performed by all available means for granulating.
La granulation est ensuite suivie d'une étape facultative de broyage (étape c) ) , notamment une étape de broyage mécanique sur un solide, de broyage mécanique après dispersion dans un solvant eau ou hydroalcoolique suivi alors d'une étape d'extraction du solide (par exemple par lyophilisation), ou de broyage cryogénique, l'objectif de ce traitement étant d'opérer une diminution des tailles de particules des granulés issus de l'étape précédente. The granulation is then followed by an optional grinding step (step c), in particular a step of mechanical grinding on a solid, mechanical grinding after dispersion in a water or aqueous-alcoholic solvent, followed by a solid extraction step. (For example by lyophilization), or cryogenic grinding, the objective of this treatment being to make a decrease in the particle sizes of the granules from the previous step.
L'étape de granulation au sens de l'invention peut également comprendre outre la granulation de l'extrudât issu de l'étape d'extrusion une étape de broyage telle que décrite précédemment. The granulation step within the meaning of the invention may also comprise, besides the granulation of the extrudate resulting from the extrusion step, a grinding step as described above.
Selon une variante, la granulation au sens de l'invention peut consister en une étape de broyage telle que décrite précédemment . Enfin, et de manière optionnelle, les granulés issus de l'étape b) ou les particules broyées issues de l'étape c) peuvent être dispersées dans l'eau ou un solvant hydroalcoolique, préférentiellement dans l'eau. De manière avantageuse, on obtient après broyage des particules d'une taille comprise entre environ 100 nm et 500 nm telle que déterminée par granulométrie par diffusion de la lumière, qui peuvent être facilement mises en dispersion aqueuse dans l'eau ou un solvant hydroalcoolique et ce, avec des teneurs en matière sèche d'au moins 20 % en poids sec d'amidon, la dispersion ainsi obtenue s' avérant tout à fait stable dans le temps. According to one variant, the granulation in the sense of the invention may consist of a grinding step as described above. Finally, and optionally, the granules from step b) or the ground particles from step c) can be dispersed in water or a hydroalcoholic solvent, preferably in water. Advantageously, after grinding, particles having a size between about 100 nm and 500 nm are obtained, as determined by light scattering particle size, which can easily be aqueous dispersion in water or a hydroalcoholic solvent and this, with dry matter contents of at least 20% by dry weight of starch, the dispersion thus obtained being quite stable over time.
L'invention vise aussi les particules d'amidon réticulées obtenues selon le procédé précédemment décrit. The invention also relates to the crosslinked starch particles obtained according to the method described above.
Un autre objet de l'invention concerne la mise en dispersion des particules de matière amylacée réticulée obtenue selon le procédé décrit précédemment ainsi que les dispersions dans l'eau ou dans un solvant résultantes. Another subject of the invention concerns the dispersion of the particles of crosslinked starchy material obtained according to the process described above as well as the dispersions in water or in a resulting solvent.
En d'autres termes, d'autres objets de la présente invention sont constitués par les granulés résultant de la mise en œuvre des étapes a) et b) du procédé de l'invention, par les particules broyées ou granulées résultant de la mise en œuvre des étapes a) , b) et c) du procédé de l'invention, par les dispersions dans l'eau ou dans un solvant hydroalcoolique de granulés ou de particules broyées ou granulées, lesdites dispersions résultant de la mise en œuvre des étapes a) , b) et d) ou a) , b) , c) et d) du procédé de l'invention. Enfin, un dernier objet réside dans l'utilisation des dispersions dans l'eau ou dans un solvant hydroalcoolique des granulés ou des particules broyées issues du procédé selon l'invention, dans la fabrication de films humides de manière générale, dans la fabrication du papier et notamment dans la fabrication de sauces de couchage, dans le domaine des médicaments comme vecteur de principe actif, dans la cosmétologie, dans l'agriculture et l'horticulture, dans la nutrition humaine et animale, dans la fabrication de mélanges avec des polymères synthétiques. In other words, other objects of the present invention are constituted by the granules resulting from the implementation of steps a) and b) of the process of the invention, by the crushed or granulated particles resulting from the setting up steps a), b) and c) of the process of the invention, by the dispersions in water or in a hydroalcoholic solvent of granules or crushed or granulated particles, said dispersions resulting from the implementation of the steps a ), b) and d) or a), b), c) and d) of the process of the invention. Finally, a last object resides in the use of dispersions in water or in a hydroalcoholic solvent of the granules or crushed particles resulting from the process according to the invention, in the manufacture of generally wet films, in the manufacture of paper. and in particular in the manufacture of coating coatings, in the field of drugs as a carrier of active principle, in cosmetology, in agriculture and horticulture, in human and animal nutrition, in the manufacture of blends with synthetic polymers.
EXEMPLES EXAMPLES
Concrètement, différents profils de vis peuvent être employés pour maîtriser l'énergie mécanique spécifique transmise à la matière et ainsi contrôler la compétition entre déstructuration de l'amidon et réactions de réticulation . Concretely, different screw profiles can be used to control the specific mechanical energy transmitted to the material and thus control the competition between destructure of the starch and crosslinking reactions.
Un profil de vis est défini à travers les différentes zones qui constituent ladite vis. Chaque zone (Z) est constituée d'un élément particulier (P) assurant notamment le transport ou le cisaillement selon un certain angle de la matière qui y transite. Chaque zone est également associée à une température particulière (T) . A screw profile is defined through the different zones that constitute said screw. Each zone (Z) consists of a particular element (P) ensuring in particular the transport or the shearing at a certain angle of the material passing through it. Each zone is also associated with a particular temperature (T).
Pour les éléments, on utilise les notations suivantes : For elements, we use the following notations:
T : éléments de convoyage à différents pas de vis T: conveying elements with different screw threads
M : éléments de mélange très dispersifs avec une très faible composante de cisaillement M: highly dispersive mixing elements with a very low shear component
C : inclut tous les éléments dont la composante de cisaillement est élevée, c'est-à-dire tous les éléments de cisaillement à 30 45 60 et 90 ° en pas direct, et aussi 30 45 60 ° en pas inverse et éléments de transport ou mélange à pas inverse. C: includes all elements with a high shear component, ie all shear elements at 30 45 60 and 90 ° in direct pitch, and also 45 60 ° in reverse pitch and transport elements or reverse mixing.
Exemple 1 Example 1
Cet exemple illustre l'art antérieur, et correspond notamment à l'extrusion d'un amidon en présence de glyoxal, selon le protocole tel que décrit dans le document EP 1 303 670 en son exemple 2. This example illustrates the prior art, and corresponds in particular to the extrusion of a starch in the presence of glyoxal, according to the protocol as described in document EP 1 303 670 in its example 2.
Un mélange d'amidon natif de maïs (113 parts en poids dont la teneur en eau est égale à 11,5 %) et de glycérol (17,9 parts en poids) est introduit dans une extrudeuse à un taux de 8,22 kg / h et ce au moyen d'une alimentation volumétrique . Ledit mélange est introduit dans la zone 1 de l' extrudeuse qui dispose de 15 zones, et présente un profil de vis et de température représenté en figure 1. La vitesse de vis est fixée à 500 tours / minute. On introduit de l'eau (21 parts) au niveau de la zone 2, à un débit de 0,6 kg / h et ce au moyen d'une pompe piston. Au moyen du même dispositif, on introduit du glyoxal (1,9 parts) et de l'eau au niveau de la zone 5, à un taux de 1,07 kg / h. Au final, la quantité d'eau dans l'extrudât est inférieure à 25 % en poids et notamment 13 % en poids de celle-ci ont été introduits avant l'ajout de l'agent de réticulation (glyoxal) . A mixture of native maize starch (113 parts by weight with a water content of 11.5%) and glycerol (17.9%) parts by weight) is introduced into an extruder at a rate of 8.22 kg / h by means of a volumetric feed. Said mixture is introduced into zone 1 of the extruder which has 15 zones, and has a screw and temperature profile shown in FIG. 1. The screw speed is set at 500 revolutions / minute. Water (21 parts) is introduced at zone 2, at a flow rate of 0.6 kg / h, by means of a piston pump. Using the same device, glyoxal (1.9 parts) and water are introduced at zone 5 at a rate of 1.07 kg / h. In the end, the amount of water in the extrudate is less than 25% by weight and especially 13% by weight thereof were introduced before the addition of the crosslinking agent (glyoxal).
Exemple 2 Example 2
Cet exemple illustre l'art antérieur, et correspond notamment à l'extrusion d'un amidon en présence de glyoxal, selon le protocole tel que décrit dans le document EP 1 303 670 en son exemple 2. This example illustrates the prior art, and corresponds in particular to the extrusion of a starch in the presence of glyoxal, according to the protocol as described in document EP 1 303 670 in its example 2.
Un mélange d'amidon natif de maïs (113 parts en poids dont la teneur en eau est égale à 11,5 %) et de glycérol (17,9 parts en poids) est introduit dans une extrudeuse à un taux de 6,46 kg/h et ce au moyen d'une alimentation volumétrique. Ledit mélange est introduit dans la zone 1 de l' extrudeuse qui dispose de 15 zones, et présente un profil de vis comme représenté sur la figure 2. La vitesse de vis est fixée à 500 tours / minute. On introduit de l'eau (20 parts dont l'eau contenue dans l'amidon natif) au niveau de la zone 2, à un débit de 0,5 kg / h et ce au moyen d'une pompe piston. Au moyen du même dispositif, on introduit du glyoxal (1 part) et de l'eau au niveau de la zone 5, à un taux de 1,39 kg / h. Au final, la quantité d'eau dans l'extrudât est inférieure à 31 % en poids et notamment 14 % en poids de celle-ci ont été introduits avant l'ajout de l'agent de réticulation (glyoxal) . A mixture of native maize starch (113 parts by weight with a water content of 11.5%) and of glycerol (17.9 parts by weight) is introduced into an extruder at a rate of 6.46 kg. / h by means of a volumetric feed. Said mixture is introduced into zone 1 of the extruder which has 15 zones, and has a screw profile as shown in FIG. 2. The screw speed is set at 500 revolutions / minute. Water (20 parts including the water contained in the native starch) is introduced at zone 2, at a flow rate of 0.5 kg / h, by means of a piston pump. Using the same device, glyoxal (1 part) and water are introduced at zone 5, at a rate of 1.39. kg / h. In the end, the amount of water in the extrudate is less than 31% by weight and especially 14% by weight thereof were introduced before the addition of the crosslinking agent (glyoxal).
Exemple 3 Example 3
Cet exemple illustre l'invention. De l'amidon natif de maïs (113 parts en poids dont la teneur en eau est égale à 12 %) est introduit dans une extrudeuse à un taux de 4,94 kg / h et ce au moyen d'une alimentation volumétrique . Il est introduit dans la zone 1 de l' extrudeuse qui dispose de 15 zones, et présente un profil de vis comme représenté sur la figure 3. La vitesse de vis est fixée à 500 tours / minute. On introduit de l'eau (170,4 parts incluant l'eau de l'amidon natif) au niveau de la zone 2, à un débit de 0,5 kg / h et ce au moyen d'une pompe piston. Au moyen du même dispositif, on introduit du trimétaphosphate de sodium (2,3 parts) en solution au niveau de la zone 5, à un taux de 0,1 kg / h. Au niveau de la zone 9, on introduit une solution d'hydroxyde de sodium (0,74 part), à un taux de 0,032 kg / h. Au final, la quantité d'eau dans l'extrudât est égale à 65,5 % en poids et notamment 60 % en poids de celle-ci ont été introduits avant l'ajout de l'agent de réticulation (trimétaphosphate) . This example illustrates the invention. Native maize starch (113 parts by weight with a water content of 12%) is introduced into an extruder at a rate of 4.94 kg / h using a volumetric feed. It is introduced into zone 1 of the extruder which has 15 zones, and has a screw profile as shown in FIG. 3. The screw speed is set at 500 revolutions / minute. Water (170.4 parts including water of the native starch) is introduced at zone 2 at a flow rate of 0.5 kg / h by means of a piston pump. Using the same device, sodium trimetaphosphate (2.3 parts) in solution at zone 5 is introduced at a rate of 0.1 kg / h. At zone 9, a sodium hydroxide solution (0.74 part) is introduced at a rate of 0.032 kg / h. Finally, the amount of water in the extrudate is equal to 65.5% by weight and especially 60% by weight thereof were introduced before the addition of the crosslinking agent (trimetaphosphate).
Exemple 4 Example 4
Cet exemple illustre l'invention ; il est identique au précédent, à la différence que l' extrudeuse possède un profil comme représenté sur la figure 4. Exemple 5 This example illustrates the invention; it is identical to the previous one, with the difference that the extruder has a profile as shown in FIG. 4. Example 5
Cet exemple illustre l'invention ; il est identique à l'exemple 3, à la différence que l'extrudeuse possède un profil comme représenté sur la figure 5. This example illustrates the invention; it is identical to Example 3, with the difference that the extruder has a profile as shown in FIG.
Exemple 6 Example 6
Cet exemple illustre également l'invention. De l'amidon natif de maïs (113 parts en poids dont la teneur en eau est égale à 12 %) est introduit dans une extrudeuse à un taux de 4,94 kg / h et ce au moyen d'une alimentation volumétrique . Il est introduit dans la zone 1 de l'extrudeuse qui dispose de 15 zones, et présente un profil de vis 1 comme représenté sur la figure 6. La vitesse de vis est fixée à 500 tours / minute. On introduit de l'eau (170,4 parts incluant l'eau de l'amidon natif) au niveau de la zone 2, à un débit de 0,5 kg / h et ce au moyen d'une pompe piston. Au moyen du même dispositif, on introduit du trimétaphosphate de sodium (2,3 parts en solution au niveau de la zone 3, à un taux de 0,1 kg / h. Au niveau de la zone 9, on introduit une solution d'hydroxyde de sodium (0,74 part), à un taux de 0, 032 kg / h. Au final, la quantité d'eau dans l'extrudât est égale à 65,5 % en poids et notamment 60 % en poids de celle-ci ont été introduits avant l'ajout de l'agent de réticulation . This example also illustrates the invention. Native maize starch (113 parts by weight with a water content of 12%) is introduced into an extruder at a rate of 4.94 kg / h using a volumetric feed. It is introduced into zone 1 of the extruder which has 15 zones, and has a screw profile 1 as shown in FIG. 6. The screw speed is set at 500 revolutions / minute. Water (170.4 parts including water of the native starch) is introduced at zone 2 at a flow rate of 0.5 kg / h by means of a piston pump. Using the same device, sodium trimetaphosphate (2.3 parts in solution at zone 3, at a rate of 0.1 kg / h) is introduced at the level of zone 9. sodium hydroxide (0.74 part) at a rate of 0.032 kg / hr Finally, the amount of water in the extrudate is equal to 65.5% by weight and especially 60% by weight of that these were introduced before the addition of the crosslinking agent.
Exemple 7 Cet exemple illustre l'invention ; il est identique au précédent, à la différence que l'extrudeuse possède un profil comme représenté sur la figure 7. Exemple 8 Example 7 This example illustrates the invention; it is identical to the previous one, with the difference that the extruder has a profile as shown in FIG. Example 8
Cet exemple illustre l'invention ; il est identique au précédent, à la différence que l'extrudeuse possède un profil comme représenté sur la figure 8 This example illustrates the invention; it is identical to the previous one, with the difference that the extruder has a profile as shown in FIG. 8
Exemple 9 Cet exemple illustre aussi l'invention ; il est identique au précédent, à la différence que l'extrudeuse possède un profil comme représenté sur la figure 9. Example 9 This example also illustrates the invention; it is identical to the previous one, with the difference that the extruder has a profile as shown in FIG. 9.
Exemple 10 Example 10
Cet exemple illustre l'invention ; il est identique à l'exemple 3, mais la vitesse de vis est réglée à 250 tours par minute. Exemple 11 This example illustrates the invention; it is identical to example 3, but the screw speed is set at 250 rpm. Example 11
Cet exemple illustre l'invention ; il est identique à l'exemple 3, à la différence que le trimétaphosphate de sodium est prémélangé à l'amidon et introduit sous cette forme au niveau de la zone 1, alors que la solution de soude est introduite en zone 9 (voir figure 10) . This example illustrates the invention; it is identical to Example 3, with the difference that sodium trimetaphosphate is premixed with starch and introduced in this form at zone 1, whereas the sodium hydroxide solution is introduced in zone 9 (see FIG. ).
Exemple 12 Cet exemple illustre l'invention ; il est identique à l'exemple 11, à la différence que l'eau est introduite avant le mélange d' amidon et de trimétaphosphate de sodium (voir figure 11) . Exemple 13 Example 12 This example illustrates the invention; it is identical to Example 11, with the difference that the water is introduced before the mixture of starch and sodium trimetaphosphate (see FIG. 11). Example 13
Cet exemple illustre l'invention ; il est identique l'exemple 3, à la différence que l'amidon est un amidon pomme de terre. This example illustrates the invention; it is identical to Example 3, with the difference that the starch is a potato starch.
Exemple 14 Example 14
Cet exemple illustre l'invention ; il est identique a l'exemple 3, à la différence que l'amidon est un amidon de riz . This example illustrates the invention; it is identical to Example 3, with the difference that the starch is a rice starch.
Exemple 15 Cet exemple illustre l'invention ; il est identique a l'exemple 3, à la différence que l'amidon est un amidon de pois . Example 15 This example illustrates the invention; it is identical to Example 3, with the difference that the starch is a pea starch.
Exemple 16 Example 16
Cet exemple illustre l'invention ; il est identique à l'exemple 3, à la différence que l'amidon est un amidon de maïs anionique. Exemple 17 This example illustrates the invention; it is identical to Example 3, with the difference that the starch is an anionic corn starch. Example 17
Cet exemple illustre l' invention ; il est identique à l'exemple 3, à la différence que l'amidon est un amidon de maïs cationique. Exemple 18 This example illustrates the invention; it is identical to Example 3, with the difference that the starch is a cationic maize starch. Example 18
Cet exemple illustre l'invention ; il est identique à l'exemple 3, à la différence que l'amidon est un amidon de maïs hydroxypropylé . This example illustrates the invention; it is identical to Example 3, with the difference that the starch is a hydroxypropyl corn starch.
Exemple 19 Example 19
Cet exemple illustre l'invention ; il est identique à l'exemple 3, à la différence que le composé introduit est un mélange d'amidon waxy et de fécule. This example illustrates the invention; it is identical to Example 3, with the difference that the compound introduced is a mixture of waxy starch and starch.
L'ensemble des essais ci-après ont été réalisés sur une extrudeuse de type Leistritz ZSE 27 maxx présentant un rapport L/D=60, et possédant 15 zones. All the tests below were carried out on a Leistritz ZSE 27 maxx type extruder having an L / D ratio of 60, and having 15 zones.
Les poudres sont introduites dans l' extrudeuse au moyen de doseurs gravimétriques solides Schlenck de type Proflex. Les liquides sont introduits dans l' extrudeuse au moyen de doseurs gravimétriques liquides de type Brabender lorsque les débits sont supérieurs à 1 kg/h. Quand les débits des liquides sont inférieurs à 1 kg/h, on utilise des microdoseurs gravimétriques. The powders are introduced into the extruder using Schlenck solid gravimetric feeders of the Proflex type. The liquids are introduced into the extruder by means of Brabender liquid gravimetric feeders when the flow rates are higher than 1 kg / h. When the flow rates of liquids are less than 1 kg / h, gravimetric microdosers are used.
Le profil de température utilisé est donné dans le tableau 1 ci-après. The temperature profile used is given in Table 1 below.
Les profils de vis utilisés sont constitués des éléments suivants : (M=élément de mélange, C = élément de cisaillement, T=élément de transport) The screw profiles used consist of the following elements: (M = mixing element, C = shear element, T = transport element)
Tableau 2  Table 2
La vitesse de vis pout tous les essais répertoriés dans le tableau ci-dessous est fixée à 400 tours/min. Dans tous les exemples les réactifs sont introduits séparément excepté l'essai 26 dans lequel un pré-mélange contenant 10 kg de fécule de pomme de terre, 13,9 kg l'eau et 543 g le trimétaphosphate de sodium (STMP) et 10 g d' Irgasan ®. The screw speed for all the tests listed in the table below is set at 400 rpm. In all the examples the reagents are introduced separately except for test 26 in which a premix containing 10 kg of potato starch, 13.9 kg of water and 543 g of sodium trimetaphosphate (STMP) and 10 gd 'Irgasan ®.
L' Irgasan ® est un agent antimicrobien. Irgasan ® is an antimicrobial agent.
L'Eurylon ® est un amidon de maïs à haute teneur en amylose Les essais 2 à 30 sont selon l'invention. L'essai 1 est non conforme à l'invention. Eurylon ® is a high amylose corn starch. Tests 2 to 30 are according to the invention. Test 1 is not in accordance with the invention.
31 31
Caractérisation du niveau de déstructuration Characterization of the level of destructuring
Afin de caractériser la présence, ou non, de grains crus ou gonflés, des observations de coupe transversale de jonc par microscopie sont réalisées en lumière polarisée à l'aide d'un microscope LEICA (modèle : Leitz DMRB) aux objectifs X10, X20 Pour ce faire, une partie des joncs ainsi obtenus est prélevée, et une coupe transversale du jonc est directement réalisée à l'aide d'une lame de rasoir. Dans le cas des joncs présentant une dureté trop importante, les coupes transversales (d'environ 10ym) peuvent être réalisées à l'aide d'un microtome LEICA (modèle : Jung RM 2055) . Dans ce cas, des morceaux de joncs d'une longueur de 2cm sont découpés, puis fixés sur un support et inclus dans une résine histologique de chez LEICA. Les coupes transversales obtenues sont alors déposées sur une lame dans une solution d'eau et/ou de glycérol, maintenue à 45°C sur un banc chauffant. La préparation est finalement recouverte par une lamelle couvre- objet pour observation. In order to characterize the presence, or not, of raw or swollen grains, microscopic cross section observations are made in polarized light using a LEICA microscope (model: Leitz DMRB) with objectives X10, X20. doing this, a portion of the rods thus obtained is removed, and a cross section of the rod is directly made using a razor blade. In the case of rods with too much hardness, cross sections (about 10 mm) can be made using a LEICA microtome (model: Jung RM 2055). In this case, pieces of rods with a length of 2 cm are cut, then fixed on a support and included in a histological resin from LEICA. The cross sections obtained are then deposited on a slide in a solution of water and / or glycerol, maintained at 45 ° C. on a heating bench. The preparation is finally covered by a coverslip for observation.
Les 2 grossissements X10 et X20 permettent d'apprécier la présence ou l'absence de grains d'amidon non déstructurés. Dans l'essai 1 non conforme à l'invention, on observe une matrice continue d'amidon dans laquelle les grains ne sont plus visibles, car ils ont été totalement déstructurés. A l'inverse, dans les essais 2 à 30 conformes à l'invention, on observe de manière très distincte des croix de polarisation (croix de Malte-polarisation en forme de croix) lors de la présence de grains non cuits (phase cristalline encore présente) . Nous confirmons par ce moyen l'intérêt de l'invention à savoir le contrôle du niveau de déstructuration de l'amidon engagé en fonction du procédé mis en œuvre.  The two magnifications X10 and X20 make it possible to assess the presence or absence of unstructured starch grains. In test 1 not in accordance with the invention, a continuous matrix of starch is observed in which the grains are no longer visible because they have been completely destructured. Conversely, in the tests 2 to 30 in accordance with the invention, polarization crosses (cross-malt cross-polarization) are observed in a very distinct manner during the presence of uncooked grains (still crystalline phase). present) . By this means, we confirm the interest of the invention, namely the control of the level of destructuring of the starch engaged as a function of the process used.

Claims

REVENDICATIONS
1 - Procédé de fabrication de particules constituées d' au moins une matière amylacée, comprenant : a) au moins une étape d'extrusion d'au moins une matière amylacée, en présence d'au moins un agent réticulant, b) une étape de granulation, 1 - Process for producing particles consisting of at least one starchy material, comprising: a) at least one step of extruding at least one starchy material, in the presence of at least one crosslinking agent, b) a step of granulation,
c) éventuellement une étape de broyage,  c) optionally a grinding stage,
d) éventuellement une étape de mise en dispersion dans un solvant . et caractérisé en ce que l'agent réticulant est un polyphosphate et en ce que l'étape a) d'extrusion est réalisée par introduction de la matière amylacée, du polyphosphate et d'un solvant dans 1 ' extrudeuse .  d) optionally a dispersion step in a solvent. and characterized in that the crosslinking agent is a polyphosphate and in that the extrusion step a) is carried out by introducing the starchy material, the polyphosphate and a solvent into the extruder.
2 - Procédé selon la revendication 1, caractérisé en ce que l'étape a) est réalisée à une température au moins égale à 40 °C, préférentiellement à au moins 50 °C, très préférentiellement à au moins 60 °C. 2 - Process according to claim 1, characterized in that step a) is carried out at a temperature of at least 40 ° C, preferably at least 50 ° C, very preferably at least 60 ° C.
3 - Procédé selon l'une des revendications 1 ou 2, caractérisé en ce que le polyphosphate représente de 0,1 % à 10 % en poids sec par rapport au poids sec de matière amylacée . 3 - Process according to one of claims 1 or 2, characterized in that the polyphosphate is from 0.1% to 10% by dry weight relative to the dry weight of starchy material.
4 - Procédé selon l'une quelconque des revendications 1 à 3, caractérisé en ce que le solvant représente au moins 40 % en poids de l'extrudat au moment où est introduit le polyphosphate . 5 - Procédé selon l'une quelconque des revendications 1 à 4, caractérisé en ce que l'étape a) d'extrusion est réalisée avec introduction d'un catalyseur alcalin dans 1 ' extrudeuse . 6 - Procédé selon la revendication 5, caractérisé en ce que le polyphosphate est introduit dans l' extrudeuse avant le catalyseur alcalin. 4 - Process according to any one of claims 1 to 3, characterized in that the solvent is at least 40% by weight of the extrudate at the time when is introduced polyphosphate. 5 - Process according to any one of claims 1 to 4, characterized in that the extrusion step a) is carried out with introduction of an alkaline catalyst into the extruder. 6 - Process according to claim 5, characterized in that the polyphosphate is introduced into the extruder before the alkaline catalyst.
7 - Procédé selon l'une quelconque des revendications 5 ou 6, caractérisé en ce que le catalyseur alcalin est choisi parmi les oxydes et hydroxydes alcalins et alcalino-terreux . 7 - Process according to any one of claims 5 or 6, characterized in that the alkaline catalyst is selected from alkali and alkaline earth oxides and hydroxides.
8 - Procédé selon l'une quelconque des revendications 1 à 7, caractérisé en ce que le solvant de l'étape a) d'extrusion est choisi parmi l'eau et les solvants hydroalcooliques, et est préférentiellement l'eau. 8 - Process according to any one of claims 1 to 7, characterized in that the solvent of the extrusion step a) is selected from water and hydroalcoholic solvents, and is preferably water.
9 - Procédé selon l'une quelconque des revendications 1 à 8, caractérisé en ce que le polyphosphate est le trimétaphosphate de sodium. 9 - Process according to any one of claims 1 to 8, characterized in that the polyphosphate is sodium trimetaphosphate.
10 - Granulés obtenus par le procédé selon l'une des revendications 1 à 9. 11 - Particules broyées obtenues par le procédé selon une des revendications 1 à 9. 10 - Granules obtained by the method according to one of claims 1 to 9. 11 - Crushed particles obtained by the method according to one of claims 1 to 9.
12 - Dispersions dans l'eau ou dans un solvant hydroalcoolique de granulés ou de particules broyées obtenus par le procédé selon l'une des revendications 1 à 9. 13 - Utilisation des granulés selon la revendication 10, des particules broyées selon la revendication 11, des dispersions selon la revendication 12, dans la fabrication de films humides, dans la fabrication du papier et dans la fabrication de sauces de couchage, dans le domaine des médicaments comme vecteur de principe actif, dans la cosmétologie, dans l'agriculture et l'horticulture, dans la nutrition humaine et animale, dans la fabrication de mélanges avec des polymères synthétiques . 12 - Dispersions in water or in a hydroalcoholic solvent of granules or crushed particles obtained by the process according to one of claims 1 to 9. 13 - Use of the granules according to claim 10, crushed particles according to claim 11, dispersions according to claim 12, in the manufacture of wet films, in the manufacture of paper and in the manufacture of coating colors, in the field of medicinal products as a carrier of active principle, in cosmetology, in agriculture and horticulture, in human and animal nutrition, in the manufacture of mixtures with synthetic polymers.
EP13756622.0A 2012-07-31 2013-07-30 Method for the reactive extrusion of an amylaceous material in the presence of a polyphosphate serving as a cross-linking agent, resulting products, and uses thereof Withdrawn EP2880061A1 (en)

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FR1257436A FR2994186B1 (en) 2012-07-31 2012-07-31 PROCESS FOR REACTIVE EXTRUSION OF AMYLACEOUS MATERIAL IN THE PRESENCE OF POLYPHOSPHATE AS CROSSLINKING AGENT, PRODUCTS OBTAINED AND USES THEREOF
PCT/FR2013/051831 WO2014020274A1 (en) 2012-07-31 2013-07-30 Method for the reactive extrusion of an amylaceous material in the presence of a polyphosphate serving as a cross-linking agent, resulting products, and uses thereof

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