EP2859146A1 - Method for producing an emulsion of alkenyl succinic anhydride (asa) in an aqueous solution of a cationic amylaceous substance, resulting emulsion, and use thereof - Google Patents

Method for producing an emulsion of alkenyl succinic anhydride (asa) in an aqueous solution of a cationic amylaceous substance, resulting emulsion, and use thereof

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Publication number
EP2859146A1
EP2859146A1 EP13737311.4A EP13737311A EP2859146A1 EP 2859146 A1 EP2859146 A1 EP 2859146A1 EP 13737311 A EP13737311 A EP 13737311A EP 2859146 A1 EP2859146 A1 EP 2859146A1
Authority
EP
European Patent Office
Prior art keywords
asa
aqueous solution
starchy material
emulsion
unit
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
EP13737311.4A
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German (de)
French (fr)
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EP2859146B1 (en
Inventor
Gilles DUTHOIT
Nicolas Leroy
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
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Roquette Freres SA
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Publication date
Application filed by Roquette Freres SA filed Critical Roquette Freres SA
Publication of EP2859146A1 publication Critical patent/EP2859146A1/en
Application granted granted Critical
Publication of EP2859146B1 publication Critical patent/EP2859146B1/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

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Classifications

    • 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
    • D21H21/00—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties
    • D21H21/14—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties characterised by function or properties in or on the paper
    • D21H21/16—Sizing or water-repelling agents
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01F—MIXING, e.g. DISSOLVING, EMULSIFYING OR DISPERSING
    • B01F23/00—Mixing according to the phases to be mixed, e.g. dispersing or emulsifying
    • B01F23/40—Mixing liquids with liquids; Emulsifying
    • B01F23/41—Emulsifying
    • 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
    • D21H17/03—Non-macromolecular organic compounds
    • D21H17/05—Non-macromolecular organic compounds containing elements other than carbon and hydrogen only
    • D21H17/14—Carboxylic acids; Derivatives thereof
    • D21H17/15—Polycarboxylic acids, e.g. maleic acid
    • 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
    • D21H17/03—Non-macromolecular organic compounds
    • D21H17/05—Non-macromolecular organic compounds containing elements other than carbon and hydrogen only
    • D21H17/14—Carboxylic acids; Derivatives thereof
    • D21H17/15—Polycarboxylic acids, e.g. maleic acid
    • D21H17/16—Addition products thereof with hydrocarbons
    • 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
    • D21H17/29—Starch cationic
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01F—MIXING, e.g. DISSOLVING, EMULSIFYING OR DISPERSING
    • B01F2101/00—Mixing characterised by the nature of the mixed materials or by the application field
    • B01F2101/2204—Mixing chemical components in generals in order to improve chemical treatment or reactions, independently from the specific application

Definitions

  • the present invention relates to a method for the manufacture of an alkenyl succinic anhydride emulsion (ASA) in an aqueous solution of cationic amylaceous material, an emulsion obtained and its use.
  • an aqueous solution of cationic starchy material it being understood that the.
  • the oily phase is constituted by ASA, the starchy solution serving to support said emulsion.
  • aqueous solution of cationic starchy material is meant a composition containing at least one cationic starch in aqueous solution.
  • bonding compositions which contain hydrophobic substances are used. Such compositions are also used in admixture with the fibrous mass of cellulose which is constitutive of the structure of the cardboard or paper (internal bonding) or in application on at least one of the faces of this structure (external bonding, sizing, surfacing or coating).
  • the present invention relates here to the exclusive field of internal bonding.
  • the term "collage” will be used to describe the term "internal collage” as defined above.
  • ASA alkenyl succinic anhydride
  • This chemical species which is not miscible in water must be emulsified in order to be advantageously used in the form of a liquid product: this allows a good contact between the ASA and the cellulose fibers.
  • the ASA emulsion in the aqueous solution of cationic starchy material must have a number of characteristics. In particular, it must have a great fineness of particle sizes, as well as a narrow spectrum of distribution of these sizes ("monodisperse" product). As explained in WO 97/35068 A1, these parameters condition the effectiveness of the bonding composition vis-à-vis the hydrophobicity properties it is supposed to confer.
  • the mean diameter is within an interval that excludes particles of too small size (the average diameter of which is less than 1 ⁇ ⁇ )
  • a "narrow” and “monodisperse” distribution of particle sizes is well defined. distribution centered on the interval from 1 ⁇ to 1.5 ⁇ .
  • the particle sizes are systematically measured from a laser granulometer marketed by MALVERN® under the name Mastersizer® 2000. The corresponding measurement procedure is reported in the experimental part of FIG. this document.
  • the prior art discloses a number of device and method related documents for making ASA emulsions in an aqueous solution of cationic starch material.
  • the general principle is as follows: first of all to carry out an aqueous solution of cationic starchy material, to mix it in a homogeneous manner with the ASA, and finally to obtain an emulsion from this mixture of ASA and of this aqueous solution of matter cationic starch in an emulsification unit.
  • This unit is characterized by the presence of mechanical means of grinding or shearing, which ensure the micronization and dispersion of the particles.
  • this makes it possible for a person skilled in the art to use, especially directly in a paper mill, and free of a recirculation loop: it is a continuous process, which leads to the desired product in a single pass in the emulsification unit.
  • the emulsion resulting from the process according to the invention has a temperature very close to those of the starting materials (ie ASA and cationic starch solution), the slight increase being due to the induced heating. at the single passage in the emulsification unit.
  • the starting materials ie ASA and cationic starch solution
  • systems of the prior art with a recirculation loop lead to significant temperature increases (sometimes more than 40 ° C) by the very principle of recirculation: this increase is detrimental to the final product because accelerates the hydrolysis phenomena of ASA.
  • a first object of the present invention is a method of manufacturing an ASA emulsion in a aqueous solution of cationic starchy material, comprising the steps of: a) producing an aqueous solution of cationic starchy material,
  • step b) mixing ASA and the aqueous solution of cationic starchy material resulting from step a), so as to obtain a dry weight ratio cationic starchy material / ASA of less than 1, preferably between 0.2 and 0, 6, and very preferably between 0.3 and 0.5,
  • step c) producing in a single pass in an emulsification unit an emulsion from the mixture resulting from step b), characterized in that the process does not involve the recirculation of the emulsion resulting from step c) at the level of the emulsification unit,
  • Step a) of producing the aqueous solution of cationic starchy material either consists in providing an aqueous solution of cationic starchy material, as commercially available, or else in diluting it with water, in order to obtain the desired dry matter content.
  • This content between 5.5% and 11.5%, preferably between 7% and 10% of the total weight of the realized solution, is the essential parameter to adjust for this first step.
  • aqueous solutions of cationic starchy materials examples include the products marketed under the VECTOR® SC and IC range ( ROQUETTE®), Raisabond® 15 (CHEMIGATE), Licocat® P (SUEDSTAERKE®), Lyckeby® LP 2145 and LP 1140 (LYCKEBY®), Redisize® 205 and Redibond® 4000 (NATIONAL STARCH®) and Raifix® 25035 and 01035 ( CIBA RAISIO®).
  • Step b) consists, from conventional mixing means, in particular for controlling the mass concentrations of the constituents, to achieve mixing between the aqueous solution of cationic starch material from step a) and the ASA.
  • Step c) consists of circulating in a single pass the mixture which has been obtained in step b), in an emulsification unit.
  • This unit refers to all devices well known to those skilled in the art, including having mechanical means whose purpose is to micronize and disperse homogeneously the liquid that is to be emulsified. Such devices are in particular the Process Pilot DR 2000/4 (I KA®) or Ytron Z (YTRON®) materials.
  • the unit in which the aqueous solution of cationic starchy material (a ') is produced, the mixer (b') and the emulsification unit (c ') are quite conventional devices which are ideally connected to each other. pipes, allowing the circulation of different liquids. Devices within the meaning of the present invention must be understood as devices capable of implementing the method according to the invention, on an industrial scale.
  • the emulsion unit (c ') is in particular connected to the paper machine, so that the emulsion useful for gluing paper or cardboard can be introduced in the wet part, generally at one or two points. introduction.
  • the manufacture of the emulsion consumes at least 5 liters of ASA per hour, preferably at least 10 liters of ASA per hour.
  • the subject of the present invention is in particular a method for producing an ASA emulsion in an aqueous solution of cationic starchy material as described above,
  • Step a) a mixing unit b 'of ASA and an aqueous solution of cationic starchy material, connected with the unit a', for carrying out step b),
  • an emulsification unit c 'of the mixture of ASA and the aqueous solution of cationic starchy material connected with the unit b', for carrying out stage c),
  • said device does not have a recirculation loop at the emulsification unit c '.
  • the process according to the present invention is also characterized in that the ASA is a product preferably of synthetic origin; these are modified oils that result from C16-C18 cuts.
  • ASA is a product preferably of synthetic origin; these are modified oils that result from C16-C18 cuts.
  • Chemsize® A 180 (CHEMEC®).
  • This process is also characterized in that the aqueous solution of cationic starchy material has a fixed nitrogen content of less than 3.5%, preferably between 0.3% and 3.5%, very preferably between 0.7% and 2% by dry weight of nitrogen relative to the total weight of cationic starchy material.
  • This cationic starchy material may optionally be modified from an operation chosen from hydrolysis, chemical and physical, mechanical, thermomechanical or even thermal transformations.
  • a hydrolysis operation very directly aimed at reducing the molecular weight and, in most cases, reducing the viscosity, can be carried out by various means such as chemical, commonly by the action of an acid, a base or an oxidizing agent or by an enzymatic action, most commonly by amylase.
  • Common chemical modifications are of various kinds such as oxidation, especially with hypochlorite, esterification, such as acetylation, etherification, for example, by cationization, carboxymethylation or hydroxypropylation.
  • Physical treatments can be practiced by thermomechanical means, such as extrusion or pregelatinization, or thermal, such as those known to those skilled in the art as Hot Moisture Treatment (HMT) or Annealing. .
  • HMT Hot Moisture Treatment
  • Another subject of the present invention consists of a device consisting of: a ') a storage unit for an aqueous solution of cationic starchy material,
  • b ' a mixing unit of ASA and aqueous solution of cationic starch material, connected with unit a') c ') an emulsification unit of the mixture of ASA and the aqueous solution of cationic starchy material, connected with the unit b ') said device having no recirculation loop at the emulsification unit.
  • Another subject of the present invention consists of an emulsion of ASA in an aqueous solution of cationic starchy material, having: a dry weight ratio cationic starchy material / ASA of less than 1, preferably of between 0.2 and 0.6, and very preferably between 0.3 and 0.5, a particle size distribution such that at least 80% by volume of said particles have a diameter of less than 2 ⁇ , and a mean diameter of between 1 ⁇ and 1.5 ⁇ as determined by laser granulometry by means of a device marketed by MALVERN® under the name astersizer ⁇ 2000.
  • This emulsion is also characterized in that the ASA it contains is a product preferably of synthetic origin.
  • the cationic starchy material which it comprises has a fixed nitrogen content of less than 3.5%, preferably between 0.3% and 3.5%, very preferably between 0.7% and 2% in dry weight of nitrogen relative to the total weight of cationic starchy material.
  • Said cationic starchy material may optionally be modified from an operation chosen from hydrolysis, chemical and physical, mechanical transformations, thermomechanical or thermal as previously indicated.
  • a final object of the present invention is the use of said emulsion in a gluing operation of a sheet of paper or cardboard.
  • Example 1 This example is intended to illustrate the manufacture of ASA emulsion in an aqueous solution of cationic starchy material in the context of a device according to the invention free of a recirculation loop at the unit level. emulsification, and with a device according to the prior art. It also aims to illustrate the influence of the dry matter content of the initial aqueous solution of cationic starchy material on the particle size of the emulsion produced.
  • ASA which is the Chemsize® A180 product marketed by CHEMEC®, is also used. This product contains 0.5% by weight sodium dioctyl sulfosuccinate as surfactant (also called "DOSS").
  • the water supply is from an existing distribution network.
  • the transfers and assays of the ASA and the aqueous solution of cationic starchy material to this emulsification platform are made from their mobile container or respective storage tank, by means of hoses and volumetric pumps, whose speeds of rotation are subject to the desired flow rate and target ratio cationic starch (dry) / ASA.
  • the aqueous solution of cationic starchy material is diluted in line.
  • the dilution water flow rate is controlled by the flow rate of the commercial aqueous cationic starch solution, depending on the desired solids content.
  • a static mixer makes it possible to homogenize this dilute aqueous solution.
  • the ASA is then introduced line, in the dilute and homogeneous aqueous solution of cationic starchy material.
  • This mixture "aqueous solution of cationic starchy material / ASA" is then conveyed via a pipe to the emulsifier.
  • This single-pass and continuous emulsification system has a series of 3 consecutive rotors / stators, each rotor and each stator is composed of 3 rows of concentric serrated crowns. This process operates at variable speed; the speed of rotation depends on the passing hydraulic flow, the nature of the constituents and their proportions, the pressure in the emulsion chamber, as well as the fineness of the desired emulsion.
  • the output of 1 emulsifier is provided with a temperature sensor, a pressure sensor, a valve for maintaining a pressure of 3 bars in the process, and a flow meter.
  • the solids content of the aqueous solution of cationic starchy material was varied from 3% to 20%, the dry cationic starch content / ASA ratio was 0.3 to 0.5, the flow rate at the outlet of the emulsifier from 80 to 140 kg / h, the peripheral speed of the rotor of the emulsifier being fixed at 40 m / s.
  • MA / ASA ratio by dry weight cationic starchy material /
  • T ° (° C) temperature of the final emulsion at the outlet of the emulsifier
  • Table 1 Tests Nos. 1 to 4 demonstrate that, at two given MA / ASA ratios and for a dry extract of cationic starchy material that is too low (3% and 5%), the result is a too large average diameter (in particular much greater than 2 ⁇ for tests n ° 3 and 4) and / or at a value of% ⁇ 2 ⁇ too low.
  • An optimal quantity of particles whose diameter is between 1 ⁇ and 1.5 ⁇ is therefore not available, which means that particles of larger size are generated which can cause fouling problems.
  • tests No. 7 and 8 carried out with a large dry extract of starchy material do not give the desired particle size.
  • This example is intended to illustrate the manufacture of an emulsion from ASA and an aqueous solution of cationic starchy material in the context of a device according to the invention without recirculation loop. It illustrates in particular the influence of the dry matter content of the initial aqueous solution of cationic starchy material on the particle size of the emulsion produced, and on the hydrophobicity of a paper made with this emulsion.
  • This example is made under the same conditions as the previous example, with the difference that the single-pass and continuous emulsification system has a single rotor / stator, each of its two parts being composed of 3 rows of serrated crowns. concentric.
  • the tests No. 12 to 16 implement, in a device according to the invention, an aqueous solution of cationic starch material marketed by the company ROQUETTE ⁇ under the name VECTOR® SCA 2015 and ASA which is the product Chemsize® A180 marketed by CHE EC®.
  • the dry weight ratio cationic starchy material (MA) / ASA is here equal to 0.3.
  • the peripheral speed is set at 40 m / s and the flow rate at the exit of the emulsifier is equal to 140 kg / h.
  • Tests No. 12, 13, 14, 15 and 16 respectively implement a solids content of 2%, 7%. %, 9%, 12% and 16% cationic starchy material at the initial aqueous solution.
  • Example 3 This example is intended to illustrate the manufacture of an emulsion from ASA and an aqueous solution of cationic starchy material in the context of a device according to the invention free of a recirculation loop. It demonstrates in particular that the particle size characteristics of the emulsions manufactured are constant over time.
  • the tests use the VECTOR® SCA 2015 aqueous cationic starch solution and the Chemsize® A180 product. They are made using a device identical to that described in the previous example.
  • Example 2 This example is carried out under the same conditions as in Example 2.
  • the solids content was fixed at 8%, the dry cationic starch content / ASA ratio at 0.32 and the discharge rate of the emulsifier at 220 L / hour. h and the peripheral speed at 40 m / s.
  • 3 granulometric analyzes on 3 samples taken at the instants 45 minutes, 3:00 and 5:00.
  • the% by volume of particles whose diameter is within a certain range has also been determined: the corresponding results are shown in Tables 3, 3a and 3b.

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  • Chemical Kinetics & Catalysis (AREA)
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Abstract

The present invention relates to a method for producing an emulsion of ASA in an aqueous solution of a cationic amylaceous substance, without having to use a loop for recirculating the product at the emulsification unit. The produced emulsion is characterized by both a fine and monodisperse particle size, and no overheating is involved that could lead to negative phenomena of hydrolyzing the ASA. The invention further relates to the corresponding production device.

Description

PROCEDE DE FABRICATION D'UNE EMULSION D'ANHYDRIDE ALKENYLE SUCCINIQUE (ASA) DANS UNE SOLUTION AQUEUSE DE MATIERE AMYLACEE CATIONIQUE, EMULSION OBTENUE ET SON UTILISATION La présente invention vise une méthode de fabrication d'une émulsion d'anhydride alkényle succinique (ASA) dans une solution aqueuse de matière amylacée cationique, étant entendu que la. phase huileuse est constituée par l'ASA, la solution amylacée jouant le rôle de support de ladite émulsion. Par solution aqueuse de matière amylacée cationique, on entend une composition contenant au moins un amidon cationique en solution aqueuse.  The present invention relates to a method for the manufacture of an alkenyl succinic anhydride emulsion (ASA) in an aqueous solution of cationic amylaceous material, an emulsion obtained and its use. an aqueous solution of cationic starchy material, it being understood that the. The oily phase is constituted by ASA, the starchy solution serving to support said emulsion. By aqueous solution of cationic starchy material is meant a composition containing at least one cationic starch in aqueous solution.
Le procédé décrit dans la présente Demande ne met pas en œuvre de boucle de recirculation du produit au niveau de l'unité d' émulsification . L'émulsion ainsi fabriquée dispose d'une granulométrie à la fois fine et monodisperse, et ne présente aucun échauffement qui pourrait conduire à des phénomènes négatifs d'hydrolyse de l'ASA. On fournit ainsi un procédé efficace, simple à mettre en œuvre, notamment sur un site de production papetier, pour délivrer une émulsion qui sera avantageusement utilisée comme agent de collage dans la fabrication de la feuille de papier. Dans le secteur des papiers et autres cartons, les opérations dites de collage visent à conférer à ces supports des propriétés améliorées, notamment en matière d' hydrophobisation, de résistance à la pénétration des espèces hydrophiles comme l'eau et les encres aqueuses. A cet égard, on met en œuvre des compositions dites de « collage » qui contiennent des substances hydrophobes. De telles compositions sont aussi bien utilisées en mélange avec la masse fibreuse de cellulose qui est constitutive de la structure du carton ou du papier (collage interne) ou en application sur au moins une des faces de cette structure (collage externe, encollage, surfaçage ou enduction) . La présente invention se rapporte ici au domaine exclusif du collage interne. Par abus de langage, on désignera sous le simple terme de « collage » l'expression « collage interne » telle que définie plus haut. The process described in the present Application does not implement a recirculation loop of the product at the emulsification unit. The emulsion thus manufactured has a granulometry that is both fine and monodisperse, and presents no heating that could lead to negative hydrolysis phenomena of ASA. This provides an efficient method, simple to implement, especially at a papermaking production site, to deliver an emulsion which will be advantageously used as a bonding agent in the manufacture of the paper sheet. In the sector of paper and other cardboard, so-called gluing operations are intended to confer on these supports improved properties, especially in terms of hydrophobization, resistance to the penetration of hydrophilic species such as water and aqueous inks. In this respect, so-called "bonding" compositions which contain hydrophobic substances are used. Such compositions are also used in admixture with the fibrous mass of cellulose which is constitutive of the structure of the cardboard or paper (internal bonding) or in application on at least one of the faces of this structure (external bonding, sizing, surfacing or coating). The present invention relates here to the exclusive field of internal bonding. By misnomer, the term "collage" will be used to describe the term "internal collage" as defined above.
Un des composés fréquemment mis en œuvre dans les compositions de collage est l'anhydride alkényle succinique ou « ASA » (selon l'acronyme anglo-saxon alkenyl succinic anhydrid) . Cette espèce chimique qui n'est pas miscible dans l'eau doit être mise en émulsion afin d'être utilisée avantageusement sous forme d'un produit liquide : on permet ainsi un bon contact entre l'ASA et les fibres de cellulose. One of the compounds frequently used in bonding compositions is alkenyl succinic anhydride or "ASA" (acronym alkenyl succinic anhydrid). This chemical species which is not miscible in water must be emulsified in order to be advantageously used in the form of a liquid product: this allows a good contact between the ASA and the cellulose fibers.
Pour réaliser cette mise en émulsion, il est connu d'utiliser de manière concomitante des solutions aqueuses de matières amylacées cationiques de différentes natures, la matière amylacée étant éventuellement modifiée ; la fonction de telles compositions est d'éviter la coalescence des particules d'ASA par ionisation positive de la surface des particules, et de rapprocher les particules d'ASA des fibres par un mécanisme ionique. De manière large, on utilise un ratio en poids sec matière amylacée cationique / ASA compris entre 0 , 2 et 4. De telles compositions liquides à base d'ASA et de matière amylacée cationique sont notamment relatées dans les documents WO 96 / 35840 Al et WO 97 / 35068 Al. Elles contiennent éventuellement des tensio-actifs qui augmentent la dispersabilité de l'ASA, ces substances pouvant néanmoins interagir de manière négative avec l'ASA selon l'enseignement du document WO 97 / 35068 Al. To carry out this emulsification, it is known to use, concomitantly, aqueous solutions of cationic starchy materials of different natures, the starchy material being optionally modified; the function of such compositions is to prevent the coalescence of the ASA particles by positive ionization of the surface of the particles, and to bring the ASA particles closer to the fibers by an ionic mechanism. In broad terms, a dry weight ratio of cationic starchy material / ASA of between 0.2 and 4 is used. Such liquid compositions based on ASA and on cationic starchy material are described in particular in documents WO 96/35840 A1 and WO 97/35068 A1. optionally contain surfactants which increase the dispersability of ASA, these substances may nevertheless interact negatively with ASA according to the teaching of WO 97/35068 A1.
Outre la capacité à conférer au produit final des propriétés améliorées, l'émulsion d'ASA dans la solution aqueuse de matière amylacée cationique doit disposer d'un certain nombre de caractéristiques. Elle doit notamment présenter une grande finesse de tailles de particules, ainsi qu'un spectre étroit de distribution de ces tailles (produit « monodisperse ») . Comme expliqué dans le document WO 97 / 35068 Al, ces paramètres conditionnent l'efficacité de la composition de collage vis-à-vis des propriétés d' hydrophobie qu'elle est censée conférer. In addition to the ability to impart improved properties to the final product, the ASA emulsion in the aqueous solution of cationic starchy material must have a number of characteristics. In particular, it must have a great fineness of particle sizes, as well as a narrow spectrum of distribution of these sizes ("monodisperse" product). As explained in WO 97/35068 A1, these parameters condition the effectiveness of the bonding composition vis-à-vis the hydrophobicity properties it is supposed to confer.
A ce sujet, il est bien connu que la présence de particules « grossières » est une source d'encrassement, notamment des matériels divers dans lesquels transite la composition de collage, mais aussi de la sècherie de la machine à papier par entraînement à la vapeur de ces particules grossières (ce qui peut parfois conduire à des incendies) . Inversement, les particules trop « fines » de ladite composition vont traverser le matelas fibreux et seront emportées dans les eaux de procédé lors de l'égouttage. Il est donc nécessaire de disposer d'une composition de collage sous forme d'une émulsion présentant un maximum de particules dont le diamètre est centré sur une taille optimale que l'homme du métier estime comprise entre 1 pm et 1,5 μιη. Afin de déterminer la répartition des tailles de particules, on a généralement recours à un granulomètre laser qui permet le comptage en nombre ou en volume des particules présentant un certain diamètre, ou présentant un diamètre moyen compris dans un certain intervalle : on parle alors de répartition granulométrique et de population de particules en fonction de l'intervalle considéré. Dans la présente demande, on parlera de distribution « étroite » de tailles de particules, lorsqu'au moins 80 % en volume desdites particules présenteront un diamètre inférieur à 2 μπι, et lorsque le diamètre moyen sera compris entre 1 μπι et 1,5 μπι. La première de ces caractéristiques traduit une proportion réduite de particules dites « grossières » (diamètre supérieur à 2 μηα) . En ajoutant que le diamètre moyen est compris dans un intervalle qui exclut des particules de tailles trop fines (dont le diamètre moyen est inférieur à 1 μπ\) , on définit bien une répartition « étroite » et « monodisperse » des tailles de particules, cette répartition étant centrée sur l'intervalle allant de 1 μιη à 1,5 μπι. Par ailleurs, on ajoute que dans la présente Demande, les tailles de particules sont systématiquement mesurées à partir d'un granulomètre laser commercialisé par la société MALVERN® sous le nom Mastersizer® 2000. La procédure de mesure correspondante est relatée dans la partie expérimentale du présent document. L'art antérieur fait état d'un certain nombre de documents relatifs à des dispositifs et des méthodes pour réaliser des émulsions d'ASA dans une solution aqueuse de matière amylacée cationique. Le principe général est le suivant : réaliser dans un premier temps une solution aqueuse de matière amylacée cationique, mélanger celle-ci de manière homogène avec l'ASA, et réaliser enfin une émulsion à partir de ce mélange d'ASA et de cette solution aqueuse de matière amylacée cationique dans une unité d' émulsification . Cette unité est caractérisée par la présence de moyens mécaniques de broyage ou de cisaillement, qui assurent la micronisation et la dispersion des particules. In this regard, it is well known that the presence of "coarse" particles is a source of fouling, in particular various materials in which the bonding composition passes, but also the drying of the paper machine by steam entrainment. of these coarse particles (which can sometimes lead to fires). Conversely, the "fine" particles of said composition will pass through the fibrous mat and will be carried into the process water during dewatering. It is therefore necessary to have a gluing composition in the form of an emulsion having a maximum of particles whose diameter is centered on an optimum size that the skilled person estimates between 1 μm and 1.5 μm. In order to determine the particle size distribution, a laser granulometer is generally used which allows the number or volume count of the particles with a certain diameter, or having a mean diameter within a certain range: this is called granulometric distribution and particle population depending on the interval considered. In the present application, we will speak of "narrow" particle size distribution, when at least 80% by volume of said particles will have a diameter less than 2 μπι, and when the average diameter will be between 1 μπι and 1.5 μπι . The first of these characteristics reflects a reduced proportion of so-called "coarse" particles (diameter greater than 2 μηα). By adding that the mean diameter is within an interval that excludes particles of too small size (the average diameter of which is less than 1 μπ \), a "narrow" and "monodisperse" distribution of particle sizes is well defined. distribution centered on the interval from 1 μιη to 1.5 μπι. Furthermore, it is added that in the present Application, the particle sizes are systematically measured from a laser granulometer marketed by MALVERN® under the name Mastersizer® 2000. The corresponding measurement procedure is reported in the experimental part of FIG. this document. The prior art discloses a number of device and method related documents for making ASA emulsions in an aqueous solution of cationic starch material. The general principle is as follows: first of all to carry out an aqueous solution of cationic starchy material, to mix it in a homogeneous manner with the ASA, and finally to obtain an emulsion from this mixture of ASA and of this aqueous solution of matter cationic starch in an emulsification unit. This unit is characterized by the presence of mechanical means of grinding or shearing, which ensure the micronization and dispersion of the particles.
En vue de réaliser une telle émulsion présentant une distribution étroite de tailles de particules, l'homme du métier a depuis longtemps réalisé qu'une des clés du procédé résidait dans l'énergie déployée pour l'opération d' émulsification proprement dite, mais aussi dans un système de recirculation de cette émulsion au niveau de l'unité d' émulsification . De manière intuitive, on comprend que cette boucle de recirculation permet de nombreux passages du produit au niveau de l'unité d' émulsification , ce qui facilite le processus de micronisation et augmente donc la dispersion des particules. In order to produce such an emulsion having a narrow particle size distribution, one skilled in the art has long realized that one of the keys to the process lies in the energy deployed for the actual emulsification operation, but also in a system for recirculating this emulsion at the level of the emulsification unit. Intuitively, it is understood that this recirculation loop allows many passages of the product at the emulsification unit, which facilitates the micronization process and thus increases the dispersion of the particles.
A titre d'exemples illustrant ce concept, on pourra notamment consulter les documents US 6 207 719 et US 5 653 915 qui concernent directement la préparation d' émulsion d'ASA, via différents dispositifs. Il apparaît clairement que le principe de la recirculation du produit au niveau de l'organe de mise en émulsion est une donnée acquise et intégrée pour l'homme du métier (voir notamment l'étape D de la revendication 1 du premier document, et l'étape C de la revendication 1 du second document) . En ce qui concerne les documents déjà évoqués, le document WO 96 / 35840 Al reste muet sur les dispositifs utilisés, alors que le document WO 97 / 35068 Al mentionne un mélangeur Gaulin dans ses exemples, dont on sait qu'il dispose d'une boucle de recirculation. Or, et de manière surprenante car contradictoire avec ce qu'enseigne l'état de la technique, la Demanderesse a aujourd'hui mis au point un procédé de fabrication d'une émulsion d'ASA dans une composition de matière amylacée cationique, sans boucle de recirculation du produit au niveau de l'unité d' émulsification . Ce procédé conduit à un produit avec les caractéristiques granulométriques requises, à savoir une distribution de tailles des particules étroite et centrée sur un intervalle compris entre 1 pm et 1,5 μπι. By way of examples illustrating this concept, it will be possible to consult the documents US Pat. No. 6,207,719 and US Pat. No. 5,653,915, which directly relate to the ASA emulsion preparation, via various devices. It is clear that the principle of recirculation of the product at the level of the emulsifier is an acquired and integrated data for those skilled in the art (see in particular step D of claim 1 of the first document, and step C of claim 1 of the second document). With regard to the documents already mentioned, the document WO 96/35840 A1 remains silent on the devices used, whereas the document WO 97/35068 A1 mentions a Gaulin mixer in its examples, which is known to have a recirculation loop. However, and surprisingly because contradictory with what teaches the state of the art, the Applicant has today developed a method of manufacturing an ASA emulsion in a composition of cationic starch material without loop recirculation of the product at the emulsification unit. This method results in a product with the required particle size characteristics, namely a narrow particle size distribution and centered on an interval of between 1 μm and 1.5 μm.
Un des mérites de la Demanderesse est d'avoir su passer outre l'idée reçue selon laquelle une boucle de recirculation était nécessaire dans un tel procédé. Un autre de ses mérites est d'avoir ensuite su adapter ledit procédé, de manière à garantir la stabilité et les propriétés granulométriques de l' émulsion fabriquée, tout en s' affranchissant d'une boucle de recirculation. Concrètement, la Demanderesse a démontré que c'était la sélection d'une certaine teneur en matière sèche allant de 5,5 % à 11,5 % pour la solution initiale de matière amylacée cationique, qui permettait non seulement de se dispenser d'une boucle de recirculation, mais qui conduisait à une distribution des tailles de particules encore plus étroite que celle observée selon l'art antérieur. Quand on sait que ce paramètre conditionne la performance future du produit au niveau du collage du papier, on comprend que le procédé selon la présente invention conduit à une émulsion qui s'avère potentiellement très performante au niveau de l'application finale . One of the merits of the Applicant is to have overcome the misconception that a recirculation loop was necessary in such a process. Another of its merits is to have subsequently adapted the process, so as to ensure the stability and the particle size properties of the emulsion manufactured, while avoiding a recirculation loop. In concrete terms, the Applicant has demonstrated that it was the selection of a certain solids content ranging from 5.5% to 11.5% for the initial solution of cationic starchy material, which made it possible not only to dispense with a recirculation loop, but which led to an even smaller particle size distribution than that observed according to the prior art. When it is known that this parameter conditions the future performance of the product at the level of the paper bonding, it is understood that the method according to the present invention leads to an emulsion which proves to be potentially very efficient at the level of the final application.
De plus et de manière tout à fait avantageuse, on met ainsi à la disposition de l'homme du métier un procédé simple à utiliser, notamment directement dans une usine papetière, et exempt d'une boucle de recirculation : c'est un procédé en continu, qui conduit au produit désiré en un seul passage dans l'unité d' émulsification . Moreover, and in a very advantageous manner, this makes it possible for a person skilled in the art to use, especially directly in a paper mill, and free of a recirculation loop: it is a continuous process, which leads to the desired product in a single pass in the emulsification unit.
En outre, l'émulsion issue du procédé selon l'invention présente une température très voisine de celles des produits de départ (i.e. de l'ASA et de la solution de matière amylacée cationique), la légère hausse étant due à 1 ' échauffement provoqué au niveau de l'unique passage dans l'unité d' émulsification . A l'inverse, les systèmes de l'art antérieur dotés d'une boucle de recirculation conduisent à des augmentations de températures importantes (parfois plus de 40 °C) de par le principe même de la recirculation : cette augmentation est néfaste au produit final, car accélère les phénomènes d'hydrolyse de l'ASA. In addition, the emulsion resulting from the process according to the invention has a temperature very close to those of the starting materials (ie ASA and cationic starch solution), the slight increase being due to the induced heating. at the single passage in the emulsification unit. Conversely, systems of the prior art with a recirculation loop lead to significant temperature increases (sometimes more than 40 ° C) by the very principle of recirculation: this increase is detrimental to the final product because accelerates the hydrolysis phenomena of ASA.
De plus, la Demanderesse a démontré que ledit procédé, qui est donc un procédé continu, pouvait être utilisé pendant plusieurs heures, sans modification des caractéristiques granulométriques de l'émulsion. Enfin, elle a aussi démontré que ce procédé autorise la mise en œuvre de tensio-actifs sans altérer le produit final, tant sur le plan de sa stabilité qu'au niveau de ses caractéristiques granulométriques. Il s'agit d'un autre avantage substantiel, les problèmes d'interaction négative entre ASA et tensio- actifs ayant été relatés dans l'art antérieur (comme déjà discuté au niveau du document WO 97 / 35068 Al) . Aussi, un premier objet de la présente invention consiste en un procédé de fabrication d'une émulsion d'ASA dans une solution aqueuse de matière amylacée cationique, comprenant les étapes de : a) réaliser une solution aqueuse de matière amylacée cationique , In addition, the Applicant has demonstrated that said process, which is therefore a continuous process, could be used for several hours, without modifying the particle size characteristics of the emulsion. Finally, it has also demonstrated that this process allows the implementation of surfactants without altering the final product, both in terms of its stability as to its particle size characteristics. This is another substantial advantage, the problems of negative interaction between ASA and surfactants having been reported in the prior art (as already discussed in WO 97/35068 A1). Also, a first object of the present invention is a method of manufacturing an ASA emulsion in a aqueous solution of cationic starchy material, comprising the steps of: a) producing an aqueous solution of cationic starchy material,
b) mélanger de l'ASA et la solution aqueuse de matière amylacée cationique issue de l'étape a), de manière à obtenir un ratio en poids sec matière amylacée cationique / ASA inférieur à 1, préférentiellement compris entre 0,2 et 0,6, et très préférentiellement entre 0,3 et 0,5,  b) mixing ASA and the aqueous solution of cationic starchy material resulting from step a), so as to obtain a dry weight ratio cationic starchy material / ASA of less than 1, preferably between 0.2 and 0, 6, and very preferably between 0.3 and 0.5,
c) réaliser en un seul passage dans une unité d' émulsification une émulsion à partir du mélange issu de l' étape b) , caractérisé en ce que le procédé ne fait pas intervenir la recirculation de l' émulsion issue de l'étape c) au niveau de l'unité d' émulsification,  c) producing in a single pass in an emulsification unit an emulsion from the mixture resulting from step b), characterized in that the process does not involve the recirculation of the emulsion resulting from step c) at the level of the emulsification unit,
et en ce que la teneur en matière sèche de la solution aqueuse de matière amylacée cationique issue de l'étape a) est comprise entre 5,5 % et 11,5 %, préférentiellement entre 7 % et 10 % de son poids total.  and in that the dry matter content of the aqueous solution of cationic starchy material resulting from step a) is between 5.5% and 11.5%, preferably between 7% and 10% of its total weight.
L'étape a) de réalisation de la solution aqueuse de matière amylacée cationique consiste soit à fournir une solution aqueuse de matière amylacée cationique, telle que commercialement disponible, ou alors à diluer celle-ci avec de l'eau, en vue d'obtenir la teneur en matière sèche désirée. Cette teneur, comprise entre 5,5 % et 11,5 %, préférentiellement entre 7 % et 10 % du poids total de la solution réalisée, est le paramètre essentiel à ajuster pour cette première étape. Step a) of producing the aqueous solution of cationic starchy material either consists in providing an aqueous solution of cationic starchy material, as commercially available, or else in diluting it with water, in order to obtain the desired dry matter content. This content, between 5.5% and 11.5%, preferably between 7% and 10% of the total weight of the realized solution, is the essential parameter to adjust for this first step.
A toutes fins utiles, on précise que l'expression matière amylacée cationique désigne une matière amylacée obtenue par n'importe lequel des procédés connus de cationisation en milieu aqueux, en milieu solvant ou en phase sèche, dès lors que ce procédé permet à un ou plusieurs groupement ( s ) azoté (s) de nature électropositive de se fixer sur ladite matière amylacée. On pourra notamment se reporter au document WO 2005 / 014709 Al. A titre d'exemples de solution aqueuse de matières amylacées cationiques pouvant être mises en œuvre selon la présente invention, on peut citer les produits commercialisés sous la gamme VECTOR® SC et IC (ROQUETTE®) , Raisabond® 15 (CHEMIGATE) , Licocat® P (SUEDSTAERKE®) , Lyckeby® LP 2145 et LP 1140 (LYCKEBY®) , Redisize® 205 et Redibond® 4000 (NATIONAL STARCH®) et Raifix® 25035 et 01035 (CIBA RAISIO®) . L'étape b) consiste, à partir de moyens de mélange classiques, permettant notamment de réguler les concentrations massiques des constituants, à réaliser le mélange entre la solution aqueuse de matière amylacée cationique issue de l'étape a) et l'ASA. Ledit mélange et l'ASA sont amenés au niveau d'un mélangeur qui est idéalement un mélangeur statique, mais peut aussi consister en un mélangeur dynamique, ou un mélangeur dit « venturi », selon l'expression bien connue de l'homme du métier. L'étape c) consiste à faire circuler en une seule passe le mélange qui a été obtenu dans l'étape b) , dans une unité d' émulsification . Cette unité désigne tous les dispositifs bien connus de l'homme du métier, et disposant notamment de moyens mécaniques dont la finalité est de microniser et de disperser de manière homogène le liquide qu'on cherche à mettre en émulsion. De tels dispositifs sont notamment les matériels Process Pilot DR 2000/4 ( I KA®) ou Ytron Z (YTRON®) . For all intents and purposes, it is specified that the term "cationic starchy material" designates a starchy material obtained by any of the known methods of cationisation in aqueous medium, in a solvent medium or in a dry phase, since this process allows one or more a plurality of nitrogen group (s) of electropositive nature to be attached to said starchy material. In particular, reference may be made to the document WO 2005/014709 A1. Examples of aqueous solutions of cationic starchy materials that may be used according to the present invention include the products marketed under the VECTOR® SC and IC range ( ROQUETTE®), Raisabond® 15 (CHEMIGATE), Licocat® P (SUEDSTAERKE®), Lyckeby® LP 2145 and LP 1140 (LYCKEBY®), Redisize® 205 and Redibond® 4000 (NATIONAL STARCH®) and Raifix® 25035 and 01035 ( CIBA RAISIO®). Step b) consists, from conventional mixing means, in particular for controlling the mass concentrations of the constituents, to achieve mixing between the aqueous solution of cationic starch material from step a) and the ASA. Said mixture and the ASA are brought to a mixer which is ideally a static mixer, but may also consist of a dynamic mixer, or a mixer called "venturi", according to the expression well known to those skilled in the art . Step c) consists of circulating in a single pass the mixture which has been obtained in step b), in an emulsification unit. This unit refers to all devices well known to those skilled in the art, including having mechanical means whose purpose is to micronize and disperse homogeneously the liquid that is to be emulsified. Such devices are in particular the Process Pilot DR 2000/4 (I KA®) or Ytron Z (YTRON®) materials.
L'unité où est réalisée la solution aqueuse de matière amylacée cationique (a'), le mélangeur (b' ) et l'unité de mise en émulsion (c') sont des dispositifs tout à fait classiques, reliés entre eux idéalement par des tuyaux, permettant la circulation des différents liquides. Les dispositifs au sens de la présente invention doivent s'entendre comme des dispositifs aptes à la mise en œuvre du procédé selon l'invention, à l'échelle industrielle. L'unité d' émulsion (c') est notamment reliée à la machine à papier, de manière à ce que l' émulsion utile pour le collage du papier ou du carton, puisse être introduite en partie humide, en généralement un ou deux points d'introduction. Typiquement, la fabrication de l' émulsion consomme au moins 5 litres d'ASA par heure, préférentiellement au moins 10 litres d'ASA par heure. The unit in which the aqueous solution of cationic starchy material (a ') is produced, the mixer (b') and the emulsification unit (c ') are quite conventional devices which are ideally connected to each other. pipes, allowing the circulation of different liquids. Devices within the meaning of the present invention must be understood as devices capable of implementing the method according to the invention, on an industrial scale. The emulsion unit (c ') is in particular connected to the paper machine, so that the emulsion useful for gluing paper or cardboard can be introduced in the wet part, generally at one or two points. introduction. Typically, the manufacture of the emulsion consumes at least 5 liters of ASA per hour, preferably at least 10 liters of ASA per hour.
Ainsi, la présente invention a en particulier pour objet un procédé de fabrication d'une émulsion d'ASA dans une solution aqueuse de matière amylacée cationique tel que décrit ci-dessus, Thus, the subject of the present invention is in particular a method for producing an ASA emulsion in an aqueous solution of cationic starchy material as described above,
qui est réalisé dans un dispositif constitué de : which is realized in a device consisting of:
- une unité de stockage a' d'une solution aqueuse de matière amylacée cationique pour la réalisation de a storage unit of an aqueous solution of cationic starchy material for the production of
1 ' étape a ) , - une unité de mélange b' d'ASA et de solution aqueuse de matière amylacée cationique, connectée avec l'unité a', pour la réalisation de l'étape b) , Step a), a mixing unit b 'of ASA and an aqueous solution of cationic starchy material, connected with the unit a', for carrying out step b),
- une unité d' émulsification c' du mélange d'ASA et de la solution aqueuse de matière amylacée cationique, connectée avec l'unité b', pour la réalisation de 1 ' étape c ) ,  an emulsification unit c 'of the mixture of ASA and the aqueous solution of cationic starchy material, connected with the unit b', for carrying out stage c),
ledit dispositif ne présentant pas de boucle de recirculation au niveau de l'unité d' émulsification c' . said device does not have a recirculation loop at the emulsification unit c '.
Le procédé selon la présente invention est également caractérisé en ce que l'ASA est un produit préférentiellement d'origine synthétique ; il s'agit d'huiles modifiées qui résultent de coupes en C16-C18. Parmi les ASA commercialement disponibles et utilisables dans la présente invention, on pourra citer le produit Chemsize® A 180 (CHEMEC®) . The process according to the present invention is also characterized in that the ASA is a product preferably of synthetic origin; these are modified oils that result from C16-C18 cuts. Among the ASAs commercially available and usable in the present invention, mention may be made of the product Chemsize® A 180 (CHEMEC®).
Ce procédé est aussi caractérisé en ce que la solution aqueuse de matière amylacée cationique présente un taux d'azote fixé inférieur à 3,5 %, préférentiellement compris entre 0,3 % et 3,5 %, très préférentiellement entre 0,7 % et 2 % en poids sec d'azote par rapport au poids total de matière amylacée cationique. This process is also characterized in that the aqueous solution of cationic starchy material has a fixed nitrogen content of less than 3.5%, preferably between 0.3% and 3.5%, very preferably between 0.7% and 2% by dry weight of nitrogen relative to the total weight of cationic starchy material.
Cette matière amylacée cationique peut éventuellement être modifiée à partir d'une opération choisie parmi l'hydrolyse, les transformations chimiques et physiques, mécaniques, thermomécaniques ou encore thermiques. Une opération d'hydrolyse, visant très directement la réduction de la masse moléculaire et, dans la plupart des cas, la réduction de la viscosité, peut être menée par divers moyens tels que chimiques, couramment par l'action d'un acide, d'une base ou d'un agent oxydant ou par une action enzymatique, le plus couramment par amylase. Les modifications chimiques courantes sont de différentes natures telles que l'oxydation, notamment à 1 ' hypochlorite , 1 ' estérification, comme 1 ' acétylation, 1 ' éthérification, par exemple, par cationisation, carboxyméthylation ou hydroxypropylation . Les traitements physiques peuvent être pratiqués grâce à des moyens thermomécaniques, comme l'extrusion ou la pré- gélatinisation, ou thermiques, comme ceux connus de l'homme de l'art sous le nom de Hot Moisture Treatment (HMT) ou d ' Annealing . This cationic starchy material may optionally be modified from an operation chosen from hydrolysis, chemical and physical, mechanical, thermomechanical or even thermal transformations. A hydrolysis operation, very directly aimed at reducing the molecular weight and, in most cases, reducing the viscosity, can be carried out by various means such as chemical, commonly by the action of an acid, a base or an oxidizing agent or by an enzymatic action, most commonly by amylase. Common chemical modifications are of various kinds such as oxidation, especially with hypochlorite, esterification, such as acetylation, etherification, for example, by cationization, carboxymethylation or hydroxypropylation. Physical treatments can be practiced by thermomechanical means, such as extrusion or pregelatinization, or thermal, such as those known to those skilled in the art as Hot Moisture Treatment (HMT) or Annealing. .
Un autre objet de la présente invention consiste en un dispositif constitué de : a') une unité de stockage d'une solution aqueuse de matière amylacée cationique, Another subject of the present invention consists of a device consisting of: a ') a storage unit for an aqueous solution of cationic starchy material,
b' ) une unité de mélange d'ASA et de solution aqueuse de matière amylacée cationique, connectée avec l'unité a') c' ) une unité d' émulsification du mélange d'ASA et de la solution aqueuse de matière amylacée cationique, connectée avec 1 ' unité b ' ) ledit dispositif ne présentant pas de boucle de recirculation au niveau de l'unité d' émulsification .  b ') a mixing unit of ASA and aqueous solution of cationic starch material, connected with unit a') c ') an emulsification unit of the mixture of ASA and the aqueous solution of cationic starchy material, connected with the unit b ') said device having no recirculation loop at the emulsification unit.
Les différentes unités ont été décrites précédemment. Elles sont connectées entre elles au moyen de tuyaux et des pompes assurent la circulation des produits au sein de ces tuyaux. L'homme du métier saura adapter ledit dispositif pour sa mise en œuvre à l'intérieur d'une usine de production papetière . The different units have been described previously. They are connected together by means of pipes and pumps ensure the circulation of products within these pipes. Those skilled in the art will be able to adapt said device for its implemented inside a paper mill.
Un autre objet de la présente invention consiste en une émulsion d'ASA dans une solution aqueuse de matière amylacée cationique, présentant : un ratio en poids sec matière amylacée cationique / ASA inférieur à 1, préférentiellement compris entre 0,2 et 0,6, et très préférentiellement entre 0,3 et 0,5, une distribution de tailles des particules telle qu'au moins 80 % en volume desdites particules présentent un diamètre inférieur à 2 μτχι , et un diamètre moyen compris entre 1 μτη et 1,5 μιτι tel que déterminé par granulométrie laser au moyen d'un dispositif commercialisé par la société MALVERN® sous le nom astersizer© 2000. Another subject of the present invention consists of an emulsion of ASA in an aqueous solution of cationic starchy material, having: a dry weight ratio cationic starchy material / ASA of less than 1, preferably of between 0.2 and 0.6, and very preferably between 0.3 and 0.5, a particle size distribution such that at least 80% by volume of said particles have a diameter of less than 2 μτχι, and a mean diameter of between 1 μτη and 1.5 μιτι as determined by laser granulometry by means of a device marketed by MALVERN® under the name astersizer © 2000.
Cette émulsion est aussi caractérisée en ce que l'ASA qu'elle contient est un produit préférentiellement d'origine synthétique . This emulsion is also characterized in that the ASA it contains is a product preferably of synthetic origin.
Elle est. aussi caractérisée en ce que la matière amylacée cationique qu'elle comprend présente un taux d'azote fixé inférieur à 3,5 %, préférentiellement compris entre 0,3 % et 3,5 %, très préférentiellement entre 0,7 % et 2 % en poids sec d'azote par rapport au poids total de matière amylacée cationique. Ladite matière amylacée cationique peut éventuellement être modifiée à partir d'une opération choisie parmi l'hydrolyse, les transformations chimiques et physiques, mécaniques, thermomécaniques ou encore thermiques comme précédemment indiqué . She is. also characterized in that the cationic starchy material which it comprises has a fixed nitrogen content of less than 3.5%, preferably between 0.3% and 3.5%, very preferably between 0.7% and 2% in dry weight of nitrogen relative to the total weight of cationic starchy material. Said cationic starchy material may optionally be modified from an operation chosen from hydrolysis, chemical and physical, mechanical transformations, thermomechanical or thermal as previously indicated.
Un dernier objet de la présente invention consiste en l'utilisation de ladite émulsion dans une opération de collage d'une feuille de papier ou de carton. A final object of the present invention is the use of said emulsion in a gluing operation of a sheet of paper or cardboard.
Les exemples qui suivent permettent de mieux apprécier la nature de la présente invention, sans toutefois en limiter la portée. The following examples make it possible to better appreciate the nature of the present invention, without however limiting its scope.
EXEMPLES Dans tous les exemples, la granulométrie des émulsions est analysée à partir d'un granulomètre laser commercialisé par la société MALVERN® sous le nom de Mastersizer® 2000, avec les paramètres suivants : EXAMPLES In all the examples, the particle size of the emulsions is analyzed from a laser granulometer marketed by MALVERN® under the name Mastersizer® 2000, with the following parameters:
800 ml d'eau déminéralisée  800 ml of demineralized water
- Agitation 1900 tours / min  - Agitation 1900 rpm
Mesure background : 10 s  Measure background: 10 s
3 mesures consécutives par échantillon (délai entre les mesures : 0 s)  3 consecutive measurements per sample (time between measurements: 0 s)
Durée de chaque mesure : 10 s  Duration of each measurement: 10 s
- obscuration Laser : entre 8 % et 13 %  - Laser obscuration: between 8% and 13%
Indice de réfraction : 1,5  Refractive index: 1.5
Dispersant (eau) indice de réfraction : 1,33  Dispersant (water) refractive index: 1.33
Absorption : 0,01  Absorption: 0.01
Modèle de forme de particules = sphérique  Particle shape model = spherical
Exemple 1 Cet exemple a pour but d'illustrer la fabrication d'émulsion d'ASA dans une solution aqueuse de matière amylacée cationique dans le cadre d'un dispositif selon l'invention exempt d'une boucle de recirculation au niveau de l'unité d' émulsification, et avec un dispositif selon l'art antérieur. Il a également pour objectif d'illustrer l'influence de la teneur en matière sèche de la solution aqueuse initiale de matière amylacée cationique sur la granulométrie de l'émulsion réalisée. Example 1 This example is intended to illustrate the manufacture of ASA emulsion in an aqueous solution of cationic starchy material in the context of a device according to the invention free of a recirculation loop at the unit level. emulsification, and with a device according to the prior art. It also aims to illustrate the influence of the dry matter content of the initial aqueous solution of cationic starchy material on the particle size of the emulsion produced.
On met en œuvre une solution aqueuse de matière amylacée cationique, commercialisée par la société ROQUETTE® sous le nom VECTOR® SCA 2015. On utilise aussi de l'ASA qui est le produit Chemsize® A180 commercialisé par la société CHEMEC®. Ce produit contient 0,5 % en poids de dioctyl suifosuccinate de sodium comme tensio-actif (encore appelé « DOSS ») . An aqueous solution of cationic starchy material marketed by ROQUETTE® under the name VECTOR® SCA 2015 is used. ASA, which is the Chemsize® A180 product marketed by CHEMEC®, is also used. This product contains 0.5% by weight sodium dioctyl sulfosuccinate as surfactant (also called "DOSS").
L'alimentation en eau se fait à partir d'un réseau de distribution existant. Les transferts et dosages de l'ASA et de la solution aqueuse de matière amylacée cationique vers cette plateforme de mise en émulsion, se font depuis leur contenant mobile ou cuve de stockage respectif, au moyen de tuyaux et de pompes volumétriques , dont les vitesses de rotation sont asservies aux consignes de débit souhaitées et au ratio visé matière amylacée cationique (sec) / ASA. The water supply is from an existing distribution network. The transfers and assays of the ASA and the aqueous solution of cationic starchy material to this emulsification platform, are made from their mobile container or respective storage tank, by means of hoses and volumetric pumps, whose speeds of rotation are subject to the desired flow rate and target ratio cationic starch (dry) / ASA.
La solution aqueuse de matière amylacée cationique est diluée en ligne. Le débit d'eau de dilution est régulé par le débit de la solution aqueuse de matière amylacée cationique commerciale, en fonction -de la matière sèche souhaitée. Un mélangeur statique permet d'homogénéiser cette solution aqueuse diluée. L'ASA est ensuite introduit en ligne, dans la solution aqueuse diluée et homogène de matière amylacée cationique. The aqueous solution of cationic starchy material is diluted in line. The dilution water flow rate is controlled by the flow rate of the commercial aqueous cationic starch solution, depending on the desired solids content. A static mixer makes it possible to homogenize this dilute aqueous solution. The ASA is then introduced line, in the dilute and homogeneous aqueous solution of cationic starchy material.
Ce mélange « solution aqueuse de matière amylacée cationique / ASA » est alors véhiculé via un tuyau jusqu'à 1 ' émulsionneur . Ce système de mise en émulsion mono-passe et continu, possède une série de 3 rotors/stators consécutifs, dont chaque rotor et chaque stator est composé de 3 rangées de couronnes dentelées concentriques. Ce procédé fonctionne à vitesse variable ; la vitesse de rotation dépend du débit hydraulique passant, de la nature des constituants et de leurs proportions, de la pression dans la chambre d' émulsion, ainsi que de la finesse de l' émulsion souhaitée. La sortie de 1 ' émulsionneur est munie d'un capteur de température, d'un capteur de pression, d'une vanne permettant de maintenir une pression de 3 bars dans le procédé, puis d'un débitmètre . This mixture "aqueous solution of cationic starchy material / ASA" is then conveyed via a pipe to the emulsifier. This single-pass and continuous emulsification system, has a series of 3 consecutive rotors / stators, each rotor and each stator is composed of 3 rows of concentric serrated crowns. This process operates at variable speed; the speed of rotation depends on the passing hydraulic flow, the nature of the constituents and their proportions, the pressure in the emulsion chamber, as well as the fineness of the desired emulsion. The output of 1 emulsifier is provided with a temperature sensor, a pressure sensor, a valve for maintaining a pressure of 3 bars in the process, and a flow meter.
Dans cet exemple, on a fait varier la matière sèche de la solution aqueuse de matière amylacée cationique de 3 % à 20 %, le ratio sec matière amylacée cationique / ASA de 0,3 à 0,5, le débit en sortie de 1 ' émul sionneur de 80 à 140 kg/h, la vitesse périphérique du rotor de l' émulsionneur étant fixée à 40 m/s. In this example, the solids content of the aqueous solution of cationic starchy material was varied from 3% to 20%, the dry cationic starch content / ASA ratio was 0.3 to 0.5, the flow rate at the outlet of the emulsifier from 80 to 140 kg / h, the peripheral speed of the rotor of the emulsifier being fixed at 40 m / s.
Dans tous les essais, on détermine la température T°C de l'émulsion à la sortie de l'unité d' émulsification, et on réalise une analyse granulométrique selon le protocole déjà exposé, de manière à déterminer le diamètre moyen ainsi que le paramètre %<2 pm. Dans tous les essais à part l'essai n° 6 on récupère l'émulsion à la sortie de l'unité d' émulsification, et selon l'essai n° 6, on fait recirculer au moins encore une fois l'émulsion dans ladite unité. In all the tests, the temperature T ° C of the emulsion at the outlet of the emulsification unit is determined, and a granulometric analysis is carried out according to the protocol already explained, so as to determine the mean diameter as well as the parameter % <2 pm. In all the tests except the test n ° 6 one recover the emulsion at the exit of the unit emulsification, and according to test No. 6, the emulsion is recirculated at least once in said unit.
Les résultats ont été reportés dans le tableau 1, avec les abréviations suivantes : The results have been reported in Table 1, with the following abbreviations:
Débit (kg/h) : débit en sortie de l' émulsionneur  Flow rate (kg / h): output flow of the emulsifier
MA / ASA : ratio en poids sec Matière Amylacée cationique / MA / ASA: ratio by dry weight cationic starchy material /
ASAASA
ES MA (%) : extrait sec en matière amylacée cationique de la solution initiale ES MA (%): dry extract of cationic amylaceous material from the initial solution
T° (°C) : température de l'émulsion finale à la sortie de 1' émulsionneur  T ° (° C): temperature of the final emulsion at the outlet of the emulsifier
%<2 μπι : % en volume de particules ayant un diamètre inférieur à 2 μτ  % <2 μπι:% by volume of particles having a diameter of less than 2 μτ
d moyen (μπι) : diamètre moyen des particules average d (μπι): mean particle diameter
* 2 circulations au niveau de l'unité d' émulsification, par passages ordonnés et consécutifs  * 2 circulations at the level of the emulsification unit, by ordered and consecutive passages
** analyse granulométrique réalisée après 90 minutes de stockage à température ambiante  ** granulometric analysis performed after 90 minutes of storage at room temperature
Tableau 1 Les essais n° 1 à 4 démontrent que, à deux ratios MA / ASA donnés et pour un extrait sec en matière amylacée cationique trop faible (3 % et 5 %), on aboutit à un diamètre moyen trop important (notamment très supérieur à 2 μιη pour les essais n° 3 et 4) et/ou à une valeur de %< 2 μιη trop faible. On ne dispose donc pas d'une quantité optimale de particules dont le diamètre est compris entre 1 μπι et 1,5 μιη, ce qui signifie qu'on engendre des particules de taille plus importante qui peuvent occasionner des problèmes d'encrassement. Table 1 Tests Nos. 1 to 4 demonstrate that, at two given MA / ASA ratios and for a dry extract of cationic starchy material that is too low (3% and 5%), the result is a too large average diameter (in particular much greater than 2 μιη for tests n ° 3 and 4) and / or at a value of% <2 μιη too low. An optimal quantity of particles whose diameter is between 1 μπι and 1.5 μιη is therefore not available, which means that particles of larger size are generated which can cause fouling problems.
De la même manière, les essais n° 7 et 8 réalisés avec un extrait sec important en matière amylacée ne donnent pas la granulométrie souhaitée. En outre, ils conduisent à des températures d'émulsion élevées qui risquent de faciliter des phénomènes néfastes d'hydrolyse de l'ASA. In the same way, tests No. 7 and 8 carried out with a large dry extract of starchy material do not give the desired particle size. In addition, they lead to high emulsion temperatures that may facilitate adverse phenomena of hydrolysis of ASA.
Quant à l'essai n° 6*, il démontre que les 2 passages ordonnés et consécutifs de l'émulsion au niveau de l'unité d' émulsification provoquent une très importante élévation de la température. As for the test No. 6 *, it demonstrates that the 2 ordered and consecutive passages of the emulsion at the emulsification unit cause a very significant rise in temperature.
En définitive, seuls les essais n° 5, 9, 10 et 11 conduisent à un produit final caractérisé par un diamètre moyen de particules compris entre 1 μη et 1,5 μπι, avec un indice %<2 μιτι supérieur à 80 %, et avec une faible élévation de la température. On dispose ainsi d'une émulsion potentiellement très efficace en tant qu'agent de collage de par sa granulométrie, et avantageusement exempte de tout phénomène néfaste d'hydrolyse. L'essai 11** démontre que sur une période de stockage importante, l'émulsion fabriquée conserve ses caractéristiques granulométriques . Exemple 2 Ultimately, only the tests No. 5, 9, 10 and 11 lead to a final product characterized by an average particle diameter of between 1 μη and 1.5 μπι, with a% <2 μιτι index greater than 80%, and with a slight rise in temperature. Thus, an emulsion is available that is potentially very effective as a sizing agent because of its particle size, and advantageously free of any harmful phenomenon of hydrolysis. Test 11 ** shows that over a long storage period, the manufactured emulsion retains its particle size characteristics. Example 2
Cet exemple a pour but d'illustrer la fabrication d'une émulsion à partir d'ASA et d'une solution aqueuse de matière amylacée cationique dans le cadre d'un dispositif selon l'invention sans boucle de recirculation. Il illustre notamment l'influence de la teneur en matière sèche de la solution aqueuse initiale de matière amylacée cationique sur la granulométrie de l' émulsion réalisée, et sur le caractère hydrophobe d'un papier fabriqué avec cette émulsion. Cet exemple est réalisé dans les mêmes conditions que l'exemple précédent, à la différence que le système de mise en émulsion mono-passe et continu, possède un seul rotor/stator dont chacune de ses 2 parties est composée de 3 rangées de couronnes dentelées concentriques. This example is intended to illustrate the manufacture of an emulsion from ASA and an aqueous solution of cationic starchy material in the context of a device according to the invention without recirculation loop. It illustrates in particular the influence of the dry matter content of the initial aqueous solution of cationic starchy material on the particle size of the emulsion produced, and on the hydrophobicity of a paper made with this emulsion. This example is made under the same conditions as the previous example, with the difference that the single-pass and continuous emulsification system has a single rotor / stator, each of its two parts being composed of 3 rows of serrated crowns. concentric.
Les essais n° 12 à 16 mettent en œuvre, dans un dispositif selon l'invention, une solution aqueuse de matière amylacée cationique commercialisée par la société ROQUETTE© sous le nom VECTOR® SCA 2015 et de l'ASA qui est le produit Chemsize® A180 commercialisé par la société CHE EC®. Le ratio en poids sec matière amylacée cationique (MA) / ASA est égal ici à 0,3. La vitesse périphérique est fixée à 40 m/s et le débit en sortie d' émulsionneur est égal à 140 kg/h Les essais n° 12, 13, 14, 15 et 16 mettent respectivement en œuvre un extrait sec de 2 %, 7 %, 9 %, 12 % et 16 % en matière amylacée cationique au niveau de la solution aqueuse initiale . Dans tous les essais, on détermine la température T°C de l'émulsion à la sortie de l'unité d' émulsification, et on réalise une analyse granulométrique selon le protocole déjà exposé, de manière à déterminer le diamètre moyen d ainsi que le paramètre %<2 μιη. L'ensemble des résultats apparaît dans le tableau 2, les abréviations n'ayant pas changé. The tests No. 12 to 16 implement, in a device according to the invention, an aqueous solution of cationic starch material marketed by the company ROQUETTE © under the name VECTOR® SCA 2015 and ASA which is the product Chemsize® A180 marketed by CHE EC®. The dry weight ratio cationic starchy material (MA) / ASA is here equal to 0.3. The peripheral speed is set at 40 m / s and the flow rate at the exit of the emulsifier is equal to 140 kg / h. Tests No. 12, 13, 14, 15 and 16 respectively implement a solids content of 2%, 7%. %, 9%, 12% and 16% cationic starchy material at the initial aqueous solution. In all the tests, the temperature T ° C of the emulsion at the outlet of the emulsification unit is determined, and a granulometric analysis is carried out according to the protocol already explained, so as to determine the average diameter d as well as the parameter% <2 μιη. All the results appear in Table 2, the abbreviations have not changed.
Tableau 2  Table 2
Il apparaît clairement que le produit obtenu selon l'essai n° 16 a subi une élévation très importante de sa température : il est donc sujet à des phénomènes d'hydrolyse de l'ASA qui sont rédhibitoires à son utilisation comme agent de collage, ce qui va être démontré ultérieurement. It is clear that the product obtained according to test No. 16 has undergone a very significant increase in its temperature: it is therefore subject to hydrolysis phenomena of ASA which are unacceptable for its use as a sizing agent, which will be demonstrated later.
Pour ces émulsions, on réalise des feuilles de papier de laboratoire appelées formettes, à partir d'un dispositif FRET (formettes de rétention) commercialisé par la société TECHPAP. Ces formettes ont des caractéristiques proches du papier industriel client, notamment en ce qui concerne la floculation et les rétentions . Le procédé de fabrication de la formette met en œuvre une pâte a papier qui est une pâte de fibres vierges (50% résineux, 50% feuillus) avec un niveau de raffinage de 35° Schopper (SR) . On ajoute 35% (en poids sec par rapport au poids total de la pâte) de carbonate de calcium naturel commercialisé par la société OMYA® sous le nom d'Omyalite® 50. La suspension fibreuse chargée a une concentration de 2,5g/l. On ajoute ensuite 0,3 % (équivalent sec / papier) d'une colle de HICAT® 5163AM (ROQUETTE®) . On ajoute enfin 0,35% (par rapport au papier) de l'émulsion d'ASA. On réalise ainsi une formette présentant un grammage de 70 g/m2. Après fabrication de la formetté, celle-ci est placée entre 2 buvards et l'ensemble est passé 2 fois dans une presse à rouleau de marque TECHPAP. La formette est ensuite séparée des buvards puis est placée sur un séchoir de marque TECHPAP, durant 5 minutes à 100°C. Un mûrissement des formettes est réalisé ensuite, en plaçant celles-ci durant 30 minutes dans une étuve à 110°C, pour permettre à l'agent de collage de conférer au papier son caractère hydrophobe . Les formettes sont ensuite placées au minimum 24 heures dans une pièce conditionnée à 23°C ( +/- 1°C) et 50 % d'humidité relative (+/- 2 %) (normes ISO 187 : 1990 et Tappi T402 sp-08) . For these emulsions, sheets of laboratory paper called formettes are produced from a FRET device (retentate formers) marketed by TECHPAP. These forms have characteristics close to the industrial customer paper, particularly with regard to flocculation and retentions. The method of manufacturing the formette uses a paper pulp which is a pulp of virgin fibers (50% resinous, 50% hardwood) with a level of refining of 35 ° Schopper (SR). 35% (by dry weight relative to the total weight of the dough) of natural calcium carbonate marketed by OMYA® under the name of Omyalite® 50 is added. The filled fibrous suspension has a concentration of 2.5 g / l. . 0.3% (dry equivalent / paper) of a HICAT® 5163AM (ROQUETTE®) glue is then added. Finally, 0.35% (relative to the paper) of the ASA emulsion is added. This produces a form having a grammage of 70 g / m 2 . After manufacturing the form, it is placed between 2 blotters and the set is passed twice in a TECHPAP brand roller press. The form is then separated from the blotters and is placed on a TECHPAP brand dryer for 5 minutes at 100 ° C. A ripening of the forms is then carried out, placing them for 30 minutes in an oven at 110 ° C, to allow the bonding agent to give the paper its hydrophobic character. The sheets are then placed for a minimum of 24 hours in a room conditioned at 23 ° C (+/- 1 ° C) and 50% relative humidity (+/- 2%) (ISO 187: 1990 and Tappi T402 standards). 08).
On réalise alors une mesure de Cobb 60 (normes ISO 535:1991 et Tappi T441 om-04) qui est relatif à 1 ' hydrophobicité du papier : plus faible est la quantité d'eau absorbée, plus le papier est hydrophobe (Tableau 3) . Pour les formettes réalisées à partir des émulsions selon les essais n° 12 à 16, on trouve respectivement une valeur moyenne de Cobb égale à 47, 28, 25, 45 et 51 g/m2. On démontre ainsi que ce sont bien les formettes réalisées selon l'invention (essais n° 13 et 14) qui présentent l' hydrophobicité la plus élevée. A measurement of Cobb 60 (ISO standards 535: 1991 and Tappi T441 om-04) is then carried out which relates to the hydrophobicity of the paper: the lower the amount of water absorbed, the more hydrophobic the paper (Table 3). . For the forms made from the emulsions according to tests no. 12 to 16, there is respectively an average value of Cobb equal to 47, 28, 25, 45 and 51 g / m 2 . It is thus demonstrated that it is indeed the forms produced according to the invention (tests Nos. 13 and 14) which exhibit the highest hydrophobicity.
Exemple 3 Cet exemple a pour but d'illustrer la fabrication d'une émulsion à partir d'ASA et d'une solution aqueuse de matière amylacée cationique dans le cadre d'un dispositif selon l'invention exempt d'une boucle de recirculation. Il démontre notamment que les caractéristiques granulométriques des émulsions fabriquées sont constantes dans le temps. Example 3 This example is intended to illustrate the manufacture of an emulsion from ASA and an aqueous solution of cationic starchy material in the context of a device according to the invention free of a recirculation loop. It demonstrates in particular that the particle size characteristics of the emulsions manufactured are constant over time.
Les essais mettent en œuvre la solution aqueuse de matière amylacée cationique VECTOR® SCA 2015 et le produit Chemsize® A180. Ils sont réalisés au moyen d'un dispositif identique à celui décrit dans l'exemple précédent. The tests use the VECTOR® SCA 2015 aqueous cationic starch solution and the Chemsize® A180 product. They are made using a device identical to that described in the previous example.
Cet exemple est réalisé dans les mêmes conditions que l'exemple 2. Ici, on a fixé la matière sèche à 8 %, le ratio sec matière amylacée cationique / ASA à 0,32 et le débit en sortie d' émulsionneur à 220 L/h et la vitesse périphérique à 40 m/s. On réalise ici 3 analyses granulométriques sur 3 échantillons prélevés aux instants 45 minutes, 3h00 et 5h00. Outre le diamètre moyen d et le paramètre %<2 μιτι, on a aussi déterminé le % en volume de particules dont le diamètre est compris dans un certain intervalle : les résultats correspondants figurent dans les tableaux 3, 3 bis et 3 ter. This example is carried out under the same conditions as in Example 2. Here, the solids content was fixed at 8%, the dry cationic starch content / ASA ratio at 0.32 and the discharge rate of the emulsifier at 220 L / hour. h and the peripheral speed at 40 m / s. Here we carry out 3 granulometric analyzes on 3 samples taken at the instants 45 minutes, 3:00 and 5:00. In addition to the average diameter d and the parameter% <2 μιτι, the% by volume of particles whose diameter is within a certain range has also been determined: the corresponding results are shown in Tables 3, 3a and 3b.
% (volume) entre (μιη) % (volume) between (μιη)
100, 00 0,48 3,80  100, 00 0.48 3.80
99,73 0,55 3,31  99.73 0.55 3.31
82,15 0,83 2,19  82.15 0.83 2.19
75, 32 0,83 1,90  75, 32 0.83 1.90
48,50 1,10 1,66  48.50 1.10 1.66
25,37 1,26 1,44 81,5 < 2 μπι 25.37 1.26 1.44 81.5 <2 μπι
diamètre moyen  average diameter
Tableau 3 (après 45 minutes de fonctionnement) Table 3 (after 45 minutes of operation)
Tableau 3 bis (après 3h00 de fonctionnement) Table 3a (after 3 hours of operation)
Tableau 3 ter (après 5h00 de fonctionnement) Table 3b (after 5 hours of operation)
Non seulement on démontre la constance des émulsions fabriquées en terme de caractéristiques granulométriques , mais on vérifie bien a posteriori que les distributions de tailles de particules sont monodisperses . Not only is the consistency of the emulsions manufactured in terms of particle size characteristics demonstrated, but it is verified a posteriori that the particle size distributions are monodisperse.

Claims

REVENDICATIONS
1 - Procédé de fabrication d'une émulsion d'anhydride alkényle succinique (ASA) dans une solution aqueuse de matière amylacée cationique, comprenant les étapes de : a) réaliser une solution aqueuse de matière amylacée cationique, 1 - Process for producing an alkenyl succinic anhydride (ASA) emulsion in an aqueous solution of cationic starchy material, comprising the steps of: a) producing an aqueous solution of cationic starchy material,
b) mélanger de 1 'ASA et la solution aqueuse de matière amylacée cationique issue de l'étape a), de manière à obtenir un ratio en poids sec matière amylacée cationique / ASA inférieur à 1, préfèrentiellement compris entre 0,2 et 0,6, et très préfèrentiellement entre 0,3 et 0,5,  b) mixing ASA and the aqueous solution of cationic starchy material from step a), so as to obtain a cationic starch / ASA dry weight ratio of less than 1, preferably between 0.2 and 0, 6, and very preferably between 0.3 and 0.5,
c) réaliser en un seul passage dans une unité d'émulsification une émulsion à partir du mélange issu de 1 ' étape b) , caractérisé en ce que : le procédé ne fait pas intervenir la recirculation de 1 'émulsion issue de l'étape c) au niveau de l'unité d ' émulsification,  c) producing in a single pass in an emulsification unit an emulsion from the mixture resulting from step b), characterized in that: the process does not involve the recirculation of the emulsion resulting from step c ) at the level of the emulsification unit,
et en ce que la teneur en matière sèche de la solution aqueuse de matière amylacée cationique issue de l'étape a) est comprise entre 5,5 % et 11,5 %, préfèrentiellement entre 7 % et 10 % de son poids total.  and in that the dry matter content of the aqueous solution of cationic starchy material from step a) is between 5.5% and 11.5%, preferably between 7% and 10% of its total weight.
2. Procédé de fabrication d'une émulsion d'ASA dans une solution aqueuse de matière amylacée cationique selon la revendication 1, caractérisé en ce que : ledit procédé est réalisé dans un dispositif constitué de :2. Process for producing an ASA emulsion in an aqueous cationic starchy material solution according to claim 1, characterized in that: said method is carried out in a device consisting of:
- une unité de stockage (a') d'une solution aqueuse de matière amylacée cationique pour la réalisation de l 'étape a) , a storage unit (a ') of an aqueous solution of cationic starchy material for carrying out step a),
- une unité de (b') mélange d'ASA et de solution aqueuse de matière amylacée cationique, connectée avec l'unité (a'), pour la réalisation de l'étape b) ,  a unit of (b ') a mixture of ASA and of an aqueous solution of cationic starchy material, connected with the unit (a'), for carrying out step b),
- une unité d'émulsification (c') du mélange d'ASA et de la solution aqueuse de matière amylacée cationique, connectée avec l'unité (b'), pour la réalisation de an emulsification unit (c ') of the mixture of ASA and the aqueous solution of cationic starchy material, connected with the unit (b'), for the production of
1 'étape c) , Step c),
ledit dispositif ne présentant pas de boucle de recirculation au niveau de l'unité d'émulsification (c'). 3 - Procédé selon la revendication 1 ou 2, caractérisé en ce que la solution aqueuse de matière amylacée cationique présente un taux d'azote fixé inférieur à 3,5 %, préfèrentiellement compris entre 0,3 % et 3,5 %, très préfèrentiellement entre 0,7 % et 2 % en poids sec d'azote par rapport au poids total sec de matière amylacée cationique . said device does not have a recirculation loop at the emulsification unit (c '). 3 - Process according to claim 1 or 2, characterized in that the aqueous solution of cationic starchy material has a fixed nitrogen content of less than 3.5%, preferably between 0.3% and 3.5%, very preferentially between 0.7% and 2% by dry weight of nitrogen relative to the total dry weight of cationic starchy material.
4 - Procédé selon une des revendications 1 à 3, caractérisé en ce que l'ASA est un produit d'origine synthétique. 4 - Process according to one of claims 1 to 3, characterized in that the ASA is a product of synthetic origin.
5 - Procédé selon une des revendications 1 à 4, caractérisé en ce que la matière amylacée cationique est modifiée à partir d'une opération choisie parmi l'hydrolyse, les transformations chimiques et physiques, mécaniques, thermomécaniques ou encore thermiques. 5 - Process according to one of claims 1 to 4, characterized in that the cationic starchy material is modified from an operation selected from hydrolysis, chemical and physical, mechanical, thermomechanical or thermal transformations.
6 - Dispositif constitué de : - une unité de stockage (a') d'une solution aqueuse de matière amylacée cationique, 6 - Device consisting of: a storage unit (a ') of an aqueous solution of cationic starchy material,
une unité de mélange (b') d'ASA et de solution aqueuse de matière amylacée cationique, connectée avec l'unité (a')  a mixing unit (b ') of ASA and an aqueous solution of cationic starch material, connected with the unit (a')
- une unité d 'émulsification (c') du mélange d'ASA dans la solution aqueuse de matière amylacée cationique, connectée avec l'unité (b') ledit dispositif ne présentant pas de boucle de recirculation au niveau de l'unité d'émulsification (c') .  an emulsification unit (c ') of the ASA mixture in the aqueous solution of cationic starchy material, connected with the unit (b'), said device having no recirculation loop at the level of the unit of emulsification (c ').
EP13737311.4A 2012-06-12 2013-06-12 Method for producing an emulsion of alkenyl succinic anhydride (asa) in an aqueous solution of a cationic amylaceous substance, resulting emulsion, and use thereof Active EP2859146B1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
FR1255493A FR2991685B1 (en) 2012-06-12 2012-06-12 PROCESS FOR PRODUCING SUCCINIC ALKENYL ANHYDRIDE (ASA) EMULSION IN AQUEOUS SOLUTION OF CATIONIC AMYLACEOUS MATERIAL, EMULSION OBTAINED AND USE THEREOF
PCT/FR2013/051374 WO2013186491A1 (en) 2012-06-12 2013-06-12 Method for producing an emulsion of alkenyl succinic anhydride (asa) in an aqueous solution of a cationic amylaceous substance, resulting emulsion, and use thereof

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FR3019823B1 (en) 2014-04-11 2017-10-27 Roquette Freres PROCESS FOR PRODUCING SUCCINIC ALKENYL ANHYDRIDE EMULSION
CN110075728A (en) * 2019-04-28 2019-08-02 邱振权 A kind of ASA emulsifier unit and control method
CN112538780A (en) * 2020-12-22 2021-03-23 浙江凯丰新材料股份有限公司 Online emulsification device of ASA sizing agent

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EP0186956A3 (en) * 1984-12-26 1986-10-08 United States Gypsum Company Paper machine polymer systems and methods for their use
US5653915A (en) 1995-05-10 1997-08-05 Pardikes; Dennis G. Method of preparing polymer succinic anhydride
FR2734005B1 (en) 1995-05-12 1997-07-18 Roquette Freres COMPOSITION AND METHOD FOR GLUING PAPER
US5595631A (en) 1995-05-17 1997-01-21 National Starch And Chemical Investment Holding Corporation Method of paper sizing using modified cationic starch
DE19610995C2 (en) 1996-03-21 2002-12-19 Betzdearborn Inc Paper sizing agents and processes
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US6207719B1 (en) 1998-08-19 2001-03-27 Dennis G. Pardikes Method and system for preparing ASA emulsion
US6787574B1 (en) * 2000-10-24 2004-09-07 Georgia-Pacific Resins, Inc. Emulsification of alkenyl succinic anhydride size
FR2857365B1 (en) 2003-07-08 2005-09-30 Roquette Freres NOVEL LIQUID CATIONIC AMYLACEE COMPOSITION AND USES THEREOF
US20100307706A1 (en) * 2005-03-03 2010-12-09 Kemira Oyj Reduced shear cellulose reactive sizing agent for wet end applications
US7455751B2 (en) * 2005-04-15 2008-11-25 Nalco Company Use of alkenyl succinic anhydride compounds derived from symmetrical olefins in internal sizing for paper production
FR2897280A1 (en) * 2006-02-13 2007-08-17 Arjowiggins Soc Par Actions Si Preparation of alkenyl succinic anhydride sizing emulsion useful for paper sizing, comprises ultrasonic usage
JP2010526945A (en) * 2007-05-09 2010-08-05 バックマン・ラボラトリーズ・インターナショナル・インコーポレーテッド ASA sizing emulsion for paper and board

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CN104364442A (en) 2015-02-18
FR2991685B1 (en) 2015-05-15
PT2859146T (en) 2020-12-04
FR2991685A1 (en) 2013-12-13
IN2014DN09917A (en) 2015-08-14
EP2859146B1 (en) 2020-09-02

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