EP2431165B1 - Compression punch of a powder material with a non-adhesive surface and press provided with such a punch - Google Patents

Compression punch of a powder material with a non-adhesive surface and press provided with such a punch Download PDF

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Publication number
EP2431165B1
EP2431165B1 EP20100305986 EP10305986A EP2431165B1 EP 2431165 B1 EP2431165 B1 EP 2431165B1 EP 20100305986 EP20100305986 EP 20100305986 EP 10305986 A EP10305986 A EP 10305986A EP 2431165 B1 EP2431165 B1 EP 2431165B1
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EP
European Patent Office
Prior art keywords
punch
punches
powder
bonding
punch according
Prior art date
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Application number
EP20100305986
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German (de)
French (fr)
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EP2431165A1 (en
Inventor
Vincent Jollivet
M. Cédric Marchand
M. Thierry Brousse
Cédric Martin
M. Pierre Tchoreloff
Virginie Busignies
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ELIZABETH EUROPE
Universite de Nantes
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Universite de Nantes
E P M O
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Priority to EP20100305986 priority Critical patent/EP2431165B1/en
Priority to ES10305986T priority patent/ES2421433T3/en
Publication of EP2431165A1 publication Critical patent/EP2431165A1/en
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D9/00—Electrolytic coating other than with metals
    • C25D9/02—Electrolytic coating other than with metals with organic materials
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B30—PRESSES
    • B30B—PRESSES IN GENERAL
    • B30B15/00—Details of, or accessories for, presses; Auxiliary measures in connection with pressing
    • B30B15/06—Platens or press rams
    • B30B15/065—Press rams

Definitions

  • the present invention relates to the manufacture of powder compression punches as well as the application of punches in industrial compression presses for the production of tablets in series, particularly in the field of drug manufacture.
  • the term "punch” refers to tools that are movable in bores and function as pistons for compacting a powder in a matrix that contains it and thereby obtain an agglomerated powder tablet.
  • the technique is used in industrial production for all kinds of products that are marketed in the form of properly dosed units for the intended use.
  • the materials used in the industrial manufacture of tablets are also very diverse.
  • the punches transmit compressive forces from the compression press (compression roller) to the powder in a cyclic and repetitive manner to produce identical tablets per batch so that said punches are subjected to repetitive stresses.
  • a major problem encountered in the production of tablets by compaction of powdery materials concerns the adhesion of the powder used which tends to accumulate on the surface of the active part of the punch, the one that comes into contact with the powder .
  • This phenomenon of adhesion, called bonding has negative consequences on the appearance and the quality of the tablets obtained, and on the feasibility of the compression process itself.
  • the document DE 296 19 564 U1 discloses a compression punch one of whose surfaces is coated with a release layer, said layer being formed of an inorganic material such as a metal, a semi-metal, carbon, a carbide, a nitride, a boride or an oxide.
  • a first type of bonding is the bonding by mechanical anchoring of the powder to the surface of the punch.
  • This physical bonding corresponds to a geometric affinity between the particles of powders that will be compressed and the surface of the tools of compression. It can take place at several levels: macroscopic at the level of etchings or strips of breakability or microscopic at the surface state of metal tools. In the latter case, the bond depends on the roughness of the original surface or created by the wear.
  • a certain level of polishing is required.
  • the surface of the punches is therefore generally polished to a greater or lesser degree depending on the characteristics of the tablets and the nature of the powder used. The surface is usually repolished during its use. Of course, such a polishing has a cost all the more high that one desires a smoothest possible surface state and that the punch is difficult to polish.
  • "Simple" surfaces are easier to polish than complex surfaces, for example having areas in excess and / or hollow.
  • a second type of bonding is a physico-chemical bonding between the powder and the punch.
  • This bonding corresponds to an energy affinity between the particles of powders to be compressed and the surface of the tools.
  • tablet manufacturers have proposed to change the formulation of their compositions to make them less sticky.
  • a solution conventionally used is in particular to add a lubricant such as magnesium stearate.
  • magnesium stearate such as magnesium stearate.
  • some presses are equipped to perform a magnesium stearate spray on the surface of the punches before filling the compression chamber. Rates are greatly reduced and tablets may have surface defects.
  • the press can also be equipped with a cooling system, the increase in temperature favoring "physico-chemical" bonding. This option is not widespread.
  • plastic inserts can be glued to the surface of the punches in a housing provided for this purpose. They must however be very regularly replaced because little wear resistant.
  • the invention proposes a compression punch of a powdery material for a press to be compressed, which is characterized in that at least the active part of the punch is made of a material on the surface of which are grafted by covalent bond radicals comprising a fluorocarbon molecular group with anti-sticking effect.
  • a molecular group means that the compound has one or more groups.
  • the anti-sticking effect of these grafts is remarkable in that it has an affinity anti-sticking effect while avoiding sticking of the powdery material by mechanical anchoring because it does not degrade the roughness of the surfaces in contact with the systems. powdery.
  • the punch with this surface treatment according to the invention has the advantage of having a surface roughness Ra (arithmetic mean roughness), for the active part of the punch, as it is required, which is preferably of order of 0.02 to 0.03 ⁇ m.
  • the invention also relates to a compression press comprising a punch with compounds grafted onto the surface of its active part, as described above.
  • the compression press comprises a tablet forming die plate, and upper punches and lower punches mounted on either side of the die plate.
  • the lower punches close the base of the matrix to regulate the quantity of pulverulent material poured in excess by the upper orifice of the matrix, and said upper punches, by their active portion exiting the punch guide, compress said powdery material in the matrix to form the tablets.
  • the press is such that at least said upper or lower punches, and in general both, are made with an active part anti-stick effect as described above.
  • the invention applies to all compression presses in which, in operation, the tablets are produced from a powder placed in a matrix (or compression chamber) and which is compacted. inside this matrix by compression action of one or more punches.
  • electrochemically grafted grafts comprising fluorocarbon-based molecular groups with an anti-sticking effect are applied to the surface of the active part of a punch.
  • This grafting is done in two stages.
  • the first step of the surface treatment consists in generating in situ, in the presence of electrolyte, a diazonium salt by reduction of an aromatic amine whose benzene nucleus has as substituent (s) one or more fluoroalkyl groups.
  • the diazonium salt can be used directly if it is commercially available.
  • the second step concerns the electrochemical grafting of said benzene ring thus substituted, by electrochemical reduction of the aryl diazonium cation on the surface of the punch.
  • the electrochemical reduction of the aromatic diazonium cation leads to the formation of an aryl radical.
  • the latter reacts with the electroconductive surface to functionalize by electron exchange to form a covalent bond.
  • This second step can be done for example by cyclic voltammetry with linear variation of potential or by chronoamperometry.
  • the cyclic voltammetry with linear variation of potential is a conventional electrochemical method which consists in applying to the working electrode (where it is desired to make an electrochemical reaction) a voltage potential which varies linearly and periodically, between two extreme values (chosen in function of the stability of the supporting electrolyte and the electrode material) and to follow the response current.
  • variable potential is imposed between the reference electrode and the working electrode while the current is measured between the working electrode and the counter-electrode.
  • the intensity is plotted as a function of the potential to obtain voltammograms which give information on the reactions occurring at the surface of the working electrode, such as the reduction or oxidation of electroreactive species.
  • the chronoamperometry is an electrochemical method which consists of imposing a fixed potential on the working electrode to allow the desired redox reaction, this potential having been determined by the voltammetry method described above.
  • the response current as a function of time is measured between the working electrode and the counter-electrode.
  • the currents decrease over time, which means that there is grafting on the surface of the punch (working electrode) as explained above.
  • the current becomes constant, the grafting reaction on the punch surface is completed.
  • the reaction is conducted for the necessary time indicated in the examples.
  • EXAMPLE 1 Fluorescent surface treatment of a punch with a tungsten doped amorphous diamond carbon (CDA-W) coating.
  • CDA-W tungsten doped amorphous diamond carbon
  • EXAMPLE 2 Fluoride surface treatment of a punch with a steel coating (GRANE).
  • the compression of the pulverulent material is carried out in a range of forces included between a minimum force and a maximum force. Each of these forces was determined according to the nature of the grain of the powder, the raw materials constituting the powder and the environmental conditions (temperature, moisture) of the compression as well as the thickness, the mass, the hardness, the friability, the desired disintegration capacity for the tablet. If the compressive force is too high, the tablet will have too much disintegration time and too little thickness. If the compression force is not high enough, then the tablet will have too little disintegration time and too much thickness. Outside this range, the resulting tablets are considered non-compliant.
  • Each powder has its own properties. Characterization of the ability of the punches not to give bonding was performed with two powders of different formulations. A first test was made with a trade powder A deemed very sticky. A second test was carried out with another powder, referenced powder B, much less tacky than powder A.
  • the bonding of the powder to the punches is force-dependent, namely that it decreases when the compressive force is increased. This is a progressive phenomenon with a more or less significant enrichment of the surface of the punches by the powder, and it is possible to determine a "threshold force" below which the bonding obtained is no longer acceptable industrially.
  • This threshold force depends on the propensity of the surfaces to cause bonding. The lower the threshold force, the less the surfaces will cause sticking.
  • the criterion for assessing bonding is a visual criterion based on the appearance or not of a residual layer of powder on the surface of the punch after compression of the powder.
  • a minimum compressive force of 7 kN and a maximum compressive force of 10 kN are determined, between which the powder must be compressed to produce tablets having the required characteristics.
  • test results are listed in the table below: tools Threshold force Result Standard steel 13.7 kN Systematic bonding in industrial conditions Standard steel, standard coating 16.5 kN Systematic bonding in industrial conditions Standard steel, polishing 11.2 kN Systematic bonding in industrial conditions Standard steel, standard coating, polishing 14.8 kN Systematic bonding in industrial conditions Standard steel with plastic insert glued on the active part 6.7 kN never sticking in the laboratory but life time too low for industrial use Standard steel, standard polishing, grafting C 6 H 3 - (CF 3 ) 2 8.5 kN Random collage based on applied compression force Standard steel, standard polishing, grafting C 6 H 4 -C 8 F 17 6.9 kN Never gluing in industrial conditions
  • the standard steel punch is tested with a standard polishing, the surface of which comprises grafts according to Example 1.
  • a standard polishing the surface of which comprises grafts according to Example 1.
  • Such a surface does not systematically give rise to bonding of the powder A, which is unacceptable under industrial conditions. bonding tolerable or sometimes crippling in the range of compressive forces.
  • the threshold force to observe no unacceptable bonding is lowered compared to the untreated punch, it is 8.5 kN. Since this threshold force is within the range of forces required, the punch thus treated generally makes it possible to produce industrially under satisfactory conditions as long as the compression force remains greater than 8.5 kN.
  • the standard steel punch is then tested with a standard polishing, the surface of which comprises grafts according to Example 2. Such a surface gives no bonding (absence of bonding) with the powder A under industrial conditions.
  • the threshold force is less than 7kN. The industrial production of tablets can be done without problem of gluing with this punch.
  • a minimum compressive force of 14 kN and a maximum compressive force of 16 kN are determined between which must be the compression of the powder B to make tablets with the required characteristics.
  • test results are listed in the table below: tools Threshold force Result Standard steel 12 kN Never gluing in industrial conditions Standard steel, standard coating 10 kN Never gluing in industrial conditions Standard steel with plastic insert glued on the active part 5 kN never sticking in the laboratory but life time too low for industrial use Standard steel, standard polishing, grafting C 6 H 3 - (CF 3 ) 2 7 kN Never gluing in industrial conditions Standard steel, standard polishing, grafting C 6 H 4 -C 8 F 17 6.1 kN Never gluing in industrial conditions
  • the standard steel punch is also tested with standard polishing, the surface of which has grafts in accordance with Example 1. Such a surface gives no bonding with powder B under industrial conditions and the threshold force is about 7kN.
  • the standard steel punch is tested with a standard polishing, the surface of which comprises grafts according to Example 2. Such a surface gives no bonding of the powder B under industrial conditions and the threshold force is about 6 kN.
  • the punch does not give any bonding, the punch once treated on the surface sees its threshold force lowered.
  • the grafting of the punch surface with a compound comprising two -CF 3 groups or the -C 8 F 17 chain decreases the threshold force below which the bonding is unacceptable.
  • the punches obtained according to the present invention thus have anti-bonding characteristics combined with an abrasion resistance never obtained before.
  • In situ tests also made it possible to validate the results obtained and to verify their significantly longer life compared with the prior art.
  • the grafting may be carried out by chemical reaction between the antiblocking molecular group radical and the surface of the punch to be treated.
  • the grafting can be done by photochemical means such as an irradiation which produces electrons on the surface of the punch to be treated.

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  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Mechanical Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Battery Electrode And Active Subsutance (AREA)
  • Solid-Sorbent Or Filter-Aiding Compositions (AREA)
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Description

La présente invention concerne la fabrication des poinçons de compression de poudre ainsi que l'application des poinçons dans les presses à comprimer industrielles servant à la fabrication de comprimés en série, notamment dans le domaine de la fabrication de médicament.The present invention relates to the manufacture of powder compression punches as well as the application of punches in industrial compression presses for the production of tablets in series, particularly in the field of drug manufacture.

D'une manière générale le terme de poinçon désigne des outils qui sont mobiles dans des alésages et fonctionnent comme des pistons pour assurer le compactage d'une poudre dans une matrice qui la contient et obtenir ainsi un comprimé de poudre agglomérée. La technique est utilisée en production industrielle pour toutes sortes de produits que l'on commercialise ainsi sous la forme d'unités correctement dosées pour l'usage envisagé.Generally, the term "punch" refers to tools that are movable in bores and function as pistons for compacting a powder in a matrix that contains it and thereby obtain an agglomerated powder tablet. The technique is used in industrial production for all kinds of products that are marketed in the form of properly dosed units for the intended use.

Sans être d'aucune manière limitatif, on peut citer le cas des poudres à laver, celui des comprimés à dissoudre dans l'industrie alimentaire, celui des compositions pharmaceutiques administrées sous forme de comprimés, ou encore l'industrie du nucléaire (retraitement).Without being in any way limiting, mention may be made of the powders to be washed, that of the tablets to be dissolved in the food industry, that of the pharmaceutical compositions administered in the form of tablets, or the nuclear industry (reprocessing).

Suivant l'application, il est plus ou moins important de respecter un degré de cohésion déterminé de la poudre dans le comprimé. Les exigences à cet égard sont particulièrement sévères quand on traite des comprimés à usage pharmaceutique, qui ne doivent en général pas se déliter avant d'être parvenus dans l'estomac du malade.Depending on the application, it is more or less important to respect a certain degree of cohesion of the powder in the tablet. The requirements in this regard are particularly severe when treating tablets for pharmaceutical use, which generally do not have to disintegrate before reaching the stomach of the patient.

Les matériels utilisés dans le cadre de la fabrication industrielle de comprimés sont également très divers. Les poinçons transmettent les forces de compression de la presse à comprimer (galet de compression) à la poudre d'une manière cyclique et répétitive permettant de produire des comprimés identiques par lot, de sorte que lesdits poinçons sont soumis à des contraintes répétitives.The materials used in the industrial manufacture of tablets are also very diverse. The punches transmit compressive forces from the compression press (compression roller) to the powder in a cyclic and repetitive manner to produce identical tablets per batch so that said punches are subjected to repetitive stresses.

Pour mieux appréhender ce que représente le besoin de résistance et longévité en fonctionnement on pourra se référer à la description d'une presse à comprimer de type particulier dans la demande de brevet FR 2 908 683 . Il s'agit alors d'une presse à tourelle rotative, mais les qualités à attendre des poinçons seraient les mêmes pour d'autres types de presses, celles à fonctionnement alternatif par exemple, ou à introduction de la poudre au milieu de la matrice par la force centrifuge.To better understand what the need for resistance and durability in operation represents, reference may be made to the description of a particular type of tablet press in the patent application. FR 2 908 683 . It is then a rotary turret press, but the qualities to expect punches would be the same for other types of presses, those to alternating operation for example, or introduction of the powder in the middle of the matrix by the centrifugal force.

Un problème important rencontré lors de la fabrication de comprimés par compactage de matières pulvérulentes concerne l'adhérence de la poudre mise en oeuvre qui tend à s'accumuler à la surface de la partie active du poinçon, celle qui vient en contact avec de la poudre. Ce phénomène d'adhérence, dit de collage, a des conséquences négatives sur l'aspect et la qualité des comprimés obtenus, et sur la faisabilité même du procédé de compression.A major problem encountered in the production of tablets by compaction of powdery materials concerns the adhesion of the powder used which tends to accumulate on the surface of the active part of the punch, the one that comes into contact with the powder . This phenomenon of adhesion, called bonding, has negative consequences on the appearance and the quality of the tablets obtained, and on the feasibility of the compression process itself.

On peut notamment observer des défauts de masse, de dimensions et d'uniformité de surface des comprimés obtenus. Dans le domaine pharmaceutique, cela peut affecter l'esthétique des comprimés tout comme leur quantité en principes actifs.In particular, defects in the mass, dimensions and uniformity of the surface of the tablets obtained can be observed. In the pharmaceutical field, this can affect the aesthetics of tablets as well as their amount of active ingredients.

Lors de l'apparition du collage, on opère un démontage, un nettoyage et un polissage des poinçons qui constitue une opération fastidieuse et qui diminue la durée de vie des poinçons.During the appearance of the bonding, it disassembles, cleaning and polishing punches which is a tedious operation and reduces the life of the punches.

Pour lutter contre ce phénomène de collage, une pratique couramment utilisée est d'augmenter la force de compression afin de renforcer la cohésion interne du comprimé. Cela présente cependant plusieurs inconvénients et engendre des désagréments, notamment le fait d'obtenir des comprimés non-conformes en termes d'épaisseur, de dureté, de durée de délitement, de sécabilité. Des phénomènes de clivage et de grippage peuvent également survenir. Enfin, la presse à comprimer et surtout les outillages sont soumis à des contraintes plus importantes qui entrainent au mieux une usure accélérée au pire une rupture des parties actives.To combat this phenomenon of sticking, a common practice is to increase the compression force to enhance the internal cohesion of the tablet. However, this has several disadvantages and causes inconvenience, including the fact of obtaining non-compliant tablets in terms of thickness, hardness, disintegration time, breakability. Cleavage and seizure phenomena can also occur. Finally, the press to compress and especially the tools are subject to greater constraints that lead at best accelerated wear at worst a rupture of the active parts.

Par ailleurs, le document DE 296 19 564 U1 décrit un poinçon de compression dont l'une des surfaces est revêtue d'une couche anti-adhérence, ladite couche étant formée d'un matériau inorganique tel qu'un métal, un semi-métal, du carbone, un carbure, un nitrure, un borure ou bien encore un oxyde.In addition, the document DE 296 19 564 U1 discloses a compression punch one of whose surfaces is coated with a release layer, said layer being formed of an inorganic material such as a metal, a semi-metal, carbon, a carbide, a nitride, a boride or an oxide.

Il existe donc un besoin de proposer des poinçons résolvant les problèmes de collage avec les poudres à la base de la fabrication des comprimés. Tel est l'objectif de la présente invention. En traitant ce problème, il n'est pas inutile de prendre en compte les connaissances acquises concernant les différentes raisons à la base des phénomènes de collage.There is therefore a need to provide punches solving gluing problems with the powders at the base of the manufacture of tablets. This is the purpose of the present invention. In dealing with this problem, it is not useless to take into account the knowledge acquired concerning the various reasons underlying the collage phenomena.

Un premier type de collage est le collage par ancrage mécanique de la poudre à la surface du poinçon. Ce collage physique correspond à une affinité géométrique entre les particules de poudres qui vont être comprimées et la surface des outillages de compression. Elle peut avoir lieu à plusieurs niveaux : macroscopique au niveau des gravures ou des barrettes de sécabilité ou microscopique au niveau de l'état de surface des outillages métalliques. Dans ce dernier cas, le collage dépend de la rugosité de la surface d'origine ou créée par l'usure. Pour éviter cet ancrage mécanique, un certain niveau de polissage est requis. La surface des poinçons est donc généralement polie à un degré plus ou moins poussé selon les caractéristiques des comprimés et de la nature de la poudre utilisée. La surface est généralement repolie au cours de son utilisation. Bien entendu, un tel polissage présente un coût d'autant plus élevé que l'on souhaite un état de surface le plus lisse possible et que le poinçon est difficile à polir. Les surfaces « simples » sont plus faciles à polir que les surfaces complexes, par exemple présentant des zones en surépaisseur et/ou en creux.A first type of bonding is the bonding by mechanical anchoring of the powder to the surface of the punch. This physical bonding corresponds to a geometric affinity between the particles of powders that will be compressed and the surface of the tools of compression. It can take place at several levels: macroscopic at the level of etchings or strips of breakability or microscopic at the surface state of metal tools. In the latter case, the bond depends on the roughness of the original surface or created by the wear. To avoid this mechanical anchoring, a certain level of polishing is required. The surface of the punches is therefore generally polished to a greater or lesser degree depending on the characteristics of the tablets and the nature of the powder used. The surface is usually repolished during its use. Of course, such a polishing has a cost all the more high that one desires a smoothest possible surface state and that the punch is difficult to polish. "Simple" surfaces are easier to polish than complex surfaces, for example having areas in excess and / or hollow.

Un deuxième type de collage est un collage de type physico-chimique entre la poudre et le poinçon. Ce collage correspond à une affinité énergétique entre les particules de poudres à comprimer et la surface des outillages. Pour lutter contre ce type de collage, en en l'absence de solution côté outillage, les fabricants de comprimés ont proposé de modifier la formulation de leurs compositions pour les rendre moins collantes. Une solution classiquement utilisée est notamment d'ajouter un lubrifiant tel que du stéarate de magnésium. Ainsi, certaines presses sont équipées pour réaliser une pulvérisation de stéarate de magnésium à la surface des poinçons avant le remplissage de la chambre de compression. Les cadences sont fortement diminuées et les comprimés peuvent présenter des défauts de surface. Pour certains produits thermosensibles, la presse peut également être équipée d'un système de refroidissement, l'accroissement de la température favorisant le collage « physico chimique ». Cette option est peu répandue. Pour certains produits présentant une géométrie appropriée (surface plane, absence de gravure), des inserts en matières plastiques peuvent être collés à la surface des poinçons dans un logement prévu à cet effet. Ils doivent être cependant très régulièrement remplacés car peu résistant à l'usure.A second type of bonding is a physico-chemical bonding between the powder and the punch. This bonding corresponds to an energy affinity between the particles of powders to be compressed and the surface of the tools. To fight against this type of bonding, in the absence of solution tooling side, tablet manufacturers have proposed to change the formulation of their compositions to make them less sticky. A solution conventionally used is in particular to add a lubricant such as magnesium stearate. Thus, some presses are equipped to perform a magnesium stearate spray on the surface of the punches before filling the compression chamber. Rates are greatly reduced and tablets may have surface defects. For certain heat-sensitive products, the press can also be equipped with a cooling system, the increase in temperature favoring "physico-chemical" bonding. This option is not widespread. For certain products with appropriate geometry (flat surface, no etching), plastic inserts can be glued to the surface of the punches in a housing provided for this purpose. They must however be very regularly replaced because little wear resistant.

Par conséquent, aucune de ces solutions n'est optimale sur un plan industriel et ne permet d'atteindre une qualité de comprimé, des cadences de fabrication élevées, et des couts réduits de fabrication, de maintenance et d'équipement.Therefore, none of these solutions are industrially optimal and can achieve tablet quality, high production rates, and reduced manufacturing, maintenance and equipment costs.

Ainsi, il a été recherché un traitement de la surface du poinçon conférant des propriétés anti-collage par non affinité vis-à-vis des poudres à comprimer, tout en permettant un niveau de rugosité de surface évitant le collage par ancrage mécanique. Dans le cadre de l'invention, il a été mis en évidence que la surface de la partie active du poinçon doit être fonctionnalisée chimiquement par des molécules apportant cet effet anti-collage.Thus, it has been sought a treatment of the surface of the punch conferring non-affinity anti-bonding properties vis-à-vis the powders to be compressed, while allowing a level of surface roughness avoiding bonding by mechanical anchoring. In the context of the invention, it has been demonstrated that the surface of the active portion of the punch must be chemically functionalized with molecules providing this anti-sticking effect.

L'invention propose un poinçon de compression d'une matière pulvérulente pour une presse à comprimer, qui se caractérise en ce qu'au moins la partie active du poinçon est réalisée en un matériau à la surface duquel sont greffés par liaison covalente des radicaux comportant un groupe moléculaire fluoro-carboné à effet anti-collage. On entend par « un » groupe moléculaire, que le composé comporte un ou plusieurs groupes.The invention proposes a compression punch of a powdery material for a press to be compressed, which is characterized in that at least the active part of the punch is made of a material on the surface of which are grafted by covalent bond radicals comprising a fluorocarbon molecular group with anti-sticking effect. The term "a" molecular group means that the compound has one or more groups.

L'effet anti-collage de ces greffons est remarquable dans la mesure où il a un effet anti-collage par affinité tout en évitant un collage de la matière pulvérulente par ancrage mécanique car elle ne dégrade pas la rugosité des surfaces en contact avec les systèmes pulvérulents.The anti-sticking effect of these grafts is remarkable in that it has an affinity anti-sticking effect while avoiding sticking of the powdery material by mechanical anchoring because it does not degrade the roughness of the surfaces in contact with the systems. powdery.

Selon des modes de réalisation préférés, l'ensemble conforme à la présente invention comprend l'une au moins des caractéristiques suivantes :

  • ledit groupe moléculaire fluoro-carboné est un groupe fluoroalkyle, de préférence un groupe alkyle dont tous les atomes d'hydrogène ont été substitués par un atome de fluor ;
  • ledit groupe moléculaire est lié à la surface dudit matériau par un groupe aryle, en particulier un groupe phényle, dont au moins un substituant sur le noyau benzénique est constitué par ledit groupe moléculaire présentant un effet anti-collage ;
  • le groupe fluoroalkyle est la chaîne linéaire CnF2n+1, n étant un entier supérieur ou égal à 1 ;
  • lorsque n est égal à 1, le noyau benzénique comporte un ou plusieurs groupes CF3 comme substituant, et lorsque n est égal à 8, le noyau benzénique comporte un seul substituant C8F17 ;
  • les radicaux greffés sont choisis parmi le trifluorométhylphényle et le perfluorooctylphényle ;
  • les radicaux sont greffés par un procédé électrochimique à deux et/ou trois électrodes tel que la voltammétrie cyclique, la chronoampérométrie ou la chronopotentiométrie,
  • les poinçons sont généralement en acier standard pour outillage, pouvant supporter des pressions élevées (5 à 50 kN/cm2) et avec une certaine capacité à subir des flexions. L'acier de base peut être un acier faiblement allié. Un acier dit « standard », ayant les propriétés requises pour des poinçons selon l'invention, peut être l'acier 55 NCD12. Cet acier comporte environ 0,55 % de carbone, 3% de nickel, ainsi que du chrome et du molybdène en plus faibles teneurs.
According to preferred embodiments, the assembly according to the present invention comprises at least one of the following characteristics:
  • said fluoro-carbon molecular group is a fluoroalkyl group, preferably an alkyl group, all of whose hydrogen atoms have been substituted by a fluorine atom;
  • said molecular group is bonded to the surface of said material by an aryl group, in particular a phenyl group, at least one substituent on the benzene ring is constituted by said molecular group having an anti-sticking effect;
  • the fluoroalkyl group is the linear chain C n F 2n + 1 , n being an integer greater than or equal to 1;
  • when n is 1, the benzene ring has one or more CF 3 groups as a substituent, and when n is 8, the benzene ring has a single C 8 F 17 substituent;
  • the grafted radicals are chosen from trifluoromethylphenyl and perfluorooctylphenyl;
  • the radicals are grafted by an electrochemical process with two and / or three electrodes such as cyclic voltammetry, chronoamperometry or chronopotentiometry,
  • the punches are generally standard tooling steel, capable of withstanding high pressures (5 to 50 kN / cm 2 ) and with some ability to flex. The base steel may be a low alloy steel. A so-called "standard" steel, having the properties required for punches according to the invention, can be steel 55 NCD12. This steel has about 0.55% carbon, 3% nickel, and lower chromium and molybdenum.

Le poinçon avec ce traitement de surface selon l'invention, présente l'avantage d'avoir une rugosité de surface Ra (rugosité moyenne arithmétique), pour la partie active du poinçon, telle qu'usuellement requise, qui est de préférence de l'ordre de 0,02 à 0,03 µm.The punch with this surface treatment according to the invention has the advantage of having a surface roughness Ra (arithmetic mean roughness), for the active part of the punch, as it is required, which is preferably of order of 0.02 to 0.03 μm.

De plus avec ce traitement de surface selon l'invention, on parvient à obtenir un poinçon qui a une dureté de surface au moins égale à 600 Hv (dureté Vickers), de préférence au moins égale à 1500 Hv, de préférence de l'ordre de 2000 à 3000 Hv. Une telle dureté confère au poinçon une durée de vie suffisante en conditions industrielles.Moreover with this surface treatment according to the invention, it is possible to obtain a punch which has a surface hardness of at least 600 Hv (Vickers hardness), preferably at least 1500 Hv, preferably of the order from 2000 to 3000 Hv. Such hardness gives the punch a sufficient life in industrial conditions.

L'invention concerne aussi une presse à comprimer comprenant un poinçon avec des composés greffés sur la surface de sa partie active, tel que décrit précédemment.The invention also relates to a compression press comprising a punch with compounds grafted onto the surface of its active part, as described above.

Selon un cas particulier de l'invention, la presse à comprimer comprend un plateau à matrices de formage des comprimés, et des poinçons supérieurs et des poinçons inférieurs montés de part et d'autre du plateau à matrices. Les poinçons inférieurs viennent obturer la base de la matrice pour régler la quantité de matière pulvérulente versée en excès par l'orifice supérieur de la matrice, et lesdits poinçons supérieurs, par leur partie active sortant du guide poinçon, viennent comprimer ladite matière pulvérulente dans la matrice pour former les comprimés. La presse est telle qu'au moins lesdits poinçons supérieurs ou inférieurs, et en général les deux, sont réalisés avec une partie active à effet anti collage comme décrit précédemment.According to a particular case of the invention, the compression press comprises a tablet forming die plate, and upper punches and lower punches mounted on either side of the die plate. The lower punches close the base of the matrix to regulate the quantity of pulverulent material poured in excess by the upper orifice of the matrix, and said upper punches, by their active portion exiting the punch guide, compress said powdery material in the matrix to form the tablets. The press is such that at least said upper or lower punches, and in general both, are made with an active part anti-stick effect as described above.

D'une façon plus générale, l'invention s'applique à toutes presses à comprimer dans lesquelles, en fonctionnement, les comprimés sont produits à partir d'une poudre mise en place dans une matrice (ou chambre de compression) et qui est compactée à l'intérieur de cette matrice par action de compression d'un ou plusieurs poinçons.In a more general manner, the invention applies to all compression presses in which, in operation, the tablets are produced from a powder placed in a matrix (or compression chamber) and which is compacted. inside this matrix by compression action of one or more punches.

L'invention sera mieux comprise à l'aide des exemples de réalisation non limitatifs décrits ci-après.The invention will be better understood with the aid of the nonlimiting exemplary embodiments described below.

Selon ces exemples, pour réaliser un poinçon de compression de poudre à comprimer selon l'invention, on greffe électrochimiquement des greffons comportant des groupes moléculaires à base de fluorocarbones à effet anti-collage à la surface de la partie active d'un poinçon.According to these examples, to produce a powder compression punch to be compressed according to the invention, electrochemically grafted grafts comprising fluorocarbon-based molecular groups with an anti-sticking effect are applied to the surface of the active part of a punch.

Ce greffage se fait en deux étapes.This grafting is done in two stages.

La première étape du traitement de surface consiste à générer in situ, en présence d'électrolyte, un sel de diazonium par réduction d'une amine aromatique dont le noyau benzénique comporte comme substituant(s) un ou plusieurs groupes fluoroalkyle. Alternativement, le sel de diazonium peut être utilisé directement s'il est disponible commercialement.The first step of the surface treatment consists in generating in situ, in the presence of electrolyte, a diazonium salt by reduction of an aromatic amine whose benzene nucleus has as substituent (s) one or more fluoroalkyl groups. Alternatively, the diazonium salt can be used directly if it is commercially available.

La seconde étape concerne le greffage électrochimique dudit noyau benzénique ainsi substitué, par réduction électrochimique du cation aryle diazonium à la surface du poinçon. La réduction électrochimique du cation diazonium aromatique conduit à la formation d'un radical aryle. Ce dernier réagit avec la surface électroconductrice à fonctionnaliser par échange d'électrons pour former une liaison covalente. Cette seconde étape peut se faire par exemple par voltammétrie cyclique à variation linéaire de potentiel ou par chronoampérométrie.The second step concerns the electrochemical grafting of said benzene ring thus substituted, by electrochemical reduction of the aryl diazonium cation on the surface of the punch. The electrochemical reduction of the aromatic diazonium cation leads to the formation of an aryl radical. The latter reacts with the electroconductive surface to functionalize by electron exchange to form a covalent bond. This second step can be done for example by cyclic voltammetry with linear variation of potential or by chronoamperometry.

De manière générale, la réduction électrochimique s'effectue avec un système à trois électrodes :

  • une électrode de référence qui est ici le couple Ag/AgCl,
  • une contre-électrode, dans le cas présent une grille de platine (Pt) avec une surface de 1 cm2,
  • l'électrode de travail est le poinçon lui-même.
In general, the electrochemical reduction is carried out with a system with three electrodes:
  • a reference electrode which is here the Ag / AgCl pair,
  • a counter electrode, in this case a platinum grid (Pt) with a surface of 1 cm 2 ,
  • the working electrode is the punch itself.

La voltammétrie cyclique à variation linéaire de potentiel est une méthode électrochimique classique qui consiste à appliquer à l'électrode de travail (où l'on souhaite faire une réaction électrochimique) un potentiel tension qui varie linéairement et périodiquement, entre deux valeurs extrêmes (choisies en fonction de la stabilité de l'électrolyte support et le matériau d'électrode) et de suivre le courant de réponse.The cyclic voltammetry with linear variation of potential is a conventional electrochemical method which consists in applying to the working electrode (where it is desired to make an electrochemical reaction) a voltage potential which varies linearly and periodically, between two extreme values (chosen in function of the stability of the supporting electrolyte and the electrode material) and to follow the response current.

Le potentiel variable est imposé entre l'électrode de référence et l'électrode de travail alors que le courant est mesuré entre l'électrode de travail et la contre-électrode. On trace l'intensité en fonction du potentiel pour obtenir les voltammogrammes qui donnent des informations sur les réactions intervenant à la surface de l'électrode de travail comme la réduction ou l'oxydation d'espèces électroréactives.The variable potential is imposed between the reference electrode and the working electrode while the current is measured between the working electrode and the counter-electrode. The intensity is plotted as a function of the potential to obtain voltammograms which give information on the reactions occurring at the surface of the working electrode, such as the reduction or oxidation of electroreactive species.

Pour les exemples qui suivent, on se place dans une fenêtre de potentiels qui induisent des courants négatifs permettant la réduction du cation diazonium concerné. On observe une vague de réduction qui traduit la réduction du sel de diazonium en radical phényle pour se greffer à la surface du poinçon et permet de déterminer le potentiel de réduction du sel de diazonium utilisé dans les conditions d'emploi. On observe aussi une diminution des courants de réponse au cours du temps qui met en évidence le greffage du radical phényle concerné à la surface du poinçon, les greffons limitant le passage des électrons à l'interface électrode/électrolyte.For the examples which follow, one places oneself in a window of potentials which induce negative currents allowing the reduction of the diazonium cation concerned. A reduction wave is observed which reflects the reduction of the diazonium salt to phenyl radical to graft on the surface of the punch and makes it possible to determine the reduction potential of the diazonium salt used in the conditions of use. There is also a decrease in the response currents over time which highlights the grafting of the phenyl radical concerned to the surface of the punch, the grafts limiting the passage of electrons to the electrode / electrolyte interface.

La chronoampérométrie est une méthode électrochimique qui consiste à imposer un potentiel fixe à l'électrode de travail pour permettre la réaction d'oxydoréduction souhaitée, ce potentiel ayant été déterminé par la méthode de voltammétrie décrite précédemment. Le courant de réponse en fonction du temps est mesuré entre l'électrode de travail et la contre-électrode.The chronoamperometry is an electrochemical method which consists of imposing a fixed potential on the working electrode to allow the desired redox reaction, this potential having been determined by the voltammetry method described above. The response current as a function of time is measured between the working electrode and the counter-electrode.

Dans les exemples qui suivent, les courants diminuent au cours du temps, ce qui traduit qu'il y a greffage à la surface du poinçon (électrode de travail) comme expliqué précédemment. Quand le courant devient constant, la réaction de greffage à la surface du poinçon est terminée. La réaction est conduite pendant le temps nécessaire indiqué aux exemples.In the examples which follow, the currents decrease over time, which means that there is grafting on the surface of the punch (working electrode) as explained above. When the current becomes constant, the grafting reaction on the punch surface is completed. The reaction is conducted for the necessary time indicated in the examples.

Dans le cas des exemples qui suivent, on applique un potentiel légèrement plus négatif que le potentiel de réduction déterminé afin de favoriser la réaction de réduction du cation diazonium.In the case of the examples which follow, a slightly more negative potential is applied than the determined reduction potential in order to promote the reduction reaction of the diazonium cation.

EXEMPLE 1 : Traitement de surface fluoré d'un poinçon avec un revêtement en carbone diamant amorphe dopé au tungstène (CDA-W). EXAMPLE 1 : Fluorescent surface treatment of a punch with a tungsten doped amorphous diamond carbon (CDA-W) coating.

Exemple 1a : Selon cet exemple 1a, on greffe le radical phényle comportant deux groupes trifluorométhyle C6H3-(CF3)2 sur la surface d'un poinçon en acier avec un revêtement en carbone diamant dopé au tungstène (CDA-W).

  • Première étape : Préparation du sel de diazonium N2 +-C6H3-(CF3)2.
    • * Dans 50 ml d'un électrolyte support (5,2 g de tétraéthylammonium tétrafluoroborate Et4NBF4 à 0,1 M dans 250 ml d'acétonitrile ACN désaéré à l'azote), on dissout 117 mg de 3,5-bis-trifluorométhylaniline [NH2-C6H3-(CF3)2]
    • * On ajoute 176 mg de réducteur tert-butylnitrite, soit 3 équivalents molaires.
    • * La solution ainsi préparée est dégazée sous bullage d'azote pendant 30 minutes.
  • Deuxième étape : Greffage du C6H3-(CF3)2 par voltammétrie cyclique à la surface du poinçon.
    • * A potentiel ouvert, on plonge le poinçon dans la solution de sel de diazonium N2 +-C6H3-(CF3)2 préparée précédemment.
    • * Après stabilisation du potentiel d'équilibre, on effectue une voltammétrie cyclique à variation linéaire de potentiel à 50 mV.s, durant 10 cycles, entre -0,5V et 0,6 V.
    • * On détermine ainsi le potentiel de réduction du sel de diazonium N2 +-C6H3-(CF3)2 sur la surface du poinçon revêtu CDA-W qui est de -0,05 V.
  • Alternative à la deuxième étape : Greffage du N2 +-C6H3-(CF3)2 par chronoampérométrie.
    • * A potentiel ouvert, on plonge le poinçon dans la solution de sel de diazonium N2 +-C6H3 (CF3)2 préparée précédemment.
    • * Après stabilisation du potentiel d'équilibre, on applique un potentiel de -0,25 V à l'électrode de travail pendant 10 minutes.
Example 1a : According to this example 1a, the phenyl radical having two C 6 H 3 - (CF 3 ) 2 trifluoromethyl groups is grafted onto the surface of a steel punch with a tungsten doped diamond carbon coating (CDA-W). .
  • First step: Preparation of the diazonium salt N 2 + -C 6 H 3 - (CF 3 ) 2 .
    • * In 50 ml of a carrier electrolyte (5.2 g of tetraethylammonium tetrafluoroborate Et 4 NBF 4 at 0.1 M in 250 ml of nitrogen-acetated ACN acetonitrile), 117 mg of 3,5-bis are dissolved -trifluoromethylaniline [NH 2 -C 6 H 3 - (CF 3 ) 2 ]
    • 176 mg of tert-butylnitrite reducer, ie 3 molar equivalents, are added.
    • * The solution thus prepared is degassed under nitrogen bubbling for 30 minutes.
  • Second step: Grafting of C 6 H 3 - (CF 3 ) 2 by cyclic voltammetry at the punch surface.
    • * At open potential, the punch is immersed in the solution of diazonium salt N 2 + -C 6 H 3 - (CF 3 ) 2 prepared above.
    • * After stabilization of the equilibrium potential, cyclic voltammetry with a linear variation of potential at 50 mV.s is carried out for 10 cycles, between -0.5V and 0.6 V.
    • The reduction potential of the diazonium salt N 2 + -C 6 H 3 - (CF 3 ) 2 on the surface of the coated punch CDA-W which is of -0.05 V. is thus determined.
  • Alternative to the second step: Grafting of N 2 + -C 6 H 3 - (CF 3 ) 2 by chronoamperometry.
    • * At open potential, the punch is immersed in the solution of diazonium salt N 2 + -C 6 H 3 (CF 3 ) 2 prepared above.
    • After stabilization of the equilibrium potential, a potential of -0.25 V is applied to the working electrode for 10 minutes.

Exemple 1b: Selon cet exemple 1b, on greffe le radical perfluorooctylphényle C6HcC8F17 sur la surface d'un poinçon en acier avec un revêtement en carbone diamant dopé au tungstène (CDA-W).

  • Première étape : Préparation du sel de diazonium N2 +-C6H4-C8F17 par réduction d'une aniline.
    • * Dans 50 ml d'un électrolyte support (5,2 g de tétraéthylammonium tétrafluoroborate Et4NBF4 à 0,1 M dans 250 ml d'acétonitrile ACN désaéré à l'azote), on dissout 255 mg de 4-perfluorooctylaniline (NH2-C6H4-C8F17).
    • * On ajoute 176 mg de tert-butylnitrite, soit 3 équivalents molaires.
    • * La solution ainsi préparée est dégazée sous bullage d'azote pendant 30 minutes.
  • Deuxième étape : greffage du C6H4C8F17 par voltammétrie cyclique.
    • * A potentiel ouvert, on plonge le poinçon dans la solution de sel de diazonium N2 +-C6H4-C8F17 préparée précédemment.
    • * Après stabilisation du potentiel d'équilibre, on effectue une voltammétrie cyclique à variation linéaire de potentiel à 50 mV.s, durant 20 cycles, entre -0,5 V et 0,2 V.
    • * On détermine le potentiel de réduction du sel de diazonium N2 +-C6H4-C8F17 sur la surface du poinçon revêtu CDA-W qui est de 0,05 V.
  • Alternative à la deuxième étape : Greffage du radical C6H4-C8F17 par chronoampérométrie :
    • * A potentiel ouvert, on plonge le poinçon en acier dans la solution du sel de diazonium N2 +-C6H4C8F17 préparée précédemment.
    • * Après stabilisation du potentiel d'équilibre, on applique un potentiel de -0,250 V à l'électrode de travail pendant 4 minutes.
Example 1b : According to this example 1b, the perfluorooctylphenyl radical C 6 H C C 8 F 17 is grafted onto the surface of a steel punch with a tungsten doped diamond carbon coating (CDA-W).
  • First step: Preparation of the diazonium salt N 2 + -C 6 H 4 -C 8 F 17 by reduction of aniline.
    • * In 50 ml of a carrier electrolyte (5.2 g of tetraethylammonium tetrafluoroborate Et 4 NBF 4 at 0.1 M in 250 ml of nitrogen-acetated ACN acetonitrile), 255 mg of 4-perfluorooctylaniline (NH 2 -C 6 H 4 -C 8 F 17 ).
    • 176 mg of tert-butylnitrite are added, ie 3 molar equivalents.
    • * The solution thus prepared is degassed under nitrogen bubbling for 30 minutes.
  • Second step: grafting of C 6 H 4 C 8 F 17 by cyclic voltammetry.
    • * A potential open, the plunger is immersed in the solution of diazonium salt N 2 + -C 6 H 4 -C 8 F 17 prepared above.
    • After stabilization of the equilibrium potential, a cyclic voltammetry with a linear variation of potential at 50 mV.s is carried out for 20 cycles, between -0.5 V and 0.2 V.
    • * The reduction potential of the diazonium salt N 2 + -C 6 H 4 -C 8 F 17 is determined on the surface of the coated punch CDA-W which is 0.05 V.
  • Alternative to the second step: Grafting of the radical C 6 H 4 -C 8 F 17 by chronoamperometry:
    • * At open potential, the steel punch is immersed in the solution of diazonium salt N 2 + -C 6 H 4 C 8 F 17 prepared above.
    • After stabilization of the equilibrium potential, a potential of -0.250 V is applied to the working electrode for 4 minutes.

EXEMPLE 2 : Traitement de surface fluoré d'un poinçon avec un revêtement en acier (GRANE). EXAMPLE 2 : Fluoride surface treatment of a punch with a steel coating (GRANE).

Exemple 2a : Selon cet exemple, on greffe le radical comportant deux groupes trifluorométhyle C6H3-(CF3)2 sur la surface d'un poinçon en acier (GRANE).

  • Première étape : Préparation du sel de diazonium N2 +-C6H3-(CF3)2.
    • * Dans 50 ml d'un électrolyte support (5,2 g de tétraéthylammonium tétrafluoroborate Et4NBF4 à 0,1 M dans 250 ml d'acétonitrile ACN désaéré à l'azote), on dissout 117 mg de 3,5-bis-trifluorométhylaniline [NH2-C6H3-(CF3)2]
    • * On ajoute 176 mg de réducteur tert-butylnitrite, soit 3 équivalents molaires.
    • * La solution ainsi préparée est dégazée sous bullage d'azote pendant 30 minutes.
  • Deuxième étape : Greffage du C6H3-(CF3)2 par voltammétrie cyclique à la surface du poinçon.
    • * A potentiel ouvert, on plonge le poinçon en acier GRANE dans la solution de sel de diazonium N2 +- C6H3-(CF3)2 préparée précédemment.
    • * Après stabilisation du potentiel d'équilibre, on effectue une voltammétrie cyclique à variation linéaire de potentiel à 50 mV.s, durant 10 cycles, entre -0,5V et 0,6 V.
    • * On détermine ainsi le potentiel de réduction du sel de diazonium N2+-C6H3-(CF3)2 sur la surface du poinçon en acier GRANE qui est de -0,05 V.
  • Alternative à la deuxième étape : Greffage du C6H3-(CF3)2 par chronoampérométrie.
    • * A potentiel ouvert, on plonge le poinçon en acier GRANE dans la solution de sel de diazonium N2 +-C6H3-(CF3)2 préparée précédemment.
    • * Après stabilisation du potentiel d'équilibre, on applique un potentiel de -0,25 V à l'électrode de travail pendant 10 minutes.
Example 2a : According to this example, the radical containing two trifluoromethyl groups C 6 H 3 - (CF 3 ) 2 is grafted onto the surface of a steel punch (GRANE).
  • First step: Preparation of the diazonium salt N 2 + -C 6 H 3 - (CF 3 ) 2 .
    • * In 50 ml of a carrier electrolyte (5.2 g of tetraethylammonium tetrafluoroborate Et 4 NBF 4 at 0.1 M in 250 ml of nitrogen-acetated ACN acetonitrile), 117 mg of 3,5-bis are dissolved -trifluoromethylaniline [NH 2 -C 6 H 3 - (CF 3 ) 2 ]
    • 176 mg of tert-butylnitrite reducer, ie 3 molar equivalents, are added.
    • * The solution thus prepared is degassed under nitrogen bubbling for 30 minutes.
  • Second step: Grafting of C 6 H 3 - (CF 3 ) 2 by cyclic voltammetry at the punch surface.
    • * At open potential, the steel punch GRANE is immersed in the solution of diazonium salt N 2 + - C 6 H 3 - (CF 3 ) 2 prepared previously.
    • * After stabilization of the equilibrium potential, cyclic voltammetry with a linear variation of potential at 50 mV.s is carried out for 10 cycles, between -0.5V and 0.6 V.
    • The reduction potential of the diazonium salt N 2 + -C 6 H 3 - (CF 3 ) 2 on the surface of the GRANE steel punch which is -0.05 V. is thus determined.
  • Alternative to the second step: grafting of C 6 H 3 - (CF 3 ) 2 by chronoamperometry.
    • * At open potential, the steel punch GRANE is immersed in the solution of diazonium salt N 2 + -C 6 H 3 - (CF 3 ) 2 prepared above.
    • After stabilization of the equilibrium potential, a potential of -0.25 V is applied to the working electrode for 10 minutes.

Exemple 2b : Selon cet exemple 3b, on greffe le radical perfluorooctylphényle C6H4-C8F17 sur la surface d'un poinçon en acier GRANE.

  • Première étape : Préparation du sel de diazonium N2 +-C6H4-C8F17 par réduction d'une aniline.
    • * Dans 50 ml d'un électrolyte support (5,2 g de tétraéthylammonium tétrafluoroborate Et4NBF4 à 0,1 M dans 250 ml d'acétonitrile ACN désaéré à l'azote), on dissout 255 mg de 4-perfluorooctylaniline (NH2-C6H4-C8F17).
    • * On ajoute 176 mg de tert-butylnitrite, soit 3 équivalents molaires.
    • * La solution ainsi préparée est dégazée sous bullage d'azote pendant 30 minutes.
  • Deuxième étape : greffage du C6H4C8F17 par voltammétrie cyclique.
    • * A potentiel ouvert, on plonge le poinçon en acier GRANE dans la solution de sel de diazonium N2 +-C6H4-C8F17 préparée précédemment.
    • * Après stabilisation du potentiel d'équilibre, on effectue une voltammétrie cyclique à variation linéaire de potentiel à 50 mV.s, durant 20 cycles, entre -0,5 V et 0,2 V.
    • * On détermine le potentiel de réduction du sel de diazonium N2 +-C6H4-C8F17 sur la surface du poinçon en acier GRANE qui est de -0,1 V.
  • Alternative à la deuxième étape : Greffage du radical N2 +-C6H4-C8F17 par chronoampérométrie :
    • * A potentiel ouvert, on plonge le poinçon en acier dans la solution du sel de diazonium N2 +-C6H4-C8F17 préparée précédemment.
    • * Après stabilisation du potentiel d'équilibre, on applique un potentiel de -0,4 V à l'électrode de travail pendant 4 minutes.
Example 2b : According to this example 3b, the perfluorooctylphenyl radical C 6 H 4 -C 8 F 17 is grafted onto the surface of a GRANE steel punch.
  • First step: Preparation of the diazonium salt N 2 + -C 6 H 4 -C 8 F 17 by reduction of aniline.
    • * In 50 ml of a carrier electrolyte (5.2 g of tetraethylammonium tetrafluoroborate Et 4 NBF 4 at 0.1 M in 250 ml of nitrogen-acetated ACN acetonitrile), 255 mg of 4-perfluorooctylaniline (NH 2 -C 6 H 4 -C 8 F 17 ).
    • 176 mg of tert-butylnitrite are added, ie 3 molar equivalents.
    • * The solution thus prepared is degassed under nitrogen bubbling for 30 minutes.
  • Second step: grafting of C 6 H 4 C 8 F 17 by cyclic voltammetry.
    • * At open potential, the steel punch GRANE is immersed in the solution of diazonium salt N 2 + -C 6 H 4 -C 8 F 17 prepared above.
    • After stabilization of the equilibrium potential, a cyclic voltammetry with a linear variation of potential at 50 mV.s is carried out for 20 cycles, between -0.5 V and 0.2 V.
    • * The reduction potential of the diazonium salt N 2 + -C 6 H 4 -C 8 F 17 is determined on the surface of the GRANE steel punch which is -0.1 V.
  • Alternative to the second step: Grafting of the radical N 2 + -C 6 H 4 -C 8 F 17 by chronoamperometry:
    • * At open potential, the steel punch is immersed in the solution of diazonium salt N 2 + -C 6 H 4 -C 8 F 17 prepared above.
    • After stabilization of the equilibrium potential, a potential of -0.4 V is applied to the working electrode for 4 minutes.

TEST ANTI-COLLAGE : ANTI-COLLAGE TEST :

On teste l'effet anti-collage des poinçons ainsi réalisés.The anti-sticking effect of the punches thus produced is tested.

En conditions industrielles, la compression de la matière pulvérulente est effectuée dans un intervalle de forces compris entre une force minimum et une force maximum. Chacune de ces forces a été déterminée selon la nature du grain de la poudre, les matières premières constituant la poudre et les conditions environnementales (température, humidité) de la compression ainsi que de l'épaisseur, la masse, la dureté, la friabilité, la capacité de désagrégation voulues pour le comprimé. Si la force de compression est trop élevée, le comprimé aura un temps de désagrégation trop élevé et une épaisseur trop faible. Si la force de compression n'est pas assez élevée, alors le comprimé aura un temps de désagrégation trop faible et une épaisseur trop forte. En dehors de cet intervalle, les comprimés obtenus sont considérés comme non-conformes.In industrial conditions, the compression of the pulverulent material is carried out in a range of forces included between a minimum force and a maximum force. Each of these forces was determined according to the nature of the grain of the powder, the raw materials constituting the powder and the environmental conditions (temperature, moisture) of the compression as well as the thickness, the mass, the hardness, the friability, the desired disintegration capacity for the tablet. If the compressive force is too high, the tablet will have too much disintegration time and too little thickness. If the compression force is not high enough, then the tablet will have too little disintegration time and too much thickness. Outside this range, the resulting tablets are considered non-compliant.

Chaque poudre possède ses propres propriétés. La caractérisation de l'aptitude des poinçons à ne pas donner de collage a été réalisée avec deux poudres de formulations différentes. Un premier test a été fait avec une poudre A du commerce réputée très collante. Un second test a été réalisé avec une autre poudre, référencée poudre B, beaucoup moins collante que la poudre A.Each powder has its own properties. Characterization of the ability of the punches not to give bonding was performed with two powders of different formulations. A first test was made with a trade powder A deemed very sticky. A second test was carried out with another powder, referenced powder B, much less tacky than powder A.

Le collage de la poudre aux poinçons est force-dépendant, à savoir qu'il diminue quand on augmente la force de compression. C'est un phénomène progressif avec un enrichissement plus ou moins important de la surface des poinçons par la poudre, et on peut déterminer une « force seuil » en dessous de laquelle le collage obtenu n'est plus acceptable industriellement. Cette force seuil dépend de la propension des surfaces à provoquer du collage. Plus la force seuil sera faible, moins les surfaces provoqueront du collage.The bonding of the powder to the punches is force-dependent, namely that it decreases when the compressive force is increased. This is a progressive phenomenon with a more or less significant enrichment of the surface of the punches by the powder, and it is possible to determine a "threshold force" below which the bonding obtained is no longer acceptable industrially. This threshold force depends on the propensity of the surfaces to cause bonding. The lower the threshold force, the less the surfaces will cause sticking.

Le critère d'appréciation du collage est un critère visuel basé sur l'apparition ou non d'une couche résiduelle de poudre à la surface du poinçon après compression de la poudre.The criterion for assessing bonding is a visual criterion based on the appearance or not of a residual layer of powder on the surface of the punch after compression of the powder.

On peut définir 3 niveaux d'appréciation :

  • l'absence de collage : pas de poudre résiduelle sur le poinçon ;
  • le collage tolérable : présence d'une fine couche de poudre qui reste stable au fil du temps et qui n'adhère que très faiblement à la surface du poinçon ; cette couche s'enlève très facilement ;
  • le collage rédhibitoire: présence d'une couche épaisse de poudre qui s'enrichit au fur et à mesure des compressions ; cette couche adhère très fortement à la surface et est difficile à enlever.
We can define 3 levels of appreciation:
  • the absence of sticking: no residual powder on the punch;
  • tolerable bonding: presence of a thin layer of powder which remains stable over time and which adheres only very weakly to the surface of the punch; this layer is very easily removed;
  • the unacceptable collage: the presence of a thick layer of powder which becomes enriched as and when the compressions; this layer adheres very strongly to the surface and is difficult to remove.

L'absence de collage et le collage tolérable permettent de produire industriellement dans de bonnes conditions alors que le collage rédhibitoire n'est plus acceptable pour produire industriellement.The absence of bonding and the tolerable bonding make it possible to produce industrially under good conditions, whereas the unacceptable bonding is no longer acceptable for industrial production.

Test avec la poudre A : Test with powder A :

Pour la poudre A, on détermine une force de compression minimum à 7 kN et une force de compression maximum à 10 kN, entre lesquelles doit se faire la compression de la poudre pour réaliser des comprimés ayant les caractéristiques requises.For powder A, a minimum compressive force of 7 kN and a maximum compressive force of 10 kN are determined, between which the powder must be compressed to produce tablets having the required characteristics.

Les résultats des tests sont répertoriés dans le tableau ci-après : Outillage Force seuil Résultat Acier standard 13,7 kN Collage systématique en conditions industrielles Acier standard, revêtement standard 16,5 kN Collage systématique en conditions industrielles Acier standard, polissage poussé 11,2 kN Collage systématique en conditions industrielles Acier standard, revêtement standard, polissage poussé 14,8 kN Collage systématique en conditions industrielles Acier standard avec insert en matière plastique collé sur la partie active 6,7 kN Jamais de collage en laboratoire mais durée de vie trop faible pour usage industriel Acier standard, polissage standard, greffage C6H3-(CF3)2 8,5 kN Collage aléatoire en fonction de la force de compression appliquée Acier standard, polissage standard, greffage C6H4-C8F17 6,9 kN Jamais de collage en conditions industrielles The test results are listed in the table below: tools Threshold force Result Standard steel 13.7 kN Systematic bonding in industrial conditions Standard steel, standard coating 16.5 kN Systematic bonding in industrial conditions Standard steel, polishing 11.2 kN Systematic bonding in industrial conditions Standard steel, standard coating, polishing 14.8 kN Systematic bonding in industrial conditions Standard steel with plastic insert glued on the active part 6.7 kN Never sticking in the laboratory but life time too low for industrial use Standard steel, standard polishing, grafting C 6 H 3 - (CF 3 ) 2 8.5 kN Random collage based on applied compression force Standard steel, standard polishing, grafting C 6 H 4 -C 8 F 17 6.9 kN Never gluing in industrial conditions

Ainsi, à titre comparatif, pour deux poinçons sans le traitement de surface par greffage de composés à effet anti-collage, qui sont respectivement en acier standard et en acier standard avec un polissage poussé, on observe un collage rédhibitoire de la poudre en conditions industrielles [7-10 kN]. Pour ces poinçons, la force seuil pour ne plus avoir de collage de la poudre A est supérieure à 10 kN, donc hors de l'intervalle des forces de compression requis.Thus, for comparison, for two punches without the surface treatment by grafting anti-sticking compounds, which are respectively standard steel and standard steel with a high polishing, there is a prohibitive bonding of the powder in industrial conditions [7-10 kN]. For these punches, the threshold force to no longer have bonding of the powder A is greater than 10 kN, therefore out of the range of compression forces required.

A titre comparatif également, on teste un poinçon en acier standard (acier 55NCD12) sur lequel a été collé un insert en matière plastique. Une telle surface ne donne pas lieu à un collage (absence de collage) de la poudre A en laboratoire, la force seuil est inférieure à 7kN mais une telle matière a une durée de vie bien trop faible (la dureté de surface Vickers est de 400 Hv) pour un usage industriel.By way of comparison also, a standard steel punch (steel 55NCD12) was tested on which a plastic insert was glued. Such a surface does not give rise to a bonding (absence of bonding) of the powder A in the laboratory, the threshold force is less than 7kN, but such a material has a life that is far too low (the Vickers surface hardness is 400 Hv) for industrial use.

On teste le poinçon en acier standard avec un polissage standard, dont la surface comporte des greffons conformément à l'exemple 1. Une telle surface ne donne pas lieu systématiquement à un collage de la poudre A qui soit rédhibitoire en conditions industrielles, on observe du collage tolérable ou parfois rédhibitoire dans l'intervalle de forces de compression. Toutefois la force seuil pour n'observer aucun collage rédhibitoire est abaissée par rapport au poinçon non traité, elle est de 8.5 kN. Cette force seuil étant comprise dans l'intervalle de forces requis, le poinçon ainsi traité permet en général de produire industriellement dans des conditions satisfaisantes tant que la force de compression reste supérieure à 8.5 kN.The standard steel punch is tested with a standard polishing, the surface of which comprises grafts according to Example 1. Such a surface does not systematically give rise to bonding of the powder A, which is unacceptable under industrial conditions. bonding tolerable or sometimes crippling in the range of compressive forces. However, the threshold force to observe no unacceptable bonding is lowered compared to the untreated punch, it is 8.5 kN. Since this threshold force is within the range of forces required, the punch thus treated generally makes it possible to produce industrially under satisfactory conditions as long as the compression force remains greater than 8.5 kN.

On teste ensuite le poinçon en acier standard avec un polissage standard, dont la surface comporte des greffons conformément à l'exemple 2. Une telle surface ne donne aucun collage (absence de collage) avec la poudre A en conditions industrielles. La force seuil est inférieure à 7kN. La production industrielle de comprimés peut se faire sans problème de collage avec ce poinçon.The standard steel punch is then tested with a standard polishing, the surface of which comprises grafts according to Example 2. Such a surface gives no bonding (absence of bonding) with the powder A under industrial conditions. The threshold force is less than 7kN. The industrial production of tablets can be done without problem of gluing with this punch.

Test avec la poudre B : Test with powder B :

Pour la poudre B, on détermine une force de compression minimum à 14 kN et une force de compression maximum à 16 kN, entre lesquelles doit se faire la compression de la poudre B pour réaliser des comprimés ayant les caractéristiques requises.For powder B, a minimum compressive force of 14 kN and a maximum compressive force of 16 kN are determined between which must be the compression of the powder B to make tablets with the required characteristics.

Les résultats des tests sont répertoriés dans le tableau ci-après : Outillage Force seuil Résultat Acier standard 12 kN Jamais de collage en conditions industrielles Acier standard, revêtement standard 10 kN Jamais de collage en conditions industrielles Acier standard avec insert en matière plastique collé sur la partie active 5 kN Jamais de collage en laboratoire mais durée de vie trop faible pour usage industriel Acier standard, polissage standard, greffage C6H3-(CF3)2 7 kN Jamais de collage en conditions industrielles Acier standard, polissage standard, greffage C6H4-C8F17 6,1 kN Jamais de collage en conditions industrielles The test results are listed in the table below: tools Threshold force Result Standard steel 12 kN Never gluing in industrial conditions Standard steel, standard coating 10 kN Never gluing in industrial conditions Standard steel with plastic insert glued on the active part 5 kN Never sticking in the laboratory but life time too low for industrial use Standard steel, standard polishing, grafting C 6 H 3 - (CF 3 ) 2 7 kN Never gluing in industrial conditions Standard steel, standard polishing, grafting C 6 H 4 -C 8 F 17 6.1 kN Never gluing in industrial conditions

A titre comparatif, pour un poinçon respectivement en acier standard ou avec un revêtement (sans traitement de surface par greffage de composés à effet anti-collage), on n'observe aucun collage (absence de collage) de la poudre B dans la plage de forces de compression requise (14-16kN). Pour ce poinçon, la force seuil pour n'avoir aucun collage de la poudre B est de 14 kN, donc dans l'intervalle de forces de compression requis.By way of comparison, for a punch made of standard steel or with a coating (without surface treatment by grafting anti-sticking compounds), there is no sticking (absence of sticking) of the powder B in the range of compression forces required (14-16kN). For this punch, the threshold force to have no bonding of the powder B is 14 kN, so in the range of compression forces required.

A titre comparatif également, on teste un poinçon en acier standard sur lequel a été collé un insert en matière plastique. Une telle surface ne donne pas lieu à un collage par affinité (absence de collage) de la poudre A en laboratoire, la force seuil est d'environ 5kN. Toutefois comme indiqué pour la poudre A, une telle matière a une durée de vie bien trop faible pour un usage industriel.For comparative purposes also, a standard steel punch is tested on which a plastic insert has been glued. Such a surface does not give rise to an affinity bonding (absence of bonding) of the powder A in the laboratory, the threshold force is about 5kN. However, as indicated for powder A, such a material has a life time far too low for industrial use.

On teste aussi le poinçon en acier standard avec un polissage standard, dont la surface comporte des greffons conformément à l'exemple 1. Une telle surface ne donne aucun collage avec la poudre B en conditions industrielles et la force seuil est d'environ 7kN.The standard steel punch is also tested with standard polishing, the surface of which has grafts in accordance with Example 1. Such a surface gives no bonding with powder B under industrial conditions and the threshold force is about 7kN.

Enfin on teste le poinçon en acier standard avec un polissage standard, dont la surface comporte des greffons conformément à l'exemple 2. Une telle surface ne donne aucun collage de la poudre B en conditions industrielles et la force seuil est d'environ 6kN.Finally, the standard steel punch is tested with a standard polishing, the surface of which comprises grafts according to Example 2. Such a surface gives no bonding of the powder B under industrial conditions and the threshold force is about 6 kN.

Bien que même sans traitement de surface, le poinçon ne donne aucun collage, le poinçon une fois traité en surface voit sa force seuil abaissée.Although even without surface treatment, the punch does not give any bonding, the punch once treated on the surface sees its threshold force lowered.

Dans tous les cas, le greffage de la surface du poinçon par un composé comportant deux groupes -CF3 ou la chaîne -C8F17 vient diminuer la force seuil en dessous de laquelle le collage est rédhibitoire.In all cases, the grafting of the punch surface with a compound comprising two -CF 3 groups or the -C 8 F 17 chain decreases the threshold force below which the bonding is unacceptable.

Les poinçons obtenus selon la présente invention présentent donc des caractéristiques anti-collages combinées à une résistance à l'abrasion jamais obtenue auparavant. Des tests in situ ont également permis de valider les résultats obtenus et de vérifier leur durée de vie nettement allongée par rapport à l'art antérieur.The punches obtained according to the present invention thus have anti-bonding characteristics combined with an abrasion resistance never obtained before. In situ tests also made it possible to validate the results obtained and to verify their significantly longer life compared with the prior art.

D'autres techniques de greffage peuvent être envisagées. Par exemple le greffage peut être réalisé par réaction chimique entre le radical à groupe moléculaire anti-collage et la surface du poinçon à traiter. Selon un autre exemple, le greffage peut se faire par voie photochimique telle qu'une irradiation qui produit des électrons à la surface du poinçon à traiter.Other grafting techniques can be envisaged. For example, the grafting may be carried out by chemical reaction between the antiblocking molecular group radical and the surface of the punch to be treated. According to another example, the grafting can be done by photochemical means such as an irradiation which produces electrons on the surface of the punch to be treated.

Claims (9)

  1. A compression punch for a pulverulent material for a tablet press comprising a preformed active part intended to contact said material in order to compress it; characterised in that said active part is made of a material on the surface of which are grafted by covalent bonds radicals with a fluorocarbon molecular group having an anti-adhesive effect.
  2. A punch according to claim 1, characterised in that said molecular group is a fluoroalkyl group, preferably an alkyl group in which all of the hydrogen atoms have been substituted by a fluorine atom.
  3. A punch according to either of the preceding claims, characterised in that said molecular group is bonded to the surface of said material by an aryl group, in particular a phenyl group in which at least one substituent on the benzene ring is formed by said molecular group having an anti-adhesive effect.
  4. A punch according to claim 2 or claim 3, characterised in that the fluoroalkyl group is a straight chain CnF2n+1, n being an integer greater than or equal to 1.
  5. A punch according to claim 4, characterised in that, when n is equal to 1, the benzene ring includes one or more CF3 groups as substituents and, when n is equal to 8, the benzene ring includes a single C8F17 substituent.
  6. A punch according to any one of the preceding claims, characterised in that the grafted radicals are selected from trifluoromethyl phenyl and perfluororoctyl phenyl.
  7. A punch according to one of claims 3 to 6, characterised in that the radicals are grafted by an electrochemical process using two and/or three electrodes, such as cyclic voltammetry, chronoamperometry or chronopotentiometry.
  8. A punch according to one of the preceding claims, characterised in that said punches are made of steel.
  9. A tablet press comprising tablet-forming dies and punches for compressing the pulverulent material forming the tablets, said punches being as defined in any one of claims 1 to 8.
EP20100305986 2010-09-15 2010-09-15 Compression punch of a powder material with a non-adhesive surface and press provided with such a punch Active EP2431165B1 (en)

Priority Applications (2)

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EP20100305986 EP2431165B1 (en) 2010-09-15 2010-09-15 Compression punch of a powder material with a non-adhesive surface and press provided with such a punch
ES10305986T ES2421433T3 (en) 2010-09-15 2010-09-15 Compression punch of a powdery material with non-stick surface and press equipped with such a punch

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Application Number Priority Date Filing Date Title
EP20100305986 EP2431165B1 (en) 2010-09-15 2010-09-15 Compression punch of a powder material with a non-adhesive surface and press provided with such a punch

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EP2431165B1 true EP2431165B1 (en) 2013-04-17

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WO2013050664A1 (en) * 2011-10-05 2013-04-11 Epmo Compression press for a pulverulent material with a non-stick surface and a press fitted with such a punch
EP3150747A1 (en) * 2015-09-29 2017-04-05 Universite De Nantes Functionalized current collector for electrochemical devices, with increased resistance to corrosion

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DE29619564U1 (en) * 1996-11-11 1997-04-03 Notter GmbH Werkzeugbau, 75248 Ölbronn-Dürrn Tableting tool with anti-adhesive coating
DE19838103B4 (en) * 1998-08-21 2014-02-20 Henkel Ag & Co. Kgaa Use of a tableting die with non-stick properties and detergent, rinse, cleaning and laundry aid tablets made therewith
FR2908683B1 (en) 2006-11-20 2009-07-17 Epmo Sa ROTATING COMPRESS PRESS

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