EP2431165B1 - Punze zur Kompression eines pulverförmigen Materials mit nicht haftender Oberfläche, und Presse mit einer solchen Punze - Google Patents

Punze zur Kompression eines pulverförmigen Materials mit nicht haftender Oberfläche, und Presse mit einer solchen Punze 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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English (en)
French (fr)
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EP2431165A1 (de
Inventor
Vincent Jollivet
M. Cédric Marchand
M. Thierry Brousse
Cédric Martin
M. Pierre Tchoreloff
Virginie Busignies
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.)
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/de
Priority to ES10305986T priority patent/ES2421433T3/es
Publication of EP2431165A1 publication Critical patent/EP2431165A1/de
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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)
  • Medicinal Preparation (AREA)
  • Solid-Sorbent Or Filter-Aiding Compositions (AREA)

Claims (9)

  1. Stempel zur Verdichtung eines pulverförmigen Materials, für eine Stauchpresse, bestehend aus einem vorgeformten aktiven Teil, das dazu bestimmt ist, das genannte Material so zu berühren, dass dieses verdichtet wird, dadurch gekennzeichnet, dass das genannte aktive Teil aus einem Material ausgeführt ist, auf dessen Oberfläche im Wege der kovalenten Bindung Radikale gepfropft sind, die eine molekulare Fluorkohlenstoffgruppe umfassen, welche bewirkt, dass die Haftung verhindert wird.
  2. Stempel nach Anspruch 1, dadurch gekennzeichnet, dass es sich bei der genannten molekularen Gruppe um eine Fluoroalkylgruppe, vorzugsweise eine Alkylgruppe handelt, deren Wasserstoffatome alle durch ein Fluoratom ersetzt wurden.
  3. Stempel nach einem beliebigen der voranstehend genannten Ansprüche, dadurch gekennzeichnet, dass die genannte Molekulargruppe mit der Oberfläche des genannten Materials verbunden ist, und zwar über eine Arylgruppe, insbesondere eine Phenylgruppe, bei der zumindest ein Substituent auf dem Benzolkern aus der genannten Molekulargruppe besteht, die die Verhinderung der Haftung bewirkt.
  4. Stempel nach Anspruch 1 oder Anspruch 3, dadurch gekennzeichnet, dass es sich bei der Fluoralkylgruppe um die lineare Kette CnF2n+1 handelt, wobei n ein Ganzes größer oder gleich 1 ist.
  5. Stempel nach Anspruch 4, dadurch gekennzeichnet, dass der Benzolkern, wenn n gleich 1 ist, eine oder mehrere CF3-Gruppen als Substituent umfasst, und dass der Benzolkern, wenn n gleich 8 ist, einen einzigen Substituenten C8F17 umfasst.
  6. Stempel nach einem beliebigen der voranstehend genannten Ansprüche, dadurch gekennzeichnet, dass als gepfropfte Radikale entweder Trifluormethylphenyl oder Perfluoroctylphenyl gewählt werden.
  7. Stempel nach einem der Ansprüche 3 bis 6, gekennzeichnet durch die Tatsache, dass die Radikalen durch ein elektrochemisches Verfahren mit zwei und/oder drei Elektroden wie die zyklische Voltametrie, die Chronoamperometrie oder die Chronopotentiometrie gepfropft werden.
  8. Stempel nach einem der voranstehend genannten Ansprüche, dadurch gekennzeichnet, dass die genannten Stempel aus Stahl bestehen.
  9. Stauchpresse, die Matrizen zur Formgebung der gestauchten Bauteile und Stempel umfasst, die das pulverförmige Material verdichten und dabei die gestauchten Bauteile formen, wobei die genannten Stempel so beschaffen sind, wie dies in einem beliebigen der voranstehend beschriebenen Ansprüche 1 bis 8 beschrieben wird.
EP20100305986 2010-09-15 2010-09-15 Punze zur Kompression eines pulverförmigen Materials mit nicht haftender Oberfläche, und Presse mit einer solchen Punze Active EP2431165B1 (de)

Priority Applications (2)

Application Number Priority Date Filing Date Title
EP20100305986 EP2431165B1 (de) 2010-09-15 2010-09-15 Punze zur Kompression eines pulverförmigen Materials mit nicht haftender Oberfläche, und Presse mit einer solchen Punze
ES10305986T ES2421433T3 (es) 2010-09-15 2010-09-15 Punzón de compresión de un material pulverulento con superficie antiadhesiva y prensa equipada con un punzón de este tipo

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
EP20100305986 EP2431165B1 (de) 2010-09-15 2010-09-15 Punze zur Kompression eines pulverförmigen Materials mit nicht haftender Oberfläche, und Presse mit einer solchen Punze

Publications (2)

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EP2431165A1 EP2431165A1 (de) 2012-03-21
EP2431165B1 true EP2431165B1 (de) 2013-04-17

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2013050664A1 (fr) * 2011-10-05 2013-04-11 Epmo Poinçon de compression d'une matière pulvérulente à surface anti collante et presse équipée d'un tel poinçon
EP3150747A1 (de) * 2015-09-29 2017-04-05 Universite De Nantes Funktionalisierter stromkollektor für elektrochemische vorrichtungen mit erhöhter korrosionsbeständigkeit

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE29619564U1 (de) * 1996-11-11 1997-04-03 Notter GmbH Werkzeugbau, 75248 Ölbronn-Dürrn Tablettierwerkzeug mit adhäsionshemmender Beschichtung
DE19861338B4 (de) * 1998-08-21 2007-04-05 Henkel Kgaa Muldentablette
FR2908683B1 (fr) 2006-11-20 2009-07-17 Epmo Sa Presse a comprimes rotative

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EP2431165A1 (de) 2012-03-21
ES2421433T3 (es) 2013-09-02

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