Classifications

• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
  • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
  • B29C43/00—Compression moulding, i.e. applying external pressure to flow the moulding material; Apparatus therefor
  • B29C43/003—Compression moulding, i.e. applying external pressure to flow the moulding material; Apparatus therefor characterised by the choice of material
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
  • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
  • B29C43/00—Compression moulding, i.e. applying external pressure to flow the moulding material; Apparatus therefor
  • B29C43/02—Compression moulding, i.e. applying external pressure to flow the moulding material; Apparatus therefor of articles of definite length, i.e. discrete articles
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
  • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
  • B29C43/00—Compression moulding, i.e. applying external pressure to flow the moulding material; Apparatus therefor
  • B29C43/32—Component parts, details or accessories; Auxiliary operations
  • B29C43/56—Compression moulding under special conditions, e.g. vacuum
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
  • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
  • B29C44/00—Shaping by internal pressure generated in the material, e.g. swelling or foaming ; Producing porous or cellular expanded plastics articles
  • B29C44/02—Shaping by internal pressure generated in the material, e.g. swelling or foaming ; Producing porous or cellular expanded plastics articles for articles of definite length, i.e. discrete articles
  • B29C44/04—Shaping by internal pressure generated in the material, e.g. swelling or foaming ; Producing porous or cellular expanded plastics articles for articles of definite length, i.e. discrete articles consisting of at least two parts of chemically or physically different materials, e.g. having different densities
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
  • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
  • B29C43/00—Compression moulding, i.e. applying external pressure to flow the moulding material; Apparatus therefor
  • B29C43/32—Component parts, details or accessories; Auxiliary operations
  • B29C43/56—Compression moulding under special conditions, e.g. vacuum
  • B29C2043/566—Compression moulding under special conditions, e.g. vacuum in a specific gas atmosphere, with or without pressure
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
  • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
  • B29C2791/00—Shaping characteristics in general
  • B29C2791/001—Shaping in several steps
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
  • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
  • B29C2791/00—Shaping characteristics in general
  • B29C2791/004—Shaping under special conditions
  • B29C2791/005—Using a particular environment, e.g. sterile fluids other than air
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
  • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
  • B29K2067/00—Use of polyesters or derivatives thereof, as moulding material
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
  • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
  • B29K2067/00—Use of polyesters or derivatives thereof, as moulding material
  • B29K2067/04—Polyesters derived from hydroxycarboxylic acids
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
  • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
  • B29K2067/00—Use of polyesters or derivatives thereof, as moulding material
  • B29K2067/04—Polyesters derived from hydroxycarboxylic acids
  • B29K2067/046—PLA, i.e. polylactic acid or polylactide
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
  • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
  • B29K2105/00—Condition, form or state of moulded material or of the material to be shaped
  • B29K2105/0005—Condition, form or state of moulded material or of the material to be shaped containing compounding ingredients
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
  • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
  • B29K2105/00—Condition, form or state of moulded material or of the material to be shaped
  • B29K2105/0085—Copolymers
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
  • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
  • B29K2105/00—Condition, form or state of moulded material or of the material to be shaped
  • B29K2105/25—Solid
  • B29K2105/251—Particles, powder or granules
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
  • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
  • B29K2105/00—Condition, form or state of moulded material or of the material to be shaped
  • B29K2105/25—Solid
  • B29K2105/253—Preform
  • B29K2105/255—Blocks or tablets
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
  • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
  • B29K2995/00—Properties of moulding materials, reinforcements, fillers, preformed parts or moulds
  • B29K2995/0037—Other properties
  • B29K2995/0039—Amorphous
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
  • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
  • B29K2995/00—Properties of moulding materials, reinforcements, fillers, preformed parts or moulds
  • B29K2995/0037—Other properties
  • B29K2995/0059—Degradable
  • B29K2995/006—Bio-degradable, e.g. bioabsorbable, bioresorbable or bioerodible

Definitions

• thermoplastics in particular resorbable thermoplastics
• the present invention relates to a new process for shaping thermoplastics - in particular bioabsorbable plastics - at temperatures below the melting temperature range using gases or substances in the liquid state under high pressure.
• thermoplastic moldings and semi-finished products are mainly produced by machining, reshaping, from solution or using the so-called primary molding process.
• the above-mentioned methods have, in principle, z. T. very serious disadvantages.
• thermoplastic In the primary molding process - such as Extrusion and injection molding - the thermoplastic must be melted in order to be able to mold it.
• the high temperature required above the melting range in the case of thermally unstable plastics - in particular in the case of resorbable polymers and some engineering plastics - leads to molecular weight reduction, which in turn has a disadvantageous influence on the mechanical properties.
• Extrusion also only allows the production of semi-finished products of simple geometry. - On the other hand, molded parts with complex geometries - as they are required for medical applications - cannot be produced by extrusion.
• thermoplastic melt is introduced into the cooled tool, the melt solidifying during the filling phase.
• the inhomogeneous cooling of the molding compound also freezes tensions which lead to undesired distortion after removal from the mold. Furthermore, it is not possible with this method to produce molded parts with a large flow length / wall thickness ratio.
• the object of the present invention is accordingly to provide a method for shaping thermoplastic materials - in particular resorbable thermoplastics - which avoids the disadvantages known from the prior art. According to the invention this object is achieved in that the viscosity of a thermoplastic - such.
• the low viscosity is an essential prerequisite for the formation of complex geometries.
• thermoplastic polymers for the process according to the invention are, in particular, amorphous polyesters, for resorbable objects - ie objects that can be broken down by the human or animal body - polyesters based on ⁇ -hydroxycarboxylic acids are particularly preferred.
• L-lactide to D L-lactide can be up to 90 to 10 - preferably 70 to 30 -, poly-meso-lactide,
• Fumigation according to the invention at low temperatures and under high pressure presupposes that the gas has good solubility in the respective polymer.
• the solubility of gases or liquids in polymers is a function of pressure and temperature. Particularly good solubility parameters are achieved when the gas changes into the so-called supercritical state.
• Supercritical liquids or gases are known from the prior art. Examples here include carbon dioxide, ethylene, propane, ammonia, nitrous oxide, water and toluene. Depending on the supercritical substance used in each case, the process according to the invention can be carried out at a pressure in a range from 50 to 800 bar - preferably 50 to 400 bar and particularly preferably 50 to 200 bar.
• carbon dioxide is particularly suitable for lowering the viscosity of polymers.
• Carbon dioxide goes into the at a temperature of 31 ° C and a pressure of just over 73.76 bar supercritical state and has a 25 times larger diffusion coefficient in polymers than, for example, nitrogen.
• Rieself ⁇ rmiger plastic is introduced into a mold cavity and gassed under high pressure. If the viscosity is reduced to such an extent that the plastic can be deformed, the mold cavity is reduced and a compact molded part is produced.
• Rieself ⁇ rmiger plastic is introduced into a mold antechamber and gassed under high pressure.
• the mold cavity is reduced - preferably by the penetration of an injection plunger - and the plastic is pressed into the mold cavity.
• the pressures for filling a previously manufactured mold are only determined by the pressure losses caused by the geometry and are therefore considerably lower than in a comparable molded part production in the injection molding process, since the viscosity in this case is not a function of time. This means that even very thin-walled molded parts with long flow paths can be manufactured.
• a precisely dosed preform - preferably in the form of a tablet - can also be processed analogously using the two methods mentioned above. Due to the almost constant viscosity of the "polymer melt" during the filling time, the molded part can be filled very slowly in order to counteract degradation of the molecular weight by shear. Internal stresses due to temperature gradients across the cross section of the molded part can also be avoided. Shaped bodies which are produced with this process are free of orientations, since molecules which have been aligned by the filling process have a sufficiently long time to relax after the mold has been filled.
• silicone tools are to be mentioned here as examples, which are suitable for the production of individual implants as well as for small series and prototypes.
• Silicone is particularly suitable due to its special diffusion properties, its high dimensional stability and its uncomplicated processability.
• Sintered metal tools with a barrier layer made of "a gas-permeable membrane are also suitable for the production of small and large series.
• a vacuum can be applied to the tool to accelerate the degassing.
• the shaped body can be removed from the mold when the viscosity has risen to such an extent that it is dimensionally stable.
• FIG. 1 shows the diagram of a gassing system suitable for the method according to the invention.
• This consists essentially of the gas supply 1 with pressure indicator 2, the filters 3 and 4, the coolers 5 and 6, the adjustable diaphragm pump 7, the pulsation damper 8 and the shut-off valves 9 and 10, the safety valve 11 and the pressure indicator 12 and the autoclave 13 with the temperature display 14 and the pressure display 15 as well as the shut-off valve 16 and the silencer 17.
• Fig. 2 shows the process autoclave 20, in which the devices required for the shaping such as press or injection unit are introduced.
• FIG 3 shows the injection unit 28 with the release mechanism 21, the spring pretensioning device 22, the spring 23, the piston rod 24, the piston 25 and the piston antechamber 26 as well as the tool 29 with the closing mechanism 27.
• the injection unit 28 serves to inject polymer plasticized by CO2 into a tool.
• the polymer granules are filled into the piston vestibule 26 of the injection unit 28.
• the spring 23 is then preloaded, the injection pressure being able to be set, for example, between 1 and 10 bar.
• the injection unit together with the flanged tool 29 is inserted into the process autoclave 13 (FIG. 1). Fumigation follows, which is characterized by the parameters of pressure, temperature and time. After reaching the desired state of fumigation, a trigger mechanism 21 is actuated from the outside and the injection is thus triggered. The plasticized polymer is injected into the mold cavity (see FIG. 4). This is followed by the pressure release, which can take place at different speeds depending on the desired molded part structure and the tool material used.
• the tool 29 consists of clamping plates made of perforated sheet metal and shaped plates which contain the cavity to be molded.
• a wide variety of materials can be used as mold plate materials. Silicone and polycarbonate are used in the application examples. Tools made of sintered metal or polyurethane foams are also possible.
• FIG. 4 shows a tool holding device 30 with a flange and a retaining valve (for example made of polycarbonate) 31, sprue nozzle 32, check valve (with ball) 33, shaped plates 34, clamping plates made of perforated plate 35 and the cavity 36.
• a retaining valve for example made of polycarbonate
• sprue nozzle 32 sprue nozzle
• check valve with ball
• shaped plates 34 clamping plates made of perforated plate 35 and the cavity 36.
• the tool in the present case a plunge edge tool for producing a compact tension rod
• the tool consists of a shaped plate 40 on which the contour of the plunger is raised (see FIG. 6).
• the form aperture 41 has exactly the negative contour of the press ram.
• a sintered metal 43 serves as the cover plate, which facilitates gas entry and exit.
• a special - gas-permeable - foil 42 prevents the material, whose viscosity is greatly reduced, from penetrating into the sintered pores.
• the bulk material resorbable polymer, addition of active ingredients
• the mold plate, mold panel and sintered metal are made of stainless steel. Procedure:
• the polymer is first mixed with the active ingredient.
• the press ram (mold plate 40) is inserted into the mold panel 41 and clamped over the screws by means of disc springs. The entire tool is placed in the autoclave 13 (Fig. 1).
• the autoclave is filled with CO2, which is compressed by means of a piston diaphragm pump, the process pressure is between 20 and 2000 bar, preferably between 60 and 200 bar.
• the process temperature is less than 37 ° C when loaded with temperature-sensitive active ingredients. However, the temperature can be freely selected between -70 ° C and 400 ° C by tempering the autoclave.
• Absorbable polymers preferably amorphous absorbable
• FIG. 7 discloses the morphology of a body made of Resomer® R 207 loaded with 50% by weight of cane sugar.
• Another object of the present invention is to foam foamed articles with a given geometry.
• the foam structure should be as integral as possible in order to increase the bending stiffness of the samples compared to a molded part with the same mass.
• a tension rod was selected as the part geometry.
• 8 shows a modular foaming tool; this tool consists of 2 support plates, 51, 52, 2 gas-permeable plastic plates 53, 54 (for example made of polycarbonate) and intermediate plates 55 with a special grinding for gas and degassing.
• the intermediate plates are centered by means of dowel bolts 45.
• the tool is clamped with screws and nuts 46, 47.
• the number of intermediate plates specifies the height of the foamed component.
• Figs. 10 and 11 show the homogeneous foam formation at a pressure of 200 bar, a temperature of 65 ° C. and a gassing time of 60 minutes.
• 11 shows the foam structure of poly (D, L-lactide-L-lactide) / poly-L-lactide at 65 ° C., 200 bar and a degree of foaming of 150.
• FIG. 12 shows the systematic process sequence when producing a self-expanding foam: step 1 relates to filling; the dry ice tablet 60 and the - loaded - polymer 61 are introduced into an appropriately designed reaction vessel. Step 2 includes closing the reaction vessel 62 with a subsequent increase in temperature. Finally, step 3 relates to the deep-cold removal of the sample body 63 with subsequent warming up to the expanding foam 64.
• Another object of the present invention relates •sexpantierende foams.
• the object of the present invention is to produce a component which is dimensionally stable at low temperature and foams at body temperature.
• a small lockable stainless steel container A small lockable stainless steel container.
• Amorphous resorbable polymer e.g. Resomer® R 207.
• the foaming temperature and the resulting removal temperature of the molded body can be specified.
• the body expands isotropically by a factor of 2, which corresponds to an eightfold increase in its volume.
• the gassing can be in a temperature range from 20 to 400 ° C. - preferably 20 to 120 ° C. and for resorbable polyesters based on lactide and Glycolide particularly preferably in a range from 20 to 80 ° C.
• Diffusion mechanisms are slowly released to the neighboring body tissue.
• the shaping takes place in the case of polymers which are loaded with fillers, analogously to the production of shaped bodies in accordance with the abovementioned methods.
• the filler In order to guarantee the finest possible distribution of the fillers in the molded body, the filler must be mixed well with the polymer.
• One possibility is to mix the polymer and filler before gassing and to reduce the viscosity of the mixture (compound) by subsequent gassing to such an extent that it can be shaped into its shaped body.
• Another variant consists in first reducing the viscosity of the polymer by gassing and then mixing in a filler.
• the filler can also be a liquid component.
• the compound can in turn be shaped into a shaped body in the manner described above.
• a compact preform - preferably in the injection molding process - is produced and inserted into a corresponding tool, which has the contour of the foamed end product.
• the tool must have sufficient ventilation options or be made of a sintered metal.
• the inserted molded part is gassed with the tool under a high pressure, so that the gas or the supercritical fluid is dissolved in the polymer. After the pressure has been released, the molded part can expand in the mold by expansion of the gas dissolved in the molded part.
• the foaming can be influenced by heating be, the temperature is significantly lower than the melting temperature. Due to the predetermined contour of the mold cavity, the molding foams in a defined manner. The degree of foaming can be specified precisely on the basis of the free volume made available.
• the plates often have to be dimensioned comparatively much larger.
• An associated mass accumulation of resorbable plastics in the body is, on the other hand, not very desirable.
• the resorption time increases with increasing implant size, which is undesirable in many cases - on the other hand, an increased use of material during the resorption can lead to undesirable reactions of the body.
• a bone plate which is only foamed in height and which is produced by the method described above, however, has an essentially increased flexural rigidity with an integral density distribution and the same mass used. Because of the foam structure, such an implant can be absorbed faster than a comparably stiff implant, which is of compact construction.
• the foaming process described above it is also possible to foam in two stages, to partially foam a previously produced molded part.
• the molded part is again placed in a tool which corresponds to the end contour of the foamed component.
• the places that should be compact in the later molded part will tightly enclosed by the tool.
• the areas to be foamed had the space around which the molded part should foam at this point.
• the production of partially foamed components proceeds analogously to the process for producing foamed molded parts described above.
• Partial foaming is particularly desirable for resorbable implants.
• the foamed bone plates described above have a significantly increased flexural strength with the same use of material as a compact shaped plate, it is hardly possible to adapt such a plate to the bone.
• a foamed structure has a very poor thermal conductivity due to the porosity, so that a foamed plate is very difficult to bend. The places where the possibility of bending should be provided should therefore be switched off compactly.

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• Engineering & Computer Science (AREA)
• Mechanical Engineering (AREA)
• Materials For Medical Uses (AREA)
• Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)

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• 1993
  • 1993-05-05 DE DE19934314869 patent/DE4314869A1/de not_active Withdrawn
• 1994
  • 1994-05-04 JP JP6523906A patent/JPH09500151A/ja active Pending
  • 1994-05-04 EP EP94916189A patent/EP0700331A1/de not_active Withdrawn
  • 1994-05-04 WO PCT/EP1994/001410 patent/WO1994025242A1/de not_active Application Discontinuation
• 1995
  • 1995-11-03 FI FI955280A patent/FI955280A0/sv not_active Application Discontinuation

Non-Patent Citations (1)

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