EP1249219A1 - Procédé et dispositif de production d'articles, en particulier de capsules, fabriqués avec un materiau biopolymère en se basant sur la raideur - Google Patents

Procédé et dispositif de production d'articles, en particulier de capsules, fabriqués avec un materiau biopolymère en se basant sur la raideur Download PDF

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Publication number
EP1249219A1
EP1249219A1 EP00128701A EP00128701A EP1249219A1 EP 1249219 A1 EP1249219 A1 EP 1249219A1 EP 00128701 A EP00128701 A EP 00128701A EP 00128701 A EP00128701 A EP 00128701A EP 1249219 A1 EP1249219 A1 EP 1249219A1
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EP
European Patent Office
Prior art keywords
extrusion
material strip
strips
heat
mold
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
EP00128701A
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German (de)
English (en)
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EP1249219B1 (fr
Inventor
Alois Peter
Rico Ménard
Valentin Lutz
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.)
Swiss Caps Rechte und Lizenzen AG
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Swiss Caps Rechte und Lizenzen AG
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Swiss Caps Rechte und Lizenzen AG filed Critical Swiss Caps Rechte und Lizenzen AG
Priority to AT00128701T priority Critical patent/ATE446075T1/de
Priority to DE50015770T priority patent/DE50015770D1/de
Priority to EP00128701A priority patent/EP1249219B1/fr
Priority to ES00128701T priority patent/ES2334973T3/es
Priority to PCT/EP2001/014837 priority patent/WO2002053088A1/fr
Priority to US10/451,936 priority patent/US20040071808A1/en
Publication of EP1249219A1 publication Critical patent/EP1249219A1/fr
Application granted granted Critical
Publication of EP1249219B1 publication Critical patent/EP1249219B1/fr
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61JCONTAINERS SPECIALLY ADAPTED FOR MEDICAL OR PHARMACEUTICAL PURPOSES; DEVICES OR METHODS SPECIALLY ADAPTED FOR BRINGING PHARMACEUTICAL PRODUCTS INTO PARTICULAR PHYSICAL OR ADMINISTERING FORMS; DEVICES FOR ADMINISTERING FOOD OR MEDICINES ORALLY; BABY COMFORTERS; DEVICES FOR RECEIVING SPITTLE
    • A61J3/00Devices or methods specially adapted for bringing pharmaceutical products into particular physical or administering forms
    • A61J3/07Devices or methods specially adapted for bringing pharmaceutical products into particular physical or administering forms into the form of capsules or similar small containers for oral use

Definitions

  • the invention relates to a method and an apparatus for Manufacture of molded articles, in particular capsules, from a biopolymer Material, especially based on starch the preamble of independent claims 1 and 8.
  • Shaped bodies in particular capsules, are today in continuous, automatable processes from endless material strips manufactured.
  • the production of the molded body shell and the filling the same happens here, especially in the case of one-piece capsules, in a single step.
  • This continuous Processes are made from which the capsule shells are made during and after filling by welding the outer edges the molded parts are put together.
  • the molding production happens either by means of diverging and merging forms, such as. in the Norton, Banner and Schering process or by means of rotating form rolls, e.g.
  • the manufacturing process for molded articles from endless strips of material has a number of requirements.
  • One of the main requirements is the ability to use endless material tapes to train a sufficient strength, which over a have sufficient elongation at break and elasticity.
  • material tapes can be made manufacture all of these conditions in almost ideally meet.
  • Gelatin tapes can be made from a homogeneous mass which is free-flowing at 40 ° C to 80 ° C Gelatin and water, which are usually additives such as glycerol and Contains sorbitol. This happens at atmospheric pressure, taking the mass from so-called spreaders Gravity poured through a slit onto a cooled drum or is extruded. The mass should be at approx. 15 ° C Solidify at 25 ° C (gel state). At lower extrusion temperatures the water content must be increased to melting point and To lower viscosity or need an extrusion below Pressure. At extrusion temperatures over 100 ° C there is a risk that the mixture exits the so-called Spreader foams.
  • EP 0 397 819 shows a process for producing thermoplastically processable starch, the crystalline fraction in the starch being below 5%.
  • the process consists of mixing native starch with at least 10% by weight of an additive which has a solubility parameter of at least 30.7 (MPa) 1/2 .
  • the mixture is converted into a melt under the application of heat in a temperature range between 120 ° C. and 220 ° C., an internal pressure of approximately 30 to 300 bar being assumed.
  • the starch's water content is reduced to below 5% in the melt.
  • the starch film which according to the method disclosed in EP 397 819 generated does not show weldability or seam strength, which meet the quality requirements in one piece Shaped body shells, in particular capsule shells would suffice.
  • this object is achieved by a device and by a method with the features in the independent claims 1 and 8 solved.
  • the material strip becomes between the extrusion die and the die for relieving tension at a treatment station at least subjected to a heat treatment.
  • the temperature for the heat treatment must be selected so that the desired relaxation of the material tapes results and the belt is controlled - without further tension build-up can be. This temperature is process and material dependent.
  • the desired relaxation in the sense of the invention is then achieved if the tape is no longer anisotropic after heat treatment but has isotropic mechanical properties, so that the mechanical properties of the tape in the longitudinal direction and are approximately identical in the transverse direction.
  • a definition for the pair of terms "anisotropic / isotropic” can be found in Römpp Chemie Lexikon, ed .: J. Falbe, M. Regitz, 9th edition, 1992, Georg Thieme Verlag, Stuttgart.
  • the tapes treated according to the invention thus also have the whole band of material has an even elongation at break and a uniform modulus of elasticity E.
  • E elongation at break
  • Soft capsules in the rotary die process are an elongation at break of at least 100% and a modulus of elasticity of less than or equal to 2 MPa in the temperature range from 40 ° C to 80 ° C especially advantageous.
  • the measurement of the elongation at break and the modulus of elasticity E can according to DIN standard 53455 or DIN EN ISO 527-1 to ISO 527-3.
  • the elongation at break is measured in accordance with this DIN standard the corresponding encapsulation temperature.
  • At least one material strip is extruded and then subjected to heat on a treatment arrangement.
  • a treatment arrangement for the production of the moldings also several Material tapes extruded and then heat treated be subjected.
  • any term should be used under the term molded body Type of moldings are understood that are suitable take up a filling material and seal it inside. This includes not only capsules but also others Shapes such as B. balls, pillows and figures. To date exist numerous developments and deviations from the basic Principle of the capsule.
  • Biopolymer materials in the sense of the invention are all materials by means of suitable processes to form endless strips of material can be extruded. According to the invention, these include also physically and / or chemically modified biopolymers. Examples of biopolymers according to the invention are cellulose, in particular partially hydroxypropylated cellulose, alginates, carrageenan, Galactomannans, glucomannans, casein and starch. As well are mixtures of different biopolymer materials in the sense the invention conceivable.
  • Starch is particularly preferred. Under the term strength should native starches, as well as physically and / or chemically modified Strengths are understood. For those in the process according to the invention Base materials used are all strengths, independent from the plant from which they are obtained. In a preferred embodiment is starch, the Amylopectin content over 50% based on the total weight of the anhydrous starch. Potato starch is particularly suitable.
  • polyglucans i.e. 1.4 and / or 1.6 poly- ⁇ -D-glucase and / or mixtures between them.
  • the method according to the invention can be an integral part of a known process for the production of moldings endless material tapes such as the Norton, Banner and Schering process or the process using rotating forming rolls, such as. in the rotary die process and in the Accogel process realized ("The capsule” Fahrig / Hofer, publisher, Stuttgart, 1983; Lachmann / Liebermann / Kanig, "The Theory and Practice of Industrial Pharmacy "; Third Edition, Philadelphia 1986).
  • At least two material strips are particularly preferred.
  • the rotary die principle processed into shaped bodies each of the material strips between extrusion and processing into shaped bodies at a treatment station at least one heat treatment is subjected.
  • the rotary die process with rotating Form rolling has been known and used for many years and today represents one of the most common encapsulation processes for the manufacture of pharmaceutical, dietetic and technical molded body.
  • the endless strips of material are subjected to heat on both sides.
  • the Heat treatment can be by radiation, in particular by IR radiation take place.
  • IR radiation take place.
  • ultrasound, Microwave and other suitable sources of radiation for heating conceivable.
  • the material tapes are heated by a bath, in particular passed an oil bath.
  • a bath temperature is preferably in a range kept between 40 ° C and 80 ° C.
  • Another object of the present invention is a device for the production of moldings, in particular capsules, made of a biopolymer material, in particular based on Starch, with at least one extrusion tool for extrusion an endless strip of material and at least one molding tool for processing the material strip under the influence of a filling compound to moldings being between the extrusion die and the molding tool at least one treatment station for loading the material band is arranged with heat.
  • the treatment arrangement has at least a radiation source, in particular an infrared radiation source on. Combinations of different ones are also conceivable Radiation sources.
  • the treatment station has at least one Has radiators, the strips of material by convection heat be charged.
  • the device according to the invention has a heated bath, especially an oil bath. So that can in addition to the desired relaxation, lubrication of the material tapes can be achieved.
  • An oil is used in the oil bath, which from a pharmaceutical and toxicological point of view in the later Application of the molded body is harmless. Such oils are known and listed in the relevant legislation.
  • other additives can be added to the oil bath be the properties of the material tapes, such as. B. Elasticity or influence elongation at break positively.
  • the use of an oil bath is particularly good for relaxing of material tapes, in particular based on Strength.
  • the device between the oil bath and molding tool at least one stripping device for stripping of liquid from the surface of the material tapes having.
  • the stripping device can be designed in this way be that the film thickness of the on the surface of the material tapes remaining film can be predetermined.
  • the device at least one compensating means, in particular a dancer roller to maintain a constant longitudinal tension of the material tapes.
  • Lengths of the tapes z. B. by Non-synchronous means of transportation can be balanced become.
  • the tension can be like this kept as low as possible, particularly advantageously below 0.5 Mpa become.
  • the mold is the device a rotary die device with two Forming rollers and a filling wedge.
  • the Device at least one adjustable positioning arrangement has, on which the extrusion die and the die relative are adjustable to each other.
  • the positioning arrangement could e.g. B. a slidable on a rail Have machine frame for the extrusion tool.
  • Figure 1 shows a schematic representation of an inventive Device for producing molded articles from endless Material tapes using the rotary die process.
  • the Rotary Die machine shown is used in a known manner for the processing of two endless strips of material 15, 15 'used.
  • the material tapes are each on an extrusion tool 1, 1 'to the Extruders 13 extruded from slot nozzles 10 and with one each Rolled pair 7a, 7b and rolled to a constant thickness.
  • the Extruders 13 are continuously filled with biopolymer material 12, especially with starch-based material.
  • the extruded strips of material 15 are one in a known manner Forming tool 2 supplied.
  • One is shown essentially horizontal feeding of the material tapes to the mold.
  • the material tapes in any to feed the mold at a different angle. Particularly advantageous is a vertical feed because of the load of the tape can be minimized by gravity.
  • the molding tool consists of two molding rolls 4a, 4b, wherein in the surfaces of the forming rolls 4a, 4b which are used to deform the Shaped body 11, in particular recesses required for capsules are arranged.
  • a filling wedge 5 is arranged, by means of which Feed pump 6 from a product tank 8 product 9 between the material belts 15, 15 'is inserted, the material tapes are deformed into capsules 11 on the forming rollers 4a, 4b.
  • Fill 9 can be liquid, pasty or in certain cases Powdery filling 9 can also be used. Is conceivable also the encapsulation of pellets, tablets and much more.
  • the material strips 15 between the extrusion tool 1 and mold 2 on a treatment arrangement 3a, 3b with heat On the treatment arrangement 3a the heat treatment takes place in the exemplary embodiment shown by radiation z. B. from an infrared radiation source 23. Es is also conceivable as shown in the treatment arrangement 3b, the strips of material 15, by convection heat, which generated by radiators 24, in particular heating coils, and in a cavity 25 is emitted to heat.
  • convection heat which generated by radiators 24, in particular heating coils, and in a cavity 25 is emitted to heat.
  • Figure 2 shows a schematic representation of an inventive Device for producing molded articles from endless Material tapes 15, 15 'in the Norton process.
  • one Extrusion tool 1 extruded a material strip 15, 15 ' and pulled off with a pair of rollers 7 and to the correct thickness rolled.
  • the material band 15 ' is in the area between the extrusion tool 1 and molding tool 2 through a treatment station 3 led to the application of heat.
  • the heat is passed through radiators 24 in a heating tunnel 26 generated.
  • the material band 15 ' can be guided and / or drive rollers 20 guided to the mold 2 become.
  • the material strips 15 which by asynchronous movements of the Rollers 20 can arise, balanced with the aid of a dancer roller 21 become. So that the longitudinal tension of the material band 15 be kept constant.
  • the dancer roll 21 is corresponding on an axis perpendicular to the running direction of the material strip 15 to maintain the longitudinal tension of the material band 15 required distance D movable. Over the dancer roller the actual tensile stress could also be measured on a sensor 29 become. The sensor could therefore also be used for feed control or used for emergency shutdown in the event of impermissible tension become. It is particularly favorable if the tensile stress is below 0.5 MPa is kept.
  • the material band 15 is in the Norton process shaped in a known manner to shaped bodies 11, in particular capsules.
  • the capsules are formed between one unit a preform 17 and a capsule forming unit 16.
  • the upper parts of the units 16, 17 are the capsules preformed in a tube-like manner and via filler channels 18, which via a filler feed 14 are supplied filled.
  • At the bottom Part of the capsule forming unit finds the final one Encapsulation instead.
  • the preforming unit is in the upper molding 17 preformed the capsule lengthways. It stays open upstairs to allow the filling 9 to be added.
  • FIG. 3 shows a schematic representation of an alternative Embodiment of a device according to the invention.
  • there becomes the material strip extruded from an extrusion tool 1 15 via drive rollers 19 which are driven by a motor M. are supplied to an oil bath 27.
  • the oil bath 27 is over a Heating unit 28 heated.
  • By immersing the material tape 15 in the oil bath 27 becomes the desired relaxation of the material band 15 by the release of conserved Tensions reached.
  • the material band 15 is through lubricated the oil bath 27.
  • a dancer roller 21 is in the area of the oil bath 27 appropriate.
  • the dancer roll 21 is otherwise the same as in the exemplary embodiment according to FIG. 2.
  • the material strip 15 is at Leaving the oil bath 27 fed to a stripping device 22. Excess oil from the Surface of the material strip 15 are removed.
  • the scraper 22 can be designed so that the Film thickness of that remaining on the surface of the material strips 15 Oil film set to a predetermined value can be.
  • the relaxed material tape is like already shown fed via a guide roller 20 to a mold 2. This is the case in the exemplary embodiment shown around the molding tool 2 a operated in the rotary die process Contraption. With this method, it has a particularly favorable effect from that additional heat, in the embodiment shown was introduced onto the starch tape 15 by the oil bath. This allows the segment temperature in the area of the filling wedge 5 be kept low.
  • An oil bath 27 as Treatment station 3 for loading the material strip 15 with Heat also has the advantage that other additives, which the belt properties such as viscosity, elasticity, Elongation at break etc. can be positively added to the bath can.
  • Other liquids instead of oil such as B. water, aqueous dispersions etc. are conceivable.
  • FIG. 4 shows a diagram for the elongation at break of starch strips 15 before and after treatment with the method according to the invention.
  • the elongation at break can be measured according to DIN standard 53455.
  • the elongation at break in percent is shown as a function of FIG on the temperature.
  • Both the values for the Elongation at break in the longitudinal and transverse directions of the starch strips 15 determined.
  • the for the forming process of the material band 15 into a shaped body 11 required elongations at break of at least 100% over the entire temperature range in both the longitudinal and transverse directions can be achieved. This is particularly important because because a minimum elongation at break of 100% is necessary in order to to encapsulate existing rotary die processes.
  • Figure 4 clearly shows that the elongation at break in longitudinal and Transverse direction before treatment with the inventive Procedures are different.
  • the starch tape shows anisotropic mechanical properties, which in particular during attributed conserved tensions to the extrusion of the tapes are.
  • Anisotropic bands can be processed misshapen moldings, especially capsules, lead, which increases also get stuck in the form rollers and the production process hinder.
  • the starch tape 15 after treatment with Heat relaxes and has isotropic properties.
  • the measured Elongation at break of the material strips 15 is in the longitudinal direction and approximately identical in the transverse direction. During further processing such material strips arise evenly Shaped body 11, which do not get caught in the molding rolls.
  • Figure 5 shows a diagram of the elastic modulus of starch tapes 15 before and after treatment with the method according to the invention.
  • the elasticity module E can be measured in accordance with DIN EN ISO 527-1 to ISO 527-3.
  • DIN EN ISO 527-1 to ISO 527-3 Through the heat treatment the modulus of elasticity, especially in the processing of the Material tapes 15 to form bodies 11 important area of 40 ° C. significantly reduced to 80 ° C to 2 MPa and less. This is particularly important because an elastic modulus of A maximum of 2 MPa is necessary to use existing rotary die processes to perform an encapsulation.
  • the maximum pressure resp. the length of stay the material tapes in the filler wedge area should be selected so that Material tape can be "inflated" into a capsule.
  • the Filling wedge floats freely on the forming rollers and sets them Seal sure. So the pressure cannot be increased arbitrarily, otherwise the filling material between the material band and the filling wedge runs out.
  • the material strips have a low modulus of elasticity 15 play a crucial role.
  • the method according to the invention it also proves in terms of the reduction achieved of the elastic modulus as particularly advantageous. All in all are the material properties of the material tapes for the subsequent processing into moldings is optimized.

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  • Health & Medical Sciences (AREA)
  • Chemical & Material Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Pharmacology & Pharmacy (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Animal Behavior & Ethology (AREA)
  • General Health & Medical Sciences (AREA)
  • Public Health (AREA)
  • Veterinary Medicine (AREA)
  • Medicinal Preparation (AREA)
  • Extrusion Moulding Of Plastics Or The Like (AREA)
  • Materials For Medical Uses (AREA)
EP00128701A 2000-12-29 2000-12-29 Procédé et dispositif de production d'articles fabriqués avec un materiau biopolymère Expired - Lifetime EP1249219B1 (fr)

Priority Applications (6)

Application Number Priority Date Filing Date Title
AT00128701T ATE446075T1 (de) 2000-12-29 2000-12-29 Verfahren und vorrichtung zum herstellen von formkörpern aus einem biopolymeren material
DE50015770T DE50015770D1 (de) 2000-12-29 2000-12-29 Verfahren und Vorrichtung zum Herstellen von Formkörpern aus einem biopolymeren Material
EP00128701A EP1249219B1 (fr) 2000-12-29 2000-12-29 Procédé et dispositif de production d'articles fabriqués avec un materiau biopolymère
ES00128701T ES2334973T3 (es) 2000-12-29 2000-12-29 Procedimiento y dispositivo para la obtencion de cuerpos moldeados a partir de un material biopolimero.
PCT/EP2001/014837 WO2002053088A1 (fr) 2000-12-29 2001-12-15 Procede et dispositif pour la production de corps moules, notamment de capsules, a partir d'un materiau biopolymerique contenant de l'amidon
US10/451,936 US20040071808A1 (en) 2000-12-29 2001-12-15 Method and device for producing shaped bodies, especially capsules, from a biopolymer material containing starch

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
EP00128701A EP1249219B1 (fr) 2000-12-29 2000-12-29 Procédé et dispositif de production d'articles fabriqués avec un materiau biopolymère

Publications (2)

Publication Number Publication Date
EP1249219A1 true EP1249219A1 (fr) 2002-10-16
EP1249219B1 EP1249219B1 (fr) 2009-10-21

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EP00128701A Expired - Lifetime EP1249219B1 (fr) 2000-12-29 2000-12-29 Procédé et dispositif de production d'articles fabriqués avec un materiau biopolymère

Country Status (6)

Country Link
US (1) US20040071808A1 (fr)
EP (1) EP1249219B1 (fr)
AT (1) ATE446075T1 (fr)
DE (1) DE50015770D1 (fr)
ES (1) ES2334973T3 (fr)
WO (1) WO2002053088A1 (fr)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7494667B2 (en) 2004-03-02 2009-02-24 Brunob Ii B.V. Blends of different acyl gellan gums and starch
EP2108677A1 (fr) 2008-04-10 2009-10-14 Swiss Caps Rechte und Lizenzen AG Matériaux thermoplastiques à base d'amidon

Families Citing this family (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7887838B2 (en) * 2002-01-18 2011-02-15 Banner Pharmacaps, Inc. Non-gelatin film and method and apparatus for producing same
US6949256B2 (en) * 2002-01-18 2005-09-27 Banner Pharmacaps, Inc. Non-gelatin capsule shell formulation
ATE376415T1 (de) * 2003-01-08 2007-11-15 Swiss Caps Rechte & Lizenzen Formkörper bestehend aus gelatinfreiem material und gefüllt mit einer flüssigen füllmasse
US20050196437A1 (en) * 2004-03-02 2005-09-08 Bednarz Christina A. Hard capsules
PT103380B (pt) * 2005-11-09 2007-09-13 Univ Do Minho Linha de extrusão laboratorial para a produção de filme tubular convencional e biorientado, com comutação simples entre as duas técnicas
EP2595610A4 (fr) * 2010-07-19 2015-10-28 Procaps S A Appareil et procédé améliorés pour la fabrication de capsules à enveloppe molle
CN105456037B (zh) * 2015-08-14 2022-05-17 新昌县恒泰隆机械设备有限公司 一种匀油机构及胶囊生产线
AU2017371180B2 (en) * 2016-12-08 2023-05-11 R.P. Scherer Technologies, Llc A method to relieve stress in capsule shells to reduce propensity to break

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US2513581A (en) * 1947-06-23 1950-07-04 Norton Co Capsulator
US2643416A (en) * 1949-03-05 1953-06-30 Norton Co Apparatus for casting ribbons of gelatin and the like
DE1009357B (de) * 1955-04-12 1957-05-29 Sueka Ges M B H Vorrichtung zur Zufuehrung der zur Bildung von mit Heil- oder Naehrstoffen od. dgl. gefuellten Kapseln dienenden elastischen Baender, vorzugsweise Gelatinebaender, zu der Form
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US3092942A (en) * 1960-04-15 1963-06-11 Sydney A Chasman Apparatus for encapsulating
EP0040446A1 (fr) * 1980-05-16 1981-11-25 Stamicarbon B.V. Procédé et dispositif de fabrication de granules de matière thermoplastique chargées

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DE59911807D1 (de) 1999-11-19 2005-04-28 Swiss Caps Rechte & Lizenzen Verfahren zum Herstellen eines Stärke enthaltenden Formkörpers, homogenisierte Stärke enthaltende Masse und Vorrichtung zum Herstellen einer Weichkapsel
EP1112740A1 (fr) * 1999-12-30 2001-07-04 Greither, Peter Utilsation d'une composition soluble dans l'eau contenant du polyglycérol
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US2390337A (en) * 1941-05-13 1945-12-04 Chester A Spotz Method and machine for making capsules, particularly gelatin capsules
US2513581A (en) * 1947-06-23 1950-07-04 Norton Co Capsulator
US2643416A (en) * 1949-03-05 1953-06-30 Norton Co Apparatus for casting ribbons of gelatin and the like
DE1009357B (de) * 1955-04-12 1957-05-29 Sueka Ges M B H Vorrichtung zur Zufuehrung der zur Bildung von mit Heil- oder Naehrstoffen od. dgl. gefuellten Kapseln dienenden elastischen Baender, vorzugsweise Gelatinebaender, zu der Form
GB908344A (en) * 1958-06-10 1962-10-17 Lionel Lavaud Method and apparatus for manufacturing capsules of thermoweldable material
US3092942A (en) * 1960-04-15 1963-06-11 Sydney A Chasman Apparatus for encapsulating
EP0040446A1 (fr) * 1980-05-16 1981-11-25 Stamicarbon B.V. Procédé et dispositif de fabrication de granules de matière thermoplastique chargées

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7494667B2 (en) 2004-03-02 2009-02-24 Brunob Ii B.V. Blends of different acyl gellan gums and starch
EP2108677A1 (fr) 2008-04-10 2009-10-14 Swiss Caps Rechte und Lizenzen AG Matériaux thermoplastiques à base d'amidon

Also Published As

Publication number Publication date
EP1249219B1 (fr) 2009-10-21
DE50015770D1 (de) 2009-12-03
ATE446075T1 (de) 2009-11-15
ES2334973T3 (es) 2010-03-18
US20040071808A1 (en) 2004-04-15
WO2002053088A1 (fr) 2002-07-11

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