AU2002210449A1 - Pectin film compositions - Google Patents
Pectin film compositionsInfo
- Publication number
- AU2002210449A1 AU2002210449A1 AU2002210449A AU2002210449A AU2002210449A1 AU 2002210449 A1 AU2002210449 A1 AU 2002210449A1 AU 2002210449 A AU2002210449 A AU 2002210449A AU 2002210449 A AU2002210449 A AU 2002210449A AU 2002210449 A1 AU2002210449 A1 AU 2002210449A1
- Authority
- AU
- Australia
- Prior art keywords
- film
- pectin
- aqueous solution
- composition according
- film composition
- 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
Links
Description
Pectin Film Compositions
The invention concerns film compositions containing pectin, at least one additional film-forming polymer and a setting system for use in pharmaceutical, veterinary, food, cosmetic or other products like films for wrapping food, aspics or jellies, preferably for predosed formulations like soft or hard capsules.
Preferably pectin compositions are used for manufacturing of hard capsules for pharmaceutical and veterinary applications. The pectin content of the compositions confers enteric properties to such capsules and at least one further film-forming polymer enhances the mechanical performance of the hard capsules. Combination with a setting system allows use of the film-forming compositions of the invention for industrial enteric capsule production by conventional dip moulding processes.
The use of conventional dip moulding equipment for gelatin capsule production allows the production of enteric capsules with equal dimensions and properties which can be used with conventional filling equipment for gelatin capsules.
Enteric materials have a pH-dependent solubility. They are insoluble under gastric conditions (simulated by a pH of 1.2) and readily soluble under intestinal conditions (simulated by a pH of 6.8). Generally, these materials are polymers containing carboxylic groups, such as cellulose acetate phthalate (CAP), hydroxypropyl methylcellulose phthalate (HPMCP), hydroxypropyl methylcellulose acetate succinate (HPMC-AS), acrylic copolymers, pectin or alginates.
Usually enteric properties of pharmaceutical compositions are achieved by a coating process with enteric materials on e.g. granules, pellets, tablets or hard or soft capsules.
Enteric film compositions for hard capsules are described for example in US 4,138,013. The film-forming composition for dip moulding consists of (1) hydroxypropyl methylcellulose and an ammonium salt of cellulose acetate phthalate polymer or (2) of gelatin and an ammonium salt of a copolymer of methacrylic acid
and methacrylic acid ester. However, it has been found that capsules made according to the mentioned techniques have the disadvantages of poor solubility in intestinal juice, high organic solvent content, inadequate stability and diffusion problems.
Improvements are described in EP-A-0 056 825 with film compositions containing film-forming polymers like cellulose esters or cellulose ether esters, plasticizers, viscosity-increasing substances like highly viscous cellulose ethers, and anti-foaming agents.
Conventional hard capsules are produced from gelatin by a dip moulding process. This process is based on the setting ability of hot gelatin solution by cooling. On a totally automatic industrial hard gelatin capsule machine, mould pins are dipped into hot gelatin solution, the pins are removed from the solution, inverted, the gelatin solution (gel) remaining on the pins dried, stripped off the capsule shells and finally cap and body of the capsules cut and pre-joined. The immediate setting of the gelatin solution on the mould pins after dipping is the key step in the process. Otherwise, the gelatin solution would flow down to form capsules with non-uniform wall thickness and unacceptable properties.
A further enteric film composition consisting of a mixed ester of an alkyl-, hydroxyalkyl- or hydroxyalkyl alkylcellulose esterified with succinyl anhydride and an aliphatic monocarboxylic acid anhydride is described in US 4,365,060. However, the solutions from these compositions do not possess any setting ability and therefore are not applicable to industrial-scale dip moulding processes.
JP-A-58138458 describes a process for dipping mould pins into an aqueous solution of hydroxypropyl-methyl-cellulose acetate succinate alkali metal salt and gelatin and thereafter dipping in aqueous acid solution. However, in this composition the gelatin content is too low to provide sufficient setting ability to the dipping solution.
Surprisingly, we have found that film compositions based on pectin as enteric material with at least a second film-forming material and a setting system have sufficient setting ability for industrial hard capsule production.
Pectin has excellent enteric properties. A relatively low content of pectin from 5 to 25 %, preferably 10 to 20 % by weight in the composition, is sufficient to obtain capsule films with enteric properties. Surprisingly, the capsule of the present invention can resist dissolution at least for 2 hours in in- vitro disintegration tests at pH 1.2, and is easily soluble at pH 6.8 (> 80 % after 45 min under USP dissolution conditions).
The aqueous solutions of the film-forming compositions of the prior art are necessarily prepared under alkaline conditions and for this reason are quite unstable. This disadvantage is overcome by the compositions of the invention because the pectin used as enteric material is water soluble and consequently, the solution is quite stable.
A further advantage of pectin is that pectin itself has the properties of a setting agent as described below.
A disadvantage of pectin is its brittleness like other enteric materials, if it is used in film-forming compositions alone or in high amounts. Surprisingly, we have found that this problem could be solved by the addition of at least one further film-forming material to the film-forming composition, which may be selected generally from all hydrosoluble film-forming materials of pharmaceutical and/or food quality grade.
Suitable are for example gelatin; pullulan; polyvinyl alcohol; modified starches such as hydroxypropylated starch or hydroxyethylated starch; cellulose ethers such as hydroxypropyl methylcellulose, hydroxypropyl cellulose, methylcellulose, hydroxyethyl cellulose or hydroxyethyl methylcellulose; and mixtures thereof.
Beside the improvement of the mechanical properties of the capsule film the addition of a second film-forming material also increases the content of solid material in the dip mould solution of the film composition.
The content of pectin is in the range of 5 to 60 %, preferably 10 to 40 %, and that of the second film-forming material in the range of 40 to 95 %, preferably 50 to 85% by weight in the film composition.
Low methoxyl pectins (LM pectins) with a degree of esterification of the carboxyl groups with methanol below 50% are especially preferred.
The dipping solution for the capsule manufacturing process has a content of the film- forming composition in the range of 15 to 40 % by weight.
For the production of enteric capsules by an industrial dipping process, it is essential that the dipping solution has a sufficient setting ability. Surprisingly, we have found that pectin, beside its enteric properties, can provide a sufficient setting behavior in the presence of divalent cations such as Ca^or Mg++. The content of the divalent salts such as CaCl2 in the dipping solution is preferably from 100 ppm to 5000 ppm (0.01 to 0.5 % by weight), this means an amount of from 0.04 to 2 % by weight of the final film composition. During the preparation of the solution, the formation of concentration peaks of the divalent salt has to be avoided. High local concentrations of the divalent salt will result in thermally irreversible local pectin gel formation.
The setting behavior of the film-forming solution of the invention may be also achieved or altered by the addition of further gelling agents, preferably polysaccharides such as carrageenan or gellan. It has been found that addition of a small quantity of such additional gelling agent can provide sufficient setting ability. The gelling agent content in the dipping solution is preferably from 0.05 to 2 % by weight, this means an amount of from 0.2 to 8 % by weight of the final film composition.
The temperature of the solution during the dipping process is also important for the setting properties of the dipping solution. Preferably the temperature should be above
50°C, and is dependent on the pectin content. It has been found that the temperature of the dipping solution has to be increased with higher pectin contents.
The inventive composition may contain in a further aspect additional pharmaceutically or food-acceptable colouring agents in the range of 0 to 10 % based upon the weight of the final film composition.
The inventive composition may contain in a further aspect additional pharmaceutically or food acceptable plasticizer or flavouring agents.
Finally, the inventive film-forming solution can be used for banding enteric capsules. This prevents the capsule from leaking or separation of body and cap in gastric fluids.
The following examples and tests illustrate hard enteric capsule production with the composition from the dipping solutions of the invention and its enteric properties.
Example 1
In 3.9 kg of deionised water at room temperature 2.5 g of CaCl2 (0.05 % by weight of the final dipping solution) and 100 g of glycerol (plasticizer, 2 %) were dissolved, then 200 g of LM pectin (4 %) and 800 g of hydroxypropyl starch (16 %) dispersed. The mixture was then heated to 95 °C to solubilize all components under stirring. After debubbling by reducing the stirring, the solution was equilibrated at 60°C.
The solution was poured into a dipping dish of a pilot machine of conventional hard gelatin capsule production equipment. Keeping the dipping solution at 60°C, natural transparent hard enteric capsules of size 0 were produced according to the conventional process with the same dimensional specifications as the conventional hard gelatin capsules. The final capsules have a film composition of 16.3% pectin, 65.3% hydroxypropyl starch, 8.1% glycerol, 0.20% CaCl2 and 10% moisture by weight.
Example 2
200 g of LM pectin was dispersed into 2.0 kg of deionised water at room temperature, and then the mixture was heated to 85°C to solubilize the pectin. After debubbling by reducing the stirring, the solution was then equilibrated at 60°C.
2.5 kg of aqueous gelatin solution at 32 % was prepared by conventional method for hard gelatin capsule manufacture. 11.75 g of CaCl2 aqueous solution at 20 % was added to the gelatin solution, which was then debubbled by standing at 60°C.
The above two solutions were mixed together by gentle stirring to avoid creating bubbles. The solution thus prepared (containing 4.25 % pectin, 17.0 % gelatin and 0.05 % CaCl2 by weight) was then poured into a dipping dish of a pilot machine of conventional hard gelatin capsule production equipment. Keeping the dipping solution at 45°C, natural transparent hard enteric capsules of size 0 were produced according to the conventional process with the same dimension specifications as the conventional hard gelatin capsules.
The final capsules have a film composition of 16.9% pectin, 67.4% gelatin, 0.20% CaCl2 and 15.5% moisture by weight.
Example 3
250 g of polyethyleneglycol 400, pre-heated at 60°C was added under gentle stirring into 4.7 kg solution at 60°C, containing by weight 4.25 % pectin, 17.0 % gelatin and 0.05 % CaCl2, prepared as in example 2.
Natural transparent enteric hard capsules were produced as in example 2. The final capsules have a film composition of 13.9 % pectin, 55.8% gelatin, 17.4% PEG400 and 0.16% CaCl2 and 12.7% moisture by weight.
Example 4
3.85 g of gellan gum and 150 g of LM pectin were dispersed into 2.0 kg of deionised water at room temperature. The mixture was then heated to 85°C for solubilization. After debubbling, the solution was then equilibrated at 60°C.
2.66 kg of aqueous gelatin solution containing 32 % gelatin by weight was prepared by conventional method for hard gelatin capsule manufacturing and equilibrated at 60°C.
The above two solutions were mixed and debubbled. The final solution contained 3.12 % pectin, 17.7 % gelatin and 0.08 % gellan gum by weight.
Natural hard enteric capsules of size 0 were produced in the same manner as in the previous examples, keeping the dipping solution at 55°C. The final capsules have a film composition of 12.8% pectin, 72.4% gelatin and 0.33% gellan gum and 14.5% moisture by weight.
All the capsules were evaluated for their enteric performance by in-vitro disintegration and dissolution tests according to the UPS XXIIII: first 2 hours in simulated gastric fluid (pH1.2) and then in simulated intestinal fluid (pH6.8). No enzyme was used in these tests.
The capsules were filled with lactose containing 0.1 % of Indigotine (FD&C blue N°2) for disintegration test or filled with acetaminophen for in-vitro dissolution test. Capsules were then banded with the same solution used respectively during the capsule manufacture for each example. The capsule banding prevents separation of capsule cap and body during the disintegration test.
The results of the disintegration tests are shown in Table 1 and the results of the dissolution tests are shown in Figure 1.
Table 1
Disintegration Results
The tests performed confirmed the excellent gastric resistance of all capsules, they remained intact even after 2 hours exposition to pH 1.2.
Capsules of examples 1-3 dissolved very quickly after passing into pH 6.8 buffer solution. Capsules of example 4 showed some delay. The use of an additional setting agent would be a possibility to modulate the dissolution profile under intestinal conditions.
Claims (16)
1. Film composition comprising a) pectin, b) a second film-forming polymer and c) a setting system.
2. Film composition according to claim 1, wherein the second film-forming polymer is selected from gelatin; pullulan; polyvinyl alcohol; hydroxypropylated starch, hydroxyethylated starch; hydroxypropyl methylcellulose, hydroxypropyl cellulose, methyl cellulose, hydroxyethyl cellulose, hydroxyethyl methylcellulose; or mixtures thereof.
3. Film composition according to claim 1 wherein the content of pectin is from 5 to 50 %, preferably 10 to 40 %, and that of the second polymer from 60 to 95 %, preferably 50 to 85%.
4. Film composition according to claim 1 wherein the setting system consists of pectin and divalent cation salts.
5. Film composition according to claim 4 wherein the divalent cation salts are selected from magnesium or calcium salts.
6. Film composition according to claim 1 wherein the setting system consists of pectin and an additional setting agent selected from carrageenan or gellan gum or mixtures thereof.
7. Film composition according to claim 1 wherein additionally colouring agents and/or flavouring agents are contained.
8. Film composition according to claim 1 wherein additionally plasticizers are contained.
9. Film-forming aqueous solution of the composition according to claim 1 for the manufacture of hard enteric capsule.
10. Solution according to claim 9 containing the film-forming composition of claim 1 in an amount of 10 to 50 %, preferably 15 to 40 % by weight of the aqueous solution.
11. Solution according to claim 9 containing the salt of a divalent cation in an amount of 0.01 to 0.5 % by weight of the aqueous solution.
12. Solution according to claim 11 characterized in that the salt of a divalent cation is a magnesium and/or calcium salt.
13. Aqueous solution according to claim 9 containing an additional setting agent selected from carrageenan and/or gellan gum, in an amount of 0.05 to 2 % by weight of the aqueous solution.
14. Use of the aqueous solution according to claim 9 for the manufacture of hard enteric capsules by a dip moulding process.
15. Manufacturing of hard enteric capsules from an aqueous solution containing 10 to
50 % by weight of the film-forming composition of claim 1 by a dip moulding process with conventional hard gelatin capsule production equipment at temperatures between 40 and 70°C.
16. Use of the aqueous solution according to claim 9 for the banding process of enteric capsules.
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP00402423.8 | 2000-09-01 | ||
EP00402423A EP1184033A1 (en) | 2000-09-01 | 2000-09-01 | Pectin film compositions |
PCT/EP2001/009594 WO2002017886A1 (en) | 2000-09-01 | 2001-08-21 | Pectin film compositions |
Publications (2)
Publication Number | Publication Date |
---|---|
AU2002210449A1 true AU2002210449A1 (en) | 2002-06-06 |
AU2002210449B2 AU2002210449B2 (en) | 2006-10-26 |
Family
ID=8173840
Family Applications (2)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
AU1044902A Pending AU1044902A (en) | 2000-09-01 | 2001-08-21 | Pectin film compositions |
AU2002210449A Ceased AU2002210449B2 (en) | 2000-09-01 | 2001-08-21 | Pectin film compositions |
Family Applications Before (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
AU1044902A Pending AU1044902A (en) | 2000-09-01 | 2001-08-21 | Pectin film compositions |
Country Status (19)
Country | Link |
---|---|
US (1) | US7041315B2 (en) |
EP (2) | EP1184033A1 (en) |
JP (1) | JP4780898B2 (en) |
KR (1) | KR20030029900A (en) |
CN (1) | CN1452481A (en) |
AT (1) | ATE345114T1 (en) |
AU (2) | AU1044902A (en) |
BR (1) | BR0113663A (en) |
CA (1) | CA2420600A1 (en) |
CY (1) | CY1105898T1 (en) |
DE (1) | DE60124563T2 (en) |
DK (1) | DK1315479T3 (en) |
EA (1) | EA007563B1 (en) |
ES (1) | ES2274905T3 (en) |
MX (1) | MXPA03001855A (en) |
NZ (1) | NZ524247A (en) |
PT (1) | PT1315479E (en) |
SI (1) | SI1315479T1 (en) |
WO (1) | WO2002017886A1 (en) |
Families Citing this family (45)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US9254270B2 (en) | 2002-10-01 | 2016-02-09 | Banner Life Sciences Llc | Enteric soft capsules |
DK2772250T3 (en) | 2002-10-01 | 2016-12-05 | Banner Life Sciences Llc | Enteric composition for the manufacture of soft capsule wall |
DE10309064A1 (en) * | 2003-03-03 | 2004-09-16 | Clariant Gmbh | Polymer composition based on PVA |
US7678817B2 (en) | 2005-06-03 | 2010-03-16 | Medrx Co., Ltd. | Enteric medicinal composition for oral use |
US20070148248A1 (en) * | 2005-12-22 | 2007-06-28 | Banner Pharmacaps, Inc. | Gastric reflux resistant dosage forms |
DE102006029200A1 (en) * | 2006-06-26 | 2007-12-27 | Siemens Ag | Tachograph for a motor vehicle |
JP2008012094A (en) * | 2006-07-06 | 2008-01-24 | Kenichi Katsu | Capsule endoscope |
US20080031928A1 (en) * | 2006-07-26 | 2008-02-07 | Remington Direct Lp | No laxation bulking system |
ES2463774T3 (en) | 2007-11-12 | 2014-05-29 | Pharmaceutics International, Inc. | Trimolecular complexes and their use in drug delivery systems |
JP4971298B2 (en) * | 2008-01-11 | 2012-07-11 | ユニメディカル株式会社 | Enteric / sustained release soft capsule and method for producing the same |
JP5253235B2 (en) * | 2009-03-02 | 2013-07-31 | クオリカプス株式会社 | Enteric capsule |
ES2804779T3 (en) | 2009-09-24 | 2021-02-09 | Capsugel Belgium Nv | Acid resistant capsules |
GB0918590D0 (en) * | 2009-10-22 | 2009-12-09 | Ayanda As | Composition |
CN101708171B (en) * | 2009-12-17 | 2011-12-07 | 安徽黄山胶囊有限公司 | Enteric plant hollow capsule |
US8101203B2 (en) * | 2010-01-14 | 2012-01-24 | Karl Wei Cao | Hard capsule composition and method of use |
US8101204B2 (en) * | 2010-01-14 | 2012-01-24 | Karl Wei Cao | Hard capsule composition and method of use |
US20110171281A1 (en) * | 2010-01-14 | 2011-07-14 | Karl Wei Cao | Soft capsule composition and method of use |
JP5995159B2 (en) * | 2011-12-05 | 2016-09-21 | 伊那食品工業株式会社 | Edible partition film for food and food |
EP2793867B1 (en) | 2011-12-22 | 2021-01-20 | Baes, Erik | Gelatin/alginate delayed release capsules comprising omega-3 fatty acids, and methods and uses thereof |
CN103113628B (en) * | 2013-02-01 | 2015-04-15 | 北京市农林科学院 | Edible composite film and preparation method thereof |
WO2015065848A1 (en) | 2013-11-04 | 2015-05-07 | Capsugel Belgium Nv | Methods and systems for improved bioavailability of active pharmaceutical ingredients including esomeprazole |
CN103893771B (en) * | 2014-04-21 | 2015-08-26 | 湖南尔康制药股份有限公司 | A kind of film-forming composition for the production of starch material soft capsule and preparation method thereof |
CN103893772B (en) | 2014-04-21 | 2015-08-26 | 湖南尔康制药股份有限公司 | A kind of hydroxypropyl starch Capsules and preparation technology thereof |
US9775814B2 (en) | 2014-06-20 | 2017-10-03 | Patheon Softgels Inc. | Enteric soft capsule compositions |
US20150366814A1 (en) | 2014-06-23 | 2015-12-24 | Banner Life Sciences Llc | All-natural enteric soft capsules comprising active ingredients |
HUE053962T2 (en) * | 2014-09-11 | 2021-08-30 | Gelita Ag | Gelatin/pectin particles |
SG11201702752RA (en) * | 2014-10-06 | 2017-06-29 | Fuji Capsule Co Ltd | Method of Manufacturing Enteric Seamless Soft Capsule |
KR101862091B1 (en) * | 2014-10-06 | 2018-05-29 | 후지 캡슐 가부시키가이샤 | Method of producing enteric soft capsule |
CN104523647A (en) * | 2014-12-15 | 2015-04-22 | 浙江宏辉胶丸有限公司 | Enteric hollow capsule made from pectin |
CN106138007A (en) * | 2015-04-10 | 2016-11-23 | 大丰胶囊工业股份有限公司 | The constituent of preparation enteric capsule shells, enteric capsule shells and preparation method |
MX2015014524A (en) * | 2015-10-15 | 2017-04-14 | Centro De Investigación Y Asistencia En Tecnología Y Diseño Del Estado De Jalisco A C | Polymer composition. |
US20170157058A1 (en) * | 2015-12-08 | 2017-06-08 | Dah Feng Capsule Industry Co., Ltd. | Acid resistant capsule shell composition, acid resistant capsule shell and its preparing process |
ITUB20156821A1 (en) | 2015-12-09 | 2017-06-09 | Altergon Sa | JELLY CAPSULES SPRINGS RELEASE INDEPENDENT pH |
CN105534945B (en) * | 2015-12-29 | 2020-12-25 | 仙乐健康科技股份有限公司 | Plant type enteric soft capsule |
CN109154155A (en) * | 2016-05-13 | 2019-01-04 | 洛科威国际有限公司 | The method of isolation is provided to structure |
JP6780412B2 (en) * | 2016-09-28 | 2020-11-04 | ライオン株式会社 | Coating composition and coating formulation and method for manufacturing the same |
US9700518B1 (en) | 2016-11-21 | 2017-07-11 | Karl Wei Cao | Dip molding process for the manufacture of hard capsule shells |
US9579292B1 (en) | 2016-11-21 | 2017-02-28 | Karl Wei Cao | Film forming hard capsule solution |
US20200071864A1 (en) | 2017-05-11 | 2020-03-05 | Rockwool International A/S | Mineral wool binder |
WO2019178444A1 (en) * | 2018-03-15 | 2019-09-19 | R.P. Scherer Technologies, Llc | Enteric softgel capsules |
US10813887B2 (en) | 2018-04-18 | 2020-10-27 | Dah Feng Capsule Industry Co., Ltd | Acid resistant capsule shell composition |
US20220400724A1 (en) * | 2019-10-28 | 2022-12-22 | R.P. Scherer Technologies, Llc | Delayed release softgel capsules in higher ph environment |
US20230407016A1 (en) * | 2020-09-22 | 2023-12-21 | Rensselaer Polytechnic Institute | Polysaccharide-including liquid material and its manufacturing method |
EP4401709A1 (en) * | 2021-09-13 | 2024-07-24 | Nutrition & Biosciences USA 1, LLC | A film-forming composition comprising pectin |
KR20230167914A (en) * | 2022-06-03 | 2023-12-12 | 주식회사 서흥 | Banding solution for enteric hard capsule and hard capsules manufactured by banding solution |
Family Cites Families (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS5326867A (en) * | 1976-08-24 | 1978-03-13 | Hayashibara Biochem Lab | Method of endowment of waterrproof ability of formed product belonging to poluran series |
JPS58172313A (en) * | 1982-04-01 | 1983-10-11 | Morishita Jintan Kk | Enteric soft capsule |
JPH0427352A (en) * | 1990-05-22 | 1992-01-30 | Fuji Capsule Kk | Enteric soft capsule for health food |
JPH0436159A (en) * | 1990-05-31 | 1992-02-06 | Fuji Capsule Kk | Royal jelly-containing soft capsule |
US5431917A (en) * | 1992-10-08 | 1995-07-11 | Japan Elanco Company, Ltd. | Hard capsule for pharmaceutical drugs and method for producing the same |
US5614217A (en) † | 1995-06-07 | 1997-03-25 | R.P. Scherer Corporation | Capsule shell formulation to produce brittle capsules |
KR100219918B1 (en) * | 1997-07-03 | 1999-09-01 | 김윤 | Composition for colon specific drug delivery |
DE69918703T3 (en) * | 1998-09-30 | 2009-04-16 | Warner-Lambert Co. Llc | FILM-FORMING COMPOSITIONS OF MODIFIED STRENGTH |
-
2000
- 2000-09-01 EP EP00402423A patent/EP1184033A1/en not_active Withdrawn
-
2001
- 2001-08-21 NZ NZ52424701A patent/NZ524247A/en unknown
- 2001-08-21 DK DK01978285T patent/DK1315479T3/en active
- 2001-08-21 DE DE60124563T patent/DE60124563T2/en not_active Expired - Lifetime
- 2001-08-21 PT PT01978285T patent/PT1315479E/en unknown
- 2001-08-21 WO PCT/EP2001/009594 patent/WO2002017886A1/en active IP Right Grant
- 2001-08-21 BR BR0113663-1A patent/BR0113663A/en not_active IP Right Cessation
- 2001-08-21 JP JP2002522860A patent/JP4780898B2/en not_active Expired - Fee Related
- 2001-08-21 KR KR10-2003-7003123A patent/KR20030029900A/en active IP Right Grant
- 2001-08-21 ES ES01978285T patent/ES2274905T3/en not_active Expired - Lifetime
- 2001-08-21 MX MXPA03001855A patent/MXPA03001855A/en active IP Right Grant
- 2001-08-21 CA CA002420600A patent/CA2420600A1/en not_active Abandoned
- 2001-08-21 AU AU1044902A patent/AU1044902A/en active Pending
- 2001-08-21 US US10/344,482 patent/US7041315B2/en not_active Expired - Lifetime
- 2001-08-21 AU AU2002210449A patent/AU2002210449B2/en not_active Ceased
- 2001-08-21 AT AT01978285T patent/ATE345114T1/en not_active IP Right Cessation
- 2001-08-21 EP EP01978285.3A patent/EP1315479B2/en not_active Expired - Lifetime
- 2001-08-21 SI SI200130678T patent/SI1315479T1/en unknown
- 2001-08-21 EA EA200300329A patent/EA007563B1/en not_active IP Right Cessation
- 2001-08-21 CN CN01815090A patent/CN1452481A/en active Pending
-
2007
- 2007-01-03 CY CY20071100003T patent/CY1105898T1/en unknown
Similar Documents
Publication | Publication Date | Title |
---|---|---|
EP1315479B1 (en) | Pectin film compositions | |
AU2002210449A1 (en) | Pectin film compositions | |
AU762692C (en) | Modified starch film compositions | |
US4365060A (en) | Enterosoluble capsules | |
CA2380068C (en) | Pullulan film compositions | |
AU648109B2 (en) | Shaped articles as obtained from a thermoplastic starch melt | |
US6635275B1 (en) | Modified starch film compositions | |
KR20030026358A (en) | Hard capsule | |
EP1593376A1 (en) | Improved pullulan capsules | |
JP2005281687A (en) | Blend of various acyl gellant gums with starch | |
WO2010114134A1 (en) | Hard capsule | |
JPH055065A (en) | New composition containing hydrophilic polymer and hydrophilic substance other than that | |
WO2023250297A1 (en) | Film forming delayed/enteric formulations for hard shell capsules, films and coatings |