WO2005026233A1 - Procede de production de nanoparticules de phtalate d'hydroxypropyle methylcellulose - Google Patents

Procede de production de nanoparticules de phtalate d'hydroxypropyle methylcellulose Download PDF

Info

Publication number
WO2005026233A1
WO2005026233A1 PCT/KR2003/002477 KR0302477W WO2005026233A1 WO 2005026233 A1 WO2005026233 A1 WO 2005026233A1 KR 0302477 W KR0302477 W KR 0302477W WO 2005026233 A1 WO2005026233 A1 WO 2005026233A1
Authority
WO
WIPO (PCT)
Prior art keywords
hydroxypropyl methylcellulose
methylcellulose phthalate
nanoparticles
water
dispersible
Prior art date
Application number
PCT/KR2003/002477
Other languages
English (en)
Inventor
Hyon-Ho Baek
Young-Ju Park
Kyung-Won Lee
Kwang-Soo Yeo
Jung-Hyun Kim
Il-Hyuk Kim
Original Assignee
Samsung Fine Chemicals, Co., Ltd.
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 Samsung Fine Chemicals, Co., Ltd. filed Critical Samsung Fine Chemicals, Co., Ltd.
Priority to AU2003284722A priority Critical patent/AU2003284722A1/en
Publication of WO2005026233A1 publication Critical patent/WO2005026233A1/fr

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/02—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques
    • C08J3/03—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in aqueous media
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K9/00—Medicinal preparations characterised by special physical form
    • A61K9/20—Pills, tablets, discs, rods
    • A61K9/28—Dragees; Coated pills or tablets, e.g. with film or compression coating
    • A61K9/2806—Coating materials
    • A61K9/2833—Organic macromolecular compounds
    • A61K9/286—Polysaccharides, e.g. gums; Cyclodextrin
    • A61K9/2866—Cellulose; Cellulose derivatives, e.g. hydroxypropyl methylcellulose
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L1/00—Compositions of cellulose, modified cellulose or cellulose derivatives
    • C08L1/08—Cellulose derivatives
    • C08L1/32—Cellulose ether-esters
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D101/00—Coating compositions based on cellulose, modified cellulose, or cellulose derivatives
    • C09D101/08—Cellulose derivatives
    • C09D101/32—Cellulose ether-esters
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2301/00—Characterised by the use of cellulose, modified cellulose or cellulose derivatives
    • C08J2301/08—Cellulose derivatives
    • C08J2301/32—Cellulose ether-esters
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L29/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical; Compositions of hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Compositions of derivatives of such polymers
    • C08L29/02—Homopolymers or copolymers of unsaturated alcohols
    • C08L29/04—Polyvinyl alcohol; Partially hydrolysed homopolymers or copolymers of esters of unsaturated alcohols with saturated carboxylic acids

Definitions

  • the present invention relates to a process for preparing enteric water- dispersible hydroxypropyl methylcellulose phthalate nanoparticles, in particular, to a process for preparing enteric water-dispersible hydroxypropyl methylcellulose phthalate nanoparticles in a cost-effective and time-saving manner, in which hydroxypropyl methylcellulose phthalate nanoparticles are prepared without using an emulsifier, wherein the residual electrolyte content is adjusted through ion exchange for a short period of time followed by the addition of a plasticizer, thereby the environment-friendly water-dispersible hydroxypropyl methylcellulose phthalate nanoparticles showing excellent film properties and enteric coating properties are prepared.
  • hydroxypropyl methylcellulose phthalate and acryl copolymer have been widely used as enteric coating materials.
  • hydroxypropyl methylcellulose phthalate is not considered advantageous in that an organic solvent should be used during a coating process, thus causing environmental problems.
  • acryl copolymer although its water-dispersible product being available, it is also not considered advantageous in that it is a synthetic polymer rather than a natural material and it has poor film properties compared to those of hydroxypropyl methylcellulose phthalate. Therefore, there has been an urgent need for the development of a novel type of an environment-friendly material.
  • a water-dispersible hydroxypropyl methylcellulose phthalate has been prepared.
  • the conventional method of preparing such water-dispersible hydroxypropyl methylcellulose phthalate comprises: completely dissolving hydroxypropyl methylcellulose phthalate in an organic solvent and dispersing it in water; and removing the organic solvent in the solution to yield a water- dispersible hydroxypropyl methylcellulose phthalate.
  • the product obtained by this method has poor stability in water-dispersible phase.
  • the use of an organic solvent causes an increase in production cost, and after emulsification, the organic solvent in the solution is hardly removed, so that the final product contains the organic solvent, thereby causing environmental problems.
  • 5,560,930 discloses a method of preparing particle of about 0.2 ⁇ m, by emulsifying hydroxypropyl methylcellulose phthalate in water after dissolving them in acetone and removing the organic solvent through distillation under reduced pressure.
  • U.S. Pat. No. 5,512,092 suggests a method of dissolving hydroxypropyl methylcellulose phthalate in ethanol and emulsifying it; and
  • U.S. Pat. No. 5,346,542 teaches a method of dissolving carboxymethyl ethylcellulose in methyl acetate and emulsifying it in water.
  • the disintegration test (using Pharmatest PTZ E) showed that the disintegration took place within 2 hr under pH 1.2. For the reasons, the commercialization of the water-dispersible hydroxypropyl methylcellulose phthalate has not been successful.
  • the present inventors have attempted a method for preparing stable nanoparticles of water-dispersible hydroxypropyl methylcellulose phthalate, which comprise introducing an aqueous emulsification process of hydroxypropyl methylcellulose phthalate and regulating the content of remaining electrolytes througln an ion exchange process.
  • the environment-friendly nanoparticles have exhibited some improvements in general properties such as disintegration and dissolution, when used as an enteric coating material.
  • the process is successful in preparing enteric coating materials with improved properties, it still has some shortcomings. That is, the process needs a high-cost emulsifier and a long period of time (4-8 hr) for ion-exchange process to improve properties of film and enteric coating materials. Therefore, there still remains a need for overcoming such disadvantages in process efficiency and cost- effectiveness.
  • the present inventors have conducted intensive researches to overcome the problems associated with the use of a high-cost emulsifier and a long period of time for the process in preparing enteric water-dispersible hydroxypropyl methylcellulose phthalate nanoparticles.
  • the present inventors have found that the hydroxypropyl methylcellulose phthalate nanoparticles with desired enteric properties could be prepared through ion exchange for 1-2 hr, in which hydroxypropyl methylcellulose phthalate is dispersed in water without using a high-cost emulsifier, nanoparticles are ion-exchanged to obtain the suitable electrolyte content and a plasticizer serving as a softener is added.
  • a process for preparing enteric water-dispersible hydroxypropyl methylcellulose phthalate nanoparticles which comprises: a step of adding a neutralizing agent to hydroxypropyl methylcellulose phthalate to obtain a nanoparticle containing a residual electrolyte content of 10.0-12.0 mS; a step of ion-exchanging the nanoparticles to adjust the residual electrolyte content to 7.0-9.0 mS; and a step of adding a plasticizer to the nanoparticle to soften the nanoparticle.
  • the present invention provides a process for preparing nanoparticles of enteric water-dispersible hydroxypropyl methylcellulose phthalate in a cost-effective and time-saving manner, in which the electrolyte content is adjusted to have a predetermined value, preferably, 7.0-9.0 mS during the ion-exchanging step and a plasticizer as a softener is used instead of a high-cost emulsifier used in the conventional process.
  • a plasticizer as a softener is used instead of a high-cost emulsifier used in the conventional process.
  • the first step of the method disclosed in the present invention is to obtain nanoparticles of hydroxypropyl methylcellulose phthalate containing a residual electrolyte content of 10.0-12.0 mS by adding a neutralizing agent to hydroxypropyl methylcellulose phthalate.
  • a neutralizing agent As a source of hydroxypropyl methylcellulose phthalate, AnyCoat-PTM (Samsung Fine Chemicals Co., Ltd., Korea) with a weight-average molecular weight of 40,000-60,000 was used.
  • Any conventional neutralizing agent can be used in this invention, however, an aqueous ammonia is preferred as a neutralizing agent because it can be easily removed from the final product and also inexpensive.
  • the neutralizing agent is used in the amount of 7-14 wt% based on the weight of hydroxypropyl methylcellulose phthalate. If the amount is less than 7 wt%, the size of particles becomes larger during their dispersion in water to render the particles instability and the presence of remaining unreacted hydroxypropyl methylcellulose phthalate would result in the decrease in solid content. If the amount is more than 14 wt%, the offensive odor of ammonia is generated and nanoparticles cannot be formed because hydroxypropyl methyl cellulose phthalate is completely dissolved.
  • the conditions for the first step of producing nanoparticles may vary depending on the type of neutralizing agents and the reaction amount.
  • the second step is an ion exchange process to adjust the residual electrolyte content of nanoparticles to be 7.0-9.0 mS by using ion exchange resin or a membrane.
  • ion exchange resin any general cation exchange resins can be used.
  • the nanoparticles obtained are preferred to stay for 1-2 hr in the resin to adjust the residual electrolyte content to 7.0-9.0 mS, more preferably, 7.0-8.0 mS. If the residual electrolyte content is less than 7.0 mS, the time for removing electrolytes becomes longer and the overall yield is decreased because there will be a loss in product due to ion exchange.
  • the third step is to add a plasticizer to the nanoparticles for the purpose of softening the nanoparticles.
  • the plasticizer used in the present invention permits the nanoparticles of hydroxypropyl methylcellulose phthalate to have enteric coating properties and excellent physical properties of film.
  • the plasticizer allows the film of hydroxypropyl methylcellulose phthalate nanoparticles to have improved physical properties such as compactness and glossiness.
  • the plasticizer can be selected from a group consisting of polyvinyl alcohol, polyethylene glycol, glycerin, propylene glycol, diethyl phthalate, triacetin, cetyl alcohol, triethyl citrate or a hydrophilic plasticizer, more preferably, polyvinyl alcohol or polyethylene glycol. It is preferred that the plasticizer be used in the amount of 10-30 wt% based on the weight of hydroxypropyl methylcellulose phthalate.
  • the film of hydroxypropyl methylcellulose phthalate nanoparticles may be swelled or partially detached when applied to a drug; in contrast, if the amount exceeds 30 wt%, there will be a heavy aggregation among tablets during coating the coating process and the drying process proceeds so slowly that the coating capacity is sharply decreased.
  • the hydroxypropyl methylcellulose phthalate nanoparticles having a size of 200 ⁇ 50 nm, an acid number of 130-15O and a pH of 4.5+1.0 are finally obtained.
  • the hydroxypropyl methylcellulose phthalate prepared according to the present process shows no particle sedimentation when stored for a long period of time in water and is not dissolved at pH 1.2, a condition similar to that of gastric acid, when it is coated on tablet. Therefore, it can be used as an environment-friendly enteric coating material.
  • the following specific examples are only intended to be illustrative of the invention and they should not be construed as limiting the scope of the invention as defined by appended claims.
  • EXAMPLE 1 400 g of purified water and 100 g of hydroxypropyl methyl cellulose phthalate were placed in a 2L reactor equipped with a stirrer and stirred at a rate of 300 rpm.
  • EXAMPLE 2 The water-dispersible hydroxypropyl methylcellulose phthalate nanoparticles were prepared according to the procedures in Example 1, except that the amount of polyvinyl alcohol used was 20 g. Thus prepared water-dispersible hydroxypropyl methylcellulose phthalate showed a particle size of 200+50 nm, an acid number of 130-150 and a pH of 4.5+1.0.
  • EXAMPLE 3 The water-dispersible hydroxypropyl methylcellulose phthalate nanoparticles "were prepared according to the procedures in Example 1, except that 10 g of polyethylene glycol was used instead of 10 g of polyvinyl alcohol. Thus prepared water-dispersible hydroxypropyl methylcellulose phthalate showed a particle size of 200+50 nm, an acid number of 130-150 and a pH of 4.5 ⁇ 1.0.
  • EXAMPLE 4 The water-dispersible hydroxypropyl methylcellulose phthalate nanoparticles were prepared according to the procedures in Example 1, except that 20 g of polyethylene glycol was used instead of 10 g of polyvinyl alcohol. Thus prepared water-dispersible hydroxypropyl methylcellulose phthalate showed a particle size of 200+50 nm, an acid number of 130-150 and a pH of 4.5+1.0.
  • EXAMPLE 5 The water-dispersible hydroxypropyl methylcellulose phthalate nanoparticles were prepared according to the procedures in Example 1, except that 25 g of glycerin was used instead of 10 g of polyvinyl alcohol. Thus prepared water-dispersible hydroxypropyl methylcellulose phthalate showed a particle size of 200 ⁇ 50 ran, an acid number of 130-150 and a pH of 4.5 ⁇ 1.0.
  • EXAMPLE 6 The water-dispersible hydroxypropyl methylcellulose phthalate nanoparticles were prepared according to the procedures in Example 1, except that 25 g of propylene glycol was used instead of 10 g of polyvinyl alcohol. Thus prepared water-dispersible hydroxypropyl methylcellulose phthalate showed a particle size of 200+50 nm, an acid number of 130-150 and a pH of 4.5 ⁇ 1.0.
  • EXAMPLE 7 The water-dispersible hydroxypropyl methyl cellulose phthalate nanoparticles were prepared according to the procedures in Example 1, except that 20 g of diethyl phthalate was used instead of 10 g of polyvinyl alcohol. Thus prepared water-dispersible hydroxypropyl methylcellulose phthalate showed a particle size of 200+50 nm, an acid number of 130-150 and a pH of 4.5+1.0.
  • EXAMPLE 8 The water-dispersible hydroxypropyl methylcellulose phthalate nanoparticles were prepared according to the procedures in Example 1, except that 30 g of triacetin was used instead of 10 g of polyvinyl alcohol. Thus prepared water-dispersible hydroxypropyl methylcellulose phthalate showed a particle size of 200+50 nm, an acid number of 130-150 and a pH of 4.5+1.0.
  • EXAMPLE 9 The water-dispersible hydroxypropyl methylcellulose phthalate nanoparticles were prepared according to the procedures in Example 1, except that 15 g of cetyl alcohol was used instead of 10 g of polyvinyl alcohol. Thus prepared water-dispersible hydroxypropyl methylcellulose phthalate showed a particle size of 200 ⁇ 50 nm, an acid number of 130-150 and a pH of 4.5+1.0.
  • EXAMPLE 10 The water-dispersible hydroxypropyl methylcellulose phthalate nanoparticles were prepared according to the procedures in Example 1, except that 20 g of triethyl citrate was used instead of 10 g of polyvinyl alcohol. Thus prepared water-dispersible hydroxypropyl methylcellulose phthalate showed a particle size of 200+50 nm, an acid number of 130-150 and a pH of 4.5+1.0.
  • COMPARATIVE EXAMPLE 1 400 g of purified water, 1.0 g of Pluronic F-68 as an emulsifier and 100 g of hydroxypropyl methylcellulose phthalate (Mw 40,000-60,000, Samsung Fine Chemicals Co., Ltd., Korea) were placed in a 1 L reactor equipped with a stirrer and stirred at a rate of 300-350 rpm. 28% NH 4 OH (8 g) was slowly added to this solution and the temperature was elevated to 60 °C. After stirring for another 4-5 hr while maintaining the temperature, the residual electrolyte concentration was adjusted to
  • COMPARATIVE EXAMPLE 2 400 g of distilled water and 100 g of hydroxypropyl methyl cellulose phthalate were placed in a 2 L reactor equipped with a stirrer and stirred at a rate of 300 rpm. To the solution, an aqueous ammonia was slowly added to yield water- dispersible hydroxypropyl methyl cellulose phthalate nanoparticles containing the electrolyte content of 10.0-12.0 mS and the residual electrolyte content was adjusted to 7.0-9.0 mS using ion-exchange resin, thereby giving water-dispersible hydroxypropyl methylcellulose phthalate nanoparticles of interest. However, the process was performed without using a plasticizer. Thus prepared water-dispersible hydroxypropyl methylcellulose phthalate showed a particle size of 200+50 nm, an acid number of 130-150 and a pH of 4.5 ⁇ 1.0.
  • EXPERIMENTAL EXAMPLE The water-dispersible hydroxypropyl methylcellulose phthalate obtained in Examples 1-10 and Comparative Examples 1-2 was processed into 1 cm X 1 cm film and allowed to stand for 2 hr in an aqueous buffer solution of pH 1.2. Then, the film sample was taken out and the occurrence of disintegration was observed, and the results are shown in Table 1. In addition, the water-dispersible hydroxypropyl methyl cellulose phthalate was diluted to 7 wt% with distilled water and coated on tablets using Hi-Coater (HCT Labo, Freund, Japan). The disintegration test using Pharmatest PTZ E was performed, and the results are shown in Table 1. TABLE 1
  • the films and tablets of the water-dispersible hydroxypropyl methylcellulose phthalate prepared using the plasticizer according to the present invention in Examples 1-10 were not disintegrated over 2 hr in the artificial gastric juice of pH 1.2, thus showing an improved enteric property.
  • Such improved enteric property is similar to that of the known water-dispersible hydroxypropyl methylcellulose phthalate prepared using an emulsifier (Comparative Example 1).
  • the film of Comparative Example 2 without using a plasticizer was not disintegrated unlike those of Examples; however, its coated tablet was observed to be disintegrated at pH 1.2.
  • plasticizer imparts the enteric property enabling to prevent disintegration for at least 2 hr at pH 1.2. Consequently, instead of using a high-cost emulsifier, the introduction of a low-price plasticizer into the production process of water-dispersible hydroxypropyl methylcellulose phthalate nanoparticles is also successful in the production of enteric products with excellent coating properties. In addition, the use of a low-cost plasticizer enables to shorten the period of time for the process.
  • the water-dispersion process of this invention comprises the step of treating with a plasticizer instead of a high-cost emulsifier used in conventional processes, which is responsible for shortening the period of time for ion exchanging and producing hydroxypropyl methylcellulose phthalate nanoparticles with excellent film properties and enteric coating properties in a cost- effective as well as time-saving manner, thereby enabling to provide environment- friendly enteric coating material.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Polymers & Plastics (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Dispersion Chemistry (AREA)
  • Bioinformatics & Cheminformatics (AREA)
  • Pharmacology & Pharmacy (AREA)
  • Epidemiology (AREA)
  • Animal Behavior & Ethology (AREA)
  • General Health & Medical Sciences (AREA)
  • Public Health (AREA)
  • Veterinary Medicine (AREA)
  • Medicinal Preparation (AREA)

Abstract

L'invention concerne un procédé de production de nanoparticules de phtalate d'hydroxypropyle méthylcellulose entériques dispersables dans l'eau et en particulier un procédé de production rentable et rapide de telles particules : production sans émulsifiant et réglage de la teneur en électrolyte résiduel à travers l'étape d'échange ionique pendant un bref laps de temps, puis adjonction de plastifiant, donnant un produit compatible avec l'environnement qui possède d'excellentes propriétés de formation de film et de revêtement entérique.
PCT/KR2003/002477 2003-09-17 2003-11-18 Procede de production de nanoparticules de phtalate d'hydroxypropyle methylcellulose WO2005026233A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AU2003284722A AU2003284722A1 (en) 2003-09-17 2003-11-18 Preparation method of enteric aqueous dispersed hydroxypropyl methylcellulose phthalate nanoparticle

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
KR10-2003-0064399 2003-09-17
KR20030064399A KR100511086B1 (ko) 2003-09-17 2003-09-17 장용성의 수계 분산 히드록시프로필 메틸셀룰로오스프탈레이트 나노입자의 제조방법

Publications (1)

Publication Number Publication Date
WO2005026233A1 true WO2005026233A1 (fr) 2005-03-24

Family

ID=34309424

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/KR2003/002477 WO2005026233A1 (fr) 2003-09-17 2003-11-18 Procede de production de nanoparticules de phtalate d'hydroxypropyle methylcellulose

Country Status (3)

Country Link
KR (1) KR100511086B1 (fr)
AU (1) AU2003284722A1 (fr)
WO (1) WO2005026233A1 (fr)

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102690358A (zh) * 2012-06-01 2012-09-26 南京信息工程大学 一种纤维素纳米晶悬浮液及其制备方法
WO2013150331A1 (fr) * 2011-11-09 2013-10-10 Capsugel Belgium Nv Solution de cerclage résistant aux acides pour capsules dures en deux parties résistant aux acides
EP2813218A1 (fr) * 2013-06-14 2014-12-17 Shin-Etsu Chemical Co., Ltd. Procédé de production de liquide d'enrobage entérosoluble aqueux, préparation solide et son procédé de production
JP2017502648A (ja) * 2013-12-31 2017-01-26 ロッテ精密化學株式会社ＬＯＴＴＥ Ｆｉｎｅ Ｃｈｅｍｉｃａｌ Ｃｏ．，Ｌｔｄ． 腸溶性コーティング組成物、腸溶性コーティング膜及び食品製剤
US11246837B2 (en) 2015-11-10 2022-02-15 Capsugel Belgium, NV Acid resistant banding or sealing solution for acid resistant two piece hard capsules

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR101971959B1 (ko) * 2012-06-11 2019-04-24 롯데정밀화학 주식회사 필름 형성용 조성물, 복합체 필름 및 상기 필름의 제조방법
CN113025130B (zh) * 2021-03-16 2022-04-22 浙江中财管道科技股份有限公司 一种模具型芯水井用防腐、阻垢、抗菌涂料及其应用

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4983403A (en) * 1987-12-15 1991-01-08 Rhone-Poulenc Sante Granules for feeding ruminants with an enzymatically degradable coating
US5356467A (en) * 1992-08-13 1994-10-18 Euroceltique S.A. Controlled release coatings derived from aqueous dispersions of zein
JPH08245423A (ja) * 1995-03-06 1996-09-24 Shionogi & Co Ltd 水系腸溶性コーティング液
US5750148A (en) * 1994-08-19 1998-05-12 Shin-Etsu Chemical Co., Ltd. Method for preparing solid enteric pharmaceutical preparation
US6139875A (en) * 1998-09-29 2000-10-31 Eastman Chemical Company Aqueous enteric coating composition and low gastric permeability enteric coating
KR20030040616A (ko) * 2001-11-15 2003-05-23 삼성정밀화학 주식회사 수계 분산 히드록시프로필메틸 셀룰로오스 프탈레이트나노입자의 제조방법

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4983403A (en) * 1987-12-15 1991-01-08 Rhone-Poulenc Sante Granules for feeding ruminants with an enzymatically degradable coating
US5356467A (en) * 1992-08-13 1994-10-18 Euroceltique S.A. Controlled release coatings derived from aqueous dispersions of zein
US5750148A (en) * 1994-08-19 1998-05-12 Shin-Etsu Chemical Co., Ltd. Method for preparing solid enteric pharmaceutical preparation
JPH08245423A (ja) * 1995-03-06 1996-09-24 Shionogi & Co Ltd 水系腸溶性コーティング液
US6139875A (en) * 1998-09-29 2000-10-31 Eastman Chemical Company Aqueous enteric coating composition and low gastric permeability enteric coating
KR20030040616A (ko) * 2001-11-15 2003-05-23 삼성정밀화학 주식회사 수계 분산 히드록시프로필메틸 셀룰로오스 프탈레이트나노입자의 제조방법

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2013150331A1 (fr) * 2011-11-09 2013-10-10 Capsugel Belgium Nv Solution de cerclage résistant aux acides pour capsules dures en deux parties résistant aux acides
US9980918B2 (en) 2011-11-09 2018-05-29 Capsugel Belgium Nv Acid resistant banding solution for acid resistant two piece hard capsules
EP3566698A1 (fr) * 2011-11-09 2019-11-13 Capsugel Belgium NV Solution de bandage résistante aux acides pour capsules dures en deux parties résistante aux acides
CN102690358A (zh) * 2012-06-01 2012-09-26 南京信息工程大学 一种纤维素纳米晶悬浮液及其制备方法
CN102690358B (zh) * 2012-06-01 2014-01-22 南京信息工程大学 一种纤维素纳米晶悬浮液及其制备方法
EP2813218A1 (fr) * 2013-06-14 2014-12-17 Shin-Etsu Chemical Co., Ltd. Procédé de production de liquide d'enrobage entérosoluble aqueux, préparation solide et son procédé de production
CN104225604A (zh) * 2013-06-14 2014-12-24 信越化学工业株式会社 制备水性肠溶包衣液的方法、固体制剂及其制备方法
JP2017502648A (ja) * 2013-12-31 2017-01-26 ロッテ精密化學株式会社ＬＯＴＴＥ Ｆｉｎｅ Ｃｈｅｍｉｃａｌ Ｃｏ．，Ｌｔｄ． 腸溶性コーティング組成物、腸溶性コーティング膜及び食品製剤
US11246837B2 (en) 2015-11-10 2022-02-15 Capsugel Belgium, NV Acid resistant banding or sealing solution for acid resistant two piece hard capsules

Also Published As

Publication number Publication date
KR100511086B1 (ko) 2005-08-30
AU2003284722A1 (en) 2005-04-06
KR20050028104A (ko) 2005-03-22

Similar Documents

Publication Publication Date Title
Chang et al. A review on the properties and applications of chitosan, cellulose and deep eutectic solvent in green chemistry
TWI417330B (zh) 新穎奈米顆粒
Habibi Key advances in the chemical modification of nanocelluloses
JP6117449B2 (ja) フィラー用ポリジオキサノン粒子の製造方法
Sekhar et al. Chitosan/guargum-g-acrylamide semi IPN microspheres for controlled release studies of 5-Fluorouracil
Espino-Pérez et al. Nanocomposites with functionalised polysaccharide nanocrystals through aqueous free radical polymerisation promoted by ozonolysis
JP4471655B2 (ja) 水系分散ヒドロキシプロピルメチルセルロースフタレートナノ粒子の製造方法
Zuppolini et al. Cellulose amphiphilic materials: Chemistry, process and applications
WO2005026233A1 (fr) Procede de production de nanoparticules de phtalate d'hydroxypropyle methylcellulose
Allasia et al. Waterborne hybrid acrylic/protein nanocomposites with enhanced hydrophobicity by incorporating a water repelling protein
Sullad et al. Blend microspheres of chitosan and polyurethane for controlled release of water-soluble antihypertensitive drugs
TWI328012B (en) Method and apparatus for production of polyvinyl alcohol with high degree of polymerization
CN103755983B (zh) 一种聚乙烯醇微球及其制备方法
Goswami et al. Pullulan films and natural compounds: applications and perspectives
WO2005074395A2 (fr) Procede de preparation d'une dispersion aqueuse d'une composition de nanoparticules d'hydroxypropyle methylcellulose phthalate
Liu et al. Cationic micelles self-assembled from quaternized cellulose-g-oligo (ε-caprolactone) amphiphilic copolymers
CN110546200B (zh) 基于氯乙烯的树脂乳胶组合物及其制备方法
Scurria et al. CytroCell micronized cellulose enhances the structural and thermal properties of IntegroPectin cross-linked films
TW589198B (en) Process for producing an aqueous dispersion containing a cellulose derivative
EP2545089B1 (fr) Copolymère greffé à comportement dépendant du ph
JPH03151330A (ja) 外用ゲル基剤
Wang et al. Cyclodextrin‐Based Porous Nanocapsules
CN105801873B (zh) 两亲性二元分子刷聚合物及其构筑的pH响应性单分子纳米胶束
Dotto et al. Frontiers in Biomaterials
TWI543990B (zh) 合成聚３，４－伸乙二氧基噻吩（ｐｅｄｏｔ）－電解共聚物之方法

Legal Events

Date Code Title Description
AK Designated states

Kind code of ref document: A1

Designated state(s): AE AG AL AM AT AU AZ BA BB BG BY BZ CA CH CN CO CR CU CZ DE DM DZ EC EE EG ES FI GB GD GE GM HR HU ID IL IN IS JP KE KG KP LC LK LR LS LT LU LV MA MD MG MN MW MX MZ NI NO NZ OM PG PH PT RO RU SC SD SE SG SK SL SY TJ TN TR TT TZ UA UG US UZ VC VN ZA ZM

AL Designated countries for regional patents

Kind code of ref document: A1

Designated state(s): BW GH GM KE LS MW MZ SD SL TZ UG ZM ZW AM AZ BY KG MD RU TJ TM AT BE BG CH CY DE DK EE ES FI FR GB GR HU IE IT MC NL PT RO SE SI SK TR BF BJ CG CI CM GA GN GQ GW ML MR NE TD TG

121 Ep: the epo has been informed by wipo that ep was designated in this application
DFPE Request for preliminary examination filed prior to expiration of 19th month from priority date (pct application filed before 20040101)
122 Ep: pct application non-entry in european phase
NENP Non-entry into the national phase

Ref country code: JP