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WO2018101662A1 - Procédé de préparation de capsule dure et capsule dure ainsi préparée - Google Patents

Procédé de préparation de capsule dure et capsule dure ainsi préparée Download PDF

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Publication number
WO2018101662A1
WO2018101662A1 PCT/KR2017/013156 KR2017013156W WO2018101662A1 WO 2018101662 A1 WO2018101662 A1 WO 2018101662A1 KR 2017013156 W KR2017013156 W KR 2017013156W WO 2018101662 A1 WO2018101662 A1 WO 2018101662A1
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WIPO (PCT)
Prior art keywords
drying
hard
aqueous composition
hard capsule
hard capsules
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.)
Ceased
Application number
PCT/KR2017/013156
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English (en)
Korean (ko)
Inventor
안재훈
손진열
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.)
Lotte Fine Chemical Co Ltd
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Lotte Fine Chemical 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 Lotte Fine Chemical Co Ltd filed Critical Lotte Fine Chemical Co Ltd
Publication of WO2018101662A1 publication Critical patent/WO2018101662A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J13/00Colloid chemistry, e.g. the production of colloidal materials or their solutions, not otherwise provided for; Making microcapsules or microballoons
    • B01J13/02Making microcapsules or microballoons
    • B01J13/04Making microcapsules or microballoons by physical processes, e.g. drying, spraying
    • AHUMAN NECESSITIES
    • A23FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
    • A23PSHAPING OR WORKING OF FOODSTUFFS, NOT FULLY COVERED BY A SINGLE OTHER SUBCLASS
    • A23P10/00Shaping or working of foodstuffs characterised by the products
    • A23P10/30Encapsulation of particles, e.g. foodstuff additives
    • 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
    • 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
    • A61J3/071Devices 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 into the form of telescopically engaged two-piece capsules
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K9/00Medicinal preparations characterised by special physical form
    • A61K9/48Preparations in capsules, e.g. of gelatin, of chocolate
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K9/00Medicinal preparations characterised by special physical form
    • A61K9/48Preparations in capsules, e.g. of gelatin, of chocolate
    • A61K9/4816Wall or shell material
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K9/00Medicinal preparations characterised by special physical form
    • A61K9/48Preparations in capsules, e.g. of gelatin, of chocolate
    • A61K9/50Microcapsules having a gas, liquid or semi-solid filling; Solid microparticles or pellets surrounded by a distinct coating layer, e.g. coated microspheres, coated drug crystals
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K9/00Medicinal preparations characterised by special physical form
    • A61K9/48Preparations in capsules, e.g. of gelatin, of chocolate
    • A61K9/50Microcapsules having a gas, liquid or semi-solid filling; Solid microparticles or pellets surrounded by a distinct coating layer, e.g. coated microspheres, coated drug crystals
    • A61K9/5005Wall or coating material
    • A61K9/5015Organic compounds, e.g. fats, sugars
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K9/00Medicinal preparations characterised by special physical form
    • A61K9/48Preparations in capsules, e.g. of gelatin, of chocolate
    • A61K9/50Microcapsules having a gas, liquid or semi-solid filling; Solid microparticles or pellets surrounded by a distinct coating layer, e.g. coated microspheres, coated drug crystals
    • A61K9/5005Wall or coating material
    • A61K9/5021Organic macromolecular compounds
    • A61K9/5036Polysaccharides, e.g. gums, alginate; Cyclodextrin
    • A61K9/5042Cellulose; Cellulose derivatives, e.g. phthalate or acetate succinate esters of hydroxypropyl methylcellulose
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K9/00Medicinal preparations characterised by special physical form
    • A61K9/48Preparations in capsules, e.g. of gelatin, of chocolate
    • A61K9/50Microcapsules having a gas, liquid or semi-solid filling; Solid microparticles or pellets surrounded by a distinct coating layer, e.g. coated microspheres, coated drug crystals
    • A61K9/5089Processes

Definitions

  • the present invention relates to a method for producing hard capsules, and more particularly, to a method for preparing high quality hard capsules at a preheating temperature and a drying temperature of a low mold pin of 55 ° C. or less, and a hard capsule prepared therefrom.
  • Capsules used in medicine and health functional foods are usually prepared based on gelatin or cellulose ether.
  • Advantages of gelatin capsules include high industrial productivity and price competitiveness, but when the moisture content is 10% by weight or less, plasticity is lost and impact resistance is significantly worsened.
  • a capsule manufactured using cellulose ether, which is a vegetable material instead of gelatin is in the spotlight.
  • a capsule is generally manufactured by a dip molding method using a hot pin process. According to this method, a hard capsule shell is obtained by dipping a mold fin preheated to a high temperature into a film forming composition, recovering the mold fin in a dipping bath to gel the film forming polymer on the mold fin, and then drying the film. It will be prepared. The dried shell is then removed from the mold pin and cut to the desired length to obtain a hard capsule cap and body. And finally, the hard capsule body is filled with powder or granule medicine or health food, and then the hard capsule cap is coupled to the body to complete the final product.
  • Patent Document 1 Domestic Patent Publication No. 10-2009-0057470
  • (a) has a methoxy content of 27.0 to 30.0%, a hydroxypropoxy content of 4.0 to 7.5% and water at 20 °C
  • an aqueous composition comprising HPMC having a viscosity of 3.5 to 6.0 cps as a 2% by weight solution in water
  • the dipping pin preheating process of step (b) is in the temperature range of 55 ⁇ 90 °C, and the drying process of the step (e) is 50 ⁇ 90 °C temperature range Is performed in In order to perform such a high temperature manufacturing process, the energy cost is excessively spent, which greatly affects the manufacturing cost of hard capsules. In addition, if heat is not correctly transferred to the mold pin or a temperature deviation occurs during drying, a problem may occur in capsule quality.
  • Patent Document 1 KR1020090057470 A
  • the problem to be solved by the present invention is to provide a method for producing a high quality hard capsule at a preheating temperature and a drying temperature of a low mold pin of 55 °C or less.
  • the present invention comprises the steps of (1) preparing an aqueous composition for hard capsules by mixing a water-soluble cellulose ether, alcohols and water; (2) immersing the mold pin preheated to 35-55 ° C. into the aqueous composition for hard capsules and then recovering; And (3) provides a method for producing a hard capsule comprising the step of drying the recovered mold pin at a temperature range of 20 ⁇ 55 °C.
  • the aqueous composition for hard capsules may be prepared in a temperature range of 10 ⁇ 25 °C.
  • it may further comprise the step of aging the aqueous composition for hard capsules prepared according to step (1) for 2 to 12 hours at a temperature range of 10 ⁇ 25 °C.
  • the content of the water-soluble cellulose ether may be 10 to 25% by weight based on 100% by weight of the aqueous composition for hard capsules, and the content of the alcohol may be 10 to 30% by weight.
  • the water soluble cellulose ether may include at least one selected from the group consisting of hydroxypropyl methyl cellulose (HPMC), hydroxyethyl methyl cellulose (HEMC) and methyl cellulose (MC), wherein the hydroxypropyl methyl cellulose (HPMC) ) May preferably have a methoxyl substitution rate of 19 to 30%, and a hydroxypropoxyl substitution rate of 4 to 8%.
  • HPMC hydroxypropyl methyl cellulose
  • HEMC hydroxyethyl methyl cellulose
  • MC methyl cellulose
  • the viscosity of the aqueous solution of 2% by weight of the cellulose ether may be 3 to 15 cps when measured at 20 ° C. under a Ubbelohde viscometer.
  • the alcohols may include one or more selected from the group consisting of ethanol, methanol, isopropanol and butanol.
  • the drying time may be 1 to 90 minutes.
  • Step (3) may include a first drying step of drying the mold pin recovered according to step (2) at 40 to 55 ° C. for 1 to 20 minutes; And a second drying step of drying the mold pin after the first drying step for 20 to 90 minutes at 20 to 40 ° C.
  • the present invention provides a hard capsule prepared according to the manufacturing method.
  • the drying process is carried out in a temperature range of 20 ⁇ 55 °C can reduce the temperature deviation that can occur during the drying process compared to the conventional method, thereby reducing the quality degradation problem of the capsule.
  • Example 1 is a photograph showing a comparison of the hard capsules prepared according to Example 1 and Comparative Example 1.
  • Figure 2 is a photograph showing a comparison of the hard capsules prepared according to Example 2 and Comparative Example 2.
  • Figure 3 is a photograph showing a comparison of the hard capsules prepared according to Example 3 and Comparative Example 3.
  • Figure 4 is a photograph showing a comparison of the hard capsules prepared according to Example 4 and Comparative Example 4.
  • the present invention comprises the steps of (1) preparing a hard capsule aqueous composition by mixing a water-soluble cellulose ether, alcohols and water; (2) immersing the mold pin preheated to 35-55 ° C. into the aqueous composition for hard capsules and then recovering; And (3) relates to a method for producing a hard capsule comprising the step of drying the recovered mold pin at a temperature range of 20 ⁇ 55 °C.
  • This step is to prepare an aqueous composition for hard capsules by mixing water-soluble cellulose ether, alcohols and water.
  • the hard capsule aqueous composition may be prepared in a temperature range of 10 ⁇ 25 °C.
  • the manufacturing process of the aqueous composition for hard capsules (a) dispersing the cellulose ether in hot water of 70 °C or more, (b) lowering the temperature of the dispersion obtained according to (a) to 50 ⁇ 60 °C And then adding alcohols to dissolve the cellulose ether, and (c) lowering the solution obtained according to the step (b) to 10 to 25 ° C. to obtain an aqueous composition for hard capsules in which cellulose ether is completely dissolved. can do.
  • the water soluble cellulose ether is the main component of the aqueous composition for hard capsules.
  • the water-soluble cellulose ether is derived from cellulose which is a vegetable material and has an advantage that is harmless to the human body.
  • cellulose ether means a cellulose derivative in which the hydroxy group of cellulose is etherified using an etherifying agent.
  • the content of the cellulose ether may be 10 to 25% by weight based on 100% by weight of the aqueous composition for hard capsules. If the content of the cellulose ether is less than 10% by weight, there is a fear that a capsule having a suitable thickness may not be obtained. On the other hand, if the content of the cellulose ether is less than 25% by weight, the viscosity may be excessive and the bubble removal may not be easy.
  • the water soluble cellulose ether may include at least one selected from the group consisting of hydroxypropyl methyl cellulose (HPMC), hydroxyethyl methyl cellulose (HEMC) and methyl cellulose (MC).
  • HPMC hydroxypropyl methyl cellulose
  • HEMC hydroxyethyl methyl cellulose
  • MC methyl cellulose
  • the hydroxypropyl methyl cellulose (HPMC) may preferably have a methoxyl substitution rate of 19 to 30% and a hydroxypropoxyl substitution rate of 4 to 12%.
  • the 2 weight% aqueous solution viscosity of the said cellulose ether is 3-15cps when measured on 20 degreeC conditions with a Uvelode viscometer.
  • the viscosity is less than 3 cps, the thickness of the hard capsules may be excessively thin.
  • the viscosity exceeds 15 cps, there is a fear that workability may be reduced when forming a capsule due to the high viscosity.
  • the alcohols serve to help the water-soluble cellulose ether to be dissolved in the aqueous composition for hard capsules.
  • the alcohol content may be 10 to 30% by weight based on 100% by weight of the aqueous composition for hard capsules. If the content of the alcohol is less than 10% by weight, there is a fear that the solubility of the cellulose ether is lowered, while if the content of the alcohol exceeds 30% by weight, the evaporation rate of the alcohol in the manufacture of capsules is faster, smooth wrinkles There is a fear that a capsule that could not be obtained.
  • the alcohols may include at least one selected from the group consisting of ethanol, methanol, isopropanol and butanol.
  • the method for preparing a hard capsule according to the present invention may further include the step of aging the aqueous composition for hard capsules prepared according to step (1) for 2 to 12 hours at a temperature range of 10 to 25 °C. .
  • the aqueous composition for hard capsules subjected to the aging process may be molded using a mold pin preheated to a low temperature, and may also produce hard capsules of excellent quality even if dried at a low temperature.
  • the aging time is less than 2 hours, the cellulose ether solution is not fully aged, there is a risk that the bubbles in the solution may not be completely removed, it may be difficult to form the capsule under low preheating temperature and drying temperature, while 12 hours If exceeded, there is a fear that the improvement effect against time will not appear.
  • This step is a step of recovering after immersing the mold pin preheated to 35 ⁇ 55 °C into the aqueous composition for hard capsules prepared according to step (1).
  • the preheating temperature of the mold pin is an important factor in determining the thickness of the capsule. As the temperature is lowered, the thickness of the mold pin can be controlled to be thin. When the temperature is increased, the thickness of the mold can be controlled to be thicker. According to the present invention, by preheating the mold pin to 35 ⁇ 55 °C as described above it is possible to mold the capsule of the desired thickness. This is an effect according to the hard capsule manufacturing method of the present invention, it is possible to reduce the energy cost compared to the conventional method was possible to preform the capsule molding only 55 °C ⁇ 90 °C temperature.
  • This effect may be more pronounced in the case of an aqueous composition for hard capsules, which has undergone a step of aging for 2 to 12 hours in the temperature range of 10 to 25 °C described above.
  • aqueous composition for hard capsules undergoing the aging process using a mold pin preheated to a low temperature of 55 °C or less, even if the drying process described below in a temperature range of 55 °C or less uniform film thickness and It is desirable to be able to produce high quality hard capsules with a smooth surface.
  • the preheating temperature is less than 35 °C is difficult to commercialize because the aqueous composition for hard capsules flow down without being fixed to the mold pin, on the other hand, if the temperature exceeds 55 °C excessive energy cost is low economical.
  • This step is a step of drying the recovered mold pin in the temperature range of 20 ⁇ 55 °C according to step (2).
  • the purpose of drying in this step is to control the flow by reducing the moisture content of the aqueous composition applied to the mold pins.
  • the above object can be achieved by performing the drying process in a temperature range of 20 to 55 ° C.
  • drying temperature is less than 20 °C flow is generated before the applied solution is fixed in the pin does not form a capsule, while if it exceeds 55 °C energy cost is excessively low and economic efficiency is low.
  • the drying time at the drying temperature may be 1 to 90 minutes. If the drying time is less than 1 minute, the applied solution may not be fixed and flow may occur. If the drying time is 90 minutes, the drying proceeds sufficiently and no further drying is necessary.
  • the drying of the mold pin may include a first drying step of drying the recovered mold pin according to the step (2) at 40 to 55 ° C. for 1 to 20 minutes; And a second drying step of drying the mold pin after the first drying step for 20 to 90 minutes at 20 to 40 ° C.
  • the drying temperature when the drying temperature is less than 40 °C or the drying time is less than 1 minute, there is a fear that the flow occurs before the applied solution is fixed in the pin may have difficulty in molding the capsule.
  • the first drying temperature exceeds 55 ° C., the energy cost is excessively low, and the economical efficiency is low.
  • the first drying time exceeds 20 minutes, the moisture is excessively dried to reduce the moisture in the capsule film within a short time. Cracks may occur in the capsule.
  • the drying temperature is less than 20 °C or the drying time is less than 20 minutes in the second drying step has a high moisture content is likely to deform the capsule, the drying temperature is more than 40 °C or drying time is more than 90 minutes In the case of overdrying, the strength of the capsules may be weakened and cracked due to the low moisture content.
  • the hard capsules produced by the production method of the present invention show excellent quality similarly to the hard capsules prepared according to the existing methods even under low preheating and drying temperatures of 55 ° C or lower. Therefore, the hard capsule produced by the above production method can be used for various uses, such as pharmaceuticals and health functional food.
  • HPMC hydroxypropyl methyl cellulose
  • ethanol a large gold, 95%) was added to the dispersion to prepare an HPMC solution.
  • the substitution rate of the methoxyl group (methoxyl) of the HPMC is 29.2%
  • hydroxypropoxyl (hydroxypropoxyl) substitution rate is 6.0%.
  • the viscosity of the HPMC is a value measured under the condition of 20 ° C. using a Ubbelohde viscometer in a 2% by weight aqueous solution.
  • the HPMC solution was cooled to 15 ° C., and then heated to 25 ° C. and aged for 6 hours to prepare an aqueous composition for hard capsules.
  • the aqueous composition for hard capsules maintained at 25 ° C. was immersed in a mold pin (prepared by TECHNOPHAR, pin, # 0) preheated at 50 ° C. to apply the aqueous composition to the mold pin.
  • the mold pins were recovered from the aqueous composition, and dried at 25 ° C. for 5 minutes to prepare hard capsules.
  • Hard capsules were prepared in the same manner as in Example 1, except that the HPMC, ethanol and purified water, and the preheating temperature and drying temperature of the mold pin were adjusted as described in Table 1 below.
  • Example 1 20 60 50 25 Example 2 20 20 60 50 50 Example 3 20 20 60 40 25 Example 4 20 20 60 40 40 Comparative Example 1 20 0 80 50 25 Comparative Example 2 20 0 80 50 50 Comparative Example 3 20 0 80 40 25 Comparative Example 4 20 0 80 40 40 40
  • 1 to 4 are pictures showing the hard capsules prepared according to Examples 1 to 4 and the hard capsules prepared according to Comparative Examples 1 to 4, respectively. 1 to 4, in the case of hard capsules prepared according to Examples 1 to 4, the flowability is appropriate compared to the hard capsules of Comparative Examples 1 to 4 prepared according to the same preheating temperature and the first drying temperature conditions, respectively It can be clearly seen that the capsule is molded stably.

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Animal Behavior & Ethology (AREA)
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Abstract

La présente invention concerne un procédé de préparation d'une capsule dure, comprenant les étapes consistant à : (1) la préparation d'une composition aqueuse pour une capsule dure en mélangeant un éther de cellulose soluble dans l'eau, un alcool et de l'eau; (2) le plongement d'une broche de moule, ayant été préchauffée à 35-55 °C, dans la composition aqueuse pour une capsule dure, puis récupérer celle-ci; et (3) le séchage de la broche de moule récupérée dans une plage de température de 20-55 °C. Selon la présente invention, une capsule dure de haute qualité peut être préparée même si une broche de moule préchauffée à une température basse de 55 °C ou moins est utilisée et un processus de séchage à 55 °C ou moins est réalisé, et, par conséquent, les coûts de la capsule peuvent être réduits en diminuant les coûts énergétiques.
PCT/KR2017/013156 2016-12-01 2017-11-20 Procédé de préparation de capsule dure et capsule dure ainsi préparée Ceased WO2018101662A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
KR1020160162867A KR20180062784A (ko) 2016-12-01 2016-12-01 경질캡슐의 제조방법 및 이로부터 제조되는 경질캡슐
KR10-2016-0162867 2016-12-01

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WO2018101662A1 true WO2018101662A1 (fr) 2018-06-07

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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20030104047A1 (en) * 2001-12-03 2003-06-05 Gan-Lin Chen Method for manufacturing hard non-gelatin pharmaceutical capsules
KR20090057470A (ko) * 2006-10-27 2009-06-05 화이자 프로덕츠 인코포레이티드 하이드록시프로필 메틸 셀룰로스 경질 캡슐 및 이의 제조 방법
WO2013164122A1 (fr) * 2012-05-02 2013-11-07 Capsugel France SAS Dispersions aqueuses de polymères à libération contrôlée et enveloppes et capsules les comprenant
KR20140013411A (ko) * 2012-07-23 2014-02-05 삼성정밀화학 주식회사 경질 캡슐용 수성 조성물과 그의 제조방법 및 상기 수성 조성물을 사용하여 제조된 경질 캡슐
WO2015179073A1 (fr) * 2014-05-20 2015-11-26 Dow Global Technologies Llc Enveloppes de capsule comprenant un éther de cellulose estérifié

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20030104047A1 (en) * 2001-12-03 2003-06-05 Gan-Lin Chen Method for manufacturing hard non-gelatin pharmaceutical capsules
KR20090057470A (ko) * 2006-10-27 2009-06-05 화이자 프로덕츠 인코포레이티드 하이드록시프로필 메틸 셀룰로스 경질 캡슐 및 이의 제조 방법
WO2013164122A1 (fr) * 2012-05-02 2013-11-07 Capsugel France SAS Dispersions aqueuses de polymères à libération contrôlée et enveloppes et capsules les comprenant
KR20140013411A (ko) * 2012-07-23 2014-02-05 삼성정밀화학 주식회사 경질 캡슐용 수성 조성물과 그의 제조방법 및 상기 수성 조성물을 사용하여 제조된 경질 캡슐
WO2015179073A1 (fr) * 2014-05-20 2015-11-26 Dow Global Technologies Llc Enveloppes de capsule comprenant un éther de cellulose estérifié

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