WO2014017756A1 - 경질 캡슐 제조용 수성 조성물, 그의 제조방법, 경질 캡슐 및 경질 캡슐 스크랩의 재활용 방법 - Google Patents

경질 캡슐 제조용 수성 조성물, 그의 제조방법, 경질 캡슐 및 경질 캡슐 스크랩의 재활용 방법 Download PDF

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WO2014017756A1
WO2014017756A1 PCT/KR2013/005927 KR2013005927W WO2014017756A1 WO 2014017756 A1 WO2014017756 A1 WO 2014017756A1 KR 2013005927 W KR2013005927 W KR 2013005927W WO 2014017756 A1 WO2014017756 A1 WO 2014017756A1
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WIPO (PCT)
Prior art keywords
hard capsule
aqueous composition
water
weight
hard
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PCT/KR2013/005927
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English (en)
French (fr)
Korean (ko)
Inventor
손진열
이상엽
전정희
방성환
신주희
Original Assignee
삼성정밀화학(주)
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.)
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Priority claimed from KR1020120080258A external-priority patent/KR102013296B1/ko
Priority claimed from KR1020120131947A external-priority patent/KR102036214B1/ko
Application filed by 삼성정밀화학(주) filed Critical 삼성정밀화학(주)
Priority to EP13823894.4A priority Critical patent/EP2875808B1/en
Priority to CA2879723A priority patent/CA2879723C/en
Priority to US14/415,006 priority patent/US11312878B2/en
Priority to JP2015524168A priority patent/JP6227646B2/ja
Priority to CN201380039127.8A priority patent/CN104487058A/zh
Priority to IN427DEN2015 priority patent/IN2015DN00427A/en
Publication of WO2014017756A1 publication Critical patent/WO2014017756A1/ko

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    • 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
    • C09D101/26—Cellulose ethers
    • C09D101/28—Alkyl ethers
    • C09D101/284—Alkyl ethers with hydroxylated hydrocarbon radicals
    • 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
    • C08J11/00—Recovery or working-up of waste materials
    • C08J11/04—Recovery or working-up of waste materials of polymers
    • C08J11/06—Recovery or working-up of waste materials of polymers without chemical reactions
    • C08J11/08—Recovery or working-up of waste materials of polymers without chemical reactions using selective solvents for polymer components
    • 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
    • A61K9/48—Preparations in capsules, e.g. of gelatin, of chocolate
    • A61K9/4816—Wall or shell material
    • 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
    • A61K9/48—Preparations in capsules, e.g. of gelatin, of chocolate
    • A61K9/4841—Filling excipients; Inactive ingredients
    • A61K9/4866—Organic macromolecular compounds
    • 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
    • C09D101/26—Cellulose ethers
    • C09D101/28—Alkyl ethers
    • 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
    • C09D105/00—Coating compositions based on polysaccharides or on their derivatives, not provided for in groups C09D101/00 or C09D103/00
    • 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
    • C09D105/00—Coating compositions based on polysaccharides or on their derivatives, not provided for in groups C09D101/00 or C09D103/00
    • C09D105/06—Pectin; Derivatives thereof
    • 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
    • C08J2301/26—Cellulose ethers
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W30/00—Technologies for solid waste management
    • Y02W30/50—Reuse, recycling or recovery technologies
    • Y02W30/62—Plastics recycling; Rubber recycling

Definitions

  • An aqueous composition for producing hard capsules, methods for making the same, hard capsules, and methods for recycling hard capsule scraps are disclosed. More specifically, an aqueous composition for producing a hard capsule containing a water-soluble cellulose ether and alcohols, a method for preparing the same, a hard capsule prepared using the aqueous composition, and recycling of the hard capsule scrap generated in the manufacturing process of the hard capsule The method is disclosed.
  • Hard capsules have generally been prepared using gelatin derived from cows or pigs. Scrap generated during the production of gelatin hard capsules can be recycled into hard capsules because they have the same gel properties as gelatin when dissolved in hot water and cooled to room temperature. Therefore, the manufacture of hard capsules using gelatin can reduce the cost of capsule manufacturing, and most capsule manufacturers still prefer to manufacture gelatin hard capsules.
  • the aqueous composition comprising gelatin can dissolve the gelatin directly in water of high temperature (eg, 60 ° C.), so that the preparation time of the aqueous composition is short, and after immersing the mold pin in the aqueous composition, it is removed and applied to the mold pin.
  • high temperature eg, 60 ° C.
  • drying the aqueous composition is a short drying time, it is possible to obtain a high-quality hard capsule with excellent elasticity, gloss and disintegration, the production yield of the hard capsule is also very high.
  • a capsule manufactured using cellulose ether which is a vegetable material that does not use gelatin, is in the spotlight.
  • cellulose ether is dissolved in water at room temperature (25 ° C.), most of the cellulose ethers are aggregated as soon as they are added to water to form aggregates.
  • cellulose ether is added to high temperature (for example, 80 ° C. or higher) water to disperse well to disperse to prepare a dispersion, and then to disperse the dispersion. After cooling to a first temperature (eg, 40-50 ° C.), the dispersed cellulose ether is dissolved in water.
  • high temperature for example, 80 ° C. or higher
  • a first temperature eg, 40-50 ° C.
  • the resultant is heated to a second temperature (eg, 55-65 ° C.), and then a gelling agent and optionally a gelling aid are added to the resultant.
  • a second temperature eg, 55-65 ° C.
  • the reason for raising the resultant temperature to the second temperature is to prevent the gelling agent and the gelling aid from hardening.
  • the cellulose ether is not completely dissolved in water, so that the aqueous composition and final hard capsule containing cellulose ether have the following disadvantages:
  • the aqueous composition is not only uniform in viscosity depending on location but also undergoes layer separation when stored for a long time.
  • the degree of mixing of the cellulose ether and the gelling agent (and the optional gelling aid) is reduced, so that the amount of the gelling agent (and the optional gelling aid) is to be increased.
  • the aqueous composition has low filtration efficiency in a subsequent filtration step to remove foreign matter (eg, fibers) therefrom.
  • the drying speed is slow when performing a drying process for evaporating water in the aqueous composition applied to the substrate (eg, mold pin) in the capsule molding process.
  • One embodiment of the present invention provides an aqueous composition for preparing a hard capsule containing a water-soluble cellulose ether and alcohols.
  • Another embodiment of the present invention provides a method of preparing the aqueous composition.
  • Another embodiment of the present invention provides a hard capsule prepared using the aqueous composition.
  • Another embodiment of the present invention provides a method of recycling hard capsule scraps comprising water soluble cellulose ethers.
  • aqueous composition for the manufacture of hard capsules comprising water.
  • the content ratio of the water-soluble cellulose ether in the aqueous composition for preparing a hard capsule may be 10 to 25% by weight, and the content ratio of the alcohols may be 5 to 30% by weight.
  • the water soluble cellulose ether may include hydroxypropyl methyl cellulose (HPMC), hydroxyethyl methyl cellulose (HEMC), methyl cellulose (MC) or a mixture of two or more thereof.
  • HPMC hydroxypropyl methyl cellulose
  • HEMC hydroxyethyl methyl cellulose
  • MC methyl cellulose
  • the alcohols may include ethanol, methanol, isopropanol, butanol or a mixture of two or more thereof.
  • the hard capsule manufacturing aqueous composition may further include a gelling agent having a content ratio of 0.05 to 5.0% by weight.
  • the gelling agent includes a water soluble gum, and the water soluble gum may include carrageenan, gellan gum, xanthan gum, pectin, or a mixture of two or more thereof.
  • the aqueous composition for preparing hard capsules may further include a gelling aid having a content ratio of more than 0% by weight and 1.0% by weight or less.
  • the gelling aid may include potassium chloride, potassium acetate, calcium chloride or a mixture of two or more thereof.
  • It provides a method for producing an aqueous composition for producing a hard capsule, comprising the step of preparing a cellulose ether solution containing water, alcohols, and water-soluble cellulose ethers and maintained at a first temperature higher than atmospheric temperature.
  • the first temperature may be 40 ⁇ 70 °C.
  • the method for preparing an aqueous composition for preparing a hard capsule may further include aging the cellulose ether solution, and adding a gelling agent to the resultant.
  • the aging step of the cellulose ether solution may be performed for 2 to 12 hours at a temperature of 40 ⁇ 70 °C.
  • It provides a hard capsule prepared using the aqueous composition for producing the hard capsule.
  • It provides a method for recycling hard capsule scrap comprising the step of dissolving a hard capsule scrap containing a water-soluble cellulose ether in a mixture of water and alcohols to produce an aqueous composition for the production of regenerated hard capsules.
  • the hard capsule scrap may include 90 to 95 parts by weight of water-soluble cellulose ether, 0.05 to 5.0 parts by weight of a gelling agent, 0 to 1.0 parts by weight of a gelling aid, and 1.0 to 7.0 parts by weight of water.
  • the step of preparing the aqueous composition for the production of regenerated hard capsules of the recycling method of the hard capsule scrap may be performed by dissolving an additional water-soluble cellulose ether in a mixture of water and alcohols together with the hard capsule scrap.
  • the recycling method of the hard capsule scrap may further include maintaining the regenerated hard capsule aqueous composition for 2 to 12 hours at a temperature of 40 to 70 °C.
  • the recycling method of the hard capsule scrap may further include adding at least one of an additional gelling agent and an additional gelling aid to the aqueous composition for preparing the regenerated hard capsule.
  • the method of recycling the hard capsule scrap may further include applying and drying the aqueous composition for preparing the regenerated hard capsule to a substrate.
  • the aqueous composition for preparing the regenerated hard capsule may include 10 to 25 wt% of the water-soluble cellulose ether, and the Alcohol may include 5 to 30% by weight.
  • the aqueous composition for preparing the regenerated hard capsule may include a gelling agent of 0.05 to 5.0% by weight.
  • the aqueous composition for the production of regenerated hard capsules may further comprise a gelling aid of more than 0% by weight 1.0% by weight or less.
  • the aqueous composition for preparing hard capsules includes water-soluble cellulose ethers and alcohols, so that the water is not only low temperature (eg, 0 to 40 ° C.) but also high temperature (eg, 40 to 70 ° C.) water. It is possible to directly dissolve the cellulose ether to shorten the manufacturing time of the aqueous composition, the drying time in the drying process during the capsule molding, it is also possible to improve the production yield of the final product of the hard capsule. In addition, the mixing of the cellulose ether and the gelling agent (and optional gelling aid) is improved so that a high quality hard capsule can be obtained even with a small amount of gelling agent (and optional gelling aid).
  • the recycling method of the hard capsule scrap it is possible to reduce the manufacturing cost of the hard capsule and the disposal cost of the hard capsule scrap, reduce environmental pollution, obtain a high quality hard capsule have.
  • aqueous composition for preparing a hard capsule according to an embodiment of the present invention.
  • the aqueous composition for preparing hard capsules (hereinafter referred to as "first composition") according to one embodiment of the present invention includes a water-soluble cellulose ether, alcohols and water.
  • the water soluble cellulose ether is a main component of the first composition.
  • a 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 ratio of the water-soluble cellulose ether in the first composition may be 10 to 25% by weight.
  • the viscosity is appropriate, bubbles are easily removed, and a capsule having a suitable thickness can be obtained.
  • the water soluble cellulose ether may include hydroxypropyl methyl cellulose (HPMC), hydroxyethyl methyl cellulose (HEMC), methyl cellulose (MC) or a mixture of two or more thereof.
  • HPMC hydroxypropyl methyl cellulose
  • HEMC hydroxyethyl methyl cellulose
  • MC methyl cellulose
  • the alcohols serve to help the water-soluble ether to liquefy (ie, dissolve) in the first composition.
  • the water-soluble cellulose ether is dissolved in a portion which is in direct contact with water when it is added to water at low temperature (20 to 30 ° C.), but the remaining portion that is not in direct contact with water aggregates to form agglomerates.
  • high temperature (40 ⁇ 70 °C) water even if the part is in direct contact with water has a property that does not dissolve well.
  • the alcohols are mixed with water to form an aqueous alcohol solution, and the water-soluble cellulose ether is well dissolved not only in the low-temperature (20-30 ° C) alcohol solution but also in the high-temperature (40-70 ° C) alcohol solution.
  • the content ratio of the alcohols may be 5 to 30% by weight.
  • the solubility of the cellulose ether is increased and the evaporation rate of the alcohols at the time of capsule manufacture is moderate, thereby obtaining a smooth capsule membrane without wrinkles.
  • the alcohols may include ethanol, methanol, isopropanol, butanol or a mixture of two or more thereof.
  • the first composition may further include a gelling agent having a content ratio of 0.05 to 5.0% by weight.
  • a gelling agent having a content ratio of 0.05 to 5.0% by weight.
  • the gelling agent may comprise a water soluble gum.
  • the water soluble gum may include carrageenan, gellan gum, xanthan gum, pectin or a mixture of two or more thereof.
  • the first composition may further include a gelling aid having a content ratio of more than 0% by weight and 1.0% by weight or less.
  • a gelling aid having a content ratio of more than 0% by weight and 1.0% by weight or less.
  • the gelling ability of the gelling agent may be improved to obtain a first composition having excellent capsule moldability, and a hard capsule without generation of haze may be obtained.
  • the gelling aid may include potassium chloride, potassium acetate, calcium chloride or a mixture of two or more thereof.
  • the first composition may further include a plasticizer having a content ratio of 0.05 to 5.0% by weight.
  • a plasticizer having a content ratio of 0.05 to 5.0% by weight.
  • the plasticizer may comprise glycerol, sorbitol, propylene glycol, polyethylene glycol or mixtures of two or more thereof.
  • the first composition has the advantages of complete dissolution of the water-soluble cellulose ether when heated to a capsule molding temperature (40-70 ° C.): First, the production time is shortened. Second, the homogeneity is high, the viscosity is uniform and layer separation does not occur even if stored for a long time. Third, the viscosity is kept constant for every manufacturing unit. Fourth, there is no undissolved substance (e.g., cellulose ether) that inhibits the function of the gelling agent and the optional gelling aid, so that the capsule formability is high. Fifth, the mixing degree of the cellulose ether and the gelling agent (and the optional gelling aid) is high, so that the amount of the gelling agent (and the optional gelling aid) is reduced.
  • a capsule molding temperature 40-70 ° C.
  • the filtration efficiency is high in a subsequent filtration process for removing foreign matter from the first composition.
  • the drying speed is high when the drying process for removing the solvent component in the aqueous composition applied to the substrate (for example, mold pin) in the capsule molding process.
  • the production time and the drying time of the first composition is short, the yield of hard capsules is high.
  • Another aspect of the present invention provides a hard capsule prepared using the first composition.
  • the hard capsule is immersed in a mold pin of room temperature (20 ⁇ 30 °C) in the first composition heated to a high temperature (40 ⁇ 70 °C), by removing the mold pin from the first composition and dried Can be prepared (called a 'cold pin process').
  • the hard capsule has a high quality (elasticity, glossiness, disintegration, etc.) because the first composition does not contain foreign substances such as fibers, and the quality is kept constant for each manufacturing unit.
  • the hard capsule may be gastric juice soluble.
  • the method of preparing the first composition includes water, alcohols, and water-soluble cellulose ether, and preparing a cellulose ether solution maintained at a first temperature (40 to 70 ° C.) higher than atmospheric temperature (0 to 39 ° C.). Include. Specifically, the method for preparing the first composition comprises the steps of preparing an aqueous alcohol solution by mixing water and alcohols (S1), heating the aqueous alcohol solution (S2), dissolving a water-soluble cellulose ether in the heated aqueous alcohol solution. To prepare a cellulose ether solution (S3), to mature the cellulose ether solution (S4), and to add a gelling agent to the resultant (S5).
  • the heating of the aqueous alcohol solution in the step (S2) may be performed up to a temperature of 40 ⁇ 70 °C from room temperature (20 ⁇ 30 °C).
  • This step (S2) is to ensure that the water-soluble cellulose ether in step (S3) is well dispersed in an aqueous solution of alcohol and dissolved well in a non-aggregated state.
  • the heating temperature is within the above range, a first composition having a high capsule moldability without hardening the gelling agent (and optional gelling aid) described later and minimizing an increase in energy cost due to unnecessary heating can be obtained.
  • the step (S3) may be carried out by slowly (for example, 1 to 2 hours) injecting the water-soluble cellulose ether to the heated aqueous alcohol solution under stirring (for example, 300rpm).
  • a water-soluble cellulose ether is dissolved in water (or alcohols) to prepare a first cellulose ether solution, followed by alcohol in the cellulose ether solution. (Or water) may be added to prepare a second cellulose ether solution.
  • Aging step (S4) of the cellulose ether solution may be performed for 2 to 12 hours at a temperature of 40 ⁇ 70 °C. If the execution time (ie, aging time) of the step (S4) is within the above range, bubbles are sufficiently removed from the resultant and its composition becomes uniform.
  • step (S4) it may be further added to the resulting gelation aid and / or plasticizer in addition to the gelling agent.
  • At least one of the steps (S1 ⁇ S5) may be performed under stirring.
  • step (S5) may further comprise the step of removing bubbles from the first composition.
  • This step S5 can be carried out by stirring.
  • the term "hard capsule scrap” refers to a material of the same material as a hard capsule as a material discarded in the manufacturing process of the hard capsule (ie, a by-product remaining after cutting). Specifically, the primary shaped hard capsule is secondarily trimmed (ie, unnecessary portions of the hard capsule are cut) to complete a hard capsule having a target shape, which is called a hard capsule scrap.
  • the hard capsule scrap may include 90 to 95 parts by weight of water-soluble cellulose ether, 0.05 to 5.0 parts by weight of a gelling agent, 0 to 1.0 parts by weight of a gelling aid and 1.0 to 5.0 parts by weight of water.
  • the step of preparing the second composition of the method for recycling the hard capsule scrap may proceed by dissolving additional water soluble cellulose ether in an aqueous alcohol solution together with the hard capsule scrap.
  • the preparing of the second composition may be performed by mixing a solution obtained by dissolving the hard capsule scrap in an aqueous solution of alcohol and a solution obtained by dissolving an additional water-soluble cellulose ether in an aqueous solution of alcohol.
  • the preparing of the second composition may be performed by dissolving the hard capsule scrap in an aqueous alcohol solution to prepare two or more solutions, and then mixing the two or more solutions in proportion to each other.
  • the additional water soluble cellulose ether may be the same as or similar to the water soluble cellulose ether included in the hard capsule scrap.
  • the additional water-soluble cellulose ether is also well soluble in aqueous alcohol solution at room temperature (20 ⁇ 30 °C) and high temperature (40 ⁇ 70 °C).
  • the step of preparing the second composition is a step of preparing an aqueous alcohol solution by mixing water and alcohols (S10), the step of heating the aqueous alcohol solution (S20), and the hard capsules in the heated aqueous alcohol solution Scrap and dissolving the optional additional water soluble cellulose ether may include preparing a cellulose ether-containing solution (S30).
  • step of preparing the second composition is similar to the method of preparing the first composition described above, the following description will focus on the differences between the two methods.
  • the preparing of the second composition may use the hard capsule scrap as a raw material and not the additional water soluble cellulose ether, and the additional water soluble cellulose ether may be used as an auxiliary raw material. This is because the hard capsule scrap already contains water-soluble cellulose ether.
  • the step of preparing the second composition is to maintain the cellulose ether-containing solution prepared in the step (S30) for 2 to 12 hours at a temperature of 40 ⁇ 70 °C (S40) (this is referred to as "aging step") It may further include.
  • the gelling agent and the gelling aid may not be added. This is because the hard capsule scrap already contains a gelling agent and a gelling aid.
  • the step of preparing the second composition, after the aging step (S40), at least one of the additional gelling agent and the additional gelling aid (for example, further gelling agent and selection in the result of the aging step (S40)) May further comprise the step of adding additional gelling aids).
  • the additional gelling agent and the additional gelling aid may be the same or similar to each of the gelling agent and the gelling aid contained in the hard capsule scrap.
  • the additional gelling agent and / or the additional gelling aid may be added to at least one of all the substeps included in preparing the second composition.
  • the hard capsule scrap may further comprise a plasticizer.
  • the plasticizer may be the same as or similar to the plasticizer included in the first composition.
  • an additional plasticizer may be further added to at least one of all sub-steps included in preparing the second composition.
  • the additional plasticizer may be the same as or similar to the plasticizer included in the hard capsule scrap.
  • the method of recycling the hard capsule scrap may further include applying and drying the second composition to the substrate.
  • the application and drying step is the same as the method for producing a hard capsule by applying and drying the first composition on the substrate, a detailed description thereof will be omitted here.
  • Ethanol and water were mixed in the ratio of Table 1 to prepare an ethanol aqueous solution. Thereafter, the ethanol aqueous solution was heated to the temperature of Table 1, and then hydroxypropyl methyl cellulose (HPMC) (Samsung Fine Chemical, AW4) was added to the ethanol aqueous solution in the ratio of Table 1 to dissolve. After 4 hours after completion of the dissolution, the appearance of the result was visually observed and evaluated in four steps as follows. In addition, the evaluation results are shown in Table 1 below.
  • Example 1-1 Table 1 Content ratio (% by weight) Temperature of Ethanol Aqueous Solution (°C) Constellation water ethanol HPMC Example 1-1 60 20 20 60 ⁇ Example 1-2 65 15 20 60 ⁇ Example 1-3 70 10 20 60 ⁇ Example 1-4 75 5 20 60 ⁇ Comparative Example 1-1 80 0 20 60
  • the results prepared in Examples 1-1 to 1-4 are HPMC is well dissolved and good properties and viscosity, while the results prepared in Comparative Examples 1 to 1 are not HPMC dissolved It exists as a condition and appears to be bad.
  • Example 2 To the resultant prepared in Example 1-2 was added K-carrageenan (K-Carrageenan, HG404) and the gelling aid of potassium chloride in the ratio of the following Table 2 to obtain an aqueous composition. Thereafter, the gelation degree of each of the aqueous compositions was measured by the following method, and the results are shown in Table 2 below. In addition, the drying rate of the aqueous composition prepared in Example 2-5 was measured in the following manner, and the results are shown in Table 3 below.
  • K-carrageenan K-Carrageenan, HG404
  • the gelling aid of potassium chloride in the ratio of the following Table 2
  • Each of the aqueous compositions was sampled with a 2 ml syringe and then sprayed on a glass plate standing upright.
  • the length of each of the aqueous compositions flowed along the glass plate was measured.
  • the shorter the length means that the degree of gelation is larger.
  • Mold pins were immersed in the aqueous composition prepared in Example 2-5. The mold pin was then removed from the aqueous composition and the weight change of the mold pin was measured over time in a state left at 25 ° C. and 55% RH (relative humidity). The drying rate of the aqueous composition was then calculated from the weight change of the mold pins. Here, the larger the drying rate change over time, the higher the drying rate.
  • the weight change and drying rate change of the mold pin over time are shown in Table 3 below. In addition, the drying rate change of the aqueous composition over time is shown graphically in FIG.
  • Examples 2-1 to 2-5 except that the resultant prepared in Comparative Example 1-1 was used instead of the resultant prepared in Example 1-2, and the amount of K-carrageenan and selective potassium chloride was changed.
  • An aqueous composition was prepared in the same manner as described above, and the gelation degree of the prepared aqueous composition was evaluated and the results are shown in Table 2 below.
  • the aqueous composition prepared in Comparative Example 2-4 was used instead of the aqueous composition prepared in Example 2-5
  • the drying rate over time of the aqueous composition in the same manner as in Example 2-5 To evaluate the results are shown in Table 3 below.
  • the drying rate change of the aqueous composition over time is shown graphically in FIG.
  • the aqueous compositions prepared in Examples 2-1 to 2-5 are gelling agents (K-carrageenan) and gelling aids (potassium chloride) as compared to the aqueous compositions prepared in Comparative Examples 2-1 to 2-3.
  • the gelation degree was excellent when the content ratio of) is the same or similar. Therefore, when the aqueous composition is prepared according to one embodiment of the present invention, the amount of the gelling agent and the gelling aid may be reduced as compared with the case of preparing the aqueous composition according to the prior art.
  • the aqueous composition prepared in Comparative Example 2-4 has a high degree of gelation, but as shown in Table 1, HPMC is present in an undissolved state, not only the capsule formability is lowered, but also a hard capsule having low quality is obtained.
  • Example 2-5 the aqueous composition prepared in Example 2-5 was found to have a faster drying rate than the aqueous composition prepared in Comparative Example 2-4.
  • Example 3-1 and Comparative Example 3-1 Solubility and Haze Evaluation of Hard Capsules
  • Mold pins were immersed in the aqueous compositions (temperature: 60 ° C.) prepared in Examples 2-5 and Comparative Examples 2-4. Thereafter, the mold pin was taken out of the aqueous composition and left for 1 hour under 25 ° C. and 55% RH (relative humidity) to obtain a hard capsule by drying the solvent component in the aqueous composition. Thereafter, the solubility and haze of each hard capsule were evaluated in the following manner, and the results are shown in Tables 4 and 5, respectively.
  • Example 3-1 the hard capsule prepared in Example 3-1 was found to have a faster dissolution rate than the hard capsule prepared in Comparative Example 3-1.
  • each hard capsule was placed in a 40 ml vial, and each vial was placed in a constant temperature and humidity chamber at 40 ° C. and 75% RH (relative humidity). Thereafter, each of the hard capsules was visually observed every week to evaluate the degree of haze in three steps as follows, and the results are shown in Table 5 below.
  • Example 3-1 Comparative Example 3-1 Early ⁇ ⁇ 1 week ⁇ ⁇ 2 weeks ⁇ ⁇ 3 weeks ⁇ ⁇ 4 Weeks ⁇ ⁇
  • Example 3-1 did not appear to have a haze even when stored for a long time, whereas the hard capsules prepared in Comparative Example 3-1 had a haze after three weeks. appear.
  • Example 4-1 to 4-2 and Reference Example 1-1 Preparation of Aqueous Composition for Hard Capsule Preparation
  • Ethanol and water were mixed in the ratio of Table 6 to prepare an ethanol aqueous solution. Then, the aqueous ethanol solution was heated to the temperature of the following Table 6, then hard capsule scrap and / or hydroxypropyl methyl cellulose (HPMC) (Samsung Fine Chemical, AW4) to the aqueous solution of ethanol in the ratio of the following Table 6 Dissolved.
  • HPMC hydroxypropyl methyl cellulose
  • AW4 hydroxypropyl methyl cellulose
  • Example 4-2 and Reference Example 1-1 an appropriate amount of K-carrageenan (Korean carogen, HG404) in the ethanol aqueous solution was obtained so that an aqueous composition for producing hard capsules containing 1.5% by weight of K-carrageenan was obtained. More was added.
  • an aqueous composition for preparing hard capsules containing 20% by weight of HPMC and 1.5% by weight of K-carrageenan was obtained, respectively.
  • Hard capsule scrap 92 weight of HPMC (AW4 of Samsung Fine Chemicals), 1.2 weight% of K-carrageenan (Carogen, Korea, HG404), 0.08 weight% of KCl, 1.72 weight% of glycerol, and 5 weight% of moisture.
  • Example 4-1 to 4-2 and Reference Example 1-1 after 4 hours of dissolution of the hard capsule scrap and / or HPMC, the properties of the resultant (ie, the aqueous composition for preparing hard capsules) were visually observed. After the evaluation in the same manner as in Examples 1-1 to 1-4 and Comparative Example 1-1, the results are shown in Table 7 below. In addition, the strength of the gel formed from each of the aqueous compositions for hard capsule preparation prepared in Examples 4-1 to 4-2 and Reference Example 1-1 and the physical properties of the film prepared from the composition were measured by the following method, and The results are shown in Table 7 below.
  • Each of the aqueous compositions for preparing hard capsules maintained at 60 ° C was gelled by cooling to room temperature (about 25 ° C). Then, using the Texture Analyser (Brookfield, CT3-4500, Probe No: TA10) to measure the strength of the gel formed from the aqueous composition for the preparation of each hard capsule, the results are shown in Table 7 below.
  • each of the aqueous compositions for preparing hard capsules maintained at 60 ° C. was applied onto a glass substrate using a film caster (manufactured by Samsung Fine Chemicals). Thereafter, the glass substrate coated with the aqueous composition for preparing a hard capsule was dried at room temperature (25 ° C.) for 24 hours to obtain a film having a thickness of 100 ⁇ m. Subsequently, each film was cut into 1cm * 10cm size and then the tensile strength of the film was measured using a LLOYD Instrument testing machine (LRX plus, LLOYD Instrument, UK). In addition, each film was cut to a size of 4cm * 5cm and then the film hardness was measured using a Texture Analyzer (Brookfield, CT3-4500, Probe No. TA-39), the results are shown in Table 7 below.
  • Example 4-2 Reference Example 1-1 Constellation ⁇ ⁇ ⁇ Gel strength (g) 110 120 130 Tensile Strength (N / mm 2 ) 65 62 66 Film hardness (g) 3,230 3,110 3,200
  • the aqueous composition for preparing hard capsules prepared in Examples 4-1 to 4-2 prepared using the hard capsule scrap and the optional HPMC was prepared in Reference Examples 1 to 1 using only HPMC.
  • the hard capsule scrap and the optional HPMC were well dissolved and showed good properties.
  • the gel prepared from the aqueous composition for preparing hard capsules prepared in Examples 4-1 to 4-2 was compared with the gel prepared from the aqueous composition for preparing hard capsules prepared in Reference Example 1-1 (K-carrageenan). Although the gel strength is slightly lower when the content of is the same, it has been shown to have a suitable gel strength ( ⁇ 100 g) for use in the manufacture of hard capsules.
  • films prepared from the aqueous composition for preparing hard capsules prepared in Examples 4-1 to 4-2 prepared using hard capsule scraps and optional HPMC were prepared in Reference Examples 1-1 prepared using only HPMC. Similar to the films made from the aqueous compositions for preparing hard capsules, the tensile strength and film hardness were found to be good.
  • the aqueous composition for preparing hard capsules includes water-soluble cellulose ethers and alcohols, so that the water is not only low temperature (eg, 0 to 40 ° C.) but also high temperature (eg, 40 to 70 ° C.) water. It is possible to directly dissolve the cellulose ether to shorten the manufacturing time of the aqueous composition, the drying time in the drying process during the capsule molding, it is also possible to improve the production yield of the final product of the hard capsule. In addition, the mixing of the cellulose ether and the gelling agent (and optional gelling aid) is improved so that a high quality hard capsule can be obtained even with a small amount of gelling agent (and optional gelling aid).
  • the recycling method of the hard capsule scrap it is possible to reduce the manufacturing cost of the hard capsule and the disposal cost of the hard capsule scrap, to reduce environmental pollution, to obtain a high quality hard capsule have.

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EP13823894.4A EP2875808B1 (en) 2012-07-23 2013-07-04 Aqueous composition for preparing hard capsule, preparation method therefor, hard capsule, and method for recycling hard capsule scraps
CA2879723A CA2879723C (en) 2012-07-23 2013-07-04 Aqueous composition for preparing hard capsule, preparation method therefor, hard capsule, and method for recycling hard capsule scraps
US14/415,006 US11312878B2 (en) 2012-07-23 2013-07-04 Aqueous composition for preparing hard capsule, preparation method therefor, hard capsule, and method for recycling hard capsule scraps
JP2015524168A JP6227646B2 (ja) 2012-07-23 2013-07-04 硬質カプセル製造用水性組成物及びその製造方法、硬質カプセル、並びに硬質カプセルスクラップの再活用方法
CN201380039127.8A CN104487058A (zh) 2012-07-23 2013-07-04 用于制备硬胶囊的含水组合物、其制备方法、硬胶囊及用于回收硬胶囊废料的方法
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US20210016471A1 (en) * 2018-03-21 2021-01-21 Ryan Selby Vaporizer capsules and methods of manufacture
US12349046B2 (en) * 2020-06-29 2025-07-01 Avalon Technology Solutions LLC Overlapping basic service set status indication for an access point cooperative transmission
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