KR20020072600A - Preparation of Microcapsules - Google Patents

Preparation of Microcapsules Download PDF

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KR20020072600A
KR20020072600A KR1020010012503A KR20010012503A KR20020072600A KR 20020072600 A KR20020072600 A KR 20020072600A KR 1020010012503 A KR1020010012503 A KR 1020010012503A KR 20010012503 A KR20010012503 A KR 20010012503A KR 20020072600 A KR20020072600 A KR 20020072600A
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solution
hlb
microcapsules
surfactant
manufacturing
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KR1020010012503A
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Korean (ko)
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조석형
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조석형
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    • 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

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Dispersion Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Cosmetics (AREA)
  • Manufacturing Of Micro-Capsules (AREA)

Abstract

PURPOSE: A manufacturing method of microcapsules having superior biocompatibility and high manufacturing efficiency is provided. CONSTITUTION: The manufacturing method of microcapsules comprises the steps of preparing a solution in which surfactant is added to a biocompatibility natural polymer solution or natural polymer solution; and manufacturing microcapsules by homogenizing the materials after adding a core material, a coagulant (a wall forming agent), and a solution in which surfactant is dissolved in an organic solvent in certain cases to the surfactant added solution, wherein the biocompatibility capsules are protein such as sodium alginate, chitosan, gelatin, keratin, lipoprotein and fibrin, the core material comprises oil, dyestuff, pigment, incense, foodstuffs, medication, agricultural chemicals, adhesive, lipophilic cosmetics, or skin activating constituents, sodium alginate and chitosan are preferably used as a capsule material, 1 to 8 wt.% of ESPR-25 (polyglycerin polylinoleate, HLB=0.5), ES-7 (glycerin monostearate, HLB=3.8-4.3), SPAN-60 (sorbitan stearate, HLB=6.8-8.6), SE-11 (sucrose fatty acid ester, HLB=11), MP-8, TW-80, TW-20(sorbitan laurate + ethylene oxide, HLB=16) or a mixture thereof depending on HLB values is used as an emulsifier for the total amount of the solution, and a solution of the capsule material is controlled to 0.1 to 5.0 wt.%, and more preferably to 1 to 3 wt.%.

Description

마이크로캡슐의 제조{Preparation of Microcapsules}Preparation of Microcapsules {Preparation of Microcapsules}

본 발명은 심물질로 잉크, 약물, 향료, 농약, 첩착제, 식품, 염료, 방청제 , 축열제 등이 포함된 환경 및 생체에 영향이 없는 천연고분자 막을 갖는 마이크로캡슐의 제조 방법에 관한 것이다.The present invention relates to a method for producing a microcapsule having a natural polymer membrane which does not affect the environment and the living body, which contains ink, drugs, flavors, pesticides, adhesives, foods, dyes, rust inhibitors, heat storage agents and the like as a core material.

압력 민감성 기록종이, 제재, 향료, 서방성 농약, 접착제, 식품, 염료, 용매, 방청제, 액정 및 건강식품을 포함한 다양한 분야에서 마이크로캡슐화가 연구되어 왔다. 특히 소수성 물질(오일성 물질 및 고체 물질)의 마이크로캡슐화에 대한 다수의 기술이 개발되었거나 개발하고 있다. 마이크로캡슐의 제조 방법은 많은 문헌에 기재되어 있다. 일반적으로, 이는 캡슐막을 형성하는 폴리머는 모노머를 계면 중합(interfacial polymerization)하여 수행되거나(특허 BE-A-808 034, BE-A-839 748, BE-A-869 107, FR-A-2 504 408, 및 FR-A-2 515 960 참조), 두 개의 상을 에멀젼화(emulsify)하여 수행된다(특허 EP-A-0 274 961, EP-A-557 489, EP-A-0 447 318, 및 WO 93/25195 참조). 한국 특허공개 제 98-72 호는 젖산균을 보호제, 지방 및 유화제에분무하여 캡슐화하는 방법을 제시하고, 한국 특허공개 제 97-700490 호는 생분해성 중합체와 지질의 혼합물로 공기를 캡슐화한 초음파 촬영을 위한 조영제를 개시하고 있다. 또한 한국 특허공개 제 95-23330 호는 전분화 유화제를 사용하여 고도불포화지방산을 캡슐화시키는 방법을 예시하고 있다.Microencapsulation has been studied in a variety of fields including pressure sensitive recording papers, formulations, fragrances, sustained-release pesticides, adhesives, foods, dyes, solvents, rust inhibitors, liquid crystals and health foods. In particular, a number of techniques have been developed or developed for microencapsulation of hydrophobic materials (oily materials and solid materials). Methods of making microcapsules are described in many literatures. Generally, this is accomplished by the polymer forming the capsule film by interfacial polymerization of monomers (Patent BE-A-808 034, BE-A-839 748, BE-A-869 107, FR-A-2 504). 408, and FR-A-2 515 960), by emulsifying two phases (Patent EP-A-0 274 961, EP-A-557 489, EP-A-0 447 318, And WO 93/25195). Korean Patent Publication No. 98-72 discloses a method of encapsulating lactic acid bacteria in a protective agent, a fat and an emulsifier, and Korean Patent Publication No. 97-700490 discloses an ultrasonography of encapsulating air with a mixture of biodegradable polymers and lipids. A contrast agent is disclosed. Korean Patent Publication No. 95-23330 also illustrates a method for encapsulating polyunsaturated fatty acids using a starch emulsifier.

따라서, 본 발명의 목적은 생체 적합성이우수하고 제조 효율이 높은 마이크로캡슐을 제공하는 것으로 폴리머막을 형성하는 폴리머를 용해시킨 용매와 서로 섞일 수 있는 유기용매에 심재와 막형성 물질을 응고시킬 수 있는 응고제를 용해시키고 막형성 폴리머와 계면활성제를 용해시킨 용액에 심재가 용해된 용액을 고속교반하면서 첨가함으로써 마이크로캡슐을 제조하는 방법에 관한 것이다.Accordingly, an object of the present invention is to provide a microcapsule having excellent biocompatibility and high manufacturing efficiency, and a coagulant capable of solidifying the core material and the film-forming material in an organic solvent which can be mixed with a solvent in which the polymer forming the polymer film is dissolved. The present invention relates to a method for preparing microcapsules by adding a solution in which a core material is dissolved in a solution in which a film-forming polymer and a surfactant are dissolved while stirring at high speed.

발명에 따라서, 생체 적합성 천연 고분자의 용액 또는 천연고분자 용액에 계면활성제가 첨가된 용액을 제조하고, 상기 용액에 심재와 응고제(벽형성 조제) 및 계면활성제가 유기 용매에 용해된 용액를 첨가하여 균질화시킴으로써 마이크로캡슐의 제조방법을 특징으로 한다.According to the invention, a solution in which a surfactant is added to a solution of a biocompatible natural polymer or a natural polymer solution is prepared and homogenized by adding a solution in which a core material, a coagulant (wall forming aid) and a surfactant are dissolved in an organic solvent. It is characterized by the preparation method of microcapsules.

본 발명에서 심재로는 오일, 염료, 안료, 향료, 식품, 의약품, 농약, 점착·접작제, 친지성 화장품 또는 피부용 활성 성분 등을 들 수 있다.In the present invention, the core material may be an oil, a dye, a pigment, a perfume, a food, a medicine, a pesticide, an adhesive, a gluing agent, a lipophilic cosmetic, or an active ingredient for skin.

본 발명에서 사용될 수 있는 캡슐 소재는 생체에 무해한 천연 고분자가 바람직하다. 캡슐 소재 농도는 캡슐의 견고성과 핵물질을 캡슐내에 유지하는 능력에 영향을 미치기 때문에 마이크로캡슐의 수율과 저장안정성에 중요한 요인으로 작용한다. 따라서, 캡슐소재(wall materials)로는 알긴산소다(sodiumalginate)와 키토산(chitosan)을 사용하는 것이 바람직하다.The capsule material that can be used in the present invention is preferably a natural polymer that is harmless to a living body. Capsule material concentration is an important factor in the yield and storage stability of microcapsules because it affects the strength of the capsule and the ability to retain the nuclear material in the capsule. Therefore, it is preferable to use sodium alginate and chitosan as the wall material.

유화제로는 HLB 값에 따라 ESPR-25(polyglycerine polylinoleate, HLB=0.5), ES-7(glycerin monostearate, HLB=3.8∼4.3), SPAN-60(sorbitan stearate, HLB=6.8∼8.6), SE-11(sucrose fatty acid ester, HLB=11), MP-8, TW-80, TW-20(sorbitanlaurate+ethylene oxide, HLB=16)을 사용하는 것이 바람직하다. 이들 유화제는 단독으로 사용될 수도 있고, 2종 이상의혼합물로 사용하는 것도 가능하다. 유화제는 용액 총량에 대하여 1% 내지 8% 첨가한다.Emulsifiers include ESPR-25 (polyglycerine polylinoleate, HLB = 0.5), ES-7 (glycerin monostearate, HLB = 3.8-4.3), SPAN-60 (sorbitan stearate, HLB = 6.8-8.6), SE-11 (sucrose fatty acid ester, HLB = 11), MP-8, TW-80, TW-20 (sorbitanlaurate + ethylene oxide, HLB = 16) is preferably used. These emulsifiers may be used alone or in combination of two or more thereof. The emulsifier is added in an amount of 1% to 8% based on the total amount of the solution.

캡슐 소재의 용액은 0.1 내지 5.0%로 조절하며, 1% 내지 3.0% 범위가 바람직하다.The solution of the capsule material is adjusted to 0.1 to 5.0%, preferably 1% to 3.0% range.

심재를 용해시킬 수 있는 용매로는 메탄올, 에탄올, 프로판올, 이소프로판올 등의 알콜류 및 아세톤, 에틸메틸케톤, 메틸에틸케톤 등 케톤류를 사용하고 메탄올, 에탄올, 아세톤을 사용하는 것이 바람직하다.As a solvent capable of dissolving the core material, alcohols such as methanol, ethanol, propanol and isopropanol and ketones such as acetone, ethyl methyl ketone and methyl ethyl ketone are preferably used, and methanol, ethanol and acetone are preferably used.

캡슐 벽형성 조제로 사용하는 물질로는 특히 캡슐 소재로 알긴산나트륨을 사용하는 경우에는 젖산 칼슘, 탄산칼슘 등의 용액을 사용하고, 키토산을 사용하는 경우에는NaOH, 황산칼슘, 황산나트륨, 황산 용액을 사용하는 것이 바람직하다. 또한 가교제를 함께 사용할 수 있다.As a material for the capsule wall formation, a solution such as calcium lactate, calcium carbonate, etc. is particularly used when using sodium alginate as a capsule material, and a solution of NaOH, calcium sulfate, sodium sulfate, and sulfuric acid when chitosan is used. It is desirable to. Crosslinking agents can also be used together.

본 발명에 따라서 제조된 마이크로캡슐의 크기는 0.1 내지 30㎛ 범위이다..The size of the microcapsules prepared according to the invention ranges from 0.1 to 30 μm.

이하에서 바람직한 실시예에 의거하여 본 발명을 상세히 설명하지만, 본 발명의 범위가 이들 실시예에 한정되는 것은 아니다Hereinafter, the present invention will be described in detail based on the preferred embodiments, but the scope of the present invention is not limited to these examples.

실시예 1Example 1

1g의 키토산을 상온에서 1 ℓ 둥근 바닥 플라스크 내 200 g의 증류수에 분산시킨 후 비이온성 계면 활성제인 MP-8 0.5 g을 상기의 수계 분산액에 첨가하였다.1 g of chitosan was dispersed in 200 g of distilled water in a 1 L round bottom flask at room temperature, and 0.5 g of MP-8, a nonionic surfactant, was added to the aqueous dispersion.

실온에서 10%의 레티놀을 함유하는 카프릴산 및 카프리산 트리글리세라이드 각각 5 g과 2% NaOH 용액 20g을 500 ㎖ 둥근 바닥 플라스크 내 200 ㎖의 에탄올에 용해시켰다.At room temperature, 5 g of caprylic and capric acid triglycerides each containing 10% retinol and 20 g of 2% NaOH solution were dissolved in 200 ml of ethanol in a 500 ml round bottom flask.

이어서, 빠른 속도로 교반하면서 에탄올 상을 수상에 첨가하여 1.2㎛의 평균 직경을 가지는 마이크로캡슐의 콜로이드 현탁액(pH 7.8)을 얻었다.The ethanol phase was then added to the aqueous phase with rapid stirring to obtain a colloidal suspension of microcapsules (pH 7.8) having an average diameter of 1.2 μm.

실시예 2Example 2

10 g의 박하향과 젓산칼슘 3% 용액 20g을 200 ㎖ 비커 내 100 ㎖의 에탄올에 용해시켰다. 1 g의 알긴산 소다를 상온에서 200 g의 증류수에 용해시킨 후 비이온성 계면 활성제인 Twin 80 0.5 g을 상기의수계 분산액에 첨가하였다.10 g of peppermint and 20 g of calcium nitrate 3% solution was dissolved in 100 ml of ethanol in a 200 ml beaker. After dissolving 1 g of sodium alginate in 200 g of distilled water at room temperature, 0.5 g of Twin 80, a nonionic surfactant, was added to the aqueous dispersion.

그런 후에, 빠른 속도로 교반하면서 상기 에탄올 상을 수상에 첨가하여 2.1㎛의 평균 직경을 가지는 캡슐의 콜로이드 현탁액(pH 6.7)을 얻었다.The ethanol phase was then added to the aqueous phase with rapid stirring to give a colloidal suspension (pH 6.7) of capsules with an average diameter of 2.1 μm.

이상의 설명으로부터 명백한 바와 같이, 본 발명에 따라 제조된 마이크로캡슐은 생체 적합성을 갖는 것으로 환경오염을 줄일 수 있을 뿐만 아니라 식품, 의약품, 화장품 등에 광범위하게 사용할 수 있다. 본 발명의 방법에 따르면, 제조 공정이 간단하고 비용이 저렴하게 마이크로캡슐을 제조할 수 있다는 장점이 있다As is apparent from the above description, the microcapsules prepared according to the present invention are biocompatible and can reduce environmental pollution, and can be widely used in food, medicine, cosmetics, and the like. According to the method of the present invention, there is an advantage that the microcapsules can be manufactured at a low cost and a simple manufacturing process.

Claims (2)

생체 적합성 천연 고분자의 용액 또는 천연고분자 용액에 계면활성제가 첨가된 용액을 제조하는 단계와 상기 용액에 심재와 응고제(벽형성 조제), 경우에 따라서 계면활성제가 유기 용매에 용해된 용액를 첨가하여 균질화시킴으로써 마이크로캡슐의 제조하는 단계로 이루어진 마이크로 캡슐의 제조방법.Preparing a solution in which a surfactant is added to a solution of a biocompatible natural polymer or a natural polymer solution and homogenizing the solution by adding a core material and a coagulant (wall forming aid), and optionally a solution in which the surfactant is dissolved in an organic solvent. Method for producing a microcapsule comprising the step of preparing a microcapsule. 1 항에 있어서, 상기 생체 적합성 캡슐이 알긴산나트륨, 키토산 및 젤라틴, 케라틴, 지질 단백질, 피브린 등의 단백질임을 특징으로 하는 방법The method of claim 1, wherein the biocompatible capsule is a protein such as sodium alginate, chitosan and gelatin, keratin, lipid protein, fibrin and the like.
KR1020010012503A 2001-03-12 2001-03-12 Preparation of Microcapsules KR20020072600A (en)

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2005002719A1 (en) * 2003-07-03 2005-01-13 Lg Chem. Ltd. Method for preparing microcapsule by miniemulsion polymerization
US8974819B2 (en) * 2007-06-18 2015-03-10 Industry-Academic Cooperation Foundation, Yonsei University Sustained-release chitosan capsules comprising chitosan and phytic acid
CN111749009A (en) * 2020-07-14 2020-10-09 福建恒安集团有限公司 Non-woven fabric for protective clothing and preparation method thereof
CN116289322A (en) * 2023-03-13 2023-06-23 浙江理工大学 Preparation method of cationized hydrophobic microcapsule flame-retardant paper

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2005002719A1 (en) * 2003-07-03 2005-01-13 Lg Chem. Ltd. Method for preparing microcapsule by miniemulsion polymerization
US8974819B2 (en) * 2007-06-18 2015-03-10 Industry-Academic Cooperation Foundation, Yonsei University Sustained-release chitosan capsules comprising chitosan and phytic acid
CN111749009A (en) * 2020-07-14 2020-10-09 福建恒安集团有限公司 Non-woven fabric for protective clothing and preparation method thereof
CN116289322A (en) * 2023-03-13 2023-06-23 浙江理工大学 Preparation method of cationized hydrophobic microcapsule flame-retardant paper

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