KR20120007817A - Chitosan/clay composite composition for improving oxygen barrier, preparation method thereof and use of the same - Google Patents
Chitosan/clay composite composition for improving oxygen barrier, preparation method thereof and use of the same Download PDFInfo
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Abstract
Description
본 발명은 산소차단성을 개선시킨 키토산/클레이 복합체 조성물 및 그 제조방법 및 그 용도에 관한 것이다.The present invention relates to a chitosan / clay composite composition having improved oxygen barrier properties, a method for preparing the same, and a use thereof.
일반적으로 플라스틱 필름의 산소차단성을 부여하기 위해서는, 산소 차단성이 우수한 합성고분자를 고분자 필름위에 코팅을 하거나, 고분자 필름층 사이에 첩합하여 다층의 플라스틱 필름 구조를 제조하는데, 이러한 방법은 산소 차단 특성은 우수하나, 환경적인 측면에서 쉽게 분해되지 않는 문제점이 있으며, 특히 소각되거나 매립되고 있는 실정으로 인해 유독가스와 잔유물등이 발생하고 토양을 황폐화하여 농작물의 생장을 저해하는 등의 단점을 가지고 있다.In general, in order to impart oxygen barrier properties of a plastic film, a synthetic polymer having excellent oxygen barrier properties is coated on a polymer film or bonded between polymer film layers to produce a multilayer plastic film structure. Is excellent, but there is a problem in that it is not easily decomposed in terms of the environment, in particular, due to the fact that incineration or landfill, toxic gases and residues are generated, and the soil has been devastated, such as deteriorating the growth of crops.
PLA(Polylactic acid) 필름은 최근 생분해되지 않은 합성 고분자 필름에 의해 야기되는 폐기물 처리를 최소화할 수 있으며, 환경유해물질의 배출량을 줄이기 위해서 생분해성 고분자 필름에 대한 관심이 높아지고 있다, PLA는 옥수수의 전분을 발효시켜 생산되는 유산을 축중합한 후 제조되어 지며 물성 조절이 자유로워 다양한 개발이 가능한 유용한 고분자이다. 그러나 PLA의 단점으로는 열수축율이 높고, 내열성과 차단성이 낮으며, 알칼리에 약하다. 따라서 생고분자의 활용도를 높이기 위해서는 물성 향상이 반드시 필요하다.Polylactic acid (PLA) film can minimize the waste treatment caused by synthetic polymer film that is not biodegradable recently, and interest in biodegradable polymer film is increasing to reduce the emission of environmentally harmful substances. It is manufactured after polycondensation of the lactic acid produced by fermentation, and it is a useful polymer that can be developed in various ways because of its free property control. However, the disadvantages of PLA are high heat shrinkage, low heat and barrier properties, and weak alkali. Therefore, it is necessary to improve the physical properties in order to increase the utilization of raw polymers.
코팅의 주요물질인 키토산은 게, 새우 등 수산갑각류의 껍질에서 얻은 키틴을 탈 아세틸화하여 얻어지는 천연 생고분자 물질로 항균작용 및 항산화작용, 콜레스테롤 조절효과와 같은 많은 생리활성 효과가 있는 천연물질이다. 이러한 다양한 생리활성으로 인해 식품산업분야, 의약품 및 생활용품 산업분야에 폭 넓게 이용되고 있다.Chitosan, the main material of the coating, is a natural raw polymer material obtained by deacetylating chitin obtained from the shells of aquatic crustaceans such as crabs and shrimps. It is a natural substance with many physiological activities such as antibacterial activity, antioxidant activity and cholesterol control effect. Due to such various physiological activities, it is widely used in the food industry, medicine, and household goods industry.
코팅물질에 소량 첨가되는 몬트모릴로나이트(MMT)는 나노클레이의 한 종류로서, 여러 개의 반복된 얇은 층으로 이루어져 있으며 두께는 1nm 이며, 길이는 100에서 수백 나노미터에 달한다. 각 층간은 양이온교환에 의해서 쉽게 분리되며 고분자 내에서 잘 섞이게 된다. 이러한 MMT의 성질은 강도 및 차단성 등의 필름물성 개선에 사용될 수 있다.Montmorillonite (MMT), which is added to coatings in small amounts, is a type of nanoclay, consisting of several repeated thin layers, 1 nm thick and 100 to several hundred nanometers long. Each layer is easily separated by cation exchange and mixes well in the polymer. The properties of the MMT can be used to improve film properties such as strength and barrier properties.
본 발명은 상기의 문제점을 해결하고 상기의 필요성에 의하여 안출된 것으로서 본 발명의 목적은 산소차단성이 개선된 생분해성 필름 코팅 조성물을 제공하는 것이다.SUMMARY OF THE INVENTION The present invention has been made in view of the above-mentioned problems and the need for the above-described object of the present invention to provide a biodegradable film coating composition having improved oxygen barrier properties.
본 발명의 다른 목적은 산소차단성이 개선된 생분해성 필름 코팅 조성물을 제조하는 방법을 제공하는 것이다.Another object of the present invention is to provide a method for preparing a biodegradable film coating composition having improved oxygen barrier properties.
본 발명의 또 다른 목적은 산소차단성이 개선된 생분해성 코팅 조성물이 코팅된 필름을 제공하는 것이다.It is another object of the present invention to provide a film coated with a biodegradable coating composition having improved oxygen barrier properties.
본 발명의 또 다른 목적은 산소차단성이 개선된 생분해성 코팅 조성물이 코팅된 필름을 제조하는 방법을 제공하는 것이다.It is another object of the present invention to provide a method for producing a film coated with a biodegradable coating composition having improved oxygen barrier properties.
상기의 목적을 달성하기 위하여 본 발명은 키토산 및 나노클레이를 유효성분으로 포함하는 산소차단성이 개선된 생분해성 필름 코팅 조성물을 제공한다.In order to achieve the above object, the present invention provides a biodegradable film coating composition having improved oxygen barrier properties including chitosan and nanoclays as active ingredients.
본 발명의 일 구현예에 있어서, 상기 나노클레이는 몬트모릴로나이트(MMT),베이딜라이트 (beidilite), 플루오로마이카 (fluoromica), 헥토라이트 (hectorite) , 논트로라이트 (nontronite), 파이로필나이트 (pyrophyllite), 사포나이트 (saponite), 버미큘라이트 (vermiculite) 혹은 이들의 조합(blend)인 것이 바람직하나 이에 한정되지 아니한다.In one embodiment of the present invention, the nanoclay is montmorillonite (MMT), beidilite, fluoromica, hectorite, nontronite, pyrophyll Pyrophyllite, saponite, vermiculite, or a combination thereof is preferred, but not limited thereto.
또 본 발명은 키토산에 나노클레이를 첨가하여 혼합용액을 제조하는 단계를 포함하는 산소차단성이 개선된 생분해성 필름 코팅 조성물 제조방법을 제공한다.In another aspect, the present invention provides a method for producing a biodegradable film coating composition improved oxygen barrier properties comprising the step of preparing a mixed solution by adding nanoclay to chitosan.
본 발명의 바람직한 구현예에 있어서 상기 방법은 혼합용액을 교반하고, 소니케이션하는 단계를 포함하는 것이 더욱 바람직하다.In a preferred embodiment of the present invention, the method further preferably comprises stirring and sonicating the mixed solution.
또한 본 발명은 상기 본 발명의 코팅 조성물이 코팅된 산소차단성이 개선된 생분해성 필름을 제공한다.In another aspect, the present invention provides a biodegradable film having improved oxygen barrier properties coated with the coating composition of the present invention.
본 발명의 일 구현예에 있어서, 상기 생분해성 필름은 폴리락트산, 폴리락트산 유도체, 전분 중합체, 다당류로 형성된 중합체, 단백질로 형성된 중합체, 지방족 또는 방향족으로 치환된 폴리에스테르, 폴리글리콜산 중합체, 폴리카프로락톤, 또는 폴리부틸렌숙시네이트인 것이 바람직하나 이에 한정되지 아니한다.In one embodiment of the present invention, the biodegradable film is polylactic acid, polylactic acid derivatives, starch polymers, polymers formed of polysaccharides, polymers formed of proteins, polyesters substituted with aliphatic or aromatic, polyglycolic acid polymers, polycapro Lactone, or polybutylene succinate is preferred but not limited thereto.
본 발명의 일 구현예에 있어서, 상기 생분해성 필름의 코팅 두께는 0.1~10㎛의 두께를 가지는 것이 바람직하고 1∼2㎛의 두께를 가지는 것이 더욱 바람직하나 이에 한정되지 아니한다.In one embodiment of the present invention, the coating thickness of the biodegradable film preferably has a thickness of 0.1 ~ 10㎛ and more preferably has a thickness of 1 ~ 2㎛, but is not limited thereto.
또한 본 발명은 생분해성 필름에 상기 본 발명의 코팅 조성물을 코팅하여 산소 차단성이 개선된 생분해성 필름을 제조하는 방법을 제공한다.The present invention also provides a method for producing a biodegradable film having improved oxygen barrier property by coating the coating composition of the present invention on a biodegradable film.
이하 본 발명을 설명한다.Hereinafter, the present invention will be described.
본 발명의 일 실시에에서는, 키토산에 소량의 나노클레이를 첨가하여 제조한 코팅물질을 사용하여, PLA필름의 산소차단성을 개선시켰으며, 코팅물질인 키토산/MMT 복합체와 기질인 PLA 필름 모두 생분해성 물질을 사용하였다.In one embodiment of the present invention, by using a coating material prepared by adding a small amount of nanoclay to chitosan, the oxygen barrier properties of the PLA film was improved, and both the chitosan / MMT composite coating material and the PLA film substrate were biodegradable. Sexual material was used.
따라서 이러한 생분해성 소재들은 사용 후 폐기하게 되면, 다양한 분해기작을 통해 저분자 물질로 분해되고, 분해된 물질은 다시 미생물에 의해 대사되어 물과 이산화탄소로 분해되므로, 환경친화적인 소재로 활용이 가능하다. Therefore, when these biodegradable materials are disposed of after use, they are decomposed into low molecular weight materials through various decomposition mechanisms, and the decomposed materials are metabolized by microorganisms and decomposed into water and carbon dioxide, and thus can be used as environmentally friendly materials.
본 발명을 통하여 알 수 있는 바와 같이 본 발명의 코팅 조성물 및 코팅 조성물이 코팅된 필름은 산소차단성을 개선시켰으며, 코팅물질인 키토산/MMT 복합체와 기질인 필름 모두를 생분해성 물질을 사용하여, 이러한 생분해성 소재들은 사용 후 폐기하게 되면, 다양한 분해기작을 통해 저분자 물질로 분해되고, 분해된 물질은 다시 미생물에 의해 대사되어 물과 이산화탄소로 분해되므로, 환경친화적인 소재로 활용이 가능하다. As can be seen through the present invention, the coating composition of the present invention and the film coated with the coating composition have improved oxygen barrier properties, and both the chitosan / MMT composite, which is a coating material, and the film, which is a substrate, use a biodegradable material. When these biodegradable materials are disposed of after use, they are decomposed into low molecular weight materials through various decomposition mechanisms, and the decomposed materials are metabolized by microorganisms and decomposed into water and carbon dioxide, and thus can be used as environmentally friendly materials.
도 1은 키토산/MMT 물질이 코팅된 PLA 필름의 단면사진이다.
도 2는 키토산과 키토산/MMT 물질이 코팅된 PLA 필름의 산소투과도를 나타낸 그래프이다.1 is a cross-sectional photograph of a PLA film coated with chitosan / MMT material.
Figure 2 is a graph showing the oxygen permeability of the chitosan and chitosan / MMT material coated PLA film.
이하 비한정적인 실시예를 통하여 본 발명을 더욱 상세하게 설명한다.The present invention will now be described in more detail by way of non-limiting examples.
단 하기 실시예는 본 발명을 예시하기 위한 의도로 기재된 것으로서 본 발명의 범위는 하기 실시예에 의하여 제한되는 것으로 해석되지 아니한다.
However, the following examples are intended to illustrate the invention and the scope of the present invention is not to be construed as limited by the following examples.
실시예Example 1: 키토산/ 1: chitosan / MMTMMT 코팅물질 제조 Coating material manufacturing
키토산 파우더 1g을 1% 아세트산을 포함하는 증류수 50mL에 완전히 녹인 후, 0.4g의 글리세롤을 첨가하여 교반하여 준다. 그리고 MMT의 한 종류인 Cloisite 30B 0.01g을 첨가하여, 이 혼합용액을 상온에서 1시간 교반, 1시간 소니케이션, 1시간 교반, 회전력 16000 rpm에서 5분간 교반, 25분간 소니케이션, 이러한 과정을 순차적으로 진행하여 키토산/MMT 코팅물질을 제조하였다1 g of chitosan powder is completely dissolved in 50 mL of distilled water containing 1% acetic acid, and then 0.4 g of glycerol is added and stirred. Then, 0.01 g of Cloisite 30B, a kind of MMT, was added, and the mixed solution was stirred at room temperature for 1 hour, 1 hour sonication, 1 hour agitation, 5 minutes of stirring at rotational force of 16000 rpm, and 25 minutes sonication. Proceed to prepare a chitosan / MMT coating material
비교예Comparative example 1: 키토산 코팅물질 제조 1: Manufacture of chitosan coating material
키토산 파우더 1g을 1% 아세트산을 포함하는 증류수 50mL에 완전히 녹인 후, 0.4g의 글리세롤을 첨가하여 교반하여 준다. 그리고 이 혼합용액을 상온에서 1시간 교반, 1시간 소니케이션, 1시간 교반, 회전력 16000 rpm에서 5분간 교반, 25분간 소니케이션, 이러한 과정을 순차적으로 진행하여 키토산 코팅물질을 제조하였다.
1 g of chitosan powder is completely dissolved in 50 mL of distilled water containing 1% acetic acid, and then 0.4 g of glycerol is added and stirred. Then, the mixed solution was stirred for 1 hour at room temperature, 1 hour sonication, 1 hour stirring, 5 minutes stirring at rotational force of 16000 rpm, 25 minutes sonication, and proceeded sequentially to prepare a chitosan coating material.
실시예Example 2: 코팅물질을 2: coating material PLAPLA 필름에 코팅 Coated on film
바코팅 기기(automatic film applicator)에 PLA 필름을 부착한 후 비교예 1에서 제조된 키토산 또는 실시예 1에서 제조된 키토산/MMT 코팅물질을 가한 다음 고르게 도포시켰고, 코팅두께는 1~2㎛로 균일하였으며, 키토산 또는 키토산/MMT가 코팅된 PLA 필름을 제조하였다.
After attaching the PLA film to an automatic film applicator, the chitosan prepared in Comparative Example 1 or the chitosan / MMT coating material prepared in Example 1 was added and then evenly applied, and the coating thickness was uniformly 1 to 2 μm. To prepare a chitosan or chitosan / MMT coated PLA film.
실험예 1: 필름의 산소투과도 비교Experimental Example 1: Comparison of Oxygen Permeability of Film
상기 실시예 2에서 제조된 비교예 1 및 실시예 1에서 제조된 키토산 또는 키토산/MMT 코팅물질이 코팅된 필름의 산소투과도는 MOCON 사의 OX-Tran® Model 2/61 장비를 사용하여 측정하였으며, 상대습도는 0%, 온도는 23℃에서 실험을 진행하였다.
Oxygen permeability of the film coated with the chitosan or chitosan / MMT coating material prepared in Comparative Example 1 and Example 1 prepared in Example 2 was measured using OX-Tran ®
도 1인 PLA 필름의 단면 사진에서 알 수 있듯이, 코팅 두께가 1.21㎛로 측정되었다.As can be seen in the cross-sectional photograph of the PLA film of Figure 1, the coating thickness was measured to 1.21㎛.
도 2에서 알 수 있는 바와 같이, 키토산이 코팅된 PLA 필름의 산소투과도는 8±2 cc/m2day 이고, 키토산/MMT가 코팅된 PLA 필름의 산소투과도는 4±2 cc/m2day로 측정되었다. 결과적으로 키토산/MMT 코팅이 PLA 필름의 산소차단성 부분에서 효과적임을 확인할 수 있었다.
As can be seen in Figure 2, the oxygen permeability of the chitosan-coated PLA film is 8 ± 2 cc / m 2 day, the oxygen permeability of the chitosan / MMT coated PLA film is 4 ± 2 cc / m 2 day Was measured. As a result, it was confirmed that the chitosan / MMT coating is effective in the oxygen barrier portion of the PLA film.
Claims (11)
10. The method of claim 9, wherein the coating thickness of the biodegradable film has a thickness of 1 to 2㎛.
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| KR101417871B1 (en) * | 2012-05-11 | 2014-07-14 | 원광대학교산학협력단 | O-acylated chitin butyrate-clay composite and antibiotic film using composite and method for preparing film |
| WO2016204698A1 (en) * | 2015-06-18 | 2016-12-22 | Agency For Science, Technology And Research | A plant protein and modified clay composite |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| KR101417871B1 (en) * | 2012-05-11 | 2014-07-14 | 원광대학교산학협력단 | O-acylated chitin butyrate-clay composite and antibiotic film using composite and method for preparing film |
| WO2016204698A1 (en) * | 2015-06-18 | 2016-12-22 | Agency For Science, Technology And Research | A plant protein and modified clay composite |
| US11709156B2 (en) | 2017-09-18 | 2023-07-25 | Waters Technologies Corporation | Use of vapor deposition coated flow paths for improved analytical analysis |
| US11709155B2 (en) | 2017-09-18 | 2023-07-25 | Waters Technologies Corporation | Use of vapor deposition coated flow paths for improved chromatography of metal interacting analytes |
| US11918936B2 (en) | 2020-01-17 | 2024-03-05 | Waters Technologies Corporation | Performance and dynamic range for oligonucleotide bioanalysis through reduction of non specific binding |
| CN112940318A (en) * | 2021-03-15 | 2021-06-11 | 深圳市通产丽星科技集团有限公司 | Method for producing organic-inorganic composite film and organic-inorganic composite film |
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