KR100752150B1 - Photocurable monomoers having imidazolium salts, antibacterial photocurable compositions comprising the same, and antibacterial polymer materials prepared therefrom - Google Patents
Photocurable monomoers having imidazolium salts, antibacterial photocurable compositions comprising the same, and antibacterial polymer materials prepared therefrom Download PDFInfo
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Abstract
Description
본 발명은 항균성 이미다졸륨 염 단량체 및 이를 이용한 항균성 광경화형 코팅용 고분자 재료에 관한 것이다.The present invention relates to an antimicrobial imidazolium salt monomer and a polymer material for antimicrobial photocurable coating using the same.
근래에 일상생활에서 위생적 생활이 적극적으로 요구됨에 따라, 항균제가 여러 분야에 사용되고 있다. 항균 기능을 갖는 제품도 많이 개발되어, 음식물, 음료수, 화장품 등의 보관용 용기, 칫솔, 문구류, 가전제품, 침구류와 같이 다양한 생활 용품과 건축자재 등 산업과 환경에서 세균 오염을 방지하는 것이 필요한 다양한 분야에서 응용되고 있다. 인간의 의식주에 관련되는 모든 일상생활 용품으로부터 다중이 함께 사용하는 공중전화, 공중 화장실, 지하철, 버스 등의 내장재를 가공이 용이한 고분자 항균 재료로 만드는 경우, 생활환경이 더욱 위생적이고 안전하게 될 수 있으므로 가공성이 우수한 코팅 재료용 항균성 고분자 재료가 요구된다. Recently, as hygienic life is actively demanded in daily life, antibacterial agents are used in various fields. Many products with antimicrobial properties have been developed, and it is necessary to prevent bacterial contamination in various industries such as food, beverages, cosmetics, storage containers, toothbrushes, stationery, home appliances, bedding, etc. It is applied in various fields. If the interior materials such as public telephones, public toilets, subways, buses, etc., which are used by multiple people from all daily household items related to human consciousness, are made of polymer antimicrobial materials that are easy to process, the living environment may be more hygienic and safe. There is a need for an antimicrobial polymer material for coating materials that is excellent in processability.
많은 항균 재료가 상품화 되었으나, 이들은 대부분 항균제를 액상이나 고분자 물질에 첨가한 혼합형이었기 때문에, 사용 중에 항균 성분이 서서히 제거되어 항균 활성이 장기간 유지되지 못하였다. 또한 항균제가 첨가제 형태로 사용되는 기존의 항균제들은 사용이 편리하기는 하지만, 주로 과량으로 사용하게 되고, 첨가된 항균 물질의 일부만이 기질 표면에서 항균 활성을 나타내며, 일정 시간이 경과되면 지속적인 세척 등으로 항균 활성이 급격히 감소하게 된다.Many antimicrobial materials have been commercialized, but most of them were mixed type in which an antimicrobial agent was added to a liquid or a high molecular material. Therefore, the antimicrobial activity was gradually removed during use, and thus the antimicrobial activity was not maintained for a long time. In addition, existing antimicrobial agents in which antimicrobial agents are used as additives are convenient to use, but are mainly used in excess, and only a part of the added antimicrobial substances exhibits antimicrobial activity on the surface of the substrate. Antimicrobial activity is drastically reduced.
이에 따라, 항균 활성이 반영구적으로 유지되어 기질에 대한 응용성이 크고, 사용에 편리하도록 유기 고분자 사슬 자체에 항균성이 부가된, 고분자형 항균 재료의 개발이 요구되고 있다. Accordingly, there is a demand for the development of a polymeric antimicrobial material in which antimicrobial activity is added to the organic polymer chain itself so that the antimicrobial activity is maintained semipermanently and thus the applicability to the substrate is large and convenient to use.
항균성, 살균성, 곰팡이 내성 등을 갖는 작용기를 고분자 사슬에 직접 결합시킴으로써 고분자 물질 그 자체가 항균성을 나타내도록 한 항균성(antibacterial) 또는 살생물성(biocidal) 고분자에 관한 연구가 진행되고 있다 [S. D. Worley, TRIP, 4 , 364 (1996); T. Tashiro, Macromol. Mater. Eng., 286 , 63 (2001)].Research has been conducted on antibacterial or biocidal polymers in which a polymer material itself exhibits antimicrobial properties by directly binding a functional group having antimicrobial, bactericidal or mold resistance to the polymer chain [SD Worley, TRIP , 4 , 364 (1996); T. Tashiro, Macromol. Mater. Eng., 286 , 63 (2001).
일반적으로 항균성을 나타내는 유기 항균제로서는 4급 암모늄 염, 포스포늄 염, 피리딘 화합물, 유기 할로겐 화합물, 티아졸린 화합물, 페놀류 등이 알려져 있다. 이들 기능기가 복합적으로 결합되어 양이온성을 나타내는 화합물이 유효하다. 현재, 티아졸-이미다졸륨 염, 클로로페놀 화합물, 피리딘티올 옥사이드염, 니트로기 함유 모폴린 화합물, 염화 트리아진 화합물 등이 항균제로서 실용화되었다. In general, quaternary ammonium salts, phosphonium salts, pyridine compounds, organic halogen compounds, thiazolin compounds, phenols and the like are known as organic antimicrobial agents exhibiting antimicrobial properties. Compounds which combine these functional groups to show cationicity are effective. Currently, thiazole-imidazolium salts, chlorophenol compounds, pyridinethiol oxide salts, nitro group-containing morpholine compounds, triazine chloride compounds and the like have been put to practical use as antibacterial agents.
항균 기능을 갖는 고분자는 미생물의 세포막 및 세포벽의 손상, 효소 단백질의 변성 또는 호흡 저해를 야기하여 항균성을 나타낸다. 항균제가 세균에 대하여 활성을 나타내는 작용은 항균제의 물리·화학적 특성 및 세균과 세포 구조의 다양성에 의해서도 크게 영향을 받는다. Polymers having an antimicrobial function exhibit antimicrobial properties by causing damage to cell membranes and cell walls of microorganisms, degeneration of enzyme proteins or inhibition of respiration. The action of an antimicrobial agent on bacteria is greatly affected by the physical and chemical properties of the antimicrobial agent and the diversity of bacteria and cell structures.
암모늄 염 또는 포스포늄 염과 같은 다중 양이온성 고분자(polycation polymers)의 항균 활성이 우수하다. 이러한 항균 활성은 세균의 세포막이 다른 생명체와 마찬가지로 음이온성 인지질 이중층 막으로 구성되어 있어서 음/양이온의 정전기적 상호 작용이 쉽게 일어나고, 이에 따라 세포막이 파괴되어 세균이 사멸하기 때문인 것으로 알려져 있다. m-크레졸과 결합된 아크릴레이트 고분자 [김우식 등, 폴리머, 26권 3호, 293 (2002)], 통상 항균제로 이용되는 트리글로산(triclosan)과 결합된 아크릴레이트 고분자[ W. J. Cho et al., J. Appl. Polym. Sci., 54 , 859 (1994)], m-다이메틸아미노페놀의 암모늄 염이 결합된 폴리스타이렌[이연식, Bull. Korean Chem. Soc. , 23권 12호, 1833 (2002)], 4급 암모늄 염이 결합된 폴리실록산 [G. Sauvet et al., J. Appl. Polym. Sci. , 75, 1005 (2000)] 등이 항균성 고분자로서 보고되었다. 또한 셀룰로오스의 당 고리 구조 단위에 이중 고리 아민인 1,4-디아자바이사이클로[2,2,2]옥탄(1,4-diazabicyclo[2,2,2]octane, DABCO)의 암모늄 염을 결합시키는 경우에 우수한 항균 특성을 나타낸다고 보고되었다[T. Abel, R. Engel et al., Carbohydrate Chem., 337 , 2495 (2002)]. 이 때는 탄소 수 16개의 긴 알킬기가 치환된 경우에 항균 활성이 높은 것으로 보고되었다. 탄소 수 12개 이상의 긴 알킬 사슬을 갖는 암모늄염기를 갖는 폴리옥사졸린의 항균성 역시 매우 우수하다고 발표되었다 [C. J. Waschinski, J. C. Tiller, Biomacromolecules, 6, 235 (2005)].The antimicrobial activity of polycation polymers such as ammonium salts or phosphonium salts is excellent. This antimicrobial activity is known to be because the cell membrane of the bacteria is composed of an anionic phospholipid bilayer membrane like other organisms, so that the electrostatic interaction of negative / positive ions easily occurs, thereby destroying the cell membrane to kill the bacteria. acrylate polymers combined with m-cresol [Kim, et al., Polymer No. 26, No. 3, 293 (2002)], acrylate polymers combined with triclosan commonly used as antimicrobial agents [WJ Cho et al. , J. Appl. Polym. Sci., 54 , 859 (1994)], polystyrenes to which ammonium salts of m-dimethylaminophenol are bound . Korean Chem. Soc. , Vol. 23, 1833 (2002)], polysiloxanes bound with quaternary ammonium salts [G. Sauvet et al., J. Appl. Polym. Sci. , 75, 1005 (2000) and the like have been reported as antimicrobial polymers. In addition, the ammonium salt of 1,4-diazabicyclo [2,2,2] octane (1,4-diazabicyclo [2,2,2] octane, DABCO), which is a bicyclic amine, is bound to the sugar ring structural unit of cellulose. It was reported to exhibit excellent antimicrobial properties in the case [T. Abel, R. Engel et al., Carbohydrate Chem., 337 , 2495 (2002)]. In this case, it was reported that the antimicrobial activity was high when the long alkyl group having 16 carbon atoms was substituted. The antimicrobial activity of polyoxazolines with ammonium bases having 12 or more carbon chains of long alkyl chains has also been reported to be very good [CJ Waschinski, JC Tiller, Biomacromolecules, 6, 235 (2005)].
그 외에, 관련 특허 문헌으로는 대한민국 특허 제405030호(주/유레이), 대한민국 공개 특허 공보 제1999-0078100호(다이니치 사키세이카고교 가부사키가이샤), 미국 특허 제6,492,445(Stepan Company, Northfield, IL), 대한민국 공개 특허 공보 제 2000-0031489호(주식회사 에스케이씨) 등이 있다.In addition, related patent documents include Korean Patent No. 405030 (Note / Yurei), Korean Unexamined Patent Publication No. 1999-0078100 (Dainichi Saki Seika High School Kabusaki Kaisha), US Patent No. 6,492,445 (Stepan Company, Northfield, IL) ), And Korean Patent Application Publication No. 2000-0031489 (SKK Co., Ltd.).
항균 작용기가 결합된 항균성 고분자 재료는 세탁하여도 항균성이 유지되므로, 의류, 침구류, 의료용 섬유 제품에 대한 응용성이 매우 크다. 따라서 항균 작용기가 고분자 사슬에 직접 결합됨으로써, 고정된 상태에서도 높은 항균 활성을 나타내는 항균 고분자의 개발이 요청된다. Since the antimicrobial polymer material combined with the antimicrobial functional group is retained antimicrobial even after washing, it is very applicable to clothing, bedding, medical textile products. Therefore, since the antimicrobial functional group is directly bonded to the polymer chain, it is required to develop an antimicrobial polymer that exhibits high antibacterial activity even in a fixed state.
그러나, 현재까지 알려진 항균성 고분자는 아직 항균 활성이 불충분하고, 대부분 암모늄 염 상태이기 때문에 유기 용제에 불용성이며, 수용성이거나 또는 표면에 후가교 결합 반응된 형태이기 때문에 코팅 재료로 사용하기에는 적합하지 않았다. However, antimicrobial polymers known to date are not suitable for use as coating materials because they have insufficient antimicrobial activity and are insoluble in organic solvents because they are mostly ammonium salts, and are water-soluble or post-crosslinked to the surface.
또한, 기존의 항균제들은 일반적으로 첨가제 형태로 사용되기 때문에 과량으로 사용하게 되고, 첨가된 항균제의 일부만이 기질 표면에서 제한적으로 항균 작용을 나타내며, 항균제 첨가 제품은 일정 기간이 경과하면 사용 기간에 따라 지속적인 세척과 외부 노출 기간 경과 등으로 인하여 유효한 항균제 성분이 감소되어 항균 활성이 급격히 감소하는 경향이 있다. In addition, the conventional antimicrobial agents are generally used in the form of additives and are used in excess, and only a part of the added antimicrobial agents exhibits limited antimicrobial activity on the surface of the substrate. The effective antimicrobial component decreases due to the lapse of washing and external exposure period, and thus the antimicrobial activity tends to decrease rapidly.
그러므로 우수한 항균 활성을 가지며, 광경화성이어서, 건축 내장 재료, 각종 전자 기기, 생활 용품, 포장재, 식품 용기 등의 표면에 광경화 반응을 이용하여 용이하게 코팅할 수 있는 항균성 단량체와 고분자 재료의 개발이 요구되고 있다. Therefore, it has excellent antimicrobial activity and is photocurable, so that the development of antimicrobial monomers and polymer materials that can be easily coated on the surface of building interior materials, various electronic devices, household goods, packaging materials, food containers, etc. using photocuring reactions It is required.
본 발명의 목적은 수용성 및 유기 용제 가용성이어서 다른 단량체와 혼합이 잘되는 항균 활성 이미다졸륨 염을 포함하는 새로운 형태의 항균성 단량체, 이를 포함하는 광경화형 항균성 조성물 및 상기 조성물로부터 제조되는 표면 코팅용 항균성 고분자 재료를 제공하는 것이다. An object of the present invention is a novel type of antimicrobial monomer comprising an antimicrobial active imidazolium salt which is water soluble and organic solvent soluble and well mixed with other monomers, a photocurable antimicrobial composition comprising the same and an antimicrobial polymer for surface coating prepared from the composition. To provide the material.
전술한 본 발명의 목적은 인체 내 히스티딘 아미노산의 구성 성분인 이미다졸에 광중합성 아크릴과 메타크릴기를 도입하고, 치환된 알킬기 탄소의 개수를 달리하여 여러 가지 작용기를 치환시켜 항균성을 극대화한 이미다졸륨 염 단량체를 제조하고, 이를 광경화하여 항균 코팅용 고분자 재료를 제공하는 것에 의하여 달성된다. The object of the present invention described above is to introduce photopolymerizable acrylic and methacryl groups into the imidazole, which is a component of histidine amino acid in the human body, and to immobilize various functional groups by varying the number of substituted alkyl group carbons, thereby maximizing antibacterial activity. It is achieved by preparing a salt monomer and photocuring it to provide a polymeric material for antimicrobial coating.
따라서, 본 발명은 인체 내에서 필수아미노산인 히스티딘의 중요한 구성 성분이면서 항균 작용이 우수하여 수용성 항균제로서 상품화되어 있는 이미다졸륨 염에 광중합성 탄소-탄소 이중 결합을 형성시킨 항균성 이미다졸륨 염 단량체, 이를 포함하는 광경화형 항균성 조성물 및 상기 조성물로부터 제조되는 표면 코팅용 항균성 고분자 재료에 관한 것이다. Accordingly, the present invention provides an antimicrobial imidazolium salt monomer which forms a photopolymerizable carbon-carbon double bond in an imidazolium salt which is an important component of histidine, an essential amino acid in the human body, and has excellent antibacterial activity and is commercialized as a water-soluble antimicrobial agent. It relates to a photocurable antimicrobial composition comprising the same and an antimicrobial polymer material for surface coating prepared from the composition.
본 발명에 따른 광경화형 항균성 이미다졸륨 염 단량체는 아래의 화학식 1로 표시된다. The photocurable antimicrobial imidazolium salt monomer according to the present invention is represented by the following formula (1).
식 중에서, X-는 염소 이온, 브롬 이온, BF4 -, PF6 -, SbF6 -, NO3 -, CF3SO3 -, (CF3SO3)2N-, ArSO3 -, CF3CO2 -, CH3CO2 - 등의 음이온이고, In formula, X - is a chlorine ion, bromine ion, BF 4 -, PF 6 - , SbF 6 -, NO 3 -, CF 3 SO 3 -, (CF 3 SO 3) 2 N -, ArSO 3 -, CF 3 an anion, such as, - CO 2 -, CH 3 CO 2
m은 1~12의 정수이며, m is an integer from 1 to 12,
R1은 H 또는 CH3를 나타내며, R 1 represents H or CH 3 ,
R2와 R3은 (CH2)xY로 표시되는 알킬기로서, x는 0~20의 정수이고, Y는 불소, 염소 및 브롬 중에서 선택되는 할로겐 원자, H, NH2, OH 또는 CO2H 등의 관능기를 나타낸다.R 2 and R 3 are alkyl groups represented by (CH 2 ) x Y, where x is an integer from 0 to 20, Y is a halogen atom selected from fluorine, chlorine and bromine, H, NH 2 , OH or CO 2 H Functional groups, such as these, are shown.
본 발명은 환경 안정성이 우수한 이온성 액체로서 잘 알려진 이미다졸륨 염을 항균 기능을 갖는 냄새 없는 광중합성 메타크릴산과 아크릴에스터 단량체를 제조하고, 이를 광경화형 항균 기능 코팅재로 이용하는 것을 특징으로 한다. The present invention is characterized by preparing an odorless photopolymerizable methacrylic acid and an acrylic ester monomer having an antibacterial function as an imidazolium salt which is well known as an ionic liquid having excellent environmental stability, and using it as a photocurable antibacterial functional coating material.
상기 화학식 1의 이미다졸륨 염 단량체는 생태계에 위해성이 낮으며, 유기 용제를 사용하지 않는 친환경적인 광경화로서 용이하게 표면 코팅할 수 있으므로, 항균 처리가 요구되는 기질에 코팅함으로써 반영구적으로 항균 작용이 나타나도록 할 수 있다. The imidazolium salt monomer of Formula 1 has low risk to the ecosystem, and can be easily surface coated as an environmentally friendly photocuring agent without using an organic solvent. You can make it appear.
상기 화학식 1로 표시되는 항균성 광경화형 이미다졸륨 염 단량체는 하기 반응식 1에 예시된 바와 같이 말단에 브롬 또는 염소와 같은 할로겐 원자를 갖는 탄소 수 1 내지 12개의 알킬 아크릴레이트 또는 알킬 메타아크릴레이트를 R2 및 R3으로 치환된 이미다졸과 반응시켜 제조될 수 있다.The antimicrobial photocurable imidazolium salt monomer represented by Chemical Formula 1 may be an alkyl acrylate or alkyl methacrylate having 1 to 12 carbon atoms having a halogen atom such as bromine or chlorine at the end as illustrated in Scheme 1 below. It can be prepared by reacting with imidazole substituted with 2 and R 3 .
식 중에서, m, R1, R2 및 R3은 화학식 1에서 정의한 것과 동일한 것이고, Wherein m, R 1 , R 2 and R 3 are the same as defined in Formula 1,
Z는 염소 및 브롬 중에서 선택되는 할로겐 원자로서, 상기 반응식 1에 나타낸 반응의 후속 반응에 의하여 BF4 -, PF6 -, SbF6 -, NO3 -, CF3SO3 -, (CF3SO3)2N-, ArSO3 -, CF3CO2 - 또는 CH3CO2 -로 치환될 수 있다. Z is a halogen atom selected from chlorine and bromine, BF 4 by subsequent reaction of the reaction shown in above Scheme 1 -, PF 6 -, SbF 6 -, NO 3 -, CF 3 SO 3 -, (CF 3 SO 3 ) 2 N -, ArSO 3 - , CF 3 CO 2 - may be substituted with - or CH 3 CO 2.
"광경화 수지(UV-curable resin) 조성물" 또는 "광경화성 조성물"이라는 것은 단파장의 자외선을 조사하여 일어나는 광화학 반응에 의하여 단시간 내에 광중합 및 가교결합 경화되는 액상 수지 조성물을 말한다. 광경화 수지 조성물은 통상적으로 감광성 프레폴리머와 희석제인 다관능성 (메타)아크릴산 에스터[multifunctional (metha)acrylates] 및 광개시제(photoinitiator)가 배합된 것 이다. 이 조성물에 자외선을 노광하면 광개시제로부터 자유 라디칼이 생성되어 프레폴리머와 희석제에서 중합성 (메타)아크릴기의 연쇄 중합이 개시되고, 그 결과 가교 결합 반응이 피막 전체에서 일어나 물성이 우수한 불용성 피막이 형성된다. The term "UV-curable resin composition" or "photocurable composition" refers to a liquid resin composition which is photopolymerized and crosslinked and cured in a short time by a photochemical reaction generated by irradiating short wavelength ultraviolet rays. The photocurable resin composition is a mixture of a photosensitive prepolymer and a difunctional multifunctional (meth) acrylates and a photoinitiator. Exposure to ultraviolet light to this composition generates free radicals from the photoinitiator to initiate chain polymerization of polymerizable (meth) acrylic groups in the prepolymer and diluent, resulting in a crosslinking reaction throughout the coating to form an insoluble coating having excellent physical properties. .
이러한 광경화 과정에 필요한 시간은 보통 수초에서 1분 미만이며, 경화 반응이 신속하게 일어나야 효율적인 광경화성 수지로 이용될 수 있다. 광경화 수지에서는 광중합 반응이 중요하다. 이것은 광에 의한 중합과 가교 반응이 동시에 신속하게 진행되어 기질에 피막으로 도포된 수지의 경화와 불용성화가 완전하게 일어나야만 피막 코팅재로서 원하는 물성과 특성을 충족할 수 있기 때문이다.The time required for this photocuring process is usually a few seconds to less than 1 minute, the curing reaction must occur quickly to be used as an efficient photocurable resin. In photocuring resin, photopolymerization reaction is important. This is because the polymerization and crosslinking reaction by the light proceeds at the same time so that the curing and insolubilization of the resin coated on the substrate can be completed to satisfy the desired physical properties and properties as the coating coating material.
감광성 프레폴리머 및 다관능성 단량체(희석제), 광개시제가 광경화 수지의 필수 3대 성분이며, 그 외에 수지의 용도에 따라 광증감제, 안료, 충전제, 레블링제, 중합 금지제 등이 첨가된다. 통상적으로 광경화 수지는 감광성 프레폴리머 50-60%, 다관능성 단량체(희석제) 30-40%, 광개시제 0.1-10%로 배합되어 조성된다. 감광성 프레폴리머는 점도가 높기 때문에 직접 도료나 코팅제로 사용할 수 없으므로, 희석제를 첨가하여 점도를 감소시켜 조성물의 가공성을 개선한다. 희석제는 광경화 수지의 경화 속도를 증가시키고, 물성을 증진시키는 역할을 하는 것으로서, 그 예로는 저 점도의 광중합성 이관능성 또는 삼관능성 트라이메틸롤프로판 트라이(메타)아크릴산 에스터, 다이에틸렌글리콜 다이(메타)아크릴레이트, 또는 일관능성 (메타)아크릴산 에스터, 엔-비닐피롤리돈과 같은 단량체를 들 수 있다.A photosensitive prepolymer, a polyfunctional monomer (diluent), and a photoinitiator are three essential components of a photocuring resin, In addition, a photosensitizer, a pigment, a filler, a labelling agent, a polymerization inhibitor, etc. are added according to the use of resin. Typically, the photocurable resin is formulated by mixing 50-60% of a photosensitive prepolymer, 30-40% of a polyfunctional monomer (diluent), and 0.1-10% of a photoinitiator. Since the photosensitive prepolymer cannot be directly used as a paint or coating agent because of its high viscosity, a diluent may be added to decrease the viscosity to improve processability of the composition. The diluent increases the curing rate of the photocuring resin and improves physical properties, such as low viscosity photopolymerizable di- or tri-functional trimethylolpropane tri (meth) acrylic acid ester, diethylene glycol die ( And monomers such as meta) acrylate or monofunctional (meth) acrylic acid ester and en-vinylpyrrolidone.
일반적으로 감광성 프레폴리머는 광경화 수지의 최종 경화 상태에서 물성과 용도에 맞는 특성을 부여하는 성분으로 작용한다. 많은 종류의 아크릴산 에스터 감 광성 프레폴리머 중에서 통상적으로 에폭시 (메타)아크릴레이트, 실록산 (메타)아크릴레이트 및 우레탄 (메타)아크릴레이트가 상업화되어 공급된다. In general, the photosensitive prepolymer acts as a component to impart properties suitable for physical properties and applications in the final curing state of the photocurable resin. Among many kinds of acrylic ester photosensitive prepolymers, epoxy (meth) acrylates, siloxane (meth) acrylates and urethane (meth) acrylates are commonly supplied commercially.
대부분의 실용화된 광개시제는 방향족 카르보닐 화합물인데, 그 대표적인 예로는 다이알킬-하이드록시-아세토페논, 다이메톡시-페닐-아세토페논, 벤조인알킬 이서, 또는 벤조페논이나 티오크산톤 유도체에 알킬아민을 부가한 제품이 알려져 있다.Most practical photoinitiators are aromatic carbonyl compounds, representative examples of which are dialkyl-hydroxy-acetophenone, dimethoxy-phenyl-acetophenone, benzoinalkyl isomer, or alkylamine to benzophenone or thioxanthone derivatives. Products with the addition of are known.
또한, 본 발명에서는 상기 화학식 1로 표시되는 항균성 이미다졸륨 염 단량체를 포함하는 항균성 광경화형 조성물이 제공된다. 이 조성물은 화학식 1로 표시되는 항균성 이미다졸륨 염 단량체를 필수 성분으로 포함하고, 임의 성분으로서 앞에 예시한 것과 같은 감광성 프레폴리머, 희석제인 동시에 가교결합제인 트라이메틸롤프로판 트라이아크릴레이트, 광개시제 등을 포함할 수 있다. In addition, the present invention provides an antimicrobial photocurable composition comprising an antimicrobial imidazolium salt monomer represented by the formula (1). The composition comprises an antimicrobial imidazolium salt monomer represented by the formula (1) as an essential component, and optionally contains a photosensitive prepolymer as exemplified above, a diluent and a crosslinker trimethylolpropane triacrylate, a photoinitiator and the like. It may include.
예로서, 상기 조성물은 조성물 총 중량을 기준으로 상기 화학식 1로 표시되는 항균성 이미다졸륨 염 단량체 3-40%, 통상의 감광성 프레폴리머 50-60%, 통상의 다관능성 단량체(희석제) 30-40% 및 통상의 광개시제 1-10%를 포함할 수 있다.By way of example, the composition may comprise 3-40% of the antimicrobial imidazolium salt monomer represented by Formula 1, 50-60% of a typical photosensitive prepolymer, 30-40 of a conventional multifunctional monomer (diluent) based on the total weight of the composition % And 1-10% of conventional photoinitiators.
또한, 본 발명은 상기 화학식 1로 표시되는 항균성 이미다졸륨 염 단량체를 필수적으로 포함하는 항균성 광경화형 조성물의 광중합으로 제조되는 항균성 고분자 재료에 관한 것이다.The present invention also relates to an antimicrobial polymer material prepared by photopolymerization of an antimicrobial photocurable composition comprising essentially the antimicrobial imidazolium salt monomer represented by Formula 1.
또한, 본 발명은 상기 화학식 1로 표시되는 항균성 이미다졸륨 염 단량체를 필수적으로 사용하여 라디칼 중합으로 제조되는, 하기 화학식 2로 표시되는 (공)중합체에 관한 것이다. The present invention also relates to a (co) polymer represented by the following Chemical Formula 2, which is prepared by radical polymerization using an antimicrobial imidazolium salt monomer represented by the above Chemical Formula 1.
식 중에서, X, m, R1, R2 및 R3은 화학식 1에서 정의한 것과 동일한 것이고, Wherein X, m, R 1 , R 2 and R 3 are the same as defined in the formula (1),
M은 본 발명 분야에 알려져 있는 다양한 구조의 공단량체로부터 유래되는 반복 단위로서, 예를 들면, (메타)아크릴산, (메타)아크릴산에스터계, 비닐아세테이트, 아크릴로니트릴, (메타)아크릴아미드계, 스타이렌계, 부타디엔계 등의 상용화된 비닐 단량체가 모두 포함되며, M is a repeating unit derived from comonomers of various structures known in the present invention, for example, (meth) acrylic acid, (meth) acrylic acid ester system, vinyl acetate, acrylonitrile, (meth) acrylamide system, All commercialized vinyl monomers such as styrene and butadiene are included.
화학식 1의 항균성 이미다졸륨 염 단량체 성분의 분율 a는 3~100%, 공단량체 A의 분율 b는 0~97%이며, a +b = 100이다. The fraction a of the antimicrobial imidazolium salt monomer component of the formula (1) is 3 to 100%, the fraction b of the comonomer A is 0 to 97%, and a + b = 100.
실시예Example
이하에서는 본 발명을 실시예를 통하여 더욱 상세히 설명한다. 그러나 실시예는 본 발명의 예시에 불과할 뿐, 본 발명의 범위가 이에 한정되는 것은 아니다.Hereinafter, the present invention will be described in more detail with reference to Examples. However, the embodiments are only examples of the present invention, and the scope of the present invention is not limited thereto.
실시예 1: 3-클로로프로필 아크릴레이트 합성Example 1: 3-chloropropyl acrylate synthesis
3-클로로-1-프로판올 9.45g (0.10mol)을 테트라히드로퓨란 (THF) 50ml에 녹 인다. 트리에틸아민 15.20g (0.15mol)을 넣고 상온에서 1시간 동안 교반시키며 반응시킨다. 반응기 온도를 얼음 냉탕에서 0℃로 조절한 후 아크릴로일 클로라이드 18.10g (0.2mol)을 천천히 부가한다. 5시간 동안 실온에서 반응 시키고 나서테트라히드로퓨란을 감압 증류하고 반응 혼합물을 에틸아세테이트와 물로 추출한다. 용매를 감압 증류하고 건조하여 연황색의 액체 생성물을 수득한다.Dissolve 9.45 g (0.10 mol) of 3-chloro-1-propanol in 50 ml of tetrahydrofuran (THF). 15.20 g (0.15 mol) of triethylamine were added thereto, followed by reaction at room temperature for 1 hour. The reactor temperature is adjusted to 0 ° C. in ice cold water followed by the slow addition of 18.10 g (0.2 mol) of acryloyl chloride. After reacting at room temperature for 5 hours, tetrahydrofuran was distilled off under reduced pressure, and the reaction mixture was extracted with ethyl acetate and water. The solvent is distilled off under reduced pressure and dried to give a light yellow liquid product.
수율 10.80g (73%)Yield 10.80 g (73%)
1H NMR (CDCl3, 200MHz) 6.4 (d, 1H), 6.1 (m, 1H), 5.8 (d, 1H), 4.3 (t, 2H), 3.6 (t, 2H), 2.1 (m,2H). 1 H NMR (CDCl 3 , 200 MHz) 6.4 (d, 1H), 6.1 (m, 1H), 5.8 (d, 1H), 4.3 (t, 2H), 3.6 (t, 2H), 2.1 (m, 2H) .
실시예 2: 3-클로로프로필 메타아크릴레이트 합성Example 2: 3-chloropropyl methacrylate synthesis
3-클로로-1-프로판올 47.30g (0.50mol)을 테트라히드로퓨란 (THF) 150ml에 녹인다. 트리에틸아민 50.60g (0.50mol)을 넣고 상온에서 1시간 동안 교반시키며 반응시킨다. 반응기 온도를 얼음 냉탕에서 0℃로 조절한 후 메타아크릴로일 클로라이드 63.30g (0.60mol)을 천천히 부가한다. 5시간 동안 실온에서 반응 시키고 나서 테트라히드로퓨란을 감압 증류하고 반응 혼합물을 에틸아세테이트와 물로 추출한다. 용매를 감압 증류하고 건조하여 연황색의 액체 생성물을 수득한다.47.30 g (0.50 mol) of 3-chloro-1-propanol are dissolved in 150 ml of tetrahydrofuran (THF). 50.60 g (0.50 mol) of triethylamine were added thereto, followed by reaction at room temperature for 1 hour. The reactor temperature is adjusted to 0 ° C. in ice cold water followed by the slow addition of 63.30 g (0.60 mol) of methacryloyl chloride. After reacting at room temperature for 5 hours, tetrahydrofuran was distilled off under reduced pressure, and the reaction mixture was extracted with ethyl acetate and water. The solvent is distilled off under reduced pressure and dried to give a light yellow liquid product.
수율 58.50g (66%)Yield 58.50 g (66%)
1H NMR (CDCl3, 200MHz) 6.1 (s, 1H), 5.5 (s, 1H), 4.3 (m, 2H), 3.6 (t, 2H), 2.1 (m,2H), 1.9 (s, 3H) 1 H NMR (CDCl 3 , 200 MHz) 6.1 (s, 1H), 5.5 (s, 1H), 4.3 (m, 2H), 3.6 (t, 2H), 2.1 (m, 2H), 1.9 (s, 3H)
실시예 3: 2-브로모에틸 메타아크릴레이트 합성Example 3: 2-bromoethyl methacrylate synthesis
2-브로모에탄올 10.00g (0.080mol)을 테트라히드로퓨란 100ml에 녹인다. 트리에틸아민 8.00g (0.080mol)을 넣고 상온에서 1시간 동안 교반시키면서 반응시킨다. 반응기 온도를 얼음 냉탕에서 0℃로 조절한 후 메타아크릴로일 클로라이드 10.00g (0.096mol)을 천천히 부가한다. 5시간 동안 실온에서 반응 시키고 나서 테트라히드로퓨란을 감압 증류하고 반응 혼합물을 에틸아세테이트와 물로 추출한다. 용매를 감압 증류하고 건조하여 연황색의 액체 생성물을 수득한다.Dissolve 10.00 g (0.080 mol) of 2-bromoethanol in 100 ml of tetrahydrofuran. 8.00 g (0.080 mol) of triethylamine was added thereto, followed by reaction with stirring at room temperature for 1 hour. The reactor temperature is adjusted to 0 ° C. in ice cold water followed by the slow addition of 10.00 g (0.096 mol) of methacryloyl chloride. After reacting at room temperature for 5 hours, tetrahydrofuran was distilled off under reduced pressure, and the reaction mixture was extracted with ethyl acetate and water. The solvent is distilled off under reduced pressure and dried to give a light yellow liquid product.
수율 13.70g (89%)Yield 13.70 g (89%)
1H NMR (CDCl3, 200MHz) 6.1 (s, 1H), 5.5 (s, 1H), 4.3 (m, 2H), 3.6 (t, 2H), 2.1 (m,2H), 1.9 (s, 3H) 1 H NMR (CDCl 3 , 200 MHz) 6.1 (s, 1H), 5.5 (s, 1H), 4.3 (m, 2H), 3.6 (t, 2H), 2.1 (m, 2H), 1.9 (s, 3H)
실시예 4: 1-헥실이미다졸 합성Example 4: 1-hexylimidazole synthesis
다이메틸포름아미드 40ml에 이미다졸 10.0g (0.147mol)을 상온에서 녹인다. 상온에서 NaH 3.5g (0.147mol)을 천천히 가한 다음 2시간 교반시키며 반응시킨다. 1-브로모헥산 12.13g (0.074mol)을 가하여 5시간 동안 실온에서 반응시킨다. 반응 종료 후 200ml의 메틸렌클로라이드와 40ml의 물로 추출한다. 메틸렌클로라이드를 감압 증류하고 건조하여 무색의 액체 생성물을 수득한다.Dissolve 10.0 g (0.147 mol) of imidazole in 40 ml of dimethylformamide at room temperature. NaH 3.5g (0.147mol) was added slowly at room temperature, followed by stirring for 2 hours. 12.13 g (0.074 mol) of 1-bromohexane was added and reacted at room temperature for 5 hours. After completion of the reaction, the mixture was extracted with 200 ml of methylene chloride and 40 ml of water. Methylene chloride is distilled under reduced pressure and dried to give a colorless liquid product.
수율 17.60 g (78%)Yield 17.60 g (78%)
1H NMR (CDCl3, 200MHz) 7.4 (s, 1H), 7.0 (s, 1H), 6.8 (s, 1H), 3.9 (t, 2H), 1.7 (m, 2H), 1.25~1.98 (m, 6H), 0.9 (t, 3H). 1 H NMR (CDCl 3 , 200 MHz) 7.4 (s, 1H), 7.0 (s, 1H), 6.8 (s, 1H), 3.9 (t, 2H), 1.7 (m, 2H), 1.25-1.98 (m, 6H), 0.9 (t, 3H).
실시예 5: 1-도데실이미다졸 합성Example 5: 1-dodecylimidazole synthesis
다이메틸포름아미드 40ml에 이미다졸 20.0g (0.294mol)을 상온에서 녹인다. NaH 7.0g (0.294mol)을 천천히 가한 다음 2시간 교반시키며 반응시킨다. 1-브로모도데칸 36.6g (0.147mol)을 가하여 5시간 동안 상온에서 반응시킨다. 반응 종료 후 200ml의 메틸렌클로라이드와 40ml의 물로 추출한다. 메틸렌클로라이드를 감압 증류하고 건조하여 무색의 액체 화합물을 수득한다.Dissolve 20.0 g (0.294 mol) of imidazole in 40 ml of dimethylformamide at room temperature. NaH 7.0g (0.294mol) was added slowly, followed by stirring for 2 hours. 36.6 g (0.147 mol) of 1-bromododecane was added thereto and allowed to react at room temperature for 5 hours. After completion of the reaction, the mixture was extracted with 200 ml of methylene chloride and 40 ml of water. Methylene chloride is distilled under reduced pressure and dried to give a colorless liquid compound.
수율 39.70 g (57%)Yield 39.70 g (57%)
1H NMR (CDCl3, 200MHz) 7.4 (s, 1H), 7.0 (s, 1H), 6.8 (s, 1H), 3.9 (t, 2H), 1.7 (m, 2H), 1.25~1.98 (m, 18H), 0.8 (t, 3H). 1 H NMR (CDCl 3 , 200 MHz) 7.4 (s, 1H), 7.0 (s, 1H), 6.8 (s, 1H), 3.9 (t, 2H), 1.7 (m, 2H), 1.25-1.98 (m, 18H), 0.8 (t, 3H).
실시예 6: 3-메틸-1-(3-아크릴로일옥시프로필)이미다졸륨 클로라이드 합성Example 6: 3-methyl-1- (3-acryloyloxypropyl) imidazolium chloride synthesis
실시예 1에서 합성한 클로로 아크릴레이트 화합물 5.73g (0.039mol)을 디메틸설폭사이드 (DMSO) 20ml에 녹이고 1-메틸이미다졸 6.57g (0.08mol)을 넣고 온도 50℃에서 6시간 동안 교반시키며 반응시킨다. 반응 종료 후 용매를 감압 증류하고 잔여물을 과량의 디에틸에테르에 침전 시키면 끈끈한 연황갈색 점성의 액체 생성물을 수득한다. 5.73 g (0.039 mol) of the chloro acrylate compound synthesized in Example 1 was dissolved in 20 ml of dimethyl sulfoxide (DMSO), and 6.57 g (0.08 mol) of 1-methylimidazole was added thereto, followed by stirring at 50 ° C. for 6 hours. Let's do it. After completion of the reaction, the solvent was distilled off under reduced pressure and the residue was precipitated in excess of diethyl ether to give a sticky pale brown viscous liquid product.
수율 7.30 g (81 %)Yield 7.30 g (81%)
1H NMR (CDCl3, 200MHz) 9.3 (s, 1H), 7.8 (s, 1H), 7.7 (s, 1H), 6.3 (d, 1H), 6.2~6.1 (m, 1H), 6.0~5.9 (d, 1H), 4.3 (t, 2H), 4.2 (t, 2H), 3.8 (s, 3H), 2.2 (m,2H). 1 H NMR (CDCl 3 , 200 MHz) 9.3 (s, 1H), 7.8 (s, 1H), 7.7 (s, 1H), 6.3 (d, 1H), 6.2 to 6.1 (m, 1H), 6.0 to 5.9 ( d, 1H), 4.3 (t, 2H), 4.2 (t, 2H), 3.8 (s, 3H), 2.2 (m, 2H).
실시예 7: 3-메틸-1-(3-메타크릴로일옥시프로필)이미다졸륨 클로라이드 합성Example 7: 3-methyl-1- (3-methacryloyloxypropyl) imidazolium chloride synthesis
실시예 2에서 합성한 클로로 메타아크릴레이트 화합물6.50g (0.04mol)을 디메틸설폭사이드 (DMSO) 20ml에 녹이고 1-메틸이미다졸 6.57g (0.08mol)을 넣고 온도 50℃에서 6시간 동안 교반시키며 반응시킨다. 반응 종료 후 용매를 감압 증류하 고 잔여물을 과량의 디에틸에테르에 침전 시키면 끈끈한 약간 황갈색의 액체 생성물을 수득한다. 6.50 g (0.04 mol) of the chloro methacrylate compound synthesized in Example 2 was dissolved in 20 ml of dimethyl sulfoxide (DMSO), and 6.57 g (0.08 mol) of 1-methylimidazole was added thereto and stirred at a temperature of 50 ° C. for 6 hours. React. After completion of the reaction, the solvent was distilled off under reduced pressure, and the residue was precipitated in excess of diethyl ether to give a sticky, slightly yellowish liquid product.
수율 8.40 g (86 %)Yield 8.40 g (86%)
1H NMR (DMSO, 200MHz) 9.5 (s, 1H), 7.8 (s, 1H), 7.7 (s, 1H), 6.0 (s, 1H), 5.7 (s, 1H), 4.3 (t, 2H), 4.2 (t, 2H), 3.8 (s, 3H), 2.2 (m, 2H), 1.8 (s, 3H). 1 H NMR (DMSO, 200 MHz) 9.5 (s, 1H), 7.8 (s, 1H), 7.7 (s, 1H), 6.0 (s, 1H), 5.7 (s, 1H), 4.3 (t, 2H), 4.2 (t, 2H), 3.8 (s, 3H), 2.2 (m, 2H), 1.8 (s, 3H).
실시예 8: 3-메틸-1-(2-메타크릴로일옥시에틸)이미다졸륨 브로마이드 합성Example 8: 3-methyl-1- (2-methacryloyloxyethyl) imidazolium bromide synthesis
실시예 3에서 합성한 브로모 메타아크릴레이트 화합물5.00g (0.026mol)을 디메틸술포사이드 (DMSO) 20ml에 녹이고 1-메틸이미다졸 2.13g (0.026mol)을 넣고 온도 50℃에서 6시간 동안 교반시키며 반응시킨다. 반응 종료 후 용매를 감압 증류하고 잔여물을 과량의 디에틸에테르에 침전 시키면 끈끈한 약간 황갈색의 액체 생성물을 수득한다.5.00 g (0.026 mol) of the bromo methacrylate compound synthesized in Example 3 was dissolved in 20 ml of dimethylsulfoside (DMSO), and 2.13 g (0.026 mol) of 1-methylimidazole was added thereto and stirred at a temperature of 50 ° C. for 6 hours. And react. After completion of the reaction, the solvent was distilled off under reduced pressure and the residue was precipitated in an excess of diethyl ether to give a sticky slightly yellowish liquid product.
수율 5.35 g (75%)Yield 5.35 g (75%)
실시예 9: 3-부틸-1-(2-메타크릴로일옥시에틸)이미다졸륨 브로마이드 합성Example 9: 3-butyl-1- (2-methacryloyloxyethyl) imidazolium bromide synthesis
실시예 3에서 합성한 브로모 메타아크릴레이트 화합물5.00g (0.026mol)을 디 메틸술폭사이드 (DMSO) 20ml에 녹이고 부틸이미다졸3.23g (0.026mol)을 넣고 온도 50℃에서 6시간 동안 교반시키며 반응시킨다. 반응 종료 후 용매를 감압 증류하고 잔여물을 과량의 디에틸에테르에 침전 시키면 끈끈한 약간 황갈색의 액체 생성물을 수득한다. 5.00 g (0.026 mol) of the bromo methacrylate compound synthesized in Example 3 was dissolved in 20 ml of dimethyl sulfoxide (DMSO), and 3.23 g (0.026 mol) of butylimidazole was added thereto and stirred at a temperature of 50 ° C. for 6 hours. React. After completion of the reaction, the solvent was distilled off under reduced pressure and the residue was precipitated in an excess of diethyl ether to give a sticky slightly yellowish liquid product.
수율 6.75 g (82 %)Yield 6.75 g (82%)
1H NMR (DMSO, 200MHz) 9.4 (s, 1H), 7.8 (m, 2H), 5.9 (s, 1H), 5.7 (s, 1H), 4.3 (t, 2H), 4.2 (m, 4H), 2.2 (m, 2H), 1.8 (s, 3H), 1.7 (m, 2H), 1.2 (m, 2H), 0.9 (t, 3H). 1 H NMR (DMSO, 200 MHz) 9.4 (s, 1H), 7.8 (m, 2H), 5.9 (s, 1H), 5.7 (s, 1H), 4.3 (t, 2H), 4.2 (m, 4H), 2.2 (m, 2H), 1.8 (s, 3H), 1.7 (m, 2H), 1.2 (m, 2H), 0.9 (t, 3H).
실시예 10: 3-헥실-1-(3-메타크릴로일옥시프로필)이미다졸륨 클로라이드 합성Example 10 3-hexyl-1- (3-methacryloyloxypropyl) imidazolium chloride synthesis
실시예 2에서 합성한 클로로 메타아크릴레이트 화합물6.50g (0.04mol)을 디메틸술폭사이드 (DMSO) 20ml에 녹이고 실시예 4에서 합성한 1- 헥실이미다졸 6.09g (0.04mol)을 넣고 온도 50℃에서 6시간 동안 교반시키며 반응시킨다. 반응 종료 후 용매를 감압 증류하고 잔여물을 과량의 디에틸에테르에 침전 시키면 끈끈한 약간 황갈색의 액체 생성물을 수득한다.6.50 g (0.04 mol) of the chloro methacrylate compound synthesized in Example 2 was dissolved in 20 ml of dimethyl sulfoxide (DMSO), and 6.09 g (0.04 mol) of 1-hexylimidazole synthesized in Example 4 was added thereto at a temperature of 50 ° C. The reaction is stirred for 6 hours at. After completion of the reaction, the solvent was distilled off under reduced pressure and the residue was precipitated in an excess of diethyl ether to give a sticky slightly yellowish liquid product.
수율 8.30 g (66 %)Yield 8.30 g (66%)
1H NMR (DMSO, 200MHz) 9.4 (s, 1H), 7.8 (m, 2H), 5.9 (s, 1H), 5.7 (s, 1H), 4.2 (m, 4H), 1.8 (s, 3H), 1.7 (m, 2H), 1.4 (m, 10H), 0.9 (t, 3H). 1 H NMR (DMSO, 200 MHz) 9.4 (s, 1H), 7.8 (m, 2H), 5.9 (s, 1H), 5.7 (s, 1H), 4.2 (m, 4H), 1.8 (s, 3H), 1.7 (m, 2H), 1.4 (m, 10H), 0.9 (t, 3H).
실시예 11: 3-헥실-1-(2-메타크릴로일옥시에틸)이미다졸륨 브로마이드 합성Example 11: 3-hexyl-1- (2-methacryloyloxyethyl) imidazolium bromide synthesis
실시예 3에서 합성한 브로모 메타아크릴레이트 화합물5.00g (0.026mol)을 디메틸술폭사이드 (DMSO) 20ml에 녹이고 실시예 4에서 합성한 1- 헥실이미다졸 3.94 (0.026mol)을 넣고 온도 50℃에서 6시간 동안 교반시키며 반응시킨다. 반응 종료 후 용매를 감압 증류하고 잔여물을 과량의 디에틸에테르에 침전 시키면 끈끈한 약간 황갈색의 액체 생성물을 수득한다.5.00 g (0.026 mol) of the bromo methacrylate compound synthesized in Example 3 was dissolved in 20 ml of dimethyl sulfoxide (DMSO), and 3.94 (0.026 mol) of 1-hexylimidazole synthesized in Example 4 was added thereto at a temperature of 50 ° C. The reaction is stirred for 6 hours at. After completion of the reaction, the solvent was distilled off under reduced pressure and the residue was precipitated in an excess of diethyl ether to give a sticky slightly yellowish liquid product.
수율 7.10 g (79 %)Yield 7.10 g (79%)
1H NMR (DMSO, 200MHz) 9.4 (s, 1H), 7.8 (m, 2H), 5.9 (s, 1H), 5.7 (s, 1H), 4.2 (m, 4H), 1.8 (s, 3H), 1.7 (m, 2H), 1.4 (m, 10H), 0.9 (t, 3H). 1 H NMR (DMSO, 200 MHz) 9.4 (s, 1H), 7.8 (m, 2H), 5.9 (s, 1H), 5.7 (s, 1H), 4.2 (m, 4H), 1.8 (s, 3H), 1.7 (m, 2H), 1.4 (m, 10H), 0.9 (t, 3H).
실시예 12: 3-도데실-1-(3-메타크릴로일옥시프로필)이미다졸륨 클로라이드 합성Example 12 Synthesis of 3-dodecyl-1- (3-methacryloyloxypropyl) imidazolium chloride
실시예 2에서 합성한 클로로 메타아크릴레이트 화합물6.50g (0.04mol)을 디메틸술폭사이드 (DMSO) 20ml에 녹이고 실시예 5에서합성한 1-도데실이미다졸 9.45g (0.04mol)을 넣고 온도 50℃에서 6시간 동안 교반시키며 반응시킨다. 반응 종료 후 용매를 감압 증류하고 잔여물을 과량의 디에틸에테르에 침전 시키면 끈끈한 약간 황갈색의 액체 생성물을 수득한다.6.50 g (0.04 mol) of the chloro methacrylate compound synthesized in Example 2 was dissolved in 20 ml of dimethyl sulfoxide (DMSO), and 9.45 g (0.04 mol) of 1-dodecylimidazole synthesized in Example 5 was added thereto to obtain a temperature of 50 ° C. The reaction is stirred at 6 ° C. for 6 hours. After completion of the reaction, the solvent was distilled off under reduced pressure and the residue was precipitated in an excess of diethyl ether to give a sticky slightly yellowish liquid product.
수율 9.90 g (62 %)Yield 9.90 g (62%)
1H NMR (DMSO, 200MHz) 9.3 (s, 1H), 7.8 (m, 2H), 5.9 (s, 1H), 5.7 (s, 1H), 4.2 (m, 4H), 1.8 (s, 3H), 1.7 (m, 2H), 1.4 (m, 22H), 0.9 (t, 3H). 1 H NMR (DMSO, 200 MHz) 9.3 (s, 1H), 7.8 (m, 2H), 5.9 (s, 1H), 5.7 (s, 1H), 4.2 (m, 4H), 1.8 (s, 3H), 1.7 (m, 2H), 1.4 (m, 22H), 0.9 (t, 3H).
실시예 13: 3-도데실-1-(2-메타크릴로일옥시에틸)이미다졸륨 브로마이드 합성 Example 13: 3-dodecyl-1- (2-methacryloyloxyethyl) imidazolium bromide synthesis
실시예 3에서 합성한 브로모 메타아크릴레이트 화합물5.00g (0.026mol)을 디메틸술폭사이드 (DMSO) 20ml에 녹이고 실시예 5에서 합성한 1-도데실이미다졸 6.12g (0.026mol)을 넣고 온도 50℃에서 6시간 동안 교반시키며 반응시킨다. 반응 종료 후 용매를 감압 증류하고 잔여물을 과량의 디에틸에테르에 침전 시키면 끈끈한 약간 황갈색의 액체 생성물을 수득한다.5.00 g (0.026 mol) of the bromo methacrylate compound synthesized in Example 3 was dissolved in 20 ml of dimethyl sulfoxide (DMSO), and 6.12 g (0.026 mol) of 1-dodecylimidazole synthesized in Example 5 was added thereto. The reaction is stirred at 50 ° C. for 6 hours. After completion of the reaction, the solvent was distilled off under reduced pressure and the residue was precipitated in an excess of diethyl ether to give a sticky slightly yellowish liquid product.
수율 8..70 g (78 %)Yield 8..70 g (78%)
1H NMR (DMSO, 200MHz) 9.3 (s, 1H), 7.8 (m, 2H), 5.9 (s, 1H), 5.7 (s, 1H), 4.2 (m, 4H), 1.8 (s, 3H), 1.7 (m, 2H), 1.4 (m, 22H), 0.9 (t, 3H) 1 H NMR (DMSO, 200 MHz) 9.3 (s, 1H), 7.8 (m, 2H), 5.9 (s, 1H), 5.7 (s, 1H), 4.2 (m, 4H), 1.8 (s, 3H), 1.7 (m, 2H), 1.4 (m, 22H), 0.9 (t, 3H)
실시예 14: 1-(2-히드록시에틸)이미다졸의 합성Example 14 Synthesis of 1- (2-hydroxyethyl) imidazole
이미다졸 10.00 g (0.146mol)을톨루엔 100ml에 교반시키며 녹인다. 에틸렌카보네이드 15.52 g (0.176mol)을 넣고 온도 110℃에서 5시간 동안 교반시키며 반응시킨다. 반응 종료 후 톨루엔을 버리고 잔여물을 디에틸이서에 침전 시키면 갈색의 끈끈한 액체 생성물을 수득한다.Dissolve 10.00 g (0.146 mol) of imidazole in 100 ml of toluene with stirring. 15.52 g (0.176 mol) of ethylene carbonide was added thereto, followed by reaction at 110 ° C. for 5 hours. After completion of the reaction, toluene was discarded and the residue precipitated in diethyl ether to give a brown sticky liquid product.
수율 14.77 g (89.7%)Yield 14.77 g (89.7%)
실시예 15: 1-(2-메타크릴로일옥시에틸)이미다졸의 합성Example 15 Synthesis of 1- (2-Methacryloyloxyethyl) imidazole
상시 실시예 14에서 합성한 1-(2-히드록시에틸)이미다졸 화합물10.00 g (0.089 mol)을 테트라히드로퓨란 (THF) 100ml에 녹인다. 트리에틸아민 8.92 g (0.089 mol)을 넣고 상온에서 1시간 동안 교반 시키며 반응 시킨다. 반응기 온도를 얼음 냉탕에서 0℃로 조절한 후 메타아크릴로일 클로라이드13.40 g (0.13 mol)을 천천히 부가한다. 5시간 동안 반응시키고 나서 테트라히드로퓨란을 감압 증류하고 반응 혼합물을 에틸아세테이트와 물로 추출한다. 용매를 감압 증류하고 건조하여 연황색의 액체 생성물을 수득한다.10.00 g (0.089 mol) of 1- (2-hydroxyethyl) imidazole compound synthesized in Example 14 was dissolved in 100 ml of tetrahydrofuran (THF). Add 8.92 g (0.089 mol) of triethylamine, and react for 1 hour at room temperature. The reactor temperature is adjusted to 0 ° C. in ice cold water followed by the slow addition of 13.40 g (0.13 mol) of methacryloyl chloride. After reacting for 5 hours, tetrahydrofuran is distilled under reduced pressure, and the reaction mixture is extracted with ethyl acetate and water. The solvent is distilled off under reduced pressure and dried to give a light yellow liquid product.
수율 12.34 g (77%)Yield 12.34 g (77%)
실시예 16: 3-메틸-1-(3-메타크릴로일옥시프로필)이미다졸륨 클로라이드 고분자 합성Example 16: 3-methyl-1- (3-methacryloyloxypropyl) imidazolium chloride polymer synthesis
실시예 7에서 합성한 3-메틸-1-(3-메타크릴로일옥시프로필)이미다졸륨 클로라이드 3.00g (0.0123mol)을 20 ml 파이렉스 유리 중합관에 넣고 개시제 AIBN (0.02 g, 단량체에 대하여 1 mol%)을 넣고 3.0 ml의 클로로포름에 용해시킨 후, 질소 기체 치환 시키면서 3 차례의 냉동과 해동 순환시킨 후 밀봉하였다. 밀봉된 중합관을 60℃에서 6 시간 동안 중합 반응시킨 후 메탄올에 희석하여 에틸아세테이트 200 ml에 적가 하여 침전된 고분자를 여과하고, 반복하여 두 차례 에틸아세테이트에 재침전 시키고 여과하여 건조하였다 3.00 g (0.0123 mol) of 3-methyl-1- (3-methacryloyloxypropyl) imidazolium chloride synthesized in Example 7 was placed in a 20 ml Pyrex glass polymerization tube and initiator AIBN (0.02 g, relative to monomer). 1 mol%) was added and dissolved in 3.0 ml of chloroform, followed by three cycles of freezing and thawing with nitrogen gas substitution and sealing. The sealed polymerization tube was polymerized at 60 ° C. for 6 hours, diluted in methanol, and added dropwise to 200 ml of ethyl acetate. The precipitated polymer was filtered, repeatedly reprecipitated in ethyl acetate twice, and dried by filtration.
수율 2.20g (73.3%)Yield 2.20 g (73.3%)
실시예 17: 3-메틸-1-(3-메타크릴로일옥시프로필)이미다졸륨 클로라이드와 Example 17: 3-methyl-1- (3-methacryloyloxypropyl) imidazolium chloride
메틸메타 아크릴레이트의 공중합Copolymerization of Methyl Methacrylate
실시예 7에서 합성한 3-메틸-1-(3-메타크릴로일옥시프로필)이미다졸륨 클로라이드 3.00g (0.012mol)을 20 ml 파이렉스 유리 중합관에 넣고 메틸메타아크릴레이트1.23g (0.012mol)과 개시제 AIBN (0.04 g, 단량체에 대하여 1 mol%)을 넣고 4.0 ml의 클로로포름에 용해시킨 후, 질소 기체 치환 시키면서 3 차례의 냉동과 해동 순환시킨 후 밀봉하였다. 밀봉된 중합관을 60℃에서 6 시간 동안 중합 반응시킨 후 메탄올에 희석하여 에틸아세테이트에 300 ml에 적가 하여 침전된 고분자를 여과하고, 반복하여 두 차례 에틸아세테이트에 재침전 시키고 여과하여 건조하였다.3.00 g (0.012 mol) of 3-methyl-1- (3-methacryloyloxypropyl) imidazolium chloride synthesized in Example 7 was placed in a 20 ml Pyrex glass polymerization tube and 1.23 g (0.012 mol) of methyl methacrylate. ) And initiator AIBN (0.04 g, 1 mol% based on monomer) were added and dissolved in 4.0 ml of chloroform, and then sealed in three cycles of freezing and thawing with nitrogen gas substitution. The sealed polymerization tube was polymerized at 60 ° C. for 6 hours, diluted in methanol, and added dropwise to ethyl acetate in 300 ml. The precipitated polymer was filtered, repeatedly reprecipitated in ethyl acetate twice, and dried by filtration.
수율 2.60g (62%)Yield 2.60 g (62%)
실시예 18: 3-메틸-1-(2-메타크릴로일옥시에틸)이미다졸륨 브로마이드 고분자의 합성Example 18 Synthesis of 3-methyl-1- (2-methacryloyloxyethyl) imidazolium bromide polymer
실시예 8에서 합성한 3-메틸-1-(2-메타크릴로일옥시에틸)이미다졸륨 브로마이드 3.00g (0.011mol)을 20 ml 파이렉스 유리 중합관에 넣고 개시제 AIBN (0.018 g, 단량체에 대하여 1 mol%)을 넣고 3.0 ml의 클로로포름에 용해시킨 후, 질소 기체 치환 시키면서 3 차례의 냉동과 해동 순환시킨 후 밀봉하였다. 밀봉된 중합관을 60℃에서 6 시간 동안 중합 반응시킨 후 메탄올에 희석하여 에틸아세테이트 200 ml에 적가 하여 침전된 고분자를 여과하고, 반복하여 두 차례 에틸아세테이트에 재침전 시키고 여과하여 건조하였다.3.00 g (0.011 mol) of 3-methyl-1- (2-methacryloyloxyethyl) imidazolium bromide synthesized in Example 8 was placed in a 20 ml Pyrex glass polymerization tube and initiator AIBN (0.018 g, relative to monomer). 1 mol%) was added and dissolved in 3.0 ml of chloroform, followed by three cycles of freezing and thawing with nitrogen gas substitution and sealing. The sealed polymerization tube was polymerized at 60 ° C. for 6 hours, diluted in methanol, added dropwise to 200 ml of ethyl acetate, and the precipitated polymer was filtered, repeatedly reprecipitated in ethyl acetate twice, and dried by filtration.
수율 2.35g (78%)Yield 2.35 g (78%)
실시예 19: 3-메틸-1-(2-메타크릴로일옥시에틸)이미다졸륨 브로마이드와 메틸 메타아크릴레이트의 공중합 Example 19 Copolymerization of 3-methyl-1- (2-methacryloyloxyethyl) imidazolium bromide with methyl methacrylate
실시예 8에서 합성한 3-메틸-1-(2-메타크릴로일옥시에틸)이미다졸륨 브로마이드 3.00g (0.011mol)을 20 ml 파이렉스 유리 중합관에 넣고 메틸 메타아크릴레이트 1.10g (0.011mol)과 개시제 AIBN (0.036 g, 단량체에 대하여 1 mol%)을 넣고 4.0 ml의 클로로포름에 용해시킨 후, 질소 기체 치환 시키면서 3 차례의 냉동과 해동 순환시킨 후 밀봉하였다. 밀봉된 중합관을 60℃에서 6 시간 동안 중합 반응시킨 후 메탄올에 희석하여 에틸 아세테이트에 200 ml에 적가 하여 침전된 고분자를 여과하고, 반복하여 두 차례 에틸 아세테이트에 재침전 시키고 여과하여 건조하였다3.00 g (0.011 mol) of 3-methyl-1- (2-methacryloyloxyethyl) imidazolium bromide synthesized in Example 8 was placed in a 20 ml Pyrex glass polymerization tube and 1.10 g (0.011 mol) of methyl methacrylate. ) And initiator AIBN (0.036 g, 1 mol% based on monomer) were added and dissolved in 4.0 ml of chloroform, and then sealed in three cycles of freezing and thawing with nitrogen gas substitution. The sealed polymerization tube was polymerized at 60 ° C. for 6 hours, diluted in methanol, and added dropwise to ethyl acetate in 200 ml. The precipitated polymer was filtered, repeatedly reprecipitated in ethyl acetate twice, and dried by filtration.
수율2.57g (63%)Yield 2.57 g (63%)
실시예 20: 3-부틸-1-(2-메타크릴로일옥시에틸)이미다졸륨 브로마이드의 고분자 합성Example 20 Polymer Synthesis of 3-butyl-1- (2-methacryloyloxyethyl) imidazolium bromide
실시예 9에서 합성한 3-부틸-1-(2-메타크릴로일옥시에틸)이미다졸륨 브로마이드 3.00g (0.0095mol)을 20 ml 파이렉스 유리 중합관에 넣고 개시제 AIBN (0.016 g, 단량체에 대하여 1 mol%)을 넣고 3.0 ml의 클로로포름에 용해시킨 후, 질소 기체 치환 시키면서 3 차례의 냉동과 해동 순환시킨 후 밀봉하였다. 밀봉된 중합관을 60℃에서 6 시간 동안 중합 반응시킨 후 메탄올에 희석하여 에틸아세테이트 200 ml에 적가 하여 침전된 고분자를 여과하고, 반복하여 두 차례 에틸아세테이트에 재침전 시키고 여과하여 건조하였다.3.00 g (0.0095 mol) of 3-butyl-1- (2-methacryloyloxyethyl) imidazolium bromide synthesized in Example 9 was placed in a 20 ml Pyrex glass polymerization tube and initiator AIBN (0.016 g, relative to monomer). 1 mol%) was added and dissolved in 3.0 ml of chloroform, followed by sealing with three cycles of freezing and thawing with nitrogen gas substitution. The sealed polymerization tube was polymerized at 60 ° C. for 6 hours, diluted in methanol, added dropwise to 200 ml of ethyl acetate, and the precipitated polymer was filtered, repeatedly reprecipitated in ethyl acetate twice, and dried by filtration.
수율 2.35g (78%)Yield 2.35 g (78%)
실시예 21: 3-헥실-1-(3-메타크릴로일옥시프로필)이미다졸륨 클로라이드의 고분자 합성Example 21 Polymer Synthesis of 3-hexyl-1- (3-methacryloyloxypropyl) imidazolium chloride
실시예 10에서 합성한 3-헥실-1-(3-메타크릴로일옥시프로필)이미다졸륨 클로라이드 3.00g (0.0096mol)을 20 ml 파이렉스 유리 중합관에 넣고 개시제 AIBN (0.0156 g, 단량체에 대하여 1 mol%)을 넣고 3.0 ml의 클로로포름에 용해시킨 후, 질소 기체 치환 시키면서 3 차례의 냉동과 해동 순환시킨 후 밀봉하였다. 밀봉된 중합관을 60℃에서 6 시간 동안 중합 반응시킨 후 메탄올에 희석하여 에틸아세테이트에 200 ml에 적가 하여 침전된 고분자를 여과하고, 반복하여 두 차례 에틸아세테이트에 재침전 시키고 여과하여 건조하였다.3.00 g (0.0096 mol) of 3-hexyl-1- (3-methacryloyloxypropyl) imidazolium chloride synthesized in Example 10 was placed in a 20 ml Pyrex glass polymerization tube and initiator AIBN (0.0156 g, relative to monomer). 1 mol%) was added and dissolved in 3.0 ml of chloroform, followed by three cycles of freezing and thawing with nitrogen gas substitution and sealing. The sealed polymerization tube was polymerized at 60 ° C. for 6 hours, diluted in methanol, added dropwise to ethyl acetate in 200 ml, and the precipitated polymer was filtered, repeatedly reprecipitated in ethyl acetate twice, and dried by filtration.
수율 2.43g (81%)Yield 2.43 g (81%)
실시예 22: 3-헥실-1-(2-메타크릴로일옥시에틸)이미다졸륨 브롬마이드와 메틸메타이크릴레이트 공중합Example 22 Copolymerization of 3-hexyl-1- (2-methacryloyloxyethyl) imidazolium bromide with methylmethacrylate
실시예 11에서 합성한 3-헥실-1-(2-메타크릴로일옥시에틸)이미다졸륨 브로마이드 3.00g (0.0087mol)을 20 ml 파이렉스 유리 중합관에 넣고 메틸메타아크릴레이트 0.87g (0.0087mol)과 개시제 AIBN (0.029g, 단량체에 대하여 1 mol%)을 넣고 4.0 ml의 클로로포름에 용해시킨 후, 질소 기체 치환 시키면서 3 차례의 냉동과 해동 순환시킨 후 밀봉하였다. 밀봉된 중합관을 60℃에서 6 시간 동안 중합 반응시킨 후 메탄올에 희석하여 에틸아세테이트에 200 ml에 적가 하여 침전된 고분자를 여과하고, 반복하여 두 차례 에틸아세테이트에 재침전 시키고 여과하여 건조하였다.3.00 g (0.0087 mol) of 3-hexyl-1- (2-methacryloyloxyethyl) imidazolium bromide synthesized in Example 11 was placed in a 20 ml Pyrex glass polymerization tube and 0.87 g (0.0087 mol) of methyl methacrylate. ) And initiator AIBN (0.029 g, 1 mol% based on monomer) were added and dissolved in 4.0 ml of chloroform, followed by sealing with three cycles of freezing and thawing with nitrogen gas substitution. The sealed polymerization tube was polymerized at 60 ° C. for 6 hours, diluted in methanol, added dropwise to ethyl acetate in 200 ml, and the precipitated polymer was filtered, repeatedly reprecipitated in ethyl acetate twice, and dried by filtration.
수율 3.15g (79%)Yield 3.15 g (79%)
실시예 23: 3-도데실-1-(2-메타크릴로일옥시에틸)이미다졸륨 브로마이드의 고분자 합성Example 23 Polymer Synthesis of 3-dodecyl-1- (2-methacryloyloxyethyl) imidazolium bromide
실시예 13에서 합성한 3-도데실-1-(2-메타크릴로일옥시에틸)이미다졸륨 브로마이드 3.00g (0.007mol)을 20 ml 파이렉스 유리 중합관에 넣고 개시제 AIBN (0.012 g, 단량체에 대하여 1 mol%)을 넣고 3.0 ml의 클로로포름에 용해시킨 후, 질소 기체 치환 시키면서 3 차례의 냉동과 해동 순환시킨 후 밀봉하였다. 밀봉된 중합관을 60℃에서 6 시간 동안 중합 반응시킨 후 메탄올에 희석하여 에틸아세테이트에 200 ml에 적가 하여 침전된 고분자를 여과하고, 반복하여 두 차례 에틸아세테이트에 재침전 시키고 여과하여 건조하였다3.00 g (0.007 mol) of 3-dodecyl-1- (2-methacryloyloxyethyl) imidazolium bromide synthesized in Example 13 was placed in a 20 ml Pyrex glass polymerization tube and the initiator AIBN (0.012 g, monomer 1 mol%), dissolved in 3.0 ml of chloroform, and then subjected to three freeze and thaw cycles under nitrogen gas replacement, followed by sealing. The sealed polymer tube was polymerized at 60 ° C. for 6 hours, diluted with methanol, and added dropwise to ethyl acetate in 200 ml. The precipitated polymer was filtered, repeatedly reprecipitated in ethyl acetate twice, and dried by filtration.
수율 2.60g (87%)Yield 2.60 g (87%)
실시예 24: 3-도데실-1-(2-메타크릴로일옥시에틸)이미다졸륨 브로마이드와Example 24: 3-dodecyl-1- (2-methacryloyloxyethyl) imidazolium bromide
메틸메타아크릴레이트 공중합 Methyl methacrylate copolymerization
실시예 13에서 합성한 3-도데실-1-(2-메타크릴로일옥시에틸)이미다졸륨 브로마이드3.00g (0.007mol)을 20 ml 파이렉스 유리 중합관에 넣고 메틸메타아크릴레이트 0.70g (0.007mol)과 개시제 AIBN (0.023g, 단량체에 대하여 1 mol%)을 넣고 4.0 ml의 클로로포름에 용해시킨 후, 질소 기체 치환 시키면서 3 차례의 냉동과 해동 순환시킨 후 밀봉하였다. 밀봉된 중합관을 60℃에서 6 시간 동안 중합 반응시킨 후 메탄올에 희석하여 에틸아세테이트에 200 ml에 적가 하여 침전된 고분자를 여과하고, 반복하여 두 차례 에틸아세테이트에 재침전 시키고 여과하여 건조하였다.3.00 g (0.007 mol) of 3-dodecyl-1- (2-methacryloyloxyethyl) imidazolium bromide synthesized in Example 13 was placed in a 20 ml Pyrex glass polymerization tube and 0.70 g (0.007) of methyl methacrylate. mol) and initiator AIBN (0.023 g, 1 mol% based on monomer) were added, dissolved in 4.0 ml of chloroform, and sealed after 3 cycles of freezing and thawing with nitrogen gas substitution. The sealed polymerization tube was polymerized at 60 ° C. for 6 hours, diluted in methanol, added dropwise to ethyl acetate in 200 ml, and the precipitated polymer was filtered, repeatedly reprecipitated in ethyl acetate twice, and dried by filtration.
수율 3.05g (82%)Yield 3.05 g (82%)
실시예 25: 이미다졸륨 염 단량체의 광경화 실험Example 25 Photocuring Experiment of Imidazolium Salt Monomer
본 발명에서 합성한 항균성 이미다졸륨 염 단량체를 이용하여 다음과 같은 광경화 조성물을 조제하여 광경화 반응을 평가하였다. Using the antimicrobial imidazolium salt monomer synthesized in the present invention, the following photocuring composition was prepared to evaluate the photocuring reaction.
상기 실시예에서 제조한 이미다졸륨 염 단량체 100 중량부, 가교 결합제로서 트라이메틸롤프로판트라이아크릴레이트 100 중량부 및 광개시제로서 벤조인이소부틸에테르 5 중량부를 잘 혼합하여 광경화성 조성물을 제조하고, 이 조성물 10 mg을 취하여 시차광열량계 (Differential Photocolorimeter, DPC)를 이용하여 광경화 반응 속도를 측정하였다. 광경화 반응 평가 장비로는 250W 수은등이 장착된 미국 TA Instruments 사의 Model DSC 2910과 결합시킨 DPC를 사용하였다.100 parts by weight of the imidazolium salt monomer prepared in the above embodiment, 100 parts by weight of trimethylolpropane triacrylate as a crosslinking agent and 5 parts by weight of benzoin isobutyl ether as a photoinitiator were mixed well to prepare a photocurable composition. 10 mg of the composition was taken and the photocuring reaction rate was measured using a differential photocolorimeter (DPC). As a photocuring reaction evaluation instrument, a DPC coupled with a Model DSC 2910 manufactured by TA Instruments of 250W mercury lamp was used.
구체적인 실험 절차는 이하에 설명한 것과 같다. 실시예 10의 항균성 이미다 졸륨 단량체 시료 1.00g, 3 관능성 트라이메틸롤프로판트라이아크릴레이트 1.00g 및 광개시제 벤조인이소부틸에테르 0.05g을 잘 혼합하여 광경화 조성물을 제조하였다. Specific experimental procedures are as described below. A photocurable composition was prepared by mixing 1.00 g of the antimicrobial imidazolium monomer sample of Example 10, 1.00 g of trifunctional trimethylolpropane triacrylate, and 0.05 g of photoinitiator benzoin isobutyl ether.
이 조성물 10mg을 취하여 DPC를 이용하여 광경화 반응속도를 측정하여 분석한 결과에서 상기한 이미다졸륨 염 단량체를 함유한 항균성 광경화 조성물의 광경화 반응속도가 충분히 빠른 것으로 평가되었다. 또한 실제적 필름 피막 형성 능력을 보기 위하여 점성이 있는 이 광경화 조성물 시료를 폴리에스터 필름 위에 두께 0.2mm의 피막으로 만들어 250W 자외선 노광기를 이용하여 10초 동안 광경화 반응시켰더니, 표면 상태가 매끄럽고 딱딱하게 경화되어 우수한 고분자 투명 막이 형성되는 것이 확인되었다.The photocuring reaction rate of the antimicrobial photocuring composition containing the imidazolium salt monomer described above was evaluated to be fast enough from the result of analyzing the photocuring reaction rate using DPC using 10 mg of the composition. Also, in order to see the actual film forming ability, the viscous photocurable composition sample was made into a 0.2mm thick film on the polyester film, and photocured for 10 seconds using a 250W ultraviolet exposure machine, so that the surface condition was smooth and hardened. It was confirmed that an excellent polymer transparent film was formed.
다른 실시예에서 제조한 항균성 이미다졸륨 단량체를 사용하여 위에 설명한 것과 동일하게 배합하여 제조한 광경화 조성물 역시 코팅되는 기질 위에서 모두 10초 이내에 광경화 반응이 일어나서 우수한 광경화 고분자 코팅 막이 형성되었다. Photocuring compositions prepared by combining in the same manner as described above using the antimicrobial imidazolium monomer prepared in another embodiment also photocuring reaction occurred within 10 seconds on the substrate to be coated to form an excellent photocurable polymer coating film.
실시예 25: 이미다졸륨 염 단량체와 이로부터 얻어진 고분자의 미생물에 대한 항균 활성 시험Example 25 Antimicrobial Activity Test on Microorganisms of Imidazolium Salt Monomers and Polymers Obtained from the
실시예 25에서는 일반적으로 병원에서 소독제, 가정용 세제 및 화장품의 제조에 있어서 항균제 또는 방부제로 사용되는 염화벤잘코늄 (BKC: 알킬벤질디메틸암모늄 클로라이드, 화학식 C12H25N(CH3)2C7HCl)과 천연물 키틴을 가공하여 항균성 고분자로 사용하는 수용성 키토산 (WSC, Mwt. 20,000)을 항균 활성 시험을 위한 대조 군으로 사용하였다.In Example 25 benzalkonium chloride (BKC: alkylbenzyldimethylammonium chloride, general formula C 12 H 25 N (CH 3 ) 2 C 7 HCl generally used as an antimicrobial or preservative in the manufacture of disinfectants, household detergents and cosmetics in hospitals ) And water-soluble chitosan (WSC, Mwt. 20,000) used as an antimicrobial polymer by processing chitin and natural products were used as a control group for the antibacterial activity test.
(1) 시험 대상 미생물 준비(1) Preparation of Test Microorganisms
항균 활성 시험을 위하여 그람 양성균인 포도상구균[Staphylococcus aureus (ATCC 25923)]과 그람 음성균인 대장균[Escherichia coli (ATCC 25922)]를 사용하였다. 포도상구균 지수기 배양체를 얻기 위하여 뉴트리언트 아가(nutrient agar) 평판 배지에 형성된 콜로니를 백금이로 소량 취해 Brain heart infusion broth (BHIB)에 접종한 후 37℃에서 3 - 5시간 동안 호기 진탕 (120 rpm) 배양하였다. 또한, 대장균 지수기 배양체를 얻기 위하여 트립티카아제 소이 아가(trypticase soy agar) 평판 배지에 형성된 콜로니를 백금이로 소량 취하여 트립티카아제 소이 브로쓰(Tryticase soy broth, TSB)에 접종한 후, 포도상구균(S. aureus)에서와 같이 37℃에서 호기적으로 진탕 배양하였다. 각 균의 지수기 배양체를 수거한 후, Mueller-hinton broth (MHB)에 희석하여 균액의 최종 농도가 1x106 ~ 1x108 CFU/ml이 되도록 조정하였다. Gram-positive bacteria Staphylococcus aureus (ATCC 25923) and Gram-negative bacteria Escherichia coli (ATCC 25922) were used for the antimicrobial activity test. To obtain the Staphylococcus aureus culture, small amounts of colonies formed on nutrient agar plates were inoculated with platinum and inoculated into Brain heart infusion broth (BHIB), followed by aerobic shaking for 3-5 hours at 37 ° C (120 rpm). ) Were cultured. In addition, a small amount of colonies formed on trypticase soy agar plate medium were obtained with platinum to obtain an E. coli exponent culture, and then inoculated into tryticase soy broth (TSB), followed by Staphylococcus aureus. As in ( S. aureus) , shaking culture was aerobic at 37 ℃. The exponential cultures of the bacteria were collected and diluted in Mueller-hinton broth (MHB) to adjust the final concentration of the bacteria solution to 1x10 6 to 1x10 8 CFU / ml.
(2) 시험 내용 및 방법(2) Test contents and method
ㄱ) 디스크 확산법 (Disk diffusion method)에 의한 항균 활성 시험 A) antimicrobial activity test by disk diffusion method
본 발명에서 합성한 단량체 또는 합성 고분자시료의 비부유성 세균에 대한 항균 활성을 시험하기 위하여 Kirby-Bauer 변법을 수행하였다. 항균 시험용 디스크를 제작하기 위하여 본 발명에서 합성한 단량체 또는 고분자 시료를 멸균 증류수나 메탄올, 디메틸술폭사이드(DMSO) 같은 용매에 각각 녹여 최종 농도가 100 mg/ml이 되도록 만들었다. 이들 각각의 용액을 20 l 씩 취해 항균제가 전혀 함유되어 있지 않은 멸균 여과지 (직경 6 mm) 중앙에 떨어뜨린 후 6시간 이상 상온에서 건조하였다. 또한, 용매 자체가 항균성 시험에 영향을 주는 지를 확인하기 위하여 단량체나 고분자시료가 전혀 함유되어 있지 않은 용매만을 이용해 위와 동일한 방법으로 디스크를 제작하였다. 용매 또는 2 mg의 항균 시험용 물질이 함유된 디스크를 멸균하기 위하여 1시간 동안 상온에서 자외선을 조사하였다. S. aureus 또는 E. coli 지수기 배양체 (1x108 CFU/ml)를 멸균된 면봉을 이용하여 MHA 평판 배지 상에 고르게 도막한 다음, 그 위에 서로 다른 종류의 항균 시험용 시료 디스크를 일정 간격을 두고 얹었다. MHA 평판 배지를 35~37℃에서 24시간 동안 도치 배양한 후 디스크 주변에 형성된 성장 억제대를 측정하여 mm 단위로 기록하여 항균 활성을 평가하였다.In order to test the antimicrobial activity of non-suspendable bacteria of the monomer or synthetic polymer sample synthesized in the present invention, Kirby-Bauer modification was performed. In order to produce an antimicrobial test disc, the monomer or polymer sample synthesized in the present invention was dissolved in a solvent such as sterile distilled water, methanol, or dimethyl sulfoxide (DMSO), respectively, to make a final concentration of 100 mg / ml. 20 l of each of these solutions was taken and dropped in the center of a sterile filter paper (6 mm in diameter) containing no antibacterial agent, and dried at room temperature for at least 6 hours. In addition, in order to determine whether the solvent itself affects the antimicrobial test, the disc was manufactured by the same method as above using only a solvent containing no monomer or polymer sample at all. Ultraviolet rays were irradiated at room temperature for 1 hour to sterilize a disk containing a solvent or 2 mg of antimicrobial test substance. S. aureus or E. coli exponential cultures (1 × 10 8 CFU / ml) were evenly coated onto the MHA plate medium using a sterile swab, and then different types of antimicrobial test discs were placed thereon at regular intervals. . After incubation of MHA plate medium at 35-37 ° C. for 24 hours, the growth inhibition zone formed around the disc was measured and recorded in mm to evaluate the antimicrobial activity.
ㄴ) 시료에 대한 미생물의 감수성 측정 B) determination of the sensitivity of the microorganisms to the sample;
본 발명에서 합성한 시료에 대한 세균의 감수성을 시험하기 위하여 액체 배지 희석법 (broth dilution method)에 따라 최소 억제 농도 (minimal inhibitory concentration, MIC)를 측정하였다. 멸균 증류수를 사용하여 2배의 농도 구배를 갖는 0 ~ 1600 ㎍/ml 범위의 시료 희석액을 만든 후, 각각의 시료 희석액을 시험관에 3 ml씩 분주하였다. 여기에 1x106 CFU/ml로 미리 조정된 각 균의 지수기 배양체를 각각 3 ml씩 첨가한 후 35~37℃에서 호기적으로 18 ~ 20시간 동안 배양하였다. 배양 후균의 증식이 육안으로 관찰되지 않는 시험관에서의 항균제의 최종 농도를 MIC 값으로 결정하였다. In order to test the susceptibility of bacteria to the samples synthesized in the present invention, the minimum inhibitory concentration (MIC) was measured according to the broth dilution method. Sterile distilled water was used to make sample dilutions in the range of 0-1600 μg / ml with a 2-fold concentration gradient, and then each sample dilution was dispensed into the test tube by 3 ml. After adding 3 ml of each of the exponential cultures of each bacterium previously adjusted to 1 × 10 6 CFU / ml, the cells were incubated at 35-37 ° C. for 18 to 20 hours. The final concentration of the antimicrobial agent in vitro where no growth of cultured bacteria was observed visually was determined by the MIC value.
(3) 시료에 대한 미생물의 항균 활성 평가 결과(3) Evaluation result of microorganism's antimicrobial activity on sample
본 발명에서 합성한 이미다졸륨 염 단량체와 고분자 시료는 두 가지 세균에 대한 디스크 확산법에 의한 항균 활성 시험 결과, 일반적인 항균 고분자로서 사용되는 수용성 키토산(WSC)과 유사하게 본 발명의 이미다졸륨 염 고분자 시료가 모두 우수한 항균 활성을 나타내었다. 디스크 확산법은 비부유성 세균에 대한 항균성 평가이므로, 부유 상태의 세균에 대한 항균성 평가를 위하여 MIC 측정을 수행하였다. The imidazolium salt monomer synthesized in the present invention and the sample of the polymer is an imidazolium salt polymer of the present invention similar to the water-soluble chitosan (WSC) used as a general antimicrobial polymer as a result of the antimicrobial activity test by the disk diffusion method for two bacteria. All the samples showed excellent antimicrobial activity. Since the disk diffusion method is an antimicrobial evaluation against non-suspendable bacteria, MIC measurement was performed to evaluate the antimicrobial activity against suspended bacteria.
하기 표 1은 이미다졸륨 염 단량체 2종, 동종 중합체 3종 및 메틸메타아크릴레이트 공중합체 3종 시료 각각에 대하여, 항균제로 쓰이고 있는 BKC와 WSC를 대조군으로 하여 비교한 세균의 감수성을 MIC로 나타낸 것이다. S. aureus를 대상으로 이들에 대한 감수성을 시험한 결과, BKC의 MIC는 1.563 g/ml로 나타났으며, 이미다졸륨 염 단량체 시료 중 도데실의 긴 알킬기 치환 이미다졸륨 염 (실시예 11)은 BKC와 같이 매우 우수한 항균 활성이 나타났다. 이미다졸륨 염 고분자를 메탄올에 용해시켜 항균 활성을 시험하였더니 모두 천연 고분자 WSC와 유사한 항균 활성을 보였고, 특히 긴 도데실 알킬 사슬을 갖는 공중합체 (실시예 23)는 BKC와 유사한 매우 우수한 활성이 나타났다. E. coli 의 경우에도 역시 본 발명에 따른 이미다졸륨 염 시료가 매우 우수한 항균 활성으로 S. aureus에서와 같이 우수한 감수성을 나타내었다.Table 1 shows the bacteria susceptibility of the two imidazolium salt monomers, three homopolymers and three methyl methacrylate copolymers, using BKC and WSC, which are used as antimicrobial agents, as a control group. will be. The susceptibility test of S. aureus showed that the MIC of BKC was 1.563 g / ml, and the long alkyl-substituted imidazolium salt of dodecyl in the imidazolium salt monomer sample (Example 11) Was very good antimicrobial activity like BKC. The antimicrobial activity was tested by dissolving the imidazolium salt polymer in methanol, and all of them showed antimicrobial activity similar to that of the natural polymer WSC. In particular, the copolymer having a long dodecyl alkyl chain (Example 23) had a very good activity similar to that of BKC. appear. In the case of E. coli , the imidazolium salt sample according to the present invention also showed excellent susceptibility as in S. aureus with very good antibacterial activity.
[표 1]TABLE 1
항균 활성 시험 결과: 최소 억제 농도 (MIC, ㎍/㎖) Antimicrobial Activity Test Results: Minimum Inhibitory Concentration (MIC, μg / ml)
본 발명에 따라 화학식 1로 표시되는 광경화형 항균성 이미다졸륨 염 단량체, 이를 포함하는 광경화형 항균 코팅용 조성물 및 상기 조성물의 광경화에 의하여 제조되는 표면 코팅용 항균성 고분자 재료가 제공되었다.According to the present invention, a photocurable antimicrobial imidazolium salt monomer represented by Formula 1, a photocurable antimicrobial coating composition comprising the same, and an antimicrobial polymer material for surface coating prepared by photocuring are provided.
본 발명에 따른 화학식 1의 광경화형 항균성 이미다졸륨 염 함유 단량체를 중합하여 고분자로 제조하거나 또는 광경화형 항균 코팅용 조성물로 조제하는 경우, 광경화에 의하여 항균성을 갖는 고분자 필름 형태로 사용된다. When the photocurable antimicrobial imidazolium salt-containing monomer according to the present invention is polymerized to prepare a polymer or a photocurable antimicrobial coating composition, it is used in the form of a polymer film having antimicrobial properties by photocuring.
본 발명에 따른 광경화형 항균성 조성물은 용제 없이 환경 친화적으로 광경화 공정에 사용될 수 있으므로 경화 공정이 간단 편리하고 항균성이 우수하므로 각종 생활, 건축 내장재 등에 항균성 코팅 처리용으로 유용하게 사용 가능하다. 즉, 장판, 벽지 등의 건축 자재, 다중이 함께 사용하는 공중 전화, 화장실, 지하철, 버스 등의 내장재에 쉽게 항균 코팅할 수 있으며, 전기 전자 제품의 하우징 외장재 코팅, 포장재, 식품 및 보관용 재료 등에 친환경적인 항균성 고분자 코팅 재료로 사용될 수 있다. Since the photocurable antimicrobial composition according to the present invention can be used in a photocuring process in an environmentally friendly manner without a solvent, the curing process is simple, convenient and excellent in antimicrobial properties. In other words, antibacterial coating can be easily applied to building materials such as floor coverings and wallpaper, and to interior materials such as public telephones, toilets, subways, buses, etc. It can be used as an environmentally friendly antimicrobial polymer coating material.
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JP2006346984A JP2007302651A (en) | 2006-05-11 | 2006-12-25 | Photocurable monomer including imidazolium salt, antimicrobial and photocurable composition containing the monomer, and antimicrobial polymeric material produced from the composition |
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KR101488701B1 (en) * | 2013-01-28 | 2015-02-04 | 한국과학기술연구원 | Antibacterial imidazolium compound and antibacterial photocurable thiol-ene compositions comprising the same, and antibacterial polymer coatings prepared therefrom |
KR20150118612A (en) * | 2014-04-14 | 2015-10-23 | 이화여자대학교 산학협력단 | Polymer compound with imidazolium as an active ingredient in antibacterial pharmaceutical composition or chemical sensors for detection of bacteria |
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