KR100509168B1 - Humidity sensor comprising polymeric membrane - Google Patents
Humidity sensor comprising polymeric membrane Download PDFInfo
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Abstract
본 발명은 3차아민기를 포함하는 비닐단량체와 염을 포함하는 비닐단량체 그리고 1 또는 2이상의 비닐공단량체를 공중합시킨 제1공중합체 및 알킬할라이드기를 포함하는 비닐단량체와 1 또는 2이상의 비닐공단량체를 공중합시킨 제2공중합체를 서로 4차암모늄화 반응을 통해 가교화시켜 형성되는 감습제를 포함하여 이루어지는 고분자막 습도센서에 관한 것으로서, 감습막, 상기 감습막과 전기적 접촉을 유지하는 전극, 상기 전극을 고정시키는 전극스냅 및 상기 전극을 외부와 연결하는 단자를 포함하는 고분자막 습도센서에 있어서, 상기 감습막이 3차아민기를 포함하는 비닐단량체와 염을 포함하는 비닐단량체 그리고 1 또는 2이상의 비닐공단량체를 공중합시킨 제1공중합체 및 알킬할라이드기를 포함하는 비닐단량체와 1 또는 2이상의 비닐공단량체를 공중합시킨 제2공중합체를 서로 4차암모늄화 반응을 통해 가교화시켜 이루어짐을 특징으로 한다.The present invention provides a vinyl monomer comprising a tertiary amine group, a vinyl monomer comprising a salt and a vinyl monomer comprising a first copolymer and an alkyl halide group copolymerized with one or two or more vinyl comonomers and one or two or more vinyl comonomers. A polymer film humidity sensor comprising a moisture sensitive agent formed by crosslinking a copolymerized second copolymer through a quaternary ammoniumation reaction, comprising: a moisture sensitive film, an electrode maintaining electrical contact with the moisture sensitive film, and the electrode A polymer membrane humidity sensor comprising an electrode snap to fix and a terminal connecting the electrode to the outside, wherein the moisture-sensitive film copolymerizes a vinyl monomer including a tertiary amine group, a vinyl monomer including a salt, and one or two or more vinyl comonomers. Vinyl monomer comprising one copolymer and an alkyl halide group and one or more vinyl comonomers By crosslinking the copolymer through which the second copolymer each other quaternary ammonium-forming reaction is characterized by true.
따라서, 감습특성이 우수하고 내수성이 뛰어난 감습막을 포함하는 습도센서를 제공하는 효과가 있다.Therefore, there is an effect of providing a humidity sensor including a moisture absorption film having excellent moisture resistance and excellent water resistance.
Description
본 발명은 고분자막 습도센서에 관한 것이다. 보다 상세하게는 본 발명은 3차아민기를 포함하는 비닐단량체와 염을 포함하는 비닐단량체 그리고 1 또는 2이상의 비닐공단량체를 공중합시킨 제1공중합체 및 알킬할라이드기를 포함하는 비닐단량체와 1 또는 2이상의 비닐공단량체를 공중합시킨 제2공중합체를 서로 4차암모늄화 반응을 통해 가교화시켜 이루어지는 감습제를 포함하여 이루어지는 고분자막 습도센서에 관한 것이다.The present invention relates to a polymer film humidity sensor. More specifically, the present invention provides a vinyl monomer comprising a tertiary amine group, a vinyl monomer comprising a salt, and a vinyl monomer comprising a first copolymer and an alkyl halide group copolymerized with one or two or more vinyl comonomers, and one or two or more vinyl monomers. The present invention relates to a polymer film humidity sensor comprising a moisture-sensitive agent formed by crosslinking a second copolymer copolymerized with a vinyl comonomer through a quaternary ammoniumation reaction.
습도 검출을 위한 고분자 감습막은 보통 염을 포함하고 있는 비닐단량체들의 중합에 의하여 얻어지는 전해질 고분자를 이용하고 있다. 그러나, 대부분의 전해질 고분자는 수용해성이 크기 때문에 장시간 결로상태나 다습한 상태에서 용해되어 경시변화가 생기는 단점을 가지고 있다.Polymeric moisture-sensitive membranes for humidity detection usually use electrolyte polymers obtained by polymerization of vinyl monomers containing salts. However, most electrolyte polymers have a disadvantage in that they are dissolved in a condensation state or a humid state for a long time because they have high water solubility.
이를 위하여 여러가지 소수성 단량체들과 공중합하거나, 소수성 중합체에 그라프트 공중합하여 전해질을 도입하는 방법을 사용하고 있다. 또한 2개 이상의 다관능성 단량체를 사용하여 가교화시키거나 또는 전해질 겔을 알루미나나 유리 같은 전극기판에 직접 결합시키는 방법 등도 시도되었다. 또한, 4차 염화가 진행될 수 있는 아민이나 포스핀과 같은 작용기를 고분자에 도입하고 디할라이드 경화제와 혼합하여 전극에 도포한 후, 열가교에 의하여 고도의 가교를 부여하는 방법 등도 응용되고 있다. 그리고 최근에는 전해질 고분자와 소수성 고분자의 IPN(interpenetrating polymer network) 형성에 의하여 내수성 개선 등 여러가지 방법이 응용되고 있다. 그러나, 내수성이 부여된 감습막을 포함하는 습도센서는 제조공정을 고려하여 상기 방법들 중에서 극히 일부만이 제한적으로 사용되고 있는 실정이다.For this purpose, a method of introducing an electrolyte by copolymerizing with various hydrophobic monomers or by graft copolymerization to a hydrophobic polymer is used. There have also been attempted methods of crosslinking using two or more polyfunctional monomers or directly bonding an electrolyte gel to an electrode substrate such as alumina or glass. In addition, a method of introducing a functional group such as amine or phosphine, which may undergo quaternary chloride, into a polymer, mixing with a dihalide curing agent, and applying it to an electrode, and then applying a high crosslinking by thermal crosslinking is also applied. In recent years, various methods such as improving water resistance have been applied by forming an interpenetrating polymer network (IPN) of an electrolyte polymer and a hydrophobic polymer. However, a humidity sensor including a moisture-sensitive film provided with water resistance is a situation in which only a limited portion of the above methods are used in consideration of the manufacturing process.
포스핀, 피리딘 그리고 3차아민기를 포함하는 공중합체들은 전극에 도포되기 전에 α, ω-디할로알칸과 혼합하거나 반대의 방법으로 알킬할라이드 또는 벤질할라이드를 포함하는 공중합체들을 디포스핀이나 N,N,N',N'-테트라메틸알킬렌디아민으로 4차염을 형성시키고, 가교화시켜 만든 감습막은 매우 좋은 내수성을 보여주며, 감습특성이 좋아 습도센서로서의 응용가능성을 보여주고 있다. 그러나, 감습막과 전극의 기판과의 접착성의 저하로 고습 조건에서 경시변화가 크게 일어나고, 기판에서부터 막의 탈리가 진행되는 문제를 야기하고 있다. 그러나, 이러한 문제가 해결된다면 4차염화를 이용한 가교화는 내수성을 향상시키는데 가장 편리한 방법 중 하나가 될 것이다.Copolymers containing phosphine, pyridine and tertiary amine groups may be mixed with α, ω-dihaloalkanes or applied in the opposite way to copolymers containing alkyl halides or benzyl halides before being applied to the electrodes. The moisture-sensitive film formed by forming a quaternary salt with, N ', N'-tetramethylalkylenediamine and crosslinking shows very good water resistance and shows good applicability as a humidity sensor due to its good moisture resistance. However, due to the deterioration of the adhesion between the moisture-sensitive film and the substrate of the electrode, a change over time occurs in high humidity conditions, causing a problem that the film detaches from the substrate. However, if this problem is solved, crosslinking using quaternization will be one of the most convenient methods for improving water resistance.
본 발명의 목적은 3차아민기를 포함하는 비닐단량체와 염을 포함하는 비닐단량체 그리고 1 또는 2이상의 비닐공단량체를 공중합시킨 제1공중합체 및 알킬할라이드기를 포함하는 비닐단량체와 1 또는 2이상의 비닐공단량체를 공중합시킨 제2공중합체를 서로 혼합하여 단순한 가열을 통하여 4차암모늄화 반응을 통해 가교화시켜 형성된 새로운 감습막 포함하는 고분자막 습도센서를 제공하는 데 있다.An object of the present invention is a vinyl monomer comprising a tertiary amine group, a vinyl monomer comprising a salt and a vinyl monomer comprising a first copolymer and an alkyl halide group copolymerized with one or two or more vinyl comonomers and one or two or more vinyl balls. The present invention provides a polymer film humidity sensor including a new moisture-sensitive film formed by mixing a second copolymer copolymerized with monomers and cross-linking through a quaternary ammonium reaction through simple heating.
본 발명에 따른 고분자막 습도센서는, 감습막, 상기 감습막과 전기적 접촉을 유지하는 전극, 상기 전극을 고정시키는 전극스냅 및 상기 전극을 외부와 연결하는 단자를 포함하는 고분자막 습도센서에 있어서, 상기 감습막이 3차아민기를 포함하는 비닐단량체와 염을 포함하는 비닐단량체 그리고 1 또는 2이상의 비닐공단량체를 공중합시킨 제1공중합체 및 알킬할라이드기를 포함하는 비닐단량체와 1 또는 2이상의 비닐공단량체를 공중합시킨 제2공중합체를 서로 4차암모늄화 반응을 통해 가교화되어 이루어지는 것이다.In the polymer film humidity sensor according to the present invention, in the polymer film humidity sensor comprising a moisture sensitive film, an electrode for maintaining electrical contact with the moisture sensitive film, an electrode snap for fixing the electrode, and a terminal for connecting the electrode to the outside, The membrane is prepared by copolymerizing a vinyl monomer comprising a tertiary amine group, a vinyl monomer comprising a salt, a first copolymer copolymerized with one or two or more vinyl comonomers, and a vinyl monomer comprising an alkyl halide group and one or two or more vinyl comonomers. The second copolymer is crosslinked with each other through a quaternary ammoniumation reaction.
이하, 본 발명의 구체적인 실시예를 첨부한 도면을 참조하여 상세히 설명한다.Hereinafter, exemplary embodiments of the present invention will be described in detail with reference to the accompanying drawings.
본 발명에 따른 고분자막 습도센서는, 감습막, 상기 감습막과 전기적 접촉을 유지하는 전극, 상기 전극을 고정시키는 전극스냅 및 상기 전극을 외부와 연결하는 단자를 포함하는 고분자막 습도센서에 있어서, 상기 감습막이 3차아민기를 포함하는 비닐단량체와 염을 포함하는 비닐단량체 그리고 1 또는 2이상의 비닐공단량체를 공중합시킨 제1공중합체 및 알킬할라이드기를 포함하는 비닐단량체와 1 또는 2이상의 비닐공단량체를 공중합시킨 제2공중합체를 서로 4차암모늄화 반응을 통해 가교화시켜 이루어짐을 특징으로 한다.In the polymer film humidity sensor according to the present invention, in the polymer film humidity sensor comprising a moisture sensitive film, an electrode for maintaining electrical contact with the moisture sensitive film, an electrode snap for fixing the electrode, and a terminal for connecting the electrode to the outside, The membrane is prepared by copolymerizing a vinyl monomer comprising a tertiary amine group, a vinyl monomer comprising a salt, a first copolymer copolymerized with one or two or more vinyl comonomers, and a vinyl monomer comprising an alkyl halide group and one or two or more vinyl comonomers. The second copolymer is cross-linked through a quaternary ammoniumation reaction with each other.
고분자막 습도센서는 습도에 따라서 임피던스가 변화하는 감습제로서 3차아민기를 포함하는 비닐단량체와 염을 포함하는 비닐단량체 그리고 1 또는 2이상의 비닐공단량체를 공중합시킨 제1공중합체 및 알킬할라이드기를 포함하는 비닐단량체와 1 또는 2이상의 비닐공단량체를 공중합시킨 제2공중합체들을 용해한 공중합체들 용액에 금전극 및 은-팔라듐을 포함하는 전극으로 된 습도센서 전극을 침적하고, 가열에 의해 4차암모늄화 반응을 통해 가교화시켜 형성된 감습막으로 이루어진다.The polymer membrane humidity sensor is a humidity sensitive agent whose impedance varies according to humidity, and includes a vinyl monomer including a tertiary amine group, a vinyl monomer including a salt, and a first copolymer and an alkyl halide group copolymerized with one or more vinyl comonomers. A humidity sensor electrode made of a gold electrode and an electrode containing silver-palladium was deposited on a solution of copolymers in which a second monomer copolymerized with a vinyl monomer and one or two or more vinyl comonomers was dissolved. It consists of a moisture sensitive film formed by crosslinking through reaction.
상기 제1공중합체를 구성하는 3차아민기를 포함하는 비닐단량체는 상기 제1공중합체에 10 내지 40중량%의 양으로 도입될 수 있다. 상기 3차아민기를 포함하는 비닐단량체가 10중량% 미만으로 포함되는 경우, 감습막의 가교도가 낮아져서 물에 대한 용해성이 증가하는 문제점이 있을 수 있으며, 반대로 40중량%를 포함하는 경우, 감습막의 유연성이 저하되는 등 물리적인 성질의 변화가 있을 수 있으며, 감습특성에도 영향을 미친다.The vinyl monomer including the tertiary amine group constituting the first copolymer may be introduced into the first copolymer in an amount of 10 to 40% by weight. When the vinyl monomer including the tertiary amine group is included in less than 10% by weight, there may be a problem in that the solubility in water is increased because the degree of crosslinking of the moisture sensitive film is lowered. There may be a change in physical properties, such as deterioration, and also affects the moisture absorption characteristics.
상기 염을 포함하는 비닐단량체는 상기 제1공중합체에 상기 3차아민기를 포함하는 비닐단량체의 양에 반대로 60 내지 90중량%의 양으로 도입될 수 있으며, 바람직하게는 60 내지 80중량%의 양으로 도입될 수 있다. 상기 염을 포함하는 비닐단량체가 60중량% 미만으로 포함되는 경우, 감습특성이 저하되는 문제점이 있을 수 있다. 또한, 상기 비닐공단량체는 상기 제1공중합체에서 3차아민기를 포함하는 비닐단량체와 상기 염을 포함하는 비닐단량체를 제외한 잔량으로 포함될 수 있다. 상기 비닐공단량체의 함량조절에 의해 수득되는 감습막의 감습특성의 조절이 가능하고 또한 막의 유연성을 증가시키는 유리전이온도가 낮은 비닐공단량체의 사용은 수득되는 감습막의 유연성 및 전극과의 접착성을 향상시킨다.The vinyl monomer including the salt may be introduced in the first copolymer in an amount of 60 to 90% by weight, in contrast to the amount of the vinyl monomer including the tertiary amine group, preferably in an amount of 60 to 80% by weight. Can be introduced. If the vinyl monomer containing the salt is included in less than 60% by weight, there may be a problem that the moisture absorption is lowered. In addition, the vinyl comonomer may be included in the remaining amount except the vinyl monomer including the tertiary amine group and the vinyl monomer including the salt in the first copolymer. The control of the moisture sensitivity of the moisture-sensitive film obtained by controlling the content of the vinyl comonomer and the use of a low-transition vinyl comonomer, which increases the flexibility of the film, improves the flexibility and adhesion to the electrode of the moisture-sensitive film obtained. Let's do it.
상기 제2공중합체를 구성하는 알킬할라이드를 포함하는 비닐단량체는 상기 제2공중합체에 10 내지 40중량%의 양으로 도입될 수 있다. 상기 알킬할라이드를 포함하는 비닐단량체가 10중량% 미만으로 포함되는 경우, 감습막의 가교도가 낮아져서 물에 대한 용해성이 증가하는 문제점이 있을 수 있으며, 반대로 40중량%를 포함하는 경우, 감습막의 유연성이 저하되는 등 물리적인 성질의 변화가 있을 수 있며, 감습특성에는 영향을 미친다.The vinyl monomer including the alkyl halide constituting the second copolymer may be introduced into the second copolymer in an amount of 10 to 40% by weight. When the vinyl monomer including the alkyl halide is included in less than 10% by weight, there may be a problem that the solubility in water is increased by lowering the degree of crosslinking of the moisture-sensitive film, on the contrary, when containing 40% by weight, the flexibility of the moisture-sensitive film is lowered. There may be a change in physical properties, such as, will affect the humidity characteristics.
상기 3차아민기를 포함하는 비닐단량체는 2-(N,N-디메틸아미노에틸)아크릴레이트, 2-(N,N-디메틸아미노에틸)메타크릴레이트, 2-(N,N-디에틸아미노에틸)아크릴레이트, 2-(N,N-디에틸아미노에틸)메타크릴레이트, 4-비닐피리딘, 2-비닐피리딘, 알릴아민, 디알릴아민, 트리알릴아민 또는 이들 중 2이상의 혼합물로 이루어지는 그룹 중에서 선택된 것이 될 수 있다.The vinyl monomer containing the tertiary amine group is 2- (N, N-dimethylaminoethyl) acrylate, 2- (N, N-dimethylaminoethyl) methacrylate, 2- (N, N-diethylaminoethyl ) Acrylate, 2- (N, N-diethylaminoethyl) methacrylate, 4-vinylpyridine, 2-vinylpyridine, allylamine, diallylamine, triallylamine or mixtures of two or more thereof Can be selected.
상기 염을 포함하는 비닐단량체는 1-(2-히드록시)-3-메타크릴옥시프로필 트리메틸암모늄할라이드, 4차 염화된 비닐피리딘, N,N,N-트리메틸암모노에틸 아크릴레이트할라이드, N,N,N-트리메틸암모노에틸 메타크릴레이트할라이드, 알릴디알킬 설포늄할라이드, 2-(N,N-디메틸아미노에틸)메타크릴아미드, 디메틸디알릴 암모늄클로라이드, 2-메타크릴옥시에틸알킬 디메틸암모늄할라이드, 2-메타크릴옥시에틸 히드록시알킬 디메틸암모늄할라이드, 알킬기의 탄소수 2 내지 18의 비닐벤질트리알킬 포스포늄할라이드, 아릴기의 탄소수 2 내지 18의 비닐벤질트리아릴 포스포늄할라이드, 나트륨 스티렌술포네이트, 나트륨 알릴술포네이트, 나트륨 트리알킬포스페이트, 나트륨 비닐술포네이트 또는 이들 중 2이상의 혼합물로 이루어진 그룹 중에서 선택된 것이 될 수 있다.Vinyl monomers comprising such salts include 1- (2-hydroxy) -3-methacryloxypropyl trimethylammonium halide, quaternary chlorided vinylpyridine, N, N, N-trimethylammonoethyl acrylate halide, N, N, N-trimethylammonoethyl methacrylate halide, allyldialkyl sulfonium halide, 2- (N, N-dimethylaminoethyl) methacrylamide, dimethyldiallyl ammonium chloride, 2-methacryloxyethylalkyl dimethylammonium Halide, 2-methacryloxyethyl hydroxyalkyl dimethylammonium halide, vinylbenzyltrialkyl phosphonium halide having 2 to 18 carbon atoms of alkyl group, vinylbenzyltriaryl phosphonium halide having 2 to 18 carbon atoms of aryl group, sodium styrenesulfonate , Sodium allylsulfonate, sodium trialkylphosphate, sodium vinylsulfonate or a mixture of two or more thereof. .
상기 알킬할라이드를 포함하는 비닐단량체는 염화비닐벤질, 2-염화에틸아크릴레이트, 2-염화에틸메타크릴레이트, 2-염화에틸비닐에테르, 염화알릴, 4-염화부텐, 6-염화헥센 또는 이들 중 2이상의 혼합물로 이루어지는 그룹 중에서 선택된 것이 될 수 있다.The vinyl monomer including the alkyl halide may be selected from vinyl benzyl chloride, 2-ethylethyl acrylate, 2-ethyl methacrylate, 2-ethyl vinyl chloride, allyl chloride, 4-butene chloride, 6-hexene chloride, and the like. It may be selected from the group consisting of two or more mixtures.
상기 비닐공단량체는 필요에 따르고, 감습막의 유연성이나 전극과의 접착성 그리고 감습성 등의 개질 등을 목적으로 사용되는 것으로서, 아크릴산, 메타크릴산, 카르복시에틸아크릴레이트, 카르복시펜틸아크릴레이트, 이타콘산, 말레산, 푸말산, 크로톤산 등의 카르복실기 함유 비닐단량체; 무수말레산, 무수이타콘산 등의 산무수물 비닐단량체; 아크릴산 히드록시에틸, 메타크릴산 히드록시에틸, 아크릴산 히드록시프로필, 메타크릴산 히드록시프로필, 아크릴산 히드록시부틸, 메타크릴산 히드록시부틸, 아크릴산 히드록시헥실, 메타크릴산 히드록시헥실 등의 히드록실기 함유 비닐단량체; N,N-디메틸 아크릴아미드, N,N-디메틸 메타크릴아미드 등의 N-치환 아미드계 비닐단량체; 아크릴산 메톡시에틸, 메타크릴산 메톡시에틸, 아크릴산 에톡시에틸, 메타크릴산 에톡시에틸 등의 아크릴산 알콕시알킬 비닐단량체; 초산비닐, 프로피온산비닐, N-비닐피롤리돈, 메틸비닐피롤리돈, 비닐피리딘,비닐피페리돈, 비닐피리미딘, 비닐피페라진, 비닐피라진, 비닐피롤, 비닐이미다졸, 비닐옥사졸, 비닐몰폴릴, N-비닐카르본산아미드, 스틸렌, α-메틸스틸렌, N-비닐카프로락탐 등의 비닐단량체; 아크릴로니트릴, 메타크릴로니트릴 등의 시아노아크릴레이트 비닐단량체; 아크릴산 글리시딜, 메타크릴산 글리시딜 등의 에폭시기 함유 아크릴 단량체; 아크릴산 폴리에틸렌글리콜, 메타크릴산 폴리에틸렌글리콜, 아크릴산 폴리프로필렌글리콜, 메타크릴산 폴리프로필렌글리콜, 아크릴산 메톡시에틸렌글리콜, 메타크릴산 메톡시폴리에틸렌글리콜, 아크릴산 메톡시폴리프로필렌글리콜, 메타크릴산 메톡시폴리프로필렌글리콜 등의 글리콜계 아크릴에스테르단량체; 아크릴산 테트라히드로퍼프릴, 메타크릴산 테트라히드로퍼프릴, 2-메톡시에틸 아크릴레이트 등의 아크릴산 에스테르단량체; 이소프렌, 부타디엔, 이소부틸렌, 비닐에테르 등의 단량체; 또는 이들 중 2이상의 혼합물로 이루어지는 그룹중에서 선택된 것이 될 수 있다.The vinyl comonomer is used for the purpose of modification such as flexibility of the moisture-sensitive film, adhesiveness with the electrode, and moisture sensitivity, if necessary, and include acrylic acid, methacrylic acid, carboxyethyl acrylate, carboxypentyl acrylate, and itaconic acid. Carboxyl group-containing vinyl monomers such as maleic acid, fumaric acid and crotonic acid; Acid anhydride vinyl monomers such as maleic anhydride and itaconic anhydride; Hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate, hydroxypropyl methacrylate, hydroxybutyl acrylate, hydroxybutyl methacrylate, hydroxyhexyl acrylate, hydroxyhexyl methacrylate Siloxane group-containing vinyl monomers; N-substituted amide vinyl monomers such as N, N-dimethyl acrylamide and N, N-dimethyl methacrylamide; Alkoxy acrylate vinyl monomers, such as methoxy ethyl acrylate, methoxy ethyl methacrylate, ethoxy ethyl acrylate, and ethoxy ethyl methacrylate; Vinyl acetate, vinyl propionate, N-vinylpyrrolidone, methylvinylpyrrolidone, vinylpyridine, vinylpiperidone, vinylpyrimidine, vinylpiperazine, vinylpyrazine, vinylpyrrole, vinylimidazole, vinyloxazole, vinyl Vinyl monomers such as morpholyl, N-vinyl carboxylic acid amide, styrene, α-methylstyrene, and N-vinyl caprolactam; Cyanoacrylate vinyl monomers such as acrylonitrile and methacrylonitrile; Epoxy group-containing acrylic monomers such as glycidyl acrylate and glycidyl methacrylate; Polyethylene glycol acrylate, polyethylene glycol methacrylate, polypropylene glycol acrylate, polypropylene glycol methacrylate, methoxy ethylene glycol methacrylate, methoxy polyethylene glycol methacrylate, methoxy polypropylene glycol acrylate, methoxy polypropylene methacrylate Glycol-based acrylic ester monomers such as glycol; Acrylic ester monomers such as tetrahydroperpril acrylate, tetrahydroperpril methacrylate and 2-methoxyethyl acrylate; Monomers such as isoprene, butadiene, isobutylene and vinyl ether; Or a group selected from the group consisting of two or more of these.
이하에서 본 발명의 바람직한 실시예 및 비교예들이 기술되어질 것이다.Hereinafter, preferred embodiments and comparative examples of the present invention will be described.
이하의 실시예들은 본 발명을 예증하기 위한 것으로서 본 발명의 범위를 국한시키는 것으로 이해되어져서는 안될 것이다.The following examples are intended to illustrate the invention and should not be understood as limiting the scope of the invention.
실시예 1 내지 실시예 5Examples 1-5
하기 표 1에 나타낸 바에 따라 감습제로서 3차아민기를 포함하는 비닐단량체와 염을 포함하는 비닐단량체 그리고 1 또는 2이상의 비닐공단량체를 공중합시킨 제1공중합체 및 알킬할라이드기를 포함하는 비닐단량체와 1 또는 2이상의 비닐공단량체를 공중합시킨 제2공중합체를 준비하였다. 공중합체의 제조에 있어서는, 단량체로서 먼저 4-비닐피리딘 40g, 2-메타크릴옥시에틸트리메틸 암모늄클로라이드 40g, n-부틸아크릴레이트 10g 그리고 2-히드록시에틸 메타크릴레이트 10g을 혼합하고, 여기에 개시제 α, α'-아조비스이소부티로니트릴 0.100g을 벤젠 300g에 용해시키고, 탈가스한 후, 60℃에서 24시간 라디칼중합을 진행하여 하나의 공중합체를 합성하였다. 중합이 완료된 후, 메틸렌클로라이드를 첨가하고, 용액을 n-헥산에 재침전시켜 공중합체를 수득하였다. 재침전 과정을 한번 더 반복한 후, 진공건조시켜, 흰색 분말상태의 공중합체(제1공중합체)를 수득하였다. 다른 공중합체는 염화비닐벤질 40g, 2-메타크릴옥시에틸트리메틸 암모늄클로라이드 40g, n-부틸아크릴레이트 10g 그리고 2-히드록시에틸메타크릴레이트 10g을 혼합하고, 여기에 개시제 α, α'-아조비스이소부티로니트릴 0.100g을 벤젠 300g에 용해시키고, 중합앰플에 넣고 질소분위기 하에서 60℃에서 12시간 라디칼중합을 진행하여 하나의 공중합체를 합성하였다. 중합이 완료된 후, 메틸렌클로라이드를 첨가하고, 석유에테르에 재침전시켜 공중합체를 수득하였다. 재침전 과정을 한번 더 반복한 후, 50℃의 진공오븐에서 진공건조시켜, 흰색 분말상태의 공중합체(제2공중합체)를 수득하였다.As shown in Table 1 below, a vinyl monomer comprising a tertiary amine group, a vinyl monomer comprising a tertiary amine group and a salt, a vinyl monomer comprising a first copolymer and an alkyl halide group copolymerized with one or two or more vinyl comonomers, and one Alternatively, a second copolymer obtained by copolymerizing two or more vinyl comonomers was prepared. In the preparation of the copolymer, first, 40 g of 4-vinylpyridine, 40 g of 2-methacryloxyethyltrimethyl ammonium chloride, 10 g of n-butyl acrylate and 10 g of 2-hydroxyethyl methacrylate are mixed as monomers, and the initiator is added thereto. 0.100 g of α and α'-azobisisobutyronitrile were dissolved in 300 g of benzene, degassed, and subjected to radical polymerization at 60 ° C. for 24 hours to synthesize one copolymer. After the polymerization was completed, methylene chloride was added and the solution was reprecipitated in n-hexane to give a copolymer. The reprecipitation process was repeated once more, followed by vacuum drying to obtain a white powdery copolymer (first copolymer). The other copolymer is mixed with 40 g of vinyl benzyl chloride, 40 g of 2-methacryloxyethyltrimethyl ammonium chloride, 10 g of n-butyl acrylate, and 10 g of 2-hydroxyethyl methacrylate, and the initiators α, α'-azobis are added thereto. 0.100 g of isobutyronitrile was dissolved in 300 g of benzene, placed in a polymerization ampoule, and subjected to radical polymerization at 60 ° C. under a nitrogen atmosphere for 12 hours to synthesize one copolymer. After the polymerization was completed, methylene chloride was added and reprecipitated in petroleum ether to obtain a copolymer. After repeating the reprecipitation process once more, it was vacuum dried in a vacuum oven at 50 ℃ to obtain a white powdery copolymer (second copolymer).
상기 제1공중합체 20g을 400g의 디메틸술폭시드에 균질하게 용해시켜 용액으로 준비하여 용기에 담아놓고, 별도의 용기에 상기 제2공중합체 20g을 역시 400g의 디메틸술폭시드에 균질하게 용해시켜 용액으로 준비하였다. 5℃, 60%RH(상대습도)의 일정한 조건에서 상기 제1공중합체용액과 제2공중합체용액을 신속하게 혼합한 후, 소형의 용기에 옮겨 20개의 습도센서 전극을 지그(jig)에 수직으로 꽂아 침적하여 전극에 도포시켜 본 발명에 따른 감습막이 도포된 전극을 제조하였다. 감습막이 도포된 상기 전극은 곧바로 수평을 유지하면서 상온에서 정치시켜 10분 동안 자연 건조시킨 후, 점차로 온도를 올려 60℃에서 4시간 동안 가열을 하여 가교화반응을 더 수행하였다. 가교화가 진행된 후, 진공건조시켜 가교화된 공중합체 감습막이 도포된 전극을 형성시켰다. 과량의 피리딜기 또는 벤질기의 존재에 의한 경시변화 방지를 위하여 진공을 조절하여 반응시킬 수 있는 플라스크에 n-염화부틸 또는 트리에틸아민을 넣어 감압상태에서 증기 상으로 60℃를 유지하면서 2시간 동안 더 정치시키고, 잔류 미반응물을 제거하기 위하여 에탄올에 30분간 침적시킨 후, 다시 진공건조시켜 습도센서의 제조를 완성시켰다.20 g of the first copolymer was homogeneously dissolved in 400 g of dimethyl sulfoxide, prepared as a solution, and placed in a container, and 20 g of the second copolymer was homogeneously dissolved in 400 g of dimethyl sulfoxide in a separate container. Ready. Rapid mixing of the first copolymer solution and the second copolymer solution at a constant condition of 5 ° C. and 60% RH (relative humidity) is carried out in a small container, and the 20 humidity sensor electrodes are perpendicular to the jig. The electrode was coated with the electrode and deposited on the electrode to apply the moisture-sensitive film according to the present invention. The electrode to which the moisture-sensitive film was applied was left to stand at room temperature immediately while being horizontally dried for 10 minutes, and then gradually heated up at 60 ° C. for 4 hours to further perform crosslinking reaction. After crosslinking progressed, it was vacuum-dried to form the electrode to which the crosslinked copolymer damping film was apply | coated. In order to prevent changes over time due to the presence of excess pyridyl or benzyl groups, n-butyl chloride or triethylamine was placed in a flask that can be reacted by controlling the vacuum for 2 hours while maintaining the temperature in the vapor phase at a reduced pressure at 60 ° C. It was left still, soaked in ethanol for 30 minutes to remove residual unreacted material, and then vacuum dried again to complete the manufacture of the humidity sensor.
한편, 수득된 습도센서를 하기 표 2에 나타낸 바의 조건으로 환경시험을 수행하였으며, 그 결과를 하기 표 3 및 도 3과 도 4에 각각 나타내었다.On the other hand, the obtained humidity sensor was subjected to an environmental test under the conditions shown in Table 2, and the results are shown in Table 3 and Figures 3 and 4, respectively.
또한, 수득된 습도센서에 대하여 전기적 성질을 조사하였다. 수득된 습도센서의 감습특성은 항온항습조의 온도가 25℃, 상대습도 30%RH로 평형이 되었을 때, LCR meter(Tabai사 모델 Espec PL-2G)의 출력을 1㎑, 1V에서 습도를 조절하여 저항값을 측정하였다. 20%RH→95%RH의 가습과정과 95%RH→20%RH의 제습과정의 순서로 히스테리시스를 측정하였다. 그 밖의 온도 의존성계수는 항온항습조의 온도를 15℃, 25℃, 35℃로 변화시켜 상기 순서에 의하여 측정하였으며, 주파수 변화에 따른 저항의 의존성은 출력을 100㎐, 1㎑ 그리고 10㎑로 변화시켜 측정하였다. 저습과 고습 사이의 응답속도는 20℃에서 MgCl2 ·6H2O의 포화용액과 K2SO4 의 포화용액의 상대습도인 33%RH 그리고 94%RH 범위에서 측정하였다.In addition, the electrical properties of the obtained humidity sensor were investigated. The humidity characteristics of the obtained humidity sensor were controlled by adjusting the humidity at 1㎑ and 1V when the temperature of the constant temperature and humidity chamber was equilibrated to 25 ° C and the relative humidity of 30% RH. The resistance value was measured. Hysteresis was measured in the order of 20% RH → 95% RH, followed by 95% RH → 20% RH. The other temperature dependence coefficient was measured by changing the temperature of the constant temperature and humidity chamber to 15 ℃, 25 ℃, and 35 ℃, and the dependence of the resistance according to the frequency change changed the output to 100㎐, 1㎑ and 10㎑. Measured. The response rate between low humidity and high humidity was measured at a relative humidity of 33% RH and 94% RH of the saturated solution of MgCl 2 · 6H 2 O and the saturated solution of K 2 SO 4 at 20 ℃.
제조된 습도센서들은 20 내지 95%RH에서의 측정결과를 도 2에 나타내었고, 그 밖에 도 3에 온도 의존성 시험결과, 도 4에 주파수 의존성 시험결과, 도 5에 응답속도 그리고 도 6에 내수성에 대한 시험결과를 나타내었다.The manufactured humidity sensors are shown in Fig. 2 at 20 to 95% RH, and the temperature dependence test results in Fig. 3, the frequency dependency test results in Fig. 4, the response speed in Fig. 5, and the water resistance in Fig. 6 are shown. The test results are shown.
상기한 실시예들을 종합한 결과, 본 발명에 따른 습도센서는 상기 표들 및 도면들에서 나타난 바와 같이 우수한 감습특성을 가짐을 확인할 수 있었다. 특히, 분자량이 큰 제1공중합체와 제2공중합체들이 서로 4차염화반응을 통해 가교화되어 내수성이 뛰어난 습도센서를 제조할 수 있음을 확인할 수 있었다.As a result of synthesizing the above embodiments, it was confirmed that the humidity sensor according to the present invention has excellent moisture absorption characteristics as shown in the tables and drawings. In particular, it was confirmed that the first copolymer and the second copolymer having a high molecular weight were crosslinked with each other through a quaternization reaction to produce a humidity sensor having excellent water resistance.
알킬할라이드와 3차아민은 서로 반응하여 4차암모늄염을 쉽게 형성할 수 있으므로 알킬할라이드와 3차아민을 포함하는 공중합체들은 공중합체들끼리 서로 반응성을 보여주며, 이러한 공중합체들끼리 반응하여 생성된 가교체는 세미-IPN 형태를 가지며, 고도의 가교를 형성하면서 4차암모늄화가 진행되어 우수한 감습특성을 갖는 감습막을 제조할 수 있음을 확인할 수 있었다.Since alkyl halides and tertiary amines can easily react with each other to form quaternary ammonium salts, copolymers containing alkyl halides and tertiary amines exhibit reactivity with each other, and these copolymers react with each other. The crosslinked product had a semi-IPN form, and it was confirmed that quaternary ammoniumation proceeded while forming highly crosslinked to prepare a moisture-sensitive film having excellent moisture absorption properties.
따라서, 본 발명에 의하면 감습특성이 우수한 감습막을 제공함은 물론 이를 포함하는 습도센서를 제공하는 효과가 있으며, 최근 자동화 및 제어시스템, 조절시스템을 목적으로 하는 가습기, 보습, 제습, 공기조절, 건조시스템 등의 부품으로 사용될 수 있으며, 자동차의 결로방지, 비디오테이프레코더(VTR ; Video tape recorder), 캠코더, 팩시밀리 등의 결로예지센서, 고습센서, 저온습도센서 등에 이용될 수 있는 습도센서를 제공하는 효과가 있다.Therefore, according to the present invention, there is an effect of providing a humidity sensor having excellent moisture sensitivity as well as providing a humidity sensor including the same. Recently, a humidifier for the purpose of automation and control system, control system, moisturizing, dehumidification, air conditioning, drying system It can be used as parts such as condensation prevention of cars, video tape recorder (VTR), camcorder, facsimile condensation sensor, high humidity sensor, low temperature and humidity sensor, etc. There is.
이상에서 본 발명은 기재된 구체예에 대해서만 상세히 설명되었지만 본 발명의 기술사상 범위 내에서 다양한 변형 및 수정이 가능함은 당업자에게 있어서 명백한 것이며, 이러한 변형 및 수정이 첨부된 특허청구범위에 속함은 당연한 것이다.Although the present invention has been described in detail only with respect to the described embodiments, it will be apparent to those skilled in the art that various modifications and variations are possible within the technical scope of the present invention, and such modifications and modifications are within the scope of the appended claims.
도 1은 본 발명에 따른 고분자막 습도센서의 전극을 개략적으로 도시한 구성도이다.1 is a configuration diagram schematically showing an electrode of a polymer film humidity sensor according to the present invention.
도 2는 본 발명에 따라 제조된 고분자막 습도센서에 사용되는 감습막의 감습특성을 도시한 그래프이다.Figure 2 is a graph showing the moisture sensitivity of the moisture-sensitive film used in the polymer film humidity sensor prepared according to the present invention.
도 3은 본 발명에 따라 제조된 고분자막 습도센서의 온도 의존성 그래프이다.3 is a temperature dependency graph of the polymer film humidity sensor manufactured according to the present invention.
도 4는 본 발명에 따라 제조된 고분자막 습도센서의 주파수 의존성 그래프이다.4 is a frequency dependency graph of the polymer film humidity sensor manufactured according to the present invention.
도 5는 본 발명에 따라 제조된 고분자막 습도센서의 응답시간을 나타낸 그래프이다.5 is a graph showing the response time of the polymer film humidity sensor manufactured according to the present invention.
도 6은 본 발명에 따라 제조된 고분자막 습도센서의 내수성을 나타낸 그래프이다.6 is a graph showing the water resistance of the polymer film humidity sensor manufactured according to the present invention.
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