JP6270201B2 - Polymer metal complex having liquid crystallinity and method for producing polymer metal complex having liquid crystallinity - Google Patents
Polymer metal complex having liquid crystallinity and method for producing polymer metal complex having liquid crystallinity Download PDFInfo
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Description
本発明は、液晶性を有する高分子金属錯体及び液晶性を有する高分子金属錯体の製造方法に関する。 The present invention relates to a polymer metal complex having liquid crystallinity and a method for producing a polymer metal complex having liquid crystallinity.
従来、液晶性高分子は、その高い配向性を利用して、高性能材料や高機能性材料への応用がなされてきた。 Conventionally, liquid crystalline polymers have been applied to high-performance materials and high-functional materials by utilizing their high orientation.
しかしながら、それら応用例の多くは液晶性ポリエステルを利用した耐熱性樹脂や、高強度・高弾性率繊維としての利用が主であり、応答性を考慮した材料の開発は行われておらず、100℃以下で応答できる液晶性高分子（特に主鎖型高分子液晶）の提案はほとんどなされていなかった。 However, many of these applications are mainly used as heat-resistant resins using liquid crystalline polyester and high-strength / high-modulus fibers, and materials that take into account responsiveness have not been developed. There has been almost no proposal of a liquid crystalline polymer (especially a main chain polymer liquid crystal) capable of responding at a temperature of ℃ or less.
そこで、長年に亘り高分子液晶の分野で研究を重ねている本発明者は、新規な液晶性高分子である液晶性ポリアミノウレタンを過去に提案している（例えば、特許文献１参照。）。 Therefore, the present inventor, who has been researching in the field of polymer liquid crystals for many years, has previously proposed a liquid crystalline polyaminourethane, which is a novel liquid crystalline polymer (see, for example, Patent Document 1).
この液晶性ポリアミノウレタンによれば、100℃以下、更には室温においても応答可能な液晶性高分子を提供することができる。 According to this liquid crystalline polyaminourethane, it is possible to provide a liquid crystalline polymer capable of responding at 100 ° C. or lower and even at room temperature.
ところで、近年、機能性を有する高分子の一つとして、金属原子を構成要素として備えるメタロポリマーが着目されている。 By the way, in recent years, metallopolymers having metal atoms as constituent elements have attracted attention as one of functional polymers.
そこで本発明者は、先に提案したポリアミノウレタンを応用したメタロポリマーの開発を行い、本発明を完成するに至った。 Therefore, the present inventor has developed a metallopolymer using the previously proposed polyaminourethane, and has completed the present invention.
本発明は、斯かる事情に鑑みてなされたものであって、液晶性を有する新たな高分子金属錯体を提供する。また、同液晶性を有する高分子金属錯体の製造方法についても提供する。 The present invention has been made in view of such circumstances, and provides a new polymer metal complex having liquid crystallinity. In addition, a method for producing a polymer metal complex having the same liquid crystallinity is also provided.
上記従来の課題を解決するために、本発明に係る液晶性を有する高分子金属錯体では、下記一般式
にて表されるポリアミノウレタンと、遷移金属イオンとを有し、
前記ポリアミノウレタンが有するアミノ基及びウレタン結合を前記遷移金属イオンに配位させて構成した。
In order to solve the above conventional problems, the polymer metal complex having liquid crystal properties according to the present invention has the following general formula:
Having a polyaminourethane represented by: and a transition metal ion,
The polyaminourethane has an amino group and a urethane bond coordinated to the transition metal ion.
また、本発明に係る液晶性を有する高分子金属錯体の製造方法では、下記一般式
にて表されるポリアミノウレタンと、遷移金属のイオンとを混合して、前記ポリアミノウレタンが有するアミノ基及びウレタン結合を前記遷移金属イオンに配位させることとした。
In the method for producing a polymer metal complex having liquid crystal properties according to the present invention, the following general formula
And the amino group and urethane bond of the polyaminourethane are coordinated to the transition metal ion.
また、本発明に係る液晶性を有する高分子金属錯体の製造方法では、前記ポリアミノウレタンと前記遷移金属のイオンとの混合は、前記ポリアミノウレタンを溶媒中に溶解又は分散させたポリアミノウレタン含有液と、前記遷移金属の塩類を溶媒に溶解させた塩類溶液とを混合して行うこととしても良い。 In the method for producing a polymer metal complex having liquid crystal properties according to the present invention, the polyaminourethane and the transition metal ions may be mixed with a polyaminourethane-containing liquid obtained by dissolving or dispersing the polyaminourethane in a solvent. The transition metal salt may be mixed with a salt solution obtained by dissolving the transition metal salt in a solvent.
また、本発明に係る液晶性を有する高分子金属錯体の製造方法では、前記ポリアミノウレタンと前記遷移金属のイオンとの混合は、粉体状又は固体状の前記ポリアミノウレタンと、前記遷移金属の塩類を溶媒に溶解させた塩類溶液とを接触させて行うこととしても良い。 In the method for producing a polymer metal complex having liquid crystallinity according to the present invention, the polyaminourethane and the transition metal ions may be mixed in the form of powder or solid polyaminourethane and the transition metal salt. It is good also as making it contact with the salt solution which melt | dissolved this in the solvent.
また、本発明に係る液晶性を有する高分子金属錯体の製造方法では、前記ポリアミノウレタンと前記遷移金属のイオンとの混合は、加熱することにより流動性を有する液晶状態とした前記ポリアミノウレタンと、前記遷移金属の塩類とを混練して行うこととしても良い。 Further, in the method for producing a polymer metal complex having liquid crystallinity according to the present invention, the mixing of the polyaminourethane and the ions of the transition metal is performed by heating the polyaminourethane in a liquid crystal state having fluidity, It may be carried out by kneading the transition metal salt.
本発明に係る液晶性を有する高分子金属錯体によれば、上記構成を有することとしたため、液晶性を有する新たな高分子金属錯体を提供することができる。 Since the polymer metal complex having liquid crystal properties according to the present invention has the above-described configuration, a new polymer metal complex having liquid crystal properties can be provided.
また、本発明に係る液晶性を有する高分子金属錯体によれば、上記構成を有することとしたため、液晶性を有する新たな高分子金属錯体の製造方法を提供することができる。 Moreover, according to the polymer metal complex having liquid crystal properties according to the present invention, since it has the above-described configuration, a new method for producing a polymer metal complex having liquid crystal properties can be provided.
本発明は、液晶性を有する高分子金属錯体（以下、液晶性高分子金属錯体ともいう。）及びその製造方法を提供するものである。 The present invention provides a polymer metal complex having liquid crystallinity (hereinafter also referred to as a liquid crystal polymer metal complex) and a method for producing the same.
本実施形態に係る液晶性高分子金属錯体は、アミノ基とウレタン結合とメソゲンとを備える単位構造の繰り返しにより構成されたポリアミノウレタンと遷移金属元素のイオンとを有するものであり、ポリアミノウレタンが有するアミノ基の窒素原子及びウレタン結合の窒素原子を遷移金属元素のイオンに配位させて構成したものである。 The liquid crystalline polymer metal complex according to the present embodiment has a polyaminourethane constituted by repeating a unit structure including an amino group, a urethane bond, and a mesogen, and an ion of a transition metal element. The nitrogen atom of the amino group and the nitrogen atom of the urethane bond are coordinated to the ion of the transition metal element.
特に、液晶性高分子金属錯体を構成するポリアミノウレタンは、下記一般式( I )にて特徴付けられるものである。
そして、上記一般式( I )で示されるポリアミノウレタンと遷移金属元素のイオンとを備え、ポリアミノウレタンが有するアミノ基及びウレタン結合を遷移金属元素のイオンに配位させて構成した本実施形態に係る液晶性高分子金属錯体によれば、液晶性を有する新たな高分子金属錯体を提供することができる。なお、以下の説明において、R1〜R15は、特に断りのない限り、上記一般式の但し書きにおけるR1〜R15と同じものであり説明を省略する場合がある。 The polyaminourethane represented by the above general formula (I) and transition metal element ions are provided, and the amino group and urethane bond of the polyaminourethane are coordinated to the transition metal element ions according to this embodiment. According to the liquid crystalline polymer metal complex, a new polymer metal complex having liquid crystallinity can be provided. In the following description, R 1 to R 15 are the same as R 1 to R 15 in the proviso of the above general formula unless otherwise specified, and the description may be omitted.
また、液晶性高分子金属錯体を構成するポリアミノウレタンは、主鎖型のポリアミノウレタンであっても良く、また、側鎖型のポリアミノウレタンであっても良い。 The polyaminourethane constituting the liquid crystalline polymer metal complex may be a main chain polyaminourethane or a side chain polyaminourethane.
具体的には、主鎖型のポリアミノウレタンは、前述の一般式( I )にて、R1を
また、側鎖型のポリアミノウレタンは、前述の一般式( I )にて、R1を
また、これらのポリアミノウレタンは、カウンターアニオンを有するものであっても良い。 These polyaminourethanes may have a counter anion.
具体的には、
このような構造を有する主鎖型や側鎖型のポリアミノウレタンを用いて調製した液晶性高分子金属錯体は、極めて高い汎用性を有する材料として使用することができる。 A liquid crystalline polymer metal complex prepared using a main chain or side chain polyaminourethane having such a structure can be used as a material having extremely high versatility.
ここで当該液晶性高分子金属錯体の利用分野の一例について言及するならば、例えば、高分子液晶材料としての使用や、色素材料としての使用、光応答材料としての使用、医療分野における使用等を挙げることができる。 Here, if an example of the application field of the liquid crystalline polymer metal complex is mentioned, for example, use as a polymer liquid crystal material, use as a dye material, use as a photoresponsive material, use in the medical field, etc. Can be mentioned.
例えば、高分子液晶材料としての用途の一つとしては、成形材料としての使用が考えられる。本実施形態に係る液晶性高分子金属錯体は異方性を有することから、特定方向において極めて高い強度を示す成形材料として使用することができる。 For example, as a polymer liquid crystal material, use as a molding material is conceivable. Since the liquid crystalline polymer metal complex according to the present embodiment has anisotropy, it can be used as a molding material exhibiting extremely high strength in a specific direction.
また、本実施形態に係る液晶性高分子金属錯体は、後に実験結果を参照しつつ説明するが、配向させることによりスメクチックＡ相を形成する。このとき、遷移金属イオンは、配向したポリアミノウレタンのウレタン結合やアミノ基の部分に配位することとなるため、この部分に熱伝導パスが形成される。従って、本実施形態に係る液晶性高分子金属錯体は、液晶状態および固体状態（ガラス転移温度以下）において、良好な熱伝導性を有する材料としても使用することができる。 Moreover, although the liquid crystalline polymer metal complex according to the present embodiment will be described later with reference to experimental results, the smectic A phase is formed by orientation. At this time, since the transition metal ion is coordinated to the urethane bond or amino group portion of the oriented polyaminourethane, a heat conduction path is formed in this portion. Therefore, the liquid crystalline polymer metal complex according to the present embodiment can also be used as a material having good thermal conductivity in a liquid crystal state and a solid state (below the glass transition temperature).
また例えば、本実施形態に係る液晶性高分子金属錯体は、色素材料としても利用することができる。本実施形態に係る液晶性高分子金属錯体は、金属イオンを配位させることによって、その金属イオンに応じた色を呈することができ、分子生物学実験等において所定の金属イオンの検出などに使用することができる。また、塗料の色素としても利用することができる。 For example, the liquid crystalline polymer metal complex according to the present embodiment can also be used as a dye material. The liquid crystalline polymer metal complex according to the present embodiment can exhibit a color corresponding to a metal ion by coordinating the metal ion, and is used for detection of a predetermined metal ion in a molecular biology experiment or the like. can do. Moreover, it can utilize also as a pigment | dye of a coating material.
また例えば、本実施形態に係る液晶性高分子金属錯体は、光応答材料としても利用することができる。本実施形態に係る高分子金属錯体は、極めて優れた光応答性を示すことができ、紫外線や可視光線の照射によって機械的な運動を行わせることができる。 For example, the liquid crystalline polymer metal complex according to the present embodiment can also be used as a photoresponsive material. The polymer metal complex according to the present embodiment can exhibit extremely excellent photoresponsiveness and can be mechanically moved by irradiation with ultraviolet rays or visible rays.
具体的には、液晶性高分子金属錯体をフィルム状とすることにより、光照射によって変形するフィルムを得ることができる。また、例えば後述する接触法などにより、薄いフィルム状でありながら、一方の面は液晶性高分子金属錯体の層を形成し、他方の面は非液晶性高分子金属錯体層（例えば、ポリアミノウレタン層）とすることにより、光応答性の違いを利用して、所定方向に運動性を示す材料を形成することも可能である。 Specifically, a film deformable by light irradiation can be obtained by forming the liquid crystalline polymer metal complex into a film. In addition, for example, by a contact method described later, a thin film is formed on one surface, and a liquid crystal polymer metal complex layer is formed on one surface, and a non-liquid crystal polymer metal complex layer (for example, polyaminourethane) is formed on the other surface. By using a layer), it is possible to form a material exhibiting mobility in a predetermined direction by utilizing the difference in photoresponsiveness.
また例えば、本実施形態に係る液晶性高分子金属錯体は、医療分野においてもその応用が考えられる。金属系の有効成分が奏功する疾患、例えば白金を有するシスプラチンが適応される所定のがんなどにおいて、その金属のドラッグデリバリー媒体や埋没式薬剤などとして利用することが考えられる。 Also, for example, the liquid crystalline polymer metal complex according to the present embodiment can be applied in the medical field. It can be considered to be used as a drug delivery medium or an implantable drug for a metal in which a metal-based active ingredient is effective, for example, a predetermined cancer to which cisplatin containing platinum is indicated.
このように、本実施形態に係る液晶性高分子金属錯体は、極めて汎用性の高い材料として利用することができる。 Thus, the liquid crystalline polymer metal complex according to the present embodiment can be used as a highly versatile material.
また、本実施形態に係る液晶性高分子金属錯体は、前述の一般式( I )にて表されるポリアミノウレタンと、遷移金属元素のイオンとを混合して、ポリアミノウレタンが有するアミノ基及びウレタン結合を遷移金属元素のイオンに配位させることで製造することができる。 In addition, the liquid crystalline polymer metal complex according to the present embodiment is a mixture of the polyaminourethane represented by the general formula (I) and the ions of the transition metal element, and the amino group and urethane of the polyaminourethane are mixed. It can be produced by coordinating a bond to an ion of a transition metal element.
より具体的には、例えば、ポリアミノウレタンと遷移金属のイオンとの混合は、ポリアミノウレタンを溶媒中に溶解又は分散させたポリアミノウレタン含有液と、遷移金属の塩類を溶媒に溶解させた塩類溶液とを混合して行うようにしても良い。このような方法によれば、比較的容易かつ速やかに液晶性高分子金属錯体を製造することができる。なお、以下の説明において、このような調製方法を溶液混合法とも称する。 More specifically, for example, the mixing of polyaminourethane and transition metal ions includes a polyaminourethane-containing liquid in which polyaminourethane is dissolved or dispersed in a solvent, and a salt solution in which transition metal salts are dissolved in a solvent. You may make it carry out by mixing. According to such a method, a liquid crystalline polymer metal complex can be produced relatively easily and quickly. In the following description, such a preparation method is also referred to as a solution mixing method.
また、別の方法として、例えば、ポリアミノウレタンと遷移金属のイオンとの混合は、粉体状又は固体状のポリアミノウレタンと、遷移金属の塩類を溶媒に溶解させた塩類溶液とを接触させて行うようにしても良い。このような方法によれば、ポリアミノウレタンの所望する部位に本実施形態に係る液晶性高分子金属錯体を形成することができる。なお、以下の説明において、このような調製方法を接触法とも称する。 As another method, for example, mixing of polyaminourethane and transition metal ions is performed by bringing powdered or solid polyaminourethane into contact with a salt solution obtained by dissolving a transition metal salt in a solvent. You may do it. According to such a method, the liquid crystalline polymer metal complex according to the present embodiment can be formed at a desired site of polyaminourethane. In the following description, such a preparation method is also referred to as a contact method.
また、別の方法として、例えば、ポリアミノウレタンと遷移金属のイオンとの混合は、加熱することにより流動性を有する液晶状態としたポリアミノウレタンと、遷移金属の塩類とを混練して行うようにしても良い。このような方法によれば、溶媒を使用することなく、液晶性高分子金属錯体を製造することができる。なお、以下の説明において、このような調製方法を混練法とも称する。 As another method, for example, the mixing of polyaminourethane and transition metal ions is performed by kneading polyaminourethane in a liquid crystal state having fluidity by heating and transition metal salts. Also good. According to such a method, a liquid crystalline polymer metal complex can be produced without using a solvent. In the following description, such a preparation method is also referred to as a kneading method.
このように、本実施形態に係る液晶性高分子金属錯体の製造方法によれば、前述の一般式( I )にて表されるポリアミノウレタンと、遷移金属元素のイオンとを混合して、ポリアミノウレタンが有するアミノ基及びウレタン結合を遷移金属元素のイオンに配位させること、より具体的には、溶液混合法や、接触法、混練法等によって液晶性高分子金属錯体を比較的容易に効率良く製造することができる。 Thus, according to the method for producing a liquid crystalline polymer metal complex according to the present embodiment, the polyaminourethane represented by the above general formula (I) and the ions of the transition metal element are mixed to obtain a polyamino Coordination of amino groups and urethane bonds of urethane to transition metal element ions, more specifically, liquid crystalline polymer metal complexes can be made relatively efficient by solution mixing method, contact method, kneading method, etc. Can be manufactured well.
なお、液晶性高分子金属錯体の製造にて使用するポリアミノウレタンは、例えば、本発明者が既に提案している特願２０１２−１２１３６６号の方法により得ることができる。 The polyaminourethane used in the production of the liquid crystalline polymer metal complex can be obtained, for example, by the method of Japanese Patent Application No. 2012-121366 already proposed by the present inventor.
その一例として、例えば、
以下、本実施形態に係る液晶性高分子金属錯体及びその製造方法について、図面を参照しつつ詳説する。 Hereinafter, the liquid crystalline polymer metal complex and the production method thereof according to the present embodiment will be described in detail with reference to the drawings.
〔１．液晶性高分子金属錯体の調製〕
（１−１．溶液混合法による調製）
まず、溶液混合法による液晶性高分子金属錯体の調製例について説明する。20ml容量のガラス製サンプル管に、図１の上部に示すポリアミノウレタン(0.15 mmol：繰り返し単位を一分子として計算)を入れ、５mlのテトラヒドロフラン（Tetrahydrofuran:THF)に溶解させた。
[1. Preparation of liquid crystalline polymer metal complex)
(1-1. Preparation by solution mixing method)
First, an example of preparing a liquid crystalline polymer metal complex by a solution mixing method will be described. A polyaminourethane (0.15 mmol: calculated as a single repeating unit) shown in the upper part of FIG. 1 was placed in a glass sample tube having a capacity of 20 ml and dissolved in 5 ml of tetrahydrofuran (Tetrahydrofuran: THF).
次に、このポリアミノウレタンのTHF溶液に対し、2mlのTHFに金属塩(0.15 mmol)を溶かした溶液を滴下し、溶液混合法によりゲル状物質を析出させた。ここで金属塩としては、塩化銅(II)二水和物、塩化鉄(III)、塩化鉄(III)六水和物、塩化亜鉛、塩化コバルト(III)、塩化コバルト(III)六水和物、塩化金(III)二水和物をそれぞれ用いた。 Next, a solution in which a metal salt (0.15 mmol) was dissolved in 2 ml of THF was added dropwise to the THF solution of polyaminourethane, and a gel-like substance was precipitated by a solution mixing method. Here, as the metal salt, copper chloride (II) dihydrate, iron chloride (III), iron chloride (III) hexahydrate, zinc chloride, cobalt chloride (III), cobalt chloride (III) hexahydrate And gold (III) chloride dihydrate were used.
析出したゲル状の物質をTHFで数回洗浄し、洗浄溶液が着色しなくなった後取り出して乾燥させることにより、液晶性高分子金属錯体を得た。なお、塩化銅一水和物は溶媒として使用したTHFに溶解しなかったため、液晶性高分子金属錯体を得ることはできなかったが、他の溶媒を用いた溶液混合法によって反応させることにより液晶性高分子金属錯体を調製可能であることは既に確認している。 The precipitated gel substance was washed several times with THF, and after the washing solution was no longer colored, it was taken out and dried to obtain a liquid crystalline polymer metal complex. Since copper chloride monohydrate was not dissolved in THF used as a solvent, a liquid crystalline polymer metal complex could not be obtained, but liquid crystal was obtained by reacting by a solution mixing method using another solvent. It has already been confirmed that a conductive polymer metal complex can be prepared.
（１−２．溶液混合法にて調製した液晶性高分子金属錯体の性状）
図２及び図３に、溶液混合法にて得られた液晶性高分子金属錯体の性状について示す。図２及び図３からも分かるように、得られた液晶性高分子金属錯体は、金属イオンに対応してさまざまな色を示した。
(1-2. Properties of Liquid Crystalline Polymer Metal Complex Prepared by Solution Mixing Method)
2 and 3 show the properties of the liquid crystalline polymer metal complex obtained by the solution mixing method. As can be seen from FIGS. 2 and 3, the obtained liquid crystalline polymer metal complex exhibited various colors corresponding to the metal ions.
また、得られた液晶性高分子金属錯体を室温〜300℃にて直交ニコル下で検鏡したところ、液晶光学組織が観察された。このことから、本実施形態に係る液晶性高分子金属錯体は、ガラス転移温度以下の室温においても液晶状態で形成された配向構造を保持する高分子金属錯体であることが分かる。 Moreover, when the obtained liquid crystalline polymer metal complex was examined under room temperature to 300 ° C. under crossed Nicols, a liquid crystal optical structure was observed. From this, it can be seen that the liquid crystalline polymer metal complex according to the present embodiment is a polymer metal complex that maintains an alignment structure formed in a liquid crystal state even at room temperature below the glass transition temperature.
また、図示は省略するが、金属塩としてユウロピウム塩を用いた場合にも錯形成が確認された。これらのことから、本実施形態に係る液晶性高分子金属錯体は、前述の一般式(I)にて示されるポリアミノウレタンを溶解させた溶液に、遷移金属の塩類を添加することにより合成可能であることが示された。 Although illustration is omitted, complex formation was also confirmed when a europium salt was used as the metal salt. Therefore, the liquid crystalline polymer metal complex according to the present embodiment can be synthesized by adding a transition metal salt to a solution in which the polyaminourethane represented by the general formula (I) is dissolved. It was shown that there is.
また、図３に示すように、金イオンを用いて形成させた液晶性高分子金属錯体は、極めて深い赤色を示すものであった。金は一般にナノレベルで分散させると赤色を呈することが知られている。このことから、液晶性高分子金属錯体中の金は、同錯体中において分散状態で存在しているものと考えられた。 Further, as shown in FIG. 3, the liquid crystalline polymer metal complex formed using gold ions showed a very deep red color. It is known that gold generally exhibits a red color when dispersed at the nano level. From this, it was considered that gold in the liquid crystal polymer metal complex was present in a dispersed state in the complex.
（１−３．混練法による調製）
次に、混練法による液晶性高分子金属錯体の調製例について説明する。図１上部に示した0.50ｇのポリアミノウレタンの樹脂塊を130℃に加熱して液晶性を有する状態で軟化させた。
(1-3. Preparation by kneading method)
Next, an example of preparing a liquid crystalline polymer metal complex by a kneading method will be described. The resin block of 0.50 g of polyaminourethane shown in the upper part of FIG. 1 was heated to 130 ° C. and softened in a state having liquid crystallinity.
次に、この樹脂塊に対し、遷移金属塩としての塩化銅(II)二水和物（粉体）を0.13ｇ添加して十分に混練し、混練法による液晶性高分子金属錯体を得た。 Next, 0.13 g of copper (II) chloride dihydrate (powder) as a transition metal salt was added to this resin mass and kneaded sufficiently to obtain a liquid crystalline polymer metal complex by a kneading method. .
（１−４．混練法にて調製した液晶性高分子金属錯体の性状）
混練法にて得られた液晶性高分子金属錯体の性状について確認を行った。前述の溶液混合法にて得られた液晶性高分子金属錯体と同様、添加した遷移金属塩としての銅イオンとアゾベンゼン基の赤色に由来するこげ茶色を呈していた。
(1-4. Properties of liquid crystalline polymer metal complex prepared by kneading method)
The properties of the liquid crystalline polymer metal complex obtained by the kneading method were confirmed. Similar to the liquid crystalline polymer metal complex obtained by the above-mentioned solution mixing method, it had a dark brown color derived from the red of the azobenzene group and the copper ion as the added transition metal salt.
また、室温下にて検鏡を行ったところ、液晶光学組織が観察された。これらのことから、混練法によっても、本実施形態に係る液晶性高分子金属錯体を製造可能であることが示された。 Moreover, when the microscope was performed under room temperature, the liquid crystal optical structure was observed. From these, it was shown that the liquid crystalline polymer metal complex according to the present embodiment can be produced also by the kneading method.
（１−５．接触法による調製）
接触法による液晶性高分子金属錯体の形成については、後述の〔７．光応答性〕にて説明するが、前述の溶液混合法や混練法にて形成した液晶性高分子金属錯体と同様に液晶光学組織が観察されたことから、接触法によっても本実施形態に係る液晶性高分子金属錯体が形成可能であることが確認された。
(1-5. Preparation by contact method)
The formation of the liquid crystalline polymer metal complex by the contact method will be described later in [7. As will be described below, the liquid crystal optical structure was observed in the same manner as the liquid crystalline polymer metal complex formed by the above-mentioned solution mixing method or kneading method. It was confirmed that a liquid crystalline polymer metal complex can be formed.
〔３．熱的性質〕
次に、形成した本実施形態に係る液晶性高分子金属錯体の熱的性質について検証を行った結果を、図４を参照しつつ説明する。なおここでは、遷移金属塩として塩化銅(II)二水和物を用い、溶液混合法にて調製した液晶性高分子金属錯体を代表サンプルとして使用した。
[3. Thermal properties)
Next, the result of verifying the thermal properties of the liquid crystalline polymer metal complex according to the present embodiment will be described with reference to FIG. Here, a liquid crystal polymer metal complex prepared by a solution mixing method using copper (II) chloride dihydrate as a transition metal salt was used as a representative sample.
図４に示すように、ネマチック相を示すポリウレタン（LCPU-Az-T）に塩化銅（II）を反応させることによって得た液晶性高分子金属錯体（PU-5）は、スメクチックA（SmA）相を形成した。ガラス転移温度（ガラス−SmA相転移温度）とSmA-等方相転移温度は、錯形成によって上昇した。 As shown in Fig. 4, the liquid crystalline polymer metal complex (PU-5) obtained by reacting copper (II) with polyurethane (LCPU-Az-T) exhibiting a nematic phase is smectic A (SmA). A phase formed. The glass transition temperature (glass-SmA phase transition temperature) and SmA-isotropic phase transition temperature increased due to complex formation.
〔４．ＸＲＤ〕
次に、形成した本実施形態に係る液晶性高分子金属錯体のＸＲＤの結果を図５に示す。
[4. XRD]
Next, FIG. 5 shows the XRD result of the liquid crystalline polymer metal complex according to this embodiment formed.
金属イオンとポリアミノウレタンの錯形成によって、スメクチックA相が誘起された。温度可変X線回折測定では、スメクチックA相の層の周期に対応する鋭い反射が小角域に観測された。この反射から求められる層間隔は、ポリアミノウレタンの繰り返し単位の伸び切り鎖長により少し長いことから、スメクチックA相では、高分子鎖が折りたたまれて配向した集合構造（folding structure）を形成しているものと考えられた。 Smectic A phase was induced by the complex formation of metal ions and polyaminourethane. In the variable temperature X-ray diffraction measurement, a sharp reflection corresponding to the period of the smectic A phase layer was observed in a small angle region. Since the layer spacing required from this reflection is a little longer due to the extended chain length of the repeating unit of polyaminourethane, the smectic A phase forms a folded structure in which polymer chains are folded and oriented. It was considered a thing.
〔５．ＮＭＲ〕
次に、形成した本実施形態に係る液晶性高分子金属錯体の1H-NMRの結果及び考察について、図６〜図９を参照しつつ説明する。
[5. NMR]
Next, 1 H-NMR results and discussion of the liquid crystalline polymer metal complex according to the present embodiment will be described with reference to FIGS.
図６（ａ）はポリアミノウレタンの1H-NMR測定結果であり、図６（ｂ）は液晶性高分子金属錯体の1H-NMR測定結果である。図６（ａ）及び図６（ｂ）に示すa,bのピークは、トリレレン基に直結したN-HのHに対応するピークで、それぞれaが2位の位置に結合しているN-Hのものであり、bが4位に結合しているN-Hに対応するものである。それぞれの測定結果を比較すると、図６（ｂ）に示すように、錯形成に関係したウレタン結合部位のN-Hに対応するピークが新たに確認された。 6 (a) is a the 1 H-NMR measurement results of the polyamino urethane, and FIG. 6 (b) is a 1 H-NMR measurement results of the liquid crystalline polymer metal complex. The peaks a and b shown in FIGS. 6 (a) and 6 (b) are peaks corresponding to H of NH directly bonded to the tolylene group, each of NH having a bonded to the 2-position. Yes, b corresponds to NH bonded to the 4-position. When each measurement result was compared, as shown in FIG. 6B, a peak corresponding to NH in the urethane binding site related to complex formation was newly confirmed.
図７及び図８は、添加する遷移金属塩（塩化鉄(III)六水和物）の添加量を違えて鉄イオンの錯形成量を変化させた時の測定結果を示した図である。図７及び図８からも分かるように、鉄イオンの錯形成量が多くなると、8〜10ppm近傍に現れるウレタン結合部分のN-Hのピークの分裂が大きくなる傾向が見られた。また、ウレタン結合のN-Hのピークだけではなく、ウレタン結合に直結したCH2のピークも低磁場側にシフトするのが観察された。また、4〜5ppm近傍に現れるアミノ基部分のピークにも変化が確認された。 FIG. 7 and FIG. 8 are diagrams showing measurement results when the amount of complex formation of iron ions is changed by changing the addition amount of the transition metal salt (iron (III) chloride hexahydrate) to be added. As can be seen from FIGS. 7 and 8, when the amount of complexed iron ions increases, the NH peak splitting of the urethane bond portion that appears in the vicinity of 8 to 10 ppm tends to increase. It was also observed that not only the peak of NH of urethane bond but also the peak of CH 2 directly connected to urethane bond shifted to the low magnetic field side. Moreover, a change was also confirmed in the peak of the amino group portion appearing in the vicinity of 4 to 5 ppm.
図９に、錯形成に関与したN-Hと関与していないN-Hのピークの面積強度の比から、それぞれのウレタン結合部位の錯形成への関与割合を算出した結果を示す。 FIG. 9 shows the calculation results of the proportion of each urethane binding site involved in complex formation from the ratio of the area intensity of N—H peaks involved in complex formation and N—H peaks not involved.
図９からも分かるように、符号ｉを付した水素原子を有するウレタン結合では、塩化鉄の添加量が0.5当量を越えたところで約40%が錯形成に関与するものと考えられる。0.5当量よりも少し前のところに極大値が見られるが、このピークが現れる理由については現在検討中である。 As can be seen from FIG. 9, in the urethane bond having a hydrogen atom labeled i, about 40% is considered to be involved in complex formation when the amount of iron chloride exceeds 0.5 equivalent. The maximum value is seen just before 0.5 equivalent, but the reason why this peak appears is currently under investigation.
また、符号ｊを付した水素原子を有するウレタン結合では、塩化鉄の添加量が0.5当量で約50％が錯形成に関与するものと考えられる。 In addition, in the urethane bond having a hydrogen atom with the symbol j, it is considered that about 50% is involved in complex formation when the amount of iron chloride added is 0.5 equivalent.
また、符号ｉを付した水素原子を備えるウレタン結合の方が、符号ｊを付した水素原子を備えるウレタン結合に比して錯形成に関与する割合が多少低くなるのは、立体障害が相対的に大きいためであると考えられた。 In addition, the ratio of the steric hindrance relative to the urethane bond having a hydrogen atom with a symbol i is somewhat lower than the urethane bond having a hydrogen atom with a symbol j. It was thought to be because it was big.
〔６．加工性〕
次に、本実施形態に係る液晶性高分子金属錯体の加工性について検討を行った。具体的には、塩化銅(II)二水和物を遷移金属塩とし混練法にて調製した液晶性高分子金属錯体（約２ｇ）の塊を、熱プレス装置に供してフィルム化した。その結果を図１０に示す。
[6. Processability)
Next, the workability of the liquid crystalline polymer metal complex according to the present embodiment was examined. Specifically, a lump of liquid crystalline polymer metal complex (about 2 g) prepared by a kneading method using copper (II) chloride dihydrate as a transition metal salt was subjected to a hot press to form a film. The result is shown in FIG.
図１０からも分かるように、フィルム化したポリアミノウレタンと同様、液晶性高分子金属錯体もまたフィルム化できることが確認された。また、フィルム化される際の様子から、一般の成型用樹脂と同様の加工性を有することが確認された。 As can be seen from FIG. 10, it was confirmed that the liquid crystalline polymer metal complex can also be formed into a film as in the case of the filmed polyaminourethane. In addition, it was confirmed that the film had the same processability as a general molding resin from the state of film formation.
また、図示は省略するが、他の遷移金属塩を用いた液晶性高分子金属錯体についても、同様に良好な加工性を有することが確認された。 Moreover, although illustration is abbreviate | omitted, it was confirmed that it has the same favorable workability similarly about the liquid crystalline polymer metal complex using another transition metal salt.
〔７．UV-Visスペクトル測定〕
次に、本実施形態に係る液晶性高分子金属錯体のUV-Visスペクトル測定を行った。ここでは、サンプルとして塩化金(III)二水和物を遷移金属塩とし混練法にて調製した液晶性高分子金属錯体を上述の方法で熱プレスしてフィルム化したものを使用した。また、サンプルフィルムは厚さ0.2μｍのものと２μｍのものの２種類を作成して試験に供した。その測定結果を図１１に示す。
[7. (UV-Vis spectrum measurement)
Next, UV-Vis spectrum measurement of the liquid crystalline polymer metal complex according to the present embodiment was performed. Here, as a sample, a liquid crystalline polymer metal complex prepared by a kneading method using gold (III) chloride dihydrate as a transition metal salt and heat-pressed by the above-described method to form a film was used. Two types of sample films having a thickness of 0.2 μm and a film having a thickness of 2 μm were prepared and used for the test. The measurement results are shown in FIG.
図１１からも分かるように、液晶性高分子金属錯体にて作成したフィルムは、ポリアミノウレタンフィルムと比較すると、長波長側に吸収帯が現れること、より具体的には、470nm付近と450nm付近にピークが現れることが確認された。 As can be seen from FIG. 11, the film made of the liquid crystalline polymer metal complex shows an absorption band on the long wavelength side as compared with the polyaminourethane film, more specifically, around 470 nm and around 450 nm. It was confirmed that a peak appeared.
〔８．光応答性〕
次に、本実施形態に係る液晶性高分子金属錯体の光応答性について検討を行った。具体的には、ポリアミノウレタンフィルムの一面側に遷移金属塩溶液としての塩化銅(II)二水和物のTHF溶液を塗布することで、接触法によって液晶性高分子金属錯体の層を形成させ、ポリアミノウレタン層と液晶性高分子金属錯体層との２層構造を有するフィルムを作製した。また、液晶性高分子金属錯体の層を形成しないポリアミノウレタンフィルムを比較対照として用いた。なお、ポリアミノウレタンフィルムの作成や、塩化銅(II)二水和物のTHF溶液のポリアミノウレタンフィルムへの塗布は、図１２の上部に示すスピンコート法にて行った。
[8. (Photoresponsiveness)
Next, the photoresponsiveness of the liquid crystalline polymer metal complex according to the present embodiment was examined. Specifically, a layer of a liquid crystalline polymer metal complex is formed by a contact method by applying a THF solution of copper (II) chloride dihydrate as a transition metal salt solution on one side of a polyaminourethane film. A film having a two-layer structure of a polyaminourethane layer and a liquid crystalline polymer metal complex layer was produced. Moreover, the polyamino urethane film which does not form the liquid crystalline polymer metal complex layer was used as a comparative control. The production of the polyaminourethane film and the application of the copper (II) chloride dihydrate THF solution to the polyaminourethane film were performed by the spin coat method shown in the upper part of FIG.
次いで、これらポリアミノウレタンフィルム及び２層構造フィルムを水平に保持し、360nmの紫外線を照射することで、それぞれのフィルムの挙動を観察した。その結果を図１２及び図１３に示す。 Subsequently, these polyaminourethane films and the two-layer structure film were held horizontally, and the behavior of each film was observed by irradiating with 360 nm ultraviolet rays. The results are shown in FIGS.
まず、図１２の中程にポリアミノウレタンフィルムに対して紫外線照射を行った際の結果を示す。図１２からも分かるように、紫外線照射前のポリアミノウレタンフィルムは水平状態を保持していたが、紫外線が照射されることにより、図面上方側である光源側に湾曲する挙動が確認された。 First, the result at the time of performing ultraviolet irradiation with respect to a polyamino urethane film in the middle of FIG. 12 is shown. As can be seen from FIG. 12, the polyaminourethane film before irradiation with ultraviolet rays was kept in a horizontal state. However, when irradiated with ultraviolet rays, it was confirmed that the polyaminourethane film bends toward the light source side, which is the upper side of the drawing.
これはポリアミノウレタンの構造中に存在するアゾベンゼンが、紫外線の照射によってトランス型からシス型に変化することに由来するものと考えられる。 This is considered to be due to the fact that azobenzene present in the structure of polyaminourethane changes from a trans type to a cis type by irradiation with ultraviolet rays.
次に、図１３に液晶性高分子金属錯体層を形成した２層構造フィルムに対して紫外線照射を行った際の結果を示す。前述のように錯体化していないポリアミノウレタンフィルムでは、紫外線を照射した際に光源側に湾曲する動きが観察されたが、２層構造フィルムでは、まず錯体化した面側から紫外線を照射した際、錯体化していない面側に湾曲する動きが観察された。 Next, the result at the time of performing ultraviolet irradiation with respect to the two-layer structure film in which the liquid crystalline polymer metal complex layer was formed in FIG. 13 is shown. In the polyaminourethane film that is not complexed as described above, a movement that curves toward the light source side when irradiated with ultraviolet rays was observed, but in the two-layer structure film, when ultraviolet rays were irradiated from the complexed side first, A curved movement toward the uncomplexed surface was observed.
また、この錯体化していない面側に湾曲した２層構造フィルムを裏返し、錯体化していない面側から紫外線を照射すると、錯体化していない面側に更に湾曲する動きが観察された。 Further, when the two-layer structure film curved to the non-complexed surface side was turned over and irradiated with ultraviolet rays from the non-complexed surface side, a further curved movement toward the non-complexed surface side was observed.
この結果は、錯形成を利用することで、フィルム表裏の特性を制御できることを示している。また、樹脂、繊維、フィルムに加工した後に、金属イオン溶液を塗布することで表面を錯形成化することができることを意味しており、一種の高分子メッキの手段としても利用可能であるといえる。 This result shows that the characteristics of the front and back of the film can be controlled by using complex formation. In addition, it means that the surface can be complexed by applying a metal ion solution after being processed into a resin, fiber, or film, and can be used as a kind of polymer plating means. .
上述してきたように、本実施形態に係る液晶性を有する高分子金属錯体によれば、前述の一般式( I )にて表されるポリアミノウレタンと、遷移金属イオンとを有し、前記ポリアミノウレタンが有するアミノ基の窒素原子及びウレタン結合の窒素原子に前記遷移金属イオンが配位して構成されたものであり、液晶性を有する新たな高分子金属錯体を提供することができる。 As described above, according to the polymer metal complex having liquid crystallinity according to the present embodiment, the polyaminourethane having the polyaminourethane represented by the general formula (I) and the transition metal ion is provided. The transition metal ion is coordinated to the nitrogen atom of the amino group and the nitrogen atom of the urethane bond, and a new polymer metal complex having liquid crystallinity can be provided.
また、本実施形態に係る液晶性を有する高分子金属錯体の製造方法によれば、前述の一般式( I )にて表されるポリアミノウレタンと、遷移金属のイオンとを混合して、前記ポリアミノウレタンが有するアミノ基の窒素原子及びウレタン結合の窒素原子に前記遷移金属のイオンを配位させることとしたため、比較的容易に液晶性を有する高分子金属錯体を製造することができる。 According to the method for producing a polymer metal complex having liquid crystallinity according to the present embodiment, the polyaminourethane represented by the general formula (I) is mixed with a transition metal ion, and the polyaminourethane is mixed. Since the transition metal ions are coordinated to the nitrogen atom of the amino group of the urethane and the nitrogen atom of the urethane bond, a polymer metal complex having liquid crystallinity can be produced relatively easily.
最後に、上述した各実施の形態の説明は本発明の一例であり、本発明は上述の実施の形態に限定されることはない。このため、上述した各実施の形態以外であっても、本発明に係る技術的思想を逸脱しない範囲であれば、設計等に応じて種々の変更が可能であることは勿論である。 Finally, the description of each embodiment described above is an example of the present invention, and the present invention is not limited to the above-described embodiment. For this reason, it is a matter of course that various modifications can be made in accordance with the design and the like as long as they do not depart from the technical idea according to the present invention other than the embodiments described above.
Claims (5)
にて表されるポリアミノウレタンと、遷移金属イオンとを有し、
前記ポリアミノウレタンが有するアミノ基及びウレタン結合を前記遷移金属イオンに配位させて構成した液晶性を有する高分子金属錯体。 The following general formula
Having a polyaminourethane represented by: and a transition metal ion,
A polymer metal complex having liquid crystallinity formed by coordinating the amino group and urethane bond of the polyaminourethane to the transition metal ion.
にて表されるポリアミノウレタンと、遷移金属のイオンとを混合して、前記ポリアミノウレタンが有するアミノ基及びウレタン結合を前記遷移金属イオンに配位させる液晶性を有する高分子金属錯体の製造方法。 The following general formula
A method for producing a polymer metal complex having liquid crystallinity in which a polyaminourethane represented by the formula (1) and a transition metal ion are mixed to coordinate the amino group and urethane bond of the polyaminourethane with the transition metal ion.
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