JP6654319B2 - Structural color expression material and sensor - Google Patents
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Description
本発明は、構造色発現材料及びセンサに関する。 The present invention relates to a structural color developing material and a sensor.
構造色は、高度に規則的な幾何学的構造による可視光の干渉による着色現象であり、オパールなどの宝石や昆虫の羽の着色など天然物や生物の着色現象と深く関わっていることが知られている。 Structural color is a coloring phenomenon caused by interference of visible light due to a highly regular geometric structure, and is known to be deeply related to coloring phenomena of natural products and living things, such as coloring of gems such as opal and insect wings. Have been.
このような着色のメカニズムを合成された有機高分子粒子や無機粒子の集積化により形成された構造で実現し応用する研究が近年注目を集めている。特に、シリカコロイド粒子が自発的に形成するコロイド結晶の構造色が代表的なものとして知られている。 In recent years, researches for realizing and applying such a coloring mechanism to a structure formed by integration of synthesized organic polymer particles and inorganic particles have attracted attention. In particular, the structural color of colloidal crystals formed spontaneously by silica colloidal particles is known as a typical one.
基本的に粒子径の完全に揃った単分散球状粒子が細密充填した構造が示す構造色が広く研究されている。 Basically, structural colors of a structure in which monodisperse spherical particles having a completely uniform particle diameter are closely packed have been widely studied.
このような構造色を人工的に作り出すためには粒子径と形態のコントロールされた高度な微粒子合成技術と、単分散微粒子の規則的な集積化の技術が必須である。 In order to artificially produce such a structural color, an advanced fine particle synthesizing technique in which the particle diameter and morphology are controlled and a technique of regularly integrating monodisperse fine particles are essential.
これらの高度な合成技術を用いて調整された単分散球状粒子の三次元規則的集積構造は、近年フォトニック結晶としても大きな注目を集めており、様々な光学的機能の発言に関心が集まっている。 The three-dimensional regular structure of monodisperse spherical particles prepared using these advanced synthetic techniques has attracted much attention as a photonic crystal in recent years, and has attracted interest in remarks on various optical functions. I have.
そして、光通信及び処理技術への応用展開が今後期待されている技術分野ともなっている。また、有機系及び無機系の色素を着色に用いる場合、耐光性や経年劣化の問題そして人体への毒性など問題となる点もあるが、構造色では色素を一切用いる必要がないためこれらの問題点の少ない環境適合性と耐久性を備えた着色手法となることが期待されている。このような観点から、色素を用いない着色という特徴により、整体関連材料への着色などの手法としての検討も進んでいる。例えば、コンタクトレンズの着色手法などの例も報告されるようになってきている。このように、単分散球状粒子を用いた構造色発現系については合成や規則的な集積構造形成の困難さがあるが、様々な応用の可能性を秘めていることから現在も多くの研究が進められている。 It is also a technical field where application development to optical communication and processing technology is expected in the future. In addition, when organic and inorganic dyes are used for coloring, there are also problems such as light resistance, deterioration over time, and toxicity to the human body. It is expected to be a coloring method with few points of environmental compatibility and durability. From such a viewpoint, due to the feature of coloring without using a pigment, studies as a method of coloring a manipulative-related material and the like have been advanced. For example, examples of coloring methods for contact lenses have been reported. As described above, the structural color expression system using monodispersed spherical particles has difficulty in synthesis and formation of a regular integrated structure, but many studies are still being conducted due to the potential of various applications. Is underway.
通常、色素分子による着色を変化させる場合、分子の構造を大きく変えることもあるが、ｐＨ変化や酸化還元反応などの簡便な操作により分子の電子状態を変化させるのみで発色を変化させることが可能である。これに対して、構造色の発色を変化させるためには、構造の構成単位である粒子の粒子径を変化させた後、規則的集積構造を再度構築する必要がある。この点についてより詳しく検討することで、色素分子を用いた着色と比べて粒子の規則的集積構造を用いて構造色を発現させる場合、次の二つの点で解決すべき問題点があることがわかる。 Normally, when changing the coloring by a dye molecule, the structure of the molecule may be significantly changed, but it is possible to change the color development only by changing the electronic state of the molecule by simple operations such as pH change and redox reaction It is. On the other hand, in order to change the coloration of the structural color, it is necessary to reconstruct a regular integrated structure after changing the particle diameter of the particles that are the constituent units of the structure. By examining this point in more detail, there are two issues that need to be solved when expressing a structural color using a regular accumulation structure of particles compared to coloring using dye molecules. Understand.
（問題点１）
単分散粒子の規則的集積構造を用いた構造色発現系では、可視光の波長と同じ４００ｎｍ〜８００ｎｍ程度の直径の粒子の揃った単分散粒子特に球状粒子が構造の構成単位となる。したがって、着色の波長を制御するためには球状粒子の粒子径を変える必要がある。そのためには、球状粒子の合成の段階からやり直す必要がある。
(Issue 1)
In a structural color developing system using a regular accumulation structure of monodisperse particles, monodisperse particles having a diameter of about 400 nm to 800 nm, which is the same as the wavelength of visible light, particularly spherical particles, are structural units. Therefore, in order to control the wavelength of coloring, it is necessary to change the particle diameter of the spherical particles. For that purpose, it is necessary to start over from the stage of synthesis of the spherical particles.
（問題点２）
構造色を発現させるためには、粒子を高度な規則性のある状態で配列させる必要がある。そのためには海面潮力などを利用して非常にゆっくりと粒子を集積させるなど時間をかけて集積構造を形成させる必要がある。また、集積構造の状態により発色が影響を受けるという問題がある。
(Issue 2)
In order to develop a structural color, the particles need to be arranged in a highly regular state. For that purpose, it is necessary to form the accumulation structure over time, for example, by accumulating particles very slowly using the sea surface tidal force. Further, there is a problem that coloring is affected by the state of the integrated structure.
通常の着色に用いられる色素分子では、分子の構造や電子状態の変化のみで発色を変化させられるのに対して、構造色では、発色の基礎となる球状粒子の粒子径とその集積構造の両方を厳密に制御する必要があることから色素を用いる場合と比べて発色材料を得るために多くの厳密に制御された工程が必要となり、コストなどの点でも改善すべき問題を有していると言える。このように構造色は作製に手間がかかる問題があるが、色素による着色にない高い耐久性や整体適合性などを有しており今後の応用の進展が求められている材料系である。 In the case of dye molecules used for ordinary coloring, the color development can be changed only by changes in the molecular structure or electronic state, whereas in the structural color, both the particle diameter of the spherical particles that form the basis of color development and their integrated structure Since it is necessary to control strictly, a number of strictly controlled steps are required to obtain a coloring material as compared with the case of using a dye, and there is a problem to be improved in terms of cost and the like. I can say. As described above, the structural color has a problem that it takes time to produce, but it is a material system that has high durability and suitability for manipulability that are not colored by a pigment, and is expected to be applied in the future.
以上、本発明は、上記課題に鑑み、より簡便な構造で、安定的に構造色を発現することのできる構造色発現材料及びセンサを提供することを目的とする。 In view of the above problems, an object of the present invention is to provide a structural color developing material and a sensor capable of stably developing a structural color with a simpler structure.
上記課題を解決する一観点に係る構造色発現材料は、糖酸分子が結合した多数の板状構造体を含む層状構造体を備えたものである。 A structural color developing material according to one aspect for solving the above problem includes a layered structure including a large number of plate-like structures to which sugar acid molecules are bonded.
また、本発明の他の一観点に係るセンサは、糖酸分子が結合した多数の板状構造体を含む層状構造体を備えた構造色発現材料を有し、板状構造体間の水素結合性化合物の量に応じて構造色を異ならせるものである。 In addition, a sensor according to another aspect of the present invention includes a structural color developing material including a layered structure including a large number of plate-like structures to which sugar acid molecules are bonded, and a hydrogen bond between the plate-like structures. The structural color varies depending on the amount of the sexual compound.
以上、本発明によって、より簡便な構造で、安定的に構造色を発現することのできる構造色発現材料及びセンサを提供することができる。 As described above, according to the present invention, it is possible to provide a structural color developing material and a sensor capable of stably developing structural colors with a simpler structure.
以下、本発明の実施形態について、図面を用いて詳細に説明する。ただし、本発明は多くの異なる形態による実施が可能であり、以下に示す実施形態、実施例の例示に限定されるものではない。 Hereinafter, embodiments of the present invention will be described in detail with reference to the drawings. However, the present invention can be implemented in many different forms, and is not limited to the following embodiments and examples.
図１は、本実施形態に係る構造色発現材料（以下「本材料」という。）の層状構造体のイメージを示す図であり、図２は、本材料において複数の板状構造体が溶媒を介して相互作用する場合のイメージを示す図である。さらに図３は、本材料が呈する色の波長の変化のイメージを示す図である。 FIG. 1 is a diagram showing an image of a layered structure of a structural color developing material (hereinafter, referred to as “the material”) according to the present embodiment. FIG. 2 shows a plurality of plate-like structures in the present material in which a solvent is used. It is a figure which shows the image at the time of interacting via. FIG. 3 is a diagram showing an image of a change in wavelength of a color exhibited by the present material.
これらの図で示すように、本材料は、糖酸分子３が結合した多数の板状構造体を備えており、多数の板状構造体を含んで層状構造体４となっている。 As shown in these figures, the present material has a large number of plate-like structures to which sugar acid molecules 3 are bonded, and is a layered structure 4 including a large number of plate-like structures.
また本材料において、板状構造体２は、上記のとおり板状のものである。板状とすることにより、複数の板状構造体２が一方向に積層して層を形成することが可能となり、この板状構造体の間隔を揃えることで、層状構造体として、いわゆるブラッグ反射による構造色の発現を可能とする。しかも本材料では、後述するように、この板状構造体同士の距離を制御することが可能であるため、本材料が呈する色の波長を変化させることが可能となる。 In the present material, the plate-like structure 2 is plate-like as described above. The plate-like structure allows a plurality of plate-like structures 2 to be stacked in one direction to form a layer, and by adjusting the intervals between the plate-like structures, a so-called Bragg reflection is obtained as a layer-like structure. Enables the expression of structural colors. Moreover, in the present material, as described later, the distance between the plate-like structures can be controlled, so that the wavelength of the color of the present material can be changed.
本材料１における板状構造体の厚さとしては、構造色を呈することができる程度の層間隔を維持することができる限りにおいて限定されない。例えば、可視領域の構造色を呈することができるためには、厚さとして、例えば０．００１μｍ以上１μｍ以下であることが好ましい。 The thickness of the plate-like structure in the present material 1 is not limited as long as a layer interval capable of exhibiting a structural color can be maintained. For example, in order to exhibit a structural color in the visible region, the thickness is preferably, for example, 0.001 μm or more and 1 μm or less.
また本材料において、板状構造体の材質としては、板状とすることができる限りにおいて限定されるわけではないが、無機ナノシートであることが好ましく、無機ナノシートのより具体的な例としては、例えば板状チタン酸化合物であることが好ましい。チタン酸化合物を用いることで、糖酸分子を付しやすくなるとともに、容易に多数の板状構造体の積層した積層状構造体とすることができる。 Further, in the present material, the material of the plate-shaped structure is not limited as long as it can be formed into a plate shape, but is preferably an inorganic nanosheet, and as a more specific example of the inorganic nanosheet, For example, a plate-like titanate compound is preferable. By using a titanate compound, a sugar acid molecule can be easily attached, and a laminated structure in which a large number of plate-like structures are easily laminated can be obtained.
また本材料において、糖酸分子は、上記板状構造体の表面に結合することができるものであって、溶媒に対して親和性を備える部位（溶媒親和性部位）と、板状構造体の表面に親和性を備える部位（構造体親和性部位）とを有する。このようにすることで、一方は板状構造体表面に結合可能であり、他方で溶媒に対して結合が可能であり、この両結合によって層間距離を制御することが可能となる。なおここで、溶媒親和性部位としては、この機能を有する限りにおいて限定されるわけではないが、例えばプロトン性溶媒に対して親和性を備えた糖鎖であることが好ましい。またここで、構造体親和性部位としては、構造体に化学的に結合できる極性ある酸部位、具体的にはカルボキシ基であることが好ましい。また本材料において糖酸分子３は、板状構造体２各々の表面全体を覆っている。 In this material, the sugar acid molecule can bind to the surface of the plate-like structure, and has a portion having an affinity for a solvent (solvent affinity portion) and a portion of the plate-like structure. And a site having affinity on the surface (structure affinity site). By doing so, one can be bonded to the surface of the plate-like structure, and the other can be bonded to the solvent, and the interlayer distance can be controlled by the two bonds. Here, the solvent affinity site is not limited as long as it has this function, but is preferably, for example, a sugar chain having affinity for a protic solvent. Here, the structure affinity site is preferably a polar acid site capable of chemically bonding to the structure, specifically a carboxy group. In the present material, the sugar acid molecules 3 cover the entire surface of each plate-like structure 2.
また本材料において、糖酸分子の具体的な例としては、限定されるわけではないが、グルコン酸、ガラクトン酸、マンノン酸等のアルドン酸、グルクロン酸、ガラクツロン酸、マンヌロン酸等のウロン酸を例示することができるが、アルドン酸、具体的にはグルコン酸であることがより簡便な構成であり好ましい。 In the present material, specific examples of sugar acid molecules include, but are not limited to, gluconic acid, galactonic acid, aldonic acids such as mannonic acid, glucuronic acid, galacturonic acid, uronic acids such as mannuronic acid. As an example, aldonic acid, specifically, gluconic acid is preferred because of its simpler structure.
また、本材料は、多数の板状構造体２の間に水素結合性化合物４を含ませており、水素結合性化合物の量によって発現する構造色の色を異ならせることができる。ここで、水素結合性化合物とは、水酸基等の水素結合性の官能基を備えた化合物であって、限定されるわけではないが例えば水、アルコール等を例示することができ、アルコール等の場合、メタノール、エタノール、プロパノール、グリコール、グリセリン等を例示することができる。また水の場合、非常に簡便に乾燥、湿潤が可能であるため好ましく、更にアルコール等を含ませることで、色の発色、制御をより効率的に行わせることができる観点から好ましい。 In addition, the present material includes the hydrogen bonding compound 4 between the large number of plate-like structures 2, and the color of the structural color developed can be changed depending on the amount of the hydrogen bonding compound. Here, the hydrogen-bonding compound is a compound having a hydrogen-bonding functional group such as a hydroxyl group, and is not limited to, for example, water, alcohol, and the like. , Methanol, ethanol, propanol, glycol, glycerin and the like. In addition, water is preferable because it can be dried and wet very easily, and is preferable from the viewpoint that color development and control can be performed more efficiently by further containing alcohol or the like.
以上、本材料は、より簡便な構造で、安定的に構造色を発現することのできる構造色発現材料となっている。 As described above, the present material is a structural color developing material capable of stably developing structural colors with a simpler structure.
また本材料は、上記図で示すように、板状構造体間の水素結合性化合物の量によって層間距離が異なり、この水素結合性化合物の量を制御することで層間距離を制御することが可能である。そして、この層間距離に応じて反射する波長が異なるため、反射する波長すなわち本材料が呈する色を制御することができる。よってこの水素結合性化合物の量を検出するセンサとしての用途がある。 Also, as shown in the above figure, the interlayer distance of this material differs depending on the amount of the hydrogen bonding compound between the plate-like structures, and the interlayer distance can be controlled by controlling the amount of the hydrogen bonding compound. It is. Since the wavelength to be reflected differs according to the interlayer distance, the wavelength to be reflected, that is, the color exhibited by the present material can be controlled. Therefore, there is a use as a sensor for detecting the amount of the hydrogen bonding compound.
また他の別の観点から表現すると、本材料は、シート状の二次元的広がりを有する形態を取りやすい層状チタン酸粒子に着目したものであって、層状チタン酸の板状構造体が等間隔に規則的に積層させ光の干渉による構造色を発現する層状構造体を簡便な方法で自発的に形成させる技術である。特に、従来の単分散球状粒子による構造色発現系では三次元空間内での規則的配列構造の形成が重要であるが、本材料での板状構造体の配列では、基本的に一次元的な積層構造を決める積層感覚を制御するのみで良いので、構造色発現に関わる構造制御が著しく簡便に行えるという特徴を有している。板状粒子の一次元的積層構造の制御は簡単に見えるが自発的に等間隔の積層構造を形成する技術は現在までにほとんど報告されていない。 From another viewpoint, the present material focuses on layered titanate particles that easily take a form having a sheet-like two-dimensional spread, and the plate-like structure of layered titanic acid has an equal interval. This is a technique for spontaneously forming, by a simple method, a layered structure which is regularly laminated on a substrate and exhibits a structural color due to light interference. In particular, the formation of a regular array structure in a three-dimensional space is important in the conventional structural color expression system using monodisperse spherical particles, but the arrangement of plate-like structures in this material is basically one-dimensional. Since it is only necessary to control the layering sensation that determines the appropriate layered structure, it has the feature that the structure control relating to the expression of structural color can be performed extremely easily. Although the control of the one-dimensional layered structure of the plate-like particles looks simple, there has been little report on a technique for spontaneously forming the layered structure at an equal interval.
本材料では、上記好ましい一例として層状チタン酸を用い、その表面に例えばグルコン酸を結合させたグルコン酸複合化層状チタン酸粒子を調整することで、板状構造体の規則的な積層構造を自発的に形成することが可能である。ここでグルコン酸は、グルコースを酸化して生成する分子であり、金属イオンに配位するカルボキシル基と高い親和性を有するグルコース由来の水酸基からなる複合機能分子である。このグルコン酸は、カルボキシル基がチタンイオンに配位することで層状チタン酸の板状粒子表面に結合させることができる。そして、グルコン酸分子と水分子の水素結合により層状チタン酸粒子が水中に安定に分散したゾルを得ることができる。さらに、グルコン酸と複合化された層状チタン酸粒子同士も水素結合により会合構造を形成することができる。 In the present material, a layered titanic acid is used as a preferable example, and gluconic acid-composited layered titanic acid particles having gluconic acid bonded thereto, for example, are adjusted to spontaneously form a regular laminated structure of a plate-like structure. It is possible to form it. Here, gluconic acid is a molecule generated by oxidizing glucose, and is a multifunctional molecule composed of a glucose-derived hydroxyl group having a high affinity with a carboxyl group coordinated to a metal ion. This gluconic acid can be bound to the plate-like particle surface of the layered titanic acid by coordinating a carboxyl group to a titanium ion. Then, a sol in which layered titanate particles are stably dispersed in water can be obtained by hydrogen bonding between gluconic acid molecules and water molecules. Furthermore, the layered titanate particles complexed with gluconic acid can also form an associated structure by hydrogen bonding.
また、本材料１は、上記の構造を得ることができる限りにおいて様々な方法を採用することができるが、たとえば、（１）板状構造体を形成し、（２）この板状構造体表面に糖酸分子を結合させることで、多数の板状構造体を含む層状構造体を備えた構造触発現材料を得ることができる。 The material 1 can employ various methods as long as the above structure can be obtained. For example, (1) a plate-like structure is formed, and (2) a surface of the plate-like structure is formed. By bonding a sugar acid molecule to the structure, it is possible to obtain a structural texture expressing material having a layered structure including a large number of plate-shaped structures.
また、本材料１において、上記したように、層状チタン酸を用い、その表面にグルコン酸を結合させたグルコン酸複合化層状チタン酸粒子を得る例においては、チタンテトライソプロポキシド（ＴＩＰ）溶液とグルコン酸水溶液を加えて乾燥させることで得ることができる。この詳細については、後述の実施例から明らかとなる。 Further, as described above, in the present material 1, in the case where layered titanic acid is used to obtain gluconic acid-composited layered titanic acid particles having gluconic acid bonded to the surface thereof, a titanium tetraisopropoxide (TIP) solution And an aqueous solution of gluconic acid, followed by drying. The details will be apparent from the examples described later.
以上、本材料は、より簡便な構造で、安定的に構造色を発現することのできる構造色発現材料となっている。 As described above, the present material is a structural color developing material capable of stably developing structural colors with a simpler structure.
ここで、実際に構造色発現材料の作製を行い、その効果について確認を行った。以下具体的に説明する。 Here, a structural color developing material was actually produced, and its effect was confirmed. This will be specifically described below.
（合成）
まず、チタンテトライソプロポキシド（ＴＩＰ）０．０１ｍｏｌと、エチレングリコール（ＥＧ）５０ｍＬを混合し、更にＤ−グルコン酸水溶液５０ｍＬを加え、ＴＩＰ−ＥＧ＋グルコン酸複合体溶液を調整した。なおＤ−グルコン酸水溶液の濃度は０〜１Ｍ（０Ｍ、０．０５Ｍ、０．１Ｍ、０．２Ｍ、０．５Ｍ、１Ｍ）に調整し、合計６種のＴＩＰ−ＥＧ＋グルコン酸複合体溶液を調整した。
(Synthesis)
First, 0.01 mol of titanium tetraisopropoxide (TIP) and 50 mL of ethylene glycol (EG) were mixed, and 50 mL of a D-gluconic acid aqueous solution was further added to prepare a TIP-EG + gluconic acid complex solution. The concentration of the D-gluconic acid aqueous solution was adjusted to 0 to 1 M (0 M, 0.05 M, 0.1 M, 0.2 M, 0.5 M, 1 M), and a total of six TIP-EG + gluconic acid complex solutions were prepared. It was adjusted.
その後、それぞれ９５℃２４時間静置し、チタン化合物ナノ粒子分散ゾル（溶媒：ＥＧ＋Ｈ２Ｏ）を得た。 Thereafter, each was allowed to stand at 95 ° C. for 24 hours to obtain a titanium compound nanoparticle dispersed sol (solvent: EG + H 2 O).
そして、このゾルに対し、セルロースチューブに入れ水中で透析し、ＥＧをＨ２Ｏに置換し、チタン酸化合物ナノ粒子分散ゾル（溶媒：Ｈ２Ｏ）を得た。そして、７５℃で１２時間乾燥させ、チタン酸化合物シート状乾燥体を得た。なおこの乾燥体に対しては、粉砕を行い粉体としたのち、各種の分析を行った。 The sol was placed in a cellulose tube and dialyzed in water to replace EG with H 2 O to obtain a titanate compound nanoparticle dispersed sol (solvent: H 2 O). And it dried at 75 degreeC for 12 hours, and obtained the titanate compound sheet-form dry body. The dried product was pulverized into powder and subjected to various analyses.
まず、図４に、得られた粉体のＸＲＤパターンを示す。 First, FIG. 4 shows an XRD pattern of the obtained powder.
本図で示すように、Ｄ−グルコン酸水溶液を加えていない（０Ｍ）の場合は、アナターゼ型のＴｉＯ２のピークが確認されているが、０．１Ｍ以上Ｄ−グルコン酸水溶液を加えた粉末においては、層状チタン酸によるピークを確認することができた。 As shown in this figure, in the case where the aqueous solution of D-gluconic acid was not added (0 M), the peak of anatase-type TiO 2 was confirmed. In, peaks due to layered titanic acid could be confirmed.
また図５に、得られた粉体のラマンスペクトルについて示す。 FIG. 5 shows the Raman spectrum of the obtained powder.
本図で示すように、２５０〜３００ｃｍ−１、４００〜５００ｃｍ−１、６００〜７００ｃｍ−１、のそれぞれ近傍において、層状チタン酸様構造に起因すると思われるピークを確認することができた。 As shown in the figure, peaks attributable to the layered titanate-like structure could be confirmed in the vicinity of each of 250 to 300 cm −1 , 400 to 500 cm −1 , and 600 to 700 cm −1 .
また図６に、加えたＤ−グルコン酸水溶液の濃度が０．０５Ｍ、１Ｍの場合において得られた粉体のＦＴ−ＩＲスペクトルについて示す。 FIG. 6 shows the FT-IR spectrum of the powder obtained when the concentration of the added aqueous solution of D-gluconic acid was 0.05 M and 1 M.
本図で示すように、Ｃ−Ｏ、Ｃ−Ｈ、ＣＯＯ−の吸収ピークを確認することができ、チタン酸が存在していることを確認できた。 As shown in this figure, absorption peaks of CO, CH and COO − could be confirmed, and it was confirmed that titanic acid was present.
また図７に、加えたＤ−グルコン酸水溶液の濃度が０．０５Ｍ、０．１Ｍ、１Ｍの場合において得られた粉体のＴＧ−ＤＴＡ曲線について示す。 FIG. 7 shows a TG-DTA curve of the powder obtained when the concentration of the added aqueous solution of D-gluconic acid was 0.05 M, 0.1 M, and 1 M.
本図で示すように、いずれの場合も２００〜３５０℃程度において未反応アルコキシドの分解及び加水分解生成物の脱水が起こり、３５０〜５５０℃程度の範囲内で配位したグルコン酸の分解と思われる変化を確認した。 As shown in this figure, in each case, decomposition of unreacted alkoxide and dehydration of hydrolysis products occur at about 200 to 350 ° C., which is considered to be decomposition of gluconic acid coordinated within the range of about 350 to 550 ° C. Confirmed changes.
以上の結果から、上記得られた化合物は、板状の構造を備えているグルコン酸と複合化した層状のチタン酸であることを確認した。 From the above results, it was confirmed that the obtained compound was a layered titanic acid complexed with gluconic acid having a plate-like structure.
（シート乾燥体）
次に、Ｄ−グルコン酸水溶液の濃度を１Ｍとした粉体に水を加えてゾルとし、水を乾燥させた後、シート状になった乾燥体（グルコン酸複合化層状チタン酸シート状乾燥体）を得た（厚さ０．３ｍｍ）。
(Dry sheet)
Next, water is added to the powder having a D-gluconic acid aqueous solution having a concentration of 1M to form a sol, and the water is dried. The dried product is formed into a sheet (gluconic acid composite layered titanate sheet-like dried product). ) Was obtained (thickness: 0.3 mm).
そして、これに水を添加したところ、水を含んで吸収し、膨潤ゲルとなり、色を呈し、厚み１０倍程度（厚さ３．４５ｍｍ）まで膨潤した。 Then, when water was added to the mixture, the mixture absorbed water and became a swollen gel, exhibited a color, and swelled to a thickness of about 10 times (thickness of 3.45 mm).
なお、更に水を加え続けると、グルコン酸複合化層状チタン酸粒子が分散したゾルとなった。 When water was further added, a sol in which gluconic acid composite layered titanate particles were dispersed was obtained.
すなわち、グルコン酸複合化層状チタン酸シート状乾燥体は、水を加え、乾燥させることにより、シート状から膨潤状態、ゲルを経て再びシート状となるサイクルを繰り返すことができる。このサイクルの写真図を図８に示す。なお、もちろん、シート状と膨潤状態の往復も可能であった。 That is, by adding water and drying the gluconic acid-composite layered titanate sheet-like dried product, a cycle of changing from a sheet-like state to a swollen state, a gel, and a sheet-like state can be repeated. A photograph of this cycle is shown in FIG. In addition, of course, reciprocation between the sheet state and the swollen state was possible.
またここで、シート状乾燥体を方眼紙上に配置し、シート状乾燥体の周囲を黒色で明示した後、水を含ませてその膨潤方向について確認した。この結果、膨潤ゲルはほぼ厚み方向に膨らむのみで、横方向には広がらず、ほぼ同じ平面形状を確保できていることが確認できた。この写真図を図９に示しておく。 Further, here, the sheet-like dried body was placed on a piece of graph paper, and the periphery of the sheet-like dried body was clearly indicated in black, and then water was contained to check the swelling direction. As a result, it was confirmed that the swollen gel only swelled in the thickness direction but did not spread in the lateral direction, and was able to secure substantially the same planar shape. This photograph is shown in FIG.
（繰り返し特性）
ここで、グルコン酸複合化層状チタン酸シート状乾燥体の繰り返し特性について確認を行った。具体的には、グルコン酸複合化層状チタン酸シート状乾燥体に水１００ｍｌを添加し、完全にグルコン酸複合化層状チタン酸シート状乾燥体が分散するまで静置して分散ゾルとし、ＵＶ−Ｖｉｓ透過率スペクトルを測定した後、再び乾燥させてグルコン酸複合化層状チタン酸シート状乾燥体とする工程を複数回繰り返した。このゾル化、乾燥の繰り返しにおけるＵＶ−Ｖｉｓ透過率スペクトルを図１０に示しておく。また本図中において、１０回目の分散ゾル及びその乾燥体の写真図も示しておく。
(Repeatability)
Here, the repetition characteristics of the dried gluconic acid composite layered titanate sheet were confirmed. Specifically, 100 ml of water is added to the dried gluconic acid composite layered titanate sheet, and the dispersion is allowed to stand until the gluconic acid composite layered titanate sheet dried is completely dispersed to form a dispersion sol. After measuring the Vis transmittance spectrum, the process of drying again to obtain a dried gluconic acid composite layered titanate sheet was repeated a plurality of times. FIG. 10 shows a UV-Vis transmittance spectrum in the repetition of this solification and drying. Further, in this figure, a photographic diagram of the tenth dispersion sol and the dried product thereof are also shown.
（構造の確認）
ここで、上記方法と同様の方法で作製したグルコン酸複合化層状チタン酸シート状乾燥体に対し、乾燥させた状態又は膨潤させた状態における構造の確認を行った。具体的には、グルコン酸複合化層状チタン酸シート状乾燥体の質量を１とした場合における水の質量比を０〜１５に調整したもの（ゲル）を液体窒素で凍結乾燥し、そのＳＥＭ像を得た。この結果を図１１に示す。
(Confirmation of structure)
Here, the structure in a dried state or a swollen state of the dried gluconic acid composite layered titanate sheet produced by the same method as described above was confirmed. Specifically, a gel (gel) in which the mass ratio of water was adjusted to 0 to 15 when the mass of the dried gluconic acid composite layered titanate sheet was 1 was freeze-dried with liquid nitrogen, and its SEM image was obtained. I got The result is shown in FIG.
本図の結果によると、質量比０の場合、層状構造体はほぼ見ることができていないものの、質量比３〜１５においては、水の質量比が増加すると多数の板状構造体すなわち層状構造体となっており、しかもその層間距離が増加していることを確認した。またこれら層状構造体は高アスペクト比を有する板状構造体がラメラ状の集積構造を形成していることを確認した。グルコン酸複合化層状チタン酸は、界面活性剤などのテンプレートを一切用いることなく、このようなラメラ構造を形成することができる。これは、溶液中のグルコン酸の会合構造を反映していると考えられる。このような二次元的広がりの大きな形態は構造色発現のための規則的な積層構造形成に有利である。 According to the results shown in the figure, when the mass ratio is 0, the layered structure is hardly seen, but at the mass ratio of 3 to 15, when the mass ratio of water increases, a large number of plate-shaped structures, that is, the layered structures are formed. It was confirmed that it was a body and that the interlayer distance was increasing. In addition, it was confirmed that these layered structures formed a plate-shaped structure having a high aspect ratio to form a lamellar integrated structure. The gluconic acid complexed layered titanic acid can form such a lamellar structure without using any template such as a surfactant. This is considered to reflect the association structure of gluconic acid in the solution. Such a form having a large two-dimensional spread is advantageous for forming a regular laminated structure for expressing structural colors.
（色制御）
またここで、色の制御について確認を行った。具体的には、グルコン酸複合化層状チタン酸シート状乾燥体に上記用いた水を加えたゾルに、さらにグリセリンを加える量を変化させてその色の制御変化を確認した。まず、図１２に、このグルコン酸複合化層状チタン酸のゾルの写真図を示しておく。なおここでは、グルコン酸複合化層状チタン酸ゾルの質量とグリセリン質量の割合を１／１０、１／１３、１／１７、１／２０とした場合の例について示しておく。１／２０の状態ではゾルは青みがかった色である一方、徐々に変化し、１／１３では赤みがかった色に変化し、１／１０程度では無色に近くなった。これは板状構造体間の距離が徐々に変化することにより生じた構造色の変化であると考えられる。
(Color control)
Here, the color control was confirmed. Specifically, the control change of the color was confirmed by changing the amount of glycerin to be added to the sol obtained by adding the above-mentioned water to the gluconic acid composite layered layered titanate sheet-like dried product. First, FIG. 12 shows a photograph of the sol of the gluconic acid composite layered titanic acid. Here, an example in which the ratio of the mass of the gluconic acid composite layered titanate sol to the mass of glycerin is 1/10, 1/13, 1/17, 1/20 will be described. In the state of 1/20, the sol had a bluish color, but gradually changed, changed to a reddish color in 1/13, and was almost colorless in about 1/10. This is considered to be a change in the structural color caused by a gradual change in the distance between the plate-like structures.
また図１３に、このゲルの透過率スペクトルについて示す。本図で示すように、グリセリンの量に応じて透過率スペクトルが変化していることが確認でき、４００ｎｍから８００ｎｍの範囲で発色を制御することが可能であることを確認した。 FIG. 13 shows the transmittance spectrum of this gel. As shown in this figure, it was confirmed that the transmittance spectrum changed according to the amount of glycerin, and it was confirmed that color development could be controlled in the range of 400 nm to 800 nm.
またこのゲルを乾燥させたものを粉砕し、そのＳＥＭ像を得た。図１４に示しておく。なお本図は、上記１／２０の青色を呈したゾルと、１／１３の赤色を呈したゾルをそれぞれ２００℃で１時間又は１．５時間乾燥させた乾燥物を粉砕させた後のＳＥＭ像である。上は１／２０（青）のゾルのＳＥＭ像であり、下は１／１３（赤）のゾルのＳＥＭ像である。 The dried gel was pulverized to obtain an SEM image. It is shown in FIG. This figure shows the SEM obtained by pulverizing a dried product obtained by drying the sol exhibiting 1/20 of the blue color and the sol exhibiting 1/13 of the red color at 200 ° C. for 1 hour or 1.5 hours, respectively. It is a statue. The upper part is a SEM image of 1/20 (blue) sol, and the lower part is a SEM image of 1/13 (red) sol.
本図においても、ラメラ状の集積構造を確認でき、若干ではあるが１／１３の方が層間距離が大きくなっている様子が確認できた。以上、これらの結果により、グリセリン等の水素結合性化合物を含ませることで、層間距離をより効率的に所望の範囲に調整することができることを確認した。 Also in this figure, a lamellar integrated structure was confirmed, and although a little, it was confirmed that the interlayer distance was larger in 1/13. From the above results, it was confirmed that the interlayer distance can be more efficiently adjusted to a desired range by including a hydrogen bonding compound such as glycerin.
以上、本実施例により、より簡便な構造で、安定的に構造色を発現することのできる構造色発現材料の効果について確認できた。 As described above, according to the present example, the effect of the structural color developing material capable of stably developing the structural color with a simpler structure was confirmed.
本発明は、構造色発現材料及びこれを用いたセンサとして産業上の利用可能性がある。
INDUSTRIAL APPLICABILITY The present invention has industrial applicability as a structural color developing material and a sensor using the same.
Claims (7)
A sensor having a structural color developing material provided with a layered structure including a large number of plate-like structures to which sugar acid molecules are bound, and having a structural color that varies depending on the amount of a hydrogen bonding compound between the plate-like structures .
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