JP2008127438A - Manufacturing method of substituted polyacetylene film - Google Patents
Manufacturing method of substituted polyacetylene film Download PDFInfo
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Abstract
Description
本発明は、置換ポリアセチレン膜の製造方法に関し、特に有機溶媒に対して難溶性のポリフェニルアセチレン膜の製造方法に関する。 The present invention relates to a method for producing a substituted polyacetylene film, and more particularly to a method for producing a polyphenylacetylene film that is hardly soluble in an organic solvent.
無置換ポリアセチレンは導電性高分子としてよく知られているが、空気中では不安定で、溶媒に難溶である。フェニルアセチレン等に代表される置換ポリアセチレンの主鎖二重結合の共役鎖長は無置換ポリアセチレンに比較して短いが、空気中で安定かつ有機溶媒に可溶である。このため、近年置換ポリアセチレンが電子材料や発光材料として研究されている（非特許文献１および２参照）。 Unsubstituted polyacetylene is well known as a conductive polymer, but is unstable in air and hardly soluble in a solvent. Although the conjugated chain length of the main chain double bond of substituted polyacetylene represented by phenylacetylene is shorter than that of unsubstituted polyacetylene, it is stable in air and soluble in an organic solvent. Therefore, in recent years, substituted polyacetylene has been studied as an electronic material or a light emitting material (see Non-Patent Documents 1 and 2).
しかし、置換ポリアセチレンの中では構造により有機溶媒に溶けにくい難溶性の置換ポリアセチレンも知られている（非特許文献３参照）。
この置換ポリアセチレンの難溶化の多くは、置換ポリアセチレンの結晶化に起因していると考えられている。つまり有機溶媒が結晶構造中に浸透しないため、その結果として有機溶媒に対する不溶性を示す。また、置換ポリアセチレンの難溶化は結晶化だけではなく、水素結合や双極子−双極子相互作用などの分子内あるいは分子間の側鎖同士の強い相互作用にも由来する場合がある。
However, among the substituted polyacetylenes, a hardly soluble substituted polyacetylene that is hardly soluble in an organic solvent due to its structure is also known (see Non-Patent Document 3).
Much of the poor solubility of the substituted polyacetylene is thought to result from crystallization of the substituted polyacetylene. That is, since the organic solvent does not penetrate into the crystal structure, the result shows insolubility in the organic solvent. Moreover, the poor solubilization of substituted polyacetylene may be derived not only from crystallization but also from strong interactions between side chains within or between molecules such as hydrogen bonds and dipole-dipole interactions.
置換ポリアセチレンの結晶構造は螺旋鎖がパッキングした六方晶構造が知られているが、その結晶化させる方法としては溶媒処理やアルキル鎖の導入等が報告されている。特に、炭素数８以上の長鎖で直鎖のアルキル基を有する置換ポリアセチレンでは、そのアルキル鎖同士のパッキングにより高い結晶化度を示す。これらの結晶性高分子はその構造規則性の差異により一部は有機溶媒に溶解する場合があるが、非常に秩序性の高い部分は不溶性部分として溶媒中に残る。このような置換ポリアセチレンの場合では、溶液を均一にするために製膜前にフィルタリングする必要があり、且つ溶液濃度の制御も難しい。また、置換ポリアセチレンに不溶性部分が無い場合でも、全ての部分を溶解させるためには、長い時間と、場合によっては超音波，加熱等を必要とする。置換ポリアセチレン類は溶液で長時間放置したり、超音波や熱を加えることにより異性化あるいは分解してしまう可能性がある。 The crystal structure of the substituted polyacetylene is known to be a hexagonal crystal structure in which helical chains are packed, and solvent treatment, introduction of an alkyl chain, and the like have been reported as crystallization methods. In particular, a substituted polyacetylene having a long chain and a straight chain alkyl group having 8 or more carbon atoms exhibits high crystallinity due to packing between the alkyl chains. Some of these crystalline polymers may be dissolved in an organic solvent due to the difference in structural regularity, but a very ordered part remains in the solvent as an insoluble part. In the case of such substituted polyacetylene, it is necessary to filter before film formation in order to make the solution uniform, and it is difficult to control the solution concentration. Further, even when the substituted polyacetylene has no insoluble portion, it takes a long time and, in some cases, ultrasonic waves, heating, etc., to dissolve all the portion. Substituted polyacetylenes may be isomerized or decomposed when left in solution for a long time, or by applying ultrasonic waves or heat.
一方で高い結晶化度を有する置換ポリアセチレンは、その規則的な構造から高い電子伝導特性等の機能を示すことが期待されており、その難溶性から製膜方法が課題となっている。
本発明は、上記課題を鑑みてなされたもので、長鎖アルキル基を有する置換ポリアセチレンを良溶媒中で合成し、直接塗布して製膜することにより、秩序性の高い有機溶媒に難溶性の置換ポリアセチレン膜を製造する方法を提供するものである。 The present invention has been made in view of the above problems, and by synthesizing a substituted polyacetylene having a long-chain alkyl group in a good solvent, and directly coating it to form a film, it is hardly soluble in a highly ordered organic solvent. A method for producing a substituted polyacetylene film is provided.
上記の課題を解決する置換ポリアセチレン膜の製造方法は、下記一般式（１）で表される置換フェニルアセチレンを触媒を用いて溶媒の存在下で重合して置換ポリアセチレンの溶液を得る工程、該置換ポリアセチレンの溶液を用いて製膜する工程を有することを特徴とする。 A method for producing a substituted polyacetylene film that solves the above-described problems includes a step of polymerizing substituted phenylacetylene represented by the following general formula (1) in the presence of a solvent using a catalyst to obtain a substituted polyacetylene solution, the substitution It has the process of forming into a film using the solution of polyacetylene, It is characterized by the above-mentioned.
（式中、Ｘ1，Ｘ2，Ｘ3は水素原子、−Ｒまたは−Ｙ−Ｒを示す。但し、Ｘ1，Ｘ2，Ｘ3の少なくとも一つは−Ｒまたは−Ｙ−Ｒである。Ｒは炭素数８以上の直鎖アルキル基、Ｙはヘテロ原子またはヘテロ原子を含む置換基を示す。） (In the formula, X 1 , X 2 and X 3 represent a hydrogen atom, —R or —Y—R, provided that at least one of X 1 , X 2 and X 3 is —R or —Y—R. R represents a linear alkyl group having 8 or more carbon atoms, and Y represents a hetero atom or a substituent containing a hetero atom.)
本発明は、長鎖で直鎖のアルキル基を有するフェニルアセチレンから、長鎖アルキル基を有する置換ポリアセチレンを良溶媒中で合成し、直接塗布して製膜することにより、秩序性の高い有機溶媒に難溶性の置換ポリアセチレン膜を製造できる。この置換ポリアセチレン膜は有機溶媒に難溶性のため耐有機溶媒性のコーティング膜として使用できる。 The present invention synthesizes a substituted polyacetylene having a long-chain alkyl group from a phenylacetylene having a long-chain linear alkyl group in a good solvent, and directly coating it to form a film. It is possible to produce a substituted polyacetylene film that is sparingly soluble in water. Since this substituted polyacetylene film is hardly soluble in organic solvents, it can be used as a coating film resistant to organic solvents.
以下、本発明を詳細に説明する。
本発明は、下記一般式（１）で表される置換フェニルアセチレンを触媒を用いて溶媒の存在下で重合して置換ポリアセチレンの溶液を得る工程、該置換ポリアセチレンの溶液を用いて製膜する工程を有し、秩序性の高い有機溶媒に難溶性の置換ポリアセチレン膜の製造方法を提供するものである。
Hereinafter, the present invention will be described in detail.
The present invention comprises a step of polymerizing substituted phenylacetylene represented by the following general formula (1) in the presence of a solvent using a catalyst to obtain a substituted polyacetylene solution, and a step of forming a film using the substituted polyacetylene solution. And a method for producing a substituted polyacetylene film that is hardly soluble in an organic solvent having high order.
一般式（１）において、Ｘ1，Ｘ2，Ｘ3は水素原子、−Ｒまたは−Ｙ−Ｒである。但し、Ｘ1，Ｘ2，Ｘ3の少なくとも一つは−Ｒまたは−Ｙ−Ｒで表される置換基であり、残りは水素原子である。 In the general formula (1), X 1 , X 2 and X 3 are a hydrogen atom, —R or —Y—R. However, at least one of X 1 , X 2 , and X 3 is a substituent represented by —R or —Y—R, and the remainder is a hydrogen atom.
Ｒは炭素数８以上、好ましくは炭素数８以上１２以下の直鎖アルキル基である。
Ｙはヘテロ原子またはヘテロ原子を含む置換基を示す。ヘテロ原子は、酸素原子、硫黄原子、窒素原子等が挙げられる。ヘテロ原子を含む置換基は、例えばエーテル結合、エステル結合、カルボニル結合、チオエーテル結合、スルホキシド結合、アミノ結合、アミド結合等が挙げられる。
R is a linear alkyl group having 8 or more carbon atoms, preferably 8 to 12 carbon atoms.
Y represents a hetero atom or a substituent containing a hetero atom. Examples of the hetero atom include an oxygen atom, a sulfur atom, and a nitrogen atom. Examples of the substituent containing a hetero atom include an ether bond, an ester bond, a carbonyl bond, a thioether bond, a sulfoxide bond, an amino bond, and an amide bond.
前記一般式（１）中のＸ1，Ｘ2，Ｘ3の少なくとも一つは−Ｏ−Ｒ（Ｒは炭素数８以上の直鎖アルキル基）であることが好ましい。
本発明に用いる置換フェニルアセチレンとしては、一般式（１）に示すように、パラ位あるいはメタ位に少なくとも一つの炭素数８以上の直鎖アルキル基（以降、アルキル鎖とも記す）からなる置換基を有することが必要である。パラ位あるいはメタ位に長鎖アルキル基を有することで、隣接フェニル基に置換したアルキル鎖間のファンデアワールス力が強く働き、アルキル鎖のシート状秩序構造を形成するために有機溶媒に対する溶解性が低下する。アルキル鎖はフェニル環にひとつ置換すればよいが、複数置換しても良い。ただし、オルト位に置換した場合は立体障害が大きく、重合そのものの進行が困難であるため、パラ位あるいはメタ位に置換することが望まれる。立体障害の小さい置換基であればオルト位やパラ位、メタ位を問わず長鎖アルキル基が置換している以外の位置に置換しても良い。立体障害の小さい置換基としては、水酸基、ハロゲン、アミノ基、カルボン酸やメチル基やエチル基などの短いアルキル鎖を有する置換基が挙げられる。
In the general formula (1), at least one of X 1 , X 2 and X 3 is preferably —O—R (R is a linear alkyl group having 8 or more carbon atoms).
As substituted phenylacetylene used in the present invention, as shown in the general formula (1), a substituent consisting of at least one linear alkyl group having 8 or more carbon atoms in the para-position or meta-position (hereinafter also referred to as an alkyl chain). It is necessary to have By having a long-chain alkyl group at the para-position or meta-position, the van der Waals force between the alkyl chains substituted by the adjacent phenyl group works strongly, and the solubility in organic solvents to form a sheet-like ordered structure of the alkyl chain Decreases. The alkyl chain may be substituted one by one on the phenyl ring, but may be substituted more than once. However, substitution at the ortho position has a large steric hindrance and it is difficult for the polymerization itself to proceed, so substitution at the para or meta position is desirable. As long as the substituent is small in steric hindrance, it may be substituted at a position other than the position where the long-chain alkyl group is substituted regardless of the ortho position, para position or meta position. Examples of the substituent having a small steric hindrance include a substituent having a short alkyl chain such as a hydroxyl group, a halogen, an amino group, a carboxylic acid, a methyl group, or an ethyl group.
炭素数８以上の直鎖アルキル基は、ベンゼン環に直接置換しても良いし、ヘテロ元素を含む結合を挟んで置換しても良い。
一般式（１）で表される置換フェニルアセチレンの重合方法としては、ロジウム（ノルボルナジエン）塩化物二量体のようなロジウム錯体触媒を用いると頭尾結合及び二重結合がシス体の立体規則性の高い置換ポリアセチレンが得られる。この立体規則性の高い置換ポリアセチレンは主鎖が螺旋構造を形成しており、集合体としては六方晶の結晶構造を形成することが報告されている。
The straight-chain alkyl group having 8 or more carbon atoms may be directly substituted on the benzene ring, or may be substituted with a bond containing a hetero element interposed therebetween.
As a polymerization method of the substituted phenylacetylene represented by the general formula (1), a rhodium complex catalyst such as a rhodium (norbornadiene) chloride dimer is used. High substituted polyacetylene. It has been reported that the substituted polyacetylene having high stereoregularity has a helical structure in the main chain and forms a hexagonal crystal structure as an aggregate.
置換ポリアセチレンの側鎖アルキル基としては、炭素数８以上の直鎖アルキル基を用いているので、側鎖間のアルキル鎖同士のパッキングによる秩序性の発現もしくはアルキル鎖の運動による分子鎖間の秩序性向上により、重合後に貧溶媒に沈殿させることで高次構造として結晶構造を形成し、その高い秩序性からクロロホルムやトルエン等の有機溶媒に対して難溶性を示す。 As the side chain alkyl group of the substituted polyacetylene, a straight chain alkyl group having 8 or more carbon atoms is used, so that the order of the molecular chain is expressed by packing of the alkyl chains between the side chains or the movement of the alkyl chain. Due to the improved property, it is precipitated in a poor solvent after polymerization to form a crystal structure as a higher order structure, and due to its high order, it is hardly soluble in organic solvents such as chloroform and toluene.
難溶性の置換ポリアセチレンは、沈殿後では有機溶媒に対して全く溶解しないか、溶解しても微量である。
難溶性の置換ポリアセチレンを溶解させるためには、加熱や超音波等の刺激が必要である。置換ポリアセチレンは溶液で長時間放置したり、超音波や熱を加えることにより異性化あるいは分解する可能性があるため、このような方法では規則性の高い膜を製造することは困難である。
The hardly soluble substituted polyacetylene does not dissolve at all in the organic solvent after precipitation, or is in a trace amount even when dissolved.
In order to dissolve the hardly soluble substituted polyacetylene, stimulation such as heating or ultrasonic waves is required. Since substituted polyacetylene may be isomerized or decomposed by leaving it in solution for a long time or applying ultrasonic waves or heat, it is difficult to produce a highly ordered film by such a method.
本発明においては、このような難溶性の置換ポリアセチレンの重合を良溶媒中で行うと、沈殿前には高濃度で溶解していおり、その溶液に更に良溶媒を加えることで濃度を調節し，得られた溶液を用いて塗布法により難溶性の置換ポリアセチレンからなる膜が得られる。 In the present invention, when such poorly soluble substituted polyacetylene is polymerized in a good solvent, it is dissolved at a high concentration before precipitation, and the concentration is adjusted by adding a good solvent to the solution. A film made of a hardly soluble substituted polyacetylene is obtained by a coating method using the obtained solution.
炭素数８以上の直鎖アルキル基を有する置換ポリアセチレンに対する良溶媒としてはクロロホルム，トルエン等があげられるが、特にこれらには限定されない。また、側鎖構造により適した良溶媒は異なり、ジメチルホルムアミドやジメチルアセトアミド等の極性溶媒が使用できる場合もある。 Examples of the good solvent for the substituted polyacetylene having a linear alkyl group having 8 or more carbon atoms include chloroform and toluene, but are not particularly limited thereto. Moreover, the good solvent suitable for the side chain structure is different, and a polar solvent such as dimethylformamide or dimethylacetamide may be used.
膜厚は溶液濃度および製膜条件により調整できる。また、膜厚は溶媒の粘度等により影響されるため，ポリマーの構造，分子量等にあわせてあらかじめ製膜条件を明らかにしておく必要がある。 The film thickness can be adjusted by the solution concentration and the film forming conditions. In addition, since the film thickness is affected by the viscosity of the solvent, it is necessary to clarify the film forming conditions in advance according to the polymer structure, molecular weight, and the like.
得られた置換ポリアセチレンは側鎖構造により溶液中では不安定であるため、重合、溶液濃度を調整した後は出来るだけ早く製膜することが望ましい。
製膜方法としては通常の高分子溶液と同様にキヤスト法やスピンコート法などを用いることができる。製膜媒体としては、ガラスやシリコン、酸化シリコン等の基板や、基板以外の粒子等の形状のものも用いることができる。
Since the obtained substituted polyacetylene is unstable in a solution due to a side chain structure, it is desirable to form a film as soon as possible after adjusting the polymerization and the solution concentration.
As a film forming method, a cast method, a spin coating method, or the like can be used as in the case of a normal polymer solution. As the film forming medium, a substrate made of glass, silicon, silicon oxide or the like, or a particle other than the substrate can be used.
また、置換ポリアセチレン膜は有機溶媒に難溶性のため耐有機溶媒性のコーティング膜として使用できる。一般に耐有機溶媒性のコーティング膜は製膜後に熱処理などの工程を必要とするが、本発明の置換ポリアセチレン膜は塗布するだけで有機溶媒に難溶性の膜が製膜できる。 Further, the substituted polyacetylene film can be used as a coating film resistant to organic solvents because it is hardly soluble in organic solvents. In general, a coating film resistant to organic solvents requires a process such as heat treatment after film formation, but a film hardly soluble in an organic solvent can be formed only by coating the substituted polyacetylene film of the present invention.
以下、実施例を示し本発明をさらに具体的に説明する
実施例１
本実施例は、ポリ（ｐ−テトラデシルオキシフェニルアセチレン）の合成の実施例である。
Hereinafter, the present invention will be described more specifically with reference to examples.
This example is an example of the synthesis of poly (p-tetradecyloxyphenylacetylene).
窒素置換後密閉した試験管にロジウム（ノルボルナジエン）塩化物二量体１．８ｍｇ、トリエチルアミン３３．７ｍｇとクロロホルム２ｍｌを入れ、下記の式２の化合物の（ｐ−テトラデシルオキシフェニルアセチレン）０．４ｇとクロロホルム２ｍｌの混合溶液を滴下することにより重合反応を開始させた。反応は室温で２時間行ってポリ（ｐ−テトラデシルオキシフェニルアセチレン）を得た。 In a test tube sealed after nitrogen substitution, 1.8 mg of rhodium (norbornadiene) chloride dimer, 33.7 mg of triethylamine and 2 ml of chloroform were placed, and 0.4 g of (p-tetradecyloxyphenylacetylene) of the compound of the following formula 2 The polymerization reaction was initiated by dropwise addition of a mixed solution of 2 ml of chloroform and 2 ml of chloroform. The reaction was carried out at room temperature for 2 hours to obtain poly (p-tetradecyloxyphenylacetylene).
得られたポリ（ｐ−テトラデシルオキシフェニルアセチレン）のクロロホルム溶液１．０ｍｌにクロロホルム９９ｍｌを加えることで濃度１．０ｇ／ｌのポリマー溶液を調整した。この溶液をガラス基板にキャストして薄膜を作成した。室温で静置し，乾燥して溶媒を除去する。得られた高分子膜はメタノール等の極性溶媒に溶解せず、クロロホルムやＴＨＦ、ヘキサン等の非極性溶媒にも溶解しない。 A polymer solution having a concentration of 1.0 g / l was prepared by adding 99 ml of chloroform to 1.0 ml of a chloroform solution of the obtained poly (p-tetradecyloxyphenylacetylene). This solution was cast on a glass substrate to form a thin film. Let stand at room temperature and dry to remove the solvent. The obtained polymer film does not dissolve in polar solvents such as methanol, and does not dissolve in nonpolar solvents such as chloroform, THF, and hexane.
実施例２
実施例１で調整した濃度１．０ｇ／ｌのポリマー溶液１．０ｍｌをシリコン基板に滴下後、回転数１５００回転／分でスピンコートして薄膜を作成した。室温で静置し，乾燥して溶媒を除去する。得られた高分子膜はメタノール等の極性溶媒に溶解せず，クロロホルムやＴＨＦ、ヘキサン等の非極性溶媒にも溶解しない。
Example 2
After 1.0 ml of a polymer solution having a concentration of 1.0 g / l prepared in Example 1 was dropped onto a silicon substrate, a thin film was formed by spin coating at a rotational speed of 1500 revolutions / minute. Let stand at room temperature and dry to remove the solvent. The obtained polymer membrane does not dissolve in polar solvents such as methanol, and does not dissolve in nonpolar solvents such as chloroform, THF, and hexane.
実施例３
モノマーを、下記の式３に示したｐ−ｎ−デシルオキシフェニルアセチレンに変えた以外は、実施例１と同様の方法で重合してポリ（ｐ―ｎ−デシルオキシフェニルアセチレン）を得た。
Example 3
Poly (pn-decyloxyphenylacetylene) was obtained by polymerization in the same manner as in Example 1 except that the monomer was changed to pn-decyloxyphenylacetylene represented by Formula 3 below.
得られたポリ（ｐ―ｎ−デシルオキシフェニルアセチレン）のクロロホルム溶液１．０ｍｌにクロロホルム９９ｍｌを加えて、濃度１．０ｇ／ｌのポリマー溶液を調整した。この溶液をガラス基板にキャストして薄膜を作成した。室温で静置し，乾燥して溶媒を除去する。得られた高分子膜はメタノール等の極性溶媒に溶解せず，クロロホルムやＴＨＦ、ヘキサン等の非極性溶媒にも溶解しない。 99 ml of chloroform was added to 1.0 ml of the chloroform solution of the obtained poly (pn-decyloxyphenylacetylene) to prepare a polymer solution having a concentration of 1.0 g / l. This solution was cast on a glass substrate to form a thin film. Let stand at room temperature and dry to remove the solvent. The obtained polymer membrane does not dissolve in polar solvents such as methanol, and does not dissolve in nonpolar solvents such as chloroform, THF, and hexane.
実施例４
モノマーを、下記の式４に示したｐ−ｎ−オクチルアミドフェニルアセチレンに、溶媒をクロロホルムからＤＭＡに変えた以外は実施例１と同様の方法で重合してポリ（ｐ―ｎ−オクチルアミドフェニルアセチレン）を得た。
Example 4
Poly (pn-octylamidophenyl) was polymerized in the same manner as in Example 1 except that the monomer was changed to pn-octylamidophenylacetylene represented by the following formula 4 and the solvent was changed from chloroform to DMA. Acetylene) was obtained.
得られたポリ（ｐ―ｎ−オクチルアミドフェニルアセチレン）のＤＭＡ溶液１．０ｍｌにＤＭＡ９９ｍｌを加えることで濃度１．０ｇ／ｌのポリマー溶液を調整した。この溶液をガラス基板にキャストして薄膜を作成した。室温で静置した後，減圧乾燥して溶媒を除去する。得られた高分子膜はメタノール等の極性溶媒に溶解せず、クロロホルムやＴＨＦ、ヘキサン等の非極性溶媒にも溶解しない。 A polymer solution having a concentration of 1.0 g / l was prepared by adding 99 ml of DMA to 1.0 ml of the obtained DMA solution of poly (pn-octylamidophenylacetylene). This solution was cast on a glass substrate to form a thin film. Allow to stand at room temperature, and then dry under reduced pressure to remove the solvent. The obtained polymer film does not dissolve in polar solvents such as methanol, and does not dissolve in nonpolar solvents such as chloroform, THF, and hexane.
本発明は、有機溶媒に難溶性の置換ポリアセチレン膜を製造できるので、この置換ポリアセチレン膜は有機溶媒に難溶性のため耐有機溶媒性のコーティング膜として利用することができる。 Since the present invention can produce a substituted polyacetylene film that is hardly soluble in an organic solvent, the substituted polyacetylene film is hardly soluble in an organic solvent and can be used as an organic solvent-resistant coating film.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS62260808A (en) * | 1986-05-06 | 1987-11-13 | Toshinobu Higashimura | O-substituted phenylacetylene polymer |
| JPH0710973A (en) * | 1993-06-21 | 1995-01-13 | Ryuichi Yamamoto | Polymerization in the presence of soluble polymer compound |
| JP2004163184A (en) * | 2002-11-11 | 2004-06-10 | National Institute Of Advanced Industrial & Technology | Pressure sensor |
| WO2006025269A1 (en) * | 2004-08-30 | 2006-03-09 | Japan Science And Technology Agency | Novel polyacetylene derivatives |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS62260808A (en) * | 1986-05-06 | 1987-11-13 | Toshinobu Higashimura | O-substituted phenylacetylene polymer |
| JPH0710973A (en) * | 1993-06-21 | 1995-01-13 | Ryuichi Yamamoto | Polymerization in the presence of soluble polymer compound |
| JP2004163184A (en) * | 2002-11-11 | 2004-06-10 | National Institute Of Advanced Industrial & Technology | Pressure sensor |
| WO2006025269A1 (en) * | 2004-08-30 | 2006-03-09 | Japan Science And Technology Agency | Novel polyacetylene derivatives |
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