JPS5962608A - Preparation of polydiacetylene thin film - Google Patents
Preparation of polydiacetylene thin filmInfo
- Publication number
- JPS5962608A JPS5962608A JP17366782A JP17366782A JPS5962608A JP S5962608 A JPS5962608 A JP S5962608A JP 17366782 A JP17366782 A JP 17366782A JP 17366782 A JP17366782 A JP 17366782A JP S5962608 A JPS5962608 A JP S5962608A
- Authority
- JP
- Japan
- Prior art keywords
- thin film
- diacetylene
- polydiacetylene
- monomer
- film
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Abstract
Description
【発明の詳細な説明】
本発明は、薄膜状ポリジアセチレンの製造方法に関する
ものである。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing thin film polydiacetylene.
ジアセチレン化合物は、熱、光、あるいはγ線などによ
り結晶状態で重合して、結晶性ポリマーを生成する極め
て特異な物質として知られ、導電は、特殊な置換基を導
入して累積膜を形成しうるようにしたもの（Ｄ Ｂｌｏ
ｏｒ、 Ｏ，Ｌ、 ＨｕｂｂｌＯ＆Ｄ、 Ｊ、Ａｎｄｏ
。Diacetylene compounds are known as extremely unique substances that can be polymerized in a crystalline state by heat, light, or gamma rays to produce crystalline polymers, and conductivity can be achieved by introducing special substituents to form a cumulative film. What I made possible (D Blo
or, O, L, HubblO&D, J, Ando
.
Ｐｒｅｐｒｊｎ’ｔｓ Ｊａｐａｎ ３］、 （４）
７０８ （１９Ｂ２） ）等数例を除いて、不溶不融
であり重合時に得られるオ・）末としてそのままの形態
で取扱わねばならず、そのための機能材料としての応／
Ｉ’Ｊが困録であった。Preprjn'ts Japan 3], (4)
708 (19B2)) Except for a few cases, it is insoluble and infusible and must be handled as it is as a powder obtained during polymerization, and therefore it cannot be used as a functional material.
I'J was in trouble.
本発明者らは、ポリジアセチレンの加工方法について鋭
意研究を行った結果、容易に素子として利用可能な薄膜
状ポリジアセチレンを製造する方法を見出し、本発明を
完結するに至った。すなわち、本発明はジアセチレン化
合物の溶液又は、懸濁液より基板へのスプレー法又は、
スピンナー法により作成したジアセチレンモノマーＮｆ
Ｎを重合させることを特徴とする薄膜状ポリジアセチレ
ンの製造方法、及びジアセチレン化合物を基板上に真空
蒸着することにより作成したジアセチレンモノマー薄膜
を重合させることを特徴とする薄膜状ポリジアセチレン
の製造方法に関するものである。The inventors of the present invention have conducted intensive research on processing methods for polydiacetylene, and as a result, they have discovered a method for producing a thin film of polydiacetylene that can be easily used as an element, and have completed the present invention. That is, the present invention involves a method of spraying a solution or suspension of a diacetylene compound onto a substrate, or
Diacetylene monomer Nf created by spinner method
A method for producing a thin film of polydiacetylene, characterized by polymerizing N, and a method for producing a thin film of polydiacetylene, characterized by polymerizing a diacetylene monomer thin film created by vacuum evaporating a diacetylene compound on a substrate. It is about the method.
本発明において用いられるジアセチレン化合物とは、共
役ジアセチレン結合を有する化合物の総称であって、そ
の各種誘導体が含まれる。代表的なものとしては、２，
４−へキサジインのごとき炭化水素類、２，４−ヘキサ
ジイン−１，６−シオー１．４−ジピリジル−１，３−
ブタジインのごとき複素環化合物類、１，３−ブタジイ
ン−カルボン酸のごとき酸類及びこれらのエステル、ア
ミド、並びに塩類などを挙げることができる。これらの
ジアセチレン化合物は、必要に応じて２種以上併用する
こともできる。The diacetylene compound used in the present invention is a general term for compounds having a conjugated diacetylene bond, and includes various derivatives thereof. Typical examples include 2.
Hydrocarbons such as 4-hexadiyne, 2,4-hexadiyne-1,6-thio-1,4-dipyridyl-1,3-
Examples include heterocyclic compounds such as butadiyne, acids such as 1,3-butadiyne-carboxylic acid, and their esters, amides, and salts. Two or more of these diacetylene compounds can be used in combination, if necessary.
本発明の第一の方法においては、前記ジアセチレン化合
物の溶液又は、懸濁液からスプレー法又は、スピンナー
法により基板へ作成したジアセチレンモノマー薄膜を重
合するところに特徴がある。The first method of the present invention is characterized in that a diacetylene monomer thin film formed on a substrate from a solution or suspension of the diacetylene compound by a spray method or a spinner method is polymerized.
スプレー法、又はスピンナー法においてジアセチレン化
合物は溶液又は懸濁液として使用するが、この除用いる
溶媒、溶液の濃度は、特に限定するものではない。薄膜
の均一性を考慮するとジアセチレン化合物モノマーの溶
解度の高い溶媒を用いるのが望ましく、代表的なものと
しては、アセトン、メチルエチルケトンのごときｔトン
類、クロロホルム、塩化メチレンのごときハロゲン化合
物。In the spray method or spinner method, the diacetylene compound is used as a solution or suspension, but the solvent used and the concentration of the solution are not particularly limited. In consideration of the uniformity of the thin film, it is desirable to use a solvent in which the diacetylene compound monomer has a high solubility, and typical examples include acetone, t-tons such as methyl ethyl ketone, chloroform, and halogen compounds such as methylene chloride.
酢酸エチルのごときエステル類、ジメチルアセトアミド
、ジメチルホルムアミド、Ｎ−メチル−２−ピロリドン
のごときアミド類、アセトニトリルのごときニトリル類
が挙げられる。Examples include esters such as ethyl acetate, amides such as dimethylacetamide, dimethylformamide, N-methyl-2-pyrrolidone, and nitrites such as acetonitrile.
本発明の第２の方法では、前記ジアセチレン化合物を基
板上に真空蒸着することにより作成したポリジアセチレ
ン薄膜を重合するところに特徴がある。蒸着は１ｔｏｒ
ｒ以下、好ましくは１０ ｔｏｒｒ以下の圧力でボート
中のジアセチレンモノマーを加熱することにより行われ
る。温度はジアセチレンモノマーのＮ＋ ｙ’Ａにより
選定されるが、〜・般的に融点以上に加熱するのが適当
である。１，６−ジ（Ｎ−カルバゾイル）−２，４−へ
キサジイン、２，４−ヘキサジインのごとき昇華性を府
するものは、融−５００００Ａ／ｍｉｎ、 ｇ厚１００
Ａ−１０μ程度が一般的である。The second method of the present invention is characterized in that a polydiacetylene thin film prepared by vacuum-depositing the diacetylene compound on a substrate is polymerized. Vapor deposition is 1 tor.
It is carried out by heating the diacetylene monomer in the boat at a pressure of less than 10 Torr, preferably less than 10 Torr. The temperature is selected depending on the N+ y'A of the diacetylene monomer, but it is generally appropriate to heat it above the melting point. Sublimable substances such as 1,6-di(N-carbazoyl)-2,4-hexadiyne and 2,4-hexadiyne have a melting rate of 50,000 A/min and a g thickness of 100
Generally, the thickness is about A-10μ.
本発明では、ポリジアセチレン薄膜を製造する際、必要
に応じて第３成分をドーピングすることも可能である。In the present invention, when manufacturing a polydiacetylene thin film, it is also possible to dope a third component as necessary.
ドーピングの方法は、特に限定するものではないが、ジ
アセチレンモノマー博膜作成時又は後にドーピング剤を
固相、液相又は気相で混入する方法、ジアセチレンモノ
マー薄膜をドーピング剤零囲気又はドーピング剤溶液の
中で重合する方法を用いた場合に、特に良好な結果を与
える。代表的なドーピング剤としては、ヨウ素。The doping method is not particularly limited, but includes a method of mixing the doping agent in solid phase, liquid phase, or gas phase during or after the preparation of the diacetylene monomer film, a method of mixing the diacetylene monomer thin film in the doping agent's atmosphere, or a method of mixing the doping agent in the doping agent's atmosphere or the doping agent. Particularly good results are given when using methods of polymerization in solution. Iodine is a typical doping agent.
臭素のごときハロゲン化合物、五フッ化アンチモン、五
７ツ化ヒ素、無水硫酸、トＩＪ７四ロ酢酸。Halogen compounds such as bromine, antimony pentafluoride, arsenic pentafluoride, sulfuric anhydride, and IJ7 tetraroacetic acid.
過塩素酸、塩化第二鉄、塩化アンモニウムのごとき酸類
、過塩素酸銀、テトラアルキリルアンモニウムフロロボ
レート、テトラアルキルアンモニウムフロロホスフェー
ト等のＪ、ｌｆ、トリニトロフルオレノン、テトラメチ
ルフルオレノン、７エナジン、シアニン色素類等が挙げ
られる。Acids such as perchloric acid, ferric chloride, ammonium chloride, silver perchlorate, tetraalkylylammonium fluoroborate, tetraalkylammonium fluorophosphate, etc., J, lf, trinitrofluorenone, tetramethylfluorenone, 7enazine, cyanine Examples include pigments.
本発明によって得られた薄膜状ポリジアセチレンは空気
中の酸素に対して非常に安定であり、適当に蕪機、有機
導電体又は、半導体を接合することにより整流特性光導
電性、光起電力、電気伝導度の温度、湿度等による可逆
的変化等の特性を示す。これを利用して、各種電子部品
、Ｎ１極、セ珂す−ラＣ電変換素ｌ智子写真感光材料な
どに利用−、Ｉ・□ることができ、その他広い分野にわ
たって用途開発され、応用されることが期待できる。The thin film polydiacetylene obtained according to the present invention is very stable against oxygen in the air, and by appropriately bonding it with an organic conductor or a semiconductor, it can have rectifying properties, photoconductivity, photovoltaic force, etc. Shows characteristics such as reversible changes in electrical conductivity due to temperature, humidity, etc. Utilizing this, it can be used in various electronic parts, N1 poles, photosensitive materials, etc., and has been developed and applied in a wide range of other fields. We can expect that.
次に実施例をあげて本発明をさらに詳細に説明する。Next, the present invention will be explained in more detail with reference to Examples.
実施例１
２．４−へキサジインジオールのｐ−）ルエンスル７オ
ン酸エステル８３．６ｍ９及び過ＬＭ ；＃ ＋ｎ銀２
０，５ｎ１９をアセトン３．□ ｆｎｌに溶解し、３ｍ
×３画 の酸化インジュウムを蒸着したガラス板の酸化
インジュウム側にスピンナー法により、厚さ１．０ミク
ロンの薄膜を作成した。これを６０℃に７２時間保つと
金第４光沢のポリジアセチレン薄膜が得られた。Example 1 2.4-hexadiynediol p-)luenesulfonate ester 83.6m9 and per LM; #+n silver 2
0.5n19 in acetone 3. □ Dissolve in fnl, 3m
A thin film of 1.0 micron in thickness was formed by a spinner method on the indium oxide side of a glass plate on which indium oxide had been deposited (×3 images). When this was kept at 60° C. for 72 hours, a polydiacetylene thin film with a quaternary gold luster was obtained.
この薄膜の表面に金電極を蒸着し素子を作成した。A gold electrode was deposited on the surface of this thin film to create a device.
であった。Met.
実施例２
付し、素子を作成した。、この素子の電気伝導度はＮ度
により可逆的に変花し、２５“Ｑ、湿度４０％で３．６
Ｘ １０ΩＧ１８０％で１．４×１０Ｑｃｍであった
。Example 2 A device was prepared. The electrical conductivity of this element changes reversibly depending on the degree of N, and is 3.6 at 25"Q and 40% humidity.
It was 1.4×10Qcm at X10ΩG180%.
実施例３
１．６−ジ（Ｎ−カルバゾイル）−２，４−へキサジイ
ン８１．７Ｔｎ９を１０ ｔｏｒｒの減圧下３０．０−
（：に加熱し、３σ×３ｃｒＬの金の透明電極を付した
ガラス板の金側に蒸着し、厚さ０．９ ミクロンの薄膜
を作成した。この薄膜を１５０℃、３時間加熱重合させ
ると青色の光沢を有するポリジアセチレンの薄膜が得ら
れた。この薄膜の表面に１−の金の透＃Ｊ電極をつくり
、素子を作成した。この素子に２７ｍｗ７’ｓ’の白色
光をＪ］α射すると２ｖの電圧下ＬＯμＡの光電流が発
生した。Example 3 1,6-di(N-carbazoyl)-2,4-hexadiyne 81.7Tn9 was dissolved under a reduced pressure of 10 torr at 30.0-
(:) and vapor deposited on the gold side of a glass plate with a transparent gold electrode of 3σ x 3crL to create a thin film with a thickness of 0.9 microns. This thin film was heated and polymerized at 150°C for 3 hours. A thin film of polydiacetylene with blue luster was obtained. A 1- gold transparent #J electrode was made on the surface of this thin film to prepare a device. White light of 27 mw7's' was applied to this device at J]α When irradiated, a photocurrent of LOμA was generated under a voltage of 2V.
実施例４
１．６−ジ（Ｎ−カルバゾイル） −２，４−へキサジ
イン８１．７二を１０ ｔｏｒｒの減圧下３ｏｏｃに加
熱し・３ｃｍ×３儂のアルミニウム透明電極を付したガ
ラス板のアルミニウム側に族７ｎシ、厚さ０．９ミヂレ
ンの薄膜が得られた。このｉｉｊ、ｉ膜の表面に１ｄの
金の透りＪ電極をつくり、素子を作成した。この素子は
良好な整流特性を示し、白色光２７．２ｍｗのＪ！＜ｆ
針下で光起電力を生じた。ｇＩＪ放電圧は０．５ Ｖ
、短終電流は０１μＡであった。Example 4 81.72 of 1,6-di(N-carbazoyl)-2,4-hexadiyne was heated to 300 °C under a reduced pressure of 10 torr and aluminum on a glass plate with a 3 cm x 3 aluminum transparent electrode attached. A thin film with a group 7n side and a thickness of 0.9 mm was obtained. A 1d gold transparent J electrode was formed on the surface of the iij, i film to produce a device. This device shows good rectification characteristics and has a J! of 27.2 mw of white light. <f
A photovoltaic force was generated under the needle. gIJ discharge voltage is 0.5 V
, the short-term final current was 01 μA.
実施例
１．６−ジ（Ｎ−カルバゾイル）−２，４−ヘギヅジイ
ン８１７〜とテトラニトロフルメレノン３．２ｍ９をジ
メチルアセトアミド１０ｍ１に溶かしアルミ。Example 1. 817 ~ of 6-di(N-carbazoyl)-2,4-hegizdiyne and 3.2 ml of tetranitroflumerenone were dissolved in 10 ml of dimethylacetamide to prepare aluminum.
ニウムを蒸着した１ ０ｃ＋ｎ Ｘ １０ｃｍのポリエ
チレンテレフタシーヘトフィルム上にスピンナー法によ
り厚光減、１．．↓特性が観測された。半減露光足はＳ
ＯＯルックス分・であった。Thick light reduction by spinner method on a 10c+n x 10cm polyethylene terephthalate film on which Ni was vapor-deposited.1. ．． ↓Characteristics were observed. Half-exposure foot is S
It was OO looks.
Claims (1)
へのスプレー法又は、スピンナー法により作成したジア
セチレンモノマー薄膜を重合させることを特徴とする薄
膜状ポリジアセチレンの製造方法。 ２ ジアセチレン化合物を基板上に真空蒸着することに
より作成したジアセチレンモノマー薄膜を重合させるこ
とを特徴とする薄膜状ポリジアセチレンの製造方法[Scope of Claims] ], A method for producing thin film polydiacetylene, characterized by polymerizing a diacetylene monomer thin film prepared by a spray method or a spinner method from a solution or suspension of a diacetylene compound onto MW. . 2. A method for producing thin film polydiacetylene, which comprises polymerizing a diacetylene monomer thin film created by vacuum-depositing a diacetylene compound onto a substrate.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP17366782A JPS5962608A (en) | 1982-10-02 | 1982-10-02 | Preparation of polydiacetylene thin film |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP17366782A JPS5962608A (en) | 1982-10-02 | 1982-10-02 | Preparation of polydiacetylene thin film |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS5962608A true JPS5962608A (en) | 1984-04-10 |
Family
ID=15964859
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP17366782A Pending JPS5962608A (en) | 1982-10-02 | 1982-10-02 | Preparation of polydiacetylene thin film |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS5962608A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0391529A (en) * | 1989-09-05 | 1991-04-17 | Asahi Chem Ind Co Ltd | High-rigidity molding |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4258079A (en) * | 1979-12-13 | 1981-03-24 | International Business Machines Corporation | Preparation of continuous films of diacetylenic polymers |
| JPS5642229A (en) * | 1979-06-25 | 1981-04-20 | University Patents Inc | New photooresist composition |
-
1982
- 1982-10-02 JP JP17366782A patent/JPS5962608A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5642229A (en) * | 1979-06-25 | 1981-04-20 | University Patents Inc | New photooresist composition |
| US4258079A (en) * | 1979-12-13 | 1981-03-24 | International Business Machines Corporation | Preparation of continuous films of diacetylenic polymers |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0391529A (en) * | 1989-09-05 | 1991-04-17 | Asahi Chem Ind Co Ltd | High-rigidity molding |
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