JPH03107839A - Organic compound having perfluoroalkyl group and monomolecular film formed by using the same and application thereof - Google Patents
Organic compound having perfluoroalkyl group and monomolecular film formed by using the same and application thereofInfo
- Publication number
- JPH03107839A JPH03107839A JP1245129A JP24512989A JPH03107839A JP H03107839 A JPH03107839 A JP H03107839A JP 1245129 A JP1245129 A JP 1245129A JP 24512989 A JP24512989 A JP 24512989A JP H03107839 A JPH03107839 A JP H03107839A
- Authority
- JP
- Japan
- Prior art keywords
- organic compound
- compound according
- integer
- light
- monomolecular 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
- 125000005010 perfluoroalkyl group Chemical group 0.000 title claims abstract description 6
- 150000002894 organic compounds Chemical class 0.000 title claims description 16
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims abstract description 6
- 229910052760 oxygen Inorganic materials 0.000 claims abstract 2
- 229910052717 sulfur Inorganic materials 0.000 claims abstract 2
- 230000003287 optical effect Effects 0.000 claims description 25
- 239000000463 material Substances 0.000 claims description 11
- 239000003795 chemical substances by application Substances 0.000 claims description 8
- 239000012769 display material Substances 0.000 claims description 6
- 238000005461 lubrication Methods 0.000 claims description 4
- 239000000758 substrate Substances 0.000 claims description 4
- 239000002352 surface water Substances 0.000 claims description 4
- 239000000126 substance Substances 0.000 claims 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 10
- 125000001153 fluoro group Chemical group F* 0.000 abstract description 4
- 229910052731 fluorine Inorganic materials 0.000 abstract description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 21
- 239000007787 solid Substances 0.000 description 16
- 229940125904 compound 1 Drugs 0.000 description 13
- NQRYJNQNLNOLGT-UHFFFAOYSA-N Piperidine Chemical compound C1CCNCC1 NQRYJNQNLNOLGT-UHFFFAOYSA-N 0.000 description 12
- 150000001875 compounds Chemical class 0.000 description 10
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 10
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 8
- 239000000203 mixture Substances 0.000 description 7
- 238000003756 stirring Methods 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- 230000002194 synthesizing effect Effects 0.000 description 5
- 238000005481 NMR spectroscopy Methods 0.000 description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 238000000921 elemental analysis Methods 0.000 description 4
- 238000002844 melting Methods 0.000 description 4
- 230000008018 melting Effects 0.000 description 4
- 239000012299 nitrogen atmosphere Substances 0.000 description 4
- 238000010992 reflux Methods 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000010898 silica gel chromatography Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 2
- RKJUIXBNRJVNHR-UHFFFAOYSA-N indolenine group Chemical group N1=CCC2=CC=CC=C12 RKJUIXBNRJVNHR-UHFFFAOYSA-N 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- 238000002834 transmittance Methods 0.000 description 2
- WTVZVRJKGOUSBA-SXOMAYOGSA-N (5s)-1-[4-[(2r)-1-benzyl-5,6-dioxopiperazin-2-yl]butyl]-4-(2-cyclohexylethyl)-5-(2-methylpropyl)piperazine-2,3-dione Chemical compound C([C@H]1CCCCN2C[C@@H](N(C(=O)C2=O)CCC2CCCCC2)CC(C)C)NC(=O)C(=O)N1CC1=CC=CC=C1 WTVZVRJKGOUSBA-SXOMAYOGSA-N 0.000 description 1
- KJCVRFUGPWSIIH-UHFFFAOYSA-N 1-naphthol Chemical compound C1=CC=C2C(O)=CC=CC2=C1 KJCVRFUGPWSIIH-UHFFFAOYSA-N 0.000 description 1
- IHFRMUGEILMHNU-UHFFFAOYSA-N 2-hydroxy-5-nitrobenzaldehyde Chemical compound OC1=CC=C([N+]([O-])=O)C=C1C=O IHFRMUGEILMHNU-UHFFFAOYSA-N 0.000 description 1
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 239000004809 Teflon Substances 0.000 description 1
- 229920006362 Teflon® Polymers 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 238000004440 column chromatography Methods 0.000 description 1
- 229940125782 compound 2 Drugs 0.000 description 1
- 229940126214 compound 3 Drugs 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- HRWJBKPFSWLQCZ-UHFFFAOYSA-N dichloromethane;hexane Chemical group ClCCl.CCCCCC.CCCCCC HRWJBKPFSWLQCZ-UHFFFAOYSA-N 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 125000001165 hydrophobic group Chemical group 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- -1 perfluoroalkyl compound Chemical class 0.000 description 1
- 239000010702 perfluoropolyether Substances 0.000 description 1
- 230000002093 peripheral effect Effects 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Non-Silver Salt Photosensitive Materials And Non-Silver Salt Photography (AREA)
- Nitrogen Condensed Heterocyclic Rings (AREA)
- Heterocyclic Carbon Compounds Containing A Hetero Ring Having Oxygen Or Sulfur (AREA)
- Nitrogen And Oxygen Or Sulfur-Condensed Heterocyclic Ring Systems (AREA)
- Materials Applied To Surfaces To Minimize Adherence Of Mist Or Water (AREA)
- Lubricants (AREA)
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明は、新規な有機化合物に係り、特に、単分子膜を
形成し、光による表面潤滑制御剤、光による表面撥水性
制御剤、光活版材料、光記録媒体及び光表示材料等に用
いられる有機化合物とその用途に関する。Detailed Description of the Invention [Industrial Field of Application] The present invention relates to a novel organic compound that forms a monomolecular film and is used as a light-induced surface lubrication control agent, a light-induced surface water repellency control agent, and a light-induced surface water repellency control agent. This field relates to organic compounds used in letterpress materials, optical recording media, optical display materials, etc., and their uses.
光照射により分子内荷電の変化するホトクロミック材料
の応用は、これまで光記録材料、光スイツチ等数多く報
告されている。また、スピロピラン誘導体を用いて単分
子膜の配向を光により制御する試みも発表されている。Many applications of photochromic materials, whose intramolecular charge changes upon irradiation with light, have been reported so far, including optical recording materials and optical switches. In addition, attempts have been made to control the orientation of monomolecular films using spiropyran derivatives with light.
（例えば、ジャーナル オブ ザ フィジカルケミスト
リー第８８巻、７１６頁、（１９８４年） （Ｊｏｕ
−ｒｎａｌ ｏｆ Ｔｈｅ Ｐｈｙｓｉｃａｌ Ｃｈｅ
ｍｉｓｔｒｙ８８ 、７１６（１９８４）） Ｌかし、
このような性質を活かした製品への応用例は今だ発表さ
れていない。(For example, Journal of the Physical Chemistry Vol. 88, p. 716, (1984)) (Jou
-rnal of The Physical Che
mistry88, 716 (1984)) L Kashi,
Application examples of products that take advantage of these properties have not yet been announced.
一方潤滑技術及び撥水性の研究においては、表面状態が
最も重要な研究対象である。しかし外的要因を利用して
表面の潤滑性、撥水性を制御した例は今まで全くなかっ
た。On the other hand, in the study of lubrication technology and water repellency, the surface condition is the most important research object. However, there have never been any examples of controlling surface lubricity and water repellency using external factors.
表面の潤滑性及び撥水性を、外敵刺激で自由にコントロ
ールする技術は従来存在しなかった。Until now, there was no technology that could freely control the lubricity and water repellency of a surface using external stimuli.
本発明の主目的は、光の照射により表面の潤滑性、撥水
性が制御できる化合物を提供し、その性質を活かした材
料、及びナノ秒単位の書き換え可能な光活版材料を提供
することにある。The main purpose of the present invention is to provide a compound whose surface lubricity and water repellency can be controlled by irradiation with light, and to provide a material that takes advantage of these properties, and a photolithographic material that can be rewritten in nanoseconds. .
また、あわせて本発明で示した化合物の合成方法及びそ
れを用いた光記録媒体、そして光表示材料を提供するこ
とにある。Another object of the present invention is to provide a method for synthesizing the compound shown in the present invention, an optical recording medium using the same, and an optical display material.
上記目的を達成するために、本発明では下記の化合物（
Ｉ）を提供する。In order to achieve the above object, the present invention uses the following compounds (
I).
一般式（Ｉ） Ｒ。General formula (I) R.
（式中、Ｒ３はＣＦ２−（ＣＦ２） ｋ−（ＣｓＬ）じ
（ＣＩ’、）。(In the formula, R3 is CF2-(CF2)k-(CsL)di(CI',).
（ＣＨ２）、、又はＣＦ３（Ｃｈ）ｍ−（０−ＣＪ−）
じ０−（ＣＦｄ−（ＣＨ□）、（ｋは１から１４までの
整数、しは０から８までの整数でＣ，Ｈ，はベンゼン環
、ｍは１から８までの整数、ｎは１から８までの整数）
Ｒ３、Ｒ８はそれぞれ別個にＨ，ＮＯ２又はＲ３とＲ５
が一緒になってベンゼン環を形成し、ＡはＣＨかＮを、
Ｂは０かＳを示す）で表わされるパーフルオロアルキル
基をもつ有機化合物。(CH2), or CF3(Ch)m-(0-CJ-)
Di0-(CFd-(CH□), (k is an integer from 1 to 14, is an integer from 0 to 8, C, H, is a benzene ring, m is an integer from 1 to 8, n is 1 to 8)
R3 and R8 are each separately H, NO2 or R3 and R5
together form a benzene ring, A is CH or N,
An organic compound having a perfluoroalkyl group represented by (B represents 0 or S).
本発明の化合物■は、例えば次のようにして合成できる
。Compound (1) of the present invention can be synthesized, for example, as follows.
まず、２．３．３−トリメチルインドレニン（ｎ）と末
端にヨウ素などのハロゲン原子を持つパーフルオロアル
キル化合物（Ｒ，Ｘ）を混ぜ合わせた後、数時間１００
〜１２０℃で加熱後、下記に示す４級アンモニウム塩（
ＩＩ［）を得る。First, after mixing 2.3.3-trimethylindolenine (n) and a perfluoroalkyl compound (R,X) having a halogen atom such as iodine at the end,
After heating at ~120°C, the quaternary ammonium salt shown below (
We get II[).
これにピペリジンなどの塩基存在下Ｏ−ベンズアルデヒ
ド類、あるいは０−二トロンフェノール類を加え、加熱
、縮合することで目的の化合物■が得られる。O-benzaldehydes or 0-nitronephenols are added to this in the presence of a base such as piperidine, and the mixture is heated and condensed to obtain the desired compound (1).
（式中、Ｒ１，Ｒ２、Ｒ３，Ａ、 Ｂは前記と同じ意味
を有する）
本発明の化合物（１）は、単独で或いは製膜補助剤と共
に単分子膜を形成する。製膜補助剤としては、例えば、
式
％式％：０２１（
）
のパーフルオロポリエーテルカルボン酸が使用できる。(In the formula, R1, R2, R3, A, and B have the same meanings as above.) The compound (1) of the present invention forms a monomolecular film alone or together with a film-forming auxiliary agent. Examples of film forming aids include:
A perfluoropolyether carboxylic acid having the formula % formula %: 021 ( ) can be used.
これらの化合物は、例えば、タライトックス１５７ＦＳ
シリーズ（デュポン社製）として市販されている。These compounds are, for example, Tallytox 157FS
Series (manufactured by DuPont).
本発明の化合物Ｉは、親水基として光により分子内荷電
が変化するホトクロミック部位と、疎水基としてパーフ
ルオロアルキル基を持つ新規有機化合物であり、該化合
物は光による表面潤滑制御剤、光による表面撥水性制御
剤、光活版材料、光記録媒体、光可変抵抗、光論理回路
、光シャッタ、光フィルタ、及び光表示材料等に使用で
きる。Compound I of the present invention is a novel organic compound having a photochromic moiety whose intramolecular charge changes when exposed to light as a hydrophilic group, and a perfluoroalkyl group as a hydrophobic group. It can be used for surface water repellency control agents, optical letterpress materials, optical recording media, optical variable resistors, optical logic circuits, optical shutters, optical filters, optical display materials, etc.
例えば、本発明の化合物１′の単分子膜は通常ランダム
配向しているが、紫外光照射により垂直配向し表面のフ
ッ素原子密度が増大し潤滑性が向上する。この理由は次
のように考えられる。化合物１′が紫外光照射により下
記の式のように親木基であるインドレニン部分に分子内
電荷を持った化合物１′に異性化する。For example, the monomolecular film of the compound 1' of the present invention is usually randomly oriented, but upon irradiation with ultraviolet light, it becomes vertically oriented, increasing the fluorine atom density on the surface and improving lubricity. The reason for this is thought to be as follows. Compound 1' is isomerized by ultraviolet light irradiation to compound 1' having an intramolecular charge in the indolenine moiety, which is the parent group, as shown in the following formula.
Ｒ＋
化合物１′
１
化合物１′
Ｒ１ニーＣＬＣＬ（ＣＦ２）、ＣＦ３（ｎ ！＝ｆ ８
）そして、親木基の極性が増大することで疎水部の垂
直配向性が上がり、表面のフッ素原子密度が増大する。R+ Compound 1' 1 Compound 1' R1nee CLCL(CF2), CF3(n !=f 8
) As the polarity of the parent wood group increases, the vertical orientation of the hydrophobic portion increases, and the density of fluorine atoms on the surface increases.
フッ素原子により接触面との表面エネルギーが下がり、
潤滑性が向上する。可視光照射により分子内荷電は消失
し親水性が低下するので、垂直配向性が下がり潤滑性が
低下する。Fluorine atoms lower the surface energy with the contact surface,
Improves lubricity. Visible light irradiation eliminates intramolecular charges and reduces hydrophilicity, resulting in a decrease in vertical alignment and lubricity.
また、紫外光照射により表面の撥水性も向上する。その
理由は、表面フッ素被覆率の増大が表面エネルギーの著
しい低下をもたらすためである。そのため、化合物１′
の膜を形成させた基板は光により印刷用のインクの付着
が制御でき、書き換え可能型光活版材料として用いるこ
とができる。Moreover, the water repellency of the surface is also improved by irradiation with ultraviolet light. The reason is that an increase in surface fluorine coverage results in a significant decrease in surface energy. Therefore, compound 1'
The substrate on which the film is formed can control the adhesion of printing ink using light, and can be used as a rewritable optical letterpress material.
さらに、化合物１′は無色であるが紫外光照射により生
成した化合物１′は、紫色である。、この色の変化を利
用すれば、光記録媒体、光シャッタ、光フィルタ、そし
て光応答型表示材料にも応用できる。Further, although Compound 1' is colorless, Compound 1' produced by irradiation with ultraviolet light is purple. If this color change is utilized, it can be applied to optical recording media, optical shutters, optical filters, and photoresponsive display materials.
以下、本発明の実施例を記載するが、本発明はこれらる
限定されない。Examples of the present invention will be described below, but the present invention is not limited thereto.
実施例１
Ｒ＋
（化合物１′）
Ｒ１： −Ｃｔｉ２ＣｔＬ （ＣＦ２） 、、口Ｆ３
（ｎ’−８）化合物１′の合成方法を示
す。Example 1 R+ (Compound 1') R1: -Cti2CtL (CF2),, Mouth F3
(n'-8) The method for synthesizing compound 1' is shown.
［”Ｐｓ（［’Ｐ２）ｈｃ’Ｈ２ｃ）Ｉ２１ （ｎ ＝
８ ） ２０ ｇに２．３゜３−トリメチルインドレ
ニン６ｇを加え、窒素雰囲気下１２０℃で１０時間、１
５０℃で６０時間かく拌する。冷却後、濾過し、固体を
ジクロルメタンでよく洗う。得られた固体をエチルメチ
ルケトン１００ｍｆに懸濁させ、ピペリジン２ｍ１２を
加え１０分間還流する。そのあと５−ニトロサリチルア
ルデヒド２ｇを加え、１時間還流する。１時間後加熱を
やめ、その後 １２時間かく拌する。反応終了後濾過し
、得られた固体をエタノールでよく洗う。その後、シリ
カゲルカラムクロマトグラフィ （展開溶媒はジクロル
メタン二ｎ−へキサン＝１
ｎ−ヘキサンで再結晶する。[”Ps(['P2)hc'H2c)I21 (n =
8) Add 6 g of 2.3°3-trimethylindolenine to 20 g and incubate for 10 hours at 120°C under nitrogen atmosphere.
Stir at 50°C for 60 hours. After cooling, filter and wash the solid well with dichloromethane. The obtained solid was suspended in 100 mf of ethyl methyl ketone, 2 ml of piperidine was added, and the mixture was refluxed for 10 minutes. Thereafter, 2 g of 5-nitrosalicylaldehyde was added and the mixture was refluxed for 1 hour. Stop heating after 1 hour, then stir for 12 hours. After the reaction is complete, filter and wash the resulting solid thoroughly with ethanol. Then, recrystallize using silica gel column chromatography (developing solvent is dichloromethane di-n-hexane=1 n-hexane).
の白色固体を得た。（融点： ℃） ｎ＝８と仮定すると、 収率：約５％ 元素分析 核磁気共鳴 実測値（％） ４４．４ ２．３ １．７ ２．３ｐｐｍ ２．４ｐｐｍ ３．１〜３．７ｐｐｍ ４．４ｐｐｍ ５．６〜５．８ｐｐｍ ５．９〜６．１ ｐｐｍ ６．６〜７．８ｐｐｍ 下記の結果になる。A white solid was obtained. (Melting point: ℃) Assuming n=8, Yield: about 5% elemental analysis nuclear magnetic resonance Actual value (%) 44.4 2.3 1.7 2.3ppm 2.4ppm 3.1-3.7ppm 4.4ppm 5.6-5.8ppm 5.9-6.1 ppm 6.6-7.8ppm The result is as below.
：３）で精製し、 こうして １．３ｇ １４０〜１４５ 計算値（％） ４５．４ ２．７ １．９ （３Ｈ） （３Ｈ） （２Ｈ） （２Ｈ） （ＩＨ） （１）１） （７Ｈ） 実施例２ 化合物２の合成方法を示す。:3), Thus 1.3g 140-145 Calculated value(%) 45.4 2.7 1.9 (3H) (3H) (2H) (2H) (IH) (1)1) (7H) Example 2 A method for synthesizing compound 2 is shown.
ＣＦ３（Ｃｈ）、Ｃ１１２Ｃｔ１２１ （ｎ ！＝＝
８ ） ２０ ｇに２．３゜３−トリメチルインドレニ
ン６ｇを加え、窒素雰囲気下１２０℃で１０時間、１５
０℃で６０時間かく拌する。冷却後、濾過し、固体をジ
クロルメタンでよく洗う。得られた固体をエチルメチル
ケトン１００ｍ１．に懸濁させ、ピペリジン２ｒｎｌを
加え１０分間還流する。そのあとオルトニトロンフェノ
ール２ｇを加え、１時間還流する。１時間後加熱をやめ
、その後１２時間かく拌する。反応終了後濾過し、得ら
れた固体をエタノールでよく洗う。その後、シリカゲル
カラムクロマトグラフィ （展開溶媒はジクロルメタン
：ｎ−へ牛サン＝１：３）で精製し、ｎ−へキサンで再
結晶する。こうして０．８ｇの黄色固体を得た。（融点
：１３６〜１４０℃）ｎ＝８と仮定すると、下記の結果
になる。CF3 (Ch), C112Ct121 (n !==
8) Add 6 g of 2.3゜3-trimethylindolenine to 20 g and incubate for 10 hours at 120°C under nitrogen atmosphere for 15 minutes.
Stir at 0°C for 60 hours. After cooling, filter and wash the solid well with dichloromethane. The obtained solid was mixed with 100 ml of ethyl methyl ketone. Add 2rnl of piperidine and reflux for 10 minutes. Then, 2 g of orthonitronephenol was added and the mixture was refluxed for 1 hour. Stop heating after 1 hour, then stir for 12 hours. After the reaction is complete, filter and wash the resulting solid thoroughly with ethanol. Thereafter, it is purified by silica gel column chromatography (developing solvent is dichloromethane:n-to-oxane=1:3) and recrystallized from n-hexane. Thus 0.8 g of yellow solid was obtained. (Melting point: 136-140°C) Assuming n=8, the following results are obtained.
収率：約６％ 元素分析 核磁気共鳴 計算値（％） ４４．２ ２．５ ３．７ （３Ｈ） （３Ｈ） ｐｐｍ （２旧 （２Ｈ） ｐｐｍ （ＬＨ） ｐｐｍ （８ｆｌ） 実測値（％） ４３．５ ２．１ ３．２ Ｊｐｐｍ ２．４ｐｐｍ ３．１〜３．７ ４．４ｐｐｍ ５．４〜５．６ ６．６〜７．４ 実施例３ 化合物３の合成方法を示す。Yield: about 6% elemental analysis nuclear magnetic resonance Calculated value(%) 44.2 2.5 3.7 (3H) (3H) ppm (2 old (2H) ppm (LH) ppm (8fl) Actual value (%) 43.5 2.1 3.2 Jppm 2.4ppm 3.1-3.7 4.4ppm 5.4-5.6 6.6-7.4 Example 3 A method for synthesizing compound 3 is shown.
ＣＦ３（ＣＦＩ）、ＣＨ２ＣＨ２Ｉ （ｎ ＝ ８ ）
２０ ｇに２，３゜３−トリメチルインドレニン６ｇ
を加え、窒素雰囲気下１２０℃で１０時間、１５０℃で
６０時間かく拌する。冷却後、濾過し、固体をジクロル
メタンでよく洗う。得られた固体をエチルメチルケトン
１００ｍｌ！に懸濁させ、ピペリジン２ｒｎｌを加え１
０分間還流する。そのあと１−トニトロソー２″ナフト
ール３ｇを加え、１時間還流する。１時間後加熱をやめ
、その後１２時間かく拌する。反応終了後濾過し、得ら
れた固体をエタノールでよく洗う。その後、シリカゲル
カラムクロマトグラフィ （展開溶媒はジクロルメタン
：ｎ−ヘキサン−１＝３）で精製し、ｎ−ヘキサンで再
結晶する。こうして ０．６ｇの黄色固体を得た。（融
点：１７６〜１８２℃）
ｎ＝８と仮定すると、下記の結果になる。CF3 (CFI), CH2CH2I (n = 8)
2,3゜3-trimethylindolenine 6g per 20g
and stirred at 120°C for 10 hours and at 150°C for 60 hours under nitrogen atmosphere. After cooling, filter and wash the solid well with dichloromethane. Pour the obtained solid into 100ml of ethyl methyl ketone! Suspend in water, add 2rnl of piperidine and add 1ml of piperidine.
Reflux for 0 minutes. Then, add 3 g of 1-tonitroso 2'' naphthol and reflux for 1 hour. Stop heating after 1 hour, then stir for 12 hours. After the reaction is complete, filter and wash the obtained solid thoroughly with ethanol. Then, silica gel Purified by column chromatography (developing solvent: dichloromethane: n-hexane-1=3) and recrystallized from n-hexane. Thus, 0.6 g of yellow solid was obtained. (Melting point: 176-182°C) n=8 Assuming that, we get the following result.
収率：約４％
元素分析 実測値（％） 計算値（％）Ｃ４６，５
４７，４
Ｈ２，０２，６
Ｎ ３．１ ３．５核磁気共鳴
２．３ ｐｐｍ （３Ｈ）２．４ ｐｐ
ｍ （３旧
３、１〜３．７ ｐｐｍ （２Ｎ）４．４ ｐｐｍ
（２Ｈ）
５、４〜５．６ ｐｐｍ （ＩＨ）６、６〜？、
４． Ｐｐｍ （１０１１）実施例４
化合物４の合成方法を示す。Yield: Approximately 4% Elemental analysis Actual value (%) Calculated value (%) C46.5
47,4 H2,02,6 N 3.1 3.5 Nuclear magnetic resonance 2.3 ppm (3H) 2.4 pp
m (3 old 3, 1-3.7 ppm (2N) 4.4 ppm
(2H) 5,4~5.6 ppm (IH)6,6~? ,
4. Ppm (1011) Example 4 A method for synthesizing compound 4 is shown.
ＣＰｚ（ＣＦｚ）ｎＣＬＣ１１２Ｉ （ｎ ！＝ｉ８
） ２０ ｇに２．３゜３−トリメチルインドレニン６
ｇを加え、窒素雰囲気下１２０℃で１０時間、１５０℃
で６０時間かく拌する。冷却後、濾過し、固体をジクロ
ルメタンでよく洗う。得られた固体をエチルメチルケト
ン１００艷に懸濁させ、ピペリジン２−を加え１０分間
還流する。そのあとオルトニトロソチオフェノール２ｇ
を加え、１時間還流する。（オルトニトロソチオフェノ
ールはケミストリーレターズ、１９８５年、１８０５頁
を参考にして合成した。）１時間後加熱をやめ、その後
１２時間かく拌する。反応終了後濾過し、得られた固体
をエタノールでよく洗う。その後、シリカゲルカラムク
ロマトグラフィ （展開溶媒はジクロルメタン：ｎ−ヘ
キサン＝１：３）でＭｌし、ｎ−ヘキサンで再結晶する
。こうして０．５ｇの黄色固体を得た。（融点：１６５
〜１７０℃）
ｎ＝８と仮定すると、下記の結果になる。CPz(CFz)nCLC112I (n !=i8
) 2.3°3-trimethylindolenine 6 in 20g
g and heated at 120°C for 10 hours at 150°C under nitrogen atmosphere.
Stir for 60 hours. After cooling, filter and wash the solid well with dichloromethane. The obtained solid was suspended in 100 μg of ethyl methyl ketone, piperidine 2-2 was added, and the mixture was refluxed for 10 minutes. Then 2g of orthonitrosothiophenol
and reflux for 1 hour. (Ortho-nitrosothiophenol was synthesized with reference to Chemistry Letters, 1985, p. 1805.) Heating was stopped after 1 hour, and the mixture was stirred for 12 hours. After the reaction is complete, filter and wash the resulting solid thoroughly with ethanol. Thereafter, the mixture was subjected to silica gel column chromatography (developing solvent: dichloromethane:n-hexane=1:3) and recrystallized from n-hexane. Thus 0.5 g of yellow solid was obtained. (Melting point: 165
~170°C) Assuming n=8, the following results are obtained.
収率：約４％
元素分析 実測値（％） 計算値（％）Ｃ４２，６
４３，３
Ｈ２，０２，５
Ｎ３゜１３．６
核磁気共鳴 ２．３ ｐｐｍ （３Ｈ）２
．４ ｐｐｍ （３）１）３、１〜３．７
ｐｐｍ （２Ｈ）４．４ ｐｐｍ （
２８）５．４〜５．６ ｐｐｍ （ＩＨ）６゜６〜
７．４ ｐｐｍ （８Ｈ）実施例５
実施例１で合成した化合物１′
を４．４ ｍｇとク
ライトックス１５７ＦＳ−Ｌ（デュポン社製でＦ （Ｃ
Ｆ（ＣＦ３）−ＣＦ２−０−） 、−ＣＦ２ＣＤ、Ｈ（
ｎ ’−１４） ）１４゜４ ｍｇを１．１．２−トリ
クＣＭ：ｌ−１，２゜２−トリフルオロエタン］、Ｏｍ
ｉ！に溶解する。この溶液の１２０μβを水面上に展開
し、単分子膜を形成すると、占有面積は約０．２ ｎｍ
２／分子である。これに５００Ｗキヤノンランプを光源
として、波長選択用フィルターを通し、３００〜４００
ｎｍの近紫外光を照射すると、占有面積は約０．４ ｎ
ｍ２／分子まで増大した。Yield: Approximately 4% Elemental analysis Actual value (%) Calculated value (%) C42,6
43,3 H2,02,5 N3゜13.6 Nuclear magnetic resonance 2.3 ppm (3H)2
．． 4 ppm (3) 1) 3, 1 to 3.7
ppm (2H)4.4 ppm (
28) 5.4~5.6 ppm (IH) 6°6~
7.4 ppm (8H) Example 5 4.4 mg of the compound 1' synthesized in Example 1 and Krytox 157FS-L (F (C
F(CF3)-CF2-0-), -CF2CD, H(
n'-14)) 14゜4 mg to 1.1.2-tricCM: l-1,2゜2-trifluoroethane], Om
i! dissolve in When 120 μβ of this solution is spread on the water surface to form a monomolecular film, the occupied area is approximately 0.2 nm.
2/Molecular. Using a 500W Canon lamp as a light source, this is passed through a wavelength selection filter to
When irradiated with near ultraviolet light of nm, the occupied area is approximately 0.4 nm.
m2/molecule.
ラングミュア・プロジェット（ＬＢと略す）膜製造装置
で、ガラス基板上に化合物１′とタライトックス１５７
ＦＳ−Ｌの上記混合溶液を用いて単分子膜を形成する。Compound 1' and Talitox 157 were deposited on a glass substrate using a Langmuir-Prodgett (abbreviated as LB) film manufacturing equipment.
A monomolecular film is formed using the above mixed solution of FS-L.
この膜の摩擦係数をピンオンディスク型摩擦試験機（周
速：２ｍ／ｓｅｃ、荷重：５ｇ）で測定した。結果を第
１図に示す。光照射前、摩擦係数は０．３以上の値を示
したが、３００〜４００ ｎｍの近紫外光を照射すると
約０．１まで下がった。４５０ｎｍ以上の可視光を照射
すると、再び摩擦係数は０．３以上に戻った。The friction coefficient of this film was measured using a pin-on-disc friction tester (peripheral speed: 2 m/sec, load: 5 g). The results are shown in Figure 1. Before irradiation with light, the coefficient of friction showed a value of 0.3 or more, but after irradiation with near-ultraviolet light of 300 to 400 nm, it decreased to about 0.1. When visible light of 450 nm or more was irradiated, the friction coefficient returned to 0.3 or more again.
実施例６
実施例５で調製した膜表面と水性インクとの接触角は９
０°であった。しかし、紫外光を照射した膜と水性イン
クとの接触角は１１３°となった。これはテフロン表面
とほぼ同等の値である。Example 6 The contact angle between the membrane surface prepared in Example 5 and the aqueous ink was 9
It was 0°. However, the contact angle between the film irradiated with ultraviolet light and the aqueous ink was 113°. This value is almost the same as that of a Teflon surface.
実施例７
実施例１で合成した化合物１′を３０ｍｇとポリ塩化ビ
ニル０．９ｇをテトラヒドロフラン１５−に溶解し、直
径９．２ ｃｍの平底シャーレに流し込み、１２時間常
圧で、そのあと５時間減圧で乾燥してテトラヒドロフラ
ンを揮発させ、厚さ０、１ ｍｍの膜を得た。この膜は
無色透明で４００〜７００ｎｍに吸収帯は存在しなかっ
た。透過率は９３％であった。５００Ｗキセノンランプ
を光源として、波長選択用フィルターを通し、３００〜
４００ ｎｍの近紫外光を照射すると紫色に変わり、５
６０ ｎｍに極大値を持つ吸収帯が出現した。これによ
りこの付近の波長の光が９０％以上カットされる。４５
０ｎｍ以上の可視光を照射すると、膜は無色に戻り５６
０ｎｍの吸収帯も消失し、透過率も９３％に戻った。Example 7 30 mg of the compound 1' synthesized in Example 1 and 0.9 g of polyvinyl chloride were dissolved in tetrahydrofuran 15-, poured into a flat-bottom petri dish with a diameter of 9.2 cm, and kept at normal pressure for 12 hours, and then for 5 hours. Tetrahydrofuran was evaporated by drying under reduced pressure to obtain a film with a thickness of 0.1 mm. This film was colorless and transparent and had no absorption band in the range of 400 to 700 nm. The transmittance was 93%. Using a 500W xenon lamp as a light source, passing through a wavelength selection filter,
When irradiated with 400 nm near-ultraviolet light, it turns purple, and
An absorption band with a maximum value at 60 nm appeared. This cuts out more than 90% of light with wavelengths around this area. 45
When irradiated with visible light of 0 nm or more, the film returns to colorless56
The absorption band at 0 nm also disappeared, and the transmittance returned to 93%.
以上により、この膜は光フィルタ、光シャッタとして使
用できる。As described above, this film can be used as an optical filter or an optical shutter.
以上から、本発明の化合物により、光による表面潤滑制
御剤、光による表面廃水性制御剤、光活版材料、さらに
新規有機光機能性材料、それを用いた光記録媒体、及び
光表示材料の作成が可能となった。From the above, the compound of the present invention can be used to create a light-induced surface lubrication control agent, a light-induced surface waste water control agent, a photolithographic material, a new organic photofunctional material, an optical recording medium using the same, and an optical display material. became possible.
第１図は本発明の単分子膜を用いた紫外光照射前後の摩
擦係数を示すグラフである。FIG. 1 is a graph showing the coefficient of friction before and after irradiation with ultraviolet light using the monomolecular film of the present invention.
Claims (1)
６Ｈ＿４）＿ｌ−（ＣＦ＿２）＿ｍ−（ＣＨ＿２）＿ｎ
又はＣＦ＿３（ＣＦ＿２）＿ｋ−（Ｏ−Ｃ＿６Ｈ＿４）
＿ｌ−Ｏ−（ＣＦ＿２）＿ｍ−（ＣＨ＿２）＿ｎ（ｋは
１から１４までの整数、Ｌは０から８までの整数でＣ＿
６Ｈ＿４はベンゼン環、ｍは１から８までの整数、ｎは
１から８までの整数）、Ｒ＿２、Ｒ＿３はそれぞれ別個
にＨ、ＮＯ＿２又はＲ＿２とＲ＿３が一緒になってベン
ゼン環を形成し、ＡはＣＨかＮを、ＢはＯかＳを示す）
で表わされるパーフルオロアルキル基をもつ有機化合物
。 ２、請求項１記載の有機化合物を３００ｎｍ以上の光を
透過する基板に形成した単分子膜。 ３、請求項２記載において、請求項１記載の有機化合物
が製膜補助剤を含有することを特徴とする単分子膜。 ４、請求項１記載の有機化合物を含有する光による可逆
型表面潤滑制御剤。 ５、請求項１記載の有機化合物を含有する光による可逆
型表面撥水性制御剤。 ６、請求項１記載の有機化合物を含有する光による書き
換え可能型光活版材料。 ７、請求項１記載の有機化合物を含有する書き換え可能
型光記録媒体。 ８、請求項７記載において、有機化合物が高分子材料中
に分散しているか、基板上に塗布されていることを特徴
とする書き換え可能型光記録媒体。 ９、請求項１記載の有機化合物を用いた光シャッタ。 １０、請求項１記載の有機化合物を用いた光フィルタ。 １１、請求項１記載の有機化合物を含有する光応答型表
示材料。[Claims] 1. General formula (I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (In the formula, R_1 is CF_3-(CF_2)_k-(C_
6H_4)_l-(CF_2)_m-(CH_2)_n
or CF_3(CF_2)_k-(OC_6H_4)
_l-O-(CF_2)_m-(CH_2)_n (k is an integer from 1 to 14, L is an integer from 0 to 8, and C_
6H_4 is a benzene ring, m is an integer from 1 to 8, n is an integer from 1 to 8), R_2 and R_3 are each independently H, NO_2 or R_2 and R_3 together form a benzene ring, A indicates CH or N, B indicates O or S)
An organic compound with a perfluoroalkyl group represented by 2. A monomolecular film formed of the organic compound according to claim 1 on a substrate that transmits light of 300 nm or more. 3. A monomolecular film according to claim 2, characterized in that the organic compound according to claim 1 contains a film-forming aid. 4. A photoreversible surface lubrication control agent containing the organic compound according to claim 1. 5. A photoreversible surface water repellency controlling agent containing the organic compound according to claim 1. 6. A photolithographic material rewritable by light, containing the organic compound according to claim 1. 7. A rewritable optical recording medium containing the organic compound according to claim 1. 8. A rewritable optical recording medium according to claim 7, characterized in that the organic compound is dispersed in a polymeric material or coated on a substrate. 9. An optical shutter using the organic compound according to claim 1. 10. An optical filter using the organic compound according to claim 1. 11. A photoresponsive display material containing the organic compound according to claim 1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1245129A JPH03107839A (en) | 1989-09-22 | 1989-09-22 | Organic compound having perfluoroalkyl group and monomolecular film formed by using the same and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1245129A JPH03107839A (en) | 1989-09-22 | 1989-09-22 | Organic compound having perfluoroalkyl group and monomolecular film formed by using the same and application thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH03107839A true JPH03107839A (en) | 1991-05-08 |
Family
ID=17129060
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP1245129A Pending JPH03107839A (en) | 1989-09-22 | 1989-09-22 | Organic compound having perfluoroalkyl group and monomolecular film formed by using the same and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH03107839A (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5730908A (en) * | 1991-07-24 | 1998-03-24 | Enichem Synthesis S.P.A. | Photochromatic and thermochromatic compounds and their application in polymeric materials |
| JP2003191075A (en) * | 2001-12-25 | 2003-07-08 | Daihen Corp | Consumable electrode type arc welding equipment |
| JP2003530400A (en) * | 2000-04-06 | 2003-10-14 | イエダ・リサーチ・アンド・デベロツプメント・カンパニー・リミテツド | Photochromic spiro (indoline) naphthoxazines |
| CN102993211A (en) * | 2011-09-19 | 2013-03-27 | 天津孚信科技有限公司 | Azacyclo-substituted benzo spirooxazine photochromic compound and preparation method thereof |
-
1989
- 1989-09-22 JP JP1245129A patent/JPH03107839A/en active Pending
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5730908A (en) * | 1991-07-24 | 1998-03-24 | Enichem Synthesis S.P.A. | Photochromatic and thermochromatic compounds and their application in polymeric materials |
| JP2003530400A (en) * | 2000-04-06 | 2003-10-14 | イエダ・リサーチ・アンド・デベロツプメント・カンパニー・リミテツド | Photochromic spiro (indoline) naphthoxazines |
| JP2003191075A (en) * | 2001-12-25 | 2003-07-08 | Daihen Corp | Consumable electrode type arc welding equipment |
| CN102993211A (en) * | 2011-09-19 | 2013-03-27 | 天津孚信科技有限公司 | Azacyclo-substituted benzo spirooxazine photochromic compound and preparation method thereof |
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