JPH0560994B2 - - Google Patents
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- Publication number
- JPH0560994B2 JPH0560994B2 JP61301320A JP30132086A JPH0560994B2 JP H0560994 B2 JPH0560994 B2 JP H0560994B2 JP 61301320 A JP61301320 A JP 61301320A JP 30132086 A JP30132086 A JP 30132086A JP H0560994 B2 JPH0560994 B2 JP H0560994B2
- Authority
- JP
- Japan
- Prior art keywords
- film
- group
- cumulative
- substrate
- groups
- 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.)
- Expired - Lifetime
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- 239000010408 film Substances 0.000 claims description 38
- 238000000034 method Methods 0.000 claims description 20
- 230000001186 cumulative effect Effects 0.000 claims description 19
- 238000010438 heat treatment Methods 0.000 claims description 8
- 229910052751 metal Inorganic materials 0.000 claims description 8
- 239000002184 metal Substances 0.000 claims description 8
- 239000010409 thin film Substances 0.000 claims description 8
- 125000000217 alkyl group Chemical group 0.000 claims description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 4
- -1 Schiff base metal complex Chemical class 0.000 claims description 4
- 125000003342 alkenyl group Chemical group 0.000 claims description 4
- 125000000304 alkynyl group Chemical group 0.000 claims description 4
- 125000004432 carbon atom Chemical group C* 0.000 claims description 3
- 229910017052 cobalt Inorganic materials 0.000 claims description 3
- 239000010941 cobalt Substances 0.000 claims description 3
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 3
- 239000002262 Schiff base Substances 0.000 claims description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 2
- QDLZHJXUBZCCAD-UHFFFAOYSA-N [Cr].[Mn] Chemical compound [Cr].[Mn] QDLZHJXUBZCCAD-UHFFFAOYSA-N 0.000 claims description 2
- 229910052742 iron Inorganic materials 0.000 claims description 2
- 229910052759 nickel Inorganic materials 0.000 claims description 2
- 229910052725 zinc Inorganic materials 0.000 claims description 2
- 239000011701 zinc Substances 0.000 claims description 2
- 239000000758 substrate Substances 0.000 description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 13
- 238000002441 X-ray diffraction Methods 0.000 description 12
- 239000000463 material Substances 0.000 description 6
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 4
- 125000001165 hydrophobic group Chemical group 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 230000006835 compression Effects 0.000 description 3
- 238000007906 compression Methods 0.000 description 3
- 125000001183 hydrocarbyl group Chemical group 0.000 description 3
- 239000012528 membrane Substances 0.000 description 3
- 150000002739 metals Chemical class 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 230000007704 transition Effects 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 238000000862 absorption spectrum Methods 0.000 description 2
- 238000009825 accumulation Methods 0.000 description 2
- 229940011182 cobalt acetate Drugs 0.000 description 2
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 description 2
- VKOBVWXKNCXXDE-UHFFFAOYSA-N icosanoic acid Chemical compound CCCCCCCCCCCCCCCCCCCC(O)=O VKOBVWXKNCXXDE-UHFFFAOYSA-N 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 235000021355 Stearic acid Nutrition 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000008346 aqueous phase Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 238000010894 electron beam technology Methods 0.000 description 1
- 125000004185 ester group Chemical group 0.000 description 1
- 230000003631 expected effect Effects 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 230000009878 intermolecular interaction Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000004528 spin coating Methods 0.000 description 1
- 230000007480 spreading Effects 0.000 description 1
- 238000003892 spreading Methods 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000000870 ultraviolet spectroscopy Methods 0.000 description 1
- 238000007740 vapor deposition Methods 0.000 description 1
Description
【発明の詳細な説明】
［技術の分野］
本発明は一旦形成されたラングミユアプロジエ
クト膜（LB膜）に代表される有機物単分子膜の
累積膜の厚み方向の規則性構造の発現方法に関す
る。[Detailed Description of the Invention] [Field of Technology] The present invention relates to a method for developing a regular structure in the thickness direction of a cumulative film of an organic monomolecular film, typically a Langmiur project film (LB film), once formed. .
［従来技術］
有機物の薄膜形成はスピンコート法、蒸着法、
プラズマ反応法、電解重合法、水面展開法等が知
られているが、最近各種の機能発現の期待効果の
為に、分子内に疏水性基、親水基を併せ持つ両親
媒性分子の単分子膜を水面上に展開して、一定の
圧縮圧力下に基板材に転移せしめて、累積膜を形
成するラングミユアプロジエクト法（LB法）が
検討並びに報告されている。[Prior art] Thin films of organic materials can be formed by spin coating, vapor deposition,
Plasma reaction methods, electrolytic polymerization methods, water surface development methods, etc. are known, but recently monomolecular films of amphiphilic molecules that have both hydrophobic and hydrophilic groups in the molecule have been developed for the expected effects of developing various functions. The Langmiur project method (LB method) has been investigated and reported, in which a cumulative film is formed by spreading the material on the water surface and transferring it to the substrate material under a constant compressive pressure.
このLB法によれば、一定圧縮圧力下で単分子
膜を累積させる作業を行うことにより、各種機能
を発揮できる形態、例えば、薄膜の積層体を構成
することができる。しかしながら、この機能を発
現するためには、少なくとも、当初に水面に展開
した分子が、適当な圧力で圧縮され、規則的に凝
縮した構造のままで基板に転移をしなければなら
ない。展開分子が、例えば、アラキジン酸、ステ
アリン酸のように、炭化水素の直線的な構造を持
ちながら、あわせて、カルボキシル基の親水性と
炭化水素基の疏水性とがバランスのよい状態にあ
る場合は、このような理想的な基板への転移が起
こるが、一般には、必ずしも理想通りに転移する
わけではなく、基板表面において規則性ある構造
が得られないことが多い。このような構造の単分
子膜は、それを何度も累積させても、構造の乱れ
た薄膜が積み重なるばかりで、期待する機能を有
効に発現しうる薄膜とはなりえない。特に、酸素
分離膜のように、単分子の累積膜の透過現象を応
用し、分離機能を有効に発現させるには、平面方
向にも、厚み方向にも構造的な規則性が必要とな
る。従来、このような面からの検討はほとんどさ
れておらず、このため、本来分子構造から期待さ
れる性能を発現しない例も少なくなかつた。 According to the LB method, by accumulating monomolecular films under a constant compression pressure, it is possible to construct a form that can exhibit various functions, for example, a laminate of thin films. However, in order to exhibit this function, at least the molecules initially expanded on the water surface must be compressed with an appropriate pressure and transferred to the substrate while maintaining a regularly condensed structure. When the developing molecule has a linear hydrocarbon structure, such as arachidic acid and stearic acid, but also has a good balance between the hydrophilicity of the carboxyl group and the hydrophobicity of the hydrocarbon group. Transfer to such an ideal substrate occurs, but in general, the transfer does not necessarily occur as ideally, and a regular structure is often not obtained on the substrate surface. Even if a monomolecular film with such a structure is accumulated many times, thin films with disordered structures will just pile up, and the film will not be able to effectively exhibit the expected functions. In particular, in order to apply the permeation phenomenon of a single molecule cumulative membrane and effectively exhibit a separation function, such as an oxygen separation membrane, structural regularity is required both in the plane direction and in the thickness direction. In the past, little consideration has been given to this aspect, and as a result, there have been many cases in which the performance originally expected from the molecular structure has not been achieved.
本発明者は、かかる現状の困難を克服する為に
鋭意検討した結果本発明に到達したものである。 The present inventor has arrived at the present invention as a result of intensive studies to overcome such current difficulties.
［発明の開示］
本発明は一般式（）
［ここで、Ｙはエステル結合、R1及びR2は10
〜25個の炭素原子を含む直鎖状のアルキル基、ア
ルケニル基、アルキニル基よりなる群から選ばれ
た基である。Ｍは鉄、コバルト、ニツケル、マン
ガンクロム及び亜鉛よりなる群から選ばれた金属
である。］
で示されるシツフ塩基金属錯体からなる累積膜を
95℃以上、200℃以下の温度で加熱処理する事を
特徴とする有機薄膜の規則構造発現方法に関する
ものである。[Disclosure of the invention] The present invention is based on the general formula () [Here, Y is an ester bond, R 1 and R 2 are 10
A group selected from the group consisting of linear alkyl, alkenyl, and alkynyl groups containing ~25 carbon atoms. M is a metal selected from the group consisting of iron, cobalt, nickel, manganese chromium, and zinc. ] A cumulative film consisting of a Schiff base metal complex represented by
The present invention relates to a method for developing an ordered structure in an organic thin film, which is characterized by heat treatment at a temperature of 95°C or higher and 200°C or lower.
本発明に用いられる一般式(1)の累積膜の形成法
に関しては、通常はまず金属Ｍを含まない下記一
般式（）で示される有機物を
［ここで、Ｙはエステル結合、R1及びR2は10
〜25個の炭素原子を含む直鎖状のアルキル基、ア
ルケニル基、アルキニル基よりなる群から選ばれ
た基である。］
一般には、水と混和し難い適当な有機溶媒に溶
解せしめた後、金属Ｍのイオンを含む水相上に展
開する事で、容易に一般式（）の単分子膜が得
られる。これを、所定の圧力に圧縮すると、直鎖
状のアルキル基、アルケニル基、アルキニル基で
表される疏水性基が、その分子間相互作用の結果
容易に凝縮した薄膜を形成する。 Regarding the method for forming the cumulative film of the general formula (1) used in the present invention, usually an organic substance represented by the following general formula () that does not contain the metal M is first formed. [Here, Y is an ester bond, R 1 and R 2 are 10
A group selected from the group consisting of linear alkyl, alkenyl, and alkynyl groups containing ~25 carbon atoms. ] In general, a monomolecular film of the general formula () can be easily obtained by dissolving it in a suitable organic solvent that is difficult to mix with water and then developing it on an aqueous phase containing metal M ions. When this is compressed to a predetermined pressure, hydrophobic groups represented by linear alkyl groups, alkenyl groups, and alkynyl groups easily condense to form a thin film as a result of their intermolecular interactions.
この際、圧縮する圧力は、一般式（）で示さ
れる化合物が、固体膜、すなわち、１ケ１ケの分
子同士が相互に分子間力で水面上で、疏水基を空
気中に出し、親水基が水中で安定化して、きつち
りと配列しているような状態をとつていることが
望ましく、過剰の圧縮圧では１ケの分子が他の分
子の上に這い上がるような構造になり好ましくな
い。かかる観点から、圧縮する圧力は、一般には
3mN／ｍ以上45mN／ｍ以下であることが望ま
しく、さらには5mN／ｍ以上35mN／ｍ以下で
あればより好適に行うことができる。かかる単位
の説明については、「新実験化学講座」18巻504頁
（丸善書店）に詳しく述べられている。 At this time, the compressing pressure is such that the compound represented by the general formula () forms a solid film, that is, each molecule exerts hydrophobic groups into the air on the water surface due to intermolecular force, and hydrophilic It is preferable that the groups are stabilized in water and arranged tightly, and excessive compression pressure will result in a structure in which one molecule creeps up on top of other molecules, which is preferable. do not have. From this point of view, the compressing pressure is generally
It is desirable that it is 3 mN/m or more and 45 mN/m or less, and more preferably 5 mN/m or more and 35 mN/m or less. A detailed explanation of such units is given in "New Experimental Chemistry Course", Volume 18, page 504 (Maruzen Shoten).
累積膜の形成方法は、単分子膜を累積する基板
を水面に対し垂直に保持し上下に昇降する事で、
単分子膜を転移するラングミユアブロジエツト法
が一般に用いられるが、新実験化学講座18巻
p504（丸善書店）記載の基板を水面に平行に保持
したまま降下し水面に接触させる事で単分子膜を
基板に転移する水平付着法、或は、水相内より基
板を水面に保つたままで上昇せしめる事で転移
し、累積する変形水平付着法も、本発明の実施を
妨げるものではない。 The method for forming a cumulative film is to hold the substrate on which the monomolecular film is to be deposited perpendicular to the water surface and move it up and down.
The Langmiur Blossom method, which transfers a monolayer, is generally used, but the New Experimental Chemistry Course, Volume 18
The horizontal adhesion method described on page 504 (Maruzen Shoten) transfers a monomolecular film to the substrate by lowering the substrate while holding it parallel to the water surface and bringing it into contact with the water surface, or the horizontal adhesion method in which the monomolecular film is transferred to the substrate by holding the substrate parallel to the water surface, or by keeping the substrate at the water surface from within the water phase. A modified horizontal deposition method in which the material is transferred and accumulated by raising it does not preclude the practice of the present invention.
該累積膜が転移する基板材料は後述する様に本
発明の特徴である熱処理に対して変形しないもの
であればその累積膜構造体の目的により、適宜選
択される。かかる材料としては、金、銀、アルミ
ニウム等に代表される各種単一又は混合体での金
属そのもの、或は該金属の蒸着体を好適に用いる
事が出来るし、比較的耐熱性の良好な高分子フイ
ルムを用いても本発明に何等の支障をもたらすも
のではない。 The substrate material to which the cumulative film is transferred is appropriately selected depending on the purpose of the cumulative film structure, as long as it does not deform due to heat treatment, which is a feature of the present invention, as will be described later. As such materials, metals themselves in the form of single or mixed metals such as gold, silver, aluminum, etc., or evaporated bodies of these metals can be suitably used. The use of molecular films does not pose any problem to the present invention.
累積により得られた薄膜は、本質的に単分子膜
の積み重ねられた構造であり、その機能を有効に
発現しうるためには、膜の厚み方向の分子配列が
規則性を有することが必要である。分子配列の規
則性は、電子線解析、Ｘ線回折、赤外線吸収スペ
クトル、紫外線吸収スペクトルなどの方法により
知ることができるが、Ｘ線回折が特に小角側での
散乱測定が最も簡便で詳しい結果を与える。 The thin film obtained by accumulation is essentially a stacked structure of monomolecular films, and in order to effectively express its function, the molecular arrangement in the thickness direction of the film must be regular. be. The regularity of molecular arrangement can be determined by methods such as electron beam analysis, X-ray diffraction, infrared absorption spectra, and ultraviolet absorption spectra. give.
Ｘ線回折によれば、本発明の一般式（）で示
される化合物の単分子膜のＹ型累積膜において
は、散乱角（回折角）2θ＝2°〜10°あたりが約50
〜20Å（面間隔）の周期構造を示し、Ｘ線回折に
よつて得られるパターンが、この部分に明瞭なピ
ークを有するものとなる。従つて、Ｘ線回折を行
い、得られたパターンにこのようなピークが存在
すれば、該累積膜の厚み方向にその程度の長さの
規則的な周期性、すなわち、一般式（）におい
てR1、R2で示されるアルキル基などの炭化水素
基が直線状にのびた長さに等しくなる面がＹ型構
造で規則的に積み重なつていることを意味し、単
分子膜が水面上で圧縮されて凝縮し、規則性をも
つて積み重ねられていることがわかる。 According to X-ray diffraction, in the Y-type cumulative film of the monomolecular film of the compound represented by the general formula () of the present invention, the scattering angle (diffraction angle) around 2θ = 2° to 10° is approximately 50°.
It exhibits a periodic structure with a spacing of ~20 Å (planar spacing), and the pattern obtained by X-ray diffraction has a clear peak in this region. Therefore, if such a peak exists in the pattern obtained by performing X-ray diffraction, it means that the cumulative film has regular periodicity of that length in the thickness direction, that is, R in the general formula (). This means that the planes whose length is equal to the linear length of hydrocarbon groups such as alkyl groups represented by 1 and R 2 are stacked regularly in a Y-shaped structure, and the monomolecular film is stacked on top of the water surface. It can be seen that they are compressed and condensed, and are stacked up with regularity.
このような方法で調べると、累積作業のみによ
り得られた薄膜は、膜の厚み方向の面間隔が不揃
いで分子の配列が不規則であるため、本発明にお
いては、累積膜に熱処理を施し、膜の厚み方向の
面間隔を揃えてその構造に規則性を発現させる。 When investigated using such a method, a thin film obtained only by cumulative work has uneven interplanar spacing in the thickness direction of the film and irregular molecular arrangement. Therefore, in the present invention, the cumulative film is heat treated, By aligning the interplanar spacing in the thickness direction of the film, regularity is created in the structure.
上述した様にして得られた累積膜の熱処理を行
うに際し、好適な温度は95℃以上，200℃以下で
ある。 When heat-treating the cumulative film obtained as described above, a suitable temperature is 95°C or higher and 200°C or lower.
該温度より低い場合には一般に規則構造の発現
が認められないか或は、発現に長時間かかる為に
実用上の見地からは実質的に意味の無い場合が多
い。 If the temperature is lower than the above range, the development of an ordered structure is generally not observed, or it takes a long time to develop, so that it is often practically meaningless from a practical standpoint.
加熱処理する雰囲気は、常圧の窒素、アルゴ
ン、ヘリウム等の不活性ガス下であれば好適であ
るが、空気中でも何等本発明の支障とはならな
い。 The atmosphere for the heat treatment is preferably an inert gas such as nitrogen, argon, or helium at normal pressure, but air does not pose any problem in the present invention.
一般に、本処理による規則構造発現の有無は熱
処理体、サンプルのＸ線回折により調べるのが簡
単であり、かつ直線的で有る。 In general, the presence or absence of regular structure development due to this treatment can be easily and linearly examined by X-ray diffraction of a heat-treated body or sample.
この様にして得られた規則構造発現体は、のそ
の規則性と（）の構造の持つ特異性の為に酸素
分離膜、酸素吸蔵体等の機能性材料として有利に
用いる事が出来る。 The ordered structure expressing body thus obtained can be advantageously used as a functional material for oxygen separation membranes, oxygen storage bodies, etc., due to the regularity of and the specificity of the structure of ().
以下に実施例をあげて本発明を詳しく述べる。 The present invention will be described in detail with reference to Examples below.
［実施例 １］
ビス（２−ヒドロキシ−４−オクタデセノイル
オキシ−ベンザル）−エチレンデイイミン（構造
式に於て、Y1，Y2はエステル基で、R1，R2は
トランス−２−オクタデセノイル基を表す。）
6.511ｍＭのクロロホルム溶液を0.99ｇ／の酢
酸コバルト水溶液上に静かに展開し、30分間静置
した。この段階で構造式（）は（）の錯体に
変化する事をUVスペクトルで確認した。この様
にして得られたコバルトを中心金属とする錯体
（）（CO（OD−Sal）と略）を圧縮圧30ｍＮ／ｍ
に設定し、表面を十分に洗浄した石英ガラス基板
上に、ラングミユアブロジエツト法に従い30回の
上下動をくりかえした。[Example 1] Bis(2-hydroxy-4-octadecenoyloxy-benzal)-ethylenediimine (in the structural formula, Y 1 and Y 2 are ester groups, and R 1 and R 2 are trans- Represents a 2-octadecenoyl group.)
A 6.511 mM chloroform solution was gently developed on a 0.99 g/aqueous cobalt acetate solution and allowed to stand for 30 minutes. At this stage, it was confirmed by UV spectroscopy that the structural formula () changed to a complex of (). The complex () (abbreviated as CO (OD-Sal)) with cobalt as the central metal obtained in this way was compressed at a pressure of 30 mN/m.
The substrate was moved up and down 30 times according to the Langmior-Blodget method on a quartz glass substrate whose surface had been thoroughly cleaned.
本方法による転移比は、1.12となり親水基同志
疏水基同志が向い合うＹ膜構造と推測された。本
膜のＸ線回折を測定した処図１に示す様に回折角
１，84°（面間隔48Å）付近に弱い回折ピークが認
められ、余り強い規則性構造が認められなかつ
た。 The transition ratio obtained by this method was 1.12, which suggested a Y film structure in which hydrophilic groups and hydrophobic groups faced each other. As shown in Figure 1, a weak diffraction peak was observed around a diffraction angle of 1.84° (planar spacing of 48 Å), and no very strong regular structure was observed.
本サンプルを100℃に設定したオーブン中に１
時間静置した。この熱処理体サンプルのＸ線回折
を行つた処回折角2.44°（面間隔35.9Å）に強い回
折ピークが観測され厚み方向での規則性が発現し
ている事が認められた。 Place this sample in an oven set at 100℃ for 1 hour.
Let it stand for a while. When this heat-treated sample was subjected to X-ray diffraction, a strong diffraction peak was observed at a diffraction angle of 2.44° (planar spacing 35.9 Å), and regularity in the thickness direction was observed.
［実施例 ２］
実施例１で用いた化合物の同濃度のクロロホル
ム溶液を、酢酸コバルト3.5ｍＭの水溶液上に展
開し、30分間静置した後、圧縮圧を20ｍＮ／ｍに
選定し、石英基板を気相側より接触する水平付着
法で、30回の累積をくりかえした。転移比は30層
平均で、1.0であり転移比からでは親水基を基板
面反対側に向けて親水基、疏水基が交互に並ぶＺ
膜を形成している事が予想されたが、本サンプル
のＸ線回折は、全体として規則性が観測されなか
つた。（図３）本サンプルを98℃に設定したオー
プン中に静置加熱処理した。[Example 2] A chloroform solution of the same concentration of the compound used in Example 1 was developed on an aqueous solution of 3.5 mM cobalt acetate, and after standing for 30 minutes, the compression pressure was selected to be 20 mN/m, and a quartz substrate was prepared. The accumulation was repeated 30 times using the horizontal adhesion method in which contact was made from the gas phase side. The transition ratio is 1.0 on the average of 30 layers, and from the transition ratio, the hydrophilic groups and hydrophobic groups are arranged alternately with the hydrophilic groups facing the opposite side of the substrate surface
Although it was expected that a film was formed, no regularity was observed in the X-ray diffraction of this sample as a whole. (Figure 3) This sample was subjected to a static heat treatment while the temperature was set at 98°C.
加熱処理後の累積膜のＸ線回折を測定した処
1.8Åの規則性を示す強い回折像が得られ、厚み
方向の規則性の大幅な向上が、観測された（図
４）。 The X-ray diffraction of the cumulative film after heat treatment was measured.
A strong diffraction image showing a regularity of 1.8 Å was obtained, and a significant improvement in the regularity in the thickness direction was observed (Figure 4).
図１はLB法による累積膜のＸ線回折パターン、
図２はLB累積膜の熱処理後のＸ線回折パターン、
図３は水平付着累積膜のＸ線回折パターン、図４
は水平付着累積膜の熱処理後のＸ線回折パターン
をそれぞれ示す。
Figure 1 shows the X-ray diffraction pattern of the cumulative film obtained by the LB method.
Figure 2 shows the X-ray diffraction pattern of the LB cumulative film after heat treatment.
Figure 3 shows the X-ray diffraction pattern of the horizontally deposited cumulative film, Figure 4
1 and 2 respectively show the X-ray diffraction patterns of horizontally deposited cumulative films after heat treatment.
Claims (1)
〜25個の炭素原子を含む直鎖状のアルキル基、ア
ルケニル基、アルキニル基よりなる群から選ばれ
た基である。Ｍは鉄、コバルト、ニツケル、マン
ガンクロム及び亜鉛よりなる群から選ばれた金属
である。］ で示されるシツフ塩基金属錯体からなる累積膜を
95℃以上200℃以下の温度で加熱処理する事を特
徴とする有機薄膜の規則構造発現方法。[Claims] 1 General formula () [Here, Y is an ester bond, R 1 and R 2 are 10
A group selected from the group consisting of linear alkyl, alkenyl, and alkynyl groups containing ~25 carbon atoms. M is a metal selected from the group consisting of iron, cobalt, nickel, manganese chromium, and zinc. ] A cumulative film consisting of a Schiff base metal complex represented by
A method for developing an ordered structure in an organic thin film, characterized by heat treatment at a temperature of 95°C or higher and 200°C or lower.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61301320A JPS63156565A (en) | 1986-12-19 | 1986-12-19 | Method for developing regular structure of thin organic film |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61301320A JPS63156565A (en) | 1986-12-19 | 1986-12-19 | Method for developing regular structure of thin organic film |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS63156565A JPS63156565A (en) | 1988-06-29 |
| JPH0560994B2 true JPH0560994B2 (en) | 1993-09-03 |
Family
ID=17895438
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP61301320A Granted JPS63156565A (en) | 1986-12-19 | 1986-12-19 | Method for developing regular structure of thin organic film |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS63156565A (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2533014B2 (en) * | 1990-06-30 | 1996-09-11 | ユニオン・カーバイド・インダストリアル・ガセズ・テクノロジー・コーポレーション | Oxygen-permeable polymer membrane |
| US5411580A (en) * | 1991-07-31 | 1995-05-02 | Praxair Technology, Inc. | Oxygen-separating porous membranes |
| CN102558203B (en) * | 2012-02-13 | 2014-09-24 | 天津师范大学 | Schiff base zinc receptor derivative as well as preparation method and application thereof |
| CN114247435B (en) * | 2021-12-25 | 2022-07-22 | 盐城工学院 | Preparation method of organic color-changing material capable of efficiently adsorbing VOCs (volatile organic compounds) |
-
1986
- 1986-12-19 JP JP61301320A patent/JPS63156565A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS63156565A (en) | 1988-06-29 |
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