JPH0746212B2 - Method for producing anisotropic LB film - Google Patents

Description

The present invention relates to a method for producing an anisotropic LB film in which a plurality of substances are arranged in anisotropic order.

[Prior Art] The LB film (Langmuir-Blodgett film) controls the surface pressure of the monomolecular film developed on the sub-phase (usually water) to obtain an aggregate film of the monomolecular film, which is placed on the substrate. A technique for transferring the molecular order formed on the sub-phase to the substrate by transferring, or a broad term for this technique, has been attracting attention in recent years as a means for providing a film structure controlled on a molecular order.

As a conventionally known LB film, for example, there is one made of an aliphatic carboxylic acid such as stearic acid, and its use is being studied because the LB film has a high insulating property. Such an LB film can be a monomolecular film or a cumulative film.

In recent years, the LB film has attracted much interest as a means for forming a functional material.

For example, a functional material consisting of multiple components needs to be intimately arranged in order for each component molecule to interact,
The LB film is a film forming means arranged in a molecular order, and is greatly expected as a means for producing a functional material.

Examples of the functional material include dyes, sensitizers, electron-donating substances, electron-accepting substances, and functional polymer materials. When such a material is used for the LB film, the LB film is formed on the material. It is common to introduce a long-chain alkyl group of as a substituent. However, these materials generally have a large molecular skeleton or atomic group for expressing functionality, and LB
It is often difficult to form a film. For this reason, mixed LB films of these materials and other LB film forming aids are widely used. LB
The film forming aid includes, for example, those that are amphipathic like linear fatty acids such as stearic acid, and are themselves good LB film forming materials, and nonpolar materials such as octadecane. When an amphipathic LB film forming aid is used, it itself forms an LB film on the sub-face, and the functional material gives an LB film dispersed between them. On the other hand, when a non-polar material is used, an LB film made of a functional material is formed.
The film-forming aid plays a role in simplifying the complicated structure of the functional material by filling the gaps remaining in the LB film and making the LB film of a strong structure capable of withstanding compression.
For example, Yonezawa et al. Reported a mixed LB film of a long-chain alkyl derivative of xanthene dye and a long-chain alkyl fatty acid such as stearic acid on page 116 of 1987 in the Chemical Society of Japan. Similarly, Sato et al. Reported a mixed LB film of a cyanine dye and a long-chain alkyl fatty acid ester in 1987 page 2108 of the Chemical Society of Japan. All of these are examples in which a LB film formation aid is used to fill the gaps and strengthen the LB film in the macro skeleton of the dye, and the dye that is the functional material is simply dispersed in this aid. I'm just there. In this example, only other counterions (halogen, perchlorate ion) are associated with the dye. Needless to say, the auxiliaries and counterions used here do not have their own unique functions, so the LB film disclosed here is an LB film consisting essentially of one kind of functional material.

As another example, Watanabe et al. Reported a mixed LB film consisting of a charged nickel dithiolene complex, a long-chain quaternary alkylammonium salt, and a long-chain alkylamide as an auxiliary agent in Proceedings of the Polymer Society of Japan, Vol. 36, page 3224 (1987). is doing. in this case,
An LB film is formed by the long-chain quaternary alkylammonium salt and the auxiliary agent, and the nickel dithiolene complex, which is a functional material, is incidentally incorporated into the LB film as its counter ion. Therefore, also in this case, one kind of LB film is used as the functional material.

On the other hand, it is possible to arrange multiple functional components in the LB film. In this case, intimate arrangement is possible by a simple means such as mixing each component molecule in the same layer, but in this case, it is difficult to realize a high function with a disordered arrangement.

On the other hand, functional substances were combined in the form of counterions.
LB film is known. For example, Molecular Crystals and Liquid Crystals
tals and Liquid Crystals) 120, p. 319 (1985), LB film of long-chain alkylpyridinium / tetracyanoquinodimethane (TCNQ) anion radical salt is disclosed. Similarly, Kawabata et al. In the Chemical Society of Japan, page 2180 (1987), tetrathiafulvalene (TTF) derivative cation radical and T
We have reported LB film of charge transfer complex consisting of long-chain derivative of CNQ anion radical. In these examples, the cation portion and the anion portion form a salt in the LB film, so that the LB film composed of two kinds of substances is formed as the functional substance.

In contrast to the method described above, a so-called heterostructure LB film in which each component is sequentially accumulated as a separate LB film is known. It is considered that the heterostructure LB film is preferable for high-performance expression because it can form an ordered array.
In this case, each functional molecule exists in each layer of the LB cumulative film, and the entire function is expressed in multiple layers. This method gives an LB film composed of two or more kinds of polyfunctional molecules in principle.

As a study of the LB film having such a hetero structure (hetero LB film), for example, Journal of American Chemical Society (J. Amer. Chem. Soc.) Vol. 104, 7407 by D. Moebius et al. An example is a study consisting of a ternary system of an electron-donating substance, an electron-accepting substance and a photosensitizer disclosed on page (1985).

In the electron transfer type LB film shown as this specific example, the respective elements contained in these materials are arranged between different layers, and the stacking order of the respective layers is also an important element. It is considered that the hetero LB film having a structure (DSA structure) in which electron-accepting substances are sequentially accumulated is useful as a structure for efficiently performing electron transfer.

The same functional molecular array has a structure in which a photosensitizer, an electron-accepting substance 1 and an electron-accepting substance 2 are sequentially accumulated (S-A1-A
2 structure) or a structure in which an electron-donating substance 1, an electron-donating substance 2 and a photosensitizer are sequentially accumulated (D1-D2-S structure), and in these cases, the photosensitizer is the electron donor. And the latter has electron accepting properties. At this time, when a plurality of electron-accepting substances or electron-donating substances are used, the relation between the reduction potential or the oxidation potential of those molecules is taken into consideration and selected in such a relation that the movement of electrons is not hindered.

The arrangement of such functional molecules is actually performed in the photoreaction center of photosynthesis in plants, and it is considered that the technology for artificially assembling the arrangement of such functional molecules has industrial application. It is extremely significant when it is played.

In order to obtain a hetero LB film, a monomolecular film of each component is formed,
It is basically achieved by sequentially transferring to the substrate. For example, for this purpose, each layer is prepared using one or more LB film manufacturing apparatuses, and LB is sequentially manufactured and laminated, or one layer is formed on the substrate and then left on the sub-phase. There is a method in which the layer to be washed is washed off and then newly developed on the next layer to be transferred to the substrate. Furthermore, recently, hetero LB
Membrane production equipment has been proposed. Although these proposals have different mechanisms, they have multiple development layers, and by various means, the substrate can freely move between these development layers during the process of transferring the monolayer on the sub-phase to the substrate. A mechanism that can be used is provided to obtain a hetero LB film.

[Problems to be Solved by the Invention] As a method for obtaining a hetero LB film, a method of forming a monomolecular film of each component as described above and sequentially transferring it to a substrate is, of course, a very troublesome method, Inefficient procedure is required.

In addition, although various proposed hetero LB film manufacturing apparatuses greatly improve the inefficiency in the hetero LB film manufacturing by the above method, there is no essential difference in that each layer is formed sequentially. In reality, even if such an apparatus is used, a considerable procedure is still required to manufacture the hetero LB film.

The first object of the present invention is to provide a method for producing a functional material composed of multiple components as an anisotropic LB film in which each component has an anisotropic arrangement with order for realizing high functionality. Secondly, to provide a method for easily obtaining the LB film.

[Means for Solving the Problems]

The method for producing an anisotropic LB film according to the present invention comprises (A) an ion having a photosensitizing function, an electron accepting property or an electron donating property (ion a) as a constituent component, in the presence of an LB film forming auxiliary agent or At least one salt capable of forming an LB film in the absence (B) having a photosensitizing function, an electron accepting property or an electron donating property,
Ion having the opposite sign to ion a (ion b)
At least one salt having hydrophilicity and (C) at least one hydrophobic substance having a photosensitizing function, an electron-accepting property or an electron-donating property, as described above in (A) and (B). And (C), one is selected to have a photosensitizing function and the other two are selected to have an electron donating or electron accepting property, and the three selected substances are added in the presence of an LB film forming auxiliary or It is characterized in that it is developed in the sub-phase in the absence of it and transferred onto the substrate while controlling the surface pressure.

In the above-mentioned production method, (A), (B) and (C) and the LB film forming auxiliary optionally used are dissolved in an appropriate solvent and added dropwise onto the sub-phase for development. At this time, the substances may be mixed in advance and used, or the substances may be dropped on the sub-phase in any order.

By compressing the substance (developed substance) developed on the sub-phase and controlling the surface pressure appropriately, an LB film having an anisotropic arrangement of at least three components (A), (B) and (C) is formed. Form. For this purpose, the surface pressure-area curve is measured in advance, an appropriate surface pressure is selected from the time when the surface pressure starts to rise until it collapses, and the spread is compressed to this surface pressure. Examples of the above solvent include benzene, chloroform, methylene chloride, hexane, etc., and a volatile solvent insoluble in the subphase is preferable. In some cases, ethanol, DM
A small amount of a substance that easily dissolves in the sub-phase such as F may be used together. Water is usually used as the subphase, but polar materials such as water (buffer salt etc.) adjusted to a specific pH, aqueous metal salt solution, ethylene glycol, glycerin etc. are used according to the purpose.

The monomolecular film formed by the substance (A) capable of forming an LB film in the presence or absence of the LB film formation auxiliary has a polar part (hydrophilic part) and a non-polar part (hydrophobic part). )
Exists, the polar part is located on the subphase side, and the nonpolar part is located on the opposite side. Salt (B) in such a system
When coexisting, it is hydrophilic, and since the ion a and the ion b have opposite charges, they are attracted to the polar part of the monolayer, and the hydrophobic substance (C) present at the same time.
Is placed near the non-polar portion of the monolayer because it is hydrophobic.

That is, when a material system consisting of at least three components (A), (B) and (C) is developed on a sub-phase together with an LB film forming aid, the above-mentioned material system has each molecule. It spontaneously changes its assembly state, reflecting the different charge states and / or polarities, and is rearranged from a mere mixture to an arrangement that gives rise to functional properties. In this way, the material system consisting of at least three components (A), (B) and (C) is a film in which these functional substances are spontaneously arranged at different positions in the film on the sub-phase. It has a structure and forms substantially three layers of molecular order in the film. By transferring such a film to the substrate, an LB film reflecting the above film structure can be obtained. This LB film is composed mainly of a substance (A) capable of forming an LB film in the presence or absence of an LB film formation aid, a salt (B) in its polar portion, and a salt (B) in its non-polar portion. It has a structure in which a hydrophobic substance (C) is arranged. Hereinafter, this structure is referred to as an anisotropic arrangement. It is a characteristic of the present invention that such an anisotropic arrangement can be obtained in a single LB film production process, and is basically the method of producing a heterostructure LB film obtained through a plurality of LB film production processes. Distinctly.

(A) contains an ion having a photosensitizing function (ion a) as a constituent and is present in the presence or absence of an LB film forming auxiliary agent.
At least one salt (photosensitizer) capable of forming an LB film, (B) is an ion (ion b) having an electron accepting or electron donating property and a charge having an opposite sign to that of the ion a When at least one salt containing C as a constituent component and (C) is at least one hydrophobic substance having an electron-accepting property or an electron-donating property, an electron-donating substance or an electron-accepting substance on the subphase is included. , A photosensitizer and an electron-donating substance or an electron-accepting substance are sequentially laminated in the film, and in particular, one of the above (B) and (C) has an electron-donating property. On the other hand, when the other has an electron-accepting property, the film has a molecular arrangement in which an electron-donating substance, a photosensitizer, and an electron-accepting substance are laminated in order or in reverse order. The above description has been given by taking as an example the case where the substance capable of forming the LB film is the photosensitizer alone or in the presence of the LB film forming auxiliary agent. In the manufacturing method, the S-A1-A2 structure and the D1-D2-S structure can be applied if attention is paid to the relationship between the LB film forming ability of the material used and the hydrophilicity and hydrophobicity.

In particular, when the ion a constituting (A) and the ion b constituting (B) are counter ions with each other, and therefore (A) and (B) are composed of one salt in advance, the photosensitizing function is improved. The intimate relationship between the component having the component and the component having the electron donating or electron accepting property is maintained in the process of preparing the LB film, and the anisotropic arrangement is more easily taken, which is preferable.

Even if (A) and (B) are not a single salt in advance, since (A) and (B) are salts, they are easily dissolved in the subphase as the counter ion of ion a and the counter ion of ion b. If (A), (B) and the hydrophobic substance (C) are dissolved in a solvent and mixed or sequentially added to the LB film development layer (sub-phase), ions will be generated in the sub-phase. The exchange of counterions of a and ion b proceeds favorably to form a salt between ion a and ion b, and an anisotropic LB film composed of the desired three components is produced. A metal ion, a halogen ion, a lower alkyl group-substituted quaternary ammonium ion, a perchlorate ion, or the like is selected as the counter ion of the above-mentioned ion a or ion b, depending on the charge state of each material.

The layer having an anisotropic arrangement formed on the sub-phase as described above is transferred to the substrate to be an anisotropic LB film.

The anisotropic LB film as described above can also be manufactured by the following alternative method.

That is, as (B), one that is soluble in the sub-phase is selected, this is dissolved in the sub-phase, (A) and (C) are developed on the sub-phase, the developed product is compressed, and the surface pressure is controlled. It is characterized by developing this on the substrate while doing.

In this alternative method, it is possible to form the LB film in the presence or absence of the LB film formation auxiliary formed on the sub-phase (A) and the LB film is dissolved during the sub-phase (B). However, since the ions a and b constituting them are oppositely charged, they are attracted, and the ion a and the ion b form a salt by ion exchange so that the ion a is stacked on the ion b. Arrange. This arrangement occurs when the material system is expanded into sub-phases and during compression.

According to this method, the material dissolved in the sub-phase is confined to the sub-phase side of the monolayer formed on the sub-phase, and finally the anisotropy is further developed in the LB film. It is considered to be arranged.

In any of the above-mentioned methods for producing an anisotropic LB film, a known production method can be applied as it is as an LB film production method. These usually include a developing water tank, a fixed barrier, a moving barrier, a means for detecting and controlling the surface pressure, and a substrate lifting device, but they have the function of transferring the monomolecular film formed on the sub-phase to the substrate at a predetermined surface pressure. There is no particular limitation as long as it is provided. For example, commercially available equipment such as LB film production equipment manufactured by Kyowa Interface Science Co., Ltd., LB film balance manufactured by Lauda Co., LB film production equipment manufactured by Joyce Label Co., Ltd. Can be used. The film forming conditions and the like should be set to the optimum conditions depending on the material used, and the present invention is not limited thereto.

The vertical dipping method and the horizontal deposition method are known as the method of pulling up the substrate, and the method is selected depending on the properties of the material.

In the method for producing an anisotropic LB film according to the present invention, it is possible to form the LB film in a normal environment, but it is preferable to perform the film formation in an atmosphere replaced with an inert gas. By doing so, it is possible to stably form a film of a material that is unstable to air. Examples of the inert gas include nitrogen gas, argon gas and helium gas. An inert gas atmosphere can be obtained by ventilating these gases into the LB film manufacturing apparatus. Prior to this, the sub-phase is also ventilated to replace the dissolved oxygen in the sub-phase with the inert gas, which gives more preferable results. Further, in the present invention, when a material sensitive to light is used, it is preferable to perform it under light shielding.

In addition, a salt containing an ion having a photosensitizing function as a constituent or a substance having a photosensitizing function and a salt containing an ion having an electron accepting property as a constituent or a substance having an electron accepting property. A salt containing an electron-accepting substance and an ion having an electron-donating property as a constituent or a substance having an electron-donating property is called an electron-donating substance.

Next, the materials used in the present invention will be described.

The photosensitizer used in the present invention is preferably a photosensitizer containing an ion having a photosensitizing function as a constituent, and has a charge in the skeleton of the constituent or in both or both of the substituent moieties. Those are preferable. It is particularly preferable to use a redox sensitizer. Polyphenylene dye, phthalocyanine dye, thiazine dye, oxazine dye, xanthene dye, iron group transition metal trisbipyridyl complex,
Iron group transition metal trisphenanthrolyl complexes and the like are particularly preferable because they have excellent ability as a photosensitizer.

Examples of the photosensitizer include 5,10,15,20-tetrakis (p-carboxyphenyl) -21H, 23H-porphyin part or all of alkali metal salts, 5,10,15,20-tetrakis ( p
-Carboxyphenyl) -21H, 23H-porphine zinc complex partially or wholly alkali metal salt, 5,10,15,20-tetrakis (p-carboxyphenyl) -21H, 23H-porphyrin magnesium complex Part or all of alkali metal salt, 5,10,15,20-tetrakis (p-carboxyphenyl) -21H, 23H-part of or all alkali metal salt of porphinine nickel complex, 5,10,15,20 -Tetrakis (p-
Carboxyphenyl) -21H, 23H-porphyin iron complex part or all alkali metal salt, 5,10,15,20-tetrakis (p-trialkylaminophenyl) -21H, 23H-
Porphinium tetrabromide, 5,10,15,20-tetrakis (p-trialkylaminophenyl) -21H, 23H-porphyin zinc complex tetrabromide, 5,10,15,20-tetrakis (p-octadecyldimethyl) Aminophenyl)-
21H, 23H-polybromine zinc tetrabromide, 5,10,
15,20-Tetrakis (p-sulfonate) -21H, 2
Alkali metal salts of part or all of 3H-porphin, 5,
10,15,20-Tetrakis (phenyl sulfonate) -21
Alkali metal salt of part or all of H, 23H-porphin zinc complex, 5,10,15,20-Tetrakis (p-phenyl sulfonate) -21H, 23H-Part of all or part of alkali metal of porphinine nickel complex A charged derivative of a tetraphenylporphyrin compound such as a salt, 5,10,15,20-tetrakis (p-phenyl sulfonate) -21H, 23H-porphyrin iron complex or a part or all of an alkali metal salt thereof, 5,10,15 , 20-Tetrakis (4-N-methylpyridinium) -21H, 23H-porphine tetrahalide, 5,10,15,2
0-Tetrakis (3-N-methylpyridinium) -21H, 2
3H-porphine tetrahalide, 5,10,15,20-tetrakis (4-N-methylpyridinium) -21H, 23H-porphin zinc complex tetrahalide, 5,10,15,20-tetrakis (4-N-methyl) Pyridinium) -21H, 23H-porphine nickel complex tetrahalide, 5,10,15,20-tetrakis (3-N-methylpyridinium) -21H, 23H-porphine zinc complex tetrahalide, 5,10,15,20- Tetrakis (3-N-methylpyridinium) -21H, 23H-porphine nickel complex tetrahalide, 5,10,15,20-tetrakis (4-N-octadecylpyridinium) -21H, 23H-
Porphyne zinc complex tetrahalide, 5,10,15,20-tetrakis (3N-octadecylpyridinium) -21H, 23H-
Porphin zinc complex tetrahalide, 5,10,15,20-tetrakis (4-N-octadecylpyridinium) -21H, 23
H-porphine nickel complex tetrahalide, 5,10,15,20
-Tetrakis (3-NN octadecylpyridinium)
-21H, 23H-porphyrin magnesium complex tetrahalide, 5,10,15,20-tetrakis (3-N-octadecylpyridinium) -21H, 23H-porphyrin iron complex tetrahalide and other charged derivatives of tetrapyridinium polyfilin compound Polyfilin dye of, part or all of alkali metal salts of copper phthalocyanine tetracarboxylic acid, part or all of alkali metal salts of copper phthalocyanine tetracarboxylic acid, part or all of alkali metal salts of zinc phthalocyanine tetracarboxylic acid,
Alkali metal salt of vanadyl phthalocyanine tetracarboxylic acid or part thereof, copper tetraaminophthalocyanine halogenated alkyl adduct, zinc tetraaminophthalocyanine halogenated alkyl adduct, nickel tetraaminophthalocyanine halogenated alkyl adduct, vanadyl tetraaminophthalocyanine halogen Phthalocyanine dyes such as charged derivatives of phthalocyanine compounds such as alkylated adducts, thionine, methylene blue, long-chain alkyl-substituted methylene blue, nile blue, methylene violet, resorufin, erythrosine B, eoxy Y, fuchsin B, rhodamine B, rhodamine 6G , Rose bengal, ruthenium tris (2,2'-bipyridyl), osmium tris (2,2'-bipyridyl) ruthenium tris (2,2'-phenanthro) Down), and the like.

In the above, part or all of the alkali metal salt is a part or all of the hydrogen atoms of a plurality of carboxyl groups Na, K, R
Examples of the alkyl halide include methyl iodide, ethyl iodide, ethyl bromide, butyl bromide, butyl iodide, octadecyl bromide, octadecyl iodide, and the like.

These photosensitizers may be used alone, and these photosensitizers may be used as quinone compounds, alkyl-substituted quinone compounds, methylviologen, di (long-chain alkyl) γ,
It may be used as a photosensitizer system in combination with an electronic relay material such as γ'-bipyridinium halide. Further, these electron relay substances may be used as a part of the LB film formation auxiliary agent.

Further, as the photosensitizer, it is preferable to selectively use a photosensitizer capable of forming an LB film in the presence or absence of the LB film formation auxiliary. Among them, those containing a long-chain aliphatic group as a substituent are particularly desirable, but it has been revealed that an LB film can be produced even with these compounds, particularly those containing no long-chain aliphatic group. The presence of a group is not an essential element. Further, even if it is difficult to form an LB film by itself, it is possible to obtain an LB film in the form of a mixed film by combining it with an LB film formation aid. LB that can be used in this case
As the film forming aid, stearic acid, arachidic acid, fatty acids containing long-chain aliphatic groups such as palmitic acid, styalinic acid amide, arachidic acid amide, acid amide compounds such as palmitic acid amide, octadecane, nonadecane,
Long chain alkanes such as eicosane, docosane and hexadecane, long chain alkyl alcohols such as eicosanol, octadecanol and hexadecanol, long chain fatty acid esters such as ethyl stearate, methyl stearate, ethyl arachidate and methyl arachidate. , Biphenyl,
Aromatic hydrocarbons such as terphenyl and bisphenyl A,
Examples thereof include lauryl phosphate and sodium long-chain alkyl sulfonate. The type and blending amount of these LB film forming aids are determined in consideration of the charge state of the photosensitizer used, the area occupied by the molecule, and the arrangement state, but generally 0.1 equivalent to the photosensitizer is used. It is preferable to use 10 equivalents. If the amount is too large, the electron transfer reaction is hindered. Therefore, it is desirable to limit the amount to the minimum level at which the LB film can be formed.

The electron-accepting substance or the electron-donating substance is preferably a transition metal complex represented by the following general formula (I), (II) or (III), and appropriately forms an ion having an electron-accepting property or an electron-donating property. A hydrophilic salt contained as a component and a hydrophobic substance having an electron accepting or electron donating property are selected and used. In the following, when m is 0, it tends to be hydrophobic, and when m is 1 or more, it is likely to be hydrophilic salt.

General formula (I) General formula (II) In the general formulas (I) and (II), Z is an atom or atomic group selected from O, S and NR (R is hydrogen or an alkyl group), and X and X ′ may be hydrogen at each position,
It is selected from an alkyl group, a substituted alkyl group, a halogen group, an alkoxy group, an alkyloxycarbonyl group, a carboxyl group, an alkylamino group, a quaternary alkylammonium group, a nitro group or a cyano group, and X and X ′ may be the same, n Is an integer of 1 to 4, m is an integer of +2 to -2, A is m
One or more anions or one or more cations having the number of charges necessary to neutralize the charge defined by and M represents a transition metal ion (provided that when m is 0, A is not exist).

General formula (III) In the general formula (III), Z ′ is selected from S and NR (R is hydrogen or an alkyl group) and may be different at each position, and Y is hydrogen, an alkyl group, a substituted alkyl group, a phenyl group, a substituted phenyl group and Selected from a cyano group, may be different at each position, m is an integer of +2 to -2, A is m
One or more anions or one or more cations having the number of charges necessary to neutralize the charge defined by and M represents a transition metal ion (provided that when m is 0, A is not exist).

These compounds are, for example, JAMclevert (JAMclevert
y) et al., Progress in Inorganic Chemistry (Prog.Inorg.Chem.), vol. 10, p. 49 (1968), Syulau Tour (GNSchrauzer) et al., Accounts of Chemical Research (Acc. Chem. Res.), vol. (1969), Inorganic Synthesis (Inorg.Syn.), Vol. 10, p. 2, its synthesis method and properties are summarized in detail. Under normal conditions, in the air from -2 anion to 0 valent state. It can be stably isolated, and its charge state varies depending on the type of central metal ion and the type of ligand. Various oxidation states have been confirmed in all or part of the range of divalent anions to divalent cations in these compounds, and it is known that some of them can be stably isolated in different oxidation states. Has been. For example, for the compound 1 which is a nickel bis (dithiomaleonitrile) complex, the following both complexes 1-
a, 1-b is stably isolated in air and shows different physical properties.

They are stable not only in air but also in solution, and both are capable of electrochemically or chemically performing reversible redox reaction at a redox potential of +0.23 V (vs. saturated calomel electrode, hereinafter abbreviated as SCE). They are converted to each other, with a large change in absorption coefficient in the near infrared region. Similar reactions can be found from various groups of these compounds. For example, the following formula can be given.

In the above, E1 / 2 is a half-wave potential.

The transition metal complexes represented by the general formulas (I) to (III) may have a mixed valence state. The mixed valence state refers to a state in which two or more types of states of a neutral state and a plurality of charged states exist individually or in a coexisting form.

Examples of the transition metal complex include cobalt bis (dithiomaleonitrile) complex, manganese bis (dithiomaleonitrile) complex, iron bis (dithiomaleonitrile) complex, copper bis (dithiomaleonitrile) complex, nickel bis (dithiomaleonitrile) complex. , Platinum bis (dithiomaleonitrile) complex, palladium bis (dithiomaleonitrile)
Complex, nickel bis (toluene-3,4-dithiolate)
Complex, nickel bis (octadecylbenzene-3,4-dithiolate) complex, platinum bis (toluene-3,4-dithiolate) complex, copper bis (toluene-3,4-dithiolate) complex, nickel bis (benzene-4-dimethylamino-) 1,2-dithiolate) complex, nickel bis (benzene-4-dioctadecylamino-1,2-dithiolate)
Complex, nickel bis (benzene-3,4,5,6-tetrabromo-1,2-dithiolate) complex, nickel bis (1,2-dithionaphthalene) complex, platinum bis (1,2-dithionaphthalene) complex, nickel bis (dithiostilibene) ) Complex,
Platinum bis (dithiostilibene) complex, palladium bis (dithiostilibene) complex, nickel bis (p-chlorodithiostilibene) complex, nickel bis (p-methoxydithiostilibene) complex, nickel bis (p-octadecyloxydithiostilibene) Complex, nickel bis (p-
Octadecyloxycarbonyldithiostilibene) complex, nickelbis (p-carboxysidithiostilibene) complex, nickelbis (p-dimethylaminodithiostilibene) complex, nickelbis (p-trimethylammoniumdithiostilibene) tetraiodide , Nickel bis (p-dioctadecylaminodithiostilibene)
Complex, nickel bis (1,2-phenylenediimine) complex, platinum bis (1,2-phenylenediimine) complex, palladium bis (1,2-phenylenediimine) complex, nickel bis (4-chloro-1) , 2-phenylenediimine) complex, nickelbis (3,4-dichloro-1,2-phenylenediimine) complex, nickelbis (4-alkyl-1,2-phenylenediimine) complex, nickelbis (diimino) Maleonitrile) complex, platinum bis (diiminomaleonitrile) complex, palladium bis (diiminomaleonitrile)
Complex, nickel bis [bis (trifluoromethyl) ethylene-1,2-dithiate] complex, platinum bis [bis (trifluoromethyl) ethylene-1,2-dithiate] complex,
Examples thereof include palladium bis [bis (trifluoromethyl) ethylene-1,2-dithiate] complex. They are,
In the general formulas (I) to (III), when m is not 0,
A suitable A, eg, tetramethylammonium ion,
Quaternary ammonium ions such as tetraethylammonium ion, tetrabutylammonium ion, dimethyldioctadecylammonium ion, sodium ion,
Cation such as alkali metal ion such as potassium ion,
It contains one or more anions such as ClO ₄ ⁻ , BF ₄ ⁻ , and halogen ions. Such a transition metal complex serves as both an electron-accepting substance and an electron-donating substance, but the redox potential and oxidation state of the substance selected from the complex, the substance selected from the complex (one or more types) , Preferably two or more) and a photosensitizer, and the arrangement of these substances determine whether they function as an electron-accepting substance or an electron-donating substance. For example, nickel bis (dithiomaleonitrile) dianion, which is used in the form of dimethyldioctadecyl ammonium salt or other salts.
Is typically used as an electron-donating substance, and the nickel dithiostilibene complex functions as both an electron-accepting substance and an electron-donating substance, but it is preferably used as an electron-accepting substance. The selection of substances from the above complexes is
These should be finally determined in consideration of the type of system, the maximum absorption position, the redox potential of the redox couple to be combined, etc., but they should be selected in consideration of the first redox reaction among various oxidation states. This is desirable from the standpoint of compound stability. The redox potential at that time should be comprehensively determined in consideration of the redox couple to be combined, but the redox potential is -0.5 V to +0.8 V (vs SCE.), Preferably -0.2 V to +0. It is preferably in the range of 0.5V. In this range, particularly preferably in the range of 0 V to +0.4 V, both oxidation states can exist stably in air and in the presence of a solvent. Of course, this is not the case when means such as sealing of the system is taken.

The transition metal complexes listed above give particularly favorable results, but the use of substances capable of taking other mixed valence states in combination with the transition metal complex or as at least one of the electron donating substance and the electron accepting substance is also possible. Conceivable. Other examples include Prussian blue, iron-sulfur cluster compounds, nickel bis (deuroquinone) complex, tetrathiofulvalene, tetracyanoquinodimethane, polypyrrole, polythiophene, polyalkylpyrrole, polyalkylthiophene, polyisothianaphthene, etc. Can be mentioned. Further, other ordinary electron-donating substances and electron-accepting substances may be used in combination with these substances having mixed valence states or alone. Examples of electron-donating substances include triethanolamine, ethylenediaminetetraacetic acid and salts thereof, N
-Alkylcarbazole, alcohol, water and the like, and examples of the electron-accepting substance include various quinones and the like. These electron-donating substances and electron-accepting substances are generally highly active, and when the difference in the redox state between the substance capable of having the mixed valence state to be combined is too large, the reason is as described above. It should be carefully selected because a quick reverse reaction or a positive reaction occurs depending on the difference.

Next, a photosensitizer and an electron-donating substance consisting of a salt containing an ion having a photosensitizing function as a constituent and capable of forming an LB film in the presence or absence of an LB film forming auxiliary agent. The function of the anisotropic LB film obtained by the present invention using an electron-accepting substance will be described.

By irradiating the photosensitizer (S) with light, the electron-donating substance (D) is passed through the excited state of the photosensitizer.
From the electron to the electron-accepting substance (Ac), that is, the charge transfer reaction is achieved by the photosensitized redox reaction (Figs. 1 (1) and (2)). electron donating material after electron transfer as shown in FIG. 2 a and is usually unstable because it is not possible to balance the charge remains the the counterion _{(+) (- -)} and an electron-accepting substance () Although it is taken in from the outside or released to the outside, in the above anisotropic LB film, the above reaction is rewritten as shown in FIG. 2B because the photosensitizer has a charge. In this case, since the photosensitizer (S) located at the center has an electric charge, the photosensitizer has an electron-donating substance ( _- ) and an electron-accepting substance ( _- ) after the electron transfer reaction. Can act as a counter ion. This reaction is achieved in the anisotropic LB film. Therefore, in this system, it is not necessary to consider the movement of the counter ion from the outside, and only the electron transfer process is the charge transfer reaction included in the system, and it can be expected that an extremely fast reaction occurs.

In the above example, the charge states of the electron-donating substance and the electron-accepting substance have been described by taking an example of a certain specific charge state, but it goes without saying that both of them can be established in other charge states. When the reaction in question is an electron transfer reaction, the target is a cation as a counter ion, and in the case of a hole transfer reaction, an anion is a counter ion, which can be reduced to an electron transfer reaction. . Usually, the electron transfer reaction mainly occurs. Therefore, if the photosensitizer having a charge mainly has a positive charge, the photosensitizer serves as a cation to be transferred, which is more convenient. Is.

In the above, one of the electron-donating substance and the electron-accepting substance is a salt, and an ion having an electron-donating property or an electron-accepting property which is a component of this salt is a component of the photosensitizer. If the ion has the opposite sign to the ion having the photosensitizing function, close contact can be expected between them,
It is thought to be useful for efficient electron transfer reaction. Furthermore, at this time, if the above ions are counterions to each other,
Permanent contact with these can be expected, and it is thought that a more efficient reaction system will be formed.

The reaction product generated by the above-mentioned charge transfer is generally unstable in many cases even if the charge balance of the counter ion is treated only inside the reaction system. However, this problem can be solved by using one or both of the electron-donating substance and the electron-accepting substance in the photosensitized redox reaction as a substance capable of having a mixed valence state. In a substance that can assume a mixed valence state, one substance has two or more possible oxidation states, and these substances can exist stably or metastable. Therefore, there is no problem in the thermodynamic stability of the product which has undergone electron transfer before and after light irradiation. In general, a substance capable of having a mixed valence state generally has a small energy difference in a plurality of oxidation states, and its redox potential is concentrated in a narrow width. Therefore, the energy difference between the two after the electron transfer reaction can be reduced by using the electron-donating substance and / or the electron-accepting substance as the substance capable of having the mixed valence state, and the thermodynamic stability of the system can be improved. Can be significantly increased.
This is important when the anisotropic LB film is used as an optical recording material.

As the electron-donating substance and / or electron-accepting substance satisfying such characteristics, the above-mentioned transition metal complex is particularly desirable. This is because the transition metal complex is likely to assume various oxidation states due to the valence of the metal and the interaction with the ligand, and the absorption in the near infrared region is easily obtained. It is also important that many of these substances are thermally stable. In the above structure, the photosensitizer is located between the electron-donating substance and the electron-accepting substance, and has a role of transferring electrons from the electron-donating substance to the electron-accepting substance during the photosensitization process. The charge contributes to stabilization of the charge distribution after the reaction, and also plays an important role as a barrier against undesired reverse electron transfer between the electron-donating substance and the electron-accepting substance after the reaction.

In the above, regarding a specific case, the function of the anisotropic LB film obtained according to the present invention has been described with respect to a specific case. However, the same function is obtained even when a photosensitizer and two kinds of electron accepting substances are used. It is also clear that this can be achieved by using a photosensitizer and a two-primary electron-donating substance. In the former combination, electron transfer proceeds from the photosensitizer to one electron-accepting substance and another electron-accepting substance in this order, and in the latter combination, electron transfer from one electron-donating substance to another electron-donating substance. The substance and the photosensitizer move in this order.

In the charge transfer reaction system as described above, in order to eliminate the factors that hinder the storage stability of information, such as the reverse electron transfer reaction, means for preventing these three components from freely diffusing should be used. Among these, it is particularly preferable to configure the electron donating substance and the electron accepting substance so that they cannot come into direct contact with each other, and the anisotropic LB film obtained by the present invention has such a constitution. . For example, taking as an example the case where a salt (photosensitizer) containing an ion having a photosensitizing function as a constituent component is capable of forming an LB film, in this constitution, at least one of the skeletal molecule and the substituent group is The charged photosensitizer is located between the electron-donating substance and the electron-accepting substance, and has a role of transferring electrons from the electron-donating substance to the electron-accepting substance during the photosensitization process. The electric charge possessed by the compound contributes to the stabilization of the charge distribution after the reaction, and also plays an important role as a barrier against the undesired reverse electron transfer between the electron-donating substance and the electron-accepting substance after the reaction. .

The photosensitizer, the electron-donating substance, the electron-accepting substance, and the LB film-forming auxiliary are appropriately selected and used, and their mixing ratios are also appropriately determined and are not particularly limited. On the other hand, the electron donating substance or the electron accepting substance is preferably used in an equimolar amount or more. When an ion having an electron-donating or electron-accepting property and an ion having a photosensitizing function are present as counterions, their abundance ratios are specified stoichiometrically. An electron-donating substance or electron-accepting substance and a photosensitizer which are not related may be additionally used.

When one of the electron-donating substance and the electron-accepting substance is a salt and it is dissolved in the subphase, it is preferably used in a large excess with respect to the photosensitizer.

The functional material of the present invention can be used as an optical recording material. This optical recording material is irradiated with light to cause the above-mentioned photosensitized redox reaction to cause a physical or chemical change in the system, and this change can be read by an appropriate detecting means. Examples of the reading means include a change in refractive index, a change in dielectric constant, a change in reflectance, a change in transmittance, and a change in capacitance, and a detecting means may be used depending on the case.

This recording material is preferably formed on a transparent substrate. As the transparent substrate, quartz glass, inorganic glass such as borosilicate glass, or plastic substrate such as polymethylmethacrylate resin, polycarbonate resin, or epoxy resin is used. Further, a conductive groove or the like may be formed on the substrate with a tracking groove and a recording layer sandwiched therebetween. It is also possible to erase information by providing a conductive electrode and applying an appropriate potential between the electrodes to cause a reverse reaction with respect to the electrons transferred to the electron-accepting substance.

In addition, it is possible to use those in which a reflective layer is further formed. By providing the reflective layer, the difference in the amount of reflected light between the signal recording portion and the non-recording portion becomes large, and optical detection becomes easier. The reflective layer is provided on the upper surface or the lower surface of the recording material. The reflective layer may be made of any material as long as it has an appropriate reflectance for writing light and reading light, but a metal thin film of aluminum, chromium, nickel, gold or the like is usually used. These are formed by a known means such as vacuum deposition. This reflective layer may also serve as the above-mentioned conductive electrode.

Further, the recording material may contain other additives for various purposes in addition to the above-mentioned LB film formation auxiliary agent, but it is used within a range that does not inhibit LB film formation. Should be. Further, these should be selected and used within a range that does not adversely affect the redox potentials of the electron-donating substance and the electron-accepting substance used and their relation.

Examples of additives include dispersion stabilizers such as surfactants, electrolyte substances, organic or inorganic fillers, metal powders and the like.

The anisotropic LB film obtained by the present invention can also be applied to a nonlinear optical material.

〔Example〕

 The present invention will be described below with reference to examples.

Example 1 3.2 g of 3-pyridinecarboxaldehyde and 200 ml of propionic acid were placed in a 300 ml reaction flask equipped with a reflux condenser and a stirrer.
It was put and heated.

Gradually add 2.0 g of purified and purified pyrrole to this,
After the dropping was completed, the mixture was refluxed for 1 hour. The reaction product was allowed to stand for one day and night, and the precipitated purple crystals were isolated and purified to give 5,10,15,20
-Tetrakis (3-pyridyl) -21H, 23H-porphin
Obtained 0.74 g. This was refluxed with acetic acid in excess in acetic acid to obtain a 5,10,15,20-tetrakis (3-pyridyl) -21H, 23H-porphin zinc complex almost quantitatively. The 5,10,15,20-tetrakis (3-pyridyl) -21H, 23H-porphin zinc complex obtained was then refluxed with excess iodooctadecane in N, N-dimethylformamide for 6 hours to give the crude product. Was repeatedly recrystallized with acetone / ethanol to give a photosensitizer 5,10,15,20
-Tetrakis (3-N-octadecylpyridinium)-
A 21H, 23H-porphine zinc tetraiodide complex (hereinafter abbreviated as C18ZnTPyP ^{4 +} · 4I ⁻ ) was obtained. This thing 5.47mg
Was dissolved in 25 ml of chloroform containing some ethanol to prepare a sample solution (solution A). A nickel dithiostilibene complex (hereinafter abbreviated as Ni (DTSB) ₂ ) 1.36 × 10 ⁻⁴ mol / l chloroform solution (solution B), which is an electron-accepting substance, was prepared. Solution A was developed by using a hetero LB film manufacturing apparatus manufactured by San-S Co., Ltd. at 20 ° C. as pure phase purified by a quartz two-stage distillation column, and its surface pressure-area (molecular occupied area) curve was measured. This result is shown in Figure 1 in graph 1.
Show as. Similarly, the surface pressure-area curve was similarly measured for the mixed solution in which the same amount of the solution B was added to the solution A. The obtained result is shown as graph 2 in FIG. In FIG. 3, the molecular occupied area is the measured area of the developed layer,
It is divided by the number of expanded C18ZnTPyP ⁴⁺ · 4I ⁻ molecules, and shows the area per molecule on the subphase. C18ZnTPyP ⁴⁺ · 4I From this measurement result ^- in, as shown in Graph 1, molecular area near the surface圧立uplink (2.5 nm ²⁾
It is presumed that the porphyrin ring has a structure arranged parallel to the water surface, but the rise of the surface pressure is gradual, and it is thought that it has a structure with many gaps. On the other hand, in the system in which about 1.2 equivalents of Ni (DTSB) ₂ (solution B) was added to this, as shown in Graph 2, the occupied area of the molecule (about 3 nm ² ) did not increase much, and the rise of the surface pressure did not occur. It is loose and the surface pressure becomes steep with compression. This result Ni (DTSB) When ₂ itself considering that exhibit significant hydrophobic Ni (DTSB) is ₂ C18ZnTPyP ⁴⁺ [This membrane in the C18ZnTPyP ⁴⁺ · 4I ^- cation medium (+4) It shows that it is incorporated between the alkyl chains.

C18ZnTPyP ⁴⁺ · 4I under the same conditions as the ^- to prepare Extracts film was controlled at a constant surface pressure to 20 mN / m. A dilute chlorotrimethylsilane solution was applied to this and dried, and a clean quartz glass substrate that had been subjected to a hydrophobic treatment was dipped at a dipping speed of 10 mm / min, and was pulled up to transfer the film to the substrate to form an LB film.

Also, under the same conditions as above, C18ZnTPyP ⁴⁺・ 4I ^- and Ni (DTS
A spread film containing B) ₂ was prepared, and an LB film was prepared in the same manner as above.

Example 2 Nickel bis (dithiomaleonitrile) dianion (hereinafter abbreviated as Ni (MNT) ₂ ²⁻ ) in which C18ZnTPyP ^{4 +} · 4I ⁻ obtained in Example 1 was dissolved in acetone and similarly dissolved in acetone
The tetrabutylammonium salt of was mixed in a small excess. Then, the solution was carefully concentrated, filtered and washed to obtain the salt C18ZnTPyP ^{4 +} · 2Ni (MNT) ₂ ²⁻ . In this salt, C18ZnTPyP ⁴⁺ is an ion having a photosensitizing function, and Ni (MNT) ₂ ²⁻ is an ion having an electron donating property. That is, the photosensitizer and the electron donating substance are realized as a bifunctional substance by one salt.

C18ZnTPyP ⁴⁺・ 2Ni (MNT) ₂ ² -0.1 mmol chloroform-methanol (chloroform: methanol = 4: 1; volume ratio) solution and an electron accepting substance, Ni (DTSB) ₂ 0.1 mmol chloroform solution Mixed.

The obtained mixed liquid was developed in the same manner as in Example 1 and its surface pressure-area curve was measured. The results are shown in FIG.
In Fig. 4, the occupied molecular area is C18ZnTPyP ⁴⁺・ 2Ni (MN
T) ₂ ^2- indicates the area per molecule. Comparing the graph of Fig. 4 with graph 2 of Fig. 3, there is not much difference in the rising point of surface pressure (near 3.2 nm ² ), but the rising of surface pressure due to compression is steeper in the graph of Fig. 4. And the arrangement of the molecules in the membrane is more dense. The schematic structure of the obtained film is shown in FIG. 5 as a schematic diagram. In Figure 5, C18Z
The nTPyP ⁴⁺ cation 3 and the Ni (MNT) ₂ ^2- anion 4 form a salt to form a monolayer, and the hydrophilic Ni (MNT) ₂ ^2- anion 4 is downward in the monolayer. In the upper part, C18ZnTPyP ⁴⁺ cation 3 having a long-chain alkyl group 5 which is a hydrophobic group is located above. Between the long-chain alkyl group 5 intrudes is Ni (DTSB) ₂ 6.

Kyowa Interface Science Co., Ltd., the pressure reduction in the closed type LB film forming apparatus and the introduction of argon gas into the apparatus were repeated, the inside of the apparatus was made an argon gas atmosphere, and then argon gas was blown in advance. Water was introduced into the trough in the above device under an argon gas stream to make a sub-phase. Water temperature 15 ℃
Keeping the above, spread the above mixed solution on pure water, and move the barrier moving speed.
Compress the surface pressure to 20 mN / m with a pressure of 20 cm ² , and apply a dilute solution of chlorotrimethylsilane to the surface of the quartz glass substrate to dry the surface while compressing to maintain this surface pressure.
The sub-phase was immersed vertically and pulled up at a speed of 10 cm / min. As a result, C18ZnTPyP ⁴⁺・ 2Ni (MNT) on the above glass
_An anisotropic LB film containing ₂ ²⁻ and Ni (DTSB) ₂ could be accumulated as a Y film.

The electronic spectrum of the obtained anisotropic LB film is shown in FIG.

Further, an anisotropic LB film was prepared in the same manner as above except that a calcium fluoride substrate was used as the substrate, and an FT-IR absorption spectrum was measured. The results are shown in FIG.

In Fig. 6, the presence of C18ZnTPyP ⁴⁺ can be confirmed by the absorption near 430 nm, and the presence of Ni (DTSB) ₂ can be confirmed by the absorption near 890 nm.
It absorbed by Ni (MNT) ^{₂ 2-} presence of near Figure 7 in 2200 cm ^-1 can be confirmed.

Example 3 In Example 2, the depressurization in the LB film forming apparatus and the introduction of argon gas into the apparatus were repeated to create an argon gas atmosphere in the apparatus and to blow argon gas into pure water in advance. Instead of the anisotropic LB according to Example 2, except that the film formation site in the LB film forming apparatus was covered with a light-shielding cover and pure was used without blowing argon gas.
A membrane was prepared. The electron spectrum of the obtained anisotropic LB film is shown in FIG.

An anisotropic LB film was prepared in the same manner as above except that a calcium fluoride substrate was used as the substrate, and the FT-IR absorption spectrum was measured. The results are shown in FIG.

As in Example 2, C18ZnTPyP ⁴⁺ , Ni (DTSB) ₂ and
Ni (MNT) ₂ presence of ² can be confirmed.

Example 4 First, nickel bis (dithio-p,
p′-di-t-butylstilibene) [molecular formula: Ni (S ₂ C ₂₂ H
₂₆ ) ₂ , hereinafter abbreviated as Ni (TBSB) ₂ ] was synthesized.

pt-Butylbenzaldehyde 40g, KCN 7.0g and N, N
7.0 g of p, p'-di-t-butylbenzoin was synthesized by benzoin synthesis using 240 ml of -dimethylformamide. Then, p, p'-di-t-butylbenzoin 5.0
g, P ₂ S ₅ 5.1 g and (NH ₄ ) ₂ SO ₄ 3.1 g were refluxed in dioxane for 2 hours and then cooled to room temperature, and the precipitate was removed by filtration. To the filtrate was added 5.5 g of NiCl ₂ .6H ₂ O dissolved in 60 ml of water, the mixture was refluxed for 2 hours, and then the reaction solution was left overnight at room temperature. The precipitate formed was collected by filtration, washed with acetone, and recrystallized from ethyl acetate to obtain dark green needle-shaped Ni (TBS
B) ₂ 2.1 g were obtained.

Then, a developing solution C was prepared by mixing Ni (TBSB) ₂ 1 × 10 ⁻⁴ mol / l chloroform solution and the same solution A (C18ZnTPyP ^{4 +} · 4I ⁻ solution) obtained in Example 1 in the same volume. Got

Also, Ni (TBSB) ₂ 1 × 10 ⁻⁴ mol / l chloroform solution and C18ZnTPyP ^{4 +} · 2Ni (MN obtained in the same manner as in Example 2 were used.
T) ₂ ² -1 × 10 ^-4 mol / l ethanol-chloroform solution was mixed in the same volume to obtain a developing solution D.

Further, an aqueous solution of 2Na ⁺ · Ni (MNT) ₂ ²⁻ was prepared as follows. Dithiomaleonitrile disodium salt purified by recrystallization three times with ethanol-ether mixed solvent Na ₂ S ₂ C
3.7 g of ₂ (CN) ₂ (hereinafter abbreviated as Na ₂ MNT) is dissolved in 10 l of water,
1.3 g of NaCl ₂ recrystallized with distilled water and dried under vacuum was dissolved.
The resulting solution was a deep red color, indicating the formation of 2Na ⁺ .Ni (MNT) ₂ ²⁻ . This is an aqueous solution E.

Aqueous solution E was filled into a Teflon developing tank of a hetero LB film manufacturing apparatus manufactured by San-S Co., Ltd. to make a subphase. Then
The developing solution C is spread on the sub-phase at 20 ° C. to give 20 cm ² /
It was compressed at a speed of minutes and the surface pressure-area curve was measured. The result is shown as graph 7 in FIG.

Separately, in the same manner as above except that the subphase is distilled water and the developing solution D is used instead of the developing solution C, the surface pressure-
The area curve was measured. The result is shown as graph 8 in FIG.

As is clear from these results, when the aqueous solution E and the developing solution C were used as the developing solution in the sub-phase (in Graph 7), the phase change region (a) was changed from the first rise of the surface pressure as it was compressed. There is another rise in the surface pressure via the transition to the region (b). The first rise of the surface pressure in graph 7 is about 1 nm ² larger in the molecular occupied area than the rise of the surface pressure when using distilled water and developing solution D as the developing solution in the sub-phase (graph 8). The region (b) in (1) substantially coincides with the surface pressure-area curve after the rise of the surface pressure in graph 8.

The above experimental results are interpreted as follows. When using the aqueous solution E and the developing solution C as the developing solution in the sub-phase, the photosensitizer C18ZnTPyP ^{4 +} · 4I ⁻ and the electron accepting substance Ni (TBSB) ₂ are developed on the gas-liquid interface. As it is compressed, a monolayer of the photosensitizer is formed, and the electron-accepting substance is attracted to the non-polar portion of the photosensitizer. On the other hand, the electron-donating substance is dissolved in the subphase, and Ni (M
NT) ₂ ^2- is present in high concentration. C18ZnTPyP, an ion with a photosensitizing function in the photosensitizer during the process of upward compression
Ion exchange occurs between the ⁴⁺ counterion, I ^−, and the electron-donating ion, Ni (MNT) ₂ ²⁻ . The phase change region (b) is interpreted as reflecting this process. Ni (M
Because NT) ₂ ^2-is only present in the sub-phase, the ion exchange gas - arise from subphase side of the monomolecular layer formed on the liquid surface only. As a result of the above, C18ZnTPyP ⁴⁺ which is an ion having a photosensitizing function, Ni (MNT) ₂ ^2- which is an ion having an electron donating property, and an electron accepting substance
A film having a structure similar to that shown in FIG. 6 is formed from Ni (TBSB) ₂ on the gas-liquid interface.

On the other hand, in the experiment using the developing solution D, C18ZnTPyP ⁴⁺ which is an ion having a photosensitizing function, Ni (MNT) ₂ ²⁻ which is an ion having an electron donating property, and Ni (T
Since BSB) ₂ is already present during the development, a film having a structure similar to that shown in FIG. 6 is initially formed on the gas-liquid interface by these three components as it is compressed. Graph 7
The fact that the region (b) of (1) and the curve of the surface pressure of the graph 8 after the rising of the graph substantially coincide with each other indicate that the film having the same arrangement is finally formed. That is, Ni (MN
T) ₂ ² -to the subphase side and C18ZnTPyP ⁴⁺ has a porphyrin ring arranged parallel to the subphase and is sufficiently hydrophobic
Ni (TBSB) ₂ extended to the opposite side of the subphase C18ZnTPyP ⁴⁺
It is considered that they are incorporated in the long-chain alkyl group portion of.

The films thus formed on the gas-liquid interface were transferred to quartz glass substrates in the same manner as in Example 2 to form anisotropic LB films.

Experimental Example 1 C18ZnTPyP ⁴⁺ · 4I ^- only LB film obtained in Experimental Example 1 (LB
The fluorescence spectra of the film 1), the LB film containing C18ZnTPyP ^{4 +} · 4I ⁻ and Ni (DTSB) ₂ (LB film 2) and the anisotropic LB film (LB film 3) obtained in Example 2 were measured. The spectrophotometer 650-60 manufactured by Hitachi, Ltd. was used for the measurement, and C18ZnTPyP with a wavelength of 430 nm was used.
The fluorescence intensity when ⁴⁺ was excited was measured. Measurement result
Shown in Figure 11. In FIG. 11, graph 9 is the fluorescence spectrum for the LB film 1, graph 10 is the fluorescence spectrum for the LB film 2, and graph 11 is the fluorescence spectrum for the LB film 3. In Graph 9, the fluorescence spectrum based on C18ZnTPyP ⁴⁺ clearly appeared, but in Graph 10, the fluorescence intensity was somewhat reduced, and the fluorescence spectrum disappeared in the anisotropic LB film (LB film 3) obtained by the present invention. did. That is, in the anisotropic LB film (LB film 3) obtained by the present invention,
It was shown that the excited state of C18ZnTPyP ⁴⁺ was completely quenched, which is based on the function of the anisotropic LB film obtained by the present invention.

〔The invention's effect〕

According to the production method of claims 1 to 9, an anisotropic LB film is obtained in which the photosensitizer and the electron-donating substance or the electron-accepting substance have an intimate anisotropic arrangement to realize a charge transfer reaction. Moreover, it can be obtained in a single LB film production process. Particularly, in the manufacturing method according to the third aspect, an anisotropic LB film containing a photosensitizer, an electron donating substance and an electron accepting substance can be obtained.

[Brief description of drawings]

FIG. 1 is a schematic diagram illustrating the movement of electrons caused by photoexcitation in the present invention, and FIG. 2 is a diagram showing the effect of the photosensitizer in the present invention upon the movement of counterions. FIG. 3 is a surface pressure-area curve measured in Example 1, FIG. 4 is a surface pressure-area curve measured in Example 2, and FIG. 5 is a schematic diagram showing the structure of the developed film obtained in Example 2. FIG. 6 is an electron spectrum of the anisotropic LB film obtained in Example 2, FIG. 7 is an FT-IR absorption spectrum of the anisotropic LB film obtained in Example 2, and FIG. The electronic spectrum of the anisotropic LB film obtained in Example 3 is shown in FIG. 9 of the anisotropic LB film obtained in Example 3.
FT-IR absorption spectrum, FIG. 10 is the surface pressure-area curve measured in Example 4, and FIG. 11 is the fluorescence spectrum measured in Experimental Example 1. DESCRIPTION OF SYMBOLS 1 ...... C18ZnTPyP ⁴⁺ · 4I ^- on the graph, 2 ...... C18ZnT
Graph of mixed system of PyP ⁴⁺・ 4I ^- and Ni (DTSB) ₂ , 3.
… C18ZnTPyP ⁴ + cation as an ion with photosensitizing function, 4… Ni (MNT as an ion with an electron donating property)
₂ ) ² -anion, 5 ... long-chain alkyl group, 6 ... Ni (DTSB) ₂ 7 as an electron-accepting substance ... Graph when aqueous solution E and developing solution C are used as a sub-phase, 8 ...... subphase of distilled water and eluent graph 9 ...... C18ZnTPyP ⁴⁺ · when using a developing solution D as 4I ^- fluorescence spectrum 10 ...... C18ZnTPyP ⁴⁺ · 4I of LB film only (LB film 1) ^- and a fluorescence spectrum of Ni (DTSB) fluorescence spectra 11 ...... obtained in example 2 was anisotropic LB film LB film (LB film 2) containing ₂ (LB film 3)

 ─────────────────────────────────────────────────── ─── Continuation of the front page (56) Reference JP 62-167089 (JP, A) JP 63-140434 (JP, A) JP 62-140886 (JP, A) JP 62- 147456 (JP, A) JP 62-149482 (JP, A) JP 60-223117 (JP, A) JP 61-128244 (JP, A) JP 61-102642 (JP, A) Japanese Patent Publication 4-55493 (JP, B2)

Claims (9)

[Claims] 1. An LB film is formed in the presence or absence of an LB film formation aid, which comprises (A) an ion having a photosensitizing function, an electron accepting property or an electron donating property (ion a) as a constituent component. At least one salt (B) having a photosensitizing function, an electron accepting property or an electron donating property,
Ion having the opposite sign to ion a (ion b)
At least one salt having hydrophilicity and (C) at least one hydrophobic substance having a photosensitizing function, an electron-accepting property or an electron-donating property, as described above in (A) and (B). And (C), one is selected to have a photosensitizing function and the other two are selected to have an electron donating or electron accepting property, and the three selected substances are added in the presence of an LB film forming auxiliary or A method for producing an anisotropic LB film, which is characterized by developing into a sub-phase in the absence of a substrate and transferring it onto the substrate while controlling the surface pressure. 2. The selected three kinds of substances include (A) an ion having a photosensitizing function (ion a) as a constituent component, and LB in the presence or absence of an LB film forming auxiliary agent.
At least one salt capable of forming a film (B) has an electron-accepting property or an electron-donating property, contains an ion (ion b) having a charge of the opposite sign to the ion a as a constituent, and is hydrophilic and At least one salt and (C) at least one having an electron accepting or electron donating property
The method for producing an anisotropic LB film according to claim 1, wherein the anisotropic LB film is a hydrophobic substance. 3. The selected three kinds of substances include (A) an ion having a photosensitizing function (ion a) as a constituent component, and LB in the presence or absence of an LB film forming auxiliary agent.
At least one salt capable of forming a film (B) has an electron-accepting property or an electron-donating property, contains an ion (ion b) having a charge of the opposite sign to the ion a as a constituent, and is hydrophilic and At least one salt and (C) at least one having an electron accepting or electron donating property
3. The method for producing an anisotropic LB film according to claim 2, wherein each of the hydrophobic substances (B) and (C) has an electron-donating property and the other has an electron-accepting property. 4. The method for producing an anisotropic LB film according to claim 2, wherein (A) according to claim 2 or 3 is a porphyrin dye or a phthalocyanine dye. 5. (B) and (C) according to any one of claims 1 to 3.
Is a transition metal complex selected from compounds represented by the following general formula (I), (II) or (III).
A method for producing the anisotropic LB film described. General formula (I) General formula (II) In the general formulas (I) and (II), Z is an atom or atomic group selected from O, S, NR (R is hydrogen or an alkyl group), and X and X ′ may be hydrogen at each position,
It is selected from an alkyl group, a substituted alkyl group, a halogen group, an alkoxy group, an alkyloxycarbonyl group, a carboxyl group, an alkylamino group, a quaternary alkylammonium group, a nitro group or a cyano group, and X and X ′ may be the same, n Is an integer of 1 to 4, m is an integer of +2 to -2, A is m
One or more anions or one or more cations having the number of charges necessary to neutralize the charge defined by and M represents a transition metal ion (provided that when m is 0, A is not exist). General formula (III) In the general formula (III), Z ′ is selected from S and NR (R is hydrogen or an alkyl group) and may be different at each position, and Y is hydrogen, an alkyl group, a substituted alkyl group, a phenyl group, a substituted phenyl group and Selected from a cyano group, may be different at each position, m is an integer of +2 to -2, A is m
One or more anions or one or more cations having the number of charges necessary to neutralize the charge defined by and M represents a transition metal ion (provided that when m is 0, A is not exist). 6. (A) and (B) according to claims 1 to 3.
4. Anisotropic LB according to any one of claims 1 to 3, wherein the ion a and the ion b according to claims 1 to 3 are counter-ions with each other to form one salt in advance.
Membrane manufacturing method. 7. (B) according to any one of claims 1 to 3 is dissolved in advance in a sub-phase, (A) and (C) according to any one of claims 1 to 3 are expanded into a sub-phase, and the expanded product is compressed. Then, the anisotropic LB film is manufactured by controlling the surface pressure and transferring it onto the substrate. 8. The method for producing an anisotropic LB film according to claim 1, wherein the LB film is produced in an atmosphere substituted with an inert gas. 9. The method according to claim 1, wherein the LB film is formed under light shielding.
The method for producing an anisotropic LB film according to any one of 1.