JPH06263874A - Aromatic polythiazole thin film and method for producing the same - Google Patents

Abstract

PURPOSE:To obtain the subject film excellent in heat resistance and rigidity by building up films of an aromatic polythiazole precursor on a substrate by a specified method and heating the buildup film to cyclize the precursor to form thiazole rings. CONSTITUTION:The production process of the thin film comprises building up films of an aromatic polythiazole of formula I [wherein Ar1 and Ar2 are aromatic residues; R is (substituted) alkylene; X1 and X2 are each a hydrophobic alkyl compound; and (n) is 4-1000] on a substrate by the Langmuir/Blodgett method and heating the buildup film to cyclize the precursor to form thiazole rings. Examples of aromatic residues Ar, of the above precursor include groups of formulas II and III, and examples of aromatic residues Ar2 include groups of formulas IV and V. This film has characteristic electrical and optical properties, excels in heat resistance and rigidity and is especially suited as a material for electronic components and optical computers.

Description

Detailed Description of the Invention

[0001]

This invention relates to Langmuir-Blodget thin films of aromatic polythiazoles.
The present invention relates to an aromatic polythiazole thin film suitable for use as a material for electronic parts and optical computers, and a method for manufacturing the same.

[0002]

2. Description of the Related Art An LB thin film is an amphipathic compound spread on a water surface as a monomolecular film.
It is a cumulative thin film transferred onto a substrate under constant surface pressure. In addition to having a highly ordered structure, it is possible to provide specific optical, magnetic, and electrical properties by controlling the array of molecular dimensions, and therefore, it is expected to be applied in various fields such as molecular electronic devices.

Conventionally, LB thin films have been studied for low molecular weight fatty acids and polymers such as polypeptides and polyalcohols, but they are not practical in terms of heat resistance and mechanical strength. Therefore, a heat-resistant polyimide thin film excellent in electrical insulation was proposed by introducing a substituent for imparting hydrophobicity to a polyamic acid unit which is a precursor of heat-resistant polyimide (Japanese Patent Publication No. 4-46631). issue).

However, the mechanical strength of polyimide,
Especially, the rigidity is not sufficient. Therefore, it is conceivable to use an aromatic polymer called a rigid polymer, for example, one having a heterocyclic ring such as a thiazole ring, an imidazole ring, an oxazole ring or an oxazinone ring in a repeating unit. Among them, aromatic polythiazole having a thiazole ring has excellent mechanical strength and is promising. But,
So far, there is no example of an LB thin film using an aromatic polythiazole.

Therefore, an object of the present invention is to provide an aromatic polythiazole thin film having excellent heat resistance and rigidity and a method for producing the same.

[0006]

As a result of earnest research in view of the above problems, the present inventors have found that if an aromatic polythiazole precursor is provided with a hydrophobic group, an aromatic polythiazole thin film can be produced by the LB method. The inventors have discovered that it is possible and completed the present invention.

That is, the Langmuir-Blodgett thin film of the present invention comprising an aromatic polythiazole has the following formula (a):

[Chemical 3] (However, Ar ₁ and Ar ₂ are aromatic residues, R is an unsubstituted or substituted alkylene group, X ₁ and X ₂ are compounds having a hydrophobic group, and n = 4 to 1000. )
It is characterized in that it is produced by accumulating an aromatic polythiazole precursor represented by the formula (3) on a substrate by the Langmuir-Blodgett method, and (b) heating it to cause a thiazole ring closure reaction of the precursor.

The method of the present invention for producing a Langmuir-Blodgett thin film comprising an aromatic polythiazole is as follows:
(A) The following formula

[Chemical 4] (However, Ar ₁ and Ar ₂ are aromatic residues, R is an unsubstituted or substituted alkylene group, X ₁ and X ₂ are compounds having a hydrophobic group, and n = 4 to 1000. )
The aromatic polythiazole precursor represented by the formula (1) is accumulated on the substrate by the Langmuir-Blodgett method, and (b) is heated to cause a thiazole ring closure reaction of the precursor.

The present invention is described in detail below. The aromatic polythiazole precursor of the present invention has the following formula

[Chemical 5] (However, Ar ₁ and Ar ₂ are aromatic residues, R is an unsubstituted or substituted alkylene group, and n is 4 to 1000.
Is. ) And a compound X ₁ or X ₂ having a hydrophobic group bonded to the hydrogen atom of the carboxyl group of the polymer by an ionic bond.

As the aromatic residue Ar ₁ in the aromatic polythiazole precursor, a benzene ring, an aromatic ring in which two or more benzene rings are condensed, or a compound in which two or more benzene rings are bonded, such as biphenyl. And so on. Preferred examples of such an aromatic residue Ar ₁ include:

[Chemical 6] Etc.

The aromatic residue Ar ₂ in the aromatic polythiazole precursor is preferably a benzene ring, one having two or more benzene rings bonded to each other, and a plurality of benzene rings having an ether group. Examples of such aromatic residue Ar ₂ include:

[Chemical 7] Etc. Among these, as the aromatic residue Ar ₂ ,

[Chemical 8] Are preferred. The aromatic residue Ar ₂ is not limited to one type, and two or more types may be used in combination.

The alkylene group R in the aromatic polythiazole precursor is a substituted or unsubstituted alkylene group, and examples of the unsubstituted alkylene group include trimethylene group, ethylene group, propylene group, tetramethylene group, 1,1 -Dimethylethylene group, 1,2-dimethylethylene group and the like can be mentioned. The alkylene group is particularly preferably an alkylene group derived from a secondary or tertiary alkyl group. As the substituted alkylene group, an alkylene group substituted with an ester group, a cyano group, a benzyl group, a halogen group, a nitro group or the like is preferable.

The compounds X ₁ and X ₂ having a hydrophobic group in the aromatic polythiazole precursor are aliphatic compounds or cycloaliphatic compounds having 1 to 30 carbon atoms, such as amino group, cyano group,
Those substituted with a methoxy group, an acetoxy group, a nitro group, an ester group, a benzyl group or the like are preferable. The hydrophobic group in the compounds X ₁ and X ₂ is an alkyl group, and is ionically bonded to the galboxyl group of the aromatic polythiazole precursor by a substituent such as an amino group. The presence of the compound having the hydrophobic group enables formation of a monomolecular film of the aromatic polythiazole precursor on the water surface. In addition,
X ₁ and X ₂ may be the same or different. Preferred examples of the compound having a hydrophobic group include unbranched alkylamines having an alkyl chain length of 16 to 30. For example,
The following formula

[Chemical 9] A tertiary amine represented by

[Chemical 10] A secondary amine represented by the following formula

[Chemical 11] Alkylpyrrolidine represented by is particularly preferable.

Degree of Polymerization n of Aromatic Polythiazole Precursor
Is preferably 4 to 1000. Polymerization degree is 4-10
If the value is out of the range of 00, there is a tendency that the strength at the time of forming the film is too low, or that the viscosity is too high to make the film well.

The method for producing the aromatic polythiazole thin film of the present invention will be described below.

In the present invention, as a method for producing an LB thin film using an aromatic polythiazole precursor, the precursor is developed on the water surface and compressed at a constant surface pressure to form a monomolecular film. In addition to the LB method, which is a method of transferring a film to a substrate, methods such as a water surface adhesion method and a rotating cylinder method can be used, and any commonly used method can be used without particular limitation.

First, the aromatic polythiazole precursor is
Dissolve in an organic solvent to prepare a developing solution for forming a monomolecular film on the water surface. Examples of such a solvent include benzene, chloroform, N-methyl-2-pyrrolidone, dimethyl sulfoxide, N, N-dimethylacetamide,
N, N-diethylacetamide, N, N-dimethylformamide, N, N-diethylformamide, N, N-dimethylmethoxyamide, pyridine, dimethyl sulfone, hexamethylphosphoramide, tetramethylene sulfone, dimethyl tetramethylene sulfone, etc. Can be mentioned. The solvent may be a single solvent, but 2 selected from the above compounds
A mixed solvent of two or more kinds is preferable. Among these, a mixed solvent composed of benzene, N-methyl-2-pyrrolidone and N, N-dimethylacetamide is particularly preferable. In addition, it is preferable to use those solvents that have been dehydrated by a known method. In addition, chlorides such as LiCl and CaCl ₂ up to 10% may be added to increase the solubility of the polymer.

The concentration of the developing solution of the aromatic polythiazole precursor is preferably 0.01 to 100 mM, assuming that the repeating unit of the precursor is one molecule. The temperature during melting is preferably about 0 to 50 ° C.

Although the above-mentioned aromatic polythiazole precursor is synthesized by a known method, the compound having a hydrophobic group constituting the aromatic polythiazole precursor and the rest of the polymer are each dissolved in an organic solvent to obtain a water surface. It is preferable to use a mixture of both immediately before the development. The raw materials may be dissolved by any method as long as a uniform solution is obtained.

The substrate on which the LB thin film is formed by using the precursor of the present invention is not particularly limited and may be selected according to the application of the formed LB thin film, but the LB thin film is heated to form polythiazole. Therefore, it is necessary that the heat resistance is good. Specific examples of such a substrate include glass, alumina, and quartz, as well as a plastic substrate, a metal substrate or a metal-plated substrate, a semiconductor such as Si, GaAs, or ZnS, or a ferroelectric substance such as PbTiO ₃ or BaTiO _3. Examples of the substrate include a magnetic substrate and a magnetic substrate. Further, it goes without saying that these substrates may be subjected to a surface treatment which is usually performed before use.

The LB thin film of the aromatic polythiazole precursor obtained using the above substrate can be dried by a known method.

Next, the LB thin film of the aromatic polythiazole precursor obtained above is heated to cause a thiazole ring closure reaction in the precursor to obtain an aromatic polythiazole thin film. In this heating, the alkyl group (R) of the precursor is eliminated, and at the site, a thiazole ring is formed to form an aromatic polythiazole. For example, from an aromatic polythiazole precursor, poly-p-
A phenylene benzobis thiazole is formed.

[Chemical 12]

The heating temperature of the precursor LB thin film varies depending on the type, but is generally 250 ° C to 400 ° C. 250 ° C
If heated below 1, no formation of thiazole ring is observed.
If the heating temperature is higher than 450 ° C, the polythiazole starts thermal decomposition, which is not preferable, and it is preferable to set the upper limit to 450 ° C. The heating may be performed not only by a constant heating temperature but also by a heating program in which the temperature is changed stepwise. For example, the heating program may be such that after heating at 120 ° C. for 30 minutes, the temperature is raised to 350 ° C. in 30 minutes and then kept at 350 ° C. for 30 minutes.

The heating time varies depending on the number of laminated LB thin films, but is preferably 1 to 20 hours. The heat treatment is preferably performed in a reduced pressure atmosphere. Preferred pressure is 1-20m
It is mHg.

According to the method described above, an aromatic polythiazole thin film having excellent heat resistance and rigidity can be obtained.

[0026]

[Working] The aromatic polythiazole thin film of the present invention has electrically and optically unique properties and is excellent in heat resistance and rigidity.

Further, according to the production method of the present invention, a solution of an aromatic polythiazole precursor dissolved in an organic solvent is added,
An aromatic polythiazole thin film can be produced by forming a thin film by the Langmuir-Blodgett method and heating it.

[0028]

The present invention will be described in detail with reference to the following specific examples. However, the reagents used in the following examples were dehydrated as follows: (1) Dimethylacetamide (hereinafter referred to as DMAC) and N-methyl-2-pyrrolidone (hereinafter referred to as NMP) Call)
It was dehydrated with calcium chloride and then distilled. (2) Benzene was washed with sulfuric acid, further washed with water, then neutralized with an aqueous potassium carbonate solution, dehydrated with calcium chloride and sodium, and distilled. (3) As lithium chloride, anhydrous lithium chloride manufactured by Wako Pure Chemical Industries, Ltd. was used. Aromatic polythiazole precursors are disclosed in JP-A-4-114.
It was prepared according to the method disclosed in No. 062.

Example 1 The following formula

[Chemical 13] Polybenzothiazole precursor shown by (hereinafter referred to as PBT-O
0.269g at room temperature DMAC: benzene =
Dissolve in a 1: 1 mixed solvent and add 1 mM PBT-OD.
A C solution was prepared. However, the molar concentration of the polymer used here is a value when the repeating unit (unit) is assumed to be one molecule. Similarly, the following formula

[Chemical 14] The amine compound represented by (hereinafter referred to as NR ₃ ) is DMAC,
It was dissolved in a benzene mixed solvent (DMAC: benzene = 1: 1) to prepare a solution having a concentration of 1 mM. PBT-ODC
The solution and the NR ₃ solution were mixed at a ratio of 1: 2 to prepare a developing solution for LB film. This developing solution is spread on the water surface for 20
The relationship between the surface pressure π and the area per repeating unit was measured at 0 ° C and is shown in FIG. 1.

Next, at 20 ° C. above the water surface, the surface pressure of the membrane is 30 m.
While maintaining the N / m, 25 layers were accumulated on the glass substrate by the LB method at a cumulative speed of 10 mm / min. This film was analyzed by FT-IR (JIR-MIXRO 6000, JEOL Ltd.), and the results are shown in FIG. 2 (a). Further, this accumulated film was heat-treated at 280 ° C. and 5 mmHg for 6 hours to cause a thiazole ring closure reaction. The generated polybenzothiazole film was analyzed by FT-IR, and the result is shown in FIG. 2 (b).

In the same manner as above, instead of NR ₃ , the following formula

[Chemical 15] Amine compound (hereinafter referred to as NR ₂ —CH ₃ ) and the following formula

[Chemical 16] A developing solution for LB film was prepared using the amine compound shown in (hereinafter referred to as C ₂₀ N5M). These two kinds of developing solutions were developed on the water surface, and the relationship between the surface pressure π and the area per repeating unit (unit) was measured at 20 ° C. and shown together with FIG. 1.

As shown in FIG. 1, when NR ₃ is used,
A sharp rise in surface pressure was observed when the area of the repeating unit was about 1.3 nm ² / unit. The surface pressure at the time of rising is about 30 mN / m. Moreover, as is clear from FIG. 2, L of the obtained aromatic polythiazole precursor was obtained.
After heat-treating the B thin film, the wave number is 2800-3000 cm
The absorption of the alkyl group and carboxyl group at ^-1 disappeared, indicating that the thiazole ring-closing reaction was performed.

Example 2 Using the same method and materials as in Example 1, a developing solution for LB film was prepared. This developing liquid is spread on the water surface and the temperature is raised to 2
Cumulative speed of 10 m, keeping membrane surface pressure at 0 ° C and 30 mN / m
Fifteen layers were accumulated on the glass substrate by the LB method at m / min.
The accumulated LB film was measured with an absorptiometer (Otsuka Electronics Co., Ltd.,
MCPD-1000) and the results are shown in FIG. Further, this accumulated film was subjected to heat treatment for 6 hours in an environment of 280 ° C. and 5 mmHg to cause a thiazole ring closure reaction. Analyze the generated polybenzothiazole film with an absorptiometer,
The results are shown in Fig. 3.

As is apparent from FIG. 3, after the obtained LB thin film of the aromatic polythiazole precursor was heat-treated,
The absorption pattern in the ultraviolet region of the thin film changed, demonstrating that the thiazole ring-closing reaction took place.

Example 3 Using the same method and materials as in Example 1, a developing solution for LB film was prepared. This developing liquid is spread on the water surface and the temperature is raised to 2
Cumulative speed of 1 at 0 ℃, keeping membrane surface pressure at 22.5 mN / m
5, 1 on the glass substrate by LB method at 0 mm / min respectively
5, 25 and 35 layers were accumulated. Wavelength 2 of these LB films
The absorbance at 80 nm was analyzed by an absorptiometer, and the results are shown in FIG. Furthermore, these cumulative films were heated at 280 ° C. for 5 m.
The heat treatment was performed for 2 to 8 hours in an environment of mHg to cause a thiazole ring closure reaction. The generated polybenzothiazole film was analyzed by an absorptiometer, and the absorbance at a wavelength of 370 nm is shown in FIG.

As is clear from FIG. 4, both the LB thin film of the aromatic polythiazole precursor and the aromatic polythiazole thin film after the heat treatment have an absorbance in the ultraviolet region proportional to the number of stacked layers, and a uniform stacked layer is obtained. It has been formed.

Example 4 Using the same method and material as in Example 1, a developing solution for LB film was prepared. This developing liquid is spread on the water surface and the temperature is raised to 2
Cumulative speed of 1 at 0 ℃, keeping membrane surface pressure at 22.5 mN / m
50 and 7 on the Si substrate by the LB method at 0 mm / min, respectively.
5, 90, 110 layers were accumulated. The film thickness of these LB films is determined by ellipsometry (Japan Infrared Industries Co., Ltd., EL
-101), and the results are shown in FIG. Further, these accumulated films were subjected to heat treatment for 8 hours in an environment of 280 ° C. and 5 mmHg to cause a thiazole ring closure reaction. The film thickness of the produced polybenzothiazole film was similarly analyzed, and the results are shown in FIG.

As shown in FIG. 5, in both the LB thin film of the aromatic polythiazole precursor and the aromatic polythiazole thin film after the heat treatment, the film thickness is proportional to the number of laminated layers,
The thickness of one layer before the heat treatment was 23.18 angstroms, and after the heat treatment was 3.53 angstroms.

Example 5 The following formula

[Chemical 17] Polybenzothiazole precursor shown by (hereinafter PBT-M
0.223g at room temperature DMAC: benzene =
Dissolve in a 1: 1 mixed solvent and add 1 mM PBT-MP.
A DC solution was made. Also, 1 mM NR ₃ DMA
C, benzene solution (DMAC: benzene = 1: 1) was prepared. PBT-MPDC solution: NR _3: benzene: DM
AC was mixed at a ratio of 1: 2: 6: 6 to prepare a 1/15 mM LB film developing solution. This developing solution was developed on the water surface, and the relationship between the surface pressure π and the area per repeating unit (unit) was measured at 20 ° C. and shown in FIG.

This developing solution is spread on the water surface and the temperature is raised to 2
Cumulative speed of 10 m, keeping membrane surface pressure at 0 ° C and 30 mN / m
Fifteen layers were accumulated on the glass substrate by the LB method at m / min.
The accumulated LB film was measured with an absorptiometer (Otsuka Electronics Co., Ltd.,
MCPD-1000) and the results are shown in FIG. 7. Further, this accumulated film was subjected to heat treatment for 6 hours in an environment of 280 ° C. and 5 mmHg to cause a thiazole ring closure reaction. Analyze the generated polybenzothiazole film with an absorptiometer,
The results are shown in Fig. 7.

As shown in FIG. 6, when the area of the repeating unit was about 1.3 nm ² / unit, a sharp rise of the surface pressure was observed. Surface pressure when rising is about 30 mN /
m. Further, as is clear from FIG. 7, after the LB thin film of the obtained aromatic polythiazole precursor was heat-treated, the absorption pattern in the ultraviolet region of the thin film was changed, which proves that the thiazole ring closure reaction was performed.

Example 6 The following formula

[Chemical 18] Polybenzothiazole precursor (hereinafter referred to as PBT-P
0.223g (called PDC) and lithium chloride at room temperature
It was dissolved in a P solvent to prepare a 1 mM PBT-PPDC solution (lithium chloride content: 9.7 × 10 ⁻² wt%). Further, a 1 mM NR ₃ DMAC and benzene solution (DMAC: benzene = 1: 1) was prepared. PBT-P
PDC solution: NR ₃ : NMP: benzene = 1: 2: 1
The mixture was mixed at a ratio of 7:18 to prepare a 1/38 mM LB film developing solution (DMAC: NMP: benzene = 1: 18: 19). This developing solution was developed on the water surface, and the relationship between the surface pressure π and the area per repeating unit (unit) was measured at 20 ° C. and shown in FIG.

This developing solution is spread on the water surface and the temperature is raised to 2
Cumulative speed of 10 m, keeping membrane surface pressure at 0 ° C and 30 mN / m
Fifteen layers were accumulated on the glass substrate by the LB method at m / min.
The accumulated LB film was measured with an absorptiometer (Otsuka Electronics Co., Ltd.,
MCPD-1000) and the results are shown in FIG. Further, this accumulated film was subjected to heat treatment for 6 hours in an environment of 280 ° C. and 5 mmHg to cause a thiazole ring closure reaction. Analyze the generated polybenzothiazole film with an absorptiometer,
The results are shown in Fig. 9.

As shown in FIG. 8, when the area of the repeating unit was about 1.3 nm ² / unit, a sharp rise of the surface pressure was observed. Surface pressure when rising is about 30 mN /
m. Further, as is clear from FIG. 9, after the LB thin film of the obtained aromatic polythiazole precursor was heat-treated, the absorption pattern in the ultraviolet region of the thin film was changed, which proves that the thiazole ring closure reaction was performed.

Example 7 The following formula

[Chemical 19] Polybenzothiazole precursor (hereinafter referred to as PBT-B
0.261 g and lithium chloride are called NM at room temperature.
It was dissolved in a P solvent to prepare a 1 mM PBT-BPDC solution (lithium chloride content: 0.194% by weight). Further, a 1 mM NR ₃ DMAC and benzene solution (DMAC: benzene = 1: 1) was prepared. PBT-B
PDC solution: NR ₃ : NMP: benzene = 1: 2: 1
The mixture was mixed at a ratio of 7:18 to prepare a 1/38 mM LB film developing solution (DMAC: NMP: benzene = 1: 18: 19). This developing solution was developed on the water surface, and the relationship between the surface pressure π and the area per repeating unit (unit) was measured at 20 ° C. and shown in FIG.

This developing solution is spread on the water surface and the temperature is raised to 2
Cumulative speed of 10 m, keeping membrane surface pressure at 0 ° C and 30 mN / m
Fifteen layers were accumulated on the glass substrate by the LB method at m / min.
The accumulated LB film was measured with an absorptiometer (Otsuka Electronics Co., Ltd.,
MCPD-1000) and the results are shown in FIG.
Further, this accumulated film was subjected to heat treatment for 6 hours in an environment of 280 ° C. and 5 mmHg to cause a thiazole ring closure reaction. The produced polybenzothiazole film was analyzed with an absorptiometer, and the results are shown in FIG.

As shown in FIG. 10, a sharp rise in the surface pressure was observed when the area of the repeating unit was about 1.3 nm ² / unit. Surface pressure at start-up is about 30mN
/ M. Further, as is clear from FIG. 11, after the obtained LB thin film of the aromatic polythiazole precursor was heat-treated, the absorption pattern in the ultraviolet region of the thin film was changed, which proves that the thiazole ring closure reaction was performed.

[0048]

As described above in detail, according to the present invention, a solution of an aromatic polythiazole precursor dissolved in an organic solvent is formed into a thin film by the Langmuir-Blodgett method, and heated to electrically, It is possible to produce an aromatic polythiazole thin film having optically unique properties and excellent heat resistance and rigidity.

The aromatic polythiazole thin film of the present invention can be widely used as a molecular electronic device such as a non-linear optical material, a heat resistant insulating film or a heat resistant conductive film.

[Brief description of drawings]

FIG. 1 is a graph showing the relationship between the surface pressure of the monolayer on the water surface obtained in Example 1 and the area of repeating units.

2 is an aromatic polythiazole precursor LB thin film obtained in Example 1 and FT-I of an aromatic polythiazole thin film.
It is a graph which shows the measurement result of R.

FIG. 3 is a graph showing absorptiometer absorbances of an aromatic polythiazole precursor LB thin film obtained in Example 2 and an aromatic polythiazole thin film produced after heat treatment.

FIG. 4 is a graph showing the relationship between the absorbance (280 nm) of the aromatic polythiazole precursor LB thin film obtained in Example 3, the absorbance (370 nm) of the aromatic polythiazole thin film, and the number of layers.

5 is a graph showing the relationship between the film thickness and the number of laminated layers of the aromatic polythiazole precursor LB thin film and the aromatic polythiazole thin film obtained in Example 5. FIG.

FIG. 6 is a graph showing the relationship between the surface pressure of the monomolecular film on the water surface obtained in Example 5 and the area of repeating units.

FIG. 7 is a graph showing the absorbance of the aromatic polythiazole precursor LB thin film obtained in Example 5 and the aromatic polythiazole thin film produced after heat treatment.

FIG. 8 is a graph showing the relationship between the surface pressure of the monolayer on the water surface obtained in Example 6 and the area of the repeating unit.

FIG. 9 is a graph showing the absorbance of the aromatic polythiazole precursor LB thin film obtained in Example 6 and the aromatic polythiazole thin film produced after heat treatment.

FIG. 10 is a graph showing the relationship between the surface pressure of the monolayer on the water surface obtained in Example 7 and the area of repeating units.

FIG. 11 is a graph showing the absorbance of the aromatic polythiazole precursor LB thin film obtained in Example 7 and the aromatic polythiazole thin film produced after heat treatment.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Masaaki Kakimoto 61-9-3-504 Ikebukuro, Naka-ku, Yokohama-shi, Kanagawa Prefecture (72) Inventor Tomoyuki Yuba 2-23-7 Higashiyukiya, Ota-ku, Tokyo

Claims (6)

[Claims] 1. A Langmuir-Blodgett thin film comprising an aromatic polythiazole, wherein (a) the following formula: (However, Ar ₁ and Ar ₂ are aromatic residues, R is an unsubstituted or substituted alkylene group, X ₁ and X ₂ are compounds having a hydrophobic group, and n = 4 to 1000. )
An aromatic polythiazole precursor represented by the following formula is accumulated on a substrate by the Langmuir-Blodgett method, and (b) is heated to cause a thiazole ring-closing reaction of the precursor, thereby producing an aromatic compound. Polythiazole thin film. 2. The aromatic polythiazole thin film according to claim 1, wherein the substituted alkylene group is an ester group,
An aromatic polythiazole thin film having a substituent consisting of a cyano group, a benzyl group, a halogen group or a nitro group. 3. The aromatic polythiazole thin film according to claim 1 or 2, wherein the aromatic residue Ar ₁ is a benzene ring. 4. The aromatic polythiazole thin film according to claim 1, wherein the aromatic residue Ar ₂
Is a phenyl group, a biphenyl group, or an oxydiphenyl group, and is an aromatic polythiazole thin film. 5. The aromatic polythiazole thin film according to claim 1, wherein the compounds X ₁ and X ₂ having a hydrophobic group are amino group, cyano group, methoxy group, acetoxy group, nitro group, An aromatic polythiazole thin film, which is an aliphatic compound having 1 to 30 carbon atoms or a cycloaliphatic compound substituted with an ester group or a benzyl group. 6. A method for producing a Langmuir-Blodgett thin film comprising an aromatic polythiazole, comprising: (a) the following formula: (However, Ar ₁ and Ar ₂ are aromatic residues, R is an unsubstituted or substituted alkylene group, X ₁ and X ₂ are hydrophobic alkyl compounds, and n = 4 to 1000.)
Of the aromatic polythiazole thin film characterized by accumulating the aromatic polythiazole precursor represented by the formula (1) on the substrate by the Langmuir-Blodgett method and causing (b) heating to cause a thiazole ring closure reaction of the precursor. Production method.