JPH07179773A - Azo compound - Google Patents

Abstract

PURPOSE:To obtain a new azo compound useful for the production of a thin film of a functional material such as dye and photoconductive material by a wet process using an aqueous solvent. CONSTITUTION:This compound is expressed by formula I (R is H or an alkyl; phi1 and phi2 are each p-phenylene; (m) is >=1; (n) is >=1 and preferably 6), e.g. the compound of formula II. The compound of formula I can be produced e.g. by mixing and dissolving sodium hydride in a polyethylene glycol having a polymerization degree of 13, adding 4-(2-bromoethoxy)-4'-hexylazobenzene to the mixture, reacting under heating, distilling out the solvent from the reaction mixture under reduced pressure, adding 1-butanol and water, fractionating the mixture, distilling out the solvent from the organic layer, dissolving the residue in benzene and developing on a silica get column.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an azo compound useful when a thin film of a functional material such as a dye or a photoconductive material is produced by a wet method using an aqueous solvent.

[0002]

2. Description of the Related Art Conventionally, color filters, electrophotographic photoconductors, photosensors, solar cells, electroluminescence devices, optical recording media, nonlinear optical devices, electro-optical devices, photochromic thin films, electrochromic devices, gas sensors, and ion sensors. Functional materials used in functional elements such as dyes, charge generation materials, charge transport materials, electroluminescent materials, photosensitive dyes, nonlinear optical materials, electro-optical materials, photochromic materials, electrochromic materials, gas sensing materials, and ions. When the sensing material or the like is hydrophobic, the following method is used as a method for manufacturing a thin film of a hydrophobic substance.

As a wet method using a solution or a dispersion liquid, a coating method such as a coating method, a blade coating method, a roll coating method, a spin coating method, a dipping method and a spray method, a lithographic plate, a letterpress, an intaglio, a stencil, a screen, a transfer method, etc. Electrochemical methods such as printing method, electrodeposition method, electrolytic polymerization method, etc.

As a method utilizing polymerization or polycondensation reaction of a liquid monomer, casting method, reaction injection molding method, etc.

Examples of methods using gas molecules or gaseous monomers include sublimation transfer method, vapor deposition method, vacuum vapor deposition method, ion beam method, sputtering method, plasma polymerization method, photopolymerization method and the like.

As a method of utilizing melting or softening by heating, there are a hot pressing method, an injection molding method, a drawing method, an electrostatic coating method using a meltable powder, and the like.

A method utilizing electrolytic oxidation of a ferrocene residue-containing surfactant, that is, a surfactant having a ferrocene residue is used to electrolyze a dispersion liquid in which fine particles of a hydrophobic substance are dispersed in water to form an anode surface. In the method of T., the function as a surfactant is lost by oxidizing the ferrocene residue, and the dispersed state of the fine particles is destroyed in the vicinity of the anode surface, and as a result, the fine particles are attached to the cathode surface [T. Saji, K.Hoshino, Y.Ishii, M.Goto, Journa
l of the American Chemical Society, Volume 113, 45
0 (1991)].

[0008]

While these conventional thin film manufacturing methods have various advantages, they have the following limitations and problems when applied to the manufacturing of the above-mentioned hydrophobic functional material thin film.

When the above-mentioned wet method is used, an organic solvent is often used instead of water. As one of the problems with the use of organic solvents, in addition to coating equipment, large-scale incidental equipment, that is, a large amount of equipment investment is required for fire prevention and safety / conservation for the human body and the natural environment. There is a problem that a large amount of energy, that is, a large operating cost is required to safely and completely remove the combustible organic solvent vapor generated in the manufacturing process.

As one of the problems associated with the use of an organic solvent, in the above-mentioned wet method, when an organic solvent is used as a dispersion solvent for fine particles of a hydrophobic substance, a dispersion process from dispersion preparation to thin film preparation, dispersion There is a problem that it is not easy to completely prevent the crystal growth, crystal transition, and / or change of the agglomeration state of the fine particles during storage and use of the fine particles, or to control the fine particle state in the thin film manufacturing process. Crystal growth, crystal transition of hydrophobic substance particles,
Also, controlling the aggregation state to produce a thin film is an extremely important issue in improving the characteristics of the above-mentioned device using a thin film of a hydrophobic functional material.

In the above-mentioned wet method, as a means for suppressing the crystal growth and crystal transition of fine particles of a hydrophobic substance in an organic solvent and controlling the aggregation state, conventionally, a binder resin (vehicle) has been used in a dispersion liquid of the fine particles. Or varnish)
The method of coexisting is widely used. That is, in the conventional method of manufacturing a thin film by a wet method, a coating liquid, a coating material, or an ink in which a hydrophobic substance is dissolved or dispersed as fine particles in an organic solvent solution of a binder resin is widely used. One of the problems when using a binder resin is that the binder resin coexists in the obtained thin film together with the hydrophobic functional material, and the amount of the functional material per unit volume of the thin film, that is, the concentration decreases. There is.
To reduce the amount of the binder resin used in the thin film and improve the concentration of the functional material, color filters, electrophotographic photoreceptors, photosensors, solar cells, electroluminescent elements, optical recording media, non-linear optical elements, electrical This is an important issue for improving the characteristics of optical elements, photochromic thin films, electrochromic elements, gas sensors, ion sensors, and the like.

One of the problems in using a binder resin in the above-mentioned wet method is the problem of selecting the resin. The binder resin used in the above-mentioned wet method thin film manufacturing method is used for various characteristics relating to thin film manufacturing, such as dispersibility and dispersion stability of the hydrophobic substance particles, suppression of crystal growth of the particles, and flow characteristics of the dispersion liquid, and mechanical properties of the thin film. It is required to simultaneously satisfy various characteristics of the thin film such as dynamic strength, stability, optical characteristics, and electrical characteristics, and its selection is not easy,
In many cases, there is a problem that it is not always possible to select a binder resin that completely satisfies all the properties.

As a problem of the method using the liquid monomer, since the liquid monomer has a high reactivity of causing a polymerization reaction by itself, a high degree of disaster prevention / safety as compared with the case of using an organic solvent can be achieved. There is a problem that ancillary equipment for environmental protection is required.

As a subject of the method using gas molecules or molecular clusters, methods such as sublimation transfer method, vapor deposition method, vacuum vapor deposition method, ion beam method, and sputtering method can make only a vaporizable hydrophobic substance into a thin film by itself. Despite its advantages, it has a serious limitation that it cannot be applied to substances that are easily decomposed by vaporization or that are not vaporized. In addition, examples applicable to the plasma polymerization method and the photopolymerization method are limited.

As a problem associated with the use of a vacuum apparatus, an expensive large vacuum apparatus is required to manufacture a large-area and uniform thin film by a method such as a vacuum vapor deposition method, an ion beam method and a sputtering method. Further, it is not easy to efficiently carry out the operation of taking a large area thin film substrate into and out of the vacuum apparatus.

As a problem of the method utilizing melting or softening by heating, there is a problem of thermal stability in the first place, and there is a serious limitation that it cannot be applied to a thermally unstable substance. Secondly, there is the problem of thin film thickness, the hot pressing method,
It is extremely difficult to produce a thin film having a film thickness of less than 1 μm by a method such as an injection molding method, a stretching method, an electrostatic coating method using a meltable powder, or the like.

As a subject of the method utilizing electrolytic oxidation of a ferrocene residue-containing surfactant, firstly, there is no residue of the surfactant having a ferrocene residue and / or its oxidation product in the obtained thin film. Is difficult to
These may adversely affect the properties of the thin film of functional material. Secondly, there is a problem with the surface material of the conductive substrate or the electrode, and in the method utilizing electrolytic oxidation of the ferrocene residue-containing surfactant, the ferrocene residue is used as the material of the surface of the conductive substrate or electrode acting as an anode. There is a constraint that a material having a redox potential higher than that of the group-containing surfactant molecule must be used.

Therefore, the present invention aims to solve the above-mentioned drawbacks of the prior art and provide an azo compound useful for producing a thin film of a hydrophobic substance and a functional material.

[0019]

Means for Solving the Problems The present inventor has used a specific azo compound as a surfactant to add a hydrophobic substance to an aqueous solvent (water alone or a mixed solvent of water and an organic solvent compatible with water). ) In the solution solubilized or dispersed in, the supporting electrolyte is added as necessary, electrolysis is performed at a potential at which the components constituting the conductive substrate or the electrode acting as the cathode do not elute, and at the cathode surface, By electrolytically reducing the azo compound of 1., the solubilized state or dispersed state of the hydrophobic substance is destroyed in the vicinity of the cathode surface, and as a result, the surface of the conductive substrate or electrode that acts as the cathode with the hydrophobic substance. Therefore, they have found that they can be attached as a thin film, and arrived at the present invention.

The present invention provides the following general formula [I] R-φ ₁ -N = N-φ ₂ -O (CH ₂ ) _m O (CH ₂ C
H ₂ O) _n H [I] [wherein R represents a hydrogen atom or an alkyl group, φ
₁ and φ ₂ represent a p-phenylene group, m represents an integer of 1 or more, and n represents an integer of 1 or more, preferably 6 or more. ] It is an azo compound represented by.

[0021]

By using the azo compound of the present invention alone or in combination, the hydrophobic functional material is dispersed in the water-based solvent (water alone or a mixed solvent of water and an organic solvent compatible with water). Alternatively, it is solubilized, the azo compound is electrolytically reduced to break the dispersed state or the solubilized state, and a functional material is attached to the cathode surface, thereby, for example, an excellent color filter, an electrophotographic photoreceptor, an optical sensor, a solar cell. , Electroluminescence element, optical recording medium, non-linear optical element,
It is possible to provide an electro-optical element, a photochromic thin film, an electrochromic element, a gas sensor, an ion sensor and the like.

[0022]

EXAMPLES The present invention will now be described in more detail with reference to examples. In the following description, the proton nuclear magnetic resonance spectrum (hereinafter referred to as ¹ H
-Abbreviated as NMR. ) Is measured at a frequency of 270 MHz using chloroform-d ₁ as a solvent,
The chemical shift value (δ) is expressed in ppm with tetramethylsilane as an internal standard, the integrated value of the signal is expressed in terms of the number of hydrogen atoms H in the molecule, and the signal pattern is
A singlet is represented by s, a doublet is represented by d, a triplet is represented by t, a quartet is represented by q, and a multiplet is represented by m.
In addition, Fourier transform infrared absorption spectrum (hereinafter referred to as FT-
Abbreviated as IR. ) Is measured by applying the sample to a plate of potassium bromide.

Example 1 In the above general formula [I], R is n-hexyl, m is 2 and n is 13, that is, the following chemical structural formula (1)

[0024]

[Chemical 1] An azo compound represented by.

Synthesis Example 1 [azo compound (1) of Example 1]
Synthesis of 1) Synthesis of Synthetic Intermediate 4-Hexyl-4′-hydroxyazobenzene Acetone 20 cm ³ and concentrated hydrochloric acid 18.1 in 20 cm ³ of water.
cm ³ (0.2 mol) was mixed, and 12.4 g (0.07 mol) of pn-hexylaniline was added thereto with thorough stirring and dissolved. The solution was cooled and kept at 0 to 5 ° C., while stirring well, a solution of 5.09 g (0.07 mol) of sodium nitrite in 20 cm ³ of water was added dropwise over 10 minutes, and then stirred for 20 minutes. A diazonium solution was obtained. On the other hand, a coupler solution prepared by dissolving 6.58 g (0.07 mol) of phenol in a solution prepared by dissolving 3 g (0.075 mol) of sodium hydroxide and 12 g (0.11 mol) of sodium carbonate in 50 cm ³ of water was added at 15 to 20 ° C. And stir well,
The diazonium solution was added dropwise over 10 minutes and then stirred for 1 hour. The reaction solution was neutralized with dilute hydrochloric acid, and the precipitated solid was filtered, washed with water, and dried under reduced pressure. The obtained solid content is dissolved in benzene, developed on a silica gel (“Silica gel 60” manufactured by Merck & Co., Inc.) column, extracted with benzene to separate impurities, and then extracted with an ethanol / benzene mixed solvent, and the solvent is removed under reduced pressure. Was distilled off to give 4-hexyl-
4'-hydroxyazobenzene was obtained.

2) Synthesis of synthetic intermediate 4- (2-bromoethoxy) -4'-hexylazobenzene 4-hexyl-4'-hydroxyazobenzene 4.23 g (15 mmol), 1,2 in 80 cm ³ of 2-butanone.
-8.46 g (45 mmol) of dibromoethane, and
4.15 g (30 mmol) of potassium carbonate was mixed, heated with thorough stirring, and stirred under reflux for 3 days.
The solid matter is filtered off, the solvent of the filtrate is distilled off under reduced pressure, and the residue is dissolved in benzene.
0 ") column, extracted with benzene to separate impurities, and then extracted with benzene, and the solvent was distilled off under reduced pressure to give 4- (2-bromoethoxy) -4'-hexylazobenzene. Obtained. The ¹ H-NMR measurement result of this compound is as shown in FIG. 1, and the chemical shift value (integral value, signal pattern, and attribution) is 0.
89 (methyl group at 6-position of 3H, m, n-hexyl group),
1.33 (methylene group at 3,4,5-position of 6H, m, n-hexyl group), 1.66 (methylene group at 2-position of 2H, m, n-hexyl group), 2.68 (2H, methylene group at 1-position of t, n-hexyl group), 3.68 (2H, t, 2-
2-position methylene group of bromoethoxy group), and 4.3
8 ppm (methylene group at 1-position of 2H, t, 2-bromoethoxy group), 7.03 (2H,
d), 7.31 (2H, d), 7.81 (2H, d),
And 7.91 ppm (2H, d).

3) Synthesis of azo compound (1) Polyethylene having a polymerization degree n of 13 in 20 cm ³ of dimethoxyethane in the following general formula [II] HO (CH ₂ CH ₂ O) _n H [II] under a nitrogen atmosphere. Glycol 8.
0 g (13.5 mmol) and sodium hydride 0.3
g (12.5 mmol) were mixed and well stirred to dissolve. To this solution, 2.13 g (5.47 mmol) of 4- (2-bromoethoxy) -4′-hexylazobenzene was added, heated, and stirred under reflux for 24 hours. After allowing to cool, the solvent was distilled off under reduced pressure, 1-butanol and water were added, and the mixture was well stirred and then separated, and the solvent was distilled off from the organic layer under reduced pressure and dissolved in benzene to dissolve in silica gel (Merck). "Silica gel 60" column made, and extracted with benzene to separate impurities, and then further extracted with benzene, under reduced pressure,
The solvent was distilled off to obtain the azo compound (1) of Example 1.

When this product was dissolved in tetrahydrofuran and subjected to gel permeation chromatography analysis (hereinafter abbreviated as GPC), results supporting the formation of azo compound (1) were obtained. That is, the raw material azobenzene derivative and polyethylene glycol were not detected, and one sharp peak was observed at the retention time suggesting that the molecular weight was larger than these.

The calculated values as the chemical composition formula C ₄₆ H ₇₈ N ₂ O ₁₅ are 61.45% carbon, 8.74% hydrogen, and 3.12% nitrogen, and the elemental analysis result is 61.79 carbon.
%, Hydrogen 9.18%, and nitrogen 2.74%.

FT-IR of azo compound (1) of Synthesis Example 1
The measurement result was as shown in FIG. The ¹ H-NMR measurement results are shown in FIG. 3, and the results of analysis of chemical shift values, integrated values, signal patterns, and attributions are shown in Table 1.
Shown in.

From the above instrumental analysis results, it was confirmed that the product of Synthesis Example 1 was the azo compound (1) of Example 1.

Application Example 1 Copper phthalocyanine which has a maximum particle diameter of 0.2 μm or less when observed in a powder state with a scanning electron microscope and whose powder X-ray diffraction pattern belongs to a known β-type crystal form. Was dispersed in water using the azo compound (1) of Example 1 by ultrasonic irradiation in the presence of hydrochloric acid as a supporting electrolyte. At this time, the concentration of each component in the dispersion liquid was 0.45 g / dm ³ (0.5 mmol /
dm ³ ), 5 mmol / β-type copper phthalocyanine
dm ³ , and the supporting electrolyte was adjusted to be 0.1 mol / dm ³ .

This dispersion was charged into the electrolytic cell shown in FIG.
An indium-tin composite oxide thin film (hereinafter abbreviated as ITO) formed on one surface of a glass plate having a width of 10 mm, a long side of 20 mm, and a thickness of 1.1 mm was dispersed in a dispersion liquid for 10 m in the long side direction.
Immerse m, use this as the cathode, platinum mesh wire as the anode,
Using a saturated sweet koh electrode (hereinafter abbreviated as SCE) as a reference electrode, the voltage applied to the ITO electrode was adjusted to -0.5 V (vs. SCE) with a potentiostat, and the temperature was adjusted to 2
At 5 ° C., constant voltage electrolysis was performed, and the amount of electricity was measured with a coulometer (coulometer). It took about 30 minutes after the start of electrolysis, and an electric quantity of 30 millicoulomb was applied to produce a greenish blue thin film (width 10 mm, length 10 mm) on the ITO electrode. After completion of electrolysis, the ITO electrode was pulled up, washed with ion-exchanged water, and dried in a blower dryer controlled at 60 ° C.

When the surface and cross section of this film were observed with a scanning electron microscope (magnification: 10,000 times), the maximum particle size was 0.2.
It was found that particles having a size of μm or less were densely packed to form a porous film. In addition, the transmission spectrum pattern and X-ray diffraction pattern of this film show the same quality I as used above.
This was the same as a film formed by coating the β-type copper phthalocyanine dispersion on the TO electrode by a coating method. That is, the used pigment (β
It was confirmed that a thin film of the pigment could be produced without changing the particle size and the crystal type of the copper phthalocyanine (type copper phthalocyanine).

Example 2 In the above general formula [I], R is n-hexyl, m is 2 and n is 12, that is, the following chemical structural formula (2)

[0036]

[Chemical 2] An azo compound represented by.

Synthesis Example 2 [Azo compound (2) of Example 2]
Synthesis of Example 2 was carried out in the same manner as in Synthesis Example 1 except that polyethylene glycol having a degree of polymerization n of 12 was used.
The azo compound (2) was synthesized. The GPC analysis result of this compound suggested that the molecular weight was slightly smaller than that of the azo compound (1), and the FT-IR measurement result was completely equivalent to that of the azo compound (1) (FIG. 2). Also, ¹ H
-The NMR measurement results show that the azo compound (1) is the same except that the integral value of the multiplet of 3.60 to 3.75 ppm assigned to the polyoxyethylene portion is 48H.
Was very similar to the case (Fig. 3). From the above instrumental analysis results, it was confirmed that the structure was the azo compound (2).

Application Example 2 The azo compound (2) was used in place of the azo compound (1), an aluminum plate was used in place of ITO as the cathode, and constant current electrolysis was performed at a current density of 50 μA / cm ² for 1 hour. A β-type copper phthalocyanine thin film was manufactured on an aluminum plate in the same manner as in Application Example 1 except for the above.

Example 3 In the above general formula [I], R is n-hexyl, m is 2 and n is 14, that is, the following chemical structural formula (3)

[0040]

[Chemical 3] An azo compound represented by.

Synthesis Example 3 [Azo compound (3) of Example 3]
Synthesis of Example 3 Example 3 was repeated in the same manner as in Synthesis Example 1 except that polyethylene glycol having a degree of polymerization n of 14 was used.
The azo compound (3) was synthesized. The GPC analysis result of this compound suggested that the molecular weight was slightly larger than that of the azo compound (1), and the FT-IR measurement result was completely equivalent to that of the azo compound (1) (FIG. 2). ¹ H-NM
The R measurement result is very similar to that of the azo compound (1) (FIG. 3) except that the integral value of the multiplet of 3.60 to 3.75 ppm attributed to the polyoxyethylene portion is 56H. Was. From the above instrumental analysis results, it was confirmed that the structure was the azo compound (3).

Application Example 3 The azo compound (3) was used in place of the azo compound (1), an aluminum plate was used in place of ITO as the cathode, and constant current electrolysis was carried out at a current density of 50 μA / cm ² for 1 hour. A β-type copper phthalocyanine thin film was manufactured on an aluminum plate in the same manner as in Application Example 1 except for the above.

Synthesis Example 4 [Mixture of azo compounds of Examples 1 to 3] Polyethylene glycol having a degree of polymerization n of 12, 13,
And the azo compounds (1), (2), and (3) of Examples 1 to 3 in the same manner as in Synthesis Example 1 except that a mixture of 14 compounds (average degree of polymerization: 13) was used. The mixture was synthesized. The GPC analysis result of this compound indicates that it is a mixture of three adjacent azo compounds, suggesting that it is a mixture of three azo compounds.
The peak of the book was shown, and the FT-IR measurement result was exactly the same as in the case of the azo compound (1) (FIG. 2). ¹ H-NM
The R measurement result was also very similar to the case of the azo compound (1) (FIG. 3).

Application Example 4 Azo compounds (1), (2), and
In the same manner as in Application Example 1 except that the mixture of (3) was used, I
A β-type copper phthalocyanine thin film was manufactured on the TO electrode.

Examples 4 to 20 Instead of pn-hexylaniline in Synthesis Example (1), aniline, p-toluidine, p-ethylaniline, pn-propylaniline, pn-butylaniline, p -N-pentylaniline, pn-heptylaniline, pn-octylaniline, pn-nonylaniline, pn-decylaniline, pn-undecylaniline, or pn-dodecylaniline , 1,
Instead of 2-dibromoethane, dibromomethane, 1,3
-Dibromopropane, 1,4-dibromobutane, 1,5
-Dibromopentane, 1,6-dibromohexane, or 1,12-dibromododecane was used, and polyethylene glycol having various degrees of polymerization was used.
In the same manner as in Examples 4 to 20 (4)
To (20) were synthesized. FT of these azo compounds
All -IR were very similar to those in Example 1 (Fig. 2). For example, the FT-IR measurement result in the case of Example 7 is shown in FIG. On the other hand, ¹ H-NMR showed a pattern that well reflected the characteristics of each structure. For example, ¹ H-NMR of the azo compounds of Examples 6, 7, 14 and 16
The measurement results are shown in FIGS. Table 1 shows the ¹ H-NMR analysis results (chemical shift, integrated value, signal pattern, and attribution) of the azo compounds of Examples 1 to 20.

[0046]

[Chemical 4]

[0047]

[Chemical 5]

[0048]

[Chemical 6]

[0049]

[Chemical 7]

[0050]

[Chemical 8]

[0051]

[Chemical 9]

[0052]

[Chemical 10]

[0053]

[Chemical 11]

[0054]

[Chemical 12]

[0055]

[Chemical 13]

[0056]

[Chemical 14]

[0057]

[Chemical 15]

[0058]

[Chemical 16]

[0059]

[Chemical 17]

[0060]

[Chemical 18]

[0061]

[Chemical 19]

[0062]

[Chemical 20]

[0063]

[Table 1] Example compound chemical shift integral value signal proton assignmentNumber Number [ppm] Pattern 1 1 0.89 3H m 6-position (terminal) of hexyl group 1.32 6H m 3,4,5 position of hexyl group 1.652 2H m 2 position of hexyl group 2.68 2H t 1-position of hexyl group 3 .60-3.75 52H m polyoxyethylene part 3.902 Ht φ_Two2nd position of adjacent oxyethylene 4.22 2H t φ_Two1st position of adjacent oxyethylene 7.03 2H d phenylene φ_TwoPosition of the azo group of 7.31 2H d phenylene φ₁M-position of azo group of 7.82 2H d phenylene φ₁O position of azo group 7.92 2H d o-position of azo group of phenylene φ ₂  2 2 0.89 3H m Hexyl group 6-position (terminal) 1.32 6H m Hexyl group 3,4,5 position 1.66 2H m Hexyl group 2 position 2.68 2H t Hexyl group 1-position 3 .60-3.75 48H m polyoxyethylene part 3.902 Ht φ_Two2nd position of adjacent oxyethylene 4.22 2H t φ_Two1st position of adjacent oxyethylene 7.03 2H d phenylene φ_TwoPosition of the azo group of 7.31 2H d phenylene φ₁Position of the azo group of 7.81 2H d phenylene φ₁O position of azo group 7.91 2H d phenylene φ ₂ o position of azo group 3 3 0.89 3H m Hexyl group 6-position (terminal) 1.32 6H m Hexyl group 3,4,5 position 1.652 2H m Hexyl group 2 position 2.68 2H t Hexyl group 1-position 3 .60-3.75 56H m polyoxyethylene part 3.902 Ht φ_Two2nd position of adjacent oxyethylene 4.22 2H t φ_Two1st position of adjacent oxyethylene 7.03 2H d phenylene φ_TwoPosition of the azo group of 7.31 2H d phenylene φ₁Position of the azo group of 7.81 2H d phenylene φ₁O position of azo group 7.92 2H d o-position of azo group of phenylene φ ₂  4 4 3.60 to 3.75 40H m polyoxyethylene part 3.902 Ht φ_Two2nd position of adjacent oxyethylene 4.22 2H t φ_Two1st position of adjacent oxyethylene 7.01 2H d phenylene φ_TwoM-position of the azo group of 7.45 1H m phenyl φ₁Position of the azo group of 7.51 2H m phenyl φ₁M-position of the azo group of 7.89 2H m phenyl φ₁O position of azo group7.92 2H d o-position of azo group of phenylene φ ₂  5 5 2.25 2H m φ_TwoAdjacent oxypropylene 2-position 3.60-polyoxyethylene moiety and 3.75 62H m φ_TwoAdjacent oxypropylene 3-position 4.12 2H t φ_TwoAdjacent oxypropylene 1-position 7.00 2H d phenylene φ_TwoM-position of the azo group of 7.45 1H m phenyl φ₁Position of the azo group of 7.51 2H m phenyl φ₁Position of the azo group of 7.88 2H m phenyl φ₁O position of azo group7.92 2H d o-position of azo group of phenylene φ ₂  6 6 1.79 2H m oxytetramethylene 2 or 3 position 1.91 2H m oxytetramethylene 2 or 3 position 3.562 2H t 4 position of oxytetramethylene 3.60-3.75 52H m polyoxyethylene moiety 4.08 2H t 1-position of oxytetramethylene 7.01 2H d phenylene φ_TwoM-position of the azo group of 7.45 1H m phenyl φ₁Position of the azo group of 7.51 2H m phenyl φ₁M-position of the azo group of 7.89 2H m phenyl φ₁O position of azo group7.92 2H d o-position of azo group of phenylene φ ₂  7 7 1.46 4H m oxyhexamethylene 3 and 4 position 1.63 2H m oxyhexamethylene 2 or 5 position 1.83 2H m oxyhexamethylene 2 or 5 position 3.48 2H t 6 position of oxyhexamethylene 3 .60-3.75 52H m polyoxyethylene moiety 4.05 2H t 1-position of oxyhexamethylene 7.00 2H d phenylene φ_TwoM-position of the azo group of 7.45 1H m phenyl φ₁Position of the azo group of 7.51 2H m phenyl φ₁Position of the azo group of 7.88 2H m phenyl φ₁O position of azo group 7.92 2H d o-position of azo group of phenylene φ ₂  8 8 1.28 to 1.60 18H m dodecyl methylene moiety 1.83 2H m dodecyl methylene moiety 3.42 2H t 12-position of dodecyl methylene 3.60 to 3.75 176 H m polyoxyethylene moiety 4.04 2H t 1st position of oxidodecyl methylene 7.00 2H d phenylene φ_TwoM-position of the azo group of 7.44 1H m phenyl φ₁Position of the azo group of 7.51 2H m phenyl φ₁M position of azo group of 7.87 2H m phenyl φ₁O position of azo group 7.91 2H d phenylene φ ₂ o position of azo group 9 9 2.23 3Hs methyl group 3.60 to 3.75 64H m polyoxyethylene moiety 3.89 2H t φ_Two2nd position of adjacent oxyethylene 4.21 2H t φ_Two1st position of adjacent oxyethylene 7.02 2H d phenylene φ_TwoPosition of the azo group of 7.31 2H d phenylene φ₁M-position of azo group of 7.82 2H d phenylene φ₁O position of azo group 7.91 2H d phenylene φ ₂ o position of azo group 10 10 1.03 3H t Terminal methyl of ethyl group 1.79 2H m oxytetramethylene 2 or 3-position 1.91 2H m oxytetramethylene 2 or 3-position 2.58 2H q Ethyl-based methylene 3.562 2H t 4-position of oxytetramethylene 3.60 to 3.75 72H m polyoxyethylene moiety 4.092Ht 1-position of oxytetramethylene 7.03 2H d phenylene φ_TwoPosition of the azo group of 7.31 2H d phenylene φ₁Position of the azo group of 7.81 2H d phenylene φ₁O position of azo group 7.92 2H d o-position of azo group of phenylene φ ₂  11. 11 11 0.93 3H t propyl group 3-position (terminal) 1.662 2H m propyl group 2-position 2.67 2H t propyl group 1-position 3.60 to 3.75 60H m polyoxyethylene moiety 5. 90 2H s φ_TwoAdjacent oxymethylene 7.02 2H d phenylene φ_TwoM-position of the azo group of 7.30 2H d phenylene φ₁M-position of azo group of 7.82 2H d phenylene φ₁O position of azo group 7.92 2H d o-position of azo group of phenylene φ ₂  12 12 0.90 3H t butyl group 4 position (terminal) 1.33 2H m butyl group 3 position 1.662 2H m butyl group 2 position 2.68 2H t butyl group 1 position 3.60-3 0.75 80H m polyoxyethylene part 3.90 2H t φ_Two2nd position of adjacent oxyethylene 4.22 2H t φ_Two1st position of adjacent oxyethylene 7.03 2H d phenylene φ_TwoPosition of the azo group of 7.31 2H d phenylene φ₁Position of the azo group of 7.81 2H d phenylene φ₁O position of azo group 7.92 2H d o-position of azo group of phenylene φ ₂  13 13 0.89 3H t 5-position (end) of pentyl group 1.32 4H m 3- and 4-position of pentyl group 1.46 4H m oxyhexamethylene 3 and 4-position 1.60-oxyhexamethylene 2 or 5-position 1.70 4H m and 2-position of pentyl group 1.83 2H m oxyhexamethylene 2 or 5 position 2.68 1-position of 2H t pentyl group 3.48 6-position of 2H t oxyhexamethylene 3.60-3. 75 96H m polyoxyethylene moiety 4.05 2H t 1-position of oxyhexamethylene 7.03 2H d phenylene φ_TwoM-position of the azo group of 7.30 2H d phenylene φ₁M-position of azo group of 7.82 2H d phenylene φ₁O position of azo group 7.91 2H d phenylene φ ₂ o position of azo group 14 14 0.89 3H m 6-position (terminal) of hexyl group 1.32 6H m 3,4,5-position of hexyl group 1.662 2H m 2-position of hexyl group 2.68 2H t 1-position of hexyl group 3 .60-3.75 88H m polyoxyethylene part 3.902 Ht φ_Two2nd position of adjacent oxyethylene 4.22 2H t φ_Two1st position of adjacent oxyethylene 7.03 2H d phenylene φ_TwoPosition of the azo group of 7.31 2H d phenylene φ₁Position of the azo group of 7.81 2H d phenylene φ₁O position of azo group 7.91 2H d phenylene φ ₂ o position of azo group 15 15 0.89 3H m 7-position (terminal) of heptyl group 1.318 3H of heptyl group 3,4,5,6 position 1.662 2H of heptyl group 2.68 2H t 1 of heptyl group Position 3.60 to 3.75 68H m polyoxyethylene part 5.90 2H s φ_TwoAdjacent oxymethylene 7.03 2H d phenylene φ_TwoM-position of the azo group of 7.30 2H d phenylene φ₁M-position of azo group of 7.82 2H d phenylene φ₁O position of azo group 7.91 2H d phenylene φ ₂ o position of azo group 16 16 0.88 3H m 8th position of octyl group (terminal) 1.31 10Hm 3rd position to 7th position of octyl group 1.662 2Hm 2nd position of octyl group 2.68 2H t 1st position of octyl group 3. 60-3.75 88H m polyoxyethylene part 3.902 Ht φ_Two2nd position of adjacent oxyethylene 4.22 2H t φ_Two1st position of adjacent oxyethylene 7.03 2H d phenylene φ_TwoM-position of the azo group of 7.30 2H d phenylene φ₁M-position of azo group of 7.82 2H d phenylene φ₁O position of azo group 7.92 2H d o-position of azo group of phenylene φ ₂  17 17 0.88 3H m 9-position (terminal) of nonyl group 1.31 12H m Nonyl group 3-position 8-8 1.662 2H m nonyl group 2-position 1.792 2H m oxytetramethylene 2 or 3 position 1.91 2H m oxytetramethylene 2 or 3 position 2.68 2H t 1 position of nonyl group 3.56 2H t 4 position of oxytetramethylene 3.60 to 3.75 120H m polyoxyethylene moiety 4.08 2H 1-position of t oxytetramethylene 7.02 2H d phenylene φ_TwoPosition of the azo group of 7.31 2H d phenylene φ₁M-position of azo group of 7.82 2H d phenylene φ₁O position of azo group 7.91 2H d phenylene φ ₂ o position of azo group 18 18 0.88 10-position (terminal) of 3H m decyl group 1.31 3 to 9-position of 14 H m decyl group 1. 6-position of 2 Hm decyl group 2. 1-position of 2 68 2 H t decyl group 3. 60-3.75 100Hm polyoxyethylene part 3.902Htφ_Two2nd position of adjacent oxyethylene 4.22 2H t φ_Two1st position of adjacent oxyethylene 7.03 2H d phenylene φ_TwoM-position of the azo group of 7.30 2H d phenylene φ₁Position of the azo group of 7.81 2H d phenylene φ₁O position of azo group 7.92 2H d o-position of azo group of phenylene φ ₂  19 19 0.88 3H m Undecyl group 11-position (terminal) 1.31 16H m undecyl group 3-position 10-6. 66 2H m undecyl group 2-position 2.68 2H t undecyl group 1-position 3. 60-3.75 80H m polyoxyethylene part 3.902 Ht φ_Two2nd position of adjacent oxyethylene 4.22 2H t φ_Two1st position of adjacent oxyethylene 7.03 2H d phenylene φ_TwoPosition of the azo group of 7.31 2H d phenylene φ₁M-position of azo group of 7.82 2H d phenylene φ₁O position of azo group 7.92 2H d o-position of azo group of phenylene φ ₂  20 20 0.88 3H t 12-position (terminal) of dodecyl group 1.31 18H m 3- to 11-position of dodecyl group 1.46 4H m oxyhexamethylene 3 and 4-position 1.60 to oxyhexamethylene 2 or 5 Position 1.70 4H m and 2-position of dodecyl group 1.83 2H m oxyhexamethylene 2 or 5 position 2.68 2H t 1-position of dodecyl group 3.48 2H t 6-position of oxyhexamethylene 3.60-3 0.75 104H m polyoxyethylene moiety 4.05 2H t 1-position of oxyhexamethylene 7.03 2H d phenylene φ_TwoM-position of the azo group of 7.30 2H d phenylene φ₁M-position of azo group of 7.82 2H d phenylene φ₁O position of azo group 7.91 2H d phenylene φ ₂ o position of azo group

Application Example 5 Instead of the copper phthalocyanine in Application Example 1, monochloro copper phthalocyanine (maximum particle size 0.2 μm) was used as a pigment.
The following) were used, the azo compounds of Examples 4 to 20 were used in place of the azo compound (1) in Application Example 1, and the dispersion was carried out by a ball mill instead of ultrasonic treatment to obtain a current density of 5
A blue thin film was produced on the electrode in the same manner as in Application Example 1 except that constant current electrolysis was performed at 0 μA / cm ² for 1 hour.

[0065]

[Effect] By using the azo compound of the present invention alone or in combination, a hydrophobic substance and a function are obtained by a wet method using water alone or a mixed solvent of water and an organic solvent compatible with water. A thin film of material can be produced, with the amount of binder resin or liquid monomer used being zero or minimal.

By using the azo compound of the present invention,
It is possible to manufacture a hydrophobic substance and functional material that is easily decomposed by vaporization, a hydrophobic substance and functional material that is not vaporized, or a thin film of a hydrophobic substance and functional material that is easily decomposed by heat.

By using the azo compound of the present invention,
A large area and uniform thin film of a hydrophobic substance and a functional material can be produced without using expensive equipment.

By using the azo compound of the present invention,
It is possible to manufacture a uniform thin film of a hydrophobic substance and a functional material having a controlled film thickness in the range of several tens nm to several μm.

By using the azo compound of the present invention,
It is possible to produce a large-area and uniform thin film of a hydrophobic substance and a functional material without being restricted by the surface material of the conductive substrate or the electrode.

[0070]

[Brief description of drawings]

FIG. 1 Synthetic intermediate 4- (2-bromoethoxy)-
270 MHz ¹ H-NM of 4'-hexylazobenzene
It is an R measurement result.

2 is an FT-IR measurement result of the azo compound (1) of Example 1. FIG.

FIG. 3 shows the azo compound (1) of Example 1 at 270 MHz.
^{It is a 1} H-NMR measurement result.

FIG. 4 is an example of an electrolysis apparatus for producing a thin film.

5 is an FT-IR measurement result of the azo compound (7) of Example 7. FIG.

6] 270 MHz of azo compound (6) of Example 6
^{It is a 1} H-NMR measurement result.

FIG. 7: 270 MHz of azo compound (7) of Example 7
^{It is a 1} H-NMR measurement result.

FIG. 8: 270M of azo compound (14) of Example 14
It is a result of Hz ¹ H-NMR measurement.

FIG. 9: 270M of azo compound (16) of Example 16
It is a result of Hz ¹ H-NMR measurement.

[0071]

[Explanation of symbols]

 B ... Residual solvent (benzene) C ... Chloroform W ... Water 1 ... Conductive substrate (cathode) 2 ... Platinum mesh (anode) 3 ... Salt bridge (connect to SCE) 4 ... Electrolyte container 5 ... Rubber stopper 6 ... Glass filter 7 ... Clamp (spring type) 8 ... Electrode holder 9 ... Conductor

Claims (1)

[Claims] 1. The following general formula [I] R-φ ₁ -N = N-φ ₂ -O (CH ₂ ) _m O (CH ₂ C
H ₂ O) _n H [I] [wherein R represents a hydrogen atom or an alkyl group, φ ₁ and φ ₂ represent a p-phenylene group, m represents an integer of 1 or more, and n represents 1 It represents an integer of at least 6, preferably at least 6. ] The azo compound represented by this.