JPH09279054A - Azo compound - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a high-quality thin film by using a specific azo compd. or a specific polymer compsn. comprising an azo compd. for forming a thin film. SOLUTION: Polyethylene glycol diglycidyl ether having a specified degree of polymn. is dissolved in a solvent (e.g. thrahydrofuran). An equimolar amt. of 4-n-butyl-4'-hydroxyazobenzene is added together with a catalyst (e.g. tetrabutylammonium hydroxide) to the resultant soln. under stirring. The soln. is then refluxed under heating for about 20-30hr, refluxed further after the addition of water to it, cooled, and subjected to a reduced pressure to remove the solvent. The resultant org. layer is concentrated under a reduced pressure and extracted, this giving an azo compd. represented by formula II(wherein R<1> is a 6-14C arly; R<2> is a 6-14C arylene; R<3> is a 3-6C hydroxyalkyl, a 1-6C alkylcarbonyl, etc.; and (n) is 1-100) (e.g. a compd. represented by formula I) or a polymer compsn. represented by formula III (wherein (m) is 10-100). The azo compd. or the polymer compsn. is added together with β-copper phthalocyanine to water to give a dispersion having a specified concn., in which a copper plate is immersed for about 20min to give a greenish-blue thin film.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to an azo compound and a polymer composition comprising the azo compound. More specifically, the present invention relates to an azo compound useful for producing a thin film using an aqueous dispersion containing a hydrophobic functional material such as a dye or a photoconductive material, and a polymer composition comprising the azo compound. is there.

[0002]

2. Description of the Related Art Dyes, charge generating materials, charge transporting materials, electroluminescent materials, photosensitive dyes, non-linear optical materials, electro-optical materials, photochromic materials, etc. are used to manufacture functional elements such as color filters and optical sensors.
It is necessary to use functional materials such as electrochromic materials, gas sensing materials, and ion sensing materials to form their uniform thin films on the device. When forming a thin film using a hydrophobic functional material, a wet method using a solution or dispersion, a method utilizing polymerization or polycondensation reaction of a liquid monomer, a method using a gas molecule or a gaseous monomer, melting by heating Alternatively, a method utilizing softening, a method utilizing electrolytic oxidation of a ferrocene residue-containing surfactant, or the like is adopted. However, these methods have various inherent problems (for the thin film forming method and its problems, refer to JP-A-7-179773
See column 3).

There is proposed an azo compound useful for producing a thin film of a hydrophobic substance and a functional material by solving the drawbacks of the conventional thin film forming method (JP-A-7-179773).
The azo compound described in the above publication is used as a surfactant to dissolve or disperse a hydrophobic substance in water or a homogeneous mixture of water and an organic solvent, and a supporting electrolyte is added if necessary, and then the azo compound is added. When electrolytically reducing the, the solubilized state or dispersed state of the hydrophobic substance is destroyed near the cathode surface,
Hydrophobic material is deposited as a thin film on the surface of a conductive substrate or electrode that acts as a cathode.

When the above azo compound is used, it is possible to reduce the amount of the binder resin or liquid monomer used for suppressing the crystal transition and aggregation of the hydrophobic substance fine particles in the organic solvent, so that the amount of the binder resin or liquid monomer can be reduced. Since the amount of the functional material per unit volume can be increased, the performance of the functional element can be improved. However, this compound is synthesized through complicated manufacturing steps, and it has been difficult to mass-produce high-purity products at low cost. Further, there is a limit to the compounding ratio of the hydrophobic substance and the azo compound in the solution or dispersion used for forming the thin film, and there is a problem that the thin film formation becomes difficult if the compounding ratio exceeds a certain level.

[0005]

An object of the present invention is to provide an azo compound having the above-mentioned thin film-forming action, which can be produced easily and inexpensively from easily available raw materials in a short process. To provide. Another object of the present invention is to provide an azo compound capable of stably producing a thin film from a solution or dispersion containing a hydrophobic substance or a hydrophobic functional material and an azo compound in various compounding ratios.

[0006]

Means for Solving the Problems As a result of diligent efforts to solve the above problems, the present inventor has found that a compound represented by the following formula is less than the azo compound described in JP-A-7-179773. It was found that a thin film can be produced with a hydrophobic substance or a hydrophobic functional material at various compounding ratios, and that the compound can be produced inexpensively and easily from easily available raw materials. Further, the present inventors have found that the compound can be used very suitably in a thin film forming process by an electroless method such as an immersion plating method or a contact plating method. The present invention has been completed based on these findings.

That is, the present invention provides the following formula (I): R ¹ -N = NR ² -O-CH ₂ -CH (OH) -CH ₂ -O-(-CH ₂ CH ₂ O-) _n -R ³ (In the formula, R ¹ represents an optionally substituted C _6-14 aryl group; R ² represents an _optionally substituted C _6-14 aryldiyl group; R ³ represents A C _3-6 alkyl group having a hydroxyl group, a C _1-6 alkylcarbonyl group, or a C _6-14 arylcarbonyl group; n represents an integer of 1 to 100).

According to another aspect of the present invention, the following formula (II): R ¹ -N = NR ² -O-CH ₂ -CH (OH) -CH ₂ -O-(-CH ₂ CH ₂ O-) _m -R ³ (In the formula, R ¹ represents a C _6-14 aryl group which may have a substituent; R ² represents a C _6-14 aryldiyl which may have a substituent. Represents a group; R ³ represents a C _3-6 alkyl group having a hydroxyl group, a C _1-6 alkylcarbonyl group, or a C _6-14 arylcarbonyl group; m is an average degree of polymerization selected from the range of 10 to 100 The present invention provides a polymer composition represented by

According to a preferred embodiment of these inventions, R ¹
Is a phenyl group or a naphthyl group (these may have one or more substituents selected from the group consisting of C _1-12 alkyl groups and C _1-12 alkoxy groups, preferably one substituent) And R ² is a phenylene group or a naphthalenediyl group, and R ³ is a group selected from the group consisting of a C _1-6 alkylcarbonyl group, a benzoyl group, and a 2,3-dihydroxypropan-1-yl group. And n is an integer of 1 to 100 and m is in the range of 10 to 50, respectively.

[0010]

BEST MODE FOR CARRYING OUT THE INVENTION In the above formulas (I) and (II),
R ¹ represents an optionally substituted aryl group having 1 to 14 carbon atoms (C _6-14 ). As the aryl group, for example, a monocyclic or condensed bicyclic aryl group can be used, and more specifically, for example, a phenyl group, a naphthyl group, an azulenyl group, a phenanthrene group, or an anthracene group can be used. it can. Of these, a phenyl group or a naphthyl group can be preferably used. As the naphthyl group, either a 1-naphthyl group or a 2-naphthyl group may be used.

These aryl groups may have one or more substituents, preferably one substituent. As the substituent, for example, a C _1-12 alkyl group, a C _1-12 alkoxy group, a hydroxyl group, a halogen atom or the like can be used. The alkyl group or alkoxy group may be linear, branched or cyclic. More specifically, as the C _1-12 alkyl group, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group,
sec-butyl group, tert-butyl group, n-pentyl group, neopentyl group, n-hexyl group, n-heptanyl group, n-octyl group, n-nonyl group, n-decanyl group, n-undecanyl group, or n -A dodecanyl group or the like can be used.

The C _1-12 alkoxy group includes methoxy group, ethoxy group, n-propoxy group, isopropoxy group,
n-butoxy group, sec-butoxy group, n-pentoxy group, neopentoxy group, n-hexoxy group, n-heptanyloxy group, n-octyloxy group, n-nonyloxy group, n-decanyloxy group, n-undecanyloxy group Group or an n-dodecanyloxy group can be used. The substitution position of these substituents on the aryl group is not particularly limited.
Among the aryl groups represented by R ^1, particularly preferred aryl groups are an unsubstituted phenyl group, a phenyl group having one C _1-12 alkyl group or a C _1-12 alkoxy group at the p-position, and an unsubstituted 1-naphthyl group. Group or an unsubstituted 2-naphthyl group.

In the above formulas (I) and (II), R ² represents a C _6-14 aryldiyl group which may have a substituent.
As the aryldiyl group, for example, a phenylene group, a naphthalenediyl group, an azulenediyl group, a phenanthrenediyl group, an anthracenediyl group, or the like can be used. Of these, a phenylene group or a naphthalenediyl group can be preferably used. The phenylene group may be any of an o-phenylene group, an m-phenylene group, or a p-phenylene group, and a naphthalenediyl group may be a naphthalene-1,3-diyl group or a naphthalene-1,4-diyl group. Group, naphthalene-2,4-diyl group, naphthalene-1,5-diyl group, naphthalene-1,6-diyl group, or any naphthalene diyl group such as naphthalene-2,6-diyl group can be used. .

These aryldiyl groups may be 1 or 2
It may have one or more, preferably one substituent.
As the substituent, for example, a C _1-6 alkyl group, a C _1-6 alkoxy group, a hydroxyl group, a halogen atom or the like can be used. As the C _1-6 alkyl group, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, sec-
A butyl group, a tert-butyl group, an n-pentyl group, a neopentyl group, or an n-hexyl group can be used, and as the C _1-6 alkoxy group, a methoxy group, an ethoxy group, an n-propoxy group, an isopropoxy group. , N-butoxy group, sec-butoxy group, n-pentoxy group, neopentoxy group, or n-hexoxy group can be used. C of these
It is preferable to use _1-6 alkyl groups. The substitution position of these substituents on the aryldiyl group is not particularly limited. Among the aryldiyl groups represented by R ^2, particularly preferable aryldiyl groups include an unsubstituted p-phenylene group, a p-phenylene group having one C _1-6 alkyl group,
An unsubstituted naphthalene-1,4-diyl group and the like can be mentioned.

R ³ is a C _3-6 alkyl group having a hydroxyl group, C _1-6
An alkylcarbonyl group or a C _6-14 arylcarbonyl group is shown. Examples of the alkyl chain forming the alkyl group having a hydroxyl group include n-propyl, isopropyl, n-butyl, se
c-butyl, tert-butyl, n-pentyl, neopentyl,
Alternatively, n-hexyl or the like can be used. The number of hydroxyl groups contained in the alkyl group is not particularly limited, and 1 or 2
It preferably has two hydroxyl groups. When the alkyl group has two hydroxyl groups, it is preferable that the hydroxyl groups are respectively substituted on two adjacent carbon atoms. As an example of this, for example,
2,3-dihydroxypropan-1-yl group [-CH ₂ CH (OH) CH-O
H] and so on.

[0016] C of C _1-6 alkylcarbonyl group represented by R ³ _1-6
As the alkyl group, those exemplified above can be preferably used, and as the C _1-6 alkylcarbonyl group, an acetyl group, an ethylcarbonyl group, an n-propylcarbonyl group or the like can be used. Examples of the arylcarbonyl group include a benzoyl group and a naphthylcarbonyl group. As R ³ , an acetyl group, a propionyl group, a benzoyl group, or 2,3-dihydroxypropane-1-
Particularly preferred is an yl group.

In the formula (I), n represents an integer of 1 to 100, and it is preferable that n is an integer of 10 to 70. Also, the formula
In (II), m represents an average degree of polymerization selected from the range of 10 to 100, preferably 10 to 50. When the compound of formula (I) is produced by a polymerization process, in addition to the main product in which n is an integer k, other compounds (n = k ± s: s is, for example, an integer of 1 to 10) may be produced at the same time. Such a reaction product contains a compound of n = k as a main product and has a degree of polymerization of k.
However, it goes without saying that such a polymer composition is also included in the scope of the present invention.

The average degree of polymerization can be measured by, for example, average molecular weight measurement using gel filtration chromatography or molecular weight distribution measurement, but the method is not limited thereto and can be used by those skilled in the art. Any thing may be used as long as it is a thing. Also, referring to the description of the examples of the present specification, those skilled in the art can produce a polymer composition having a desired degree of polymerization distribution or average degree of polymerization by appropriately modifying or modifying reaction conditions, reagents and the like. It is possible. Further, from such a polymer composition, for example, by means such as liquid chromatography, n = k and n = k.
It is possible to isolate and purify each compound having +1.

The compound represented by the formula (I) of the present invention has asymmetric carbons substituted by two secondary hydroxyl groups present in the molecule, as well as R ¹ and / or R ² depending on the kind. Further, it may have an asymmetric carbon. Any optically pure optical isomers based on these asymmetric carbons, mixtures of any optical isomers in any ratio, racemates, any pure diastereomers based on two or more asymmetric carbons, Any mixtures of any diastereomers in any proportion are within the scope of the invention.

Hereinafter, among the compounds of the present invention represented by the formula (I), preferred compounds will be exemplified, but the scope of the present invention is not limited to these preferred compounds. Particularly preferred compounds are compounds 1, 2, 3, 9 and 10.

[0021]

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[0022]

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[0023]

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[0024]

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[0025]

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[0026]

[Chemical 6]

[0027]

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[0028]

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[0029]

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The compounds of formula (I) of the present invention are, for example, R ¹ -N
It can be easily produced by reacting a compound (III) represented by ═NR ² —OH (the definition in the formula is the same as above) with a glycidyl derivative of polyethylene glycol. As the polyethylene glycol / glycidyl derivative, for example, polyethylene glycol / diglycidyl ether can be used. The above reaction can be carried out, for example, in a solvent such as tetrahydrofuran, preferably in the presence of a catalyst such as tetrabutylammonium hydroxide, and generally, at a reflux temperature of the solvent for about 10 to 50 hours, preferably Is completed in about 20 to 30 hours.

4-butyl-4'-hydroxyazobenzene was used as the raw material compound (III), and polyethylene glycol
Compound as glycidyl derivative (IV): by reacting a polyethylene glycol diglycidyl ether, R ¹ = p-CH ₃ in formula _{(I) (CH 2) 3} -C 6 H 4 -; R 2 = pC 6 H 4 -; R ³ = CH ₂ -CH
A scheme for producing a compound of (OH) -CH ₂ OH; and n = 22 is shown below, but the production method of the compound of the present invention is not limited to the following method.

[0032]

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A method for producing a compound in which R ³ is an alkylcarbonyl group or an arylcarbonyl group is shown in the following scheme. In the scheme, R ⁵ represents a substituent on the aryl group represented by R ¹ , such as a C _1-6 alkyl group, and R ₆ represents C 1.
_1-6 represents an aryl group such as an alkyl group or a phenyl group. In the production of a compound in which R ³ is an alkylcarbonyl group or an arylcarbonyl group, the intermediate compound (V) having an ester group can be prepared by reacting a corresponding carboxylic acid anhydride or acid halide with a polyoxyethylene compound. Can be manufactured (New Experimental Chemistry Course Volume 14,
Synthesis and Reactions of Organic Compounds II, pp.1012-1016, edited by The Chemical Society of Japan, published by Maruzen Co., Ltd., 1978).

[0034]

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The glycidyl derivative used as a raw material can be produced, for example, according to the production method shown in the following scheme (for example, New Experimental Chemistry Course, Vol. 19, Polymer Chemistry I, pp.227-229 and pp.295-. 298, edited by The Chemical Society of Japan, published by Maruzen Co., Ltd., 1978; New Experimental Chemistry Course, Volume 19, Organic Compound Synthesis, pp.196-197, edited by The Chemical Society of Japan, published by Maruzen Co., Ltd., 1959 ).

[0036]

[Chemical 12]

When the polyethylene glycol / glycidyl derivative used as a raw material is a polymer composition having an average degree of polymerization m (for example, in the above scheme, 22 attached to the repeating unit of the compound of the formula (IV) has an average degree of polymerization of (Where indicated), according to the scheme above, the formula for average degree of polymerization m
The polymer composition of (II) can be produced. Further, a method for producing polyoxyethylene having almost no molecular weight distribution is known (Aida, T. et al., Macromolecules, 1
4, pp.1162-1166, 1981; Aida, T. et al., Macromolec
ules, 21, pp.1195-1202, 1988), it is possible to produce a compound of formula (I) by using such polyoxyethylene. As is clear from the above scheme, the compound and polymer composition of the present invention are shorter than conventionally known compounds or polymer compositions (for example, the compounds described in JP-A-7-179773). It has a feature that it can be manufactured easily and inexpensively in the process.

The compound or polymer composition of the present invention is useful for producing a thin film using a hydrophobic substance or a hydrophobic functional material. For example, a compound or composition selected from the group consisting of the compound of the present invention, a polymer composition, and any mixture thereof is used as a surfactant, and a hydrophobic substance or a hydrophobic functional material is mixed with water or an organic solvent. Dispersed or dissolved in a uniform mixture with water, and then subjecting the dispersion or solution to electrolytic reduction, the dispersion or solubilized state of the hydrophobic substance or the hydrophobic functional material is destroyed in the vicinity of the cathode surface, A hydrophobic substance or a hydrophobic functional material is deposited as a thin film on the surface of a conductive substrate or electrode that acts as a cathode.

The type of conductive substrate or electrode used as the cathode is not particularly limited, and any shape and material can be used. The thickness of the thin film is generally several μm to several tens of μm, and a uniform thin film can be formed in an arbitrary area. As a method for forming the thin film, for example, the methods described in JP-A Nos. 7-62594 and 7-179773 can be adopted.

The compound or polymer composition of the present invention may be used as a thin film forming agent in the electroless thin film forming step. The electroless thin film forming step does not require a constant voltage electrolyzer, and is characterized in that a simple device can be used to form a high quality thin film easily at low cost. Examples of the electroless thin film forming process that can suitably use the thin film forming agent of the present invention include a dipping plating process or a contact plating process, or a plating process by a combination of these processes.

In the immersion plating step, the compound or polymer composition of the present invention is used to disperse a hydrophobic compound or the like, and a substrate having a metal surface in which the compound or polymer composition is more susceptible to metal ions than the compound or polymer composition. Can be performed by dipping. Since metal ions are eluted from the immersed metal surface and electrons accumulate on the metal surface, the compound or polymer composition of the present invention is reduced by the electrons, and the compound or polymer composition of the present invention disperses. The formed hydrophobic compound adheres to the metal surface of the substrate to form a thin film.

Examples of metals that can be suitably used in the immersion plating process include copper, cobalt, chromium, nickel, molybdenum, lead, tin, iron, titanium, vanadium, zinc, aluminum and magnesium.
Further, alloys composed of these metals, for example, brass, bronze, nickel silver, duralumin, etc. may be used. Further, a metal or non-metal substrate to which these metals or alloys are attached, for example, tin, a metal plated with nickel or chromium, plastic, glass or the like may be used.

In the contact plating step, the compound or polymer composition of the present invention is used to disperse a hydrophobic compound or the like, and a metal that is more likely to become a metal ion than the compound or polymer composition and the compound or polymer composition. It can be carried out by connecting a substrate having a metal surface that is less likely to become metal ions than other objects with a wire and immersing it in the dispersion liquid. Metal ions are eluted from the surface of the immersed metal and electrons are accumulated on the surface, but the electrons are transferred to the substrate surface through a conductive wire, and the compound or polymer composition of the present invention is reduced on the substrate surface. The hydrophobic compound dispersed by the action of the compound or the polymer composition of the present invention adheres to the surface of the substrate to form a thin film.

Examples of the metal preferably used in the contact plating step include copper, cobalt, chromium, nickel, molybdenum, lead, tin, iron, titanium, vanadium, zinc, aluminum and magnesium. As the substrate, platinum, gold, silver, palladium, stainless steel, etc. can be used, and as a conductive substrate other than metal, tin-doped indium oxide (ITO) -coated plastic or glass, antimony-doped substrate is used. A plastic or glass coated with tin oxide, or a semiconductor such as titanium oxide can be used.

The compound or polymer composition of the present invention can be used, for example, in color filters, electrophotographic photoreceptors, photosensors,
It is useful for forming thin films such as solar cells, electroluminescent devices, optical recording media, nonlinear optical devices, electro-optical devices, photochromic thin films, electrochromic devices, gas sensors, and ion sensors. By using the compound or the polymer composition of the present invention, it is possible to reduce the binder resin and the liquid monomer, and the hydrophobic substance or the hydrophobic functional material which is easily decomposed by vaporization, the nonvolatile hydrophobic substance. Alternatively, a thin film can be easily manufactured using a hydrophobic functional material, a hydrophobic substance that is easily decomposed by heat, or a hydrophobic functional material.

[0046]

EXAMPLES Hereinafter, the present invention will be described more specifically with reference to Examples, but the scope of the present invention is not limited to these Examples. Example 1: polymer composition of formula ^{(II) (R 1 = p} -CH 3 (CH 2) 3 -C 6 H 4 -;
_{^{R 2 = pC 6 H 4 -}} ; R 3 = CH 2 CH (OH) -CH 2 OH; m = 22) were mixed 200 ml of concentrated hydrochloric acid 87 ml and acetone produced water 200 ml of this mixture pn- Butylaniline 49.0 g (328 mmo
l) was added with sufficient stirring to dissolve. This solution was cooled and kept at 0 to 5 ° C, and while stirring well, a solution of 23.9 g (346 mmol) of sodium nitrite in 93 ml of water was added.
The solution was added dropwise over 0 minutes and then stirred for 20 minutes to obtain a diazonium solution.

On the other hand, 53.3 ml of sodium carbonate was added to 700 ml of water.
In a solution of g (503 mmol), phenol 30.9 (32
(8 mmol) dissolved coupler solution is kept at 0-5 ℃,
The above-mentioned diazonium solution was added dropwise over 30 minutes while stirring well, and then stirred for 1 hour. The reaction solution was neutralized with concentrated hydrochloric acid, and the precipitated solid was collected by filtration, washed with water and dried under reduced pressure. The obtained solid was dissolved in benzene and developed on a silica gel column (silica gel 60, manufactured by Merck).
The obtained fraction was eluted with benzene to separate impurities, extracted with a mixed solution of ethanol / benzene, and the solvent was distilled off under reduced pressure to obtain 4-n-butyl-4'-hydroxyazobenzene.

50 ml of tetrahydrofuran under nitrogen atmosphere
Polyethylene glycol diglycidyl ether having an average degree of polymerization of 22 (polymerization product containing a compound represented by IVa in the above scheme as a main component) 11.5 g (9.8 mmo
l) was dissolved. Tetrabutylammonium hydroxide 0.13 g (0.5 mmol) and 4-n-butyl-4'-hydroxyazobenzene 2.76 g (9.8 mmol) were added to this solution, and the mixture was heated under reflux for 24 hours with stirring. 50 ml of water was added to the obtained reaction mixture, and the mixture was heated under reflux for 24 hours with stirring, allowed to cool, and the solvent was evaporated under reduced pressure. 1-Butanol and water were added to the residue, and the mixture was well stirred and then separated, and the organic layer was concentrated under reduced pressure. The residue is dissolved in chloroform and the silica gel column (silica gel 6
0, manufactured by Merck). The obtained fraction was extracted with chloroform to separate impurities, and then extracted with a mixed solution of methanol / chloroform, and the solvent was distilled off under reduced pressure to remove the compound of formula (I) (R ¹ = p-CH _{3 (CH 2) 3 -C 6 H} 4 -; R 2 = pC 6 H 4
A polymer composition containing-; R ³ = CH ₂ CH (OH) -CH ₂ OH; m = 22) as a main component was obtained.

When this polymer composition was dissolved in tetrahydrofuran and subjected to gel filtration chromatography analysis, the hydrolysis products of the starting materials 4-butyl-4'-hydroxyazobenzene and polyethylene glycol diglycidyl ether were detected. However, a broad main peak having a shorter retention time than these raw materials (having a larger molecular weight than the raw materials) was observed. A calibration curve of molecular weight was prepared using standard polystyrene, and the number average molecular weight and the molecular weight distribution (value obtained by dividing the weight average molecular weight by the number average molecular weight) of this main product were determined to be 1450 and 2.1, respectively. On the other hand, the number average molecular weight and molecular weight distribution of the hydrolysis product of the raw material polyethylene glycol diglycidyl ether are 1
It was 200 and 2.1. Therefore, it was confirmed that the above-mentioned polymer composition had an increased molecular weight as compared with the raw material, but had almost no change in the molecular weight distribution. FIG. 1 shows the infrared absorption spectrum of the polymer composition.

¹ H-NMR (200 MHz, solvent: CDCl ₃ , the same in the following examples) 0.91 (3H, t) 4-position of butyl group (terminal) 1.37 (2H, m) 3-position of butyl group 1.64 (2H, m) 2-position of butyl group 2.67 (2H, t) 1-position of butyl group 3.42-3.96 (95H, m) Polyoxyethylene moiety, 2,3-dihydroxypropan-1-yl group (terminal ), R ² adjacent ² , 3-dihydroxypropan-1-yl group 3 position 4.01-4.25 (3H, m) R ² adjacent 2,3-dihydroxypropane-1
-1,2-position of yl group 7.02 (2H, d) m-position of azo group of phenylene (R ² ) 7.29 (2H, d) m-position of azo group of phenylene (R ¹ ) 7.79 (2H, d) O-position of azo group of phenylene (R ¹ ) 7.88 (2H, d) o-position of azo group of phenylene (R ² ).

Example 2: Polymer composition of formula (II) (R ¹ = p-CH ₃ (C
_{H 2) 3 -C 6 H 4} -; R 2 = pC 6 H 4 -; R 3 = CH 2 CH (OH) -CH 2 OH; m = 13)
Production of Polyethylene Glycol Diglycidyl Ether A title polymer composition was produced in the same manner as in Example 1 except that the average degree of polymerization was 13. Gel filtration chromatography analysis showed that the polymer composition had a number average molecular weight and a molecular weight distribution of 1050 and 2.0, respectively.
Met. On the other hand, the number average molecular weight and molecular weight distribution of the hydrolysis product of the raw material polyethylene glycol diglycidyl ether were 800 and 2.0, respectively. Therefore, it was confirmed that the above-mentioned polymer composition had an increased molecular weight as compared with the raw material, but had almost no change in the molecular weight distribution. Further, the infrared absorption spectrum gives the same result as that of the polymer composition of Example 1, and the ¹ H-NMR measurement result shows that the polyoxyethylene moiety and the 2,3-dihydroxypropan-1-yl group are 3.42. It was similar to the ¹ H-NMR spectrum of the polymer composition of Example 1 except that the integral of the multiplet from ppm to 3.96 ppm was 59H. ¹ H-NMR 0.91 (3H, t), 1.37 (2H, m), 1.64 (2H, m), 2.6
7 (2H, t), 3.42-3.96 (59H, m), 4.01-4.25 (3H, m), 7.0
2 (2H, d), 7.29 (2H, d), 7.79 (2H, d), 7.88 (2H, d)

Example 3: Polymer composition of formula (II) (R ¹ = p-CH ₃ (C
_{H 2) 5 -C 6 H 4} -; R 2 = pC 6 H 4 -; R 3 = CH 2 CH (OH) -CH 2 OH; m = 22)
Preparation of 4-n-hexyl-4'-hydroxyazobenzene was synthesized according to the method of Example 1 using pn-hexylaniline instead of pn-butylaniline, and polyethylene glycol diglycidyl ether having an average degree of polymerization of 22 was prepared. Was used to make the title polymer composition by the method of Example 1. Gel filtration chromatography analysis showed that the polymer composition had a number average molecular weight and a molecular weight distribution of 1500 and 2.1, respectively.
Met. On the other hand, the number average molecular weight and the molecular weight distribution of the hydrolysis product of the raw material polyethylene glycol diglycidyl ether were 1200 and 2.1, respectively. Therefore, it was confirmed that the above-mentioned polymer composition had an increased molecular weight as compared with the raw material, but had almost no change in the molecular weight distribution. Further, the infrared absorption spectrum gave the same result as that of the polymer composition of Example 1, and the measurement result of ¹ H-NMR was that the integral value of the 1.37 ppm multiplet attributed to the alkyl moiety was 6H. ¹ H of the polymer composition of Example 1
-Similar to NMR spectrum. ¹ H-NMR 0.91 (3H, t), 1.37 (6H, m), 1.64 (2H, m), 2.6
7 (2H, t), 3.42-3.96 (95H, m), 4.01-4.25 (3H, m), 7.0
2 (2H, d), 7.29 (2H, d), 7.79 (2H, d), 7.88 (2H, d)

¹ H-NMR spectral data of the polymer compositions of Examples 4 to 33 prepared in the same manner as the polymer compositions of Examples 1 to 3 above and the compounds of formula (I) of Examples 34 to 46 are shown. It is shown below. The structural formulas of the compounds which are the main products of the polymer compositions 1-33 and the compounds 34-46 are the same as those shown above as the preferable compounds. Example 4: 0.91 (3H, t), 1.37 (10H, m), 1.64 (2H, m), 2.67
(2H, t), 3.42-3.96 (147H, m), 4.01-4.25 (3H, m), 7.0
2 (2H, d), 7.29 (2H, d), 7.79 (2H, d), 7.88 (2H, d) Example 5: 0.91 (3H, t), 1.37 (18H, m), 1.64 (2H, m) , 2.67
(2H, t), 3.42-3.96 (207H, m), 4.01-4.25 (3H, m), 7.0
2 (2H, d), 7.29 (2H, d), 7.79 (2H, d), 7.88 (2H, d) Example 6: 1.28 (9H, s), 3.42-3.96 (95H, m), 4.01-4.25 ( 3
H, m), 7.02 (2H, d), 7.29 (2H, d), 7.79 (2H, d), 7.88
(2H, d) Example 7: 0.91 (6H, d), 1.37 (1H, m), 1.64 (2H, d), 3.42-
3.96 (95H, m), 4.01-4.25 (3H, m), 7.02 (2H, d), 7.29
(2H, d), 7.79 (2H, d), 7.88 (2H, d) Example 8: 1.31 (3H, t), 3.42-3.96 (97H, m), 4.01-4.25 (3
H, m), 7.02 (2H, d), 7.05 (2H, d), 7.81 (2H, d), 7.88
(2H, d) Example 9: 0.91 (3H, t), 1.24-2.04 (4H, m), 3.42-3.96 (97
H, m), 4.01-4.25 (3H, m), 7.02 (2H, d), 7.06 (2H, d),
7.82 (2H, d), 7.88 (2H, d)

Example 10: 0.91 (3H, t), 1.15-2.04 (20H, m),
3.42-3.96 (97H, m), 4.01-4.25 (3H, m), 7.02 (2H, d),
7.05 (2H, d), 7.80 (2H, d), 7.88 (2H, d) Example 11: 0.91 (9H, s), 3.42-3.96 (97H, m), 4.01-4.25 (3
H, m), 7.02 (2H, d), 7.06 (2H, d), 7.81 (2H, d), 7.88
(2H, d) Example 12: 0.91 (6H, d), 1.78 (1H, m), 3.42-3.96 (97H, m),
4.01-4.25 (3H, m), 7.02 (2H, d), 7.05 (2H, d), 7.81
(2H, d), 7.88 (2H, d) Example 13: 0.91 (3H, t), 1.37 (6H, m), 1.64 (2H, m), 2.48
(3H, s), 2.67 (2H, t), 3.42-3.96 (90H, m), 4.01-4.25
(3H, m), 7.02 (2H, d), 7.29 (2H, d), 7.79 (2H, d), 7.
88 (2H, d) Example 14: 0.91 (3H, t), 1.12 (3H, t), 1.37 (6H, m), 1.64
(2H, m), 2.35 (3H, q), 2.67 (2H, t), 3.42-3.96 (90H,
m), 4.01-4.25 (3H, m), 7.02 (2H, d), 7.29 (2H, d), 7.
79 (2H, d), 7.88 (2H, d) Example 15: 3.42-3.96 (95H, m), 4.01-4.25 (3H, m), 7.02 (2
H, d), 7.45 (1H, m), 7.51 (2H, m), 7.89 (2H, m), 7.92
(2H, d)

Example 16: 0.91 (9H, s), 2.28 (2H, s), 3.42-
3.96 (95H, m), 4.01-4.25 (3H, m), 7.29 (2H, d), 7.36-
7.43 (2H, m), 7.55-7.63 (2H, m), 7.79 (2H, m) Example 17: 1.34 (9H, s), 3.42-3.96 (95H, m), 4.01-4.25 (3
H, m), 6.98-7.10 (4H, m), 7.79 (2H, d), 7.88 (1H, m),
7.94 (1H, m) Example 18: 0.91 (3H, t), 1.37 (2H, m), 1.64 (2H, m), 2.67
(2H, t), 3.42-3.96 (95H, m), 4.01-4.25 (3H, m), 7.02
(2H, d), 7.34 (1H, m), 7.45-7.52 (3H, m), 7.88 (2H,
d) Example 19: 0.91 (3H, t), 1.37 (2H, m), 1.64 (2H, m), 2.67
(2H, t), 3.42-3.96 (95H, m), 4.01-4.25 (3H, m), 7.02
(2H, d), 7.23 (2H, m), 7.62 (1H, m), 7.79 (1H, m), 7.
88 (2H, d) Example 20: O.91 (3H, t), 1.37 (2H, m), 1.64 (2H, m), 2.25
(3H, s), 2.67 (2H, t), 3.42-3.96 (98H, m), 4.01-4.25
(3H, m), 6.72 (1H, s), 6.88 (1H, d), 7.10 (1H, s), 7.
29 (1H, d), 7.56 (1H, d), 7.66 (1H, d)

Example 21: 0.91 (3H, t), 1.37 (2H, m), 1.64 (2
H, m), 2.25 (3H, s), 2.67 (2H, t), 3.42-3.96 (95H,
m), 4.01-4.25 (3H, m), 6.90 (1H, s), 7.12 (1H, s), 7.
22 (1H, d), 7.28 (1H, s), 7.88 (1H, d), 7.95 (1H, d) Example 22: 1.10-2.10 (14H, m), 2.75 (5H, m), 3.42-3.96 ( 96
H, m), 4.01-4.25 (3H, m), 6.82 (1H, d), 7.02 (2H, d),
7.66 (1H, d), 7.82 (2H, d) Example 23: 2.25 (3H, s), 3.42-3.96 (95H, m), 4.01-4.25 (3
H, m), 6.71 (1H, d), 7.45 (1H, m), 7.51 (2H, m), 7.59
(1H, s), 7.66 (1H, d), 7.89 (2H, m) Example 24: 0.91 (3H, t), 1.03 (3H, t), 1.37 (6H, m), 1.64
(2H, m), 2.23 (2H, q), 2.53 (3H, s), 2.67 (2H, t), 3.
42-3.96 (95H, m), 4.01-4.25 (3H, m), 6.89 (1H, s), 7.
00 (1H, s), 7.19 (1H, s), 7.33 (1H, s) Example 25: 1.31 (3H, t), 3.42-3.96 (97H, m), 4.01-4.25 (3
H, m), 7.02 (1H, d), 7.12 (2H, d), 7.42-7.70 (6H, m),
7.75 (1H, d)

Example 26: 3.42-3.96 (95H, m), 4.01-4.25 (3H,
m), 6.83 (1H, d), 6.90 (1H, d), 7.12-7.80 (7H, m),
7.85 (1H, d), 7.90 (1H, d), 8.06 (1H, d), 8.15 (1H, d) Example 27: 3.42-3.96 (95H, m), 4.01-4.25 (3H, m), 6.83 ( 1
H, s), 6.88 (1H, s), 7.12-7.70 (9H, m), 7.85 (1H, d),
7.90 (1H, s) Example 28: 2.09 (2H, t), 2.91 (4H, t), 3.42-3.96 (95H, m),
4.01-4.25 (3H, m), 6.85 (1H, s), 7.05 (1H, s), 7.12-
7.80 (5H, m), 8.06 (1H, d), 8.60 (1H, d) Example 29: 2.51 (3H, s), 3.42-3.96 (95H, m), 4.01-4.25 (3
H, m), 7.03 (1H, d), 7.05 (1H, d), 7.22-7.80 (8H, m),
7.85 (1H, s), 7.90 (1H, d) Example 30: 1.31 (3H, t), 3.42-3.96 (97H, m), 4.01-4.25 (3
H, m), 7.03 (1H, s), 7.05 (1H, d), 7.12 (1H, d), 7.42
-7.70 (6H, m), 7.85 (1H, d), 7.90 (1H, s), 7.90 (1H,
d)

Example 31: 3.42-3.96 (95H, m), 4.01-4.25 (3H,
m), 6.83 (1H, d), 7.12-7.80 (13H, m), 7.88 (1H, d),
7.99 (1H, d), 8.06 (1H, d) Example 32: 3.42-3.96 (95H, m), 4.01-4.25 (3H, m), 6.85 (1
H, d), 7.22-7.80 (11H, m), 7.86 (2H, s), 8.06 (1H, d) Example 33: 3.42-3.96 (95H, m), 4.01-4.25 (3H, m), 6.85 ( 1
H, d), 7.10-7.77 (11H, m), 7.88 (2H, s), 8.10 (1H, d) Example 34: 0.91 (3H, t), 1.37 (2H, m), 1.64 (2H, m) , 2.67
(2H, t), 3.42-3.96 (27H, m), 4.01-4.25 (3H, m), 7.02
(2H, d), 7.29 (2H, d), 7.79 (2H, d), 7.88 (2H, d) Example 35: 0.91 (3H, t), 1.37 (2H, m), 1.64 (2H, m), 2.67
(2H, t), 3.42-3.96 (59H, m), 4.01-4.25 (3H, m), 7.02
(2H, d), 7.29 (2H, d), 7.79 (2H, d), 7.88 (2H, d)

Example 36: 0.91 (3H, t), 1.37 (6H, m), 1.64 (2
H, m), 2.67 (2H, t), 3.42-3.96 (95H, m), 4.01-4.25 (3
H, m), 7.02 (2H, d), 7.29 (2H, d), 7.79 (2H, d), 7.88
(2H, d) Example 37: 0.91 (3H, t), 1.37 (10H, m), 1.64 (2H, m), 2.67
(2H, t), 3.42-3.96 (147H, m), 4.01-4.25 (3H, m), 7.0
2 (2H, d), 7.29 (2H, d), 7.79 (2H, d), 7.88 (2H, d) Example 38: 0.91 (3H, t), 1.37 (18H, m), 1.64 (2H, m) , 2.67
(2H, t), 3.42-3.96 (187H, m), 4.01-4.25 (3H, m), 7.0
2 (2H, d), 7.29 (2H, d), 7.79 (2H, d), 7.88 (2H, d) Example 39: 1.28 (9H, s), 3.42-3.96 (247H, m), 4.01-4.25 ( 3
H, m), 7.02 (2H, d), 7.29 (2H, d), 7.79 (2H, d), 7.88
(2H, d) Example 40: 0.91 (6H, d), 1.37 (1H, m), 1.64 (2H, d), 3.42-
3.96 (287H, m), 4.01-4.25 (3H, m), 7.02 (2H, d), 7.29
(2H, d), 7.79 (2H, d), 7.88 (2H, d)

Example 41: 1.31 (3H, t), 3.42-3.96 (61H, m),
4.01-4.25 (3H, m), 7.02 (2H, d), 7.05 (2H, d), 7.81 (2
H, d), 7.88 (2H, d) Example 42: 0.91 (3H, t), 1.24-2.04 (4H, m), 3.42-3.96 (209
H, m), 4.01-4.25 (3H, m), 7.02 (2H, d), 7.06 (2H, d),
7.82 (2H, d), 7.88 (2H, d) Example 43: 0.91 (3H, t), 1.15-2.04 (20H, m), 3.42-3.96 (16
9H, m), 4.01-4.25 (3H, m), 7.02 (2H, d), 7.05 (2H, d),
7.80 (2H, d), 7.88 (2H, d) Example 44: 3.42-3.96 (167H, m), 4.01-4.25 (3H, m), 6.83 (1
H, d), 6.90 (1H, d), 7.12-7.80 (7H, m), 7.85 (1H, d),
7.90 (1H, d), 8.06 (1H, d), 8.15 (1H, d) Example 45: 2.51 (3H, s), 3.42-3.96 (47H, m), 4.01-4.25 (3
H, m), 7.03 (1H, d), 7.05 (1H, d), 7.22-7.80 (8H, m),
7.85 (1H, s), 7.90 (1H, d) Example 46: 3.42-3.96 (95H, m), 4.01-4.25 (3H, m), 6.85 (1
H, d), 7.10-7.77 (11H, m), 7.88 (2H, s), 8.10 (1H, d)

Example 47: Production of thin film by electrolytic method The maximum diameter of particles when observed in a scanning electron microscope was 0.2 μm or less, and the powder X-ray diffraction pattern was in a known β-type crystal form. A thin film was prepared using the assigned copper phthalocyanine. Copper phthalocyanine and the polymer composition of Example 1 were added to water, and hydrochloric acid was added as a supporting electrolyte, followed by ultrasonic irradiation to prepare a dispersion liquid. The concentration of each component in the dispersion liquid is 0.68 g / dm ³ (0.5 mmo
l / dm ³ ), copper phthalocyanine 5 mmol / dm ³ , supporting electrolyte
It was 0.1 mol / dm ³ .

This dispersion is shown in FIG. 4 of JP-A-7-179773.
Prepared in the electrolytic cell shown in, width 10 mm, long side 20 mm, thickness
An indium-tin composite oxide thin film (ITO) formed on one surface of a 1.1 mm glass plate was immersed in the dispersion liquid for 10 mm in the long side direction to form a cathode. The platinum mesh wire is used as an anode, and the saturated sweet koh electrode (SCE) is used as a reference electrode.
Adjust the voltage applied to the O electrode to -0.5 V (against SCE) and
Constant voltage electrolysis was performed at ℃ and the amount of electricity was measured by a coulometer. About 30 minutes after the start of electrolysis, 30 millicoulombs of electricity was consumed, and a greenish blue thin film (width 10 mm, length 10 m) on the ITO electrode.
m) was formed. After the electrolysis was completed, the ITO electrode was pulled up, washed with ion-exchanged water, and dried in a blast 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 μm.
It was confirmed that particles of m or less were densely packed to form a porous film. The transmission spectrum pattern and X-ray diffraction pattern of this film are consistent with those of the same quality ITO electrode formed by coating the β-type copper phthalocyanine dispersion liquid by a coating method, and the pigment (β-type copper phthalocyanine) particles It was confirmed that a thin film can be produced without changing the diameter and crystal type.

Example 48: Formation of thin film by electrolytic method (comparative example) As a control composition, p-CH ₃ (CH ₂ ) ₃ was prepared according to the method of Synthesis Example 1 described in JP-A-7-179773. -C ₆ H ₄ -N = NpC ₆
A polymer composition containing H ₄ -O- (CH ₂ ) ₂ -O- (CH ₂ CH ₂ O) ₂₂ -H as the main component was produced. This control polymer composition and Example 1 of the polymer composition _{[p-CH 3 (CH 2} ) 3 -C 6 H 4 -N = NpC 6 H 4 -O-CH 2 CH (OH) -
CH ₂ -O- (CH ₂ CH ₂ O) ₂₂ -CH ₂ CH (OH) -CH ₂ OH],
A thin film was formed according to the method of Example 47 using copper phthalocyanine at 20 mM or 15 mM, polymer composition at 2 mM, and supporting electrolyte at 0.1 M. As a result, when the control polymer composition was used, a thin film was formed at a copper phthalocyanine concentration of 20 mM, but a thin film could not be formed at a concentration of 15 mM. On the other hand, when the polymer composition of the present invention is used,
Good thin films were formed at both copper phthalocyanine concentrations of 20 mM and 15 mM. Therefore, by using the polymer composition of the present invention, it is possible to form a film with a wide concentration of copper phthalocyanine.

Example 49: Production of thin film by electroless method (immersion plating) A copper phthalocyanine dispersion was prepared in the same manner as in Example 47. However, the concentration of the polymer composition of Example 1 was 2 mM,
The β-type copper phthalocyanine concentration was set to 20 mM. Width 10 mm,
A 20 mm tip of a copper plate with a long side of 30 mm and a thickness of 0.3 mm is immersed in this dispersion liquid for 20 minutes at 25 ° C, and a green-blue thin film (width
10 mm, length 20 mm). Then, it was dried in the same manner as in Example 47. When the obtained thin film was observed with a scanning electron microscope, the same results as in Example 47 were obtained.
In addition, the transmission spectrum of the solution obtained by dispersing this thin film in a 5 mmol / liter Brij35 aqueous solution was in agreement with that of the β-type copper phthalocyanine used, which was dispersed in a 5 mmol / liter Brij35 aqueous solution. Therefore, according to this method,
It was confirmed that a thin film can be produced without changing the particle size and crystal form of β-type copper phthalocyanine.

Example 50: Production of thin film by electroless method (immersion plating: comparative example) Using the polymer composition of Example 1 and the control composition used in Example 48, immersion plating is carried out according to the method of Example 49. It was The concentration of each polymer composition was 2 mM, and the concentration of β-type copper phthalocyanine was 2
The supporting electrolyte concentration was 0.1 mM with 0 mM or 15 mM. As a result, when the control polymer composition was used, a thin film was formed at a copper phthalocyanine concentration of 20 mM.
A thin film could not be formed at the concentration of mM. On the other hand, when the polymer composition of the present invention was used, good thin films were formed at both copper phthalocyanine concentrations of 20 mM and 15 mM. Therefore, using the polymer composition of the present invention,
It was confirmed by the immersion plating method that a film could be formed with a wide copper phthalocyanine concentration.

Example 51: Production of Thin Film by Electroless Method (Contact Plating) A copper phthalocyanine dispersion was prepared in the same manner as in Example 47. However, the concentration of the polymer composition of Example 1 was 2 mM,
The β-type copper phthalocyanine concentration was set to 20 mM. Width 10 mm,
An indium-tin complex oxide thin film (ITO) formed on one surface of a glass plate with a long side of 20 mm and a thickness of 1.1 mm and an aluminum plate of the same size as the glass plate are stacked, and the upper part of both is clipped with a metal clip. And place the tip 20 mm into the dispersion at 25 ° C.
It was dipped for 20 minutes to form a green-blue thin film (width 10 mm, length 20 mm) on the ITO film. Thereafter, when drying and analysis were carried out in the same manner as in Example 47, the same results as in Example 47 were obtained. Therefore, it is clear that according to this method, a thin film can be produced without changing the particle size and crystal form of β-type copper phthalocyanine.

Example 52: Production of a thin film by electroless method (contact plating: comparative example) Using the polymer composition of Example 1 and the control composition used in Example 48, contact plating is carried out according to the method of Example 51. It was The concentration of each polymer composition was 2 mM, and the concentration of β-type copper phthalocyanine was 2
The concentration of the supporting electrolyte was set to 0 mM or 15 mM and 0.1 mM. As a result, when the control polymer composition was used, a thin film was formed at a copper phthalocyanine concentration of 20 mM.
A thin film could not be formed at the concentration of mM. On the other hand, when the polymer composition of the present invention was used, good thin films were formed at both copper phthalocyanine concentrations of 20 mM and 15 mM. Therefore, using the polymer composition of the present invention,
It was confirmed by the contact plating method that a film could be formed with a wide copper phthalocyanine concentration.

[0069]

Industrial Applicability The compound and polymer composition of the present invention are useful for forming a thin film of a hydrophobic substance or a hydrophobic functional material.
In particular, the compound and the polymer composition of the present invention can be produced easily and inexpensively from easily available raw materials in a short process, and also a dispersion liquid containing various concentrations of a hydrophobic substance or a hydrophobic functional material. The feature is that a thin film can be produced from a solution or solution. In particular, the compound and the polymer composition of the present invention can be suitably used in a thin film forming step by an electroless method such as an immersion plating method or a contact plating method, and can form a high quality thin film by an extremely simple operation. There is a feature called.

[Brief description of drawings]

FIG. 1 shows a polymer composition of the present invention (R ¹ = p-CH ₃ (CH ₂ ) ₃ -C ₆ H
FIG. 4 is a diagram showing an infrared absorption spectrum of ₄ −; R ² = pC ₆ H ₄ −; R ³ = CH ₂ CH (OH) —CH ₂ OH; m = 22).

Claims (8)

[Claims] 1. The following formula: R ¹ -N = NR ² -O-CH ₂ -CH (OH) -CH ₂ -O-(-CH ₂ CH ₂ O-) _n -R ³ (wherein R ¹ represents an optionally substituted C _6-14 aryl group; R ² represents an _optionally substituted C _6-14 aryldiyl group; R ³ represents a hydroxyl group-containing C _{3- 6} alkyl group, C _1-6 alkylcarbonyl group, or C _6-14 arylcarbonyl group; and n represents an integer of 1 to 100). 2. R ¹ is a phenyl group or a naphthyl group (these groups may have a substituent selected from the group consisting of a C _1-12 alkyl group and a C _1-12 alkoxy group),
R ² is a phenylene group or a naphthalenediyl group,
R ³ is a C _1-6 alkylcarbonyl group, a benzoyl group, and 2,
The compound according to claim 1, wherein the compound is a group selected from the group consisting of 3-dihydroxypropan-1-yl group, and n is an integer of 10 to 70. 3. A thin film-forming agent comprising the compound according to claim 1 or 2. 4. The following formula: R ¹ -N = NR ² -O-CH ₂ -CH (OH) -CH ₂ -O-(-CH ₂ CH ₂ O-) _m -R ³ (wherein R ¹ represents an optionally substituted C _6-14 aryl group; R ² represents an _optionally substituted C _6-14 aryldiyl group; R ³ represents a hydroxyl group-containing C _{3- 6} alkyl group, C _1-6 alkylcarbonyl group, or C _6-14 arylcarbonyl group; and m represents an average degree of polymerization selected from the range of 10 to 100). 5. R ¹ is a phenyl group or a naphthyl group (these groups may have a substituent selected from the group consisting of a C _1-12 alkyl group and a C _1-12 alkoxy group),
R ² is a phenylene group or a naphthalenediyl group,
R ³ is a C _1-6 alkylcarbonyl group, a benzoyl group, and 2,
The polymer composition according to claim 4, which is a group selected from the group consisting of 3-dihydroxypropan-1-yl groups and m is in the range of 10 to 50. 6. A thin film forming agent comprising the polymer composition according to claim 4. 7. The thin film forming agent according to claim 6, which is used in an electroless thin film forming step. 8. The thin film forming agent according to claim 7, wherein the electroless thin film forming step is an immersion plating step or a contact plating step.