JP6938063B2 - A method for producing a photoresponsive azo compound, a photoresponsive composition, a photoresponsive polymer compound, an adhesive, a photoresponsive substance, and a photoresponsive polymer compound. - Google Patents

Description

The present application relates to a photoresponsive azo compound, a photoresponsive composition containing the photoresponsive azo compound as an active ingredient, a photoresponsive polymer compound obtained by polymerizing the photoresponsive azo compound, and the like.

Photochromic compounds such as azobenzene and spirooxazine are known as materials that respond to light irradiation. For example, Patent Document 1, Patent Document 2, and Non-Patent Document 1 to Non-Patent Document 4 describe azobenzene derivatives that change between solid and liquid with light. Prior to the advent of this photoresponsive azobenzene derivative, photosensitive materials that were discarded after use were known, but none of them changed between solid and liquid with light.

For this reason, photoresponsive azobenzene derivatives are expected to attract academic attention and to be applied as industrial materials with a new concept. In addition, polymer compounds that change between solid and liquid with light and change the glass transition temperature (Tg) or melting point with light have also been reported (see Non-Patent Documents 5 and 6). Further, a polymer material which is composed of a polymer of a mixture of a liquid crystal-based main agent monomer and an azobenzene derivative monomer and which is deformed by light has also been reported in recent years (see Non-Patent Document 7).

International Publication No. WO2011 / 142124 Japanese Patent No. 5765751

Chem. Commun. 47, 1770-1772 (2011). Adv. Mater., 24, 2353 (2012). Chem. Eur. J. 19, 17391-17397 (2013). J. Photopolym. Sci. Tech. 29, 149-157 (2016). Nat. Chem. 9, 145-151 (2017). The Journal of Adhesion, 93, 823-830 (2017). Nat. Mater. 8, 677-682 (2009).

The inventor of the present application examined the above-mentioned prior art and recognized that the following problems (a) to (e) exist.
(A) The photoresponsiveness of a material containing a photochromic compound such as azobenzene and spirooxazine depends on the viscosity of the polymer compound as the matrix. By lowering the glass transition temperature (Tg) of this polymer compound, the photoresponsiveness of the material is improved. On the other hand, polymer compounds with low Tg are soft. Therefore, the hardness of the material using the polymer compound having a low Tg as a matrix is impaired. It is desirable to develop a material that has both high photoresponsiveness and mechanical strength.
(B) Compounds whose solids are liquefied by light irradiation are known. In order to liquefy this compound, it is necessary to irradiate with light having an ^{intensity of 40 to 100 mW / cm 2 for 30 minutes.} This compound has low photoresponsiveness, and it is desired to develop a material having improved photoresponsiveness.

(C) The azobenzene derivative is a small molecule molecular compound, and is generally in a solid and crystalline state. However, low molecular weight crystalline compounds are brittle and inferior in mechanical strength to high molecular weight compounds. In order to use it as a material, it is desirable to disperse this crystalline compound in a polymer compound or to copolymerize this crystalline compound. When this crystalline compound is dispersed in a polymer compound, there are problems that the crystal compound is eluted and that the characteristics of the dispersed crystal compound are not easily reflected in the properties of the polymer compound. Therefore, it is more desirable to copolymerize this crystalline compound. However, there are no reports on crystalline compounds that have polymerizable substituents and are soluble in light.

(D) So far, monomers containing azobenzene have been used in the production of photoresponsive polymer compounds. However, there have been no reports of monomers that can be used in the production of photoresponsive polymer compounds and dissolve by light irradiation.
(E) In the photoresponsive liquid crystal actuators so far, specific monomers (both azobenzene and liquid crystal monomers) have been used. However, liquid crystal monomers are difficult to synthesize and expensive.
The present application is based on the above-mentioned prior art and the above-mentioned recognition of the present inventor for the prior art, and an object of the present application is to provide a photoresponsive compound and composition. Another object of the present application is to provide a photoresponsive polymer compound.

As a result of diligent studies to solve the above problems, the inventors of the present application show that the azo compound represented by the following formula (A) exhibits photoresponsiveness such as being dissolved by light irradiation, and the following formula ( It has been found that the polymer compound containing the azo compound-based repeating unit represented by B) exhibits photoresponsiveness such as change or deformation of Tg due to light irradiation. The invention of the present application has been completed based on the above findings and the like, and the following inventions are provided in the present application.

（式（Ａ）中、ｍは１〜１８の整数、Ｒは水素またはメチル基。）
＜２＞＜１＞に記載の光応答性アゾ化合物を含む光応答性組成物。<1> A photoresponsive azo compound represented by the following formula (A).

(In formula (A), m is an integer of 1 to 18, R is a hydrogen or methyl group.)
<2> A photoresponsive composition containing the photoresponsive azo compound according to <1>.

（式（Ｂ）中、ｍは１〜１８の整数、Ｒは水素またはメチル基。）<3> A photoresponsive polymer compound containing an azo compound-based repeating unit represented by the following formula (B).

(In formula (B), m is an integer of 1 to 18, R is a hydrogen or methyl group.)

（式（Ｃ）中、ｎは４〜１７の整数。）<4> The photoresponsive polymer compound according to <3>, which further contains an alkylglyceryl itakonate-based repeating unit represented by the following formula (C).

(In formula (C), n is an integer of 4 to 17.)

<5> An adhesive containing the photoresponsive polymer compound according to <3> or <4> as an active ingredient and whose adhesive strength changes upon light irradiation.
<6> A photoresponsive substance containing the photoresponsive polymer compound according to <3> or <4> as an active ingredient and reversibly deforming in response to light irradiation.
<7> The photoresponsive body according to <6>, which is deformed by irradiation with one of ultraviolet light and visible light and returns to its original shape by irradiation with the other.
<8> The photoresponsive body according to <6> or <7>, which has a film-like shape, a sheet-like shape, or a plate-like shape and is curved or bent by irradiation with light.

（式（Ａ）中、ｍは１〜１８の整数、Ｒは水素またはメチル基。）<9> A method for producing a photoresponsive polymer compound that polymerizes a monomer containing an azo compound represented by the following formula (A).

(In formula (A), m is an integer of 1 to 18, R is a hydrogen or methyl group.)

<10> The method for producing a photoresponsive polymer compound according to <9>, wherein the monomer further contains one or more of an acrylic monomer having an azobenzene structure, a diacrylic monomer, a vinyl monomer, and a divinyl monomer.
<11> The method for producing a photoresponsive polymer compound according to <9>, wherein the monomer further contains at least one selected from alkyl glyceryl itakonate, an acrylic ester, and a diacrylic ester.

The photoresponsive azo compound of the present application has photoresponsiveness such as being soluble when irradiated with light. Further, the photoresponsive polymer compound of the present application has photoresponsiveness such that Tg is changed or deformed by light irradiation.

The photograph which shows the photophase transition (photoliquefaction) of the azo compound (M-azo) of Example 3-1. (A) is a photograph before irradiation with ultraviolet light. (B) is a photograph after irradiation with ultraviolet light for several seconds. A photomicrograph showing the photophase transition of the azo compound (M-azo) of Example 3-2. (A) and (c) are photographs before ultraviolet light irradiation. (B) and (d) are photographs after ultraviolet light irradiation. The photograph which shows the time-dependent change in the photophase transition of the azo compound (M-azo) of Example 3-2. (A) is a photograph before ultraviolet light irradiation (0 sec). (B) is a photograph 0.5 seconds after irradiation. (C) is a photograph 1 second after irradiation. (D) is a photograph 2 seconds after irradiation. A micrograph of the azo compound (M-azo) of Example 3-4 when it was patterned by irradiating it with ultraviolet light. (A) is a photograph before irradiation. (B) is a photograph after irradiation. (C) is an enlarged photograph of a part of (b). Photographs of Example 3-5 when the azo compound (M-azo) of Example and the azo compound (H-azo) of Comparative Example were irradiated with ultraviolet light. (A) is a photograph before irradiation. (B) is a photograph 6 seconds after the start of irradiation. (C) is a photograph 25 seconds after the start of irradiation. (D) is a photograph 40 seconds after the start of irradiation. (A) is a schematic diagram showing an experimental apparatus used for measuring the photophase transition rate of Example 3-6. (B) is a graph showing the measurement results of the optical phase transition rates of the azo compound (M-azo) of the example and the azo compound (H-azo) of the comparative example. In Example 3-7, each of (a) a monomer for a polymer compound (DGI), (b) an azo compound (M-azo) of an example, and (c) an azo compound (H-azo) of a comparative example. The graph which shows the differential scanning calorimetry (DSC) curve. The graph which shows the XRD profile of the polymer film of Example 2. FIG. A polarizing microscope image of the polymer film of Example 2. (A) is an image in which the sample is placed along the axial direction of A. (B) is an image in which the sample is placed at a direction of about 45 ° with respect to the axis of A. The graph which shows the DSC profile measured before and after the ultraviolet light irradiation about the polymer film of Example 2. The graph which shows the light absorption spectrum of the polymer film of Example 2. (A) is a spectral change before and after irradiation with ultraviolet light for 4 seconds. (B) is a spectral change after irradiation with ultraviolet light, before irradiation with visible light, and after irradiation for 2 seconds. A photograph of a shape change when the polymer film of Example 2 is alternately irradiated with ultraviolet light and visible light. (A) is a photograph in the initial state. (B) is a photograph after irradiation with ultraviolet light. (C) is a photograph after irradiation with visible light. (D) is a photograph after irradiation with ultraviolet light. The graph which shows the light intensity dependence of the bending behavior (bending speed) when the light intensity of the ultraviolet light irradiating the polymer film of Example 2 is changed. The photograph which shows an example of the bending behavior by light of the polymer film of Example 2. (A) is a photograph before bending. (B) is a photograph after bending.

Hereinafter, embodiments for carrying out the present invention will be described with reference to specific examples. The invention of the present application is not limited to the following contents as long as it does not deviate from the gist of the invention of the present application, and can be appropriately modified and implemented. In the present specification, "~" indicating a numerical range is used to mean that the numerical values described before and after the numerical range are included as the lower limit value and the upper limit value.

（式（Ａ）中、ｍは１〜１８の整数、Ｒは水素またはメチル基。）<Photoresponsive azo compound>
The photoresponsive azo compound of the embodiment of the present invention is represented by the following formula (A).

(In formula (A), m is an integer of 1 to 18, R is a hydrogen or methyl group.)

The photoresponsive azo compound of the present embodiment is characterized by having a vinyl structure at both ends and an azobenzene structure in the middle, and having a methyl group at the position 3 of one of the benzenes in the azobenzene structure. Comparative Example azo compound having the same chemical structure as the azo compound of the present embodiment except that it does not have a methyl group at the position 3 of one of the benzenes having an azobenzene structure, as seen in Examples 3-5 and the like described later. Has no photoresponsiveness. On the other hand, the azo compound of the present embodiment exhibits photoresponsiveness such as being dissolved by irradiation with ultraviolet light.

The photoresponsive azo compound of the present embodiment exhibits various photoresponsiveness as described in the following (1) and (2), as described in Examples described later.
(1) It dissolves (liquefies) by irradiation with ultraviolet light.
(2) The color changes due to photoisomerization by ultraviolet light irradiation.
To determine whether or not the azo compound of the present embodiment has been dissolved, birefringence (optical anisotropy) disappears by observation with a polarizing microscope, the shape changes into droplets by observing the morphology of the powder, or This can be done depending on the presence or absence of fluidity when touched.

The photoresponsive azo compound of the present embodiment may be used alone as a composition, but within a range that does not significantly impair the photoresponsiveness (for example, 50% by mass or less, preferably 20% by mass or less, more preferably 10). It can also be used as a composition containing other compounds (in the range of mass% or less). Such other compounds include, but are not limited to, other photoresponsive azo compounds (eg, azobenzene and derivatives thereof), non-photoresponsive compounds (eg, DGI, comparisons described below). Examples include azo compounds and liquid crystal compounds such as cyanobiphenyl derivatives), and photoresponsive compounds other than azo compounds (spiropyrane, spiroxazine, diarylethane, and flugide).

（式（Ｂ）中、ｍは１〜１８の整数、Ｒは水素またはメチル基。）<Photoresponsive polymer compound>
The photoresponsive polymer compound of the present embodiment is obtained by polymerizing the azo compound of the present embodiment as a monomer, and contains a repeating unit represented by the following formula (B).

(In formula (B), m is an integer of 1 to 18, R is a hydrogen or methyl group.)

The photoresponsive polymer compound of the present embodiment may be obtained by using a monomer copolymerizable with the azo compound of the present embodiment together with the azo compound of the present embodiment. Examples of such copolymerizable monomers include, but are not limited to, acrylic monomers having an azobenzene structure, diacrylic monomers, vinyl monomers, divinyl monomers, and other alkene-based monomers. Other alkene-based monomers include, but are not limited to, alkylglyceryl itakonate, acrylic esters, diacrylic esters and the like.

The polymerization initiator for polymerizing these monomers is not limited, for example, 1,1'-azobis- (cyclohexane-1-carbonitrile) and 1,1'-azobis- (isobutyro). Examples thereof include an azo-based polymerization initiator such as nitrile, a peroxide such as benzoyl peroxide and lauroyl peroxide, an acylphosphine oxide-based polymerization initiator, and an alkylphenone-based polymerization initiator. These can be used alone or in combination of two or more. The amount of the polymerization initiator used is usually 0.05 to 5% by mass, preferably 0.1 to 1% by mass, based on the total amount of the azo compound monomer and other monomers.

（式中、ｉ、ｊ、ｋ、およびｌは正の整数、ｍは１〜１８の整数、ｎは４〜１７の整数、Ｒは水素またはメチル基。）The chemical structure of the photoresponsive polymer compound of the present embodiment is difficult to express as a general formula, but when the azo compound monomer of the present embodiment and the alkylglyceryl itaconate monomer are copolymerized, for example, the following It is considered that it has a polymer chemical structure as shown in the chemical formula of.

(In the formula, i, j, k, and l are positive integers, m is an integer from 1 to 18, n is an integer from 4 to 17, and R is a hydrogen or methyl group.)

The photoresponsive polymer compound of the present embodiment and the film formed from the same exhibit various photoresponsiveness as described in (1) to (4) below, as described in Examples described later.
(1) In the photoresponsive polymer compound of the present embodiment, Tg decreases by irradiation with ultraviolet light, and then increases by irradiation with visible light.
(2) The light absorption spectrum of the photoresponsive polymer compound of the present embodiment changes due to ultraviolet light irradiation and subsequent visible light irradiation. In particular, the absorption of light in the wavelength range of about 330 to 430 nm is greatly reduced by irradiation with ultraviolet light, then increased by irradiation with visible light, and is almost restored to the original state.
(3) The film formed from the photoresponsive polymer compound of the present embodiment is bent by irradiation with ultraviolet light and then restored to a substantially original planar shape by irradiation with visible light.
(4) The bending speed of the film formed from the photoresponsive polymer compound of the present embodiment by irradiation with ultraviolet light increases when the light intensity is high.

The photoresponsive polymer compound of the present embodiment may be used alone as a photoresponsive composition, but within a range that does not significantly impair the photoresponsiveness (for example, 60% by mass or less, preferably 50% by mass or less, and more. It is preferably 30% by mass or less), and can also be used as a photoresponsive composition containing other polymers and various additives. Examples of other polymers include, but are not limited to, acrylic polymers, silicone-based polymers, and urethane-based polymers. Additives include, but are not limited to, fillers, reinforcing agents, functional additives and the like.

The adhesive of the embodiment of the present invention contains the photoresponsive polymer compound of the present embodiment as an active ingredient, and the adhesive strength changes by light irradiation. That is, the change in the adhesive strength of this adhesive is due to the presence of the photoresponsive polymer compound of the present embodiment. Further, the photoresponsive body of the embodiment of the present invention contains the photoresponsive polymer compound of the present embodiment as an active ingredient and is reversibly deformed in response to light irradiation. That is, this deformation of the photoresponsive body is due to the presence of the photoresponsive polymer compound of the present embodiment. The photoresponsive body may be deformed by irradiation with one of ultraviolet light and visible light, and may return to its original shape by irradiation with the other. Further, the photoresponsive body is in the form of a film, a sheet, or a plate, and may be curved or bent by irradiation with light.

Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples, but the present invention can be appropriately modified as long as it does not deviate from the gist of the present invention. Therefore, the scope of the present invention should not be construed as limited by the specific examples shown below.

Reagents used in the experiment and equipment Commercially available reagents and solvents used for synthesis and characterization were used as they were. For column chromatography, silica gel 60 manufactured by Kanto Chemical Co., Inc. was used. For the NMR (nuclear magnetic resonance) spectrum, an Avance 400 type or 500 type NMR device manufactured by Bruker was used. The thermal behavior of the synthesized compound was analyzed by differential scanning calorimetry (DSC) (DSC6100 manufactured by SII Nanotechnology Inc.) under dark conditions. The measurement was performed with the temperature rising rate and the temperature lowering rate set to 2 ° C./min. Regarding the optical properties of the synthesized compound, the molecular orientation was observed using a BX51 polarizing microscope manufactured by Olympus and a temperature variable stage (1033L) manufactured by Linkam.

Changes in the absorption spectrum of the compound when irradiated with ultraviolet light or visible light were observed using a V-670 absorptiometer manufactured by Nippon Spectroscopy. For light irradiation, a high-pressure mercury lamp (REX-250) manufactured by Asahi Spectroscopy was combined with an optical filter to extract light of an arbitrary wavelength. For the XRD spectrum of the compound, SmartLab (CuKα (λ = 1.5418Å)) manufactured by Rigaku was used. The FT-IR spectrum of the compound was measured in the range of ^{370 to 4000 cm -1 using Spectrum 2000 manufactured by PerkinElmer.}

Synthesis of azo compounds The azo compounds of Examples and Comparative Examples were synthesized according to the synthesis scheme shown in the following chemical reaction formula. Each synthesis is shown below.

[Example 1-1: Synthesis of Example Intermediates 1a and 4,4'-Dihydroxy-3-methylazobenzene]
Example Intermediate 1a was synthesized according to the synthesis scheme shown in the following chemical reaction formula.

After adding 50 mL of 2.4N hydrochloric acid to 4-aminophenol (4.36 g, 40 mmol), a solution of sodium nitrite (3.32 g, 48 mmol) dissolved in 4 mL of distilled water was added while cooling and stirring at -3 ° C. The mixture was added dropwise, and stirring was continued at 0 ° C. for 30 minutes. When this solution was added dropwise at -3 ° C. to a mixed solution of o-cresol (4.32 g, 40 mmol) and 16 mL of a 20% sodium hydroxide aqueous solution, a yellow precipitate was formed.

The mixture was stirred at room temperature for 22 hours. The solution was acidified with 2.4N hydrochloric acid while cooling, the brown precipitate precipitated was filtered, the solid was washed with water and then dried. The obtained black solid was purified by silica gel column chromatography using a mixed solution of ethyl acetate: hexane = 1: 2 as a developing solvent, and recrystallized from a mixed solvent of acetone and hexane to obtain a yellow solid 1a.

¹ H NMR (400MHz, DMSO-d ₆ ) δ 10.08 (s, 1H), 10.04 (s, 1H), 7.70 (dd, J1 = 6.8Hz, J2 = 1.9 Hz, 2H), 7.60 (d, J = 2.0) Hz, 1H), 7.55 (dd, J1 = 8.4Hz, J2 = 2.4Hz, 1H), 6.92 (d, J = 8.4Hz, 1H), 6.90 (dd, J1 = 6.8Hz, J2 = 1.9Hz, 2H) , 2.20 (s, 3H)
¹³ C NMR (125MHz, DMSO-d ₆ ) δ 160.1, 158.4, 145.5, 145.3, 125.1, 124.3, 122.6, 116.0, 115.1, 16.2

[Comparative Example 1-1: Synthesis of Comparative Example Intermediates 1b and 4,4'-Dihydroxy-azobenzene]
Comparative Example intermediate 1b was obtained by the same method as in Example 1-1 using phenol instead of o-cresol used in the synthesis of 1a above (see the chemical reaction formula below).

¹ H NMR (400MHz, DMSO-d ₆ ) δ 10.12 (s, 2H) 7.72 (dd, J1 = 3.08 Hz, J2 = 2.08 Hz, 2H), 7.70 (dd, J1 = 2.16 Hz, J2 = 3.04 Hz, 2H ), 6.92 (dd, J1 = 3.12 Hz, J2 = 2.08 Hz, 2H), 6.89 (dd, J1 = 2.12 Hz, J2 = 3.12 Hz, 2H)
¹³ C NMR (100MHz, DMSO-d ₆ ) δ 159.98, 145.25, 124.14, 115.78

[Example 1-21: Synthesis of Example Intermediate 2a (m = 3)] Example Intermediate 2a (m = 3) was synthesized according to the synthesis scheme shown in the following chemical reaction formula.

4,4'-Dihydroxy-3-methylazobenzene (1a) (1.03 g, 4.5 mmol), 3-bromo-1-propanol (2.08 g, 15 mmol), potassium carbonate (1.87 g, 13.5 mmol), And 15 mL of N, N-dimethylformamide (DMF) was added to potassium iodide (44.8 mg, 0.27 mmol). The mixture was stirred at 120 ° C. for 48 hours, after which water was added to precipitate the product. The precipitate was filtered and recrystallized from ethanol to obtain a yellow powder 2a (m = 3) (yield 23.2%).

^{1 1} H NMR (500MHz, CDCl ₃ ) δ 7.86 (d, J = 9.0, 2H), 7.73-7.76 (m, 2H), 7.01 (d, J = 9.0, 2H), 6.94 (d, J = 8.4, 1H) ), 4.19-4.23 (m, 4H), 3.88-3.92 (m, 4H), 2.29 (s, 3H), 2.09-2.13 (m, 4H) ¹³ C NMR ( _{125MHz, CDCl 3} ) δ 160.75, 159.11, 147.24 , 146.68, 127.36, 124.30, 123.69, 123.42, 114.71, 110.64, 65.89, 65.82, 60.38, 60.17, 32.11, 32.02, 16.43

[Example 1-2-2: Synthesis of Example Intermediate 2a (m = 4)] Example Intermediate 2a (m = 4) was synthesized according to the synthesis scheme shown in the following chemical reaction formula.

Place 4,4'-Dihydroxy-3-methylazobenzene (1a) (1.14 g, 5.0 mmol) in a reaction vessel, potassium carbonate (1.73 g, 12.5 mmol), potassium iodide (83.0 mg, 0. 5 mmol) and anhydrous acetone (18 mL) were added. The mixture was cooled to 0 ° C., 4-chlorobutylbenzoate (2.05 mL, 11.0 mmol) was added dropwise at 0 ° C., and the mixture was heated under reflux in an oil bath at 85 ° C. for 24 hours. After 24 hours, anhydrous acetone (10 mL) was further added and reflux was continued for 16 hours.

After evaporating acetone, KOH (65.0 mmol) dissolved in a mixed solution (25 mL) of ethanol: water = 1: 1 was added, and saponification was carried out under reflux in an oil bath at 110 ° C. for 2 hours. The reaction mixture was extracted 3 times with 30 mL of EtOAc and the collected organic phase was dried over anhydrous magnesium sulfate and filtered. The crude product was purified by column chromatography (silica gel 100-200 μM, ethyl acetate: hexane = 1: 4 mixture → 100% ethyl acetate) to obtain a yellow solid 2a (m = 4) (350.0 mg). , Yield 19%).

^{1 1} H NMR (500MHz, CDCl ₃ ) δ 7.86 (d, J = 9.0, 2H), 7.76-7.72 (m, 2H), 6.99 (d, J = 9.0, 2H), 6.92 (d, J = 9.3, 1H) ), 4.13-4.07 (m, 4H), 3.80-3.73 (m, 4H), 2.31 (s, 3H), 1.99-1.90 (m, 4H), 1.85-1.76 (m, 4H)
¹³ C NMR ( _{125MHz, CDCl 3} ) δ 160.83, 159.23, 147.19, 146.59, 127.48, 124.25, 123.62, 123.36, 114.69, 110.62, 68.06, 68.02, 62.61, 62.57, 29.54, 29.44, 25.83, 25.78, 16.37

[Example 1-2-3: Synthesis of Example Intermediate 2a (m = 5)] 4-Chlorobutylbenzoate (2.) Instead of 4-chloropentyl acetate used in the synthesis of 2a (m = 4) above. Using 05 mL (11.0 mmol), a yellow solid 2a (m = 5) was obtained by the same method as in Example 1-2-2 (324.0 mg, yield 16%) (see the chemical reaction formula below).

^{1 1} H NMR (500MHz, CDCl ₃ ) δ 7.86 (d, J = 9.0, 2H), 7.76-7.72 (m, 2H), 6.99 (d, J = 9.1, 2H), 6.91 (d, J = 9.4, 1H) ), 4.09-4.04 (m, 4H), 3.73-3.69 (m, 4H), 2.30 (s, 3H), 1.93-1.84 (m, 4H), 1.72-1.54 (m, 12H)
¹³ C NMR ( _{125MHz, CDCl 3} ) δ 160.97, 159.35, 147.12, 146.52, 127.52, 124.23, 123.57, 123.35, 114.67, 110.58, 68.12, 68.07, 62.85, 62.82, 32.45, 29.69, 29.08, 29.02, 22.46, 22.38, 16.36

[Example 1-2-4: Synthesis of Example Intermediate 2a (m = 6)]

Example Intermediate 2a (m = 6) was synthesized according to the synthesis scheme shown in the following chemical reaction formula.

Dissolve 4,4'-Dihydroxy-3-methylazobenzene (1a) (2.28 g, 10 mmol), potassium carbonate (4.14 g, 30 mmol), and potassium iodide (0.01 g, 0.06 mmol) in 40 mL DMF. bottom. A solution prepared by dissolving 6-chloro-1-hexanol (3.0 g, 22 mmol) in 10 mL of DMF was added dropwise thereto. The mixture was stirred at 120 ° C. for 70 hours, then water was added to precipitate the product. The precipitate was filtered and recrystallized from ethanol to obtain a yellow powder 2a (m = 6) (yield 51.2%).

¹ H NMR (400MHz, CDCl ₃ ) δ 7.88 (d, J1 = 6.9 Hz, J2 = 2.0 Hz, 2H), 7.76 (d, J = 2.4Hz, 1H), 7.75 (d, J = 2.7Hz, 1H) , 7.01 (dd, J1 = 6.9Hz, J2 = 1.9Hz, 2H), 6.92 (d, J = 9.4Hz, 1H), 4.08 (dd, J1 = 11.32Hz, J2 = 6.32Hz, 4H), 3.71 (t , J1 = 12.52Hz, J2 = 6.16Hz, 4H), 2.31 (s, 3H), 1.82-1.92 (m, 4H), 1.46-1.68 (m, 12H)
¹³ C NMR (100MHz, CDCl ₃ ) δ 161.39, 159.79, 147.44, 146.83, 127.90, 124.62, 123.85, 115.05, 110.93, 68.54, 68.48, 63.33, 33.11, 29.65, 29.61, 26.39, 26.29, 25.96, 16.80

[Example 1-2-5: Synthesis of Example Intermediate 2a (m = 8)]
8-Bromo-1-octanol (3.14 g, 15 mmol) was used instead of 3-bromo-1-propanol used in the synthesis of 2a (m = 3) above, and the same method as in Example 1-2-1 was used. Obtained a yellow powder 2a (m = 8). Further, the filtrate was purified with a chloroform solvent by gel permeation chromatography to obtain a yellow powder 2a (m = 8) (yield 75.6%) (see the chemical reaction formula below).

^{1 1} H NMR (500MHz, CDCl ₃ ) δ 7.85 (d, J = 8.9, 2H), 7.72-7.74 (m, 2H), 6.98 (d, J = 9.0, 2H), 6.90 (d, J = 9.4, 1H) ), 4.01-4.06 (m, 4H), 3.63-3.67 (m, 4H), 2.29 (s, 3H), 1.78-1.86 (m, 4H), 1.54-1.59 (m, 4H), 1.44-1.51 (m) , 4H), 1.28-1.40 (m, 20H)
¹³ C NMR ( _{125MHz, CDCl 3} ) δ 161.06, 159.45, 147.07, 146.46, 127.51, 124.22, 123.54, 123.36, 114.68, 110.59, 68.29, 68.25, 62.99, 32.77, 29.34, 29.26, 29.21, 26.07, 25.97, 25.70, 16.37

[Example 1-2-6: Synthesis of Example Intermediate 2a (m = 11)]
Instead of 3-bromo-1-propanol used in the synthesis of 2a (m = 3) above, 11-bromo-1-undecanol (3.01 g, 12 mmol) was used, and the stirring time was changed to 24 hours. Yellow powder 2a (m = 11) was obtained by the same method as in Example 1-2-1 (see the chemical reaction formula below).

^{1 1} H NMR (500MHz, CDCl ₃ ) δ 7.85 (d, J = 9.0, 2H), 7.71-7.74 (m, 2H), 6.98 (d, J = 9.0, 2H), 6.90 (d, J = 9.4, 1H) ), 4.01-4.06 (m, 4H), 3.64 (t, J = 6.7, 4H), 2.29 (s, 3H), 1.79-1.87 (m, 4H), 1.57-1.61 (m, 4H), 1.46-1.52 (m, 4H), 1.35-1.42 (m, 32H)
¹³ C NMR ( _{125MHz, CDCl 3} ) δ 161.08, 159.47, 147.06, 146.46, 127.53, 124.21, 123.53, 123.36, 114.69, 110.59, 68.34, 68.28, 63.07, 32.82, 29.58, 29.53, 29.50, 29.43, 29.36, 29.27, 29.23, 26.11, 26.02, 25.76, 16.38

[Example 1-2-7: Synthesis of Example Intermediate 2a (m = 12)]
Instead of 3-bromo-1-propanol used in the synthesis of 2a (m = 3) above, 12-bromo-1-dodecanol (3.18 g, 12 mmol) was used, and the stirring time was changed to 22 hours. Yellow powder 2a (m = 12) was obtained by the same method as in Example 1-2-1 (see the chemical reaction formula below).

^{1 1} H NMR (500MHz, CDCl ₃ ) δ 7.85 (d, J = 9.0, 2H), 7.71-7.74 (m, 2H), 6.98 (d, J = 9.0, 2H), 6.90 (d, J = 9.4, 1H) ), 4.01-4.06 (m, 4H), 3.64 (t, J = 6.6, 4H), 2.29 (s, 3H), 1.78-1.86 (m, 4H), 1.54-1.59 (m, 4H), 1.44-1.52 (m, 4H), 1.26-1.40 (m, 36 H)
¹³ C NMR ( _{125MHz, CDCl 3} ) δ 161.08, 159.48, 147.06, 146.46, 127.54, 124.22, 123.52, 123.37, 114.69, 110.59, 68.35, 68.29, 63.09, 32.83, 29.60, 29.56, 29.44, 29.37, 29.27, 29.23, 26.11, 26.03, 25.76, 16.38

[Example 1-2-8: Synthesis of Example Intermediate 2a (m = 16)]
16-Bromo-1-hexadecanol (0.48 g, 1.5 mmol) was used in place of 3-bromo-1-propanol used in the synthesis of 2a (m = 3) above, and 4,4'-Dihydroxy-. The amounts of 3-methylazobenzene (1a), potassium carbonate, and potassium iodide used were changed to 0.16 g (0.7 mmol), 0.69 g (5 mmol), and 33 mg (0.20 mmol), respectively, and the stirring time was further increased. Was changed to 72 hours to obtain yellow powder 2a (m = 16) by the same method as in Example 1-2-1 (yield 73.1%) (see the chemical reaction formula below).

^{1 1} H NMR (500MHz, CDCl ₃ ) δ 7.85 (d, J = 8.9, 2H), 7.71-7.74 (m, 2H), 6.98 (d, J = 9.0, 2H), 6.90 (d, J = 9.3, 1H) ), 4.01-4.06 (m, 4H), 3.64 (t, J = 6.7, 4H), 2.29 (s, 3H), 1.78-1.86 (m, 4H), 1.54-1.59 (m, 4H), 1.44-1.52 (m, 4H), 1.26-1.40 (m, 36H) ¹³ C NMR (100MHz, CDCl ₃ ) δ 161.04, 159.45, 146.99, 146.37, 127.51, 124.19, 123. 45, 123.38, 114. 64, 110.51, 68.31, 68.25, 63.10, 32. 81, 29.66, 29.60, 29.44, 29.39, 29.25, 29.22, 26.11, 26.02, 25.74, 16.41

[Example 1-3-1: Synthesis of Example azo compound 3a (m = 3)]
Example azo compound 3a (m = 3) was synthesized according to the synthesis scheme shown in the following chemical reaction formula.

While dissolving the above 2a (m = 3) (4.30 g, 10 mmol), triethylamine (2.02 g, 20 mmol), and 4-dimethylaminopyridine (0.28 g) in dehydrated tetrahydrofuran (THF) and cooling to 0 ° C. , A mixed solution of methacryloyl chloride (35 mmol) and THF (30 mL) was added. The reaction was followed by thin layer chromatography, and after confirming that 2a (m = 3) was consumed, water was added. The mixed solution was extracted with chloroform, the organic phases were collected and dried over anhydrous magnesium sulfate. After filtration, the solvent was distilled off and the obtained yellow solid was purified twice by silica gel column chromatography using a mixed solution of ethyl acetate: hexane = 1:10 as a developing solvent to obtain 3a (m = 3). (Yield 62.0%).

^{1 1} H NMR (400MHz, CDCl ₃ ) δ 7.85-7.88 (d, J = 9.04, 2H), 7.73-7.75 (m, 2H), 7.02 (d, J = 9.04, 2H), 6.92 (d, J = 9.28) , 1H), 6.12 (s, 2H), 5.57 (s, 2H), 4.35-4.41 (m, 4H), 4.13-4.17 (m, 4H), 2.29 (s, 3H), 2.18-2.27 (m, 4H) ) 1.95 (s, 6H)
¹³ C NMR (100MHz, CDCl ₃ ) δ 167.41, 160.67, 159.02, 147.19, 146.62, 136.28, 127.59, 125.63, 124.29, 123.58, 123.45, 114.65, 110.49, 64.73, 64. 62, 61. 50, 61.44, 28.74, 28.65, 18.36, 16.39

[Example 1-3-2: Synthesis of Example azo compound 3a (m = 4)]
Example azo compound 3a (m = 4) was synthesized according to the synthesis scheme shown in the following chemical reaction formula.

The above 2a (m = 4) (307.0 mg, 0.82 mmol) was dissolved in THF (15 mL), and triethylamine (250 μL, 1.80 mmol) and N, N-dimethyl-4-aminopyridine (DMAP) (9. 9 mg, 0.082 mmol, 10 mol%) was added. The mixture was cooled to 0 ° C. and methacryloyl chloride (280 μL, 2.87 mmol) was added dropwise at 0 ° C. The reaction was stirred at 0 ° C. for 6 hours and then warmed to room temperature with stirring overnight. After 16 hours, the reaction was cooled to 0 ° C. and water (about 3 mL) was added dropwise to quench.

Na ₂ CO ₃ (30 mL) was added and the mixture was extracted 3 times with 30 mL chloroform. The collected organic phase was dried over anhydrous magnesium sulfate, filtered and concentrated in vacuo. Purification by column chromatography (mixture of silica gel 40 to 60 μM, ethyl acetate: hexane = 1: 12 → ethyl acetate: hexane = 1: 4) produces an orange crystalline solid 3a (m = 4). Obtained (143.0 mg, yield 34.3%).

^{1 1} H NMR (500MHz, CDCl ₃ ) δ 7.86 (d, J = 9.0, 2H), 7.76-7.72 (m, 2H), 6.99 (d, J = 9.0, 2H), 6.90 (d, J = 9.3, 1H) ), 6.12 (br. S, 2H), 5.57 (br. S, 2H), 4.29-4.23 (m, 4H), 4.13-4.07 (m, 4H), 2.30 (s, 3H), 1.99-1.92 (m) , 14H)
¹³ C NMR ( _{125MHz, CDCl 3} ) δ 167.44, 160.83, 159.18, 147.18, 146.58, 136.43, 127.51, 125.33, 124.25, 123.62, 123.35, 114.65, 110.52, 67.61, 67.57, 64.32, 64.27, 26.03, 25.95, 25.55, 25.44, 18.29, 16.35

[Example 1-3-3: Synthesis of Example azo compound 3a (m = 5)]
2a (m = 5) (324.0 mg, 0.81 mmol) was used instead of 2a (m = 4) used in the synthesis of 3a (m = 4), and the same method as in Example 1-3-2 was used. Obtained an orange crystalline solid 3a (m = 5) (80.0 mg, yield 14.9%) (see the chemical reaction formula below).

^{1 1} H NMR (500MHz, CDCl ₃ ) δ 7.86 (d, J = 8.9, 2H), 7.76-7.71 (m, 2H), 6.98 (d, J = 9.0, 2H), 6.90 (d, J = 9.4, 1H) ), 6.12 (br. S, 2H), 5.57 (br. S, 2H), 4.24-4.18 (m, 4H), 4.09-4.04 (m, 4H), 2.29 (s, 3H), 1.96 (s, 6H) ), 1.94-1.84 (m, 4H), 1.84-1.75 (m, 4H), 1.70-1.57 (m, 4H)
¹³ C NMR ( _{125MHz, CDCl 3} ) δ 167.49, 160.93, 159.30, 147.13, 146.53, 136.50, 127.50, 125.23, 124.23, 123.57, 123.35, 114.66, 110.54, 67.95, 67.89, 64.49, 28.91, 28.86, 28.40, 22.74 22.65, 18.30, 16.32

[Example 1-3-4: Synthesis of Example azo compound 3a (m = 6)]
Instead of 2a (m = 3) used in the synthesis of 3a (m = 3), 2a (m = 6) (324.0 mg, 0.81 mmol) was used, and the amount of triethylamine used was 2.02 g (20 mmol). To obtain a yellow solid 3a (m = 6) by the same method as in Example 1-3-1 (hereinafter, may be referred to as “M-azo”) (yield 52.2%). (See the chemical reaction formula below).

^{1 1} H NMR (500MHz, CDCl ₃ ) δ 7.86-7.88 (d, J = 9.0, 2H), 7.74-7.76 (m, 2H), 7.00 (d, J = 9.0, 2H), 6.92 (d, J = 9.4) , 1H), 6.12 (s, 2H), 5.57 (s, 2H), 4.17-4.21 (m, 4H), 4.04-4.08 (m, 4H), 2.30 (s, 3H), 1.96 (s, 6H), 1.84-1.87 (m, 4H), 1.73-1.76 (m, 4H), 1.52-1.62 (8H)
¹³ C NMR ( _{125MHz, CDCl 3} ) δ 167.54, 161.01, 147.13, 146.53, 136.56, 127.53, 125.18, 124.24, 123.58, 123.36, 114.68, 110.59, 68.12, 68.08, 64.64, 29.19, 29.14, 28.60, 25.83, 25.77, 18.32, 16.37

[Comparative Example 1-3: Synthesis of Comparative Example Azo Compound 3b (m = 6)]
Comparative Example azo compound (hereinafter referred to as "H-") was used in the same manner as in the synthesis of M-azo in Examples 1-3-4, except that the following 2b (m = 6) was used instead of 2a (m = 6). (Sometimes referred to as "azo") was obtained (see the chemical reaction formula below). Regarding the synthetic reaction of Comparative Example Intermediate 2b, the following Document A was referred to.
Reference A: S. Muhammed, O. Jesper, T. Helena, S. Kent, K. Mikhail, Liquid Crystals, 2005, 32, 901-908.

^{1 1} H NMR (400MHz, CDCl3) δ 7.84-7.87 (m, 4H), 6.97-6.99 (m, 4H), 6.12 (m, 2H), 5.55 (m, 2H), 4.15-4.18 (m, 4H), 4.02-4.06 (m, 4H), 1.48-1.96 (m, 22H)
¹³ C NMR (100MHz, CDCl3) δ 161.09, 146.98, 136.51, 125.28, 124.32, 114.65, 102.13, 68.10, 64.66, 29.12, 28.58, 25.83, 25.76, 18.36

[Example 1-3-5: Synthesis of Example azo compound 3a (m = 8)]
Example azo compound 3a (m = 8) was synthesized according to the synthesis scheme shown in the following chemical reaction formula.

The above 2a (m = 8) (0.97 g, 2 mmol) and 4-dimethylaminopyridine (0.59 g, 4.8 mmol) were dissolved in 20 mL of dehydrated THF, and triethylamine (0.49 g, 4.8 mmol) was added. After that, the solution was cooled to 0 ° C. A solution of dehydrated THF (20 mL) of methacryloyl chloride (0.63 g, 6 mmol) was slowly added dropwise thereto. After completion of the dropping, the mixture was stirred at 0 ° C. for 10 minutes and then at room temperature for 24 hours. After the reaction, the solvent was evaporated under reduced pressure, methylene chloride and 0.1N hydrochloric acid were added to the residue to separate the solutions, and then the organic phase was dried over anhydrous magnesium sulfate. After the magnesium sulfate was filtered off, the solvent was distilled off under reduced pressure. Using a mixed solution of ethyl acetate: hexane = 1: 12, the obtained residue was purified by silica gel column chromatography to obtain 3a (m = 8) (yield 8.1%).

^{1 1} H NMR (500MHz, CDCl ₃ ) δ 7.85 (d, J = 9.0, 2H), 7.72-7.74 (m, 2H), 6.98 (d, J = 9.0, 2H), 6.90 (d, J = 9.4, 1H) ), 6.10 (bs, 2H), 5.54 (bs, 2H), 4.15 (t, J = 6.7, 4H), 4.01-4.06 (m, 4H), 2.29 (s, 3H), 1.94 (s, 6H), 1.80-1.85 (m, 4H), 1.66-1.70 (m, 4H), 1.46-1.53 (m, 4H), 1.37-1.43 (m, 20H)
¹³ C NMR ( _{125MHz, CDCl 3} ) δ 167.56, 161.06, 159.44, 147.10, 146.50, 136.60, 127.53, 125.12, 124.23, 123.55, 123.37, 114.69, 110.60, 68.27, 68.23, 64.78, 29.26, 29.21, 28.64, 26.07, 25.95, 18.32, 16.37

[Example 1-3-6: Synthesis of Example azo compound 3a (m = 11)]
Instead of 2a (m = 8) used in the synthesis of 3a (m = 8) above, 2a (m = 11) (1.14 g, 2 mmol) was used, and the stirring at room temperature was changed to 3 hours. 3a (m = 11) was obtained by the same method as in Examples 1-3-5 (yield 17.8%) (see the chemical reaction formula below).

^{1 1} H NMR (500MHz, CDCl ₃ ) δ 7.76 (d, J = 9.0, 2H), 7.62-7.65 (m, 2H), 6.87 (d, J = 9.0, 2H), 6.78 (d, J = 9.4, 1H) ), 6.00 (bs, 2H), 5.43 (bs, 2H), 4.04 (t, J = 6.7, 4H), 3.87-3.92 (m, 4H), 2.19 (s, 3H), 1.84 (s, 6H), 1.66-1.74 (m, 4H), 1.54-1.59 (m, 4H), 1.17-1.38 (m, 28H)
¹³ C NMR ( _{125MHz, CDCl 3} ) δ 166.38, 160.01, 158.37, 146.00, 145.40, 135.53, 126.35, 123.98, 123.16, 122.51, 122.32, 113.58, 109.48, 67.22, 67.18, 63.72, 28.78, 28.44, 28.33, 28.20, 27.59, 25.07, 24.98, 24.94, 17.25, 15.31

[Example 1-3-7: Synthesis of Example azo compound 3a (m = 12)]
Example azo compound 3a (m = 8) was synthesized according to the synthesis scheme shown in the following chemical reaction formula.

The above 2a (m = 12) (0.60 g, 1 mmol) was dissolved in 20 mL of dehydrated THF, triethylamine (0.23 g, 2.4 mmol) was added, and then the solution was cooled to 0 ° C. A solution of dehydrated THF (10 mL) of methacryloyl chloride (0.25 g, 2.4 mmol) was slowly added dropwise thereto. After completion of the dropping, the mixture was stirred at 0 ° C. for 10 minutes and then at room temperature for 24 hours. After the reaction, the solvent was evaporated under reduced pressure, methylene chloride and 0.1N hydrochloric acid were added to the residue to separate the solutions, and then the organic phase was dried over anhydrous magnesium sulfate. After the magnesium sulfate was filtered off, the solvent was distilled off under reduced pressure. The obtained residue was purified by silica gel column chromatography using a mixed solution of ethyl acetate: hexane = 1: 12 to obtain 3a (m = 12) (yield 38.6%).

^{1 1} H NMR (500MHz, CDCl ₃ ) δ 7.85 (d, J = 9.1, 2H), 7.62-7.65 (m, 2H), 6.98 (d, J = 9.0, 2H), 6.90 (d, J = 9.5, 1H) ), 6.10 (bs, 2H), 5.54 (bs, 2H), 4.14 (t, J = 6.7, 4H), 4.01-4.06 (m, 4H), 2.29 (s, 3H), 1.94 (s, 6H), 1.78-1.86 (m, 4H), 1.64-1.70 (m, 4H), 1.44-1.52 (m, 4H), 1.26-1.40 (m, 28H)
¹³ C NMR ( _{125MHz, CDCl 3} ) δ 167.55, 161.08, 159.47, 147.08, 146.48, 136.62, 127.52, 125.07, 124.22, 123.54, 123.36, 114.69. 110.59, 68.34, 68.29, 64.84, 29.55, 29.52, 29.39, 29.26. 28.65, 26.13, 26.04, 26.00, 18.32, 16.37

[Example 1-3-8: Synthesis of Example azo compound 3a (m = 16)]
2a (m = 16) (4.30 g, 10 mmol) was used instead of 2a (m = 4) used in the synthesis of 3a (m = 4), and the amount of triethylamine used was changed to 2.02 g (20 mmol). Then, 3a (m = 16) was obtained by the same method as in Example 1-3-2 (yield 8.1%) (see the chemical reaction formula below).

^{1 1} H NMR (500MHz, CDCl ₃ ) δ 7.85 (d, J = 9.0, 2H), 7.72-7.73 (m, 2H), 6.99 (d, J = 9.0, 2H), 6.90 (d, J = 9.3, 1H) ), 6.09 (s, 2H), 5.54 (s, 2H), 4.14 (t, J = 6.74, 4H), 4.01-4.04 (m, 4H), 2.29 (s, 3H), 1.94 (s, 6H), 1.78-1.86 (m, 4H), 1.63-1.69 (m, 4H), 1.26-1.54 (m, 48H)
¹³ C NMR ( _{125MHz, CDCl 3} ) δ 169.39, 167.57, 147.07, 144.96, 143.21, 135.31, 128.68, 125.06, 124.21, 123.54, 123.35, 114.70, 110.61, 68.37, 64.86, 29.67, 29.59, 29.53, 29.40, 29.27, 28.65, 26.14, 26.05, 26.00, 18.32, 16.37

[Reference Example 1: Synthesis of Monomer DGI for Polymer Compounds]
Itaconic acid 1- (2,3-dihydroxypropyl) 4-dodecyl (DGI) was synthesized according to the following documents B and C (see the chemical reaction formula below).
Reference B: K. Naitoh, Y. Ishii, K. Tsujii, J. Phys. Chem. 1991, 95, 7915-7918.
Reference C: K. Tsujii, M. Hayakawa, T. Onda, T. Tanaka, Macromolecules 1997, 30.

Itaconic anhydride (50.0 g) and 1-dodecanol (80.0 g) were stirred at 110 ° C. for 50 minutes. After cooling to room temperature, 100 mL of hexane was added with vigorous stirring to precipitate a white solid. The solid was filtered and recrystallized twice in ethanol to give the intermediate dodecyl itaconic acid. Dodecyl itaconic acid (5.0 g) was dissolved in 5 mL of toluene, glycidol (3.75 g) and the catalyst pyridinium p-toluenesulfonate (10 μg) were added, and the mixture was stirred at 100 ° C. for 5 hours. After cooling, the solvent was distilled off, and the obtained crude product was purified by silica gel column chromatography using a mixed solution of ethyl acetate: hexane = 6: 4 as a developing solvent, and then mixed with acetone: hexane = 1: 1. DGI was obtained by recrystallization with a solvent.

¹ H NMR (400MHz, DMSO-d ₆ ) δ 6.24 (s, 1H), 5.83 (s, 1H), 4.93 (d, J = 5.16Hz, 1H), 4.66 (t, J1 = 11.24Hz, J2 = 5.64 Hz, 1H), 4.12 (dd, J1 = 11.12Hz, J2 = 4.32Hz, 1H), 3.95-4.02 (m, 3H), 3.67 (m, 1H), 3.36 (m, 2H), 1.54 (m, 2H) ), 1.25 (m, 18H), 0.86 (t, 3H)
¹³ C NMR (100MHz, DMSO-d6) δ 171.16, 166.53, 134.88, 129.53, 70.09, 67.04, 65.09, 63.39, 37.98, 32. 17, 29.91, 29.88, 29.83, 29.80, 29.58, 29.49, 28.92, 26.16, 22.97 , 14.82

[Example 2: Synthesis of polymer compound and preparation of a film thereof]
DGI (22 mg), M-azo (7 mg), and polymerization initiator 1,1'-azobis- (cyclohexane-1-carbonitrile) (0.3 mg) were placed in a vial and heated to 70 ° C. to melt. .. To reduce the viscosity, 20 μL of toluene was added thereto. This mixture was poured into a liquid crystal cell (parallel orientation, cell thickness: 5 μm or 10 μm, area: 2 cm × 2 cm, KSRP-50 / A107P1NSS manufactured by EHC). The cell was heated on a hot plate at 60 ° C. for 1 hour and then at 125 ° C. for 24 hours in a nitrogen atmosphere. The above operation was performed under illumination that cuts light having a wavelength of 500 nm or less. After heating, the film was allowed to cool to room temperature, and the film was removed from the glass constituting the liquid crystal cell before use.

[Example 3-1: Photophase transition (photoliquefaction) experiment of M-azo]
When M-azo fine powder (particle size of about 2 mm) was ^{irradiated with ultraviolet light (wavelength: 365 nm, intensity: 125 mW / cm 2} ), the color changed from yellow to orange due to liquefaction and photoisomerization after 6 seconds. I observed the change. The photographs before and after the light irradiation are shown in FIG.

[Example 3-2: Observation of optical phase transition of M-azo]
A photograph of the thin film of M-azo before and after irradiation with ultraviolet light is shown in FIG. Ultraviolet light having an intensity of 100 mW / cm ² was irradiated for 10 seconds. 2 (a) and 2 (c) show before light irradiation, and FIGS. 2 (b) and 2 (d) show after 10 seconds of light irradiation, respectively. 2 (a) and 2 (b) were taken with a polarizing microscope under a cross Nicol. 2 (c) and 2 (d) were taken with an optical microscope. Since birefringence was confirmed in FIG. 2 (a) and there was optical anisotropy, it was confirmed that M-azo in FIG. 2 (a) was not a liquid. On the other hand, in FIG. 2B, a dark image was observed in the entire visual field, and it was confirmed that the birefringence had disappeared. Further, in FIG. 2D, liquefaction of the sample was confirmed.

[Example 3-3: Observation of changes over time in photophase transition]
FIG. 3 shows a photograph of the change over time of the M-azo thin film during ultraviolet light irradiation observed with a polarizing microscope under a cross Nicol. As the irradiation time elapsed, the black region increased, indicating a phase transition to the isotropic phase.

[Example 3-4: Patterning experiment using M-azo]
When a metal mask was placed on a glass substrate coated with M-azo and irradiated with ultraviolet light for 1 second, a pattern was formed (FIGS. 4 (a) and 4 (b)). The light-irradiated portion was liquefied to form a solid-liquid pattern (FIG. 4 (c)). In the figure, "1" indicates a solid portion and "2" indicates a liquid portion.

[Example 3-5: Comparison of M-azo and H-azo]
H-azo and M-azo are placed side by side on a slide glass, and both are simultaneously irradiated with ultraviolet light (wavelength: 365 nm, intensity: 80 mW / cm ² ). The photograph taken in FIG. 5 is shown in FIG. 5 (a) shows before irradiation, FIG. 5 (b) shows 6 seconds after the start of irradiation, FIG. 5 (c) shows 25 seconds after the start of irradiation, and FIG. 5 (d) shows 40 seconds after the start of irradiation. ing. It is shown that as the irradiation time elapses, only M-azo changes and the phase transitions to the isotropic phase by light.

[Example 3-6: Measurement of photophase transition rate]
The rate of photophase transition between M-azo and H-azo was measured by combining a polarizing microscope and a spectrophotometer. FIG. 6A is a schematic view of the experimental device, in which the transmittance of the backlight illumination (white light) at the bottom at 650 nm was monitored by a spectrometer. The irradiation light was emitted from diagonally above the sample. By forming the two polarizing plates (Polarizer and Analyzer) into cross Nicols, the transmittance decreases when the two polarizing plates are transferred to the isotropic phase. FIG. 6B shows the measurement results of M-azo and H-azo, respectively. The transmittance of M-azo decreased about 10 seconds after the start of light irradiation, while the transmittance of H-azo did not change.

[Example 3-7: DSC measurement]
DGI, M-azo, and H-azo were analyzed by differential scanning calorimetry (DSC) under dark conditions where the rate of temperature rise and fall was 2 ° C./min. FIG. 7 (a) shows the DGI, FIG. 7 (b) shows the M-azo, and FIG. 7 (c) shows the DSC curve of H-azo. In FIG. 7A, a crystal-to-liquid phase transition was observed at 63 ° C. during heating, and a liquid-to-crystal phase transition was observed at 28 ° C. during cooling. In FIG. 7B, a crystal-to-liquid phase transition was observed at 65 ° C. during heating, and a liquid-to-crystal phase transition was observed at 29 ° C. during cooling. In FIG. 7C, a crystal-to-liquid phase transition was observed at 73 ° C. during heating, and a liquid-to-crystal phase transition was observed at 65 to 67 ° C. during cooling.

[Example 4-1: Measurement of physical properties of polymer film XRD]
The XRD profile of the polymer film produced in Example 2 was measured at room temperature (see FIG. 8). The peak of diffraction intensity (2θ = 2.3 °) corresponds to about 38 Å.

[Example 4-2: Observation of a cross section of a polymer film with a polarizing microscope]
FIG. 9 shows a photograph of a cross-sectional sample of the polymer film produced in Example 2 observed with a polarizing microscope under a cross Nicol. FIG. 9A is a polarizing microscope in which the sample is placed along the axial direction of A, but it is dark. On the other hand, in FIG. 9B, a bright image was observed with a polarizing microscope in which the sample was placed at a direction of about 45 ° with respect to the axis A. The elliptical pictures in FIGS. 9 (a) and 9 (b) are schematic views of molecular orientation.

[Example 4-3: DSC measurement before and after ultraviolet light irradiation of polymer film]
The DSC profile of the polymer film produced in Example 2 during heating before and after irradiation with ultraviolet light was measured. The result is shown in FIG. Before and after irradiation with ultraviolet light, Tg decreased from about 20 ° C to 9 ° C. Since the adhesive strength and the adhesive strength change when Tg changes, it is expected that this polymer film will be used as an adhesive or an adhesive whose adhesive strength changes by light irradiation.

[Example 4-4: Measurement of absorption spectrum of polymer film]
The absorption spectrum of the polymer film produced in Example 2 when irradiated with ultraviolet light or visible light was measured. The result is shown in FIG. FIG. 11A shows changes in the light absorption spectrum of the polymer film before (0 sec) and after 4 seconds (4 sec) of irradiation with ultraviolet light (wavelength: 365 nm). FIG. 11B shows changes in the light absorption spectrum of the polymer film after irradiation with ultraviolet light, before irradiation with visible light (wavelength: 465 nm) (0 sec) and after irradiation for 2 seconds (2 sec). In the polymer film of Example 2, the absorption spectrum in the wavelength range of 330 to 430 nm was significantly changed by the irradiation with ultraviolet light and the irradiation with visible light. Therefore, it is assumed that the polymer film of Example 2 is used as an irradiation history sensor for ultraviolet light or visible light.

[Example 4-5: Investigation of bending behavior of polymer film by light]
Shape change when the polymer film produced in Example 2 is alternately irradiated with ultraviolet light (wavelength: 365 nm, intensity: 11 mW / cm ² ) and visible light (wavelength: 465 nm, intensity: 30 mW / cm ^{2), etc.} I examined. A photograph at that time is shown in FIG. 12 (a) shows the initial state, FIG. 12 (b) shows after irradiation with ultraviolet light, FIG. 12 (c) shows after irradiation with visible light, and FIG. 12 (d) shows after irradiation with ultraviolet light. As shown in FIG. 12B, the lower right end side was bent upward by irradiation with ultraviolet light, and the color changed to reddish. As shown in FIG. 12B, further visible light irradiation returned the upward bending to the initial flat state and changed to the initial yellow color. It is assumed that the polymer film of Example 2 exhibiting such behavior is used not only as the above-mentioned ultraviolet light or visible light irradiation history sensor, but also as an optical response actuator or the like.

[Example 4-6: Measurement of light intensity dependence of bending behavior of polymer film by light]
The bending speed when the light intensity of the ultraviolet light (wavelength: 365 nm) irradiated to the polymer film produced in Example 2 was changed was measured. The result is shown in FIG. It was found that the bending speed of the polymer film increased as the light intensity increased. Note that FIG. 14 shows a photograph of an example of the bending behavior of the polymer film of Example 2 due to light. FIG. 14 (a) is a photograph before bending, and FIG. 14 (b) is a photograph after bending.

Since the azo compound of the present application and the composition containing this azo compound as an active ingredient are dissolved by light irradiation, it is expected to be used as a material for photo-modeling, a light irradiation history sensor, and the like. Further, in the polymer compound of the present application, Tg is reversibly changed by ultraviolet light irradiation and visible light irradiation, and bending-flattening occurs reversibly. It is expected to be used as an optical responder such as an actuator.

Claims (11)

A photoresponsive azo compound represented by the following formula (A).

(In formula (A), m is an integer of 1 to 18, R is a hydrogen or methyl group.) A photoresponsive composition comprising the photoresponsive azo compound according to claim 1. A photoresponsive polymer compound containing an azo compound-based repeating unit represented by the following formula (B).

(In formula (B), m is an integer of 1 to 18, R is a hydrogen or methyl group.) The photoresponsive polymer compound according to claim 3, further comprising an alkylglyceryl itakonate-based repeating unit represented by the following formula (C).

(In formula (C), n is an integer of 4 to 17.) An adhesive containing the photoresponsive polymer compound according to claim 3 or 4 as an active ingredient and whose adhesive strength changes by light irradiation. A photoresponsive substance containing the photoresponsive polymer compound according to claim 3 or 4 as an active ingredient and reversibly deforming in response to light irradiation. The photoresponsive body according to claim 6, which is deformed by irradiation with one of ultraviolet light and visible light and returns to its original shape by irradiation with the other. The photoresponsive body according to claim 6 or 7, which is in the form of a film, a sheet, or a plate, and is curved or bent by irradiation with light. A method for producing a photoresponsive polymer compound that polymerizes a monomer containing an azo compound represented by the following formula (A).

(In formula (A), m is an integer of 1 to 18, R is a hydrogen or methyl group.) The method for producing a photoresponsive polymer compound according to claim 9, wherein the monomer further comprises one or more of an acrylic monomer having an azobenzene structure, a diacrylic monomer, a vinyl monomer, and a divinyl monomer. The method for producing a photoresponsive polymer compound according to claim 9, wherein the monomer further comprises one or more selected from alkyl glyceryl itakonate, an acrylic ester, and a diacrylic ester.

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