WO2019181784A1 - Photoresponsive azo compound, photoresponsive composition, photoresponsive polymer compound, adhesive, optical responder, and method for producing photoresponsive polymer compound - Google Patents

Abstract

Provided are a photoresponsive compound, composition, and polymer compound. A photoresponsive polymer compound according to the present invention contains an azo compound-based repeating unit represented by formula (B). (In formula (B), m represents an integer of 1-18; and R represents a hydrogen atom or a methyl group.)

Description

Photoresponsive azo compound, photoresponsive composition, photoresponsive polymer compound, adhesive, photoresponsive material, and method for producing photoresponsive polymer compound

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

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 a solid and a liquid by light. Prior to the advent of this photoresponsive azobenzene derivative, photosensitive materials that were discarded after use were known, but there was no material that changed between solid and liquid by light.

Therefore, photoresponsive azobenzene derivatives are attracting academic attention and are expected to be applied as industrial materials with new concepts. In addition, a polymer compound that changes between a solid and a liquid by light and changes in glass transition temperature (Tg) or melting point by light has been reported (see Non-Patent Document 5 and Non-Patent Document 6). In recent years, a polymer material comprising a polymer of a mixture of a liquid crystalline main monomer and an azobenzene derivative monomer and deformed by light has been reported (see Non-Patent Document 7).

International Publication No. WO2011 / 142124 Japanese Patent No. 57655751

The inventor of the present application has studied the above 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 a matrix. The photoresponsiveness of the material is improved by lowering the glass transition temperature (Tg) of the polymer compound. On the other hand, a polymer compound having a low Tg is soft. For this reason, the hardness of a material using a polymer compound having a low Tg as a matrix is impaired. It is desirable to develop a material that has both high light response and mechanical strength.
(B) Compounds in which a solid is liquefied by light irradiation are known. In order to liquefy this compound, it is necessary to irradiate light having an intensity of 40 to 100 mW / cm ² for 30 minutes. This compound has low photoresponsiveness, and the appearance of a material with improved photoresponsiveness is desired.

(C) An azobenzene derivative is a low molecular molecular compound and generally takes a solid crystalline state. However, a low molecular weight crystalline compound is brittle and inferior in mechanical strength as compared with a polymer compound. For use as a material, it is desirable to disperse the crystalline compound in a polymer compound or to copolymerize the crystalline compound. When this crystalline compound is dispersed in a polymer compound, there are problems such as the elution of this crystalline compound and the characteristics of the dispersed crystal compound are hardly reflected in the properties of the polymer compound. For this reason, it is more desirable to copolymerize this crystalline compound. However, there is no report on a crystalline compound having a polymerizable substituent and soluble by light.

(D) So far, monomers containing azobenzene have been used in the production of photoresponsive polymer compounds. However, there has been no report of a monomer that can be used for production of a photoresponsive polymer compound and can be dissolved by light irradiation.
(E) Conventional photoresponsive liquid crystal actuators have used specific monomers (both azobenzene and liquid crystal monomers). However, liquid crystalline monomers are difficult to synthesize and are expensive.
The present application is based on the above-described conventional technology and the above-mentioned recognition of the present inventors with respect to this conventional technology, and an object thereof 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 intensive 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 melting 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 Tg changing or deformation by light irradiation. The invention of the present application has been completed based on the above knowledge and the like, and the following invention is provided in the present application.

<1> A photoresponsive azo compound represented by the following formula (A).

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

<3> A photoresponsive polymer compound containing an azo compound-based repeating unit represented by the following formula (B).

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

<4> The photoresponsive polymer compound according to <3>, further comprising an alkyl glyceryl itaconate-based repeating unit represented by the following formula (C).

(In the 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 having an adhesive force that changes by light irradiation.
<6> A photoresponsive body 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 one irradiation of ultraviolet light or visible light and returns to its original shape by the other irradiation.
<8> The photoresponsive body according to <6> or <7>, which has a film shape, a sheet shape, or a plate shape, and is curved or bent by light irradiation.

<9> A method for producing a photoresponsive polymer compound, wherein a monomer containing an azo compound represented by the following formula (A) is polymerized.

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

<10> The method for producing a photoresponsive polymer compound according to <9>, wherein the monomer further includes 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 includes at least one selected from alkyl glyceryl itaconate, acrylic ester, and diacrylic ester.

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

3 is a photograph showing a photo phase transition (photo liquefaction) of an azo compound (M-azo) of Example 3-1. (A) is a photograph before ultraviolet light irradiation. (B) is a photograph after irradiation with ultraviolet light for several seconds. 4 is a photomicrograph showing the photo phase 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. 3 is a photograph showing the change over time in the optical phase 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. 4 is a photomicrograph of the azo compound (M-azo) of Example 3-4 patterned by irradiating with ultraviolet light. (A) is a photograph before irradiation. (B) is a photograph after irradiation. (C) is an enlarged photograph of part of (b). In Example 3-5, a photograph when the azo compound (M-azo) of the example and the azo compound (H-azo) of the comparative example are 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 measurement of the optical phase transition speed in 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, (a) monomer for polymer compound (DGI), (b) azo compound (M-azo) of Example, and (c) azo compound (H-azo) of Comparative Example The graph which shows a differential scanning calorimetry (DSC) curve. The graph which shows the XRD profile of the polymer film of Example 2. The polarization 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 in the direction of about 45 ° with respect to the A axis. The graph which shows the DSC profile measured before and after ultraviolet light irradiation about the polymer film of Example 2. FIG. 5 is a graph showing a light absorption spectrum of the polymer film of Example 2. (A) is a spectrum change before and after irradiation of ultraviolet light for 4 seconds. (B) shows the change in spectrum after irradiation with ultraviolet light and before irradiation with visible light and after irradiation for 2 seconds. The photograph which image | photographed the shape change at the time of irradiating the polymer film of Example 2 with ultraviolet light and visible light alternately. (A) is a photograph of the initial state. (B) is a photograph after ultraviolet light irradiation. (C) is a photograph after irradiation with visible light. (D) is a photograph after ultraviolet light irradiation. The graph which shows the light intensity dependence of the bending | flexion behavior (bending speed) at the time of changing the light intensity of the ultraviolet light irradiated to the polymer film of Example 2. FIG. The photograph which shows an example of the bending behavior by the light of the polymer film of Example 2. FIG. (A) is a photograph before bending. (B) is a photograph after bending.

The form for carrying out the present invention will be described below with a specific example. Unless it deviates from the meaning of this invention, this invention is not limited to the following content, It can change suitably and can implement. In the present specification, “˜” indicating a numerical range is used as a meaning including numerical values described before and after the numerical value as a lower limit value and an upper limit value.

<Photoresponsive azo compound>
The photoresponsive azo compound of the embodiment of the present invention is represented by the following formula (A).

(In the formula (A), m is an integer of 1 to 18, and R is hydrogen or a 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 a methyl group at the 3 position of one benzene of 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 3-position of one benzene of the 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 melting by irradiation with ultraviolet light.

The photoresponsive azo compound of the present embodiment exhibits various photoresponsive properties such as the following (1) and (2), as described in Examples described later.
(1) It melts (liquefies) when irradiated with ultraviolet light.
(2) The color is changed by photoisomerization by ultraviolet light irradiation.
The determination as to whether or not the azo compound of the present embodiment has dissolved is that birefringence (optical anisotropy) disappears by observation with a polarizing microscope, changes in shape into droplets by observation of powder morphology, 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 not significantly impairing the photoresponsiveness (for example, 50% by mass or less, preferably 20% by mass or less, more preferably 10%). (In the range of mass% or less), it can also be used as a composition containing other compounds. Examples of such other compounds include, but are not limited to, other azo compounds having photoresponsiveness (for example, azobenzene and derivatives thereof), compounds having no photoresponsiveness (for example, DGI, comparison described below) Examples include azo compounds and liquid crystal compounds such as cyanobiphenyl derivatives, and photoresponsive compounds other than azo compounds (spiropyran, spirooxazine, diarylethene, and fulgide).

<Photoresponsive polymer compound>
The photoresponsive polymer compound of this embodiment is obtained by polymerizing the azo compound of this embodiment as a monomer, and includes a repeating unit represented by the following formula (B).

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

The photoresponsive polymer compound of this embodiment may be obtained using a monomer copolymerizable with the azo compound of this embodiment together with the azo compound of this 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 monomers. Other alkene monomers include, but are not limited to, alkyl glyceryl itaconate, acrylic esters, and diacrylic esters.

The polymerization initiator for polymerizing these monomers is not limited, and examples thereof include 1,1′-azobis- (cyclohexane-1-carbonitrile) and 1,1′-azobis- (isobutyro). Nitrile) and the like, peroxides such as benzoyl peroxide and lauroyl peroxide, acylphosphine oxide polymerization initiators, and alkylphenone polymerization initiators. 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.

The chemical structure of the photoresponsive polymer compound of this embodiment is difficult to express as a general formula, but when the azo compound monomer of this embodiment and an alkylglyceryl itaconate monomer are copolymerized, for example, It is thought that it has a polymer chemical structure as shown in the chemical formula.

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

The photoresponsive polymer compound of the present embodiment and the film formed therefrom exhibit various photoresponsiveness as described in the following (1) to (4), as described in Examples below.
(1) In the photoresponsive polymer compound of the present embodiment, Tg is decreased by ultraviolet light irradiation, and then Tg is increased by visible light irradiation.
(2) In the photoresponsive polymer compound of this embodiment, the light absorption spectrum is changed by 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 significantly reduced by irradiation with ultraviolet light, and is increased by subsequent visible light irradiation, and is almost restored.
(3) A film molded from the photoresponsive polymer compound of the present embodiment is bent by ultraviolet light irradiation and recovered to an almost flat shape by subsequent visible light irradiation.
(4) The bending of the film formed from the photoresponsive polymer compound of the present embodiment by ultraviolet light irradiation increases in speed when the light intensity is high.

The photoresponsive polymer compound of the present embodiment may be used alone as a photoresponsive composition, but does not greatly impair the photoresponsiveness (for example, 60% by mass or less, preferably 50% by mass or less, 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 polymers, and urethane polymers. Additives include, but are not limited to, fillers, reinforcing agents, and functional additives.

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

Hereinafter, the present invention will be described more specifically with reference to examples and comparative examples, but can be appropriately changed without departing from the gist of the present invention. Therefore, the scope of the present invention should not be construed as being limited by the specific examples shown below.

Commercially available reagents and solvents used for the experiments and for device synthesis and property evaluation were used as they were. In addition, silica gel 60 manufactured by Kanto Chemical Co., Ltd. was used for column chromatography. For NMR (nuclear magnetic resonance) spectrum, Bruker Avance 400 type or 500 type NMR apparatus was used. The thermal behavior of the synthesized compound was analyzed by differential scanning calorimetry (DSC) (DSC6100 manufactured by SII Nanotechnology) under dark conditions. Note that the measurement was performed at a rate of temperature increase and a rate of temperature decrease of 2 ° C./min. Regarding the optical characteristics of the synthesized compound, molecular orientation was observed using an Olympus BX51 polarizing microscope and a Linkam temperature variable stage (1033L).

Changes in the absorption spectrum of the compound upon irradiation with ultraviolet light or visible light were observed using a JASCO V-670 absorptiometer. For light irradiation, an optical filter was combined with a high pressure mercury lamp (REX-250) manufactured by Asahi Spectroscopy, and light having an arbitrary wavelength was extracted. For the XRD spectrum of the compound, Rigaku SmartLab (CuKα (λ = 1.5418Å)) 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 Compound 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 Intermediate 1a, 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 obtained by dissolving sodium nitrite (3.32 g, 48 mmol) in 4 mL of distilled water while cooling and stirring at −3 ° C. The solution 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 20% aqueous sodium hydroxide solution (16 mL), 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 precipitated brown precipitate was filtered, the solid 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 with 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 (125 MHz, 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 Intermediate 1b, 4,4′-Dihydroxy-azobenzene]
Comparative Example Intermediate 1b was obtained in the same manner as in Example 1-1 using phenol instead of o-cresol used in the synthesis of 1a (see the following chemical reaction formula).

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 1-2-1: 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 with ethanol to obtain yellow powder 2a (m = 3) (yield 23.2%).

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 (125 MHz, 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.

4,4′-Dihydroxy-3-methylazobenzene (1a) (1.14 g, 5.0 mmol) was placed in a reaction vessel, and potassium carbonate (1.73 g, 12.5 mmol), potassium iodide (83.0 mg, 0.8 mmol). 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 to reflux for 24 hours in an 85 ° C. oil bath. After 24 hours, further anhydrous acetone (10 mL) was added and refluxing was continued for 16 hours.

After evaporating acetone, KOH (65.0 mmol) dissolved in a mixed solution of ethanol: water = 1: 1 (25 mL) was added, and saponification was performed under reflux in a 110 ° C. oil bath 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, mixture of ethyl acetate: hexane = 1: 4 → 100% ethyl acetate) to obtain yellow solid 2a (m = 4) (350.0 mg) Yield 19%).

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 (125 MHz, 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)] Instead of 4-chloropentyl acetate used in the synthesis of 2a (m = 4) above, 4-chlorobutylbenzoate (2. (05 mL, 11.0 mmol), and yellow solid 2a (m = 5) was obtained in the same manner as in Example 1-2-2 (324.0 mg, yield 16%) (see the chemical reaction formula below).

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 (125 MHz, 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.

4,4′-Dihydroxy-3-methylazobenzenemethyl (1a) (2.28 g, 10 mmol), potassium carbonate (4.14 g, 30 mmol), and potassium iodide (0.01 g, 0.06 mmol) were dissolved in 40 mL of DMF. did. A solution of 6-chloro-1-hexanol (3.0 g, 22 mmol) dissolved in 10 mL of DMF was added dropwise thereto. The mixture was stirred at 120 ° C. for 70 hours, after which water was added to precipitate the product. The precipitate was filtered and recrystallized with ethanol to obtain 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 (100 MHz, 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)]
The same method as in Example 1-2-1, except that 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. Gave yellow powder 2a (m = 8). Furthermore, the filtrate was purified with a chloroform solvent by gel permeation chromatography to obtain yellow powder 2a (m = 8) (yield: 75.6%) (see the following chemical reaction formula).

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 (125 MHz, 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)
11-Bromo-1-undecanol (3.01 g, 12 mmol) was used instead of 3-bromo-1-propanol used in the synthesis of 2a (m = 3) above, and the stirring time was changed to 24 hours. Yellow powder 2a (m = 11) was obtained in the same manner as in Example 1-2-1 (see the chemical reaction formula below).

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 (125 MHz, 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)
12-Bromo-1-dodecanol (3.18 g, 12 mmol) was used instead of 3-bromo-1-propanol used in the synthesis of 2a (m = 3) above, and the stirring time was changed to 22 hours. Yellow powder 2a (m = 12) was obtained in the same manner as in Example 1-2-1 (see the chemical reaction formula below).

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 (125 MHz, 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)]
Using 16-bromo-1-hexadecanol (0.48 g, 1.5 mmol) instead of 3-bromo-1-propanol used in the synthesis of 2a (m = 3) above, 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, and yellow powder 2a (m = 16) was obtained in the same manner as in Example 1-2-1 (yield 73.1%) (see the chemical reaction formula below).

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 (100 MHz, 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.

The above 2a (m = 3) (4.30 g, 10 mmol), triethylamine (2.02 g, 20 mmol), and 4-dimethylaminopyridine (0.28 g) were dissolved in dehydrated tetrahydrofuran (THF) and cooled 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. After confirming that 2a (m = 3) was consumed, water was added. The mixed solution was extracted with chloroform, and the organic phase was collected and dried over anhydrous magnesium sulfate. After filtration, the yellow solid obtained by distilling off the solvent 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 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.

2a (m = 4) (307.0 mg, 0.82 mmol) was dissolved in THF (15 mL), 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 warmed to room temperature with further stirring overnight. After 16 hours, the reaction was cooled to 0 ° C. and quenched by the dropwise addition of water (about 3 mL).

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 (silica gel 40-60 μM, mixture of ethyl acetate: hexane = 1: 1 → mixture of ethyl acetate: hexane = 1: 4) gave an orange crystalline solid 3a (m = 4). Obtained (143.0 mg, yield 34.3%).

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 (125 MHz, 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)
The same method as in Example 1-3-2 except that 2a (m = 5) (324.0 mg, 0.81 mmol) was used instead of 2a (m = 4) used in the synthesis of 3a (m = 4) above. Yielded an orange crystalline solid 3a (m = 5) (80.0 mg, 14.9% yield) (see chemical reaction formula below).

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 (125 MHz, 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)
2a (m = 6) (324.0 mg, 0.81 mmol) was used instead of 2a (m = 3) used in the above synthesis of 3a (m = 3), and the amount of triethylamine used was 2.02 g (20 mmol). The yellow solid 3a (m = 6) was obtained in the same manner as in Example 1-3-1 (hereinafter sometimes referred to as “M-azo”) (yield 52.2%) (See chemical reaction formula below).

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 (125 MHz, 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 Azo Compound 3b (m = 6)]
A comparative example azo compound (hereinafter referred to as “H-”) was prepared in the same manner as the synthesis of M-azo in Example 1-3-4 except that the following 2b (m = 6) was used instead of 2a (m = 6). azo ”) (see chemical reaction formula below). For the synthesis reaction of Comparative Example Intermediate 2b, Reference A below was referred to.
Reference A: S. Muhammed, O. Jesper, T. Helena, S. Kent, K. Mikhail, Liquid Crystals, 2005, 32, 901-908.

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.

2a (m = 8) (0.97 g, 2 mmol) and 4-dimethylaminopyridine (0.59 g, 4.8 mmol) are dissolved in 20 mL of dehydrated THF, and triethylamine (0.49 g, 4.8 mmol) is added. After that, the solution was cooled to 0 ° C. A solution of methacryloyl chloride (0.63 g, 6 mmol) in dehydrated THF (20 mL) was slowly added dropwise thereto. After completion of dropping, the mixture was stirred at 0 ° C. for 10 minutes, and then stirred at room temperature for 24 hours. After the reaction, the solvent was distilled off under reduced pressure, and methylene chloride and 0.1N hydrochloric acid were added to the residue for liquid separation, and then the organic phase was dried over anhydrous magnesium sulfate. After 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 = 8) (yield 8.1%).

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 (125 MHz, 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 in the same manner as in Example 1-3-5 (yield 17.8%) (see the chemical reaction formula below).

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 (125 MHz, 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.

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 the solution was cooled to 0 ° C. A solution of methacryloyl chloride (0.25 g, 2.4 mmol) in dehydrated THF (10 mL) was slowly added dropwise thereto. After completion of dropping, the mixture was stirred at 0 ° C. for 10 minutes, and then stirred at room temperature for 24 hours. After the reaction, the solvent was distilled off under reduced pressure, methylene chloride and 0.1N hydrochloric acid were added to the residue for liquid separation, and the organic phase was dried over anhydrous magnesium sulfate. After 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 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 (125 MHz, 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)
Instead of 2a (m = 4) used in the synthesis of 3a (m = 4) above, 2a (m = 16) (4.30 g, 10 mmol) was used, and the amount of triethylamine used was changed to 2.02 g (20 mmol) Thus, 3a (m = 16) was obtained in the same manner as in Example 1-3-2 (yield 8.1%) (see the following chemical reaction formula).

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 (125 MHz, 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 compound]
Itaconic acid 1- (2,3-dihydroxypropyl) 4-dodecyl (DGI) was synthesized according to the following documents B and C (see the following chemical reaction formula).
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 with ethanol to obtain an intermediate dodecyl itaconate. Dodecyl itaconate (5.0 g) was dissolved in 5 mL of toluene, glycidol (3.75 g) and pyridinium p-toluenesulfonate (10 μg) as a catalyst were added, and the mixture was stirred at 100 ° C. for 5 hours. After cooling, the solvent was distilled off, and the resulting 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 production of 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. . In order to lower the viscosity, 20 μL of toluene was added thereto. This mixture was poured into a liquid crystal cell (parallel alignment, 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 under a nitrogen atmosphere at 60 ° C. for 1 hour and then at 125 ° C. for 24 hours. The said operation was performed under the illumination which cut | disconnected the light of wavelength 500nm or less. After heating, the mixture was allowed to cool to room temperature, and the film was removed from the glass constituting the liquid crystal cell and used.

[Example 3-1: Experiment of optical phase transition (photo-liquefaction) of M-azo]
When M-azo fine powder (particle size: about 2 mm) was irradiated with ultraviolet light (wavelength: 365 nm, intensity: 125 mW / cm ² ), the color changed from yellow to orange following liquefaction and photoisomerization after 6 seconds. Changes were observed. The photographs before and after the light irradiation are shown in FIG.

[Example 3-2: Observation of optical phase transition of M-azo]
FIG. 2 shows photographs of the M-azo thin film before and after irradiation with ultraviolet light. Ultraviolet light with an intensity of 100 mW / cm ² was irradiated for 10 seconds. 2A and 2C show before light irradiation, and FIGS. 2B and 2D show after light irradiation for 10 seconds, respectively. 2 (a) and 2 (b) were taken with a polarizing microscope under crossed Nicols. 2C and 2D were taken with an optical microscope. Since birefringence was confirmed in FIG. 2A and there was optical anisotropy, it was confirmed that M-azo in FIG. 2A 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 birefringence disappeared. Furthermore, in FIG. 2D, liquefaction of the sample was confirmed.

[Example 3-3: Observation of time-dependent change in optical phase transition]
FIG. 3 shows a photograph of the change with time of the M-azo thin film during irradiation with ultraviolet light, observed with a polarizing microscope under crossed Nicols. As the irradiation time elapses, the black area increases, 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. 4A and 4B). The part which received light irradiation liquefied and the pattern of solid and liquid was formed (FIG.4 (c)). In the figure, “1” indicates a solid portion and “2” indicates a liquid portion.

[Example 3-5: Comparison between M-azo and H-azo]
Place H-azo and M-azo side by side on a slide glass, and simultaneously irradiate both with ultraviolet light (wavelength: 365 nm, intensity: 80 mW / cm ² ). A 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. As the irradiation time elapses, only M-azo changes, indicating that the phase transition to the isotropic phase is caused by light.

[Example 3-6: Measurement of speed of optical phase transition]
The speed of the optical phase transition of M-azo and H-azo was measured by combining a polarizing microscope and a spectrophotometer. FIG. 6A is a schematic diagram of the experimental apparatus, and the transmittance of 650 nm of the lowermost backlight illumination (white light) was monitored with a spectrometer. Irradiation light was applied from an obliquely upward direction of the sample. When the two polarizing plates (Polarizer and Analyzer) are crossed Nicols and are transferred to the isotropic phase, the transmittance decreases. FIG. 6B shows the measurement results of M-azo and H-azo. The transmittance of M-azo decreased about 10 seconds after the start of light irradiation, whereas 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 temperature rising rate and temperature falling rate were 2 ° C./min. 7A shows the DGI, FIG. 7B shows the M-azo, and FIG. 7C shows the H-azo DSC curve. In FIG. 7A, a phase transition from a crystal to a liquid was observed at 63 ° C. during heating, and a phase transition from a liquid to a crystal was observed at 28 ° C. during cooling. In FIG. 7B, a phase transition from a crystal to a liquid was observed at 65 ° C. during heating, and a phase transition from a liquid to a crystal was observed at 29 ° C. during cooling. In FIG. 7C, a phase transition from a crystal to a liquid was observed at 73 ° C. during heating, and a phase transition from a liquid to a crystal was observed at 65 to 67 ° C. during cooling.

Example 4-1 Physical Property XRD Measurement of Polymer Film
The XRD profile at room temperature was measured for the polymer film produced in Example 2 (see FIG. 8). The peak of diffraction intensity (2θ = 2.3 °) corresponds to about 38 °.

[Example 4-2: Observation of cross section of polymer film by polarizing microscope]
A photograph of a cross-sectional sample of the polymer film produced in Example 2 observed with a polarizing microscope under crossed Nicols is shown in FIG. FIG. 9A is a polarization microscope in which the sample is placed along the axial direction of A, but is dark. On the other hand, in FIG. 9B, a bright image was observed with a polarizing microscope in which the sample was placed in a direction of about 45 ° with respect to the axis A. In addition, the ellipse picture in Fig.9 (a) and FIG.9 (b) is a schematic diagram of molecular orientation.

[Example 4-3: DSC measurement before and after UV irradiation of polymer film]
About the polymer film produced in Example 2, the DSC profile at the time of a heating before and behind ultraviolet light irradiation was measured. The result is shown in FIG. The Tg decreased from about 20 ° C. to 9 ° C. before and after irradiation with ultraviolet light. When Tg changes, the adhesive force and the adhesive force change, so this polymer film is assumed to be used as an adhesive or an adhesive whose adhesive force changes due to light irradiation.

[Example 4-4: Measurement of absorption spectrum of polymer film]
About the polymer film produced in Example 2, the absorption spectrum at the time of ultraviolet light or visible light irradiation was measured. The result is shown in FIG. FIG. 11A shows changes in the light absorption spectrum of the polymer film before irradiation (0 sec) and after irradiation for 4 seconds (4 sec) 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 with 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 ultraviolet light irradiation and the visible light irradiation. For this reason, 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]
Change in shape when ultraviolet light (wavelength: 365 nm, intensity: 11 mW / cm ² ) and visible light (wavelength: 465 nm, intensity: 30 mW / cm ² ) are alternately applied to the polymer film produced in Example 2 I investigated. The photograph at that time is shown in FIG. 12A shows the initial state, FIG. 12B shows the state after irradiation with ultraviolet light, FIG. 12C shows the state after irradiation with visible light, and FIG. 12D shows the state after irradiation with ultraviolet light. As shown in FIG. 12 (b), the right lower end side was bent upward by ultraviolet light irradiation and changed to a reddish color. As shown in FIG. 12 (b), the upward bending returned to the initial flat shape and further changed to the initial yellow color by irradiation with visible light. The polymer film of Example 2 showing such behavior is assumed to be used not only as the above-described irradiation history sensor of ultraviolet light and visible light but also as a light-responsive actuator.

[Example 4-6: Measurement of light intensity dependency of bending behavior of polymer film by light]
The bending speed was measured when the light intensity of ultraviolet light (wavelength: 365 nm) applied to the polymer film produced in Example 2 was changed. The result is shown in FIG. It was found that the bending speed of the polymer film increases with increasing light intensity. In addition, in FIG. 14, the photograph of an example of the bending behavior by the light of the polymer film of Example 2 is shown. FIG. 14A is a photograph before bending, and FIG. 14B 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, use as an optical modeling material, a light irradiation history sensor or the like is assumed. In addition, the polymer compound of the present application undergoes reversible changes in Tg and reversal of bending-flattening due to ultraviolet light irradiation and visible light irradiation. It is assumed to be used as a light responder such as an actuator.

Claims (11)

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

   

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

   

   (In the formula (B), m is an integer of 1 to 18, and R is hydrogen or a methyl group.)
4. The photoresponsive high molecular compound of Claim 3 which further contains the alkylglyceryl itaconate type | system | group repeating unit represented by a following formula (C).
   

   

   (In the formula (C), n is an integer of 4 to 17)
5. 5. An adhesive comprising the photoresponsive polymer compound according to claim 3 or 4 as an active ingredient, the adhesive strength of which changes by light irradiation.
6. A photoresponsive body comprising the photoresponsive polymer compound according to claim 3 or 4 as an active ingredient and reversibly deforming in response to light irradiation.
7. The photoresponsive body according to claim 6, wherein the photoresponsive body is deformed by one irradiation of ultraviolet light or visible light and returns to its original shape by the other irradiation.
8. The photoresponsive body according to claim 6 or 7, which has a film shape, a sheet shape, or a plate shape, and is bent or bent by light irradiation.
9. The manufacturing method of the photoresponsive high molecular compound which superpose | polymerizes the monomer containing the azo compound represented by a following formula (A).
   

   

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

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