KR100333578B1 - Diarylethene compounds - Google Patents

Abstract

The present invention relates to a diarylethene compound represented by the following Chemical Formula 2, and is used as a monomer for preparing a photochromic diarylethene polymer having a high photochromic speed and excellent mechanical strength.

[Formula 2]

[Wherein, R ₁ represents a hydrogen atom or a C _1-22 alkyl group or a fluorine group, a substituted or unsubstituted phenyl group, a substituted or unsubstituted phenylalkyl group; R ₂ represents a C _1-22 alkylene group unsubstituted or substituted with fluorine; R ₃ represents a C _1-3 alkylene group unsubstituted or substituted with a bond line, an oxygen atom, or fluorine; X and Y each independently represent an oxygen, nitrogen or sulfur atom; Z represents a methylene group or a carbonyl group unsubstituted or substituted with fluorine.]

Description

Diaryethene Compound {DIARYLETHENE COMPOUNDS}

The present invention relates to a diaryl ethene compound, which is excellent in adhesiveness, has a fast photochromic speed, excellent adhesion, and excellent workability. Can be used as.

Since diarylethene-based photochromic compounds have been synthesized in 1985, they have been known as stable photochromic compounds without heat discoloration after irradiation (Japan Kokai Tokkyo Koho; JP 86263935 A2, J. Org. Chem., 1991, 49, 373). Accordingly, the synthesis method of various derivatives has been studied, and many studies have been published to use it for reversible optical disks, erasable optical disks, optical switches for optical integrated devices, organic photoreceptors, photoelectrodes, etc. (Japan Kokai Tokkyo Koho; JP 91261782 A2 ,; JP 91261781 A2, JP 91261762 A2, JP 92178383 A2, JP 92178382 A2, JP 94199846 A2 ,, JP 91135977 A2, JP 9359025 A2, JP 93169820 A2, JP 9311406 A2, JP 93301873 A2, JP 94267071 A67 , JP 9669083 A2, JP 96245579 A2, JP 9761647 A2, JP 9780681 A2; Takeshita, M; Uchida, K .; Irie, M. Chem. Commun, 1996, 1807-1808, etc.).

The diarylethene-based compound changes color when exposed to ultraviolet light, and then returns to the original color of the compound when irradiated with light of a different wavelength. Several types of photochromic compounds have been proposed (Japan Kokai Tokkyo Koho; JP 9589954 A2, JP 9771585 A2, JP 9777743 A2, JP 9777767 A2, JP 05-301873 A2, etc.).

Among them, fluorine-substituted diarylethene and maleic anhydride-diarylethene have high dark stability, fast photochromic properties, and are compatible with polymer resins. Has been published (J. Org. Chem., 1991, 49, 373).

However, when the low molecular weight diarylethene compound is introduced into the polymer resin, the compatibility is not sufficient, and the diarylethene photochromic compound is eluted from the polymer medium during long-term storage and phase separation occurs. Accordingly, there is a problem in that the reliability and storage stability of the optical record is poor when used for a long time. In particular, when applied optically, photochromic reversibly occurs and accompanied by refractive index change. The problem of phase separation of low molecular weight diaryethene is different every time the photochromicity or refractive index change is repeated. It will lead to an error.

In order to solve this problem, polymers in which diarylethene is substituted with a side chain in the polymethacryl main chain have been developed (Japan Kokai Tokkyo Koho; JP 06/240242 A2). However, the synthesis of diaryethene methacrylate monomers is difficult using low temperature reaction, the polymer produced has poor mechanical properties, and the adhesive strength on the plastic plate, such as glass plate, PC, PMMA, PE has a disadvantage.

In addition, since it is substituted with alkylene substituted with hydrogen or fluorine between diarylethene and methacryl group, it cannot stabilize the polarized excited state structure generated when the diarylethene group is irradiated by light and excited within an extremely short time. There is a limit to the application to the photochromic thin film using the polarity of the excited state, such as the application of a fast refractive index change.

In order to solve the above problems, the present inventors are connected to a polar group such as a carboxyl group, and are easily synthesized and separated, have excellent photochromic properties, excellent mechanical properties, and a diaryl which can solve the problem of phase separation or compound formation. A method for synthesizing ten-based polymers has been studied. As a result, the styrene-based monomer of the formula (3) and the following formula are substituted with a diarylethene monomer substituted with XR ₂ OC (= O)-(where X is a methacryl group) in the benzene ring of the diaryl ethene as shown in the formula (2) Polymerization from the composition comprising the compound of 4 in the presence of an initiator produces a photochromic polymer of formula 1 having excellent mechanical properties, fast photochromic speed, and excellent processability, and from the composition in which the polymer is dissolved in an organic solvent. It has been found to form a discolored thin film to complete the present invention.

1 is a TGA showing the weight loss with respect to the heat of the copolymer of diarylethene-styrene prepared in Example 5;

FIG. 2 is a graph showing changes in the spectrum absorption spectrum (dotted line: before light irradiation and solid line: 1 minute after light irradiation) that appear when irradiating a short wavelength of 310 nm to the thin film prepared in Example 11. FIG.

Accordingly, it is a first object of the present invention to provide a diarylethene-based polymer having excellent photochromic properties. Diaryl ethene-based polymer according to the invention corresponds to the formula (4).

[In the above formula,

R ₁ represents a hydrogen atom or a C _1-22 alkyl group or a fluorine group, a substituted or unsubstituted phenyl group, a substituted or unsubstituted phenylalkyl group;

R ₂ represents a C _1-22 alkylene group unsubstituted or substituted with fluorine;

R ₃ represents a C _1-3 alkylene group unsubstituted or substituted with a bond line, an oxygen atom, or fluorine;

X and Y each independently represent an oxygen, nitrogen or sulfur atom;

Z represents a methylene group or a carbonyl group unsubstituted or substituted with fluorine;

R ₄ is the same as R ₁ or represents a C _1-22 alkylene or alkyleneoxy alkyl ester group unsubstituted or substituted with fluorine, and the alkylene group or alkyleneoxyalkyl ester group described above is a methacryl group, an acryl group, a It may be substituted with one or more selected from fluoroacryl groups and the like;

R ₅ is the same as R ₂ or represents a C _1-22 alkyleneoxy group unsubstituted or substituted with fluorine;

o, p, q and r are numbers representing mole fractions, satisfying o + p + q + r = 1 and each representing a number of 0 or more and 1 or less.]

The diarylethene-based polymer of the formula (1) according to the present invention has excellent photochromic properties, such as fast photochromic speed.

The diarylethene-based polymer represented by Formula 1 may be prepared from a diarylethene compound of Formula 2, a styrene monomer of Formula 3, and a compound of Formula 4.

Accordingly, a second object of the present invention is to provide a method for preparing a diaryethene-based polymer of Formula 1 from a diarylethene compound of Formula 2, a styrene monomer of Formula 3, and a compound of Formula 4.

[Formula 1]

[Wherein R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , X, Y, Z, o, p, q and r are as defined above.]

According to one preferred embodiment of the present invention, the diarylethene-based polymer of Formula 1 may be selected from the group consisting of tetrahydrofuran, toluene, C _1-10 alcohol, acetonitrile, acetone, DMSO, DMF, α-methylnaphthalene, 30 ° C. to 400 hours for 0.5 to 10 hours in the presence of at least one solvent selected from the group consisting of methoxynaphthalene, chloronaphthalene, diphenylethane, ethylene glycol, quinoline, dichlorobenzene, dichlorotoluene, propylenecarbonate, sulfolane and xylene It is manufactured by reacting at the temperature of ° C.

A third object of the present invention is to provide a composition comprising a diarylethene compound of formula (2), a styrene monomer of formula (3) and a compound of formula (4) for the preparation of the diarylethene-based polymer of formula (1) according to the present invention will be.

The composition according to the present invention is tetrahydrofuran, toluene, C _1-10 alcohol, acetonitrile, acetone, DMSO, DMF, α-methylnaphthalene, methoxynaphthalene, chloronaphthalene, diphenylethane, ethylene glycol, quinoline, dichloro It may include one or more solvents selected from the group consisting of benzene, dichlorotoluene, propylene carbonate, sulfolane and xylene.

A fifth object of the present invention is to provide a diarylethene compound of formula (2) for preparing a diarylethene-based polymer of formula (1) according to the present invention. The diarylethene compound of the formula (2) is substituted with XR ₂ OC (═O) —, where X is a methacryl group, in the benzene ring of diarylethene.

A sixth object of the present invention is to provide a photochromic thin film of the diarylethene-based polymer of formula (1). The photochromic thin film may be prepared by heat treating or photocrosslinking a composition composed of a diarylethene compound of Formula 2, a styrene monomer of Formula 3, and a compound of Formula 4 in the presence or absence of a solvent and in the presence of an initiator. . The photochromic thin film thus prepared has a fast photochromic speed and excellent mechanical properties.

The diarylethene compound of formula (2) of the present invention reacts diarylethene, which is commercially available or prepared by a known method, with acetyl chloride to prepare monoacetyl-substituted diarylethene, followed by hydration, and then methacryl It is prepared by reacting with a substituted alkylene alcohol and can generally be obtained in a yield of at least 90%.

For example, 1- [6 '-(methacryloyloxyethyloxycarbonyl) -2'-methylbenzo [b] thiophen-3'-yl] -2- (2'-methylbenzo [b] Thiophen-3'-yl) hexafluorocyclopentene is prepared from 1,2-bis (2-methylbenzo [b] thiophen-3-yl) hexafluorocyclopentene.

Specifically, aluminum trichloride (AlCl ₃ ) is slowly added to a solution of 1,2-bis (2-methylbenzo [b] thiophen-3-yl) hexafluorocyclopentene and acetyl chloride in nitrobenzene at room temperature. After the addition, the mixture was reacted at room temperature for 5 hours, and then water was added to stop the reaction. When extracted with chloroform, 1- [6'-acetyl-2'-methylbenzo [b] thiophen-3'-yl]- 2- (2'-methylbenzo [b] thiophen-3'-yl) hexafluorocyclopentene is obtained in 84% yield. The resulting product is dissolved in dioxane, the resulting solution is slowly added dropwise to the sodium hypochlorite / dioxane solution at 30-80 ^o C and the resulting reaction mixture is continued at 50-110 ^o C for 0.5-10 hours. After reaction and purification, 1- (6'-carboxy-2'-methylbenzo [b] thiophen-3'-yl) -2- (2'-methylbenzo [b] thiophen-3'-yl) Hexafluorocyclopentene is obtained in a yield of 99%.

Prepared 1- (6'-carboxy-2'-methylbenzo [b] thiophen-3'-yl] -2- (2'-methylbenzo [b] thiophen-3'-yl) hexafluoro Cyclopentene is dissolved in 2-hydroxyethyl methacrylate, DCC, DMAP, and dichloromethane and stirred at room temperature to produce a yield of 92% .The above formulas (2) and (3) of the present invention may use commercially available compounds. .

As described above, the photochromic polymer of the present invention dissolves at least one compound selected from the diarylethene compound of Formula 1 and the compounds of Formulas 2 and 3 in an organic solvent, and after adding a thermosetting agent, 30 ° C. to 150 ° C. Preferably, the resulting mixture is heated and reacted at a temperature of 40 ° C. to 120 ° C. for 0.5 to 150 hours, preferably 2 to 100 hours. As an example, the styrene copolymer of photochromic diarylethene may contain 38% of 1- [6 '-(methacryloyloxyethyloxycarbonyl) -2'-methylbenzo [b] thiophen-3' by weight ratio. -Yl] -2- (2'-methylbenzo [b] thiophen-3'-yl) hexafluorocyclopentene, 40% styrene, 22% butyl methacrylate in THF, followed by addition of a thermosetting agent And refluxed under nitrogen atmosphere. The weight average molecular weight of the prepared polymer is 10500, based on polystyrene, and the dispersity (M _w / M _n ) is 1.49, so that a photochromic polymer can be prepared by dissolving in a solution.

Furthermore, 22% by weight of 1- [6 '-(methacryloyloxyethyloxycarbonyl) -2'-methylbenzo [b] thiophen-3'-yl] -2- (2'-methylbenzo [ b] TGA showing a weight loss with respect to heat of the copolymer prepared from thiophen-3'-yl) hexafluorocyclopentene, indicating that the temperature showing a 10% weight loss from the TGA is 350 ° C. or higher, indicating very excellent thermal stability. Diarylethene-based polymers provided in accordance with the present invention can be dissolved in conventional solvents or mixtures thereof, such as toluene, xylene, chloroform, lower alcohols and the like.

It is still another object of the present invention to provide a composition comprising a diarylethene-based polymer having excellent thermal stability, and according to the present invention, the following composition is provided: toluene, chloroform, hexane, acetone, lower alcohol, 1 At least one solvent selected from the group consisting of conventional organic solvents such as 2-dichloroethane, methyl ethyl ketone, sulfolane, xylene, 3-nitro-α, α, and α-trifluoronitro, or mixtures thereof A composition comprising a diarylethene-based polymer prepared by the method, wherein the composition further contains at least one compound selected from the group consisting of tetraalkoxysilane, trialcohol glycidylsilane, tetraalkoxytitanium, hydrochloric acid and organic acid One composition; A composition comprising at least one resin selected from the group consisting of polyolefins, polystyrenes, polyvinyl butyral, polycarbonates, polyesters, polyacrylates, polyurethanes, and diarylethene-based polymers of the formula (4).

The polymer composition of the present invention described above is at least one selected from the group consisting of α-methylnaphthalene, methoxynaphthalene, chloronaphthalene, diphenylethane, ethylene glycol, sulfolane, quinoline, dichlorobenzene, dichlorotoluene, propylene carbonate and xylene It may further contain a high boiling point solvent.

The component ratio of each component of the composition of the present invention may be different depending on the use of the composition, but when the composition is used to produce a photochromic thin film as described below, the arylethene-based polymer of the formula (4) Preference is given to using in a proportion of 0.01 to 100% by weight of the total weight and using other components in a proportion of 0 to 99% by weight. When each component of the composition of the present invention is out of the component ratio, it is not preferable because the mechanical properties of the resulting thin film is not good. In addition, when the diarylethene-based polymer of the present invention is used in cosmetics, fibers, clays, and other compositions for light stabilizers or other purposes, the ratio of weight% may be used from 0.01 to several FPM units.

The above-described polymer composition of the present invention may be added various additives, lubricants and thickeners and the like apparent to those skilled in the art in order to improve heat resistance, mechanical properties, processing properties and the like.

Still another object of the present invention is to provide a photosensitive thin film having photosensitivity to ultraviolet light, visible light and near infrared light in the region of 200 to 800 nm using the above-described composition.

When the composition containing the diarylethene-based polymer prepared as described above is coated on a general support such as a plastic resin, a glass plate, an aluminum plate, a mylar film, or a conductive glass, it exhibits excellent absorption in a wavelength range of 200 to 500 nm. Diarylethene-based polymer thin films are provided. In addition, when the thin film is irradiated with light such as sunlight or ultraviolet rays, there is provided a diaryl ethene-based polymer thin film showing good absorption in the wavelength range of 300 ~ 800 nm. In this case, the coating may be a method such as roll coating or spin coating, bar coating, spray coating, dip coating, or the like.

In addition, the diarylethene-based polymer of the formula (1) of the present invention is processed by dissolving in one or more solvents selected from the group consisting of ether, alcohol, aromatic hydrocarbon, monoterpene hydrocarbon and liquid paraffin or polyvinyl butyral (PVB), A photochromic thin film is also provided by mixing with a general purpose polymer such as polycarbonate (PC) and milling and then applying it onto the support.

The diaryl ethene-based polymer provided in the present invention is capable of solution processing but exhibits an absorption peak in the range of 200 to 800 nm and thermal stability of 350 ° C. or higher, so that the display device, the optical switch device, the light integrated device, the solar cell, the sensor, etc. The possibility of application to other recording elements and optical elements is very high and these also belong to the scope of the present invention.

Features and other advantages of the present invention as described above will be more clearly described with reference to the following examples, but the scope of the present invention is not limited only to the following examples.

Examples 1-4 Preparation of Substituted Diarylethene Monomers

Example 1: Of 1- (6'-acetyl-2'-methylbenzo [b] thiophen-3'-yl) -2- (2'-methylbenzo [b] thiophen-3'-yl) hexafulocyclopentene synthesis

2.67 g of 1,2-bis (2-methylbenzo [b] thiophen-3-yl) hexafluorocyclopentene and 0.8 ml of acetyl chloride synthesized by a known method were dissolved in 40 ml of nitrobenzene, and then 2.28 g at room temperature. AlCl ₃ is slowly added. After reacting the reaction mixture at room temperature for 5 hours, the reaction was stopped with H ₂ O and extracted with chloroform. The organic layer was dried with MgSO ₄ , removed with solvent under reduced pressure and separated by column chromatography (20% ethyl acetate-hexane) to give 2.44 g of 1- (6'-acetyl-2'-methylbenzo [b] thiophene. -3'-yl) -2- (2'-methylbenzo [b] thiophen-3'-yl) hexafluorocyclopentene is prepared. Yield 84%.

mp = 62 ^o C

IR (KBr, Cm ⁻¹ ); 1684 (-CO group)

¹ H-NMR (300 MHz, CDCl ₃ ) δ 8.29-7.54 (4H), 7.39-7.17 (3H), 2.63 (3H), 2.56-2.46 (3H), 2.24,2.20 (3H)

¹³ C-NMR δ15.6, 15.9, 27.1, 119.3, 119.7, 122.3, 122.4, 122.6, 123.2, 123.5, 124.7, 124.9, 125.1, 133.7, 138.5, 138.6, 142.0, 143.1, 147.9, 197.6

MS (m / z); 510 (M ⁺ , 100), 495 (67), 452 (10), 419 (13), 84 (71)

high-resolution MS; Theoretical value C ₂₅ H ₁₆ OF ₆ S ₂ : 510.0547 Experimental value: 510.0529

Example 2: Of 1- (6'-carboxy-2'-methylbenzo [b] thiophen-3'-yl) -2- (2'-methylbenzo [b] thiophen-3'-yl) hexafluorocyclopentene synthesis

1- (6'-acetyl-2'-methylbenzo [b] thiophen-3'-yl) -2- (2'-methylbenzo [b] thiophen-3'-yl prepared by Example 1 A solution of 0.11 g of hexafluorocyclopentene in 0.7 ml of dioxane is added dropwise to 2.8 ml (10% solution) of sodium hypochlorite and 0.4 ml of dioxane with stirring at 50 ^° C. The reaction mixture is further stirred at 80 ^° C. for 2 hours, and then the reaction is stopped with saturated sodium carbonate and extracted with chloroform. The organic layer was dried with MgSO ₄ , the solvent was removed under reduced pressure, and dried in a vacuum oven (60 ^o C) for 24 hours. The colorless 1- (6'-carboxy-2'-methylbenzo [b] thiophene-3 ' -Yl) -2- (2'-methylbenzo [b] thiophen-3'-yl) hexafluorocyclopentene is prepared in a yield of 99%. The melting point of the prepared compound is 98 ^° C., and the -COOH group is characteristic of 1692 Cm ⁻¹ (KBr pellet) in the infrared spectral absorption spectrum.

¹ H-NMR (300 MHz, CDCl ₃ ) δ 8.46-7.53 (4H), 7.34-7.19 (3H), 2.52,2.48 (3H), 2.27,2.22 (3H)

¹³ C-NMR δ15.6, 15.9, 119.3, 119.8, 122.3, 122.6, 124.9, 125.1, 125.4, 125.7, 126.3, 126.4, 138.3, 138.5, 138.7, 142.7, 143.2, 148.2, 172.5

MS (m / z); 512 (M ⁺ , 100), 482 (11), 464 (5), 445 (11), 419 (24)

high-resolution MS; Theoretical value: C ₂₄ H ₁₄ O ₂ F ₆ S ₂ : 512.0339 Experimental value: 512.0352

Example 3: 1- (6'-methacryloyloxyethyloxycarboxy-2'-methylbenzo [b] thiophen-3'-yl) -2- (2'-methylbenzo [b] thiophen-3'-yl Synthesis of Hexafluorocyclopentene

1- (6'-carboxy-2'-methylbenzo [b] thiophen-3'-yl) -2- (2'-methylbenzo [b] thiophen-3'-yl) prepared in Example 2 2.3 g of hexafluorocyclopentene, 0.69 ml of methacrylic acid 2-hydroxy ester, 1.2 g of DCC, and 60 mg of DMAP are added to 50 ml of dichloromethane and stirred at room temperature for 5 hours. 50 ml of dichloromethane was added thereto, diluted with water, washed with water, and the dichloromethane layer was separated. Purification by flash chromatography (10% ethyl acetate-hexane) after removal of water with MgSO ₄ was carried out to yield colorless 1- (6'-methacryloyloxyethyloxycarboxy-2'-methylbenzo [b] thiophene-3. '-Yl) -2- (2'-methylbenzo [b] thiophen-3'-yl) hexafluorocyclopentene is prepared in a yield of 92%.

mp = 52 ^o C

IR (KBr, Cm ⁻¹ ); 1723 (-COO- group)

¹ H-NMR (300 MHz, CDCl ₃ ) δ 8.41-7.54 (4H), 7.37-7.17 (3H), 6.15 (s, 1H), 5.59 (s, 1H), 4.63-4.49 (m, 4H), 2.51 , 2.47 (3H), 2.24, 2.20 (3H), 1.95 (s, 1H)

¹³ C-NMR δ15.6, 15.9, 18.7, 62.8, 63.3, 119.3, 119.7, 122.3, 122.6, 124.8, 124.9, 125.1, 126.0, 126.3, 126.6, 136.3, 138.2, 138.3, 138.6, 142.1, 143.1, 166.4, 167.6

MS (m / z); 624 (M ⁺ , 100), 593 (3), 495 (43), 479 (7), 419 (4), 248 (9), 113 (55), 69 (24)

high-resolution MS; Theoretical value C ₃₀ H ₂₂ O ₄ F ₆ S ₂ : 624.0864 Experimental value: 624.0862

Example 4: 1- (6'-methacryloyloxypolyethyleneoxycarboxy-2'-methylbenzo [b] thiophen-3'-yl) -2- (2 "-methylbenzo [b] thiophen-3'-yl Synthesis of Hexafluorocyclopentene

1- (6'-carboxy-2'-methylbenzo [b] thiophen-3'-yl) -2- (2'-methylbenzo [b] thiophen-3'-yl) prepared in Example 2 2.3 g of hexafluorocyclopentene, 1 g of methacrylatopolyethyleneoxycarboxylic acid (weight average molecular weight 350), 1.5 g of DCC, and 79 mg of DMAP were added to 60 ml of dichloromethane and stirred at room temperature for 5 hours. 60 ml of dichloromethane was added thereto, diluted with water, washed with water, and the dichloromethane layer was separated. Removal of solvent and purification afforded colorless 1- (6'-methacryloyloxypolyethyleneoxycarboxy-2'-methylbenzo [b] thiophen-3'-yl) -2- (2 "-methylbenzo [b ] Thiophen-3'-yl) hexafluorocyclopentene is prepared in a yield of 90%.

Example 5-7 Preparation of Copolymers of Substituted Spirobenzopyran Compounds

Example 5

0.4 g of the diarylethene derivative prepared in Example 3, 0.89 g of styrene, and 0.52 g of butyl methacrylate are dissolved in THF, followed by addition of 1 wt% of AIBN of the total single molecule. The reaction is refluxed for 72 hours under a nitrogen atmosphere, then cooled to room temperature and the solvent is removed under reduced pressure to give a solid polymer. Reprecipitation with ethyl ether and hexane and drying under reduced pressure for 24 hours at 60 ^° C. yielded a diarylethene styrene copolymer in a yield of 40%. The glass transition temperature of the prepared polymer is 66 degrees, the weight average molecular weight is 11500, the dispersity (M _w / M _n ) is 1.60 to dissolve in the solution to prepare a photochromic polymer easy to process. A thermogravimetric analysis showing the pyrolysis temperature is shown in FIG. 1.

Example 6

0.93 g of the diarylethene derivative prepared in Example 3, 0.91 g of styrene, and 0.57 g of butyl methacrylate are dissolved in THF, followed by addition of 1 Wt% of AIBN of the total single molecule. The reaction was refluxed for 72 hours under a nitrogen atmosphere, then cooled to room temperature and the solvent removed under reduced pressure to prepare a solid polymer. Reprecipitation with ethyl ether and hexane and drying under reduced pressure at 60 ^° C. for 24 hours yields a diarylethene styrene copolymer in a yield of 60%. The glass transition temperature of the prepared polymer is 77 degrees, the weight average molecular weight is 10500, the dispersity (M _w / M _n ) is 1.49 to dissolve in a solution to prepare a photochromic polymer easy to process.

Example 7

The diarylethene derivatives prepared in Example 4 were used instead of the diarylethene derivatives prepared in Example 3, and the copolymer was prepared as in Example 5 and stirred for 90 hours. The yield of the copolymer produced is 56%.

Example 8

0.69 g of the diarylethene derivative prepared in Example 3, 0.35 g of bisallylcarbonate (CR-39, including 3% IPP), and 0.12 g of styrene in 2 mL of THF were stirred at 40 ° C. for 4 hours. After cooling to room temperature, and precipitated by addition of hexane, 0.5 g of diarylethene-based polymer is prepared. The polymer produced shows high solubility in DMF.

Example 9

In the course of Example 5, 0.6 g polyethylene glycol monomethacrylate (molecular weight 350) was added, and the same procedure was repeated to prepare a copolymer in a yield of 60%.

Examples 10 to 13 Preparation of Photochromic Thin Films

Example 10

0.5 g of the diarylethene copolymer prepared in Example 5 was dissolved in 5 ml of xylene and 2 ml of toluene, and then stirred at room temperature for 1 hour, and then concentrated until the weight change was reduced by 30%. The prepared solution was filtered using a 0.45 micron syringe filter, and then the solution was applied onto a glass plate using a spin coater and dried under reduced pressure in an oven at 50 ° C. for 12 hours. Are manufactured. When light of 300 nm or more is irradiated on the manufactured thin film, the color turns red. Phase separation did not occur even after 6 months of storage in the dark, and no association was found. In addition, no phase separation phenomenon was observed when repeatedly irradiated with light. FIG. 2 shows a change in absorption spectrum of a thin film when irradiated with a short wavelength of 310 nm.

Example 11

0.1 g of the diarylethene copolymer prepared in Example 6 was dissolved in 0.8 ml of xylene and 0.2 ml of toluene, stirred at room temperature for 1 hour, and then filtered using a 0.45 micron syringe filter. Coating on a plate and drying for 12 hours under reduced pressure in an oven at 50 degrees yields a transparent photochromic thin film having excellent adhesion and strength on a PC plate. Irradiation of short wavelength of 340 nm to the prepared thin film turns red and blocks the light and keeps red when stored in dark room. Phase separation did not occur even after 6 months of storage in the dark, and no association was found.

Example 12 [Comparative Example]

1- (6'-methacryloyloxyethyl-2'-methylbenzo [b] thiophen-3'-yl) -2- (2 by known method (Japan Kokai Tokkyo Koho; JP 06/240242 A2) A polyketylmethacrylic acid polymer was prepared by reacting '-methylbenzo [b] thiophen-3'-yl) hexafluorocyclopentene (40% by weight) with methacrylic acid methyl ester (60% by weight). The resultant copolymer was dissolved in chloroform and applied to a glass plate, resulting in poor mechanical properties and poor adhesion.

Example 13

0.2 g of the diaryethene copolymer prepared in Example 8 was dissolved in a mixed solvent of 0.8 ml of DMF, 0.2 ml of THF and ethylene glycol, stirred at room temperature for 1 hour, and filtered using a 0.45 micron syringe filter. Coating on a polyester film using a bar coater and drying for 12 hours under reduced pressure in an oven at 50 degrees produces a transparent photochromic thin film having excellent adhesiveness and excellent strength on the polyester film. Irradiation of short wavelength of 340 nm to the prepared thin film turns red and blocks the light and keeps red when stored in dark room. Phase separation did not occur even after 6 months of storage in the dark, and no association was found.

As described above, according to the present invention, a copolymer of diaryethene-styrene having a high photochromic speed, excellent adhesion, and excellent workability, and a diaryl which enables the preparation of a photochromic composition and a photochromic thin film using the same Ten compounds can be prepared.

Claims (1)

Diaryl ethene compound represented by the following formula (2). [Formula 2] [Wherein, R ₁ represents a hydrogen atom or a C _1-22 alkyl group or a fluorine group, a phenyl group, a phenylalkyl group; R ₂ represents a C _1-22 alkylene group unsubstituted or substituted with fluorine; R ₃ represents a C _1-3 alkylene group unsubstituted or substituted with a bond line, an oxygen atom, or fluorine; X and Y each independently represent an oxygen, nitrogen or sulfur atom; Z represents a methylene group or a carbonyl group unsubstituted or substituted with fluorine.]