COMPOSITION, FILM, LAMINATE, AND DISPLAY DEVICE

Abstract

Provided is a composition containing a compound of formula (1), and a polymerizable liquid crystal compound or a liquid crystalline polymer compound. n represents 1 or 2; Ar.sup.1, Ar.sup.2, and Ar.sup.3 each represent a 1,4-phenylene group or a divalent sulfur-containing aromatic heterocyclic group; At least one of Art and Ar.sup.2 has a fluorine atom; R.sup.1 represents a single bond or a group selected from —OC(═O)—, —C(═O)O—, —C≡C—, —CH═CH—, —CH═N—, —N═N—, and —N═CH—; R.sup.2 represents an alkylamino group or an alkoxy group; R.sup.3 represents a group selected from an alkanediyl group, an alkanediyloxy group, an alkanediyloxycarbonyl group, and an alkanediylcarbonyloxy group; and R.sup.4 represents a polymerizable group or a hydrogen atom.

R.sup.4—R.sup.3—Ar.sup.1—(—R.sup.1—Ar.sup.2—).sub.n—N═N—Ar—R.sup.2   (1)

Claims

1. A composition comprising: a compound represented by the following formula (1) and having a maximum absorption wavelength in a range of 420 nm or more and 520 nm or less; and at least one of a polymerizable liquid crystal compound and a liquid crystalline polymer compound:
R.sup.4—R.sup.3—Ar.sup.1—(—R.sup.1—Ar.sup.2—).sub.n—N═N—Ar.sup.3—R.sup.2   (1) wherein n is an integer of 1 or 2; Ar.sup.1, Ar.sup.2, and Ar.sup.3 each independently represent a 1,4-phenylene group optionally having a substituent or a divalent sulfur-containing aromatic heterocyclic group optionally having a substituent, and at least one of AO and Ar.sup.2 has a fluorine atom as a substituent; R.sup.e represents a single bond or at least one group selected from the group consisting of —OC(═O)—, —C(═O)O—, —C≡C—, —CH═CH—, —CH═N—, —N═N—, and —N═CH—; R.sup.2 represents an alkylamino group optionally having a polymerizable group or an alkoxy group optionally having a polymerizable group; R.sup.3 represents at least one group selected from the group consisting of an alkanediyl group having 4 to 20 carbon atoms, an alkanediyloxy group having 2 to 20 carbon atoms, an alkanediyloxycarbonyl group having 2 to 20 carbon atoms, and an alkanediylcarbonyloxy group having 2 to 20 carbon atoms; R.sup.4 represents a polymerizable group or a hydrogen atom; and when n is 2, two R.sup.1s may be the same as or different from each other, and two Ar.sup.2s may be the same as or different from each other.

2. The composition according to claim 1, wherein the polymerizable liquid crystal compound and the liquid crystalline polymer compound are a polymerizable smectic liquid crystal compound and a smectic liquid crystalline polymer compound, respectively.

3. The composition according to claim 1, wherein the polymerizable liquid crystal compound is a compound represented by the following formula (A):
U.sup.1—V.sup.1—W.sup.1—(X.sup.1—Y.sup.1).sub.m—X.sup.2—Y.sup.2—X.sup.3—W.sup.2—V.sup.2—U.sup.2   (A) wherein m is an integer of 1 to 3; X.sup.1, X.sup.2, and X.sup.3 each independently represent a divalent aromatic group or a divalent alicyclic hydrocarbon group; when m is 2 or 3, a plurality of X.sup.1s may be the same as or different from each other; at least three selected from the group consisting of X.sup.1, X.sup.2, and X.sup.3 each represent a divalent hydrocarbon six-membered ring group; Y.sup.1, Y.sup.2, W.sup.1 and W.sup.2 each independently represent a single bond or a divalent linking group; when m is 2 or 3, a plurality of Y.sup.1s may be the same as or different from each other; V.sup.1 and V.sup.2 each independently represent an alkanediyl group having 1 to 20 carbon atoms and optionally having a substituent; at least one of —CH.sub.2-s constituting the alkanediyl group may be substituted with —O—, —CO—, —S—, or —NH—; and U.sup.1 and U.sup.2 each independently represent a polymerizable group or a hydrogen atom, and at least one of U.sup.1 and U.sup.2 represents a polymerizable group.

4. The composition according to claim 1, wherein at least one of Ar.sup.1 and Ar.sup.2 has 1 to 4 fluorine atoms as a substituent in the formula (1).

5. The composition according to claim 1, wherein at least one of Ar.sup.1 and Ar.sup.2 has 1 or 2 fluorine atoms as a substituent in the formula (1).

6. The composition according to claim 1, wherein n is 1 in the formula (1).

7. The composition according to claim 1, wherein the polymerizable group is a radically polymerizable group.

8. A film comprising the composition according to claim 1, as a forming material.

9. A laminate comprising the film according to claim 8.

10. A display device comprising the laminate according to claim 9.

Description

EXAMPLES

[0204] Hereinafter, the present invention will be specifically described with reference to Examples, but the present invention is not limited to these Examples.

Synthesis Example 1: Synthesis of Compound (2-1)

[0205] In order to synthesize compound (2-1), compound (2-1-a) was first synthesized. In addition, compound (2-1-c) was synthesized via compound (2-1-b). Subsequently, compound (2-1-a) and compound (2-1-c) were subjected to Suzuki coupling to obtain compound (2-1).

Synthesis of Compound (2-1-a)

[0206] To a chloroform (240 mL) solution of EDC.HCl (1-ethyl-3-(3-dimethylaminopropyl) carbodiimide hydrochloride, 4.83 g, 25.2 mmol) and DMAP (N,N-dimethylaminopyridine, 0.29 g, 2.4 mmol), n-butanol (3.57 g, 48.1 mmol) and 4-bromobenzoic acid (4.83 g, 24.0 mmol) were added in order. The mixture was stirred at room temperature for six hours. Thereafter, the reaction solution was washed with water and then with saturated saline, dried over magnesium sulfate, and concentrated with an evaporator to obtain compound (2-1-a) (5.38 g, yield 87%).

##STR00042##

Synthesis of Compound (2-1-b)

[0207] 4-Bromoaniline (13.2 g, 77.6 mmol), 35% hydrochloric acid (22.0 mL, 249 mmol), and water (200 mL) were mixed and cooled to a temperature of 0° C. to 5° C. To the mixture, a water (26 mL) solution of sodium nitrite (13.0 g, 189 mmol) was added dropwise. Thereafter, the mixture was stirred for 30 minutes while the temperature was maintained at 0° C. to 5° C., and amide sulfuric acid (11.0 g, 113 mmol) was further added thereto to prepare a diazo liquid. Meanwhile, N,N-dimethylaniline (14.0 mL, 111 mmol), sodium acetate (24.8 g, 302 mmol), methanol (200 mL), and water (100 mL) were mixed and cooled to a temperature of 0° C. to 5° C. To the mixture, the whole amount of the diazo liquid prepared above was added dropwise. After completion of the dropwise addition, the temperature was raised to normal temperature, and the precipitated solid was separated by filtration to obtain compound (2-1-b) (21.0 g, yield 90%).

##STR00043##

Synthesis of Compound (2-1-c)

[0208] A THF (450 mL) solution of compound (2-1-b) (18.3 g, 60.0 mmol) was cooled to −78° C. To the solution, a 1.57 M n-butyllithium hexane solution of (38.0 mL, 59.7 mmol) was added dropwise. Thereafter, the mixture was stirred for 30 minutes while the temperature was maintained at −78° C., and iPrOBpin (abbreviation of 2-isopropoxy-4,4,5,5-tetramethyl-1,3,2-dioxaborolane, 11.0 mL, 64.8 mmol) was further added dropwise thereto. After completion of the dropwise addition, the temperature was raised to normal temperature, and the mixture was stirred for 30 minutes. To the mixture, a water (400 mL) solution of ammonium chloride (60 g) was added to stop the reaction. The organic layer was separated, washed with saturated saline, then dried over magnesium sulfate, and concentrated with an evaporator. The obtained solid was purified by reprecipitation from chloroform/hexane to obtain compound (2-1-c) (16.7 g, yield 79%).

##STR00044##

Synthesis of Compound (2-1)

[0209] To a THF (10 mL) solution of compound (2-1-a) (286 mg, 1.10 mmol) and compound (2-1-c) (352 mg, 1.00 mmol), Pd.sub.2(dba).sub.3 (22.7 mg, 0.0248 mmol) and P(t-Bu).sub.3.HBF.sub.4 (15.3 mg, 0.0527 mmol) were added, and the mixture was stirred. To the mixture, a 3 M potassium phosphate aqueous solution (1.0 mL, 3.0 mmol) was further added, and the mixture was heated and stirred at 60° C. for 3.6 hours. To the reaction solution, methanol (20 mL) was added, and the precipitated solid was collected by filtration and purified by silica gel column chromatography using chloroform as an eluent to obtain compound (2-1) (256 mg, yield 71%).

[0210] .sup.1H-NMR (400 MHz, CDCl.sub.3) : δ (ppm)=8.14-8.10 (m, 2H), 7.95-7.89 (m, 4H), 7.76-7.71 (m, 4H), 6.80-6.76 (m, 2H), 4.36 (t, 2H), 3.11 (s, 6H), 1.78 (tt, 2H), 1.55-1.46 (m, 2H), 1.00 (t, 3H).

[0211] UV visible light spectrum: λmax=436 nm (in acetonitrile)

##STR00045##

Synthesis Example 2: Synthesis of Compound (3)

[0212] In order to synthesize compound (3), compound (3-a) was first synthesized. Subsequently, compound (3-a) and the above-described compound (2-1-c) were subjected to Suzuki coupling to obtain compound (3).

Synthesis of Compound (3-a)

[0213] To a dichloromethane (60 mL) solution of EDC.HCl (1.36 g, 7.10 mmol) and DMAP (0.083 g, 0.68 mmol), n-hexanol (0.90 mL, 7.2 mmol) and 4-bromobenzoic acid (1.36 g, 6.76 mmol) were added in order. The mixture was stirred at room temperature for six hours. Thereafter, the reaction solution was washed with water and then with saturated saline, dried over magnesium sulfate, and concentrated with an evaporator to obtain compound (3-a) (1.70 g, yield 88%).

##STR00046##

Synthesis of Compound (3)

[0214] To a diethylene glycol dimethyl ether (13 mL) and water (2 mL) mixed solution of compound (3-a) (285 mg, 1.00 mmol), compound (2-1-c) (457 mg, 1.30 mmol), potassium acetate (650 mg, 6.63 mmol), PdCl.sub.2dppf (41.0 mg, 0.0502 mmol) was added, and the mixture was heated and stirred at 140° C. for four hours. To the reaction solution, THF was added, and the mixture was caused to pass through a silica gel short column and then concentrated with an evaporator. The obtained solid was washed with methanol/water and then purified by silica gel column chromatography (chloroform/toluene=20/80) to obtain compound (3) (238 mg, yield 55%).

[0215] .sup.1H-NMR (400 MHz, CDCl.sub.3) : δ (ppm)=8.14-8.11 (m, 2H), 7.95-7.89 (m, 4H), 7.76-7.71 (m, 4H), 6.80-6.76 (m, 2H), 4.35 (t, 2H), 3.11 (s, 6H), 1.79 (tt, 2H), 1.51-1.44 (m, 2H), 1.37-1.33 (m, 4H), 0.92 (t, 3H).

[0216] UV visible light spectrum: λmax=430 nm (in acetonitrile)

##STR00047##

Synthesis Example 3: Synthesis of Compound (2-3)

[0217] In order to synthesize compound (2-3), compound (2-3-a) was first synthesized. Subsequently, compound (2-3-a) and the above-described compound (2-1-c) were subjected to Suzuki coupling to obtain compound (2-3).

Synthesis of Compound (2-3-a)

[0218] To a chloroform (80 mL) solution of EDC.HCl (1.61 g, 8.41 mmol) and DMAP (0.098 g, 0.80 mmol), ethanol (1.85 g, 40.1 mmol) and 4-bromo-2,6-difluorobenzoic acid (1.90 g, 8.01 mmol) were added in order. The mixture was stirred at room temperature for four hours. Thereafter, the reaction solution was washed with water and then with saturated saline, dried over magnesium sulfate, and concentrated with an evaporator. The concentrated product was dissolved in a mixed solvent of chloroform/hexane=1/1, caused to pass through a silica gel short column, and then concentrated with an evaporator to obtain compound (2-3-a) (1.32 g, yield 62%).

##STR00048##

Synthesis of Compound (2-3)

[0219] To a THF (10 mL) solution of compound (2-3-a) (292 mg, 1.10 mmol) and compound (2-1-c) (351 mg, 1.00 mmol), Pd.sub.2(dba).sub.3 (22.7 mg, 0.0248 mmol) and P(t-Bu).sub.3.HBF.sub.4 (15.2 mg, 0.0524 mmol) were added, and the mixture was stirred. To the mixture, a 3 M potassium phosphate aqueous solution (1.0 mL, 3.0 mmol) was further added, and the mixture was heated and stirred at 60° C. for 4.5 hours. To the reaction solution, methanol (20 mL) was added, and the precipitated solid was collected by filtration and purified by silica gel column chromatography using chloroform as an eluent to obtain compound (2-3) (161 mg, yield 39%).

[0220] .sup.1H-NMR (400 MHz, CDCl.sub.3) : δ (ppm)=7.95-7.89 (m, 4H), 7.69-7.66 (m, 2H), 7.26-7.22 (m, 2H), 6.79-6.75 (m, 2H), 4.45 (q, 2H), 3.11 (s, 6H), 1.42 (t, 3H).

[0221] UV visible light spectrum: λmax=437 nm (in acetonitrile)

##STR00049##

Synthesis Example 4: Synthesis of Compound (2-106)

[0222] In order to synthesize compound (2-106), compound (2-106-a) was first synthesized.

[0223] Subsequently, compound (2-106-a) and the above-described compound (2-1-c) were subjected to Suzuki coupling to obtain compound (2-106).

Synthesis of Compound (2-106-a)

[0224] To a chloroform (80 mt) solution of EDC.HCl (1.61 g, 8.41 mmol) and DMAP (0.098 g, 0.80 mmol), n-buthanol (1.19 g, 16.0 mmol) and 4-bromo-2,6-difluorobenzoic acid (1.90 g, 8.01 mmol) were added in order. The mixture was stirred at room temperature for 3.5 hours. Thereafter, the reaction solution was washed with water and then with saturated saline. The washed product was dried over magnesium sulfate and concentrated with an evaporator to obtain compound (2-106-a) (1.47 g, yield 62%).

##STR00050##

Synthesis of Compound (2-106)

[0225] To a THF (10 mL) solution of compound (2-106-a) (323 mg, 1.10 mmol) and compound (2-1-c) (352 mg, 1.00 mmol), Pd.sub.2(dba).sub.3 (23.2 mg, 0.0253 mmol) and P(t-Bu).sub.3.HBF.sub.4 (15.8 mg, 0.0545 mmol) were added, and the mixture was stirred. To the mixture, a 3 M potassium phosphate aqueous solution (1.0 mL, 3.0 mmol) was further added, and the mixture was heated and stirred at 60° C. for four hours. To the reaction solution, methanol (20 mL) was added, and the precipitated solid was collected by filtration and purified by silica gel column chromatography using chloroform as an eluent to obtain compound (2-106) (154 mg, yield 35%).

[0226] .sup.1H-NMR (400 MHz, CDCl.sub.3) : δ (ppm)=7.95-7.89 (m, 4H), 7.69-7.66 (m, 2H), 7.26-7.22 (m, 2H), 6.79-6.75 (m, 2H), 4.39 (t, 2H), 3.11 (s, 6H), 1.76 (tt, 2H), 1.49 (tq, 2H), 0.99 (t, 3H).

[0227] UV visible light spectrum: λmax=436 nm (in acetonitrile)

##STR00051##

Synthesis Example 5: Synthesis of Compound (2-4)

[0228] In order to synthesize compound 2-4, compound (2-4-b) was first synthesized via compound (2-4-a). Subsequently, compound (2-4-b) and ethyl 4-bromobenzoate were subjected to Suzuki coupling to obtain compound (2-4).

Synthesis of Compound (2-4-a)

[0229] To a chloroform (80 mt) solution of EDC.HCl (1.61 g, 8.41 mmol) and DMAP (0.098 g, 0.80 mmol), ethanol (1.84 g, 40.0 mmol) and 4-bromo-2-fluorobenzoic acid (1.75 g, 8.00 mmol) were added in order. The mixture was stirred at room temperature for 3.5 hours. Thereafter, the reaction solution was washed with water and then with saturated saline. The washed product was dried over magnesium sulfate and concentrated with an evaporator to obtain compound (2-4-a) (1.60 g, yield 81%).

##STR00052##

Synthesis of Compound (2-4)

[0230] To a THF (10 mL) solution of compound (2-4-a) (552 mg, 2.23 mmol) and compound (2-1-c) (704 mg, 2.01 mmol), Pd.sub.2(dba).sub.3 (46.1 mg, 0.0503 mmol) and P(t-Bu).sub.3.HBF.sub.4 (29.0 mg, 0.100 mmol) were added, and the mixture was stirred. To the mixture, a 3 M potassium phosphate aqueous solution (2.0 mL, 6.0 mmol) was further added, and the mixture was heated and stirred at 60° C. for 3.5 hours. To the reaction solution, water (20 mL) was added, and the precipitated solid was collected by filtration and purified by silica gel column chromatography using chloroform as an eluent to obtain compound (2-4) (480 mg, yield 61%).

[0231] .sup.1H-NMR (400 MHz, CDCl.sub.3) : δ (ppm)=8.02 (dd, IH), 7.95-7.89 (m, 4H), 7.74-7.70 (m, 2H), 7.50 (dd, 1H), 7.43 (dd, 1H), 6.80-6.76 (m, 2H), 4.43 (q, 2H), 3.11 (s, 6H), 1.43 (t, 3H).

[0232] UV visible light spectrum: λmax=436 nm (in acetonitrile)

##STR00053##

Synthesis Example 6: Synthesis of Compound (2-6)

[0233] In order to synthesize compound (2-6), compound (2-6-b) was first synthesized via compound (2-6-a). Subsequently, compound (2-6-b) and ethyl 4-bromobenzoate were subjected to Suzuki coupling to obtain compound (2-6).

Synthesis of Compound (2-6-a)

[0234] 4-Bromo-2-fluoroaniline (14.3 g, 75.0 mmol), 35% hydrochloric acid (22.0 mL, 249 mmol), and water (200 mL) were mixed and cooled to a temperature of 0° C. to 5° C. To the mixture, a water (26 mL) solution of sodium nitrite (7.76 g, 112 mmol) was added dropwise. Thereafter, the mixture was stirred for 30 minutes while the temperature was maintained at 0° C. to 5° C., and amide sulfuric acid (4.36 g, 45.0 mmol) was further added thereto to prepare a diazo liquid. Meanwhile, N,N-dimethylaniline (13.6 g, 113 mmol), sodium acetate (24.6 g, 300 mmol), methanol (200 mL), and water (100 mL) were mixed and cooled to a temperature of 0° C. to 5° C. To the mixture, the whole amount of the diazo liquid prepared above was added dropwise. After completion of the dropwise addition, the temperature was raised to normal temperature, and the precipitated solid was separated by filtration to obtain compound (2-6-a) (15.8 g, yield 66%).

##STR00054##

Synthesis of Compound (2-6-b)

[0235] To a 1,4-dioxane (60 mL) solution of compound (2-6-a) (3.23 g, 10.0 mmol), B.sub.2pin.sub.2 (bis(pinacolato) diboron, 2.79 g, 11.0 mmol), and potassium acetate (2.99 g, 30.4 mmol), PdCl.sub.2dppf (249 mg, 0.305 mmol) was added, and the mixture was heated and stirred at 80° C. for seven hours. The reaction solution was separated with toluene/water, and the organic layer was washed with water and then with saturated saline, then dried over magnesium sulfate, and concentrated with an evaporator. The obtained solid was purified by reprecipitation from chloroform/hexane to obtain compound (2-6-b) (2.53 g, yield 69%).

##STR00055##

Synthesis of Compound (2-6)

[0236] To a THF (30 mL) solution of ethyl 4-bromobenzoate (0.763 g, 3.33 mmol) and compound (2-6-b) (1.11 g, 3.00 mmol), Pd.sub.2(dba).sub.3 (69.8 mg, 0.0762 mmol) and P(t-Bu) : 3.HBF.sub.4 (45.0 mg, 0.155 mmol) were added, and the mixture was stirred. To the mixture, a 3 M potassium phosphate aqueous solution (4.0 mL, 12.0 mmol) was further added, and the mixture was heated and stirred at 60° C. for four hours. To the reaction solution, methanol (20 mL) was added, and the precipitated solid was collected by filtration and purified by silica gel column chromatography using chloroform as an eluent to obtain compound (2-6) (904 mg, yield 77%).

[0237] .sup.1H-NMR (400 MHz, CDCl.sub.3) : δ (ppm)=8.15-8.12 (m, 2H), 7.95-7.91 (m, 2H), 7.84 (d, 1H), 7.72-7.68 (m, 2H), 7.52-7.45 (m, 2H), 6.79-6.75 (m, 2H), 4.42 (q, 2H), 3.12 (s, 6H), 1.43 (t, 3H).

[0238] UV visible light spectrum: λmax=452 nm (in acetonitrile)

##STR00056##

Synthesis Example 7: Synthesis of Compound (2-116)

[0239] In order to synthesize compound 2-116, compound (2-116-b) was first synthesized via compound (2-116-a). Subsequently, compound (2-116-b) and n-butyl zinc bromide were subjected to Negishi coupling to obtain compound (2-116).

Synthesis of Compound (2-116-a)

[0240] 4-Bromo-3-fluoroaniline (9.50 g, 50.0 mmol), 35% hydrochloric acid (14.8 mL, 167 mmol), and water (95 mL) were mixed and cooled to a temperature of 0° C. to 5° C. To the mixture, a water (5 mL) solution of sodium nitrite (3.45 g, 50.0 mmol) was added dropwise to prepare a diazo liquid. Meanwhile, sodium (phenylamino) methanesulfonate (11.5 g, 55.0 mmol), sodium acetate (16.4 g, 55.0 mmol), and water (100 mt) were mixed and cooled to a temperature of 0° C. to 5° C. To the mixture, the whole amount of the diazo liquid prepared above was added dropwise. After completion of the dropwise addition, the temperature was raised to normal temperature, sodium hydroxide (12.0 g, 300 mmol) was added thereto, and the mixture was heated and stirred at 90° C. for 2.5 hours. The precipitated solid was collected by filtration to obtain compound (2-116-a) (13.9 g, yield 94%).

##STR00057##

[0241] Compound (2-116-a) (1.47 g, 10.0 mmol), 35% hydrochloric acid (1.5 mL, 17 mmol), and water (9 mL) were mixed and cooled to a temperature of 0° C. to 5° C. To the mixture, a water (1 mL) solution of sodium nitrite (345 mg, 5.00 mmol) was added dropwise. Thereafter, the mixture was stirred for 45 minutes while the temperature was maintained at 10° C. to 15° C. to prepare a diazo liquid. Meanwhile, N,N-dimethylaniline (895 mg, 6.00 mmol), sodium acetate (1.64 g, 20.0 mmol), methanol (20 mL), and water (10 mL) were mixed and cooled to a temperature of 10° C. to 15° C. To the mixture, the whole amount of the diazo liquid prepared above was added dropwise. After completion of the dropwise addition, the temperature was raised to normal temperature, and the precipitated solid was collected by filtration, dissolved in chloroform, and washed with water and then with saturated saline.

[0242] The washed product was dried over magnesium sulfate and concentrated with an evaporator. The obtained solid was purified by silica gel column chromatography (chloroform/hexane=50/50) to obtain compound (2-116-b) (1.26 g, yield 55%).

##STR00058##

[0243] A mixed solution of compound (2-116-b) (213 mg, 0.500 mmol), PdCl.sub.2dppf (8.1 mg, 0.010 mmol), and THF (5.0 mL) was heated and stirred at 55° C. To the mixed solution, 0.50 M n--butylzinc bromide (1.2 mL, 0.60 mmol) was added dropwise. Thereafter, the mixture was heated and refluxed for 3.5 hours. To the reaction solution, water (20 mL) was added, and the precipitated solid was collected by filtration and purified by silica silica gel column chromatography (chloroform/hexane=50/50). The purified solid was further purified by reprecipitation from chloroform/hexane to obtain compound (2-116) (137 mg, yield 64%).

[0244] .sup.1H-NMR (400 MHz, CDCl.sub.3) : δ (ppm)=8.03-8.00 (m, 2H), 7.98-7.95 (m, 2H), 7.92-7.88 (m, 2H), 7.71 (dd, 1H), 7.60 (dd, IH), 7.34 (dd, 1H), 6.76-6.72 (m, 2H), 3.46 (q, 4H), 2.72 (t, 2H), 1.65 (tt, 2H), 1.41 (tq, 2H), 1.25 (t, 6H), 0.96 (t, 3H).

[0245] UV visible light spectrum: λmax=499 nm (in acetonitrile)

##STR00059##

Synthesis Example 8: Synthesis of Compound (2-166)

[0246] 2-Bromo-5-n-butylthienothiazole and the above-described compound (2-6-b) were subjected to Suzuki coupling to obtain compound (2-166).

Synthesis of Compound (2-166)

[0247] To a THF (10 mL) solution of 2-bromo-5-n-butylthienothiazole (0.304 g, 1.10 mmol) and compound (2-6-b) (0.369 g, 1.00 mmol), Pd.sub.2(dba).sub.3 (0.0367 mg, 0.0400 mmol) and P(t-B)3.HBF.sub.4 (0.0232 mg, 0.0800 mmol) were added, and the mixture was stirred.

[0248] To the mixture, a 3 M potassium phosphate aqueous solution (2.0 mL, 6.0 mmol) was further added, and the mixture was heated and stirred for 16 hours. To the reaction solution, methanol was added, and the precipitated solid was collected by filtration and purified by silica gel column chromatography (chloroform/toluene=10/90) to obtain compound (2-166) (0.127 g, yield 29%).

[0249] .sup.1H-NMR (400 MHz, CDCl.sub.3) : δ (ppm)=9.95-7.91 (m, 2H), 7.87-7.81 (m, 2H), 7.77 (dd, 1H), 6.95 (s, 1H), 6.78-6.74 (m, 2H), 3.12 (s, 6H), 2.92 (t, 2H), 1.74 (tt, 2H),1.44 (tq, 2H), 0.97 (t, 3H).

[0250] UV visible light spectrum: λmax=475 nm (in acetonitrile)

##STR00060##

Synthesis Example 9: Synthesis of Compound (2-167)

[0251] 2-Bromo-5-n-butylthienothiazole and compound (2-167-b) synthesized via compound (2-167-a) were subjected to Suzuki coupling to obtain compound (2-167).

Synthesis of Compound (2-167-a)

[0252] 4-Bromo-3-fluoroaniline (1.90 g, 10.0 mmol), 35% hydrochloric acid (3.0 mL, 34 mmol), and water (25 mL) were mixed and cooled to a temperature of 0° C. to 5° C. To the mixture, a water (2.5 mL) solution of sodium nitrite (0.69 mg, 10.0 mmol) was added dropwise to prepare a diazo liquid. Meanwhile, dimethylaniline (1.33 g, 11.0 mmol), sodium acetate (3.28 g, 40.0 mmol), methanol (25.0 mL), and water (12.5 mL) were mixed and cooled to a temperature of 0° C. to 5° C. To the mixture, the whole amount of the diazo liquid prepared above was added dropwise. After completion of the dropwise addition, the temperature was raised to normal temperature, and the precipitated solid was separated by filtration to obtain compound (2-167-a) (2.59 g, yield 80%).

##STR00061##

Synthesis of Compound (2-167-b)

[0253] To a 1,4-dioxane (35 mt) solution of compound (2-167-a) (2.26 g, 7.00 mmol), B.sub.2pin.sub.2 (official name is bis(pinacolato) diboron, 1.96 g, 7.70 mmol), and potassium acetate (2.06 g, 21.0 mmol), PdCl.sub.2dppf (0.286 g, 0.351 mmol) was added, and the mixture was heated and stirred at 80° C. for 15 hours. The reaction solution was separated with toluene/water, and the organic layer was washed with water and then with saturated saline, then dried over magnesium sulfate, and concentrated with an evaporator. The obtained solid was purified by reprecipitation from chloroform/hexane to obtain compound (2-167-b) (1.74 g, yield 67%).

##STR00062##

Synthesis of Compound (2-167)

[0254] To a 1,4-dioxane (10 mL) solution of 2-bromo-5-n-butylthienothiazole (0.307 g, 1.11 mmol) and compound (2-167-b) (0.370 g, 1.00 mmol), Pd.sub.2(dba).sub.3 (0.023 g, 0.0251 mmol) and P(t-Bu).sub.3.HBF.sub.4 (0.015 g, 0.0517 mmol) were added, and the mixture was stirred. To the mixture, a 3 M potassium phosphate aqueous solution (1.0 mL, 3.0 mmol) was further added, and the mixture was heated and stirred for four hours. To the reaction solution, methanol was added, and the precipitated solid was collected by filtration and purified by silica gel column chromatography using chloroform as an eluent, and further purified by reprecipitation from chloroform/methanol to obtain compound (2-167) (0.317 g, yield 72%).

[0255] .sup.1H-NMR (400 MHz, CDCl.sub.3) : δ (ppm)=8.42 (dd, IH), 7.92-7.89 (m, 2H), 7.78 (dd, IH), 7.68 (dd, IH), 6.97 (s, 1H), 6.79-6.75 (m, 2H), 3.12 (s, 6H), 2.93 (t, 2H), 1.75 (tt, 2H), 1.45 (tq, 2H), 0.97 (t, 3H).

[0256] UV visible light spectrum: λmax=471 nm (in acetonitrile)

##STR00063##

Synthesis Example 10: Synthesis of Compound (2-184)

[0257] In order to synthesize compound (2-184), compound (2-184-a) was first synthesized.

[0258] Subsequently, compound (2-184-a) and the above-described compound (2-6-b) were subjected to Suzuki coupling to obtain compound (2-184-b). Subsequently, compound (2-184-b) was subjected to a transesterification reaction to obtain compound (2-184).

Synthesis of Compound (2-184-a)

[0259] To an acetonitrile (200 mL) solution of copper (II) bromide (6.48 g, 29.0 mmol), isobutyl nitrite (4.40 mL, 37 mmol) and ethyl 2-aminobenzothiazole-6 carboxylate (5.56 g, 25.0 mmol) were added in order. The mixture was stirred at 65° C. for 1.5 hours. Thereafter, the reaction solution was cooled to room temperature, and then poured into 0.4 M hydrochloric acid (200 mL) to stop the reaction. The reaction solution was separated with chloroform/water Thereafter, the organic layer was washed with water and then with saturated saline, dried over magnesium sulfate, and concentrated with an evaporator to obtain compound (2-184-a) (6.56 g, yield 92%).

##STR00064##

Synthesis of compound (2-184-b)

[0260] To a THF (20 mL) solution of compound 2-184-a (0.631 g, 2.21 mmol) and compound 2-6-b (0.739 g, 2.00 mmol), Pd.sub.2(dba).sub.3 (0.0464 g, 0.0507 mmol) and P(t-Bu).sub.3.HBF.sub.4 (0.0290 g, 0.100 mmol) were added, and the mixture was stirred. To the mixture, a 3 N potassium phosphate aqueous solution (2.0 mL, 6.0 mmol) was further added, and the mixture was heated and stirred at 60° C. for 12 hours. To the reaction solution, methanol was added, and the precipitated solid was collected by filtration to obtain compound (2-184-b) (0.782 g, yield 87%).

##STR00065##

Synthesis of Compound (2-184)

[0261] A p-xylene (15 mL) solution of compound (2-184-b) (0.450 g, 1.00 mmol), TiO(acac).sub.2 (abbreviation of bis(2,4-pentanedionato) titanium (IV) oxide, 0.132 g, 0.504 mmol), and n-hexanol (0.512 g, 5.01 mmol) was heated and refluxed for four hours. To the reaction solution, methanol was added, and the precipitated solid was collected by filtration and purified by silica gel column chromatography using chloroform as an eluent to obtain compound (2-184) (0.366 g, yield 72%).

[0262] .sup.1H-NMR (400 MHz, CDCl.sub.3) : δ (ppm)=8.65 (d, 1H), 8.19 (dd, IH), 8.11 (d, 1H), 8.02 (dd, 1H), 7.97-7.91 (m, 3H), 7.88 (dd, 1H), 6.79-6.75 (m, 2H), 4.38 (t, 2H), 3.13 (s, 6H), 1.82 (tt, 2H), 1.52-1.45 (m, 2H), 1.40-1.34 (m, 4H), 0.92 (t, 3H).

[0263] UV visible light spectrum: λmax=482 nm (in acetonitrile)

##STR00066##

Example 11: Preparation of Composition Containing Compound (2-3)

[0264] The following components were mixed and stirred at 80° C. for one hour to obtain composition E1.

[0265] Polymerizable liquid crystal compound (A-6) 75 parts by mass

[0266] Polymerizable liquid crystal compound (A-7) 25 parts by mass

[0267] Compound (2-3) 4.0 parts by mass

[0268] Polymerization initiator: 2-dimethylamino-2-benzyl-1-(4-morpholinophenyl) butan-1-one (IRGACURE 369); manufactured by BASF Japan Ltd.)

[0269] 6 parts by mass

[0270] Leveling agent: polyacrylate compound (BYK-361N; manufactured by BYK-Chemie)

[0271] 1.2 parts by mass

[0272] Solvent: o-xylene 250 parts by mass

[0273] Polymerizable liquid crystal compound (A-6)

##STR00067##

[0274] Polymerizable liquid crystal compound (A-7)

##STR00068##

[0275] Note that polymerizable liquid crystal compound (A-6) was synthesized by a method described in Lub et al. Recl. Tray. Chim. Pays-Bas, 115, 321-328 (1996). In addition, polymerizable liquid crystal compound (A-7) was produced in accordance with this method.

Example 2: Preparation of Composition Containing Compound (2-106)

[0276] Composition E2 was obtained in a similar manner to Example 1 except that compound (2-106) was used instead of compound (2-3).

Example 3: Preparation of Composition Containing Compound (2-4)

[0277] Composition E3 was obtained in a similar manner to Example 1 except that compound (2-4) was used instead of compound (2-3).

Example 4: Preparation of Composition Containing Compound (2-6)

[0278] Composition E4 was obtained in a similar manner to Example 1 except that compound (2-6) was used instead of compound (2-3).

Example 5: Preparation of Composition Containing Compound (2-116)

[0279] Composition E5 was obtained in a similar manner to Example 1 except that compound (2-116) was used instead of compound (2-3).

Example 6: Preparation of Composition Containing Compound (2-166)

[0280] Composition E6 was obtained in a similar manner to Example 1 except that compound (2-166) was used instead of compound (2-3).

[0281] Example 7: Preparation of Composition Containing Compound (2-167)

[0282] Composition E7 was obtained in a similar manner to Example 1 except that compound (2-167) was used instead of compound (2-3).

[0283] Example 8: Preparation of Composition Containing Compound (2-184)

[0284] Composition E8>: was obtained in a similar manner to Example 1 except that compound (2-184) was used instead of compound (2-3).

Comparative Example 1: Preparation of Composition Containing Compound (2-1)

[0285] Composition C1 was obtained in a similar manner to Example 1 except that compound (2-1) was used instead of compound (2-3).

Comparative Example 2: Preparation of Composition Containing Compound (3)

[0286] Composition C2 was obtained in a similar manner to Example 1 except that compound (3) was used instead of compound (2-3).

[0287] <Production of Polarizing Plate>

[0288] 1. Formation of Orientation Film

[0289] A glass substrate was used as a transparent substrate. A 2% by mass polyvinyl alcohol (polyvinyl alcohol 1000 completely saponified type manufactured by Wako Pure Chemical Industries, Ltd.) aqueous solution (composition for forming an orientation layer) was applied onto the glass substrate by a spin coating method, and dried to form a film having a thickness of 100 nm. Subsequently, a surface of the obtained film was subjected to a rubbing treatment to form an orientation film, thus obtaining laminate 1 in which the orientation film was formed on the glass substrate.

[0290] 2. Formation of Polarizing Film

[0291] The composition obtained above was applied onto the orientation film of laminate 1 obtained above by a spin coating method, heated and dried on a hot plate at 120° C. for three minutes, and then rapidly cooled to 70° C. (temperature at which a smectic liquid crystal phase is exhibited at the time of temperature drop) or lower to obtain laminate 2 having a first dry film formed on the orientation film.

[0292] Subsequently, using a UV irradiation device (SPOT CURE SP-7; manufactured by USHIO Inc.), the polarizing film was irradiated with an ultraviolet ray at an exposure amount of 2400 mJ/cm.sup.2 (365 nm standard) to polymerize a polymerizable liquid crystal compound contained in the first dried film while the liquid crystal state of the composition was maintained to form a polarizing film from the first dried film, thus obtaining a polarizing plate as laminate 3.

[0293] <Evaluation>

[0294] For laminate 2 with the polarizing film formed on the orientation film of laminate 1, a dichroic ratio was measured as follows. Absorbance (A1) of the polarizing film of laminate 2 at a maximum absorption wavelength (λmax) in a transmission axis direction and absorbance (A2) of the polarizing film of laminate 2 at a maximum absorption wavelength (λmax) in an absorption axis direction were measured by a double beam method using a device in which a folder including laminate 1 was set in a spectrophotometer (UV-3150 manufactured by Shimadzu Corporation). In the folder, a mesh for cutting the amount of light by 50% was disposed on a reference side. From the measured values of absorbance (A1) in the transmission axis direction and absorbance (A2) in the absorption axis direction, a ratio (A2/A1) was calculated and taken as a dichroic ratio before UV exposure (DR1).

[0295] For laminate after UV exposure, absorbance of the polarizing film of laminate at a maximum absorption wavelength (λmax) in a transmission axis direction and absorbance of the polarizing film of laminate at a maximum absorption wavelength (λmax) in an absorption axis direction were measured in a similar manner to the above, and a dichroic ratio after UV exposure (DR2) was calculated. The dichroic ratio after UV exposure (DR2) was divided by the dichroic ratio before UV exposure (DR1) to calculate a dichroic ratio retention ratio (DR2/DR1; 8). The results were summarized in Table 1. When the dichroic ratio retention ratio of laminate exceeds 50%, the laminate 1 is regarded as a favorable polarizing plate.

TABLE-US-00001 TABLE 1 λmax λmax Dichroic Dichroic (nm) (nm) ratio Dichroic ratio of of before ratio retention polarizing polarizing UV after UV ratio film of film of exposure exposure (DR2/DR1; Compound laminate 2 laminate 3 (DR1) (DR2) %) Example 1 2-3 474 483 30.8 19.9 65 Example 2 2-106 475 482 28.9 18.7 65 Example 3 2-4 472 481 43.0 37.0 86 Example 4 2-6 482 490 24.0 23.0 96 Example 5 2-116 535 535 33.7 27.6 82 Example 6 2-166 507 514 35.0 23.8 68 Example 7 2-167 506 514 57.3 46.4 81 Example 8 2-184 520 528 49.8 42.4 85 Comparative 2-1 468 474 42.7 21.1 49 Example 1 Comparative 3 466 473 39.6 14.9 38 Example 2

[0296] Table 1 indicates that a polarizing plate including a polarizing film formed from a composition containing a compound represented by formula (1) and having a maximum absorption wavelength in a wavelength range of 420 nm or more and 520 nm or less and at least one of a polymerizable liquid crystal compound and a liquid crystalline polymer compound has an excellent dichroic ratio retention ratio before and after UV irradiation when UV irradiation is included in a process for producing the polarizing plate.