POLYMERIZABLE COMPOSITION AND OPTICALLY ANISOTROPIC BODY USING SAME

Abstract

The present invention provides a polymerizable composition containing a specific polymerizable compound and a fluorosurfactant having a specific polyoxyalkylene skeleton and having specific molecular weight. The invention also provides an optically anisotropic body, a retardation film, an antireflective film, and a liquid crystal display device that are produced using the polymerizable composition of the present invention. The present invention is useful because, when an optically anisotropic body is produced by photo-polymerization of the polymerizable composition, three features including the leveling properties of the surface of the optically anisotropic body, offset onto the substrate, and liquid crystal alignment can be improved simultaneously.

Claims

1. A method for producing a polymer product; providing a polymerizable composition; and polymerizing the polymerizable composition, wherein the polymerizable composition comprising: a) a polymerizable compound having one polymerizable group or two or more polymerizable groups and satisfying formula (I)
Re(450 nm)/Re(550 nm)<1.0 (I) (wherein Re(450 nm) is an in-plane retardation at a wavelength of 450 nm when the polymerizable compound having one polymerizable group is aligned on a substrate such that the direction of long axes of molecules of the polymerizable compound is substantially horizontal to the substrate, and Re(550 nm) is an in-plane retardation at a wavelength of 550 nm when the polymerizable compound having one polymerizable group is aligned on the substrate such that the direction of the long axes of the molecules of the polymerizable compound is substantially horizontal to the substrate); and b) at least one fluorosurfactant selected from the group consisting of copolymers (III) having a weight average molecular weight of 2,500 to 30,000 and each obtained by copolymerizing essential monomers including a polymerizable monomer containing a fluorine atom and a polymerizable monomer represented by general formula (B), having a solubility parameter (SP value) of 8.9 to 10.5 (cal/cm..sup.3).sup.0.5, and satisfying the following formula (1A):
1.00<100(s+t+u)/MB<2.10 (1A) (wherein s is an integer of 1 or more; t and u are each an integer of 0 or 1 or more; and MB is the molecular weight of the polymerizable monomer represented by general formula (B)): ##STR00193## (wherein R is a hydrogen atom or a methyl group; X, Y, and Z are each independently an alkylene group; s is an integer of 1 or more; t and u are each an integer of 0 or 1 or more; and W is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or an aryl group).

2. The method according to claim 1, wherein the polymer product is an optically anisotropic body.

3. The method according to claim 1, wherein the polymer product is a retardation film.

4. The method according to claim 1, further comprising using the polymer product as an optically anisotropic body to obtain a display device.

5. The method according to claim 1, further comprising using the polymer product as an optically anisotropic body to obtain a light-emitting device.

6. The method according to claim 1, further comprising using the polymer product to obtain a light-emitting diode lighting device.

7. The method according to claim 1, further comprising using the polymer product to obtain a lens sheet.

8. The method according to claim 1, wherein the polymerizable composition further comprises a dichroic pigment.

9. The method according to claim 1, further comprising using the polymer product to obtain a polarizing film.

10. The method according to claim 1, further comprising using the polymer product as a retardation film to obtain a display device.

11. The method according to claim 1, further comprising using the polymer product as a retardation film to obtain a a light-emitting device.

12. A polymer product made of a polymerizable composition comprising: a) a polymerizable compound having one polymerizable group or two or more polymerizable groups and satisfying formula (I)
Re(450 nm)/Re(550 nm)<1.0 (I) (wherein Re(450 nm) is an in-plane retardation at a wavelength of 450 nm when the polymerizable compound having one polymerizable group is aligned on a substrate such that the direction of long axes of molecules of the polymerizable compound is substantially horizontal to the substrate, and Re(550 nm) is an in-plane retardation at a wavelength of 550 nm when the polymerizable compound having one polymerizable group is aligned on the substrate such that the direction of the long axes of the molecules of the polymerizable compound is substantially horizontal to the substrate); and b) at least one fluorosurfactant selected from the group consisting of copolymers (III) having a weight average molecular weight of 2,500 to 30,000 and each obtained by copolymerizing essential monomers including a polymerizable monomer containing a fluorine atom and a polymerizable monomer represented by general formula (B), having a solubility parameter (SP value) of 8.9 to 10.5 (cal/cm..sup.3).sup.0.5, and satisfying the following formula (1A):
1.00<100(s+t+u)/MB<2.10 (1A) (wherein s is an integer of 1 or more; t and u are each an integer of 0 or 1 or more; and MB is the molecular weight of the polymerizable monomer represented by general formula (B)): ##STR00194## (wherein R is a hydrogen atom or a methyl group; X, Y, and Z are each independently an alkylene group; s is an integer of 1 or more; t and u are each an integer of 0 or 1 or more; and W is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or an aryl group).

Description

EXAMPLES

[0211] The present invention will next be described by way of Examples and Comparative Examples. However, the present invention is not limited thereto. Parts and % are based on mass, unless otherwise specified.

Example 1

[0212] 55 Parts of the compound represented by formula (1-a-5), 25 parts of the compound represented by formula (1-a-6), 20 parts of the compound represented by formula (2-a-1) with n=6, and 0.1 parts of p-methoxyphenol (MEHQ) were added to 400 parts of cyclopentanone (CPN), heated to 60 C., and stirred to dissolve. After dissolution was complete, the mixture was returned to room temperature. Then 3 parts of IRGACURE 907 (Irg 907: manufactured by BASF Japan Ltd.) and 0.15 parts of the surfactant represented by formula (H-1) were added, and the resulting mixture was further stirred to thereby obtain a solution. The solution was clear and uniform. The solution obtained was filtered through a 0.20 m membrane filter to thereby obtain a polymerizable composition (1) in Example 1.

Examples 2 to 58 and Comparative Examples 1 to 11

[0213] Polymerizable compositions (2) to (58) in Examples 2 to 58 and polymerizable compositions (C1) to (C11) in Comparative Examples 1 to 11 were obtained under the same conditions as in the preparation of the polymerizable composition (1) in Example 1 except that ratios of compounds shown in tables below were changed as shown in Tables 1 to 12.

[0214] Specific compositions of the polymerizable compositions (1) to (58) of the present invention and the polymerizable compositions (C1) to (C11) for comparison are shown in the tables below. Table 13 shows the SP value of the polymerizable monomer represented by general formula (B) in each of compounds represented by formula (H-1) to formula (H-13), the value of formula (1) for the polymerizable monomer, the weight average molecular weight (Mw) of each of the compounds represented by formula (H-1) to formula (H-13), and the value of the mass ratio [(X)/(B)] of the polymerizable monomer (X) containing a fluorine atom to the polymerizable monomer represented by general formula (B) for each of the compounds represented by formula (H-1) to formula (H-13).

TABLE-US-00001 TABLE 1 Polymerizable composition (1) (2) (3) (4) (5) (6) 1-a-5 55 55 55 55 55 55 1-a-6 25 25 25 25 25 25 2-a-1 (n = 6) 20 20 20 20 20 20 Irg 907 3 3 3 3 3 3 MEHQ 0.1 0.1 0.1 0.1 0.1 0.1 H-1 0.15 H-2 0.15 H-3 0.15 H-4 0.10 H-5 0.15 H-6 0.15 CPN 400 400 400 400 400 400

TABLE-US-00002 TABLE 2 Polymerizable composition (7) (8) (9) (10) (11) (12) 1-a-5 55 55 55 55 55 55 1-a-6 25 25 25 25 25 25 2-a-1 (n = 6) 20 20 2-a-1 (n = 3) 20 20 20 20 Irg 907 3 3 3 3 3 3 MEHQ 0.1 0.1 0.1 0.1 0.1 0.1 H-7 0.15 H-8 0.15 H-2 0.15 H-3 0.15 H-4 0.10 H-5 0.15 CPN 400 400 400 400 400 400

TABLE-US-00003 TABLE 3 Polymerizable composition (13) (14) (15) (16) (17) (18) 1-a-5 55 55 55 55 55 55 1-a-6 25 25 25 25 25 25 2-a-1 (n = 6) 10 10 10 10 10 2-a-1 (n = 3) 20 10 10 10 10 10 Irg 907 3 3 3 3 3 3 MEHQ 0.1 0.1 0.1 0.1 0.1 0.1 H-2 0.15 H-3 0.15 H-4 0.10 H-5 0.15 H-8 0.15 0.15 CPN 400 400 400 400 400 400

TABLE-US-00004 TABLE 4 Polymerizable composition (19) (20) (21) (22) (23) (24) 1-a-5 80 80 80 80 80 55 1-a-6 25 2-a-1 (n = 6) 10 10 10 10 2-a-1 (n = 3) 10 10 10 10 2-b-1 10 10 (m = n = 3) 2-b-1 10 10 (m = n = 4) 2-a-31 10 Irg 907 3 3 3 3 3 3 MEHQ 0.1 0.1 0.1 0.1 0.1 0.1 H-2 0.15 0.15 H-3 0.15 0.15 H-4 0.10 H-5 0.15 CPN 400 400 400 400 400 400

TABLE-US-00005 TABLE 5 Polymerizable composition (25) (26) (27) (28) (29) (30) 1-a-5 55 1-a-6 25 50 50 55 55 55 1-a-1 25 25 1-a-2 20 20 25 2-a-1 (n = 6) 10 15 15 10 10 10 2-a-1 (n = 3) 10 10 10 2-a-28 10 15 15 2-a-31 10 Irg 907 3 3 3 3 3 3 MEHQ 0.1 0.1 0.1 0.1 0.1 0.1 H-2 0.15 0.15 0.15 H-3 0.15 0.15 0.15 CPN 400 400 400 400 400 400

TABLE-US-00006 TABLE 6 Polymerizable composition (31) (32) (33) (34) (35) (36) 1-a-5 30 30 30 1-a-6 55 55 55 40 40 40 1-a-2 25 1-a-83 25 25 2-a-1 (n = 6) 10 10 10 20 20 20 2-a-1 (n = 3) 10 10 10 3-a-7 10 1-b-27 10 (m11 = 6, n11 = 2) 1-b-1 10 (m11 = 6, n11 = 0) Irg 907 3 3 3 3 3 3 MEHQ 0.1 0.1 0.1 0.1 0.1 0.1 H-2 0.15 0.15 0.15 0.15 H-3 0.15 0.15 CPN 400 400 400 400 400 400

TABLE-US-00007 TABLE 7 Polymerizable composition (37) (38) (39) (40) (41) (42) 1-a-5 30 30 30 30 1-a-6 40 40 40 40 2-a-1 (n = 6) 20 20 20 20 2-a-1 (n = 3) 2-a-31 10 100 2-a-40 10 100 2-b-1 10 (m = n = 3) 2-b-1 10 (m = n = 4) Irg 907 3 3 3 3 3 3 MEHQ 0.1 0.1 0.1 0.1 0.1 0.1 H-2 0.15 0.15 0.15 0.15 0.15 0.15 CPN 400 400 400 400 CLF 400 TCE 400

TABLE-US-00008 TABLE 8 Polymerizable composition (43) (44) (45) (46) (47) (48) 1-a-5 40 1-a-6 40 40 40 50 50 30 1-a-2 40 30 30 1-a-83 40 30 2-a-1 10 20 20 5 5 25 (n = 6) 2-a-28 15 15 15 Irg 907 3 3 3 3 3 3 MEHQ 0.1 0.1 0.1 0.1 0.1 0.1 H-2 0.15 0.15 0.15 0.15 0.15 0.15 MEK 400 400 400 400 400 400

TABLE-US-00009 TABLE 9 Polymerizable composition (49) (50) (51) (52) (53) (54) 1-a-6 40 40 40 40 40 40 1-a-2 30 1-a-83 30 30 30 30 30 2-a-1 (n = 6) 20 20 20 20 20 20 2-a-1 (n = 3) 10 3-a-7 10 1-b-27 10 (m11 = 6, n11 = 2) 1-b-1 10 (m11 = 6, n11 = 0) 2-b-1 10 (m = n = 3) 2-b-1 10 (m = n = 4) Irg 907 3 3 3 3 3 3 MEHQ 0.1 0.1 0.1 0.1 0.1 0.1 H-2 0.15 0.15 0.15 0.15 0.15 0.15 MEK 400 400 CPN 400 400 400 400

TABLE-US-00010 TABLE 10 Polymerizable composition (55) (56) (57) (58) 1-a-5 10 1-a-6 50 50 40 50 1-a-2 25 20 1-a-83 25 10 2-a-1 (n = 6) 25 25 20 20 2-a-28 10 2-b-1 (m = n = 3) 10 2-b-1 (m = n = 4) 10 Irg 907 3 3 3 3 MEHQ 0.1 0.1 0.1 0.1 H-2 0.15 0.15 0.15 0.15 MEK 200 200 300 200 MIBK 200 200 100 200

TABLE-US-00011 TABLE 11 Composition (C1) (C2) (C3) (C4) (C5) (C6) 1-a-5 55 55 55 55 55 40 1-a-6 25 25 25 25 25 40 1-a-2 10 2-a-1 (n = 6) 20 20 20 20 20 2-a-28 10 Irg 907 3 3 3 3 3 3 MEHQ 0.1 0.1 0.1 0.1 0.1 0.1 H-9 0.15 0.15 H-10 0.15 H-11 0.15 H-12 0.15 H-13 0.15 CPN 400 400 400 400 400 MEK 400

TABLE-US-00012 TABLE 12 Composition (C7) (C8) (C9) (C10) (C11) 1-a-5 40 40 40 40 1-a-6 40 40 40 40 40 1-a-2 10 10 10 10 20 2-a-1 (n = 6) 20 2-a-28 10 10 10 10 10 2-b-1 (m = n = 3) 10 Irg 907 3 3 3 3 3 MEHQ 0.1 0.1 0.1 0.1 0.1 H-9 0.15 H-10 0.15 H-11 0.15 H-12 0.15 H-13 0.15 MEK 400 400 400 400 300 MIBK 100

##STR00181## ##STR00182## ##STR00183## ##STR00184## ##STR00185## ##STR00186## ##STR00187## ##STR00188## ##STR00189## ##STR00190## ##STR00191##

TABLE-US-00013 TABLE 13 SP value of Weight polymerizable monomer average represented by general Value of molecular formula (B) formula (1) weight (X)/(B) H-1 9.68 1.22 2,800 30/70 H-2 9.68 1.22 9,500 30/70 H-3 9.15 1.89 11,000 30/70 H-4 9.88 1.33 28,000 35/65 H-5 9.68 1.22 3,600 30/70 H-6 9.68 1.22 11,000 30/70 H-7 9.68 1.22 20,000 30/70 H-8 9.68 1.22 4,600 45/55 H-9 9.88 1.33 38,000 35/65 H-10 8.69 1.55 5,000 35/65 H-11 11.48 1.15 3,800 35/65 H-12 9.36 2.22 7,000 35/65 H-13 9.68 0.85 3,500 35/65

[0215] Chloroform (CLF)

[0216] 1,1,2-Trichloroethane (TCE)

[0217] N-methylpyrrolidone (NMP)

[0218] Cyclopentanone (CPN)

[0219] Methyl ethyl ketone (MEK)

[0220] Methyl isobutyl ketone (MIBK)

[0221] Toluene (TOL)

[0222] The values of Re(450 nm)/Re(550 nm) of the compounds represented by the above formulas are shown in the following table.

TABLE-US-00014 TABLE 14 Compound Re(450 nm)/Re(550 nm) Formula (1-a-5) 0.881 Formula (1-a-6) 0.784 Formula (1-a-1) 0.716 Formula (1-a-2) 0.773 Formula (1-a-83) 0.957 Formula (1-a-93) 0.664 Formula (1-a-100) 0.571 Formula (1-a-101) 0.601 Formula (1-a-102) 0.769 Formula (1-a-103) 0.749 Formula (1-a-104) 0.867 Formula (1-a-105) 0.363 Formula (2-a-1) with n = 6 0.988 Formula (2-a-1) with n = 3 0.802 Formula (2-a-31) 0.900 Formula (2-a-40) 0.832 Formula (2-a-28) 0.845 Formula (2-a-53) 0.622 Formula (2-a-55) 0.838 Formula (2-a-56) 0.554 Formula (2-a-57) 0.675 Formula (2-a-58) 0.878 Formula (2-a-59) 0.723 Formula (2-a-60) 0.823 Formula (2-a-61) 0.758 Formula (3-a-7) 0.850

(Solubility Evaluation)

[0223] The solubility in each of Examples 1 to 58 and Comparative Examples 1 to 11 was evaluated as follows.

[0224] A: After preparation, the clear and uniform state can be visually observed.

[0225] B: The clear and uniform state can be visually observed after heating and stirring, but precipitates of compounds are found when the mixture is returned to room temperature.

[0226] C: Compounds cannot be uniformly dissolved even after heating and stirring.

(Storage Stability Evaluation)

[0227] For each of Examples 1 to 58 and Comparative Examples 1 to 11, the state after the polymerizable composition was left to stand at room temperature for 1 week was visually checked. The storage stability of the polymerizable composition was evaluated as follows.

[0228] A: The clear and uniform state is maintained even after the polymerizable composition is left to stand at room temperature for 3 days.

[0229] B: The clear and uniform state is maintained even after the polymerizable composition is left to stand at room temperature for 1 day.

[0230] C: Precipitates of compounds are found after the polymerizable composition is left to stand at room temperature for 1 hour.

[0231] The results obtained are shown in the following tables.

TABLE-US-00015 TABLE 15 Polymerizable composition Solubility Storage stability Example 1 (1) A A Example 2 (2) A A Example 3 (3) A A Example 4 (4) A A Example 5 (5) A A Example 6 (6) A A Example 7 (7) A A Example 8 (8) A A Example 9 (9) A A Example 10 (10) A A Example 11 (11) A A Example 12 (12) A A Example 13 (13) A A Example 14 (14) A A Example 15 (15) A A Example 16 (16) A A

TABLE-US-00016 TABLE 16 Polymerizable composition Solubility Storage stability Example 17 (17) A A Example 18 (18) A A Example 19 (19) A A Example 20 (20) A A Example 21 (21) A A Example 22 (22) A A Example 23 (23) A A Example 24 (24) A A Example 25 (25) A A Example 26 (26) A A Example 27 (27) A A Example 28 (28) A A Example 29 (29) A A Example 30 (30) A A Example 31 (31) A A Example 32 (32) A A Example 33 (33) A A Example 34 (34) A A

TABLE-US-00017 TABLE 17 Polymerizable composition Solubility Storage stability Example 35 (35) A A Example 36 (36) A A Example 37 (37) A A Example 38 (38) A A Example 39 (39) A A Example 40 (40) A A Example 41 (41) A A Example 42 (42) A A Example 43 (43) A A Example 44 (44) A A Example 45 (45) A A Example 46 (46) A A Example 47 (47) A A Example 48 (48) A A Example 49 (49) A A Example 50 (50) A A

TABLE-US-00018 TABLE 18 Polymerizable composition Solubility Storage stability Example 51 (51) A A Example 52 (52) A A Example 53 (53) A A Example 54 (54) A A Example 55 (55) A A Example 56 (56) A A Example 57 (57) A A Example 58 (58) A A Comparative (C1) A A Example 1 Comparative (C2) A A Example 2 Comparative (C3) A A Example 3 Comparative (C4) A A Example 4 Comparative (C5) A A Example 5 Comparative (C6) A A Example 6 Comparative (C7) A A Example 7

Example 59

[0232] A polyimide solution for an alignment film was applied to a 0.7 mm-thick glass substrate by spin coating, dried at 100 C. for 10 minutes, and then fired at 200 C. for 60 minutes to obtain a coating film. The coating film obtained was subjected to rubbing treatment. The rubbing treatment was performed using a commercial rubbing device.

[0233] The polymerizable composition (1) of the present invention was applied to the substrate subjected to rubbing by spin coating and dried at 100 C. for 2 minutes. The coating film obtained was cooled to room temperature and irradiated with UV rays at an intensity of 30 mW/cm.sup.2 for 30 seconds using a high-pressure mercury lamp to thereby obtain an optically anisotropic body serving as a positive A-plate. The optically anisotropic body obtained was subjected to alignment evaluation, retardation ratio, leveling property evaluation, and offset evaluation according to the following criteria.

(Alignment Evaluation)

[0234] AA: No defects are found at all by visual inspection, and no defects are found at all by polarizing microscope observation.

[0235] A: No defects are found by visual inspection, but non-aligned portions are found in some parts by polarizing microscope observation.

[0236] B: No defects are found by visual inspection, but non-aligned portions are found over the entire region by polarizing microscope observation.

[0237] C: Defects are found in some parts by visual inspection, and non-aligned portions are found over the entire region by polarizing microscope observation.

(Retardation Ratio)

[0238] The retardation of the optically anisotropic body produced as an evaluation sample was measured using a retardation film-optical material inspection device RETS-100 (manufactured by Otsuka Electronics Co., Ltd.), and the in-plane retardation (Re(550)) at a wavelength of 550 nm was 130 nm. The ratio of the in-plane retardation (Re(450)) at a wavelength of 450 nm to Re(550), i.e., Re(450)/Re(550), was 0.855, and the retardation film obtained had high uniformity.

(Leveling Property Evaluation)

[0239] The degree of cissing in the optically anisotropic body produced as the evaluation sample was checked visually under crossed Nicols.

[0240] AA: No cissing defects are found at all on the surface of the coating film.

[0241] A: A very small number of cissing defects are found on the surface of the coating film.

[0242] B: A small number of cissing defects are found on the surface of the coating film.

[0243] C: A large number of cissing defects are found on the surface of the coating film.

(Offset Evaluation)

[0244] A TAC film (B) was placed on a polymerizable composition surface (A) of the optically anisotropic body produced as the evaluation sample, and the resulting stack was held under a load of 40 g/cm.sup.2 at 80 C. for 30 minutes and then cooled to room temperature while the stacked state was maintained. Then the film (B) was removed, and whether or not the surfactant in the polymerizable composition was offset onto the film (B) was visually checked. When the surfactant is transferred to the film (B), the offset portion is observed as a whitish portion.

[0245] AA: Not observed at all.

[0246] A: Very slightly observed.

[0247] B: Slightly observed.

[0248] C: Observed over the entire region.

Examples 60 to 100 and Comparative Examples 12 to 16

[0249] Optically anisotropic bodies in Examples 60 to 100 each serving as a positive A-plate and optically anisotropic bodies in Comparative Examples 12 to 16 each serving as a positive A-plate were obtained under the same conditions as in Example 59 except that the polymerizable composition used was changed to one of the polymerizable compositions (2) to (42) of the present invention and the polymerizable compositions (C1) to (C5) for comparison. The results obtained are shown in the following tables.

TABLE-US-00019 TABLE 19 Poly- Leveling Offset merizable Alignment Retardation property evalu- composition evaluation ratio evaluation ation Example 59 (1) AA 0.855 AA AA Example 60 (2) AA 0.850 AA AA Example 61 (3) AA 0.866 A AA Example 62 (4) AA 0.857 A AA Example 63 (5) AA 0.856 A AA Example 64 (6) AA 0.863 A AA Example 65 (7) AA 0.855 A AA Example 66 (8) AA 0.853 A AA Example 67 (9) AA 0.824 AA AA Example 68 (10) AA 0.822 AA AA Example 69 (11) AA 0.832 A AA Example 70 (12) AA 0.836 A AA Example 71 (13) AA 0.822 A AA Example 72 (14) AA 0.847 AA AA Example 73 (15) AA 0.848 AA AA Example 74 (16) AA 0.849 A AA Example 75 (17) AA 0.839 A AA Example 76 (18) AA 0.842 A AA Example 77 (19) AA 0.944 AA AA Example 78 (20) AA 0.943 AA AA Example 79 (21) AA 0.955 A AA

TABLE-US-00020 TABLE 20 Poly- Re- Leveling merizable Alignment tardation property Offset composition evaluation ratio evaluation evaluation Example 80 (22) AA 0.943 A AA Example 81 (23) AA 0.943 A AA Example 82 (24) AA 0.852 AA AA Example 83 (25) AA 0.834 AA AA Example 84 (26) AA 0.816 AA AA Example 85 (27) AA 0.800 AA AA Example 86 (28) AA 0.785 AA AA Example 87 (29) AA 0.787 AA AA Example 88 (30) AA 0.788 AA AA Example 89 (31) AA 0.788 AA AA Example 90 (32) AA 0.787 AA AA Example 91 (33) AA 0.839 AA AA Example 92 (34) AA 0.848 AA AA Example 93 (35) AA 0.886 AA AA Example 94 (36) AA 0.886 AA AA Example 95 (37) AA 0.895 AA AA Example 96 (38) AA 0.892 AA AA Example 97 (39) AA 0.840 AA AA Example 98 (40) AA 0.832 AA AA Example 99 (41) A 0.900 A A Example 100 (42) A 0.832 A A Comparative (C1) B 0.858 C B Example 12 Comparative (C2) A 0.859 B B Example 13 Comparative (C3) A 0.863 B B Example 14 Comparative (C4) A 0.856 B B Example 15 Comparative (C5) A 0.865 C C Example 16

Example 101

[0250] A uniaxially stretched 50 m-thick PET film was subjected to rubbing treatment using a commercial rubbing device, and the polymerizable composition (43) of the present invention was applied by bar coating and dried at 80 C. for 2 minutes. The coating film obtained was cooled to room temperature and irradiated with UV rays at a conveying speed of 6 m/min using a UV conveyer device (manufactured by GS Yuasa Corporation) to thereby obtain an optically anisotropic body in Example 101 serving as a positive A-plate. The optically anisotropic body obtained was subjected to alignment evaluation, retardation ratio, leveling property evaluation, and offset evaluation in the same manner as in Example 59.

Examples 102 to 112 and Comparative Examples 17 to 21

[0251] Optically anisotropic bodies in Examples 102 to 112 and Comparative Examples 17 to 21 each serving as a positive A-plate were obtained under the same conditions as in Example 101 except that the polymerizable composition used was changed to one of the polymerizable compositions (44) to (54) of the present invention and the polymerizable compositions (C6) to (C10) for comparison. For each of the optically anisotropic bodies obtained, the alignment evaluation, the retardation ratio, the leveling property evaluation, and the offset evaluation were performed in the same manner as in Example 59.

Example 113

[0252] A non-stretched 40 m-thick cycloolefin polymer film ZEONOR (manufactured by ZEON CORPORATION) was subjected to rubbing treatment using a commercial rubbing device, and the polymerizable composition (55) of the present invention was applied by bar coating and dried at 80 C. for 2 minutes. The coating film obtained was cooled to room temperature and irradiated with UV rays at a conveying speed of 6 m/min using a UV conveyer device (manufactured by GS Yuasa Corporation) to thereby obtain an optically anisotropic body in Example 113 serving as a positive A-plate. The optically anisotropic body obtained was subjected to alignment evaluation, retardation ratio, leveling property evaluation, and offset evaluation in the same manner as in Example 59.

Example 114

[0253] An optically anisotropic body in Example 114 serving as a positive A-plate was obtained under the same conditions as in Example 113 except that the polymerizable composition used was changed to the polymerizable composition (56) of the present invention. The optically anisotropic body obtained was subjected to alignment evaluation, retardation ratio, leveling property evaluation, and offset evaluation in the same manner as in Example 59. The results obtained are shown in the following table.

TABLE-US-00021 TABLE 21 Poly- Re- Leveling merizable Alignment tardation property Offset composition evaluation ratio evaluation evaluation Example 101 (43) AA 0.837 AA AA Example 102 (44) AA 0.812 AA AA Example 103 (45) AA 0.878 AA AA Example 104 (46) AA 0.791 AA AA Example 105 (47) AA 0.831 AA AA Example 106 (48) AA 0.829 AA AA Example 107 (49) AA 0.815 AA AA Example 108 (50) AA 0.868 AA AA Example 109 (51) AA 0.896 AA AA Example 110 (52) AA 0.910 AA AA Example 111 (53) AA 0.921 AA AA Example 112 (54) AA 0.912 AA AA Example 113 (55) AA 0.818 AA AA Example 114 (56) AA 0.854 AA AA Comparative (C6) B 0.824 C B Example 17 Comparative (C7) A 0.822 B B Example 18 Comparative (C8) A 0.822 B B Example 19 Comparative (C9) A 0.815 B B Example 20 Comparative (C10) A 0.821 C C Example 21

Example 115

[0254] 5 Parts of a photo-alignment material represented by formula (12-4) below was dissolved in 95 parts of cyclopentanone to obtain a solution. The solution obtained was filtered through a 0.45 m membrane filter to thereby obtain a photo-alignment solution (1). Next, the solution obtained was applied to a 0.7 mm-thick glass substrate by spin coating, dried at 80 C. for 2 minutes, and then irradiated with linearly polarized light of 313 nm at an intensity of 10 mW/cm.sup.2 for 20 seconds to thereby obtain a photo-alignment film (1). The polymerizable composition (57) was applied to the obtained photo-alignment film by spin coating and dried at 100 C. for 2 minutes. The coating film obtained was cooled to room temperature and irradiated with UV rays at an intensity of 30 mW/cm.sup.2 for 30 seconds using a high-pressure mercury lamp to thereby obtain an optically anisotropic body in Example 115 serving as a positive A-plate. The optically anisotropic body obtained was subjected to alignment evaluation, retardation ratio, leveling property evaluation, and offset evaluation in the same manner as in Example 59. The results of the alignment evaluation showed that no defects were found at all by visual inspection and that no defects were found at all by polarizing microscope observation. The retardation of the optically anisotropic body obtained was measured using the RETS-100 (manufactured by Otsuka Electronics Co., Ltd.). The in-plane retardation (Re(550)) at a wavelength of 550 nm was 125 nm, and the retardation film obtained had high uniformity.

Example 116

[0255] 5 Parts of a photo-alignment material represented by formula (12-9) below was dissolved in 95 parts of N-methyl-2-pyrrolidone, and the solution obtained was filtered through a 0.45 m membrane filter to thereby obtain a photo-alignment solution (2). Next, the solution obtained was applied to a 0.7 mm-thick glass substrate by spin coating, dried at 100 C. for 5 minutes, further dried at 130 C. for 10 minutes, and then irradiated with linearly polarized light of 313 nm at an intensity of 10 mW/cm.sup.2 for 1 minute to thereby obtain a photo-alignment film (2). The polymerizable composition (57) was applied to the obtained photo-alignment film by spin coating and dried at 100 C. for 2 minutes. The coating film obtained was cooled to room temperature and irradiated with UV rays at an intensity of 30 mW/cm.sup.2 for 30 seconds using a high-pressure mercury lamp to thereby obtain an optically anisotropic body in Example 116 serving as a positive A-plate. The optically anisotropic body obtained was subjected to alignment evaluation, retardation ratio, leveling property evaluation, and offset evaluation in the same manner as in Example 59. The results of the alignment evaluation showed that no defects were found at all by visual inspection and that no defects were found at all by polarizing microscope observation. The retardation of the optically anisotropic body obtained was measured using the RETS-100 (manufactured by Otsuka Electronics Co., Ltd.). The in-plane retardation (Re(550)) at a wavelength of 550 nm was 120 nm, and the retardation film obtained had high uniformity.

##STR00192##

Example 117

[0256] 1 Part of a photo-alignment material represented by formula (12-8) above was dissolved in 50 parts of (2-ethoxyethoxy) ethanol and 49 parts of 2-butoxyethanol, and the solution obtained was filtered through a 0.45 m membrane filter to thereby obtain a photo-alignment solution (3). Next, the solution obtained was applied to an 80 m-thick polymethyl methacrylate (PMMA) film by bar coating, dried at 80 C. for 2 minutes, and irradiated with linearly polarized light of 365 nm at an intensity of 10 mW/cm.sup.2 for 50 seconds to thereby obtain a photo-alignment film (3). The polymerizable composition (57) was applied to the obtained photo-alignment film by spin coating and dried at 100 C. for 2 minutes. The coating film obtained was cooled to room temperature and irradiated with UV rays at an intensity of 30 mW/cm.sup.2 for 30 seconds using a high-pressure mercury lamp to thereby obtain an optically anisotropic body in Example 117 serving as a positive A-plate. The optically anisotropic body obtained was subjected to alignment evaluation, retardation ratio, leveling property evaluation, and offset evaluation in the same manner as in Example 59. The results of the alignment evaluation showed that no defects were found at all by visual inspection and that no defects were found at all by polarizing microscope observation. The retardation of the optically anisotropic body obtained was measured using the RETS-100 (manufactured by Otsuka Electronics Co., Ltd.). The in-plane retardation (Re(550)) at a wavelength of 550 nm was 137 nm, and the retardation film obtained had high uniformity.

Comparative Examples 22 to 24

[0257] An optically anisotropic body in Comparative Example 22 serving as a positive A-plate was obtained under the same conditions as in Example 115 except that the polymerizable composition (C11) for comparison was used. An optically anisotropic body in Comparative Example 23 serving as a positive A-plate was obtained under the same conditions as in Example 116 except that the polymerizable composition (C11) for comparison was used. An optically anisotropic body in Comparative Example 24 serving as a positive A-plate was obtained under the same conditions as in Example 117 except that the polymerizable composition (C11) for comparison was used. The optically anisotropic bodies obtained were subjected to alignment evaluation, retardation ratio, leveling property evaluation, and offset evaluation in the same manner as in Example 59. The results of the alignment evaluation showed that no defects were found at all by visual inspection and that no defects were found at all by polarizing microscope observation. The retardation films obtained had high uniformity. The degree of cissing of each of the obtained optically anisotropic bodies (22) to (24) for comparison was visually inspected under crossed Nicols, and a small number of cissing defects were found on the surfaces of the coating films. For each of the obtained optically anisotropic bodies (22) to (24) for comparison, whether or not the surfactant in the polymerizable composition was offset was visually checked, and slight offset was observed.

Example 118

[0258] A 180 m-thick PET film was subjected to rubbing treatment using a commercial rubbing device, and the polymerizable composition (58) of the present invention was applied by bar coating and dried at 80 C. for 2 minutes. The coating film obtained was cooled to room temperature and irradiated with UV rays at a conveying speed of 5 m/min using a UV conveyer device (manufactured by GS Yuasa Corporation) with a lamp power of 2 kW to thereby obtain an optically anisotropic body serving as a positive A-plate. The optically anisotropic body obtained was subjected to alignment evaluation, retardation ratio, leveling property evaluation, and offset evaluation in the same manner as in Example 59.

[0259] The retardation Re(550) of the optically anisotropic body obtained was 137 nm, and the ratio of the in-plane retardation (Re(450)) at a wavelength of 450 nm to Re(550), i.e., Re(450)/Re(550), was 0.872. The retardation film obtained had high uniformity. The degree of cissing in the optically anisotropic body (106) obtained was checked visually under crossed Nicols. No cissing defects were observed at all on the surface of the coating film.

[0260] Next, a 75 m-thick polyvinyl alcohol film with an average polymerization degree of about 2,400 and a saponification degree of 99.9 mol% or more was uniaxially stretched by a factor of about 5.5 under dry conditions. While the stretched state was maintained, the film was immersed in pure water at 60 C. for 60 seconds and then immersed in an aqueous solution with an iodine/potassium iodide/water ratio of 0.05/5/100 by weight at 28 C. for 20 seconds. The resulting film was immersed in an aqueous solution with a potassium iodide/boric acid/water ratio of 8.5/8.5/100 by weight at 72 C. for 300 seconds. Then the resulting film was washed with pure water at 26 C. for 20 seconds and dried at 65 C. to thereby obtain a polarizing film in which iodine was adsorbed and aligned on the polyvinyl alcohol resin.

[0261] Saponified triacetylcellulose films (KC8UX2MW manufactured by Konica Minolta Opto Products Co., Ltd.) were applied to opposite surfaces of the thus-obtained polarizer through a polyvinyl alcohol-based adhesive prepared using 3 parts of carboxyl group-modified polyvinyl alcohol [KURARAY POVAL KL318 manufactured by KURARAY Co., Ltd.] and 1.5 parts of water-soluble polyamide epoxy resin [Sumirez Resin 650 (an aqueous solution with a solid content of 30%) manufactured by Sumika Chemtex Co., Ltd.] to protect the opposite surfaces, and a polarizing film was thereby produced.

[0262] The polarizing film obtained and the retardation film were laminated through an adhesive such that the angle between the polarizing axis of the polarizing film and the slow axis of the retardation film was 45 to thereby obtain an antireflective film of the present invention. The antireflective film obtained and an aluminum plate used as an alternative to an organic light-emitting element were laminated through an adhesive, and reflective visibility from the aluminum plate was visually checked from the front and at an oblique angle of 45. No reflection from the aluminum plate was observed. The results obtained are shown in the following table.

TABLE-US-00022 TABLE 22 Poly- Re- Leveling merizable Alignment tardation property Offset composition evaluation ratio evaluation evaluation Example 115 (57) AA 0.876 AA AA Example 116 (57) AA 0.864 AA AA Example 117 (57) AA 0.863 AA AA Example 118 (58) AA 0.872 AA AA Comparative (C11) B 0.878 B B Example 22 Comparative (C11) B 0.872 B B Example 23 Comparative (C11) B 0.871 B B Example 24

Examples 119 to 137

[0263] Polymerizable compositions (59) to (77) in Examples 119 to 137 were obtained under the same conditions as in the preparation of the polymerizable composition (1) in Example 1 except that ratios of compounds shown in tables below were changed as shown in the tables below. Specific compositions of the polymerizable compositions (59) to (77) of the present invention are shown in the following tables.

TABLE-US-00023 TABLE 23 Polymerizable composition (59) (60) (61) (62) (63) (64) 1-a-5 25 40 1-a-6 20 20 25 40 1-a-93 40 40 1-a-100 40 2-a-1 (n = 6) 50 50 50 2-a-1 (n = 3) 10 20 2-a-11 40 2-a-53 20 2-a-57 40 20 2-b-19 10 (m = n = 6) Irg 907 6 6 6 6 6 6 MEHQ 0.1 0.1 0.1 0.1 0.1 0.1 H-2 0.15 0.15 0.05 0.05 0.05 0.15 TOL 400 400 400 400 400 400

TABLE-US-00024 TABLE 24 Polymerizable composition (65) (66) (67) (68) (69) (70) 1-a-93 50 1-a-101 20 1-a-105 10 2-a-11 50 2-a-55 50 2-a-56 20 2-a-58 50 2-a-59 85 50 2-a-60 100 50 15 50 Irg 907 6 6 6 6 6 6 MEHQ 0.1 0.1 0.1 0.1 0.1 0.1 H-2 0.05 0.15 0.15 0.15 0.15 0.15 CPN 400 TOL 400 400 400 400 400

TABLE-US-00025 TABLE 25 Polymerizable composition (71) (72) (73) (74) (75) (76) (77) 1-a-102 20 50 25 50 1-a-103 20 25 1-a-104 20 2-a-59 50 50 50 50 50 2-a-60 30 30 30 50 50 2-a-61 50 Irg 907 6 6 6 6 6 6 6 MEHQ 0.1 0.1 0.1 0.1 0.1 0.1 0.1 H-2 0.15 0.15 0.15 0.15 0.15 0.15 0.05 TOL 400 400 400 400 400 400 400

(Solubility Evaluation)

[0264] The solubility in each of Examples 119 to 137 was evaluated as follows.

[0265] A: After preparation, the clear and uniform state can be visually observed.

[0266] B: The clear and uniform state can be visually observed after heating and stirring, but precipitates of compounds are found when the mixture is returned to room temperature.

[0267] C: Compounds cannot be uniformly dissolved even after heating and stirring.

(Storage Stability Evaluation)

[0268] For each of Examples 119 to 137, the state after the polymerizable composition was left to stand at room temperature for 1 week was visually checked. The storage stability was evaluated as follows.

[0269] A: The clear and uniform state is maintained even after the polymerizable composition is left to stand at room temperature for 3 days.

[0270] B: The clear and uniform state is maintained even after the polymerizable composition is left to stand at room temperature for 1 day.

[0271] C: Precipitates of compounds are found after the polymerizable composition is left to stand at room temperature for 1 hour.

[0272] The results obtained are shown in the following table.

TABLE-US-00026 TABLE 26 Polymerizable composition Solubility Storage stability Example 119 (59) A A Example 120 (60) A A Example 121 (61) A A Example 122 (62) A A Example 123 (63) A A Example 124 (64) A A Example 125 (65) A A Example 126 (66) A A Example 127 (67) A A Example 128 (68) A A Example 129 (69) A A Example 130 (70) A A Example 131 (71) A A Example 132 (72) A A Example 133 (73) A A Example 134 (74) A A Example 135 (75) A A Example 136 (76) A A Example 137 (77) A A

Examples 138 to 151

[0273] Optically anisotropic bodies in Examples 138 to 151 each serving as a positive A-plate were obtained under the same conditions as in Example 101 except that the polymerizable composition used was changed to one of the polymerizable compositions (119) to (120), (124), and (126) to (136) of the present invention. The optically anisotropic bodies obtained were subjected to alignment evaluation, retardation ratio, leveling property evaluation, and offset evaluation in the same manner as in Example 59. The results obtained are shown in the following table.

TABLE-US-00027 TABLE 27 Poly- Re- Leveling merizable Alignment tardation property Offset composition evaluation ratio evaluation evaluation Example 138 (119) AA 0.856 AA AA Example 139 (120) AA 0.843 AA AA Example 140 (124) AA 0.843 AA AA Example 141 (126) AA 0.846 AA AA Example 142 (127) AA 0.831 AA AA Example 143 (128) AA 0.855 AA AA Example 144 (129) AA 0.822 AA AA Example 145 (130) AA 0.830 AA AA Example 146 (131) AA 0.818 AA AA Example 147 (132) AA 0.827 AA AA Example 148 (133) AA 0.842 AA AA Example 149 (134) AA 0.854 AA AA Example 150 (135) AA 0.870 AA AA Example 151 (136) AA 0.865 AA AA

Examples 152 to 155

[0274] One of the polymerizable compositions (121) to (123) and (137) of the present invention was applied by bar coating to a film prepared by stacking a silane coupling agent-based vertical alignment film on a COP film substrate and then dried at 100 C. for 2 minutes. The coating films obtained were cooled to room temperature and irradiated with UV rays at a conveying speed of 6 m/min using a UV conveyer device (manufactured by GS Yuasa Corporation) to thereby obtain optically anisotropic bodies in Examples 152 to 155 each serving as a positive C-plate. The optically anisotropic bodies obtained were subjected to alignment evaluation, retardation ratio, leveling property evaluation, and offset property evaluation in the same manner as in Example 59. The results obtained are shown in the following table.

TABLE-US-00028 TABLE 28 Poly- Re- Leveling merizable Alignment tardation property Offset composition evaluation ratio evaluation evaluation Example 152 (121) AA 0.861 AA AA Example 153 (122) AA 0.878 AA AA Example 154 (123) AA 0.874 AA AA Example 155 (137) AA 0.872 AA AA

Examples 156 to 157

[0275] A uniaxially stretched 50 m-thick PET film was subjected to rubbing treatment using a commercial rubbing device, and one of the polymerizable compositions (125) and (137) of the present invention was applied by bar coating to the PET film and dried at 100 C. for 2 minutes. The coating films obtained were cooled to room temperature and irradiated with UV rays at a conveying speed of 6 m/min using a UV conveyer device (manufactured by GS Yuasa Corporation) to thereby obtain optically anisotropic bodies in Examples 156 to 157 each serving as a positive 0-plate. The optically anisotropic bodies obtained were subjected to alignment evaluation, retardation ratio, leveling property evaluation, and offset property evaluation in the same manner as in Example 59. The results obtained are shown in the following table.

TABLE-US-00029 TABLE 29 Poly- Re- Leveling merizable Alignment tardation property Offset composition evaluation ratio evaluation evaluation Example 156 (125) AA 0.826 AA AA Example 157 (137) AA 0.854 AA AA

[0276] The polymerizable compositions of the present invention using the surfactants represented by formula (H-1) to formula (H-8) (Examples 1 to 58 and Examples 138 to 157) were excellent in solubility and storage stability. In the optically anisotropic bodies formed from the polymerizable compositions (1) to (77) (Examples 59 to 118 and Examples 138 to 157), the results of all the leveling property evaluation, offset evaluation, and alignment evaluation were good, and the productivity of these optically anisotropic bodies was good. In particular, in the polymerizable compositions using the fluorosurfactants having a specific polyoxyalkylene skeleton and having a specific molecular weight, the results of the alignment evaluation, leveling property evaluation, and offset evaluation were very good. As can be seen from the results in Comparative Examples 1 to 24, when the fluorosurfactants having no polyoxyalkylene skeleton and having a molecular weight outside the specific range were used, the results of any of the alignment evaluation, leveling property evaluation, and offset evaluation were poor. These results were poorer than those in the polymerizable compositions of the present invention.