TWI354684B - Cellulose film, polarizing film and liquid crystal - Google Patents

Description

[Technical Field] The present invention relates to a cellulose film suitable for use as a retardation film or the like, and a polarizing plate and a liquid crystal display device comprising the film. [Prior Art] A liquid crystal display device is an image display device which is low in power consumption and requires a small space and is increasingly used. In the past, although the dependence of the viewing angle of the image is large, it is a major drawback of the liquid crystal display device. However, in recent years, the high viewing angle liquid crystal mode such as the VA (vertical alignment) mode and the IPS (in-plane switching) mode has been practical. 'Therefore, in the market where TVs and the like require a high viewing angle, the demand for liquid crystal display devices is rapidly expanding. Therefore, the retardation film used in the liquid crystal display device and the polarizing plate used therewith are also required to further improve the performance. In particular, the durability of improved temperature and humidity is a major technical problem of polarizing plates. A problem that is particularly problematic in the durability test of a polarizing plate is a decrease in the degree of polarization, which is caused by the action of iodine adsorbed on the polarizing film due to the action of water. Therefore, a known effective countermeasure is to reduce the protection of the polarizing plate. The permeability of the membrane. However, the cellulose which is used as a protective film for a polarizing plate is itself a polymer having a very hydrophilic property, and since it has a high water permeability, it has been proposed to add various hydrophobizing agents to lower its water permeability. For example, Patent Document 1 discloses a method of adding a rosin derivative or an epoxy resin to a deuterated cellulose film to lower the moisture permeability. However, according to these methods, its improved efficacy is still imperfect. On the other hand, the cellulose acetate film has an optically different directionality as its 1354684 advantage. Therefore, it has been used as a protective film for a polarizing plate, but in recent years, it has been gradually increased by means of biaxial stretching or the like. The tendency to give a phase difference to *have the function of a retardation film at the same time. In the invention patent, Document 2 discloses a method of adding a highly planar compound to a deuterated cellulose film. However, according to these methods, it is still difficult to coexist both the optical characteristics required for the retardation film and the water permeability required for the polarizing plate protective film, and the humidity dependence of the optical characteristics of the retardation film itself is large. presence. [Patent Document 1] Japanese Patent Laid-Open No. 2002-146044 (Invention Patent Document 2) Japanese Patent Laid-Open No. 2001-1 66144 [Draft of the Invention] [Technical Problem to be Solved by the Invention] The object of the present invention is to provide a cellulose film which can be used as, for example, a retardation film due to a small change in heat and humidity. Further, another object of the present invention is to provide a polarized light having a small transmittance and a degree of polarization due to changes in heat and humidity. Another object of the invention is to use a polarizing plate formed by disposing a retardation film having a superior viewing angle compensation φ energy and/or a low-humidity protective film on both sides of the polarizing film for liquid crystal display. The device can provide a liquid crystal display device having a wide viewing angle and high display quality without causing light leakage, etc. [Technical method for solving the problem] The present inventors focused on the results and found that if high planarity is to be achieved The disc-shaped compound and the compound having an aromatic ring but having low planarity are added to 1354684, which is remarkable when added to a deuterated cellulose film. The water permeability of the obtained deuterated cellulose film is lowered, and the humidity dependence of the optical properties of the deuterated cellulose film is made small. Moreover, the ratio of the above discotic compound to the low planar compound is found. By adjusting, it is possible to adjust the range to a wide range of optical characteristics while maintaining the humidity dependence of the moisture permeability and the optical characteristics. The former has the effect of increasing the delay 値, and the latter has the effect of lowering the delay 値. That is, the present invention provides the following method: (1) A cellulose film characterized by containing at least two kinds of retardation modifiers. (2) The cellulose film according to item (1), which respectively contains At least one retardation-increasing agent and a retardation-lowering agent. (3) A cellulose film characterized by containing at least one of the compounds represented by the following general formula (I), and having the following general formula (11), (III) Or at least 1354684 30 nm of the compound represented by (IV), RthS 3 00 nm, 2 nm SRe$80 nm, and Rth/Re ratio of 1 or more and 6 or less: (A) Re (Nai m)=(nx-ny)xd (B ) Rth (nano) = {(nx + ny) / 2-nz} xd [wherein, nx is the refractive index of the retardation axis in the plane of the film; ny is the refractive index of the phase axis in the plane of the film The Zn is a film of the thickness of the film in the thickness direction of the film; and d is the thickness of the film (nano). (5) The cellulose film according to any one of the items (1) to (4) The moisture permeability of any one of the items (1) to (5) is at least 60 hr. The film had an equilibrium moisture content of 3.0% or less at 25 ° C and 80% RH, and an equilibrium moisture content of 25 at 80 ° RH at 25 ° C. (1) The cellulose film according to any one of (1) to (6), which is 10% at 25 ° C, is a ratio of the ratio of the moisture content of the 10% RH to 3 or more. The ratio of the Rth of RH to the Rth of 25t of 80% RH is 0.65 or more. (8) The cellulose film according to any one of (1) to (7) which is 10% RH at 25 ° C. The ratio of Re to Re at 80% RH at 25 ° C is 0.65 or more. (9) A polarizing plate which is formed by laminating a protective film on both sides of a polarizing film, which is characterized by the protective film. At least one of the sheets is a cellulose film as described in any one of the items (1) to (8). (10) A polarizing plate characterized by being disposed in the polarizing plate of the item (9). (11) The polarizing plate according to the item (9), wherein an anti-glare layer is provided on the air-side protective film. (1 2) The polarizing plate according to item (9), which is on the air side A reflective layer or a semi-transmissive reflective layer is provided on the protective film. The polarizing plate described in the item (9) has a phase difference layer or a φ λ /4 layer. (14) The polarizing plate according to Item (9), which has a viewing angle compensation film (viewing angle compensation layer). (15) The polarizing plate according to the item (9), comprising: a brightness enhancement layer (16) - a liquid crystal display device comprising: a liquid crystal cell and two polarizing plates disposed on both sides thereof; And at least one of the polarizing plates is one of the polarizing plates as in items (9) to (15). In the present invention, the term "delay modifier" means to use a retardation change of a cellulose film, and if at least two of these are used, excellent effects can be obtained, but it is preferable to contain a retardation enhancer and a delay, respectively. At least one of the reducing agents. Wherein the "delay riser J system means that when 0.1 to 30 parts by mass, preferably 1 to 10 parts by mass, is added to 1 part by mass of the deuterated cellulose film, it is compared with the delay when not added. The retardation of the deuterated cellulose film is increased by 10 nm or more, preferably by 50 nm or more and 250 nm or less. In contrast, the "delay reducing agent j" means 100 mass. In the case of the cellulose film, 0. 1 to 3 parts by mass, preferably 〇5 to 10 parts by mass, when compared with the delay when not added,値 is reduced to 5 nm or less, preferably a compound having a decrease of 5 nm or less and 100 nm or more. In addition, the ratio of the retardation-lowering agent to the retardation-increasing agent (mass ratio) is better than #10/10 10, more preferably 1/10~1. Lu will, the delay system is measured as follows. Ellipter (ellip someter) (M-150 'Japan spectrophotometer (product name)) And measure the in-plane retardation 値Re (〇) of the cellulose film at 25 ° C 10% RH, and the in-plane retardation axis is Move the shaft and shift the shaft by 4〇° and -40° to measure the retardation 値Re ( 40 ) and Re ( - 40 ). Then, the refractive index nx in the film thickness and the slow axis direction is used as a parameter to approximate The refractive index ny in the direction of the axis of the phase and the refractive index nz in the thickness direction are calculated by the method of measuring 値Re(〇), Re(40), and Re(-40) to determine the Rth φ delay 値. The measurement wavelength was 632.8 nm, and the same measurement was carried out at 25 ° C 80 ° RH. [Effect of the invention] According to the present invention, it is possible to provide a superior heat and humidity. It is also suitable as a cellulose film for a protective film or a retardation film of a polarizing plate, preferably a cellulose-deposited film. Further, according to the present invention, it is possible to provide a superior heat, -12- 1354684 Polarizing plate for durability of humidity The above polarizing plate has optical compensation function and is suitable for use in TN (Twisted Nematic), OCB (Optically Compensated Bend), ECB (Electronic Control Double) Electrically Controlled Birefringence), VA (Vertical (Vertically Aligned) type, IPS (In-Plane Switching) type liquid crystal display device. [Best form of the invention] The inventor focused on the results and found that if the plane is high planarity The disk-like φ. compound and the compound having an aromatic ring but having low planarity are simultaneously added to the bismuth cellulose film, so that the water permeability of the obtained fluorinated cellulose film can be remarkably lowered, and The humidity dependence of the optical characteristics of the deuterated cellulose film becomes small. Further, it has been found that by adjusting the ratio of the above-mentioned discotic compound to the compound having low planarity, it is possible to adjust the optical characteristics of a wide range while maintaining the humidity dependence of the moisture permeability and the optical characteristics. The former has the effect of increasing the retardation enthalpy, for example, ® can be represented by the above formula (I), and the latter has the effect of reducing the retardation φ by φ, for example, the above formula (II), (III) or (IV) Representative. However, it has also been found that it is unexpectedly possible to obtain an effect which is superior to the expected effect of separately adding each compound as a separate effect when the film of the above-mentioned deuterated cellulose film is contained. That is, it is possible to obtain an excellent deuterated cellulose film which has a function of lowering the humidity-reducing effect than that which can be expected by the addition alone, and having a small temperature dependency of the optical characteristics, and the film can be used as a phase. Poor film. -13- 1354684 1 to 30, more preferably 丨 to 2 〇, more preferably 1 to 1 进, and further to 〜1, preferably 1 to 8, preferably 1 to 6. The alkyl group may have a substituent. Examples of the substituent include: a halogen atom, an alkoxy group (e.g., a methoxy 'ethoxy group, an epoxy ethoxy group), and a decyloxy group (including, for example, an acrylonitrile group, a methyl propyl oxime group). . The above alkenyl group is a comparative cyclic alkenyl group, and a chain alkenyl group is preferred. It is preferred to use a branched alkenyl group having a branched chain and a linear alkenyl group. The number of carbon atoms of the alkenyl group is preferably from 2 to 30, more preferably from 2 to 20, still more preferably from 2 to 1 Torr, still more preferably from 2 to 8, most preferably from 2 to 6. The alkenyl group may also have a substituent. Examples of the substituent include a halogen atom, an alkoxy group (e.g., methoxy group, ethoxy group, epoxy ethoxy group), and a decyloxy group (for example, an acryloyl group, a methacryloxy group). The above aryl group ' is preferably a phenyl group or a naphthyl group, and particularly preferably a phenyl group. The aryl group may also have a substituent. Examples of the substituent include: a halogen atom, a hydroxyl group, a cyano group, a nitro group, a carbonyl group, an alkyl group, an alkenyl group, an aryl group, an alkoxy group, an alkenyloxy group, an aryloxy group, a decyloxy group, an alkoxycarbonyl group, Alkenyloxycarbonyl, aryloxycarbonyl, sulfonyl, alkylsulfonyl substituted with alkyl, aminesulfonyl substituted with alkenyl, sulfonyl substituted with aryl, sulfonamide , aminomethyl sulfhydryl, an aminomethyl group substituted with an alkyl group, an amine methyl group substituted with an alkenyl group, an amine carbenyl group substituted with an aryl group, a decylamino group, an alkylthio group, an alkene sulfide Base, aryl sulfhydryl and fluorenyl. The above alkyl group has the same definition as the above alkyl group. Alkoxy, anthracenyloxy, alkoxycarbonyl, aminesulfonyl substituted with alkyl, sulfonyl, amine methyl hydrazide substituted with alkenyl, decylamino, alkylthio and decyl alkane The base moiety is also the same as the above alkyl group. The above alkenyl group has the same definition as the above alkenyl group. Alkenyloxy, oxime -15- 1354684 〔6 (Hc-l) h3c (Hc-2) (Hc-3) -Np

H3C-0-CO CH,

(7) (8) (Hc-4)_nS^CH: (Hc-5) 0 M -C2H5 _ n-C4He (Hc-6)

(Hc-7)

(Hc-8) CO-NH-CK (Hc-9)

CO-NH-CHg HgC

〔化9〕

(Hc-10) /' —N (Hc‘ll) (Hc-12) .ch3 -N,

Br n-C4He-

The molecular weight of the compound having the oxime represented by the above formula (i) and the L 5 -triazole trap ring is preferably from 300 to 2, 〇〇〇. The boiling point of the compound is preferably 260 ° C or higher. The boiling point can be measured using a commercially available measuring device (for example, TG/DTA100, trade name, manufactured by Seiko Electronics Co., Ltd.). Specific examples of the compound having a 1,3,5-triazine trap represented by the above formula (I) are shown below. In addition, the several R systems shown in each example mean the same basis. The definition of R will be shown after the formula with the specific example number -17- 1354684. 〔化1 〇〕 (1)-(12)

XT (1 ) butyl (2) 2-methoxy-2 · ethoxyethyl (3 ) 5 - undecenyl (4) phenyl

(5) 4-Ethoxycarbonylphenyl(6)4-butoxyphenyl(7) p-biphenyl(8)4-pyridyl(9)2-naphthyl(10)2-methyl Phenyl (11) 3, 4-dimethoxyphenyl

(12) 2 -furanyl

[Chemical 1 2]

(14)-(79) R

I

-18 - 1354684 (14) Phenyl (15) 3-ethoxycarbonylphenyl '(16) 3 -butoxyphenyl · (17) m-biphenyl (18) 3-phenylthiophenyl (19) 3-Chlorophenyl (20) 3-benzylidenephenyl (21) 3-ethoxycarbonylphenyl (22) 3-benzylideneoxyphenyl φ (23 ) 3 -phenyloxy Phenylcarbonylphenyl(24)3-methoxyphenyl(25)3-anilinophenyl(26)3-isobutylaminophenyl(27)-3-phenoxycarbonylaminophenyl (28) 3-(3-ethylureido)phenyl(29)3-(3,3-diethylureido)phenyl(30)3-methylphenyl-(31)3-phenoxybenzene (32) 3-hydroxyphenyl(33) 4-ethoxycarbonylphenyl(34)4-butoxyphenyl(35) p-biphenyl(36)4-phenylthiophenyl (37 4 -Chlorophenyl-19- 1354684 (38 ) 4-Benzylmercaptophenyl (39) 4-Ethyloxyphenyl (40) 4-Benzylmethoxyphenyl (41) 4-Benzene Oxycarbonylphenyl (42) 4-methoxyphenyl (43) 4-anilinophenyl (44) 4-isobutylguanidinophenyl (45) 4-phenoxycarbonylaminophenyl

(46) 4-(3-ethylureido)phenyl(47) 4-(3,3-diethylureido)phenyl(48) 4-methylphenyl(49)4-benzyl Phenyl (50) 4-hydroxyphenyl (51) 3, 4-diethoxycarbonylphenyl (52) 3,4-dibutoxyphenyl (53) 3,4-diphenylphenyl

(54) 3,4-diphenylthiophenyl(55) 3,4-dichlorophenyl(56) 3,4-diphenylmercaptophenyl (57) 3,4-diethyloxy Phenyl (58) 3, 4-dibenyloxyphenyl (59) 3,4-diphenoxycarbonylphenyl (60) 3,4-dimethoxyphenyl (61) 3, 4 -diphenylaminophenyl-20- 1354684

(62) (63) (64) (65) (66) (67) (68) (69) (70) (71) (72) (73) (74) (75) (76) (77) (78 (79) 3,4-Dimethylphenyl 3,4-diphenoxyphenyl 3,4-dihydroxyphenyl 2-naphthyl 3,4,5-triethoxycarbonylphenyl 3, 4,5-tributyloxyphenyl 3, 4, 5 · triphenylphenyl 3, 4, 5-triphenylthiophenyl 3, 4,5-trichlorophenyl 3, 4, 5 - three Benzylmercaptophenyl 3,4,5-triethoxymethoxyphenyl 3,4,5-trityloxyphenyl 3,4,5-triphenyloxycarbonylphenyl 3, 4, 5-trimethoxyphenyl 3,4,5-triphenylaminophenyl 3,4,5-trimethylphenyl 3,4,5-triphenyloxyphenyl 3,4,5-trihydroxybenzene base

(80)-(145) R

(80) Phenyl (81) 3-ethoxycarbonylphenyl-21 - 1354684 (82) 3-butoxyphenyl (83) m-biphenyl (84) 3-phenylthiophenyl (85 3 -Chlorophenyl(86 ) 3 -benzimidylphenyl(87 ) 3 -acetoxyphenyl (88) 3-benzylideneoxyphenyl (89) 3-phenoxycarbonylbenzene base

(90) 3-methoxyphenyl(91)3-anilinophenyl(92)3-isobutyldecylaminophenyl(93)3-phenoxycarbonylaminophenyl(94) 3-(3 -ethylureido)phenyl(95)3-(3,3-diethylureido)phenyl(96)3-methylphenyl(97)3-phenoxyphenyl

(98) 3-Hydroxyphenyl(99) 4-ethoxycarbonylphenyl(100) 4-butoxyphenyl(101) p-biphenyl(102) 4-phenylthiophenyl (103) 4-Chlorophenyl(104)4-benzylidenylphenyl (105) 4-ethenyloxyphenyl-22- 1354684 (106) 4-Benzylmethoxyphenyl (107) 4-phenoxy Phenylcarbonylphenyl (108) 4-methoxyphenyl (109) 4-anilinophenyl (110) 4-isobutylguanidinophenyl (111) 4-phenoxycarbonylaminophenyl (112) 4-(3-ethylureido)phenyl(113) 4-(3,3-diethylureido)phenyl

(114) 4-Methylphenyl (115) 4-phenoxyphenyl (1 1 6 ) 4-hydroxyphenyl (117) 3, 4-diethoxycarbonylphenyl (118) 3, 4- Dibutoxyphenyl (119) 3, 4-diphenylphenyl (120) 3, 4-diphenylthiophenyl (121) 3, 4-dichlorophenyl

(122) 3, 4-Diphenylmercaptophenyl (123) 3, 4-diethoxycarbonylphenyl (124) 3, 4-dibenylmethoxyphenyl (125) 3, 4- Diphenoxycarbonylphenyl (126) 3,4-dimethoxyphenyl (127) 3,4-diphenylaminophenyl (128) 3,4 · dimethylphenyl (129 ) 3, 4 -diphenoxyphenyl-23- (130)1354684

(131) (132) (133) (134) (135) (136) (137) (138) (139) (140) (141) (142) (143) (144) (145) [Chem. 1 4] 3,4-dihydroxyphenyl 2-naphthyl 3,4,5-triethoxycarbonylphenyl 3,4,5-tributyloxyphenyl 3,4,5-triphenylphenyl 3, 4,5-triphenylthiophenyl 3,4,5-trichlorophenyl 3,4,5-tritylphenylphenyl 3,4,5-triethoxymethoxyphenyl 3, 4, 5-tritylmethoxyphenyl 3,4,5-triphenyloxycarbonylphenyl 3,4,5-trimethoxyphenyl 3,4,5-triphenylaminophenyl 3, 4, 5 -trimethylphenyl 3,4,5-triphenyloxyphenyl 3,4,5-trihydroxyphenyl

(146)-(164)

(146) Phenyl(147)4-ethoxycarbonylphenyl(148)4-butoxyphenyl(M9) p-biphenyl-24- 1354684 (150) 4-phenylthiophenyl (151) 4-chlorophenyl(152) 4-benzylidenephenyl (153) 4-ethyloxyphenyl (154) 4-benzyloxyphenyl (155) 4-phenoxycarbonylbenzene (156) 4-methoxyphenyl (157) 4-anilinophenyl

#(I58) 4-Isobutyl decylaminophenyl (159 ) 4-phenoxycarbonylaminophenyl (160 ) 4 - (3-ethylureido)phenyl (161) 4-(3,3- Diethylureido)phenyl(162) 4 ·methylphenyl(163 ) 4 -phenoxyphenyl(164 ) 4 -hydroxyphenyl [Chemical 1 5]

• (165)-(183) R (165) Phenyl (166) 4-ethoxycarbonylphenyl (167 ) 4 · Butoxyphenyl (168 ) p-biphenyl (169 ) 4 -phenyl Thiophenyl-25 - 1354684 (1 70 ) 4-chlorophenyl (171) 4-benzylidenephenyl (172) 4-ethyloxyphenyl (173) 4-benzylideneoxyphenyl (174) 4-Phenoxycarbonylphenyl(175)4-methoxyphenyl(176)4-anilinylphenyl(177)4-isobutyldecylaminophenyl

• (178) 4-Phenoxycarbonylaminophenyl(179)4-(3-ethylureido)phenyl(180) 4-(3,3-diethylureido)phenyl (181) 4-methylphenyl(182)4-phenoxyphenyl(18 3) 4 -hydroxyphenyl[Chemical 16]

(184)-(202) R

(184) Phenyl

(185) 4-Ethoxycarbonylphenyl(186)4-butoxyphenyl(187) p-biphenyl(188) 4-phenylthiophenyl(189) 4-chlorophenyl-26- 1354684

(190) 4-Benzylmercaptophenyl (191) 4-Ethyloxyphenyl (192) 4-Benzylmethoxyphenyl (193) 4-Phenoxycarbonylphenyl (194) 4 - Methoxyphenyl(195 ) 4 -anilinylphenyl (196) 4-isobutylguanidinophenyl (197) 4-phenoxycarbonylaminophenyl (198 ) 4 - (3-ethylureido Phenyl(199) 4-(3,3-diethylureido)phenyl(200)4-methylphenyl(201)4-phenoxyphenyl(2 02 ) 4 -hydroxyphenyl 1 7] (203)-(221) R η

(203) Phenyl (204) 4-ethoxycarbonylphenyl (205) 4-butoxyphenyl (2〇6) p-biphenyl (207) 4-phenylthiophenyl (208) 4 -Chlorophenyl(209 ) 4 -benzimidylphenyl-27- 1354684 (210) 4-Ethyloxyphenyl (211) 4-benzylideneoxyphenyl (212) 4-phenoxy Carbonylphenyl (213) 4-methoxyphenyl (214) 4-anilinophenyl (215) 4-isobutylguanidinophenyl (216) 4-phenoxycarbonylaminophenyl (217) 4 -(3-ethylureido)phenyl

φ (218) 4 -( 3, 3 -Diethylureido)phenyl (219) 4-methylphenyl(220 ) 4 -phenoxyphenyl(221 ) 4 -hydroxyphenyl [Chemical 1 8 〕

yVn'r N 丫N

(222)-(419) R HN ftnh

(222) phenyl(223)4-butylphenyl(224) 4-(2-methoxy-2-ethoxyethyl)phenyl(225)4-(5-decenyl)phenyl (226) p-Biphenyl(227) 4 ·ethoxycarbonylphenyl(228 ) 4 -butoxyphenyl(229 ) 4 -methylphenyl-28- 1354684 (230 ) 4 -chlorophenyl (231) 4-Phenylthiophenyl (232) 4-Benzylmercaptophenyl (23 3) 4-Ethyloxyphenyl (234) 4-benzylideneoxyphenyl (23 5 ) 4 -phenoxycarbonylphenyl (236) 4-methoxyphenyl (237) 4-anilinophenyl

( 23 8 ) 4 -Isobutyl decylaminophenyl (239) 4-phenoxycarbonylaminophenyl (240 ) 4 - ( 3 -ethylureido)phenyl (241) 4 -( 3,3 - Diethylureido)phenyl(242)4-phenoxyphenyl(243) 4-hydroxyphenyl(244)3-butylphenyl(245)3- (2-methoxy-2-ethyl) Oxyethyl)phenyl

(246 ) 3 · ( 5 · fluorenyl) phenyl (247 ) m-biphenyl (2M) 3 -ethoxycarbonylphenyl (249 ) 3 -butoxyphenyl (250 ) 3 -methyl Phenyl (251) 3-chlorophenyl (252) 3-phenylthiophenyl (253) 3-benzylidenephenyl-29- 1354684 (254) 3-ethoxylated phenyl (25 5 ) 3-benzylideneoxyphenyl(25 6 ) 3 -phenoxycarbonylphenyl (25 7 ) 3 -methoxyphenyl (25 8 ) 3 -anilinylphenyl (259 ) 3 -isobutylguanamine Phenylphenyl (260 ) 3 -phenoxycarbonylaminophenyl (261 ) 3 - ( 3 ·ethylureido)phenyl

(262) 3-(3,3-Diethylureido)phenyl(263 ) 3 -phenoxyphenyl(264 ) 3 -hydroxyphenyl(265 ) 2 -butylphenyl (266) 2- (2-methoxy-2-ethoxyethyl)phenyl(267) 2 -( 5 -decenyl)phenyl (268 ) o-biphenyl ( 269 ) 2-ethoxycarbonylphenyl

(270) 2-butoxyphenyl(271)2-methylphenyl(272)2-chlorophenyl(273) 2-phenylthiophenyl(274)2-benzylidenephenyl (275) 2 -Ethyloxyphenyl(276) 2 -benzimidyloxyphenyl (277 ) 2 -phenoxycarbonylphenyl-30- 1354684 (278 ) 2-methoxyphenyl (2 79 ) 2-anilinylphenyl(280)2-isobutyldecylaminophenyl (281) 2-phenoxycarbonylaminophenyl(2 82 ) 2 -( 3 -ethylureido)phenyl ( 283 ) 2 -( 3, 3 -diethylureido)phenyl(284 ) 2 -phenoxyphenyl(2 85 ) 2 -hydroxyphenyl

(286) 3,4-dibutylphenyl (287) 3,4-bis(2-methoxy-2-ethoxyethyl)phenyl (2 88 ) 3,4-diphenylphenyl (2 89 ) 3,4-diethoxycarbonylphenyl(290) 3,4-di-dodecyloxyphenyl(291) 3,4-dimethylphenyl(292) 3, 4 - Dichlorophenyl (293) 3,4-diphenylmercaptophenyl

(294) 3,4-diethoxymethoxyphenyl(295) 3,4-dimethoxyphenyl(296) 3,4-di-N-methylaminophenyl (297) 3, 4 -isobutyl decylaminophenyl (298 ) 3, 4 -diphenoxyphenyl (299) 3, 4 · dihydroxyphenyl (3 00 ) 3, 5 -dibutylphenyl (301) 3, 5 - bis(2-methoxy-2-ethoxyethyl)phenyl-31 - 1354684 (3 02 ) 3,5-diphenylphenyl (3 03 ) 3,5-diethoxycarbonylbenzene (3 04 ) 3,5-di-dodecyloxyphenyl (3 05 ) 3,5-dimethylphenyl (3 06 ) 3,5-dichlorophenyl (3 07 ) 3, 5 -Diphenylmercaptophenyl (3 08 ) 3,5-diethoxymethoxyphenyl (3〇9) 3,5-dimethoxyphenyl

(310) 3,5-Di-N-methylaminophenyl (311) 3,5-diisobutylamylaminophenyl (312) 3,5-diphenoxyphenyl (313) 3, 5 -dihydroxyphenyl(314) 2,4-dibutylphenyl(315) 2,4-bis(2-methoxy-2-ethoxyethyl)phenyl (316) 2, 4 - two Phenylphenyl (317) 2, 4-diethoxycarbonylphenyl

(318) 2,4-di-dodecyloxyphenyl(319) 2,4-dimethylphenyl(320) 2,4-dichlorophenyl(321) 2,4-dibenzimidazole Phenylphenyl (3 22 ) 2, 4-diethoxymethoxyphenyl (3 23 ) 2, 4-dimethoxyphenyl (324) 2, 4-di-N-methylaminophenyl ( 325) 2,4-diisobutyl decylaminophenyl-32 - 1354684 (326 ) 2, 4-diphenoxyphenyl (327 ) 2, 4 -dihydroxyphenyl (328 ) 2, 3 -dibutyl Phenylphenyl (329) 2, 3-bis(2-methoxy-2-ethoxyethyl)phenyl (330) 2,3-diphenylphenyl (331) 2, 3-diethoxy Phenylcarbonylphenyl (332) 2,3-di-dodecyloxyphenyl (333) 2,3-dimethylphenyl

(3 34 ) 2, 3-dichlorophenyl (335) 2, 3-diphenylmethylphenyl (3 3 6 ) 2, 3-diethoxymethoxyphenyl (337) 2, 3 - Methoxyphenyl (338) 2,3-di-N-methylaminophenyl (339) 2,3-diisobutylaminophenyl (3 40 ) 2,3-diphenoxyphenyl (341) 2, 3-dihydroxyphenyl

(3 42 ) 2,6-Dibutylphenyl(343) 2,6-bis(2-methoxy-2-ethoxyethyl)phenyl(344) 2,6-diphenylphenyl (345) 2,6-Diethyloxycarbonylphenyl (346) 2,6-di-dodecyloxyphenyl (3 47 ) 2,6-dimethylphenyl (348 ) 2, 6 -dichlorophenyl(349) 2,6-diphenylmercaptophenyl-33 - 1354684 (3 50 ) 2,6-diethoxymethoxyphenyl (351) 2,6-dimethoxybenzene (3 52 ) 2, 6 -di-N-methylaminophenyl(3 53 ) 2,6-diisobutylguanidinophenyl (354 ) 2,6-diphenoxyphenyl (3 55 2,6-dihydroxyphenyl (3 56 ) 3, 4,5-tributylphenyl (357) 3, 4, 5-tris(2-methoxy-2-ethoxyethyl)benzene base

(3 5 8 ) 3, 4,5-triphenylphenyl (359) 3, 4, 5-triethoxycarbonylphenyl (360) 3, 4,5-tri-dodecyloxyphenyl (361) 3,4,5-trimethylphenyl(362) 3,4,5-trichlorophenyl( 363 ) 3, 4,5-tritylmethylphenyl (364 ) 3, 4, 5-triethoxyindolyl (365) 3, 4, 5-trimethoxyphenyl

(366) 3,4,5-tri-N-methylaminophenyl(3 67 ) 3,4,5-triisobutylamylaminophenyl (368) 3,4,5-triphenyloxonium benzene (3 69 ) 3, 4, 5 -trihydroxyphenyl (370 ) 2, 4, 6 - tributylphenyl (371) 2, 4, 6-tris(2-methoxy-2-ethoxy Benzyl)phenyl(372) 2,4,6-triphenylphenyl(3 73 ) 2; 4,6-triethoxycarbonylphenyl-34- 1354684 (374) 2, 4, 6- Tri-dodecyloxyphenyl (3 75 ) 2, 4,6-trimethylphenyl·(3 76 ) 2, 4,6-trichlorophenyl-(377 ) 2, 4, 6 · three Benzyl phenylphenyl (378 ) 2, 4, 6 -triethoxymethoxyphenyl (379 ) 2, 4, 6 -trimethoxyphenyl ( 3 80 ) 2,4,6 -tri-N- Methylaminophenyl (381) 2, 4, 6-triisobutyl decyl phenyl

(3 82 ) 2, 4, 6 - Triphenyloxyphenyl · (383) 2,4, 6 -trihydroxyphenyl (3 84 ) pentafluorophenyl (3 8 5 ) pentachlorophenyl (3 86 Pentamethoxyphenyl (387) 6-N-methylamine sulfonyl-8-methoxy-2-naphthyl (388) 5-N-methylamine sulfonyl-2-naphthyl ( 389) 6-N-Phenylaminesulfonyl-2-naphthyl

(3 90 ) 5-ethoxy-7-N-methylaminesulfonyl-2-naphthylφ(391)3-methoxy-2-naphthyl(3 92 ) 1-ethoxy-2 -naphthyl (393) 6-N-phenylamine sulfonyl-8-methoxy-2-naphthyl (394) 5-methoxy- 7-N-phenylamine sulfonyl-2-naphthalene (3 95 ) 1 - ( 4-methyl)-2-naphthyl (396) 6, 8-di-N-methylamine sulfonyl-2-naphthyl (397) 6-N-2-B Nonyloxyethylamine sulfonyl-8-methoxy-2- 1354684 naphthyl (3 98 ) 5-ethoxycarbonyl-7-N-phenylamine sulfonyl-2-naphthyl' (3 99 ) 3 - benzyl methoxy-2-naphthyl · (400 ) 5 - ethoxymethylamino-1 -naphthyl (401 ) 2 -methoxy-1 -naphthyl (402 ) 4 - phenoxy Base-1 -naphthyl (403) 5-N-methylamine sulfonyl-1-naphthyl (4〇4) 3-N-methylaminemethanyl-4-hydroxy-1-naphthyl

( 405 ) 5 -Methoxy-6 - N -ethylaminesulfonyl-1 -naphthyl (406 ) 7 -tetradecyl-1-naphthyl (407 ) 4 - ( 4 -methylbenzene Oxy)-1 -naphthyl (408) 6-N-methylamine sulfonyl-1-naphthyl (409) 3-11--dimethylamine-mercapto-4-methoxy-1- Naphthyl (410) 5-methoxy-6-N-benzylaminesulfonyl-1-naphthyl (411) 3,6-di->^-phenylaminesulfonyl-1-naphthalene Base (412) methyl

(413) ethyl φ (414) butyl (415 ) octyl (416 ) dodeca (417) 2 -butoxy-2-ethoxyethyl (418 ) benzyl (419) 4- Oxybenzyl-36- 1354684

(424) Methyl (425) phenyl (426) butyl -37- 1354684 [Chem. 2 2] (427) (428) (429)

OC2Hb

[Chem. 2 3]

(430) methyl (431) ethyl (432) butyl (43 3 ) octyl (434 ) dodeca. ( 43 5 ) 2 -butoxy-2-ethoxyethyl 436 437 benzyl Lu 4-methoxybenzyl-38- 1354684 [Chem. 24]

[Chem. 2 5]

-39- 1354684化28] (ΜΡ·1)-(ΜΡ-50) —0-CH2 H2C——ΝγΝ Μ R1S, IV, R14

Ppppppp Μ Μ Μ Μ Μ M 1 tj u ) u R R R R R R 3 3 3 3 3 3 1 9J mj ej 1 u R R R R R R 12 3 4 5 6

5 5 5 5 5 8 J 14 3 1« R R R R R R

T°-06 6 6 6 u «J u 1* 1 u RR ΌΑ RRR CH2OH CH2OCH3 CH2〇-i-C4Hs CH2O-11-C4H9 CH2NHCOCH=CH2 CHaNHCO {CH2)7CH=CH (CHalvCHa MP-7 :Ri3, RJ4 , R]5: CHzOH; R16: CH2〇CH3 MP-8: Ri3, RJ6: CH2〇H; Ri5: CH2〇CH3 • MP-9: R!3, Ri4: CH20H: Ri5, R]6: ch2〇 CH3 win MP-1 0 : Ri3, Ri6: CH20H: R14, R15: CH2〇CH3 ·

MP-1 1 :R]3:CH2〇H;R]4, R15,.ri6:Ch2〇ch3 MP-1 2 :K]3, R]4' R]6:CH2〇CH3;R]5: CH2〇H MP-13 :Ri3, Ri6:CH2〇CH3;R14, R15:CH2〇H 4 5 6 7 8 9 0 1 1 1 1 1 1 2 ------- ppppppp

12 3 4 5 6 7 2 2 2 2 2 2 2 -1111--ppp-i P-* P-t O-i p* MMMMMMM

Ri3, Ri4N Ri5; CH2〇H; Ri6:CH2〇-i-C4H9 R]3, R14, R16:CH2〇H; R15:CH2〇-i-C4H9 R]3, R]4:ch2〇H;R 】5, R]6:CH2〇-Bu C4H9 R]3, R16:CH2〇H;R]4, R15:CH2〇-i-C4H9

R]3: CH2〇H; R]4, R]5, Ri6:CH2〇-i-C4H9 R]3, R]4, Ri6:CH20-iC〇H9:R15:CH2〇HR]3, R] 6: CH2〇-i-C4H9; R14, K] 5: CH2〇H

RJ3, R1^ Ri5:CH2OH; Rl6:CH2〇-n-C4H9 Ri3. R^( Ri6;CH2OH;Ri5:CH2〇-n-C<iH9 R.,R]4:CH2〇H;Ris' Ri6: cH2〇-n-C4H9 RJ3, r)6:ch20H;R]4, R15:CH2〇-n-C4H9 R]3:CH2〇H;Rm' R】5, RI6:CH2〇-n-C4H9 R】 3, R14, R]6:CH2〇-n-C4H3; R]5:cH2〇HR]3, Ri6:CH2〇-n-C4H9:K]4, R15:CH2〇H MP-2 8 :RJ3, RM:CH2〇H; Ri5:CH2〇CH3; R16:CH2〇-n-C4H9 MP-2 9 :Ri3, Ri4:CH2〇H;Ri5:CH2〇-n-C4H9;R^:CH2〇CH3 MP- 3 0 :R]3' R16:CH2〇H:R]4:CH2〇CH3:RJ5:CH2〇-n-C<iH9 MP-3 1 : RJ3:CH2〇H;Ri^ Ri5:CH2〇CH3: R,6:CH2〇-n-C4H9 MP— 3 2 :R】3:CH2〇mr】6:ch20CH3;P5:.CH2(Hi-C4H£) MP-3 3 :R】3:CH2〇H; Km:CH2OCH3;R]5,R]6:CH2〇-nC,jH9 MP—3 4 :Ri3:CH2〇H:RM,Ri^cHjKHi-C,££>;R】6:ch2〇CH3 MP -3 5 :R>3, R>〇:CH2〇CH3;K15:Cl]2〇H; RJ6:CH2〇-n-C4H9 MP-3 6 :Ri3, Ri6;CH2〇CH3;R^:CH2〇 H;Ri5:CH2〇-n-C<iH9 MP-3 7 :R]3:Ch2〇CH3; Rm, Ri5:cH2〇|.l;R)6:cH2〇-n-C4H9 -41 - 1354684 MP - 3 8

9 0 12 3 4 3 4 4 4 4 4 2 22 p p p p p p MMMMMM

P2p3p3p2p3p2 NCNCNCNCNCNC 5 4 6 4 7 4 8 4 9 4 o 5 R丨3 RJ6.CH2〇_n-C4H9:R]4:CH2OCH3; R15:CH2〇H γη,ΟΗ-R14·CH2〇CH3:R15:CHz 〇-n-C4H9; RJ 6:CH2NHCOCH=CH2 pJ, 〇h:R)4CH2OCH3; R]5:CH2NHCOCH=CH2; Ri6:CH2O-JI-C4H9 γη,ΟΗ:R14CH20-n-C4H9;R1 &: CH2NHCOCH=CH2; Ri6:CH2OCH3 rS,0CH3·R14:CHz0H:R15:CH2〇-n-C4H9;R16:CH2NHC0CH=CH2 fH^OCHs:R14:CH2OH;R^ s;CHiNHCOCH=CH2;RJ 6:CH20- n-C4H9 R) 3: CH2〇-n-C4H9; H14: CH2OCH3 '.R15: CH2OH; R>6: CH2NHCOCH=CH2 rj3:CH2OH; R14:CH2OCH3; R15:CH2NHCO (CH2) 7CH=CH (CH2) 7CH3; R16: CH2NHC0CH = F) 3: CHzOH; R14: CH2〇CHa; R»5; CH2NHC0CH=CH2: R16: CH2NHCO(CH2) vCH=CH (CH2)7 RJ3: CH2OH; R, 4: CH2NHCO (CH2 7CH=CH(CHz) 7CH3; RJ5: CHzNHCOCH=CH2; Ri6:CH2〇RJ3: CH2〇CH3; R14:CH2OH; R15:CH2NHCO(CH2)?CH=CH(CH2)7CH3;R16:CH2NHCOCH=R» 3:CH2OCH3; R14:CH2OH; RJ5:CH2NHCOCH=CH2; R16:CH2NHCO(CH2)?CH=CH(CH2)7 Ri3:CH2NHCO(CH2)?CH=CH(CH2)7CH3;R14:CH2OCH3;Ri5: CH2OH; Ri6: CHZNHCOCH= 9 2 (MP-51)-(MP- 100)

MP- 5 1 : R13, R14, R15, R16: ch2〇H MP-5 2 : R13, R14, RJ5, r] 6: ch2 〇 CH3 MP-5 3 : R] 3, R14, R] 5' R 】6: CH2〇-i-C4H9 MP-5 4 : RJ3, R14, RJ5, R16; CH20-n-C4H9 MP-5 5 : R13, R) <1% R15, R3 6; ch2NHC0CH=CH2 MP- 5 6 :Ri3, RM, R]5, R16:ch2NHC0(CH2)7CH=CH(CH2)7CH3

MP-5 7 :R»3, RJ4, Ri5:CH2OH;R>6:CH2〇CH3 MP-5 8 :Ri3, Ri4, Ri6:CH2〇H;R«5:CH2〇CH3 MP-5 9 :R 】3, R]4:ch2〇H:R15,ri6:ch20CH3 MP-6 0 :Ri3,Ri6:CH2〇H;R]4,ri5:ch20CH3 MP-6 1 : RJ3:CH2〇H;RJ^ RJS , RJ6.CH2OCH3 MP-6 2 : Ri3, RJ4, RJ6: CH20CH3; R) 5: CH20H MP-6 3 : U3, ri6: ch2〇CH3; R14' R] 5: CH2〇H CH2〇-i-〇 4Hg CH2〇-i-C4Hs CH2〇-i-C4H9 CH2〇-i-C4Hg CHsO-i-CoHs MP-6 4 : Ri3, Ri4, R)5; CH2〇H; RJ6 MP- 6 5 : RJ3, RJ4 , RJ6: CHZ〇H; K15 MP-6 6 : Ri3, Ri4; CH2〇H: R > 5, R^6 MP- 6 7 : Ri3, Ri6: CH2〇H; RM, Ris MP-6 8 : K 】3: CM; RM, RJ5, Ri6 -42- 1354684

MP-6 9 :R)3, R36;CH2〇-i-C4H9; RlS:CH2〇H MP-7 0 ;R13, R)6:cH20-i-C4H9;R14. R15:CH2〇H MP-7 l : R) 3, Rl4% R) 5; cH20H; R, 6: CH20-n-C4H9 MP-7 2 : Ri3x Ri6: cH2〇H; R, 5: CH2〇-n-C4H9 MP - 7 3 : RJ3, R)4; CH20H; R1S, RJ6: CH2〇-n-C4H9 7 4 :R)3, R]6:CH20H; R14, R>5:CH2〇-h-C4H9:R13:CH2〇H; Ri^ Ris, R)6: CH2〇-n-C4H9 7 g . m 〇. ...«tt Λ λ 11 _. οι ς - ru-HU

VJP VIP-7 5 ............ ^JP-7 6 : Ri3, Rir'R]6; CH2〇-n-C4H9: R15: CH2〇H-77: R13, Ri6: CH2〇-n-C4H9: R14, R15: CH2〇H MP - 7 8 MP — 7 g MP - 8 〇MP - 8 1 : R13 : R13, R14 : R13, R14R13, R16 CH20H; R1S CH2〇H; R16 CH20H; R14 CH2〇H; R!4, R15 CH20CH3; R16 CH2〇~n~C4H9CH2〇CH3; R15 ch2och3;r16 CH2〇CH3; R15 MP - 8 2 : RJ3;ch2〇h;R14% rj6. yP- 8 3 :K]3: Ch2〇h:rm:ch2〇CH3; R1s, R]6 MP-8 4 : RJ3:CH2〇H; Ri4, Ri5:CH2〇-n-C4H9 MP-8 5 :Ri3% R14: ch2OCH3; R) 5: CH2〇H; R16 MP-8 6 : RJ3, R16; ch2〇CH3; R) 4: CH2〇H; RiS MP - 8 7 : R13; CH2〇CH3; Rj4% rj5; cH2〇H; R16 MP-8 8 :Ri3, Ri6:f;H9f)-n-CmcH2〇CH3 CH2O-JI-C4H9 R16:CH2〇CH3 CH20-H-C4H9 CH20-I1-C4H9 CH20-11-C4H9 CH2 〇-n-C4H9 RJ6: CH2〇CH3 CH2O-11-C4H9 CH2〇~n_C4H9 CH2〇-n-C4Hg .Tii c:.ru^nu MP - 8 9 MP- 9 Ο MP- 9 1 MP- 9 2 Μ P - 9 3 MP- 9 4

2 9 3 2 9 2 Η Η Η Η Η H c 4 cc 4C tic o tl cu Η I 2 HtH c η H cnc 0 jco 1 o Co : coc H 2 6 H 2 HN Η ] N Η N 2 c R 2C 2 H · . ♦ · Η · · H c 6 2 c 6 c * · · 4 u · « 6 R c 6 R 6 R 2 HR 2 R • » H c ; H : 9 c 0 -9 c HH=c H=o 4 HH 4 H 2 cc N cc H -o 2 - oc Π c Η nc : -He - H 5 Λν ox. : «^1 1 2 2 5 2 2 R Η Η ] Η H : cc R cc 3 ..........H 5 5 9 5 5 C_3 ii 14uJ ΤΛ 1 Λυ R RC4R R 2 3 3 IHH c Η Π Π oo : cc Family 2 2 4 ο ο ο Η H 1 2 2 2 Cc R Η Η H... ccc 4 4 9 4 4 4 RR 1 J u · _ « t RRR 3 3 I ......Η Η n Η Η H cc -000000 2 2 2 2 2 2 Η Η Η Η Η H cccccc 3 3 3 3 3 3 RRKKRR MP- 9 5 : R]3: CH2〇H:R]4:CH2〇CH3; R15:CH2NHCO(CH2)7CH=CH(CH2)7CH3: K16:CH2NHCOCH= CHz MP - 9 6 : R13:CH20H; R^:CH20CH3; R15:CH2NHC0CH=CH2; R16:CH2NHC0(CH2)7CH=CH(CH2)7 CHs MP- 9 7 : R13;CH20H;R14: CH2NHC0(CH2)7CH=CH(CH2)7CH3; R15:CH2NHC0CH=CH2:R16:CH20 ch3 MP - 9 8 : Ri3:CH2〇CH3;R>4:CH2〇H;Ris:CH2NHCO(CH2)7C H=CH(CH2)7CH3: Ri6:CH2NHCOCH=CH2 MP - 9 9 : R13:CH2〇CH3; R14:CH2〇H; R15:CH2NHCOCH=CH2;R16:CH2NHCO〇2)7CH=CH(CH2)7CHs MP - 1 0 0 : RJ3; CH2NHCO(CH2)7CH=CH(CH2)7CH3; RJ4: CHzOCH3; R)5: CH2〇H; R16:CH2NHCOCh=ch2

-43- 1354684 [Chem. 30 (MP-101HMP-150) 9 HC 1-O-CH is called '丫1^ 丫N, R13 R1S, N, R14 MP-1 0 1 MP- 1 0 2 MP-1 0 3 MP-1 0 4 MP-1 0 5 MP-1 0 6

J t# I* 1 u 1J RRRRRR ','''' 5 5 ss 5 5 u —J 1 1 J 1 RRRRRR ''*·'* 4 4 4 4 4 4 I ti u 1 1 JRRRRRR,··' ·, 3 3 3 3 3 3 II )« u 1 «JRRRERR CH20H CH2OCH3 ΟΗ2〇_)_"Η9 CH2O-H-C4H9 CH2NHC0CH=CH2 CH2NHC0(CH2)7CH=CH (CH2)7CH3

MP-1 0 7 :K]3, R]4, K]5:〇H2〇H;R]6:CH2〇CH3 MP- 1 0 8 : R13, R14, Ri6:CH2〇H;Ri5:CH2〇 CH3 MP— 1 0 9 : R13, R】4: ch2〇H; RU, RI6: ch2〇CH3 MP— 1 1 0 : R】3, R]6: cH20H: R14, R】5: CH2〇CH3 MP -1 1 1 : Ri3; CH20H; Ri4, R15, Ri6; CH20CH3 MP-1 12: R] 3, R] 4, R] 6: cH2 〇 CH3; Rj5: CH2 〇 H MP- 1 1 3 : Ri3, Ri6:CH2〇CH3:ri4,ris:ch2〇H MP- 1 MP- 1 MP- 1 MP- 1 MP- 1 MP- 1 MP-1 4 5 6 7 8 9 0 1 1 1 1 1 -X C> 3

:Ri3, Ri4, Ri5:CH2〇H;R)6:CH2〇-i-C4H9:Ri3% R)4% Ri6:CH2〇H;Ri5:CH2〇-i-C4H9 :K]3,Rh:CH2 〇H;R]5' R16:CH2〇-i-C4H9 :K]3, R]6:CH2〇H:R]4, R]5:CH2〇-i-C4H9:Ri3:CH20H;R^, Ris, R]6; CH2〇-i-C4H9: Ri3' RH, ri6: ch2〇-Bu C4H9; R]5: CH20H Ri6: CH2〇-i-C4H9; R14, R]5: CH2〇H MP- 1 2 1 : R]3, R]4, R]5:CH2〇H; R]6:CH2〇-n-C4H9 MP-1 2 2 :R]3, RH, R36:CH2〇H:Ri5: CH2〇-n-C4H9 MP-1 2 3 : R]3, Rh:ch2〇H; R]5, R]6:CH2〇-n-C4H9 MP-1 2 4 :Ri3, RJ6:CH20H; RJ4. Ri5:CH2〇-n-C4H9 MP - 1 2 5 : R13:ch2〇H:R]4, Ris, R]6:CH2〇-n-C4H9 MP-1 26 :R]3,r,R】6 :CH2〇-nC〇H9; R15:CH2〇H MP_ 1 2 7 : R]3' Rj6:CH2〇-n-c4H9;R]4,R)s:CH2〇H MP-1 2 8 :R] 3' R]4:CH2〇H:R]5:CH2〇CH3;R]6:CH2〇-n-C4H9 MP-1 2 9 :R>3, R'4:CH2OH;RJs:CH2〇-n -C4H9;R)6:CH2〇CH3 MP-1 3 0 :Ri3, Ri6:CH2〇H;R)4:CH2〇CH3;R15:CH2〇-n-C4H9 MP-1 3 1 :R)3: CH2〇H; R>4<Ri5:CH2〇CH3; RJ6:CH2〇'H-C4H9 MP-1 3 2 :RJ3:CH2〇H:Rm,Ri6:cH2OCH3:R 】5:CH2〇-n-C4H9 MP- 1 3 3 : Ri3;CH2〇H;Ki^:CH2OCH3;KJ6. K)6:CH2〇-)]-C^9 MP-1 3 4 : Ri3:CH20H ; R14, R15: CH2〇-n-C4H9; R, 6: CH2〇CH3 MP- 13 5: Ri3, R^: CH2〇CH3; R) 5: CH2〇H; Ri6: CH2〇-n-C4Hg MP -1 3 6 :Ri3, Ri6:CH2〇CH3; RH:CH2〇H; RJ5:CH2〇-n-C4H9 MP- 1 3 7 : R)3:CH20CH3;Rh.R)5:CH2〇H:R )6:CH2〇-n-CdH9

-44 - 1354684 Μ p _ 1 3 8 Μ Ρ - 1 3 9 ΜΡ-1 4 0 Μ Ρ - 1 4 1 ΜΡ-1 4 2 Μρ- 1 4 3 ΜΡ-1 4 4 ΜΡ-1 4 5 H=CH2 ΜΡ- 1 4 6 )7〇Η3 ΜΡ- 1 4 7 2〇CH3 ΜΡ - 1 4 8 H=CHz Μ Ρ - 1 4 9 )7CH3 ΜΡ - 1 5 0 H=CH2

Rl3: CH2〇CH3; R]4 Rl3:CH2〇-n-〇4H9

;RJ3:CH2〇H; Rl3:CH2〇H :R13:CH20H

.ri3, RJ6: CH2〇-n-C4Hg; RM: CH2〇CH3; R15: CH2〇H ρ 13 · CH2OH R14 : CH2OCH3 ; R15 : CH2O-11-C4H9; R16: CH2NHC0CH=CH2 5 j 3·CHzOH: R'4·CH2OCH3; RJ 5:CH2NHCOCH=CH2; Ri 6:CHzO-nC^Hs ί 】3:CH2OH:R14:CH2〇-n-C4H9:R]5:CH2NHCOCH=CH2;R]6:Ch2〇 CH3 ί 13 '· CH2OCH3 ; R14 : CHaOH ; R J5: CH20-n-C4H9 ; Ri 6: CH2NHCOCH=CH2 ' -CH2〇H; K15:CH2NHCOCH=CH2; Ri6:CH2〇-n-C4H9 R m : CH2OCH3 ; R15 : CH2OH; R J6: CH2NHC0CH=CH2

Ri4;CH2〇CH3; R15:CH2NHCO(CH2)?CH=CH(CH2)7CH3; R16:CH2NHC0C R)4:CH2OCH3;RJ5:CH2NHCOCH=CH2;R16:CHzNHC0 (CH2)7CH=CH (CH2 Ri4:CHzNHCO (CH2)7CH=CH(CH2)7CH3; RJ5:CH2NHCOCH=CH2;R>6:CH R13:CH2OCH3;R14:CH2OH;R15:CH2NHCO(CHZ)?CH=CH(CHz)7CH3;R16:CHzNHCOC Ri 3 :CH2OCH3;R]4:CH2OH;R]5:CH2NHC0CH=CH2;R]6:CH2NHCO(CH2)7CH=CH(CH2 Ri3;CH2NHCO(CHz)7CH=CH(CH2)7CH3;R14:CH2OCH3;RJ5 :CH2OH;Ri6;CH2NHCOC [31 (MP-151)-(MP-200) pppppp _HaYHs ριβ^'γίΝ N^r13 R15,N,R14 "DtO CO AO"p J u tj tj tj JRRRRRK ,*, ,,, s 5 5 5 5 5 rr,r,rirr, 4 4 4 4 4 4 RRRRRR ,·'*·· 3 3 3 3 3 3 RRRKRK 12 3 4 5 6 5 5 5 5 5 5 CH20H CH20CH3 CH20-卜C4H9 CH2〇-n-C4H9 CH2NHCOCM2 CH2NHCO (CH2) 7CH=CH (CH2) 7CH3 MP - 1 5 7 : Ri3, RJ4, Ri5:CH2〇H; Ri6:CH2〇CH3 MP - 1 5 8 : R13, RH , Ri6:CH2〇H:RJ5:CH2〇CH3 MP - 1 5 9 : Ri3, R)4;CH20H;RJ5, RJ6:CH2〇CH3 MP - 1 6 0 : R]3,ri6:ch2〇H;Rh , ri5:cH20CH3

MP-1 6 6 : RJ3:CH20H; R»4, rj5, R)6; cH2〇CH3 MP- 1 6 2 : RJ3, Ri4, RJ6:CH2〇CH3;R,5:CH2〇H MP- 1 6 3 : Ri3, Ri6: CH20CH3; R^, RJ5: CH20H MP - 1 6 4 : R) 3, R' <*, R15: CH2〇H; RJ6: CH2〇-i-C4H9 MP - 1 6 5 : RJ3, RJ6; CH2〇H; R»5: CH2〇-i-C4H9 MP - 1 6 6 : R]3, rm:ch2〇H; RI5, Ri6:CH2〇-i-C4H3 MP - 1 6 7 : R13, RI6: CH20H; RH, Ri5: cH20-iC-jH9 MP - 1 6 8 : RJ3: CH2〇H; R'l RJ5, R)6: CH2〇-iC-sH9 -45- 1354684

MP-1 6 9 : Ri3^ R34^ RJ6; cH2〇-i-C4H9; RJ5: CH2〇H MP— 1 7 0 : Ri3, R16: CH2〇—Bu C4H9; R14′ r】5: cH2〇H MP - 1 7 1 MP- 1 7 2 MP- 1 7 3 MP- 1 7 4 MP- 1 7 5 MP- 1 7 6 MP- 1 7 7

Rl3, V4, RI5: CH2〇H; Ri6: CH2〇-n-C4H9 RJ6; cH2〇H; RJ5: CH2〇-n-C4H9

Ri3s R14: CH2〇H; R15, R16: CH2〇-n-C4H9

Rl3, R16: CH2〇H; R]4, R]5:CH2〇-n-C4H9 R33:CH2〇H; R14, Rjs, R16:CH2〇-n-C4H9

R]3, RH, Ri6: cH2OtC4H9; R] 5: CH2〇H

Rl3, R]6: CH2(Hi-C4H9;R]4, R]5:CH2〇H

MP — MP-MP-MP — MP — MP-MP-MP-MP-MP-MP- 17 8 17 9 18 0 18 1 18 2 18 3 18 4 18 5 18 6 18 7 18 8 R!3, K】 3, K!3, Rl3; R)3; Rl3 R]3; Rl3, R]3: Rl3: RJ3

CH2〇CH3;R)6:CH2〇-n-C4H9 CH2〇-D_C4H9|R,6-CH2〇CH3 CH2〇CH3:R]5:CH2〇-n-C4H9 CH2〇CH3;R)6:CH2〇 -n-C4H9 ..............CH2〇CH3; RJS:CH2〇-n-C4H9 CH2OH; R14 : CH2OCH3; R1 R16 :CH2O-11-C4H9 CH20H; Ri4, Ri5: cH20-n-C4H9; R16: CH2〇CH3 Ri4:CH2〇CH3; R15:CH2〇H; R36:CH2〇-n-C4H9 R)6:CH2OCH3;R14:CH2OH;R15:CH2〇-n-C4H9 CH2OCH3 :R]4, R15:CH2OH:R]6:CH2O-11-C4H9 R]6:CH2〇-n-C4H9:R14:CH2OCH3:R 】5:CH2OH R]4 R]6

CH2〇H CH2OH CH2OH R]5 Ris CH20H; R^s R35 CH20H; RM, R]6 8 9 : R}3:CH2〇H; RJ4:CH2〇CH3; R15:CH2〇-n-C4H9;Ri6: CH2NHCOCH=CH2 9 0 : R33:CH2〇H; R14:CH2〇CH3; R15:CH2NHCOCH=CH2; RJ6:CH2〇-n-C4H9 9 1 : RJ3:CH2〇H;R^;CH2〇-n-C4H9 ; R15:CH2NHCOCH=CH2; R^:CH2〇CH3 9 2 : R33:CH2〇CH3; RJ4:CH2OH; R»5:CH2〇-n-C4H9;R16:CH2NHCOCH=CH2 9 3 : R13:CH2OCH3;RJ4 :CH2〇H; R15:CH2NHCOCH=CH2; RJ6:CH2〇-n-C4H9 9 4 : R13:CH2〇-n-C4H9; R14:CH2〇CH3; R15:CH2〇H;Ri6:CH2NHCOCH=CH2 MP- 1 9 5 : Ri3:CH2〇H; Ri4;CH2〇CH3; RJ5:CH2NHCO(CH2)7CH=CH(CH2)7CH3; RI6:CH2NHCOC H=CH2 MP - 1 9 6 : Ri3:ch2〇H;R14: CH2〇CH3: R15:CH2NHCOCH=CH2; R16:CH2NHCO(CH2)7CH=CH(CH2)?CH3 MP- 1 9 7 : R)3:CH20H; R14:CH2NHC0(CH2)7CH=CH(CH2)7CH3; R15: CH2NHC0CH=CH2: R16: CH 20CH3

MP- 1 MP- 1 MP- 1 MP- 1 MP- 1 MP- 1 MP - 1 9 8 : R13:CH2OCH3; R1 <1:CH2OH;R>5:CH2NHCO(CH2)7CH=CH(CH2)7CH3; RJ6: CH2NHCOC H=CH2 MP- 1 9 9 : Ri3:CH2〇CH3; RH:CH2〇H; Ri5:CH2NHCOCH=CH2; Ri6:CH2NHCO(CH2)7CH=CH(CH2)7CH3 MP — 2 0 0 : R 】3: ch2NHCO(CH2>7CH=CH(CH2)7CH3:R14:CH2〇CH3;R]5.CH2〇HR]6.CH2NHCOC H=CH2 ' It is also possible to use a copolymer in which two or more repeating units are combined. It is also possible to use two or more kinds of homopolymers or copolymers, and it is also possible to use two or more compounds having a 1,3,5-triazine trap ring represented by the above formula (I). Two or more kinds of discotic compounds (for example, a compound having an i,3,5-diazepine ring represented by the above formula (I) and a compound having a porphyrin skeleton) are used. - 1354684 Next, the compound represented by the formula (II) used in the present invention is explained in detail as follows. Formula (II) [Chemical 3 2]

In the above formula (II), R21, R22 and R23 are preferably each independently a hydrogen atom or an alkyl group having 1 to 5 carbon atoms (for example, methyl group, ethyl group, propyl group, isopropyl group). , butyl, pentyl, isopentyl): particularly preferably at least one of R21, R22 and R23 is an alkyl group having 1 to 3 carbon atoms (for example: methyl, ethyl, propyl, isopropyl) base). Preferably, the oxime 21 is selected from the group consisting of: a single bond, _0—, —C0—, an alkylene group (preferably having 1 to 6 carbon atoms, more preferably 1 to 3), for example, a methylene group or a stretching group. Ethyl, propyl) or aryl (preferably having a carbon number of 6 to 24, more preferably 6 to 12, for example, a phenyl group, a phenyl group, a naphthyl group) A divalent linking group formed by one or more kinds of groups; particularly preferably a divalent linking group formed of one or more groups selected from the group consisting of: 〇〇, an alkylene group or an extended aryl group. Y21 is a hydrogen atom or an alkyl group (preferably, the number of carbon atoms is from 2 to 25, more preferably from 2 to 20), for example, ethyl, isopropyl, tert-butyl, hexyl, 2-ethyl Hexyl, tertiary-octyl, decyl, cyclyl, cyclohexyl'dicyclohexyl, adamantyl) -47- 1354684 aryl (preferably having a carbon number of 6 to 24, more preferably 6 to 18) For example: phenyl, biphenyl, terphenyl, naphthyl, or aralkyl (preferably having a carbon number of 7 to 30, more preferably 7 to 20). For example: benzo The group is a phenol-based 'tertiary-butylphenyl group, a diphenylmethyl group, a triphenylmethyl group); particularly preferably an alkyl group, an aryl group or an aralkyl group. A combination of x21-y21, preferably a X21 - Υ21, has a total carbon number of 〇~40, more preferably 1-30, and particularly preferably 1~25. Preferred examples of the compound represented by the above formula (II) are shown below, but the present invention is not limited to such specific examples.

-48 - 1354684

-49- 1354684

Next, the compound represented by the formula (III) used in the present invention will be described in detail below. General formula (III) -50- 1354684 [Chemical 3 5] 0 R33 31 1 I 32 S——N——R32

I 0

In the above formula (III), R31 represents an alkyl group or an aryl group, and R32 and R33 each independently represent a hydrogen atom, an alkyl group or an aryl group. Further, it is particularly preferable that the total number of carbon atoms of R31, R32 and R33 is 10 or more. The substituent is preferably a fluorine atom, an alkyl group, an aryl group, an alkoxy group, a sulfonic acid group, and a sulfonyl group; particularly preferably an alkyl group, an aryl group, an alkoxy group, a sulfonic acid group, and a sulfonamide group. Further, the alkyl group may be linear, branched, or cyclic, and the number of carbon atoms is preferably from 1 to 25, more preferably from 6 to 25, particularly preferably from 6 to 20 (for example, methyl or ethyl) Base, propyl, isopropyl, butyl, isobutyl, tert-butyl, pentyl, isopentyl, tert-pentyl, hexyl, cyclohexyl, heptyl, octyl, bicyclooctyl,壬基,金刚院基,癸基,三级-辛基,--

Base, twelve base, thirteen base, fourteen base, fifteen base, sixteen base, seventeen base, eighteen base, nineteen base, two base). The aryl group is preferably those having a carbon number of from 0 6 to 30, particularly preferably from 6 to 24 (for example, phenyl, biphenyl, terphenyl, naphthyl 'binaphthyl, triphenylphenyl). " R31 and R32 series can also be linked to each other to form a ring. Further, the amount of the modifier added in the present invention is preferably from 2 to 30% by mass relative to the bismuth cellulose. /. More preferably, it is 2 to 25% by mass, and particularly preferably 2 to 20% by mass. Preferred examples of the compound represented by the formula (III) are as follows -51 - 1354684, but the invention is not limited to the specific examples.化 II Λ n-C6H13- S -N-C6H13-n O H A- 1

0 II · n*C12H25_'S^N—C12H25-n

A- 2 O

!1 H

A- 5

-52- 1354684

Next, the compound represented by the general formula (IV) used in the present invention will be described in detail as follows: General formula (IV) -53 - 1354684 R52, R53, R54, R55, R61 'R62, R63, R64 and R65 They each independently represent a hydrogen atom or a substituent. If possible, two of the above R41 to R65 (e.g., R51) may be bonded to each other to form a ring. ]. In the general formulae (IV) and (IVA), X42 represents B, C-R70 (R70 represents a hydrogen atom or a substituent.), N, P, P = Ο; X42 is preferably B, C-R7() (R7() is preferably an aryl group, a substituted or unsubstituted amino group, an alkoxy group, an aryloxy group, a decyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, an awoxy group, an amine group, Oxalylamine, aryloxyindenyl, fluorenylamine, thiol, thiol, halogen atom (for example, fluorine atom, chlorine atom, bromine atom, atom), residue, more preferably square , alkoxy, aryloxy, thiol, halogen atom; further more preferably alkoxy, hydroxy, particularly preferably hydroxy.), N, P = 〇; further preferably C - R70' N; Preferably, C—r7〇〇R41, R42, R43, R44, R45, R51, rW, r53, r54, r55, RH, R62′′ R “ and a hydrogen atom or a substituent are used, and the substituent may be substituted as described below. The groups h R41, R43, r44, r45, r51, R52, R», R", R"', R., R., r64 and r65 are preferably: an alkyl group, an alkenyl group, an alkynyl group, an aryl group, Substituted or unsubstituted amine group, alkoxy , aryloxy, fluorenyl, alkoxycarbonyl, aryloxycarbonyl, decyloxy, decylamino, alkoxycarbonylamino, aryloxycarbonylamino'sulfonylamino, amine sulfonyl, amine Sulfhydryl, thiol, arylthio, sulfonyl, sulfinyl 'ureido, guanidinoamine 'hydroxyl, thiol, halogen atom (eg fluorinated atom, chlorine atom, bromine atom, iodine atom) ), cyano, sulfonate, carboxyl, nitro, hydroxamic acid 'sulfinyl' hydrazin oxime, imine-55- 1354684, heterocyclic (preferably carbon atom) The number is 丨~30, more preferably 1 to 12, and the hetero atom includes, for example, a nitrogen atom, an oxygen atom, a sulfur atom, and specifically, includes, for example, an imidazolyl group, a pyridyl group, a quinolyl group, a furyl group. Mercapto, benzofluorenyl N-morpholino, benzofluorenyl, benzimidyl, benzothiazolyl, etc., decylalkyl; more preferably alkyl, aryl, substituted or Unsubstituted amino group, alkoxy 'aryloxy group; further more preferably a group, an aryl group or an alkoxy group. The substituents may be further substituted. In addition, if the substituent has two When the amount is more than one, it may be different. If possible, it may be bonded to each other to form a ring. The substituent T is described below. The "substituent tau" includes, for example, "alkyl" (compare Preferably, the number of carbon atoms is from 1 to 20, more preferably from 1 to 12 carbon atoms, and particularly preferably from 1 to 8 carbon atoms, including, for example, methyl, ethyl, isopropyl, and tertiary. -butyl, n-octyl 'n-fluorenyl, n-hexadecyl, cyclopropyl 'cyclopentyl, cyclohexyl, etc.); "dilute group" (preferably having 2 to 20 carbon atoms) More preferably, the number of carbon atoms is 2 to 12, and particularly preferably, the number of carbon atoms is 2 to 8', including, for example, vinyl, aryl, 2-butenyl, 3-pentenyl, etc.; More preferably, the number of carbon atoms is 2 to 20', more preferably 2 to 12 carbon atoms, and particularly preferably 2 to 8 carbon atoms, for example, including propargyl groups and 3-pentyl groups. Alkenyl and the like. "Aryl j (preferably, the number of carbon atoms is 6 to 30, more preferably 6 to 20 carbon atoms, and particularly preferably 6 to 12 carbon atoms, for example, including: phenyl, p- -methylphenyl, naphthyl, etc.); "substituted or unsubstituted amine group" (preferably having a carbon number of 〇~20, more preferably a carbon number of 〇~10'- 56- 1354684 Preferably, the number of carbon atoms is Ο~6', including, for example, an amino group 'methylamino group, dimethylamino group, diethylamino group, benzhydrylamino group, etc.); The base j (preferably having a carbon number of 1 to 20, more preferably a carbon number of -12' is particularly preferably a carbon number of 1 to 8, and includes, for example, a methoxy group and an ethoxy group. Oxyl, etc.); "decyloxy" (preferably having a carbon number of 6 to 20' is more preferably a carbon number of 6 to 16, and particularly preferably a carbon number of 6 to 12, for example, : phenoxy group, 2-naphthyloxy group, etc.); "mercapto group" (preferably, the number of carbon atoms is 1 to 20', more preferably the number of carbon atoms is 1 to 16, and particularly preferably the number of carbon atoms It is 1 to 12, and includes, for example, an ethyl fluorenyl group, a benzamidine group, a methyl group, Trimethylethenyl, etc.); "alkoxycarbonyl" (preferably having 2 to 20 carbon atoms, more preferably 2 to 16 carbon atoms, and particularly preferably 2 carbon atoms) ～12, for example, includes: a methoxycarbonyl group, an ethoxycarbonyl group, etc.); “醯oxycarbonyl group” (preferably having a carbon number of 7 to 20, more preferably a carbon number of 7 to 16, Particularly preferred is a carbon atom number of 7 to 10, for example, including: phenoxycarbonyl group, etc.); "decyloxy group" (preferably having 2 to 20 carbon atoms, more preferably 2 carbon atoms) ～16, particularly preferably, the number of carbon atoms is 2 to 10, and includes, for example, an ethoxy group, a benzyl group, a fluorenyl group, etc.; "a guanamine group" (preferably, the number of carbon atoms is 2 to 20, More preferably, the number of carbon atoms is from 2 to 16', and particularly preferably, the number of carbon atoms is from 2 to 10, and includes, for example, an acetamino group, a benzylamino group, etc.); "alkoxycarbonylamino group" ( Preferably, the number of carbon atoms is from 2 to 20', more preferably from 2 to 16 carbon atoms, particularly preferably from 2 to 12 carbon atoms, and includes, for example, a methoxycarbonylamine group, etc. Carbonyl group" (preferably having 7 carbon atoms) ~2〇' More preferably, the number of carbon atoms is 7 to 16', and the number of carbon atoms is 7 to 12'. Examples -57- 1354684 include: phenoxycarbonylamine group, etc.); "sulfonamide group" (preferably, the number of carbon atoms is from 1 to 20, more preferably from 1 to 16 carbon atoms). The carbon number is preferably from 1 to 12, and includes, for example, a methanesulfonylamino group and a phenyl extended amine group. '); "Aminesulfonyl" (preferably having a carbon number of 0 to 20' is more preferably a carbon number of 〇~16, particularly preferably a carbon number of 〇~12' including, for example, an amine sulfonyl group , methylamine sulfonyl, dimethylamine sulfonyl, phenylsulfonylamino and the like. "Aminomethyl sulfhydryl group J (preferably having a carbon number of from 1 to 20' is more preferably a carbon number of from 1 to 16, particularly preferably a carbon number of from 1 to 12", for example. , methylamine, mercapto, diethylamine, mercapto, phenyl, carbamoyl, etc.; "alkylthio" (preferably having 1 to 20 carbon atoms, more preferably carbon atoms) 1 to 16, particularly preferably a carbon atom of 1 to 12', for example, including: methylthio group, ethylthio group, etc.); "arylthio group" (preferably having a carbon number of 6 to 20' is more preferably The number of carbon atoms is 0 to 10', and the number of carbon atoms is 6 to 12', for example, including: phenylthio group, etc.); "expansion base" (preferably, the number of carbon atoms is 1 to 20' is more preferably The number of carbon atoms is 1 to 16, and particularly preferably, the number of carbon atoms is 1 to 12', for example, including: methanesulfonyl 'toluene · sulfonyl group, etc.); "sulfinyl group j (preferably having a carbon number of 1 to 20 ^, more preferably 1 to 16 carbon atoms, particularly preferably 1 to 12 carbon atoms, for example, including: sulfinyl, phenylsulfinyl, etc.); "ureido" ( Preferably, the number of carbon atoms is 1 to 2 Å, more preferably the number of carbon atoms. It is preferably from 1 to 16 ', and the number of carbon atoms is from 1 to 12', including, for example, urea group, methylurea group, phenylurea group, etc.); "phosphonium phosphate group" (preferably having 1 to 20 carbon atoms) More preferably, the number of carbon atoms is from 1 to 16, and particularly preferably from 1 to 12' carbon atoms, for example, including: diethylphosphonium phosphinate, phenylphosphonium amide; transbasic, hydrogen-58- 1354684 sulfur a halogen atom (for example, a fluorine atom, a chlorine atom 'bromine atom, an iodine atom), a cyano group, a sulfonic acid group, a carboxyl group, a nitro group, a hydroxamic acid group, a sulfinic acid group, a hydrazino group, An imido group; a "heterocyclic group" (preferably having a carbon number of from 1 to 30, more preferably from 1 to 12), and the hetero atom includes, for example, a nitrogen atom, an oxygen atom, a sulfur atom, and specifically includes, for example. : imidazolyl, pyridyl, quinolyl, furyl, piperidinyl, morpholino, benzoxazolyl, benzimidazolyl, benzothiazolyl, etc.); "decylalkyl" (preferably The number of carbon atoms is from 3 to 40', more preferably from 3 to 30 carbon atoms, and particularly preferably from 3 to 24' carbon atoms, for example, including: trimethyldecyl, triphenylsulfonium φ alkyl And the substituents may be further substituted. In addition, when there are two or more substituents, they may be the same or different. If possible, they may be bonded to each other to form a ring. The compounds represented by IV) are specifically described below by way of specific examples, but the present invention is not limited to the specific examples.

-59- 1354684 [Chem. 4 1] F - 1 F - 6

-60- 1354684

-61 - 1354684

-62 - 1354684

B - 2 B - 7

-63- 1354684 〔化 45〕 B -11

巳一12 B-16 CH,

Ch3

B -13 B-18

H3C\ /CH3 N

Ν' xh3 , ch3 B -14

B -19

Η U

巳一 15

F

B -20 CH,

N -64- 1354684

-65 - 1354684 [Chem. 4 7] D- 6

Ε- Ί

The compound represented by the formula (I) and the compound represented by the formula (II), (III) or (IV) are used in an amount of 0.01 to 20 parts by mass based on 100 parts by mass of the cellulose ester. More preferably, it is used in an amount of 0.5 to 10 parts by mass. The above compounds are used in this range, whereby the retardation and water permeability of the film can be appropriately controlled. If the amount used is less than 0.01 part by mass, the control of delayed enthalpy and water permeability will be insufficient. If the amount used is more than 20 parts by mass, the additive will not be compatible with the cellulose ester and may be crystallized in the film. Further, the compound represented by the formula (I) is used in an amount of from 1 to 10 parts by mass, preferably from 1 to 10 parts by mass, per 100 parts by mass of the cellulose ester. The compound represented by the formula (II) '(III) or (IV) is used in an amount of 0.1 to 10 parts by mass, preferably 0.5 to 7 parts by mass, per part by mass of the cellulose vinegar. Next, the cellulose film suitable for use in the present invention will be described below. The cellulose which can be used in the cellulose film of the present invention is a cellulose compound and a compound having a cellulose skeleton obtained by using cellulose as a raw material and introducing a functional group biologically or chemically. Among them, cellulose ester is preferred, and more preferably _ is cellulose. - The cellulose-deposited film used in the present invention is described below. [Production of Deuterated Cellulose and Deuterated Cellulose Film] The mercapto group of the deuterated cellulose film is not particularly limited, but is preferably The use of an ethyl group, a propyl group, and a butyl group is particularly preferred. The degree of substitution of the total thiol group is preferably from 2.7 to 3.0, more preferably from 2.8 to 2.95. When a cellulose acetate having a fluorenyl group is used, the degree of substitution of acetyl group φ is preferably from 2.7 to 2.95, more preferably from 2.8 to 2.95, and most preferably from 2.84 to 2.89. In addition, it is also described in the above-mentioned Japanese Patent Application Laid-Open No. 1-3-3562-14, 2.50 or more and 2.86 or less, or the Ethylene-based substitution degree of 2.75 or more and 2.86 or less as described in JP-A- 13-226495. use. If it is too low, Re is liable to be larger than the desired one due to the tension in the flow delay, and there is also a problem that the in-plane unevenness is liable to occur. Further, the degree of substitution of the thiol group of 6 is suitably 0.9 or more. When the degree of substitution is 0.9 or less, it is easy to cause unevenness of Re and Rth. In addition, the degree of substitution in the thiol group of the present invention is calculated according to ASTM D817. In the present invention, cellulose acetate having a degree of acetylation of from 59.0 to 61.5% is preferably used. "Ethylation degree" means the amount of combined acetic acid per unit mass of cellulose. The degree of acetylation is obtained by measuring and calculating the degree of acetylation in ASTM: D-8 17-91 (test method for cellulose acetate, etc.). -67- 1354684 The average degree of polymerization (DP) of the deuterated cellulose is preferably 25 or more, more preferably more than 290. Further, in the cellulose deuterated film used in the present invention, the molecular weight distribution of Mw/Mn (Mw is a mass average molecular weight and Μη is a number average molecular weight) according to gel permeation chromatography is preferably a narrow size. The specific M w / Mn is preferably in the range of 1.0 to 1.7, more preferably in the range of 1.3 to 1.65, and most preferably in the range of 1.4 to 1.6. In the cellulose acetate of the present invention, the synthesis example 1 and the paragraph number 0048 to 0049 described in the paragraphs 0043 to 0044 of the Japanese Patent Laid-Open No. Hei. Cellulose acetate obtained by the synthesis method of Synthesis Example 3 described in 005 1 to 0052. [Production of Deuterated Cellulose Film] The deuterated cellulose film of the present invention is preferably produced by a solvent casting method. In the solvent casting method, a film is produced by using a solution (coating liquid: dope) in which deuterated cellulose is dissolved in an organic solvent. The organic solvent preferably contains an ether selected from the group consisting of 3 to 12 carbon atoms, a ketone having 3 to 12 carbon atoms, an ester having 3 to 12 carbon atoms, and a halogenated hydrocarbon having 1 to 6 carbon atoms. The solvent oxime ether, ketone and ester system in the group consisting of the compound solvent may have a cyclic structure. The compound having at least two of the functional groups of the ether, the ketone and the ester (i.e., mono-, -C0-, and -C00-) can also be used as the organic solvent. The organic solvent may also have other functional groups like an alcoholic hydroxyl group. In the case of the organic -68-1354684 solvent having two or more functional groups, the number of carbon atoms is preferably a solvent having any of the above-mentioned preferred functional groups. Examples of the ether having 3 to 12 carbon atoms include: diisopropyl ether, dimethoxymethane, dimethoxyethane, 1,4-dioxane, 1,3-dioxene Pentane, tetrahydrofuran, methoxybenzene, and phenylethyl ether. Examples of the ketone having 3 to 12 carbon atoms include acetone, methyl ethyl ketone, diethyl ketone, diisobutyl ketone, cyclohexanone, and methylcyclohexanone. Examples of the vinegar having 3 to 12 carbon atoms include ethyl formate, propyl formate, amyl formate, methyl acetate, ethyl acetate, and amyl acetate. Examples of the organic solvent having φ or more of two or more functional groups include 2-ethoxyethyl acetate, 2-methoxyethanol, and 2-butoxyethanol. The number of carbon atoms of the halogenated hydrocarbon is preferably 1 or 2, and most preferably 1. The halogen of the halogenated hydrocarbon is preferably chlorine. The ratio of the hydrogen atom of the halogenated hydrocarbon to halogen is preferably from 25 to 75 mol%, more preferably from 30 to 70 mol%, still more preferably from 35 to 65 mol%, and most preferably 4 0 to 60 0% by mole. Dichloromethane is a representative halogenated hydrocarbon. It is also possible to mix two or more organic solvents. The deuterated cellulose solution can be prepared by a general method comprising treatment at a temperature above 〇c (normal temperature or temperature). The preparation of the solution can be carried out by a method and apparatus for preparing a coating liquid by a usual solvent casting method. Further, when a general method is used, it is preferred to use a halogenated hydrocarbon (especially dichloromethane) for the organic solvent. The amount of deuterated cellulose should be adjusted to be from 10 to 40% by mass in the prepared solution -69-1354684. The amount of deuterated cellulose is preferably from 10 to 30% by mass. Any of the additives (plasticizers, anti-deterioration agents, etc.) described later may be added to the organic solvent (main solvent). The solution can be prepared by stirring the deuterated cellulose with an organic solvent at normal temperature (0 to 40 ° C). The high concentration solution can be stirred under pressure and under heating. Specifically, the deuterated cellulose and the organic solvent are placed in a pressurized container and sealed, and then heated under pressure to a temperature above the boiling point of the solvent at a normal temperature, and the solvent is not boiled while stirring. . The heating temperature of φ is usually 40 ° C or higher, preferably 60 to 200 ° C, more preferably 80 to 110 ° C. The components may also be coarsely mixed beforehand and then placed in a container. Moreover, it can be loaded gradually. The container must have a structure that can be agitated. An inert gas such as nitrogen may be injected to pressurize the container. Further, it is also possible to use an increase in the solvent vapor pressure caused by heating. Or, after passing through a closed container, add the ingredients under pressure. When heating, it should be heated from the outside of the container. For example, a jacket type heating device can be used. Further, it is also possible to adopt a method in which a plate heater is provided outside the container and piping is provided to circulate the liquid to heat the entire container. It is preferred to provide a stirring wing inside the container and use it for agitation. It is preferred that the agitating wing system has a length that is accessible to the vicinity of the wall of the container. At the end of the agitating wing, a scraper wall is preferably provided to renew the liquid film of the container wall. A pressure gauge 'a thermometer or the like can be placed in the container to dissolve the components in the solvent in the container. The coating liquid prepared by the preparation is taken out from the container after being cooled -70 to 1354684, or taken out first, and then cooled by using a heat exchanger or the like. The solution can also be prepared by a cooling dissolution method. The cooling dissolution method can dissolve the deuterated cellulose in an organic solvent which is difficult to dissolve according to a usual dissolution method. Further, even if it is a solvent capable of dissolving deuterated cellulose according to a usual dissolution method, when a cooling dissolution method is employed, the effect of a uniform solution can be quickly obtained. The cooling dissolution method was initially carried out by slowly adding deuterated cellulose at room temperature in an organic solvent while stirring. The amount of deuterated cellulose is preferably adjusted to be from 1 to 40% by mass in the mixture. The amount of deuterated cellulose is preferably from 10 to 30% by mass. Further, any additives described later may be added to the mixture in advance, and the mixture is cooled to -100 to -10 ° C (preferably -80 to -lot, more preferably -50 to 20 ° C, preferably It is -50 to -30 °C). The cooling system can be carried out, for example, in a dry ice/methanol bath (-75 ° C) or a cooled diethylene glycol solution (-30 to -20 ° C). After cooling, the mixture of chemical fiber ® vitamin and organic solvent will harden. The cooling rate is preferably 4 ° C / min or more, more preferably 8 ° C / min or more, and most preferably 12 ° C / min or more. The faster the cooling rate, the better, but 10,000 ° C / sec is the theoretical upper limit, l, 〇〇〇 ° C / sec is the technical upper limit, and l 〇〇 ° C / sec is practical The upper limit. Further, the cooling rate is obtained by dividing the difference between the temperature at which cooling starts and the last cooling temperature by the time required from the start of cooling to the time of reaching the final cooling temperature. -71 - 1354684 Then 'when heating it to 〇200〇C (preferably 〇 to 15〇 °C, more preferably 0 to 120°C 'best 〇 to 5〇-c) The cellulose is about to dissolve in an organic solvent. The temperature rise can be placed only at room temperature or can be warmed in a warm bath. The heating rate is preferably 4 ° C / min or more, more preferably 8 ° C / min or more and most preferably 12 ° C / min or more. Although the heating rate is as fast as possible, 10,000 ° C / sec is the theoretical upper limit, and uoirc / sec is the technical upper limit ' and 1 〇 0. (: / second is the practical upper limit. The heating speed is obtained by dividing the difference between the temperature at which heating starts and the last heating temperature by the time from the start of heating to the time of reaching the final heating temperature.値. A uniform solution can be obtained as described above. If the dissolution is not sufficient, the cooling and heating operations can be repeated. Whether the dissolution is sufficient or not is only to visually observe the solution. The appearance can be judged. In the cooling dissolution method, in order to avoid the incorporation of moisture due to condensation during cooling, it is preferred to use a closed container. In addition, in the cooling and heating operation, it is added during cooling. When the pressure is reduced, the dissolution time can be shortened. When pressure and pressure are reduced, it is preferred to use a pressure-resistant container. In addition, cellulose acetate (acetylation degree: 60.9) %, viscosity average degree of polymerization: 2 99) 20% by mass of a solution dissolved in methyl acetate by a cooling dissolution method, if measured by a differential scanning calorimetry (DSC), at around 33 ° C Sol state and gelatinous The pseudo phase transfer point exists, and below this temperature is a uniform gel state. Therefore, the solution must be above the pseudo phase transfer temperature, preferably at the gel phase transfer temperature plus l〇 ° C left -72 - 1354684 right The temperature is preserved. However, the pseudo phase transfer temperature differs depending on the degree of acetylation of cellulose acetate, the average degree of polymerization of the viscosity, the concentration of the solution, or the organic solvent used. The solution (coating solution) is a solvent-casting method for producing a cellulose-deposited film. It is preferred to add the retardation-increasing agent and the retardation-lowering agent to the coating liquid. The coating liquid is cast on a drum or a belt. And evaporating the solvent to form a film. Preferably, the coating liquid before casting is adjusted to have a solid content of 18 to 35%. The surface of the drum or belt is preferably pre-finished into a mirror state. The coating liquid is preferably cast on a drum or belt having a surface temperature of 1 〇 ° C or less. In the present invention, 'If the coating liquid (deuterated cellulose solution) is cast on the belt At the time of the first half of the drying before peeling, The step of drying in a substantially windless state is carried out for 10 seconds or more and 90 seconds or less, preferably for 15 seconds or more and 90 seconds or less. As for the coating liquid is cast on the rotation. In the case of the tube, the first half of the drying before the stripping is carried out in a substantially airless state for a period of from 1 second to 10 seconds, preferably from 2 seconds to 5 seconds. In the present invention, the term "drying before stripping" means a dryer which is applied to the belt or the drum until the coating liquid is peeled off as a film. It means to return to the previous step from the application of the coating liquid until one half of the total time required for stripping. "Substantially no wind" is measured at a distance of 200 mm or less from the surface of the self-contained surface or the surface of the drum. The state of wind speed exceeding 0.5 m / sec. -73- 1354684 Before the stripping, the first half of the drying is carried out, usually in the range of 30 to 300 seconds, but only 10 of them. More than 90 seconds in seconds, preferably 15 seconds or more and 90 seconds or less Time, then without wind · Dry. In the case of a drum, it is usually about 5 to 30 seconds, but in the case of 1 second or more and 10 seconds or less, it is preferably 2 seconds or more and 5 seconds or less in a strong wind. dry. The atmosphere temperature is preferably 〇 ° C ~ 180 ° C ' more preferably 40 ° C ~ 150 ° C. The operation of drying without wind can be carried out at any stage before the drying before stripping, but is preferably carried out immediately after casting. If the time of airless drying is shorter than 10 seconds, # it is difficult to evenly distribute the retardation increasing agent and the retarding reducing agent in the film. When it is longer than 90 seconds, it will be forced to be peeled off under insufficient drying. Taken so that the surface of the film is deteriorated. The inert gas may be blown for drying at a time other than drying without drying in the drying before stripping. The hot air temperature at this time is preferably 〇 ° C to l S 〇 ° C, more preferably 40 ° C to 150 ° C. The drying method in the solvent casting method is disclosed in U.S. Patent Nos. 2, 3, 36, 3, 0, 2, 367, 603, and 2, 492, 078, 'the same as the number 2, 492, 977, the same as 2, 492, 978, and the second, 607, 704. No. 2,739,069, the same as No. 2,739,070, 'British invention patent No. 640,731, the same as No. 736,892, Japanese Patent Special Publication No. 45-4554, the same as 49-5614, Special Open No. 60- No. 176,834, the same as in the publications of the same as No. 60-203430 and the same as No. 62-1 1 5035. The drying on the belt or the drum can be carried out by blowing an inert gas such as air or nitrogen. -74- 1354684 The obtained film may also be stripped from a drum or belt and dried by a hot air which gradually changes temperature from 1 Torr to 160 ° C to evaporate residual solvent ‘ . The above method is described in Japanese Patent Laid-Open No. 5-17844. According to this method, the time required from the self-flow to the stripping can be shortened. To carry out the process, the coating liquid must be gelled at the surface temperature of the rotating drum or belt. It is also possible to carry out casting of two or more layers to form a film by using a adjusted deuterated cellulose solution (coating liquid). In this case, it is preferred to produce a deuterated cellulose film by a solvent casting method. The coating liquid is cast on a drum or belt and then evaporates to form a film. The coating liquid before casting is preferably adjusted to have a solid content of from 10 to 40% by weight. The surface of the drum or belt is preferably pre-finished into a mirrored state. When casting a plurality of layers of deuterated cellulose liquid, it is also possible to cast several kinds of deuterated cellulose solutions, that is, several castings can be taken from the direction of the support body through the interval. The method of casting a solution containing deuterated cellulose into a film on one side of the layer. For example, it is possible to use the Japanese Patent Laid-Open No. 6 1 - 1 5 84 1 4, the same Japanese Patent Laid-Open No. 1 - 1 2241 9 Xin, and the Japanese Patent Laid-Open No. 1 1 - 1 9 8 8 8 The method described. In addition, the thinning of the cellulose solution by the two casting openings can also be made into a thin film. For example, the Japanese Patent Publication No. 60-275 62, the same Japanese Patent Publication No. 61-94724, and the same can be used. Bulletin of Kaisho No. 6 1 - 947245, Tong Tekai No. 61-1〇4813, Tongte Kaizhao No. 6 1 - 1 584 1 3, and Tongte Kaiping No. 6-1 3 493 3 The method described in the article. In addition, the state in which the fluid of the high-viscosity deuterated cellulose-75 - 1354684 solution is coated with a low-viscosity deuterated cellulose solution as described in JP-A-56-160 167 177 can also be used. A casting method of a bismuth cellulose film which is simultaneously extruded with a high- and low-viscosity bismuth cellulose solution. In addition, it is also possible to use two casting openings and peeling off through the first casting opening. The film on the support is then subjected to a second casting on the side contacting one side of the support surface to produce a film. For example, the method described in Japanese Patent Publication No. Sho 44-2 0235 can be used. The same solution can also be used for the cast cellulose channel solution, and different deuterated cellulose solutions can also be used. In order for the deuterated cellulose layer to have several functions, it is preferred to extrude the deuterated cellulose solution according to its function from the respective casting openings. Further, the deuterated cellulose solution of the present invention may be cast simultaneously with other functional layers (e.g., adhesive layer, dye layer, antistatic agent, anti-corona layer, ultraviolet absorbing layer, polarizing layer, etc.). In the previous single layer liquid, in order to achieve the desired film thickness, it is necessary to extrude a high viscosity deuterated cellulose solution at a high concentration. At this time, the stability of the bismuth cellulose solution is poor, and a solid matter is formed to constitute a defect of a small unevenness, or the planarity is deteriorated, and most of them become a problem. For the solution to this problem, if several kinds of deuterated cellulose solution are delayed from the casting mouth, the high viscosity solution can be simultaneously extruded on the support, so that not only the flatness but also the goodness can be obtained. The film has an excellent surface shape, and the drying load can be reduced by using a concentrated deuterated cellulose solution to increase the production rate of the film. The following plasticizer can be used for the deuterated cellulose film to improve its mechanical properties. As the plasticizer, a phosphate or a carboxylate can be used. Examples of phosphates are -76-1354684 including: triphenyl phosphate (ΤΡΡ), and tricresyl phosphate (TCP). Carboxylic acid esters are represented by phthalic acid esters and citrate esters. Examples of phthalates include: dimethyl phthalate (DMP), diethyl phthalate (DEP), dibutyl phthalate (DBP), phthalic acid Octyl ester (DOP), diphenyl phthalate (DPP), and diethylhexyl phthalate (DEHP). Examples of the citric acid esters include: 0-acetic acid triethyl citrate (OACTE), and 0-ethyl decyl tributyl citrate (OACTB). Examples of other carboxylic acid esters include: butyl oleate, methyl decyl ricinoleate, dibutyl sebacate, and various various 1,2,4-benzenetricarboxylates. Phthalate plasticizers (DMP, DEP 'DBP, DOP, DPP, DEHP) are suitable for use. Among them, the best ones are DEP and DPP. The amount of the plasticizer added is preferably from 1 to 25% by mass, more preferably from 1 to 20% by mass, and most preferably from 3 to 15% by mass. An anti-deterioration agent (for example, an antioxidant, a peroxide decomposing agent, a radical inhibitor, a metal inerting agent, an acid scavenger, an amine agent) may be added to the deuterated cellulose film. Regarding the anti-deterioration agent, Japanese Patent Laid-Open No. 3--199201, the same as No. 5-190073, the same as No. 5-149789, the same as No. 5-27 1 47 1 and the same No. 6-1 07854 It is described in each bulletin. The amount of the anti-deterioration agent to be added is preferably 0.01 to 1% by mass, more preferably 〇1 to 0.2% by mass, based on the target solution (coating solution) to be prepared. When the amount added is less than 0.01% by mass, the effect of the anti-deterioration agent is hardly observed. If the amount of addition is more than 1% by mass, there is a possibility that the anti-deterioration agent has an anti-deterioration effect on the film-forming base, and the anti-deterioration agent has a problem of being inferior to the surface-77- 1354684 Hydroxyl toluene (BHT), tritylamine (ΤΒΑ) These steps from self-casting to post-drying, may also be carried out in the production of alumized cellulose film under an inert gas atmosphere such as nitrogen. The machine system, that is, the tension method, the constant torque method, the program tension control method with a constant taper force, etc., the name of the roll (the surface treatment of the bismuth cellulose film) The surface method to be applied thereto may be a corona discharge treatment, a glow discharge treatment, an alkali treatment, or an ultraviolet irradiation treatment. Further, the layer described in Japanese Laid-Open Patent Publication No. 7-3 3 3 3 3 3 is incorporated. From the viewpoint of maintaining the planarity of the film, the temperature of the bismuth fibrite film is set to Tg (hereinafter, specifically, it is preferably set to 1501 or less. When using a transparent protective film as a polarizing plate, It is particularly preferable to carry out the saponification treatment by acid treatment or alkali treatment. The surface energy is preferably 5 5 mN/m or more, and more preferably 75 mN/m or less. For example, alkaline alkalization treatment is used. Specifically, the alkaline alkalization treatment of the bismuth cellulose film is carried out by neutralizing with an acidic solution after the alkali solution, and then circulating. It is carried out under an air atmosphere. It can be used in the present invention. The user-shaped torque method and the internal S should be taken up. The specific square, flame treatment, and acidity φ can also be set as in Japan, when the substrate is applied to the treatment, the glass transition temperature) The adhesion of the polarizing film, that is, the 醯Chemical Fiber® is preferably 60 mN/m or more. Preferably, the surface of the film is immersed in water and dried. -78-1354684 The alkali solution includes a potassium hydroxide solution, a sodium hydroxide solution, and a predetermined concentration of hydroxide ions, preferably in the range of 0.1 to 3.0 N, more preferably Range of 0.5 ' to 2·0 N. The temperature of the alkali solution is preferably from room temperature to 90 ° C, more preferably from 40 to 70 ° C. The surface energy of solids can be determined by the contact angle method 'wet heat method and adsorption method as described in the book "Basic and Application of Wetting" (Realize Corporation, published on December 10, 1989). In the case of the deuterated cellulose film of the present invention, it is preferred to use a contact angle method. Specifically, the two kinds of solutions having the surface energy are known to be dropped on the deuterated fiber Russin film at the intersection of the surface of the droplet and the surface of the film to draw the angle formed by the wiring of the droplet and the surface of the film, and The angle of the person including the drop is defined as the contact angle, and the surface energy of the film can be calculated by calculation. [Heat permeability] The moisture permeability is measured according to the method described in JIS Z0208, and the moisture content of each sample is measured in 24 hours per 1 m2 area (g). The moisture permeability of the cellulose film can be Various methods are adjusted. β can add a hydrophobic compound to the deuterated cellulose film to lower the water absorption of the deuterated cellulose film to lower the moisture permeability. In this case, it is preferred to use an additive having low compatibility with deuterated cellulose and having a small plasticizing effect. The compounds represented by the above formulas (I) to (IV) are suitably used as a hydrophobizing agent.

The water absorption of the deuterated cellulose film can be evaluated by measuring the equilibrium moisture content at a certain temperature and humidity. The equilibrium water content of the deuterated cellulose film at 25 ° C - 79 - i354684 80% RH is preferably 5% by mass or less, more preferably 3% by mass or less. The equilibrium moisture content is determined by Karl Fischer analysis method after the above temperature and humidity is placed for 24 hours, and the amount of water to be balanced is measured by the Karl Fischer analysis method, and then the amount of water (grams) is divided by the mass of the sample (g). Calculated. Further, the 'transparent humidity system can also be made to reduce the alignment of the deuterated cellulose molecular chain by making it dense in the direction of transport and/or in the width direction at the time of film formation. The extension can be implemented in either the uniaxial stretching method or the biaxial stretching method. Although the biaxial stretching method includes two kinds of simultaneous biaxial stretching method and sequential biaxial stretching method, from the viewpoint of continuous manufacturing, the sequential biaxial stretching method is preferred, which is cast coating. After the liquid, the film is peeled off from the belt or the drum to extend in the width direction (longitudinal direction) and then in the longitudinal direction (width direction). The method of extending in the width direction is described, for example, in the Japanese Patent Laid-Open No. 62-119 503 5, the Japanese Patent Laid-Open No. 4- 1 52 1 25, the same as the 4-2842 1 1 -2983 No. 1, No. 1 1 -4827 No. 1 and the like. The extension of the film is carried out under normal temperature or heating conditions. The heating temperature is preferably below the glass transition temperature of the film. The film can be extended by treatment in a dry state, which is effective especially when a solvent remains. When the length direction is extended, for example, the film transport roller speed is adjusted so that the film take-up speed is faster than the film stripping speed to extend the film. When extending in the width direction, the film can be stretched by the method of holding the width of the film while being carried by the tenter and slowly expanding the width of the -80-1354684 frame. It can also be extended using an extension machine after the film has been dried (preferably using a uniaxial extension of a long stretcher). The stretching ratio of the film (the ratio of the original portion due to the extension of the original length) is preferably in the range of 5 to 50%, more preferably in the range of 10 to 4%, and most preferably in the range of 15 to 35%. . Further, by treating the cellulose film at a high temperature to increase the degree of crystallization, the water permeability can be lowered. The above treatment must be carried out at a temperature and time at which the volatilization of the low molecular compound and the thermal cracking of the cellulose film itself are not problematic. The treatment temperature is preferably from 1 60 ° C to 2 600 t, more preferably from 180 ° C to 240 ° C. The treatment time is preferably 5 minutes or more and 2 hours or less, and more preferably 10 minutes or more and 1 hour or less. [Moisture absorption coefficient] The "hygroscopic expansion coefficient" is a change in the length of the sample when the relative humidity is changed at a certain temperature. In order to prevent the frame-like transmittance from increasing, the hygroscopic expansion coefficient of the deuterated cellulose film is preferably 3〇xl (T5/%RH or less, more preferably 15χ10_5/% RH or less, and most preferably l) 〇x 10_5/% RH or less. In addition, although the hygroscopic expansion coefficient is preferably small, it is usually l.〇xl (T5/%RH or more. The measurement method of the hygroscopic expansion coefficient is as follows. The obtained polymer film (phase difference plate) was cut into a sample having a width of 5 mm and a length of 20 mm, and one end was fixed, and then suspended at 25 ° C in an atmosphere of 20% RH (R0). At the other end. Suspension 〇·5g weight 'after 1〇 minutes, measure 1354684 length (L0). Then the temperature is still at 25 °C to make the humidity 80%RH (R1) to determine the length (L1). The coefficient of expansion is calculated by the following formula. The measurement system performs 10 sample times for the same sample and then uses its average 値^6 hygroscopic expansion coefficient [/%RH]= { ( LI - LO ) /LO} / ( Rl - R0) In order to reduce the dimensional change caused by the above moisture absorption, it is preferred to reduce the amount of residual solvent at the time of film formation, and to free the polymer film. The general method for reducing the residual solvent is to carry out drying at a high temperature and for a long time φ, but if it is too long, the productivity is of course lowered. Therefore, for the cellulose-deposited film The amount of the residual solvent is preferably in the range of 0.01 to 1% by mass, more preferably in the range of 0.02 to 0.07% by mass, most preferably in the range of 0.03 to 〇.5% by mass. The amount of the residual solvent is controlled thereby That is, a polarizing plate having optical compensation energy can be obtained at low cost and high productivity. The amount of residual solvent is obtained by dissolving a certain amount of the sample in chloroform and using gas chromatography (GC 1 8 A, Shimadzu Corporation) The solution casting method uses a solution (coating liquid) obtained by dissolving a polymer material in an organic solvent to produce a film. The drying in the solution casting method can be classified as follows. Drying on the drum (or belt) surface and drying during film transport. When drying on the drum (or belt) surface, it is preferably not higher than the boiling temperature of the solvent used (if Above the boiling point will change Drying slowly for the bubble. As for drying during film transport, it is preferably ±3 玻璃 at the glass transition point of the polymer material. 〇, more preferably in the “^下-82- 1354684. Another method which can reduce the dimensional change caused by the above moisture absorption is to add a compound having a hydrophobic group. A material having a hydrophobic group, if it is a material having a hydrophobic group such as an alkyl group or a phenyl group in the molecule There is no particular limitation, but it is preferably a material which can be qualified in the above-mentioned plasticizer or anti-deterioration agent added to the deuterated cellulose film. Examples of such preferred materials include ··· Phenyl ester (TPP), tritylamine (TBA), and the like. The amount of the compound having such a hydrophobic group is preferably from 0.01 to 30% by mass, more preferably from 0.1 to 20% by mass, based on the solution (coating liquid) to be adjusted. [Delay of film] Re retardation 値 (nano) and Rth retardation 奈 (nano) of the film can be defined by the following formulas (A) and (B), respectively. (A ) Re = (nx-ny) xd (B) Rth={(nx + ny) /2 - nz } xd In the formulas (A) and (B), nx is the direction of the slow phase axis in the plane of the film ( The refractive index of the refractive index will become the largest direction. In the formulae (A) and (B), ny is a refractive index in the direction of the phase in the film plane (the direction in which the refractive index will become the smallest). In the formula (B), nz is the refractive index in the thickness direction of the film * In the formulae (A) and (B), d is the thickness of the film in nanometers, and the cellulose film of the present invention is suitable. Used as a retardation film corresponding to liquid crystal mode -83-1354684. The preferred optical properties of the deuterated cellulose film vary depending on the liquid crystal mode. For the OCB mode, the Re is preferably 10 to 1 ,, and more preferably 20 to 70. Rth is preferably from 50 to 300, more preferably from 1 to 250. The VA mode user preferably has a Re of 20 to 100, more preferably 30 to 70. Rth is preferably 50 to 250, and more preferably 80 to 180. In addition, the 'TN users are better with Re as 〇~50, and more preferably 2~30. Rth is preferably from 10 to 200, more preferably from 30 to 150. φ In the OCB mode and the aging mode, an optically anisotropic layer may be coated on the fluorinated cellulose film having the above retardation to be used as an optical compensation film. Further, the birefringence (An: nx-ny) of the brewed cellulose film is preferably in the range of 0.00 to 0.002. Further, the birefringence { (nx + ny) /2 - nz } in the thickness direction of the support film and the opposite film is in the range of 0.00 to G·04. The thickness (dry film thickness) of the deuterated cellulose film is 120 μm or less, preferably 20 to 110 μm, more preferably 40 to 100 μm. [Photoelasticity] The photoelastic coefficient of the protective film of the present invention is preferably 6 〇χ 10·8 cm 2 /N or less, and more preferably 2 〇 x l 0·8 cm 2 /N or less. The photoelastic coefficient can be obtained by an elliptical meter. [Glass Transfer Temperature] The glass transition temperature of the protective film of the present invention is preferably 1201 or more, more preferably 84 - 1354684 or more preferably 1 40 °C or more. The glass transition temperature is measured by differential scanning calorimetry (DSC), which is the temperature at which the baseline of the glass transition from the film will start to change and the temperature returned to the baseline again when the temperature is raised at 10 ° C / min. The average is the one sought. 1. Configuration of polarizing plate First, the protective film and polarizing film for constituting the polarizing plate of the present invention will be described below. The polarizing plate of the present invention may have a binder layer, a separator film, and a protective film as constituent elements in addition to the polarizing film or the protective film. (1) Protective film The polarizing plate of the present invention has a protective film of a total of two sheets on both sides of the polarizing film, but at least one of them preferably has a function as a phase difference film at the same time. The protective film of the present invention is preferably via a norbornene resin, polyethylene terephthalate (PET), polyethylene naphthalate, polycarbonate, polystyrene, polyarylate, poly maple, The polymer film produced by deuterated cellulose or the like is preferably the above-mentioned deuterated cellulose. (2) Polarizing film The polarizing film of the present invention is preferably composed of polyvinyl alcohol (PVA) and dichroic molecules, but may be used as described in Japanese Patent Laid-Open No. H-248937. The PVA or the polyvinyl chloride is dehydrated and dechlorinated to form a polyene structure, and the aligned ethylene-based polarizing film is aligned. PVA is a polymer material obtained by alkalizing polyvinyl acetate, -85-1354684 but may also contain, for example, an unsaturated carboxylic acid, an unsaturated sulfonic acid, a hydrocarbon, a vinyl ether, and vinyl acetate. Copolymerized ingredients. Further, a modified PVA containing an ethylene sulfonate group, a sulfonic acid group, a carboxyl group, an alkylene oxide or the like can also be used. The degree of saponification of PVA is not particularly limited, but is preferably from 80 to 100 mol%, particularly preferably from 90 to 100 mol%, from the viewpoint of solubility and the like. Further, although the degree of polymerization of the PVA is not particularly limited, it is preferably from 1,000 to 10,000, and particularly preferably from 1,500 to 5,000. pv A is a pair of (regular) regularity as the second invention patent. In the case of improving the durability, it is preferably 55% or more, but it is also possible to use 45 to 52.5% as described in Japanese Patent No. 3,317,494. After P V A is thinned, it is preferred to introduce a dichroic molecule to form a polarizing film. The method for producing a PVA film is generally a method in which a PVA-based resin is dissolved in a liquid solution of water or an organic solvent to form a film. The concentration of the polyvinyl alcohol-based resin in the stock solution is usually 5 to 20% by mass, and the raw material is formed into a film by a casting method to obtain a PVA film having a film thickness of 10 to 200 μm. For the production of the PVA film, the method described in the invention patents No. 3, 342, 516, JP-A No. 09-3 285, No. JP-A No. Hei No. Hei No. Hei No. Hei No. Hei. . The degree of crystallization of the PVA film is not particularly limited, but the average degree of crystallinity (Xc) described in Patent No. 3,251,073 can be 50 to 75 mass%, or the variability of the in-plane hue can be reduced. A PVA film having a crystallinity of 38% or less is described in JP-A No. M-2 3 62 1 . The birefringence (Δ n ) of the PVA film is preferably small, and the invention patent is -86- 1354684

The PVA film having a birefringence of 1 〇χ 1 〇·3 or less as described in 3,342,5 1 6 is suitable for use. However, as described in Japanese Laid-Open Patent Publication No. 14-228835, in order to prevent the PVA film from being cut at the time of stretching and to obtain a high degree of polarization, the birefringence of the PVA film can be set to 0.02 or more and 〇. The enthalpy of { ( nx + ny) /2 - nz } can be set to 0.0003 or more and 0.01 or less as described in Japanese Laid-Open Patent Publication No. 14-060505. The retardation 値 (in-plane) of the PVA film is preferably 1 nm or less, more preferably 0 nm or more and 50 nm or less. Further, the Rth (film thickness direction) of the PVA film is preferably from not less than 500 nm to more than 500 nm, more preferably not more than 〇 nanometer and not more than 300 nm.

In addition, the polarizing plate of the present invention is also suitable for use in a PVA film having a 1,2-ethylene glycol bond amount of 1.5 mol% or less as described in Japanese Patent No. 3,021,494, and Japanese Patent Laid-Open No. 13 -31 64 The optical foreign matter of 5 μm or more per 100 cm 2 described in No. 92 is a PVA film of 500 or less, and the TD of the film described in JP-A No. 1 4-030 1 63

The direction of the hot water cutting temperature change is 1. 5 ° C or less of the PV A film, and the mixing of 1 to 100 parts by mass of glycerin or the like 3 to 6 yuan of the polyol, or a mixture of 15% by mass or more A PVA film formed by a solution of a plasticizer described in No. 06-289225. The film thickness of the PV A film before stretching is not particularly limited, but it is preferably 1 μm to 1 mm from the viewpoint of maintaining the stability of the film and the homogeneity of the extension, and particularly preferably 20 ~ 200 microns. It is also possible to use a thin PVA film of -87 - 1354684 which has a stress of 1 〇 N or less which is generated by applying a 4 to 6 times extension in water as described in Japanese Patent Laid-Open No. Hei 14-236212. As the dichroic molecule, a higher order iodide ion or a dichroic dye such as Ι3· or Ι5· can be used. In the present invention, a higher order iodide ion is particularly suitable for use. The higher-order iodide ion can be immersed in the dissolution of iodine in potassium iodide solution as described in "Application of Polarizing Plates, J. Yongda Liang, CMC Publishing or Industrial Materials, Vol. 28, No. 7, pp. 39-45. The liquid and/or the aqueous boric acid solution are produced in a state of being adsorbed and aligned to PVA. When a dichroic dye is used as the dichroic dye, an azo dye is preferable, especially a disazo Preferably, the dichroic dye is preferably a water-soluble one. Therefore, a hydrophilic substituent such as a sulfonic acid group, an amine group or a hydroxyl group is introduced into the dichroic molecule to be used as a free acid. Or a salt of an alkali metal salt, an ammonium salt or an amine. Specific examples of the dichroic dye as described above include: CI direct red 3 7 , Congo red (c. I · direct red 2 8 ) ' c. I · Direct purple i 2 , CI direct blue 90, CI direct blue 22, CI direct blue l'c I · direct blue 151, C. 1_ direct green 1 etc. benzidine system; CI direct yellow 44, CI direct red 23, CI direct red 79 and other diphenyl urea system; CI direct yellow 12 and other styrene system; CI direct Di-naphthylamine series such as red 31; CI direct red 81, c. I. direct violet 9, c. I. direct blue 78 and other J acid system. Other than this: CI direct yellow 8, CI direct yellow 28, CI direct yellow 86, CI direct yellow 87, CI direct yellow 142, C. Ϊ · direct orange 26, CI direct orange 39, CI direct orange 72 ' CI -88- 1354684

Direct orange 106, CI direct orange l〇7, C. 1_ direct red 2, CI direct red 39, CI direct red 83, CI direct red 89, CI direct red 240, CI direct red 242, CI direct red 247, CI Direct Violet 48, CI Direct Violet 51, CI·Direct Violet 98, CI·Direct Blue 15, <:.1. Direct Blue 67' (:.1. Direct Blue 71, (:.1. Direct Blue 98, ( :.1. Direct Blue 168, C_ I_ Direct Blue 202, CI Direct Blue 236, CI Direct Blue 249, CI Direct Blue 270, CI Direct Green 59, CI Direct Green 85, CI Direct Brown 44, CI Direct Brown 106, CI Direct Brown 195, CI Direct Brown 210, CI Direct Brown 223, CI Direct Brown 224, CI Direct Black 1, CI Direct Black 17, C·I. Direct Black 19, CI Direct Black 54, etc.; and Japanese Patent Special Open昭第62-

708 02, Special Kaiping No. 1-161202 'Special Kaiping No. 1-172906, Special Kaiping No. 1 - 1 72907, Special Kaiping No. 1 - 1 83 602, Special Kaiping No. 1 - 248 1 05, Special A dichroic dye described in each of the publications of Japanese Laid-Open Patent Publication No. Hei. No. Hei. No. Hei. In order to produce a dichroic molecule having various hues, the dichroic dye may be mixed in two or more kinds. When a dichroic dye is used, the thickness of the absorber is 4 μm or more as described in JP-A-H14-082222. When the content of the dichroic molecule in the film is too small, the degree of polarization will be low. If the content of the dichroic molecule is too small, the transmittance of the veneer will decrease. Therefore, the polyvinyl alcohol which is a matrix constituting the film is usually used. The polymer is adjusted to a mass of 〇〇1. /. Up to 5 mass%. The preferred film thickness of the pre-film is from 5 micrometers to 40 micrometers, more preferably from 1 micrometer to 30 micrometers. The ratio of the thickness of the polarizing film to the thickness of the protective film described later is set to -89 - 1354684, and 0.01 A (polarizing film thickness) / B (protective film thickness) described in Japanese Patent Laid-Open No. Hei No. 1 4-1 74727 ) The range of $〇.16 is also available. The angle of intersection of the retardation axis of the protective film and the absorption axis of the polarizing film may be any parallel or preferably a parallel or 45 ± 20° azimuth angle. 2. Manufacturing Step of Polarizing Plate Next, the manufacturing steps of the polarizing plate of the present invention will be described below. The manufacturing step of the polarizing plate of the present invention is preferably constituted by a swelling step, a dyeing step, a solid film step, an extending step, a drying step, a protective film bonding step, and a drying step after bonding. The order of the dyeing step and the solid film step 'extension step may be arbitrarily changed, or several steps may be combined to be simultaneously performed. Alternatively, it may be washed with water after the solid film step as described in Patent Nos. 3, 3 3 1, 6 15 . In the present invention, it is preferred that the swelling step, the dyeing step, the solid film step, the stretching step 'drying step, the protective film bonding step, and the drying step after bonding are sequentially performed in the order described. However, a planar inspection step on the line can also be provided during or after the above steps. The swelling step is preferably carried out only by using water, but as described in Japanese Patent Laid-Open No. Hei. No. Hei. No. Hei. Wrinkles may also swell the polarizing plate substrate with an aqueous solution of boric acid to manage the degree of swelling of the polarizing plate substrate. The temperature 'time of the swelling step' can be arbitrarily set, but it is preferably l 〇 ° C or more and 60 ° C or less, and 5 seconds or more and 2,000 seconds or less. The dyeing step can be carried out by the method described in Japanese Patent Laid-Open Publication No. 2002-86554. Further, the dyeing method is not limited to the dipping method, and any method such as coating or -90- Ϊ 354684 spray iodine or a dye solution may be used. Further, it is also possible to use a method of adjusting the concentration of iodine, the temperature of the dye bath, the stretching ratio in the bath, and the bath in the stirring bath as described in Japanese Patent Laid-Open No. Hei. . When a dichromatic molecule is used as a high-order iodide ion, in order to obtain a highly contrasting polarizing plate, the dyeing step is preferably a solution in which iodine is dissolved in an aqueous solution of potassium iodide. In the iodine-potassium iodide aqueous solution at this time, a preferred content range is iodine 〇 5 ～ 20 g / liter, potassium iodide is 3 to 200 g / liter, and mass ratio of iodine to potassium iodide is 1 to 2,000. The dyeing time is preferably 10 to 1,200 seconds, and the liquid temperature is preferably 10 to 6 CTC. Further preferably, the iodine is 0.5 to 2 g/liter, the potassium iodide is 30 to 120 g/liter, the mass ratio of iodine to potassium iodide is 30 to 120, the dyeing time is 30 to 600 seconds, and the liquid temperature is 20 to 501 〇. As described in Japanese Patent No. 3,145,747, a boron-based compound such as boric acid or borax may be added to the dyeing liquid. The solid filming step is preferably carried out by immersing in a crosslinking agent solution or by subjecting a crosslinking agent to a coating solution. The solid filming step can be carried out by dividing the solid filming step into several times as described in Japanese Patent Laid-Open No. Hei 1-52130. The cross-linking agent can be used as described in U.S. Patent Publication No. 232,897, and the polyvalent aldehyde as a crosslinking agent can be used to improve dimensional stability as described in Japanese Patent No. 3,357,109. The best use is boric acid. When the boric acid used in the solid film step is used, if a boric acid is used, a metal ion may be added to the boric acid-potassium iodide aqueous solution. The metal ion is preferably zinc chloride-91 - 1354684. However, as described in Japanese Patent Laid-Open No. 2000-35512, zinc halide, zinc sulfate, and acetic acid such as zinc iodide may be used instead of zinc chloride. A zinc salt such as zinc. In the present invention, it is preferred to adopt a method of first preparing a boric acid-potassium iodide aqueous solution to which zinc chloride is added, and then immersing the PVA film therein to solidify the film. Preferably, boric acid is 1 to 100 g/liter, and potassium iodide is used. 1 to 12 g / liter, zinc chloride is 0.01 to 10 g / liter, solid film time is 10 to L 200 seconds ' and the liquid temperature is 10 to 60 ° C. More preferably, the boric acid is 1 〇 80 g / liter, the potassium iodide is 5 ~ 100 g / liter, the zinc chloride is 0.02 ~ 8 g / liter, the solid film time is 30 to 600 seconds, and the liquid temperature is 20~ 50 ° C. The stretching step is suitable for the longitudinal single axial stretching method described in U.S. Patent No. 2,454,515, or the like, or the tenter method described in Japanese Patent Laid-Open No. 2002-86554. A preferred stretching ratio is 2 times or more and 12 times or less 'more preferably 3 times or more and 1 〇 or less. In addition, the relationship between the stretching ratio and the thickness of the original counter-thickness and the thickness of the polarizing film is also set as described in Japanese Patent Laid-Open No. Hei 14-040256 (the thickness of the polarizing film after the protective film is bonded/the thickness of the original film) x (full-expansion ratio) > 0.17, the relationship between the width of the polarizing film when the last bath is released and the width of the polarizing film when the protective film is bonded is also suitable for use in the 0.80$ described in JP-A- 14-040247 (Protection) The width of the polarizing film when the film is bonded/the width of the polarizing film when it is taken out from the last bath is $0.95. The drying step can be carried out by the method described in Japanese Laid-Open Patent Publication No. 2002-86554, but the preferred temperature range is from 30 ° C to 100 ° C, and the drying time is from 30 seconds to 60 minutes. It is also suitable to apply a heat treatment for setting the fading temperature in water to 50 ° C or higher, as in Japanese Patent Laid-Open No. 07-325215 or No. JP-A No. JP-A No. 07-325215 As described in 07-3 252 1 8 , the aging treatment is applied in an atmosphere subjected to temperature and humidity management. The protective film bonding step is a step of bonding two protective films to both sides of the above-mentioned polarizing film subjected to the drying step. It is preferably a method in which a binder is supplied immediately before the bonding, and then a pair of rolls are attached by laminating a polarizing film and a protective film. In addition, as described in Japanese Patent Laid-Open Publication No. 2001-2-86264 and JP-A-2002-86554, it is preferable to adjust the moisture ratio of the polarizing film to suppress the groove of the disc which is caused by the extension of the polarizing film. Bumpy shape. In the present invention, it is suitable to use a moisture content of 0.1 to 30%. The binder of the polarizing film and the protective film is preferably a PVA-based resin (modified PVA including acetamidine, sulfonate, carboxyl, oxyalkylene, etc.) or a boron compound, although it is not particularly limited. An aqueous solution or the like is preferably a PVA-based resin. The thickness of the adhesive layer is preferably from 〇1 to 5 μm after drying, more preferably from 5 to 3 μm. Further, it is also suitable to adopt a method in which the protective film is surface-treated to be hydrophilized and then bonded to improve the adhesion between the polarizing film and the protective film. The method of surface treatment is not particularly limited, and any method such as a method of saponification using an alkali solution, a corona treatment method, or the like can be employed. Further, an easy-adhesion layer such as a base coat layer may be provided after the surface treatment. The contact angle of the surface of the protective film with water is preferably 50 or less as described in Japanese Patent Laid-Open No. Hei 14-267 83-9. The drying conditions after lamination can be in accordance with the method of 1354684 described in JP-A-2002-86554, but the preferred temperature range is from 30 ° C to 100 ° C, and the preferred drying time is from 30 seconds to 60 minutes. In addition, it can be aged under the atmosphere of temperature and humidity management as described in Japanese Patent Laid-Open No. Hei 07-325220. The element content in the polarizing film is preferably 0.1 to 3.0 g/m2 for iodine, 0.1 to 5.0 g/m for boron, 0.1 to 2.0 g/m for potassium, and 0 to 2.0 g/m2 for zinc. In addition, the amount of potassium in the polarizing film may be set to be 0.2% by mass or less, and the amount of zinc in the polarizing film may be set to be the same as that of the above-mentioned Japanese Patent Laid-Open No. 1 2-03 5 5 1 2 0. 0 4% by mass to 0.5% by mass as described in the number. It is also possible to add an organic titanium compound and/or an organic compound in any of the dyeing step, the stretching step and the solid film step to improve the dimensional stability of the polarizing plate as described in the Patent No. 3, 3 23, 25 5 The zirconium compound contains at least one compound selected from the group consisting of an organic compound and an organic zirconium compound. Further, in order to adjust the hue of the polarizing plate, a dichroic dye may also be added. 3. Characteristics of polarizing plate (1) Transmittance and degree of polarization The preferred single-plate transmittance of the polarizing plate of the present invention is 42.5 % or more and 49.5% or less, but more preferably 42.8% or more and 49 % by weight or less. The preferred range of the degree of polarization defined by the formula 4 is 99.900% or more and 99.999% or less, more preferably 99.94% or more and 99.995% or less. A preferred range of the parallel transmittance is 36% or more and 42% or less, and a preferable range of the orthogonal transmittance is 0.001% or more and 〇.〇5% or less. A preferred range of the dichroic ratio defined by Formula 5 is 48 or more and 1,215 or less, but more preferably 53 or more and -94 - 525 or less. The above transmittance may be defined by ns Ζ 8701 as follows. :

[Number U r 2 ν (乂)) r (a ) In the formula, K, S (A), y (A), r (in) are as follows: [Number 2]

100

ΓΞ(λ)γ(λ)άλ (Formula 3) κ ^ s(λ): the spectral distribution of the standard light used to display the color; y ( λ ) · the isochromatic parameter in the χγζ system; τ ( λ): Spectral transmittance; λ: measurement wavelength (nano). [Number 3]

(Formula 4) Polarization (%) = 100 (parallel transmittance - orthogonal transmittance parallel transmittance + orthogonal transmittance

(Equation 5) Dichroism ratio _ = log Veneer transmittance Λ Polarimetry, · 100 Γ 1〇〇) log Veneer transmittance 偏 . Polarization, 1 100 I1 100 ]] Iodine concentration and veneer transmittance The range described in Japanese Patent Laid-Open No. Hei 14-95- 1354684 No. 258051. The parallel transmittance is as described in Japanese Laid-Open Patent Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. The polarizing plate is disposed in the optical characteristics of the crossed Nicols, and is also in the range described in Japanese Laid-Open Patent Publication No. 13-091736, and the relationship between the parallel transmittance and the orthogonal transmittance may be the same as that of the same. In the range described in No. 14_174728, as described in the national patent special opening No. 4_22 i 6 i 8 , the wavelength of light is between 420 and 700 nm, and the standard deviation of the parallel transmittance per 〇 nanometer is φ. The difference can be 3 or less, and the wavelength of light is between 420 and 700 nm, and the minimum 値 per 10 nm (parallel transmittance/orthogonal transmittance) can be more than 300 〇, and the polarizing plate can also be used at 440. Parallel transmittance and orthogonal transmittance of the nanometer wavelength, parallel transmittance, parallel transmittance and orthogonal transmittance at a wavelength of 550 nm, and parallel transmittance and orthogonal transmittance at a wavelength of 610 nm, set It is the range described in Japanese Patent Laid-Open No. 14/258 (No. 2 or Tongte Kaiping No. 1 No. 25 8 043. Lu (2) Hue The hue of the polarizing plate of the present invention can be used as the C1E equal sensible space. The brightness index and chromaticity index a* and b* in the L*a*b* chromaticity system Evaluate. L*, a*, b* can use the above X'Y'Z and define it as (Equation 6) 〇 [Number 5] -96 - 1354684 I* = 116(y/y0)l-l6 ( Equation 6) α* = 50〇|(χ/ζ〇)5 -(y/y0)3 ^ = 2〇o[(y/y0)i-(z/z0)3 where X〇, Y〇, The Z 〇 represents the three stimuli of the illumination source, in the case of standard light C, X〇= 98.072, Y〇=100, Z〇=118.225, and X in the case of standard light D65. = 95.045, Y = 100, z. = 108.892 The preferred a* range of the polarizing plate monolith is -2 5 or more and 0.2 or less 'more preferably -2.0 or more and less than 。. The preferred b of the polarizing plate single piece * The range is 1.5 or more and 5 or less 'more preferably 2 or more and 4. 5 or less. The preferred range of a* of the parallel transmitted light of the two polarizing plates is -4.0 or more and the following is more preferably -3.5 or more. And -0.5 or less. The preferred range of b* of the parallel transmitted light of the two polarizing plates is 2. 〇 or more and 8 or less, more preferably 2 5 or more and 7 or less. Orthogonal transmitted light of the two polarizing plates * The preferred range is - 〇 · 5 or more and 2 or less, more preferably 〇 or more and 1 〇 or less. Orthogonal transmitted light of two polarizing plates b * The preferred range is -2.0 or more and 2 or less, more preferably -1.5 or more and 〇.5 or less. The hue system can also be evaluated by the chromaticity coordinates (χ, y) calculated by X, Y, and Z above. For example, the chromaticity (h) of the parallel transmitted light of two polarizing plates and the chromaticity (Xe, ye) of the orthogonally transmitted light can be set as the Japanese Patent Laid-Open No. l4-2; u43 6 No. 13_1 66 1 36 or the same as -97- 1354684, the general description of the relationship between the hue and the absorbance is set within the range described in Japanese Patent Application Laid-Open No. 13-311827. (3) Viewing angle characteristics. When the polarizing plate is arranged in crossed Nicols and the light of 550 nm wavelength is incident, it can also make the vertical light incident, and the polarizing axis is 45 degrees. The transmittance ratio or the xy chromaticity difference in the case where the normal is incident at a 40 degree angle is set as described in Japanese Patent Laid-Open No. Hei 13-166135 or No. 13-1 661 37. The scope. Further, as described in Japanese Laid-Open Patent Publication No. Hei. No. 0-0688 No. 7, the vertical light transmittance (T〇) of the φ polarizing plate laminated body arranged in crossed Nicols and the method of the laminated body can be used. The ratio of the light transmittance (T6G) in the direction in which the line is inclined by 60° (t6 (j/Tq) is set to 10,000 or less, or as described in Japanese Patent Laid-Open No. Hei. No. Hei. When the natural light is incident at any angle, the transmission spectrum is in the wavelength range of 520 to 640 nm, and the transmittance difference of the transmitted light within the wavelength range of 20 nm is set to 6% or less, or the special opening is made. The difference in brightness of transmitted light at a position of 1 cm at any distance on the film described in No. 08-24820 No. 1 is set within 30%. Lu (4) Durability (4 - 1) Damp heat durability such as Japanese Patent Special Open In the case of placing in an atmosphere of 60 ° C '90% RH for 500 hours as described in No. 1 3-1 1 6922, the rate of change of the light transmittance and the degree of polarization before and after the comparison is based on absolute enthalpy. Preferably, it is 3% or less. In particular, the rate of change of light transmittance is 2% or less, or the rate of change of the degree of polarization is in absolute terms. It is preferably 1.0% or less, and further preferably 〇·1% or less -98-1354684. Further, as described in JP-A-H07-077608, it is preferably placed at 80 ° C, 90% RH for 500 hours. The degree of polarization is 95% or more, and the transmittance of the monomer is 38% or more. (4 - 2) Dry durability at 80 ° C in a dry atmosphere for 500 hours, before and after the light transmittance and polarization The rate of change is preferably 3% or less in absolute enthalpy. In particular, the rate of change in light transmittance is 2% or less, and the rate of change in polarization is preferably 1.0% or less in absolute enthalpy, more preferably 0.1. (4 - 3) Other durability is also 'as can be described in Japanese Patent Laid-Open No. 06-1 676 1 1 'The shrinkage rate after 2 hours at 8 ° C is set to 〇. 5% or less, or a polarizing plate laminate which is arranged on both sides of the glass plate, and placed in an atmosphere of 69 ° C for 75 hours, X 値 and y 値 are set to the same level. In the range described in -06 8 8 1 8 or after being placed in an atmosphere of 80 ° C and 90% RH for 200 hours, it will be 105 cm by Raman spectroscopy. The change in the spectral intensity ratio of 157 cm·1 is set as described in JP-A-H08-094834 or JP-A-09-197127. (5) The better the alignment of the PVA is, the better the better. Polarization performance, but the order parameter calculated by a method such as polarized Raman scattering or polarized FT-IR is preferably 0.2 to 1. In addition, as described in Japanese Patent Laid-Open No. 5 9- 1 33 5 09, the difference between the alignment coefficient of the polymer portion of the entire amorphous domain of the polarizing film and the occupational molecular alignment coefficient (0.7 5 or more) may be used. It is set to at least 〇·15, or as described in JP-A-2004-204907, the non-99-1354684 domain alignment coefficient of the polarizing film is set to 0.65 ~ 〇·85, or the higher secondary iodine of yttrium or yttrium. The alignment of the ions, set its order parameter to 1 〇. (6) Other characteristics · The absorption axis direction contraction force per unit width when heated at 80 ° C for 30 minutes can also be set as described in Japanese Patent Laid-Open No. Hei No. 1 4 - 0 0 6 1 3 3 It is 4.0 N/cm or less, or as shown in Unexamined No. 1 4-2362 1 3, after the polarizing plate is placed under heating at 7 ° C for 1 20 hours, the dimensional change rate of the absorption axis direction of the polarizing plate is made. The dimensional change rate in the direction of the polarizing axis is set to be within ±0.6%, or the moisture content of the polarizing plate is set to be 3% by mass or less as described in the special opening φ flat No. 14-090546. Further, as described in JP-A No. 1 2-249832, the surface roughness perpendicular to the direction of the extension axis is set to be 〇.〇4 μm or less in terms of the center line average roughness, or as in the case of the special opening. In the case of No. 10-268294, the refractive index no in the transmission axis direction is set to be larger than '1.6, or the relationship between the thickness of the polarizing plate and the thickness of the protective film is set to be the same as that described in the first opening of the first 〇-1 Π 4 1 1 Scope 4. Functionalization of Polarizing Plate Φ The polarizing plate of the present invention is suitable for use as a λ Μ plate required for a viewing angle expansion film having an LCD, which is required for a reflective LCD, and for improving the visibility of the display. An optical film of an antireflection film, a brightness enhancement film, or a functional layer such as a hard coat layer, a front scattering layer, and an antiglare layer is combined into a composite functionalized polarizing plate. A cross-sectional schematic view showing an example in which a polarizing plate of the present invention is combined with the above functional optical film is shown in Fig. 1. As shown in Figure 1, it can also be used as -100-1354684

The functional optical film 3 and the polarizing film 2 (Fig. 1(A)) are bonded to the protective film 1 on one side of the polarizing plate via the adhesive, and the functional optical film 3 can also be bonded to the polarized light via the adhesive layer 4. A polarizing plate of a protective film ia · and lb is provided on both surfaces of the film 2 (Fig. 1 (B)). In the case of the former, any other protective film can be used for the other protective film. The peeling strength between the respective layers of the functional layer or the protective film may be set to 4.0 N/25 mm or more as described in Japanese Patent Laid-Open No. Hei No. 1 4-3 1 1 2 3 8 . The functional optical film is preferably disposed on the liquid crystal module side according to the intended function, or on the opposite side to the liquid crystal phase group, that is, on the display side or the backlight side. _ The following describes a functional optical film for use in combination with the polarizing plate of the present invention. (1) Viewing angle expansion film (optical auxiliary film) The polarizing plate of the present invention can be used in combination for use in, for example,:

TN (Twisted Nematic type), IPS (In-Plane Switching type), OCB (Optically Compensatory Bend type), VA (Vertically Aligned type), ECB (electric field control birefringence type·· .

Electrically Controlled Birefringence type) The viewing angle expansion film of the display mode. The viewing angle expansion film for the TN mode can be used in the Japan Printing Society Journal No. 36, No. 3 (1 999), pages 40 to 44, 'Monitoring Monthly, August (2002), pages 20 to 24, Japan WV film (Fuji Photo-10) as described in Japanese Patent Laid-Open No. Hei 4-22982, No. Hei 6-75115, Tong Kaiping No. 6-214116, and Tongkaiping No. 8-5006. 1354684 Phase film (stock) system is used in combination. In the TN mode, a preferred structure of the viewing angle expansion film is obtained by aligning the alignment layer and the optically anisotropic layer on the above transparent polymer film in this order. Although the viewing angle expansion film can be used as a bonding material to bond with a polarizing plate, as described in SID' 00 Dig., p. 551 (2000), from the viewpoint of thinning, It is particularly preferable as one of the protective films of the above polarizing film. The alignment layer can be provided by a rubbing treatment of an organic compound (preferably a polymer), an oblique vapor deposition of an inorganic compound, and a method of forming a layer having microgrooves. Further, it is known that an alignment layer which imparts an alignment function by imparting an electric field, imparting a magnetic field or irradiating with light is particularly preferable, but an alignment layer formed by a rubbing treatment of a polymer is particularly preferable. The rubbing treatment is carried out by rubbing the surface of the polymer layer in a certain direction with paper or cloth several times. The direction of the absorption axis of the polarizing film and the direction of rubbing are preferably substantially parallel. For the type of the polymer to be used as the alignment layer, a polymer having a polymerizable group described in JP-A-H09-152509, and the like can be used. The thickness of the alignment layer is preferably from 0.01 to 5 μm, more preferably from 0.05 to 2 μm. The optically anisotropic layer preferably contains a liquid crystalline compound. The liquid crystalline compound used in the present invention can be particularly preferably provided with a discotic compound (disc liquid crystal). The discotic liquid crystal molecule is a structure in which the phenyl derivative of the triphenylene has a disc-shaped core and the side chain is radially extended. Further, in order to impart stability over time, it is also possible to introduce a group which can react with heat, light or the like. A preferred example of the above-described disk-shaped liquid crystal is disclosed in Japanese Laid-Open Patent Publication No. Hei. No. Hei.

The discotic liquid crystal molecules are arranged substantially parallel to the plane of the film at a pretilt angle in the rubbing direction in the vicinity of the alignment layer, and the φ-like liquid crystal molecules in the opposite side of the air surface are aligned perpendicularly to the surface. The dish-like liquid crystal layer is formed into a mixed alignment by the whole system, whereby the layer structure can realize the viewing angle expansion effect of the TFT-LCD (thin film transistor-liquid crystal display device) of the TN mode.

The optically anisotropic layer is generally prepared by dissolving a disk-like compound and other compounds (and further, for example, a polymerizable monomer or a photopolymerization initiator) in a solvent, applying the solution to an alignment layer, drying, and then drying. After heating to a dish-like nematic phase forming temperature, it is obtained by irradiating UV (ultraviolet) light Φ or the like to be polymerized, followed by cooling. The dish-like liquid crystal phase-solid phase transfer temperature for the discotic liquid crystalline compound used in the present invention is preferably from 70 to 300 ° C, and particularly preferably from 70 to 170 ° C. Further, the compound other than the disc-like compound which can be added to the optically anisotropic layer is compatible with the disc-like compound and can impart a positive tilt angle change to the liquid crystal disc compound or does not hinder Orientation 'any compound can be used. Among these, an air of a polymerizable mono-103 - 1354684 (for example, a compound having a vinyl group, a vinyloxy group, an acryloyl group, and a methacryloxy group), or a trifluoride compound containing a fluorine atom can be used. An additive for alignment control on the interface side, a polymer such as cellulose acetate, cellulose acetate propionate, hydroxypropyl cellulose, and cellulose acetate butyrate. The amount of the compound to be added to the disc compound is usually 0.1 to 50% by mass, preferably 0.1 to 30% by mass. The thickness of the optically anisotropic layer is preferably 0.1 to 10 μm, and more preferably 0.5. Up to 5 microns. A preferred embodiment of the viewing angle expansion film is formed of a deuterated cellulose film as a transparent substrate thin φ film, an alignment layer disposed thereon, and a discotic liquid crystal formed on the alignment layer. The optically anisotropic layer is formed, and the optically anisotropic layer is crosslinked by irradiation of UV light. Further, in addition to the above, when the viewing angle expansion film is combined with the polarizing plate of the present invention, it may be, for example, described in Japanese Patent Laid-Open No. Hei 9 8942, which has a direction intersecting the plate surface. A mode in which the optical axis exhibits a phase difference plate in which the birefringence is different in the direction of the birefringence, or the dimensional change rate of the protective film and the optically different φ layer is substantially the same as described in JP-A-H14-258052. The way. In addition, the moisture content of the polarizing plate to be bonded to the viewing angle expansion film may be set to 2.4% or less as described in JP-A-H12-258632, or may be taken as in JP-A No. 14-267839. It is described that the contact angle with the water of the viewing angle expansion film surface is set to 70 or less. IPS mode liquid crystal cell viewing angle expansion film is used to improve the optical compensation of the liquid crystal sub-104- 1354684 parallel to the substrate surface and the orthogonal transmittance of the polarizing plate when the black display is not applied. Viewing angle characteristics. The IPS mode is black in the absence of an applied electric field, and the transmission axes of the upper and lower polarizing plates are orthogonal. However, when viewed from the oblique direction, the transmission angle of the axis is no longer 90°, so that light leakage is caused to cause the contrast to decrease. When the polarizing plate of the present invention is used for the IPS mode liquid crystal cell, the phase difference in the in-plane of the Japanese Patent Publication No. 10-54982, which is disclosed in Japanese Patent Laid-Open No. 10-54982, is close to 0, and has a thickness in the thickness direction. The viewing angle of the phase difference is enlarged and the film combination is used in combination. The OCB mode liquid crystal cell viewing angle expansion film is used to optically compensate a liquid crystal layer which becomes a vertical alignment in the central portion of the liquid crystal layer by applying an electric field of φ and which is inclined in the vicinity of the substrate interface, thereby improving the visual field in black display. Angular characteristics. When the polarizing plate of the present invention is used in an OCB mode liquid crystal cell, it can be suitably used in combination with a viewing angle expansion film which is mixed with a discotic liquid crystalline compound as described in U.S. Patent No. 5,805,253. The VA mode liquid crystal cell viewing angle expansion film is used to improve the viewing angle characteristic of the black display when the liquid crystal molecules are vertically aligned with respect to the substrate surface without applying an electric field. Such a viewing angle expansion film can be a film having a phase difference of 0 in the in-plane direction and a disc-shaped compound system and substrate as described in Japanese Patent Publication No. 2,866,357. Forming a film in parallel, or laminating an extension film having the same in-plane retardation 成 to form a film in which the slow phase axis is orthogonal, or to prevent the orthogonal transmittance of the oblique direction of the polarizing plate from deteriorating A film composed of a molecule-like rod-like compound is used in combination with a laminate. -105- 1354684 (2) In/4 Trigger The polarizing plate of the present invention can be used as a circular polarizing plate laminated with an A/4 plate. The circular polarizing plate has a function of converting incident light into circularly polarized light, and is preferably used in a transflective liquid crystal display device such as a reflective liquid crystal display device or an ECB mode, or an organic EL (electroluminescence element) device. The Λ/4 plate used in the present invention is capable of obtaining substantially complete circularly polarized light in the visible light wavelength range, preferably having a retardation (Re) of substantially 1/4 of the wavelength in the visible light wavelength range. Phase difference film. The so-called "a delay of 1/4 in the range of the visible light wavelength" means that the longer the wavelength is from φ 4 〇〇 to 700 nm, the longer the delay, and the compliance is at 450 nm. The retardation Re (Re450) measured by the wavelength of the meter is 80 to 125 nm, and the retardation Re (Re5 90 ) measured at a wavelength of 590 nm is 120 to 160 nm, but more preferably Re590 - Re450 2 5 nm, particularly preferably Re590 - Re450gl0 Nano" The λ Μ plate used in the present invention is not particularly limited as long as it satisfies the above conditions, but can be used, for example, in Japanese Patent Laid-Open No. 5 - λ /4 plate which laminates several polymer films as described in Japanese Laid-Open Patent Publication No. Hei. No. Hei. Japanese Laid-Open Patent Publication No. 2000-284126, the same as JP-A No. 2000-284 λ of at least one or more optical anisotropic layers provided on the polymer film as described in the Japanese Patent Publication No. 7-17 Any of the λ / 4 plates in the fascia board. Further, the retardation axis direction of the polymer film or the alignment direction of the optically anisotropic layer is arranged in any direction by the -106-1354684 liquid crystal cell. In the circularly polarizing plate, the retardation axis of the λ/4 plate and the transmission axis of the polarizing film may be crossed at an arbitrary angle, but it is preferably in the range of 45 ° ± 20 °. However, the retardation axis of the λ/4 plate and the transmission axis of the polarizing film may be crossed in a range other than the above. When the A Μ plate is formed by laminating λ "plates and λ /2 plates, the invention patent number is as follows. It is preferable to describe the angle formed by the in-plane slow axis of the λ/4 plate and the 1/2 plate and the transmission axis of the polarizing plate as described in Japanese Laid-Open Patent Publication No. H10-68816. (3) Antireflection film The polarizing plate of the present invention can be used in combination with an antireflection film. The antireflection film can be a fluorine-based polymer or the like which is provided only to a single layer. The film having a reflectance of the low refractive index material of about 1.5% or a film having a multilayer interference of 1% or less by the multilayer interference of the film. In the present invention, it is preferred to use a low refractive index on the transparent support. The layer of the rate layer and the layer having at least one of the high refractive index of the low refractive index layer (that is, the high refractive index layer and the medium refractive index layer) are laminated in a layered structure. In addition, it is also suitable for use in the Japanese technology. Report No. 38, No. 1, May 2000, pages 26-28, The antireflection film described in Japanese Patent Laid-Open Publication No. 2002-301783, etc. The refractive index of each layer is as follows. The refractive index of the high refractive index layer > the refractive index of the medium refractive index layer > The transparent support Refractive Index> The refractive index of the low refractive index layer can be used as a transparent support for the antireflection film, and a transparent polymer film for the protective film of the above-mentioned -107-1354684 polarizing layer can be used. It is 1.20 to 1.55, preferably 1.30 to 1.50. The low refractive index layer is preferably used as the outermost layer having scratch resistance and antifouling properties. To improve the scratch resistance, it is also possible to use a polyfluorene. The oxy group or the fluorin-containing material imparts lubricity to the surface. The fluorine-containing compound can be used, for example, in the specification of the Japanese Patent Application Laid-Open No. Hei 9-222503, paragraph number [0018] to [0026], and the same Paragraph No. -38202, paragraph number [〇〇19]~[0030], the same as the opening paragraph No. 2001-40284, paragraph number [〇〇27]~[0028 φ], Tongtekai 2000-284 1 02 No. The compound contains a polyoxane-based compound, preferably a compound having a polyoxyalkylene structure, but a reactive polyfluorene (for example, Sairaplein (manufactured by Nitrogen Co., Ltd.) or a sterol group-containing polymer at both ends may also be used. A oxane (Japanese Patent Laid-Open No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. The reaction is hardened by the same. (Japanese Unexamined Patent Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. Japanese Unexamined Patent Publication No. Publication No. No. 2000- 1 1 7902, the same as the No. 200-48590, and the compounds described in the Japanese Patent Publication No. 2002-5 3 804. The low refractive index layer may contain, in addition to the above additives, an average of primary particles such as silica, fluorine-containing particles (magnesium fluoride, calcium fluoride, barium fluoride). a low-refractive-index inorganic compound having a diameter of from 1 to 150 nm, and an organic fine particle described in paragraphs [002 0] to [003 8] of JP-A No. 1 -3 820 -108-3544684, A decane coupling agent, a lubricant, a surfactant, and the like. · The low refractive index layer may be formed by a vapor phase method (vacuum vapor deposition method, sputtering method, ion plating method, plasma CVD method, etc.), but from the viewpoint of being inexpensive to manufacture, it is coated. The law is formed as good. The coating method may be a dipping method 'air knife coating method, curtain coating method' roll coating method, wire bar coating method, photographic gravure coating method, or micro gravure coating method. The film thickness of the low refractive index layer is preferably from 30 to 200 nm, more preferably from 50 to 150 nm, and most preferably from 60 to 120 nm. φ medium refractive index layer and high refractive index layer. It is preferable to disperse the high-refractive-index inorganic compound ultrafine particles having an average particle diameter of 1 nm or less in a matrix material. As the inorganic compound fine particles having a high refractive index, an inorganic compound having a refractive index of 1.65 or more, for example, an oxide of Ti, Zn, Sb, Sn, Zr, Ce, Ta, La, In or the like, containing the complex oxidation of the metal atoms can be used. Things and so on. The ultrafine particles can be treated with a surface treatment agent (the silane coupling agent, etc., JP-A No. 1 1 - 2955 〇 3, the same as the first 1 - 1 53 703 #, and the special 2000- 9908, an anionic compound or an organic metal coupling agent: JP-A-2001-31(R) 432, etc., a core-sheath structure having a high refractive index particle as a core (Specially, No. 2001 - 1 66104, etc.) A dispersing agent is used in a mode such as, for example, Japanese Laid-Open Patent Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. For the material for the substrate, any thermoplastic resin, (thermal) hardened -109-1354684 resin film, or the like may be used. However, it is also possible to use the Japanese Patent Publication No. 2000-00-7-04, the same as JP-A No. 200 1 - 3 15242 And the polyfunctional material described in the above-mentioned Japanese Patent Publication No. 2001-31, No. 1, No. 1, the disclosure of which is incorporated herein by reference. A hardened film made of a metal alkoxide composition. The refractive index of the high refractive index layer is preferably 1.70 to 2.20. The thickness of the high refractive index layer is preferably from 5 nm to 10 μm, more preferably from 10 nm to 1 μm. The refractive index of the medium refractive index layer should be adjusted to be between the refractive index of the low refractive index layer and the refractive index of the high refractive index layer. The refractive index of the medium refractive index layer is preferably 1.50 to 1.70. The haze of the antireflection film is preferably 5% or less, more preferably 3% or less. Further, the strength of the film is preferably Η or more, more preferably 2H or more, and most preferably 3H or more, according to the pencil hardness test according to IS Κ 5400. (4) Brightness improving film The polarizing plate of the present invention can be used in combination with a brightness improving film. Brightness Enhancement The film has a separation function of circularly polarized or linearly polarized light, and is used to arrange φ between the polarizing plate and the backlight module so that one of the circularly polarized or linearly polarized light is reflected rearward or backscattered toward the backlight side. The re-reflected light from the backlight portion can locally change the polarization state, and when incident on the brightness enhancement film and the polarizing plate, it can be partially transmitted, and the process is repeated to improve light utilization efficiency. Increase the front brightness by about 1.4 times. The brightness enhancement film is known to have a different directional reflection mode and an isotropic scatter mode, and the like can be used in combination with the polarizing plate of the present invention. -110- 1354684 In terms of the anisotropic reflection method, it is known to laminate a uniaxially stretched film and an unstretched film into a plurality of layers to increase the refractive index difference in the extending direction to have a different direction of reflectance and transmittance. A multilayer film method for improving the brightness of a film and using the principle of a dielectric mirror (described in World Invention Patent No. WO 95/1 7691, the same as WO 95/1 7692, the same as WO 95/1) The specification of the No. 7699) or the cholesteric liquid crystal method (described in the specification of the European Patent No. 606940 A2, Japanese Patent Laid-Open No. Hei 8-27 1 73 1). A multi-layer brightness enhancement film using the principle of a dielectric mirror is available as DBEF-E, DBEF-D, and DBEF-M (all manufactured by 3M Company), which is suitable for use in the present invention, and a brightness-enhancing film of a cholesteric liquid crystal type. Then, NIPOCS (Nitto Electric Co., Ltd.) is suitable for use in the present invention. For NIP OCS, please refer to Nitto Technology News No. 38, No. 1, May 2000, '19th to 21st pages, etc. Furthermore, in the present invention, the inventions of the World Patent No. WO 97/32223, the same as WO 97/32224, the same as WO 97/3 2225, the same as WO 97/32226, and the The intrinsic birefringence polymer described in each of the publications of the Japanese Patent Publication No. 9-2 741-8, and the above-mentioned publication No. 1 1 - 1 423 1 is incorporated with a negative intrinsic birefringence polymer, and A unidirectionally extended isotropic scattering mode brightness enhancement film is used in combination. The isotropic scattering type brightness enhancement film is preferably DRPF-H (manufactured by 3M Co., Ltd.). The polarizing plate and the brightness-enhancing film of the present invention are preferably used in a form in which they are bonded via an adhesive or in which one of the protective films of the polarizing plate is formed as a brightness-enhancing film. -111 - 1354684 (5) Other functional optical films The polarizing plate of the present invention may also be combined with a hard coat layer, a front scattering layer, an antiglare layer, a gas barrier layer, a lubricating layer, an antistatic layer, a base coat layer or a setting A functional optical film such as a protective layer is used in combination. Further, the functional layers may be used in combination in the same layer as each other or in the same layer as the above-mentioned antireflection layer or optically anisotropic layer. (5 - 1 ) Hard coat layer The polarizing plate of the present invention is preferably a combination of a "hard coat" and a functional φ optical film provided on the surface of a transparent support in order to impart mechanical strength such as scratch resistance. The method. When the hard coat layer is applied to the above antireflection film, it is preferably provided between the transparent support and the high refractive index layer. The hard coat layer is preferably formed by a crosslinking reaction using a light and/or heat curable compound or via a polymerization reaction. The curable functional group is preferably a photopolymerizable functional group, and the organometallic compound containing a hydrolyzable functional group is preferably an organoalkoxyalkylene compound. The specific structural composition of the hard coat layer can be described, for example, in Japanese Laid-Open Patent Publication No. 2002-144913, Japanese Patent No. 2000-9908, and Japanese Patent No. WO No. 0/466,197. By. The film thickness of the hard coat layer is preferably 0.2 to 100 μm. The strength of the hard coat layer is preferably Η or more according to the pencil hardness test of 〖IS K54 〇 0, more preferably 2 Η or more, and most preferably 3 Η or more. Further, in the results of the Taber abrasion test according to JIS Κ 54〇0, the amount of abrasion of the test piece before and after the test is preferably as small as possible. -112- 1354684 A material which can form a hard coat layer, a compound containing an ethylenically unsaturated group, and a compound containing a ring-opening polymerizable group, which can be used singly or in combination, can be used. Preferred examples of the compound containing an ethylenically unsaturated group include: ethylene glycol diacrylate, trimethylolpropane triacrylate, di-trimethylolpropane tetraacrylate, and neopentyl glycol triacrylate. Polyacrylates of polyols such as neopentyl glycol tetraacrylate, dipentaerythritol pentaacrylate, and neopentyl glycol hexaacrylate; diacrylates of bisphenol A diglycidyl ether, An epoxy acrylate such as a diacrylate of an alcohol glycidyl ether; an urethane acrylate obtained by a reaction of a polyisocyanate with a hydroxy group-containing acrylate such as hydroxyethyl acrylate. In addition, commercially available commercial grade compounds include: EB-600, EB-40, EB-140, EB-1150, EB-1290K, IRR214, EB-2220, TMPTA, TMPTMA (all of which are DAICEL. UCB (shares) System), UV-6300, UV-170 0B (all of which are manufactured by Japan Synthetic Chemical Industry Co., Ltd. (all are trade names)). Further, preferred examples of the compound containing a ring-opening polymerizable group include:

The glycidyl ethers are: ethylene glycol diglycidyl ether, bisphenol A di-φ glycidyl ether, trimethylolethane triglycidyl ether, trimethylolpropane triglycidyl ether, Glycerol triglycidyl ether, triglycidyl trihydroxy ether isomeric cyanurate, sorbitol tetraglycidyl ether, neopentyl alcohol tetraglycidyl ether, cresol novolac resin polyglycidyl Ether ether; polyglycidyl ether of phenol novolak resin; alicyclic epoxy type: 361 (^<^ 2021?, 361(^<^ 2081, £?〇16&<101' -301, Epolead GT-401 'EHPE3150CE (all of them are DAICEL -113- 1354684 Chemical Industry Co., Ltd. (all are trade names)): polycyclohexyl epoxy methyl ether of phenol novolak resin; Cyclobutanes are: OXT- '121, OXT-221, OX-SQ, PNOX-1009 (all of which are East Asian Syntheses - (shares) (all are trade names)), etc. Others can also be (methyl a polymer of glycidyl acrylate or a copolymer of a monomer copolymerizable with glycidyl acrylate as a hard Coating. For hard coating, it is suitable for reducing the hardening shrinkage of the hard coating, improving the adhesion with the substrate, reducing the curl of the hard coated article of the present invention, and also adding bismuth, titanium, chromium, Oxide fine particles such as aluminum, or crosslinked particles such as φ polyethylene, polystyrene, poly(meth)acrylate, polydimethyl siloxane, SBR (styrene-butadiene rubber), NBR A method of crosslinking fine particles such as organic fine particles such as a rubber powder such as a nitrile rubber. The average particle diameter of the crosslinked fine particles is preferably from 1 nm to 20,000 nm. Further, the shape of the crosslinked fine particles The spherical shape, the rod shape, the needle shape, the plate shape, and the like are used without particular limitation. The amount of the fine particles added is preferably 60% by volume or less, more preferably 40% by volume or less, based on the hardened hard coat layer. When the inorganic fine particles described above are added, generally, since the affinity with the binder polymer is not good, it is also suitable to use a metal containing cerium, aluminum, titanium, or the like, and have an alkoxide group. Carboxylic acid group A surface treatment agent for a functional group such as a group or a phosphonic acid group is used for the surface treatment. The hard coat layer is preferably hardened by using heat or active energy rays, and among them, radiation, gamma rays, and α-ray are preferably used. Active energy ray such as electron beam or violet-114- 1354684 external line, except for safety and productivity, it is particularly good to use electron rays and ultraviolet rays. When it is hardened by heat, it is from the plastic itself. From the viewpoint of heat resistance, the heating temperature is preferably 140 ° C or lower, more preferably 10 ° C or lower. (5 - 2) Front Scattering Layer The "front scattering layer" is used to improve the viewing angle characteristics (hue and brightness distribution) in the up, down, left, and right directions when the liquid crystal display device is applied to the polarizing plate of the present invention. In the present invention, it is preferable to use a structure in which fine particles having different refractive indices are dispersed by a binder. For example, a method of specifying a forward scattering coefficient can be used. Japanese Patent Laid-Open No. Hei No. 1 -38208 The relative refractive index of the microparticles is defined as a structure of the Japanese Patent Laid-Open Publication No. 2000-199809, and the Japanese Patent Laid-Open No. 20 01-20752, which is a 4 〇 or more. In addition, in order to control the viewing angle characteristics of the haze, the polarizing plate of the present invention can be used in combination with "L umisuty" described on pages 31 to 39 of the technical report "Light Functional Film" of Sumitomo Chemical Industries Co., Ltd. . (5 - 3) Anti-glare layer · The "anti-glare layer" is used to scatter reflected light to prevent image reflection. The anti-glare function is obtained by forming irregularities on the outermost surface (display side) of the liquid crystal display device. The haze of the optical film having an anti-glare function is preferably 3 to 30%, more preferably 5 to 20%, and most preferably 7 to 2 0 °/〇. In the method of forming the unevenness on the surface of the film, for example, a method of adding fine particles to form irregularities on the surface of the film (for example, Japanese Patent Laid-Open Publication No. 2000-27 1 8 78, etc.) is added, and a small amount (0.1 to 50% by mass) is added. a method of forming a surface unevenness film by a larger particle (particle size of 0.05 to 2 μm) than that of the above-mentioned method (for example, Japanese Patent Laid-Open No. 2000-281410, the same as No. 2000-95893, the same as 2001). Japanese Laid-Open Patent Publication No. SHO-63-278839 8 3 7 1 0, the same as those described in JP-A-2000-27540, and the like. The functional layers may be disposed on one side or both sides of either the polarizing film side and the reverse side of the polarizing film. 5. Liquid crystal display device using a polarizing plate. Next, a liquid crystal display device using the polarizing plate of the present invention will be described. The second drawing below is an example of a liquid crystal display device using the polarizing plate of the present invention. As shown in Fig. 2, the liquid crystal display device has liquid crystal cells (15 to 19), and an upper polarizing plate 11 and a lower polarizing plate 22 are disposed via liquid crystal cells (15 to 19). The polarizing plate holds the polarizing film and the pair of transparent protective films, but in Fig. 2, it is shown as an integrated polarizing plate, and the detailed structure thereof is omitted. The liquid crystal cell includes a liquid crystal layer formed of the upper substrate 15 and the lower substrate 18 and the liquid crystal molecules 17 sandwiched therebetween. The liquid crystal cell can be turned ON/OFF (on/off) The liquid crystal molecules displayed are classified into TN (Twisted Nematic, IPS (In-Plane Switching), OC (In-Plane Switching), 0CB (Optically Compensatory Bend), VA ( Vertically Aligned; Vertical Alignment), ECB ( Electrically 116 1354684

Controlled Birefringence; electronically controlled birefringence), but the polarizing plate of the present invention is versatile and can be used regardless of the transmissive type and the reflective type. - an alignment film (not shown) is formed on the surface of the liquid crystal molecules 17 contacting the substrates 15 and 18 (hereinafter also referred to as "inner surface"), and liquid crystal molecules are not applied in an electric field or in a low applied state. The alignment is controlled by a rubbing treatment or the like applied to the alignment film. Further, on the inner surfaces of the substrates 15 and 18, a transparent electrode (not shown) capable of applying an electric field to the liquid crystal layer composed of the liquid crystal molecules 17 is formed. The rubbing direction of the φ TN mode is applied in a direction in which the upper and lower substrates are orthogonal to each other, and the magnitude of the tilt angle can be controlled by the intensity and the number of rubbing times. The alignment film is formed by coating a polyimide film and baking it. The magnitude of the twist angle of the liquid crystal layer depends on the intersection angle of the rubbing direction of the upper and lower substrates and the chiral agent added to the liquid crystal material. In this case, a pair of palms having a pitch of about 60 μm is added to make the twist angle 90°. In addition, when the twist angle is in the case of a liquid crystal display device for a notebook computer or a personal computer monitor or a television set, it is set to be near 90° (85 to 95°), and is used as a reflection type of a portable telephone or the like. In the case of a display device, it is set to 〇~70°. In IPS mode or ECB mode, the twist angle will be 〇°. In the IPS mode, the electrodes are disposed only on the lower substrate 18 to apply an electric field parallel to the substrate surface. As for the 0CB mode, there is no twist angle, and the tilt angle is set to be larger, and in the VA mode, the liquid crystal molecules 17 are aligned perpendicular to the upper and lower substrates. However, the size of the liquid crystal layer thickness d and the refractive index anisotropy Δη 値And -117-1354684 causes the brightness to change in white display. Therefore, in order to obtain the maximum brightness, the range is set for each display mode. The intersection angle of the absorption axis 12 of the upper polarizing plate 1 1 and the absorption axis -23 of the lower polarizing plate 22 is generally made to be substantially orthogonal, whereby high contrast can be obtained. The angle of intersection of the absorption axis 1 2 of the upper polarizing plate 1 of the liquid crystal cell and the rubbing direction of the upper substrate 15 differs depending on the liquid crystal display mode, but is generally parallel or perpendicular in the TN and IPS modes. In the OCB and ECB modes, it is mostly set at 45°. However, in order to adjust the color tone of the display color or the field angle, the optimum mode is different in each display mode, so it is not limited to the range of φ. The liquid crystal display device to which the polarizing plate of the present invention can be used is not limited to the structure of Fig. 2, and may include other members. For example, a color filter may be disposed between the liquid crystal cell and the polarizing film. Further, the viewing angle expansion films 13 and 20 may be disposed between the liquid crystal cell and the polarizing plate. The polarizing plates 11 and 22 and the viewing angle expansion film 1 3 ' 20 may be disposed in a laminated form in which the adhesive is bonded, or may be used as one of the liquid crystal cell side protective films in the viewing angle. The so-called integrated ellipsometer is configured. φ Further, when used as a transmissive type, a backlight having a cold cathode or a hot cathode fluorescent tube or a light-emitting diode 'field emission element or an electroluminescence element as a light source can be disposed on the back surface. Further, the liquid crystal display device for using the polarizing plate of the present invention may also be of a reflective type. In this case, the polarizing plate may be disposed only on the observation side, and may be on the back surface of the liquid crystal cell or in the lower substrate of the liquid crystal cell. A reflective film is provided on the surface. It is of course also possible to arrange the optical module on the viewing cell side of the liquid crystal before using the above-mentioned light source. [Embodiment] [Embodiment] The present invention will be described in more detail below based on the embodiments, but the present invention is not limited thereto. [Example 1] (Production of fluorinated cellulose film (1)) The following composition was placed in a mixing tank, and stirred while heating to dissolve each component to prepare a bismuth cellulose solution A. <Composition of bismuth cellulose solution A> Cellulose acetate having a degree of acetylation of 60.9% 100 parts by mass of triphenyl silicate (plasticizer) 7.8 parts by mass of biphenyl diphenyl phosphate (plasticizer) 3.9 Parts by mass of chloroform (first solvent) 300 parts by mass of methanol (second solvent) 54 parts by mass of 1-butanol hydrazine

The following composition was placed in another mixing tank, and stirred while heating to dissolve the components to prepare additive solutions B-1 to B-6. <Composition of additive solution B-1~B-6>

E_I Coating solution Dichloromethane (parts by mass) Methanol (parts by mass) Ultraviolet absorber (A) (parts by mass) Ultraviolet absorber (B) (parts by mass) Compound (446) (parts by mass) Compound (F-7) (Parts by mass) Β·ΐ 80 20 2 4 No Β-2 80 20 2 4 30 No Β-3 80 20 2 4 Μ 30 Β - 4 80 20 2 4 10 20 _ Β-5 80 20 2 4 20 10 Β - 80 20 2 4 15 15 〔化49〕 -119- 1354684

Ch3 c-ch3 ch3 h3c*c_ch3 ch3 UWMA

UV absorbing agent B <Production of cellulose acetate film (1)> To 474 parts by mass of the fluorinated cellulose solution A, 40 parts by mass of the additive solution B - 1 ' was sufficiently stirred to prepare a coating liquid. The coating liquid was cast from the casting port on a drum cooled to 〇 °C. The solvent is contained in a state in which the solvent content is 70% by mass, and the needle-clamping type is described in the third embodiment in the width direction of the film. The tenter was fixed, and the solvent was contained in a state where the solvent content was 3 to 5% by mass, and the elongation in the transverse direction (direction perpendicular to the machine direction) was maintained at 3%. Thereafter, it was re-dried by transfer between rolls of the heat treatment apparatus to obtain a cellulose acetate film (1) having a thickness of 80 μm. <Manufacture of cellulose acetate film (2) to (8) In the production of the cellulose acetate film (1), the additive solution and the thickness are as shown in Table 2, and the cellulose acetate film (2) was obtained in the same manner as the cellulose acetate film (1). (8). -120- Table 2 Bucket Number Additive Solution Thickness (μm) Add Qi (% by mass, relative) D Addition to _Acetate) Moisture Permeability (g/m2 · 24hr) Remarks (446) F-7) (1) Β-1 80 0 0 1,950 Comparative example (2) Β-2 80 8.8 0 1,530 Comparative example (3) Β-3 80 0 8.8 1,610 Comparative example (4) Β-4 80 2.9 5.9 1,100 The present invention (5) Β-5 80 5.9 2.9 1,040 The present invention (6) Β-6 80 4.4 4.4 810 The present invention (7) Β-7 60 4.4 4.4 1,080 The present invention (8) Β-8 40 4.4 4.5 1,340 The present invention 1354684 [Example 2] (Alkalization treatment) - The cellulose acetate films (1) to (8) were immersed in a sodium hydroxide aqueous solution of 1.5 ° C at 1.5 ° C for 2 minutes. Then, it was washed in a water bath at room temperature, and neutralized using sulfuric acid specified at 0.1 °C at 30 °C. It was again washed in a water bath at room temperature and then dried at a temperature of 100 °C. The surface of the cellulose acetate film is saponified in this manner. Further, a WV film manufactured by Fuji Photo Film Co., Ltd. was alkalized under the same conditions to be used for the production of the following samples. [Example 3] - The iodine was adsorbed on the stretched polyvinyl alcohol film to obtain a polarizing film, and the cellulose acetate film (1) obtained in Example 1 was attached using a polyvinyl alcohol-based adhesive. On one side of the polarizing film. And the transmission axis of the polarizing film and the late phase axis of the cellulose acetate film are arranged in parallel" and the WV film alkalized by the embodiment 2 is attached to the opposite side of the polarizing film using a polyvinyl alcohol-based adhesive. . The polarizing plate (1) was produced in this manner. -121 - 1354684 [Example 4] In the same manner as in Example 3, polarizing plates (2) to (8) were produced by a combination of cellulose acetate films shown in Table 3. [Example 5] The polarizing plate obtained in such a manner was attached to a glass plate in such a manner that its WV film was on the glass side, and it was allowed to stand at 1,000 ° C for 9 hours at 90 ° C for 9 hours. The parallel transmittance and the orthogonal transmittance were measured with a Shimadzu UV 2200 spectrophotometer, and then the degree of polarization was calculated by the above (Formula 4). The results are shown in Table 3. According to the results of Table 3, it was found that the polarizing plate of the present invention has a small change in the degree of polarization of heat and humidity, and therefore has excellent durability. ^__3 Polarizer air interface side protective film polarizing remarks (1) Deuterated cellulose film (1) 97.4 Comparative example (2) Deuterated cellulose film (2) 98.1 Comparative example (3) Deuterated cellulose film (1) 98.4 Comparative Example (4) Deuterated cellulose film (4) 99.1 The present invention (5) Deuterated cellulose film (1) 99.3 Inventive (6) Deuterated cellulose film (6) 99.7 The present invention (7) Deuterated cellulose film (7) 99.0 The present invention (8) Deuterated cellulose film (8) 98.9. The present invention [Example 6] A 20-inch liquid crystal display device (LC-20V1, Sharp) which is provided in a liquid crystal cell using TN type The polarizing plate is peeled off, and the polarizing plate obtained in the embodiment 5 is replaced with the adhesive so that the optical compensation sheet is positioned on the liquid crystal cell side on the observer side and the backlight side. Each one is attached. Further, the transmission axis of the polarizing plate on the observer side and the transmission axis of the polarizing plate on the backlight side are arranged to be orthogonal. Then, under the environmental conditions of 25 ° C, phase -122 - 1354684 and humidity of 60%, the backlight module is continuously lit for 1 , hours, and the overall black display state is visually observed in the dark room to evaluate the light leakage. . As a result, in the polarizing plate of the comparative example, light leakage in a frame shape was observed on the display image of the liquid crystal display device, whereas the liquid crystal display device using the polarizing plate of the present invention was not observed. [Example 7] (Preparation of cellulose acetate solution) The following composition was placed in a mixing tank, stirred, and each component was dissolved to prepare a cellulose acetate solution. Composition of cellulose acetate solution A1 Acetate acetate 60.9% cellulose acetate 100.0 parts by mass dichloromethane (first solvent) 402.0 parts by mass methanol (second solvent) 60.0 parts by mass (modulation of matting agent solution) The following composition was charged into a disperser, stirred, and each component was dissolved to prepare a matting agent solution. The matting agent solution has a composition average particle diameter of 16 nm of cerium oxide particles (AEROSIL R972, trade name, manufactured by Nippon Aerosil Co., Ltd.) 2.0 parts by mass of dichloromethane (first solvent) 76.3 parts by mass of alcohol (second Solvent) 11.4 parts by mass of cellulose acetate solution A1 10.3 parts by mass (modulation of additive solution) The following composition was placed in a mixing tank, and stirred while heating to dissolve each component to prepare an additive (delaying agent) solution. -123 - 1354684 Additives for additive solution (446) 19.8 parts by mass of dichloromethane (first solvent) 58.4 parts by mass of methanol (second solvent) 8.7 parts by mass of cellulose acetate solution A1 12.8 mass dressing (0268 &gt; 50]

(446)

(Production of Cellulose Acetate Film (u)) 94.6 parts by mass of the cellulose acetate solution A1, 1.3 parts by mass of the matting agent solution, and 4.1 parts by mass of the retardation agent solution were separately filtered and mixed, and then the tape was used. The casting machine is cast. The mass ratio of the delayed riser to cellulose acetate was 4.6%. When the residual solvent amount was 30%, the film was peeled off from the casting tape, and at a temperature of 1 30 ° C, the film having a residual solvent amount of 13% by mass was laterally extended by a tenter at a stretching ratio of 28%. And still hold at 140 ° C for 30 seconds at the extended width. Then, the jig was removed, and dried at 14 (TC for 40 minutes to obtain a cellulose acetate film. The residual solvent amount of the cellulose acetate film obtained was 0.2% -124 to 1354684, and the film thickness was 92 μm. The type and amount of the additive in the additive solution were changed to the contents shown in Table 4, and the cellulose acetate film (12) to (18) was obtained in the same manner. (Measurement of optical characteristics) The cellulose acetate film was measured for delayed enthalpy by the following method.

The measurement method of Rth砥樨値 Lu uses an ellipsometer (M-150, manufactured by JASCO Corporation) at 25. . The in-plane retardation 値Re ( 0 ) was measured at φ 1 0% RH. Further, the in-plane retardation axis was used as the rotation axis, and the axis was rotated by 40° and -40° to measure the retardation 値Re ( 40 ) and Re ( - 40 ). The refractive index nx in the film thickness and the slow axis direction is used as a parameter, and the direction of the phase axis can be calculated by calculation so as to be close to the measured 値Re ( 0 ), Re ( 40 ), and Re ( - 40 ). The refractive index ny and the refractive index nz in the thickness direction determine the Rth delay 値. The measurement wavelength was selected to be 6 3 2.8 nm. In addition, the same measurement was carried out at 25 ° C and 80% RH. The results _ are shown in Table 5. φ In addition, it was confirmed that when Compound 446 and Compound 250 were added, Rth increased, and when A-4, PL-29, and F-2 were added, Rth decreased -125- Ϊ354684. Table 4 团号_Reagent Remarks_ Quantity (% by mass) Number of noodles (% by mass) Sasin acetate film (1)) (446) 4.6 - 0 Comparative Example Cellulose Acetate Film 02) (250) 7 - 0 Ί Comparative Example Cellulose Acetate Film (13) (250) 3 - 0 Comparative Example Cellulose Acetate Film U4) (250) 5 (A-4) 2 Cellulose Acetate Film of the Invention (15) (250) 6 (A-4) 3 Cellulose Acetate of the Invention Ester film (16) (250) 7 (A-4) 2 Cellulose acetate film of the invention (17) (446) 7 (PL-29) 2 Cellulose acetate film of the invention (18) (446) 7 ( F-2) 2 Determination of the invention number at 25 ° C 〇 % RH 値 Determination at 25 ° C 80% RH 値 at 25 ° C Measured at 25 ° C t 80% RH 値 10% RH 値Remarks Re Re (n) Rth (nano) Re (nano) Rth (nano) Rth/Re Re ratio Rth ratio Cellulose acetate film (11) 46 210 39 176 4.5 0.61 0.65 Comparative fiber Acetate Film (12) 54 240 43 186 4.3 0.63 0.68 Comparative Example Cellulose Acetate Film (13) 35 172 28 146 5.2 0.59 0.61 Comparative Example Cellulose Acetate Film (14) 48 152 38 138 3.6 0.74 0.71 Cellulose Acetate of the Invention Ester film (15) 51 159 43 156 3.6 0.72 0.73 Cellulose acetate film of the invention (16) 55 170 47 150 3.2 0.77 0.78 Cellulose acetate film of the invention (17) 53 177 48 162 3.4 0.78 0.75 Cellulose of the invention Acetate mm (is) 54 173 48 153 3.2 0.75 0.73 According to the results of Table 5, it is known that the cellulose-degraded cellulose film of the present invention can realize a wide range of optical characteristics, and the humidity dependence of optical characteristics is small, so An ideal retardation film. [Example 8] (Baification treatment) -126- 1354684 On the cellulose acetate film (11) obtained in Example 7, a liquid of the following composition of 5.2 ml/m2 was applied and dried at 60 °C. 10 seconds. After washing the surface of the film with running water, the surface of the film was blown dry with air at 25 °C. Composition of alkalizing solution __ Isopropanol 818 parts by mass Water 167 parts by mass Propylene glycol 187 parts by mass Potassium hydroxide 68.3 parts by mass (Formation of alignment film)

On the saponified surface of the cellulose acetate vinegar film (11), 24 ml/m2 of a coating liquid having the composition shown below was applied using a #14 bar coater. Drying under a warm air of 60 ° C for 60 seconds' and drying under a warm air of 90 ° C for 150 seconds 0 Then, for the film formed to extend toward the cellulose acetate film (transparent support) (roughly The phase of the slow phase is consistent) to 45. Direction

Modified polyvinyl alcohol - (CH2-CH) b7.8 - OH - (CH2-CH)

0.7T -(CH2-CH)12i〇- c=o IC=( CH, rubbing treatment. The composition of the alignment coating liquid is as follows: modified polyvinyl alcohol 20 parts by mass Ϊ - - 360 parts by mass of methanol 120 mass份戊二醒_ (交#剂) 1.0 parts by mass [化5 1] 〇(CH2)4OCOCH=CH2 -127- 1354684 (formation of optical anisotropic layer (optical compensation sheet)) on the alignment film 'use# A wire bar coater of 3.6 is applied to 91 parts by mass of 6.2 ml/m 2 of a disc-shaped liquid crystalline molecule (I) of the following formula, and a ring of 9 parts by mass.

Oxygen ethane modified trimethylolpropane triacrylate (V #360, trade name 'Osaka Organic Chemical Co., Ltd.), 1.5 parts by mass of cellulose acetate butyrate (CAB 5 31-1, trade name , 3 parts by mass of a photopolymerization initiator (irgacure-9〇7, trade name, manufactured by Ciba-Geigy Co., Ltd.), and 1 part by mass of a sensitizer (Kayacure -DETX 'product) 1.0 parts by mass of a citric acid ester mixture represented by the following formula φ is dissolved in 214.2 parts by mass of a methyl ethyl ketone coating liquid. This was attached to a metal frame and heated in a thermostat of 14 Torr for 2 minutes to align the liquid crystal molecules. Then, a 120 W/cm high-pressure mercury lamp was used at 90 ° C, and UV (ultraviolet rays) was irradiated for 1 minute to polymerize the discotic liquid crystalline compound, and then allowed to cool to room temperature.

Discotic liquid crystalline molecules (I)

HsC-COR! ho-c~co2r2 H2〇~ C-〇_ R3 δ -128- 1354684 R! = Η or C2H5 R2 = Η or C2H5 R3 = Η or C2H5 citrate mixture (manufactured by polarizing plate) The film was adsorbed on the stretched polyvinyl alcohol to obtain a polarizing film. The transparent support side of the obtained optical compensation sheet was attached to one side of the polarizing film using a polyvinyl alcohol-based adhesive. The retardation axis of the transparent support and the transmission axis of the polarizing film are arranged in parallel. A commercial grade cellulose triacetate film (Fujitac TD80UF 'Fuji Photo Film Co., Ltd.) was applied and saponified in the same manner as in Example 2. Then, a polyvinyl alcohol-based adhesive was attached to the opposite side of the polarizing film (the side on which the optical compensation sheet was not attached). Polarizing plate (1 1 ) was produced as described above » (Manufacture of curved alignment liquid crystal cell) On a glass substrate with an ITO (indium tin oxide) electrode, a polyimide film was provided as an alignment film, and for alignment The film is subjected to a rubbing treatment. The two glass substrates thus obtained were arranged so that the rubbing treatment direction was parallel, and the lattice gap was set to 5.7 μm. A liquid crystal compound (ZLI1 132, trade name, manufactured by Merck) having a Δη of 0.1396 was injected into the lattice gap to obtain a curved alignment liquid crystal cell. (Manufacturing of Liquid Crystal Display Device) Two polarizing plates were attached by sandwiching the obtained curved alignment lattice. It is arranged such that the optically anisotropic layer of the polarizing plate is antiparallel to the lattice-129- 1354684 substrate such that the rubbing direction of the liquid crystal cell and the opposite optical anisotropic layer are opposite. [Example 9] A polarizing plate (12) to (1) was obtained in the same manner except that the cellulose-deposited cellulose film was changed to (I2) to (18) in the polarizing plate (11) of Example 8. ° ° Under the environmental conditions of 25 ° C temperature and relative humidity of 60%, the backlight module is continuously lit for 500 hours, and the overall black display state is visually observed in the dark room to evaluate the light leakage. As a result, in the polarizing plate of the comparative example, the light leakage in the frame shape was observed on the display image of the liquid crystal display device, whereas the liquid crystal display device using the polarizing plate of the present invention did not observe such a case. 1 0] The polarizing plate was peeled off from one of a 22-inch liquid crystal display device (manufactured by Sharp Co., Ltd.) using a VA type liquid crystal cell, and replaced with a binder, which was obtained in the same manner as in Example 9. The polarizing plate was attached to each of the viewer side and the backlight side so that the cellulose-defluorinated film obtained in Example 7 could be positioned on the liquid crystal cell side. Further, the transmission axis of the polarizing plate on the observer side and the transmission axis of the polarizing plate on the backlight side are arranged to be orthogonal. As a result, it was found that the polarizing plate of the present invention is a particularly excellent polarizing plate having a wide viewing angle. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a view showing an example of a structure in which a polarizing plate and a functional optical film of the present invention are combined to show a function of bonding a functional optical film-130-1354684 and a polarizing film to a polarizing plate via an adhesive, respectively. An example (A) of a one-sided protective film, and an example (B) of bonding a functional optical film to a polarizing plate provided with a protective film on both sides of a polarizing film via an adhesive. Fig. 2 is a view showing an example of a liquid crystal display device for use in the polarizing plate of the present invention. Main component symbol description]

2 3 4 11 12 13 14 15 16 17 1 8 19 20 21 22 23 lb protective film polarizing film functional optical film adhesive layer polarizing plate on polarizing plate absorption axis optical anisotropic layer (viewing angle expansion film) Isotropic direction layer alignment control direction liquid crystal cell upper electrode substrate upper substrate alignment control direction liquid crystal layer liquid crystal cell lower electrode substrate lower substrate alignment control direction optical anisotropic layer (viewing angle expansion film) optical anisotropic layer alignment control direction Lower polarizer absorption axis under lower polarizer

-131 -

Claims (1)

1354684 Factory-] Amendment of this Ic·# yyyyyyyyyyyyyyyyyyyyyyyyyyyyyyyyyyyyyyyyyyyyyyyyyyyyyyyyyyyyyyyyyyyyyyyyyyyyyyyyyyyyyyyyyyyyyyyy A cellulose film characterized by containing at least one of the compounds represented by the following general formula (1), and at least one of the compounds represented by the following general formula (11), (111) or (IV) One: [wherein, χΐ is a single bond, an NR4—, a 〇-, or _s—; X2 is a single bond, —NR5—, —〇—, or an S—; X3 is a single bond, an NR6—, — 〇—, or —S — ; R 1 , R 2 and R 3 each independently represent an alkyl group, an alkenyl group, an aryl group or a heterocyclic group; and R 4 , R 5 and R 6 each independently represent a hydrogen atom, an alkyl group or an alkenyl group. a base group, an aryl group or a heterocyclic group, and each of the alkyl group, the alkenyl group, the aryl group and the heterocyclic group may have a substituent]; the formula (II) ^54684 Revision 0 223 1Γ» / ί [wherein R21, R22 and R23 each independently represent a hydrogen atom or an alkyl group; and X21 represents a group selected from a linking group! a divalent linking group formed by one or more of the groups; Y21 represents a hydrogen atom, an alkyl group, an aryl group or an aralkyl group; (linked group 1) a single bond '—0 — ' — CO—, — NR24 − , alkylene and aryl groups: R24 represents a hydrogen atom, an alkyl group, an aryl group, or an aralkyl group; Formula (III), 33, 31. N-R 32 0 [wherein R31 represents an alkane Or a aryl group, R32 and R33 each independently represent a hydrogen atom, an alkyl group or an aryl group, and the sum of the number of carbon atoms of R31, R32 and R33 is 10 or more, and each alkyl group and aryl group may have a substituent. , R31 and R32 can also be joined to form a ring]; General formula (IV) -2- «54684 _ • MFr month A correction replacement page revision this! R40\ /R50, 42 R60 [wherein x42 represents C - OH ' R4g, R5Q and R60 each independently represent an aryl group, a cycloalkyl group or a heterocyclic group, and each aryl group, cycloalkyl group and heterocyclic group may also have a substituent, and R4C) and R5() are also Can be joined to form a ring]. 2. For the cellulose film of Patent Application No. 1, Rth (nano) and Re (nano) defined by the following formulas (a) and (B) are 30 nm S RthS 3 00 nm. 2 nm S Re S 80 nm, and the Rth/Re ratio is 1 or more and 6 or less: (A) Re (nano) = (nx-ny) χ d (B) Rth (nano) = { ( nx + ny) /2 - nz } χ d [wherein iix is the refractive index of the retardation axis in the plane of the film; ny is the refractive index of the phase axis in the plane of the film; nz is the thickness of the film The refractive index of the direction; and d is the thickness of the film (nano). 3. The cellulose film according to claim 1 of the patent scope, which has a moisture permeability of 500 g/m2 · 24 hr or more and 2,000 g/m 2 · 24 hr or less at 60 ° C 95% RH 24 hr. 4. The cellulose film according to claim 1 of the patent application, wherein the equilibrium moisture content at 80 ° RH at 25 ° C is 3.0% or less, and the equilibrium moisture content at 80 ° RH at 25 ° C is at 25 °. (: The ratio of the equilibrium moisture content of 1 0% RH is 3 or more and 1 0 to 1354684 The cellulose film according to the first aspect of the invention is a ratio of Rth at 10 °RH at 25 °C to Rth at 80 °C of 80 °C of 0.65 or more. 6. The cellulose film of claim 1, wherein the ratio of Re at 10 ° RH at 25 ° C to Re at 25 ° C 80 ° RH is 0.65 or more. A polarizing plate is formed by laminating a protective film on both sides of a polarizer, and is characterized in that at least one of the protective films is a cellulose film as in the first aspect of the patent application. 8. The polarizing plate of claim 7, wherein at least one of an adhesive layer, an antiglare layer, a reflective layer, a transflective layer, a phase difference layer, a viewing angle compensation layer, and a brightness enhancement layer is provided. 9. The polarizing plate of claim 8 of the patent application, wherein the phase difference layer is λ/4 layer. A liquid crystal display device comprising a liquid crystal cell and two polarizing plates disposed on both sides thereof, and at least one of the polarizing plates is a polarizing plate according to claim 7 of the patent application. -4-