TW200526728A - Cellulose film, polarizing film and liquid crystal display - Google Patents

Abstract

The present invention provides a cellulose film having small variation in optical compensation energy resulted from the influence of heat and humidity, and comprising at least two kinds of retardation regulator, and a polarizing plate and a liquid crystal display device are constituted by using the said film.

Description

200526728 IX. Description of the invention: [Technical field to which the invention belongs] The present invention relates to a cellulose film suitable for use as a retardation film, etc., and a polarizing plate and a liquid crystal display device using the film. [Prior Art] A liquid crystal display device is an image display device with low power consumption and small space required, and its use is expanding. In the past, although the dependence of the viewing angle of the image is a major disadvantage of the liquid crystal display device, 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 become practical. Therefore, in the markets that require high viewing angles such as televisions, the demand for liquid crystal display devices is also rapidly expanding. Therefore, the retardation film used in the liquid crystal display device and the polarizing plate using the retardation film are required to further improve the performance. In particular, durability for improving temperature and humidity is a major technical issue for polarizing plates. What is particularly problematic in the durability test of polarizing plates is the reduction in polarization, which is caused by the decomposition of iodine adsorbed on the polarizing film due to the action of water. Therefore, the known effective countermeasure is to reduce the protection of polarizing plates. The permeability of the membrane. However, tritiated cellulose used as a protective film for polarizing plates is a very hydrophilic polymer in itself, and because of its high water permeability, various methods of adding various hydrophobizing agents to reduce its water permeability have been proposed. For example, Patent Document 1 discloses a method of reducing the moisture permeability by adding a rosin derivative or an epoxy resin to a tritiated cellulose film. However, according to these methods, the improvement effect is still imperfect. On the other hand, cellulose acetate film has the advantage of low optical anisotropy. 200526728 'It has always been used as a protective film for polarizing plates, but in recent years, it has been gradually increased by methods such as biaxial stretching The tendency to give retardation so that it also has the function of a retardation film at the same time. Patent Document 2 discloses a method of adding a compound having a high planarity to a tritiated cellulose film. However, according to these methods, it is still difficult to coexist the optical characteristics required for the retardation film and the water permeability required for the protective film of the polarizing plate, and there is also a problem that the humidity dependence of the optical characteristics of the retardation film is large presence. • [Invention Patent Document 1] Japanese Patent Laid-Open No. 2002-1 46044 φ [Invention Patent Document 2] Japanese Patent Laid-Open No. 2001-166144 [Inventive Content] [Technical Problems to be Solved by the Invention] The present invention The object is to provide a cellulose film that can be used as a retardation film with small optical compensation energy due to changes in heat and humidity. Another object of the present invention is to provide a polarizing plate having small changes in transmittance and polarization due to heat and humidity. • Another object of the present invention is to use a polarizing plate formed by arranging a retardation film and / or a low-moisture-permeability protective film having excellent viewing angle compensation for Cinergy on both sides of a polarizing film for use in a liquid crystal display device, That is, a liquid crystal display device having a wide viewing angle and high display quality can be provided without causing problems such as light leakage. [Technical method to solve the problem] After intensive discussion, the inventors found that if a compound having a high planarity and a compound having an aromatic ring but a low planarity are added to the compound-6-200526728 When the cellulose film is used, the water permeability of the halogenated cellulose film can be significantly reduced, and the humidity dependence of the optical properties of the halogenated cellulose film can be reduced. Furthermore, it has been found that by adjusting the ratio of the above-mentioned discoid compound to the low-planarity compound, a wide range of optical characteristics can be adjusted while maintaining the humidity dependence of the moisture permeability and optical characteristics. The former has the effect of increasing the delay 値, and the latter has the effect of decreasing the delay 値. That is, this invention provides the following method. • (1) Cellulose thin φ film characterized by containing at least two retardation modifiers. (2) The cellulose film according to item (1), which contains at least one retardation increasing agent and retardation decreasing agent, respectively. (3) A cellulose film characterized by containing at least one of the compounds represented by the following general formula (I) and the compounds represented by the following general formula (II), (III), or (IV) At least one of: • General formula (I) Φ [Chemical formula 1] R3 〆

N people N 200526728

[In the formula, X1 is a single bond, a NR4—, —〇—, or; X2 is a single bond, —NR5—, — 〇—, or _ s—; early bond, —NR6—, — 〇—, or — S —; R1, each independently represents an alkyl, alkenyl, aryl, or aryl group, and R4, R5, and R6 each independently represent a hydrogen alkyl, alkenyl, aryl, or composite ring group. Each of the alkyl group, the aryl group, and the composite ring group system may have a substituent. ] General formula (II) [Chemical formula 2]-S-X3 is and R3

[In the formula, r21, R22, and R23 are each independently a proton or an alkyl group. X21 represents a divalent linking group formed by a group selected from linking group 1 or more. γ2 I represents a, alkyl, aryl, or aralkyl group. (Linking group 1) single bond, —〇 一, —CO—, —-, alkylene and aryl. R24 represents a hydrogen atom, an aryl group or an aralkyl group. ]; General formula (III) hydrogen atom one atom NR24 group, 200526728 0 R33 R31-S-N-R32

II 0 [wherein R31 represents an alkyl group or an aryl group; R32 and R33 each independently represent a hydrogen atom, an alkyl group, or an aryl group. The total number of carbon atoms of R32 and R33 is 10 or more, and each radical and aryl system may have a substituent. R31 and R32 may be connected to form a ring. ] General formula (IV) [Chemical formula 4] r4〇 \ 4〆 R60 [wherein X42 represents B and C-R70 (r7〇 represents hydrogen atom or substituent.) ,! ^,? or? = 〇. 1 ^ 4. ,: ^ 50 and R6G each independently represent an aryl group, a cycloalkyl group, or a composite ring group (R4G, R5G, and ROG preferably each independently represent a substituted or unsubstituted phenyl group.). Each aryl group, cycloalkyl group, and composite ring group may have a substituent. R4〇 may also be connected to form a ring.] (4) The halogenated cellulose film as described in any one of items (1) to (3), which is expressed by the following formula (A) and (B) The defined Rth (nano) and Re (nano) are 200526728 30 nm S RthS 3 00 nm, 2 nm $ ReS80 nm, and the Rth / Re ratio is 1 or more and 6 or less: (A) Formula Re (nano) = (nx-liy) xd (B) Formula Rth (nano) = {(nx + ny) / 2-nz} X d [where nx is the direction of the late phase axis in the film plane Refractive index; ny is the refractive index in the direction of the advancing axis in the film plane; nz is the refractive index in the thickness direction of the film; and d is the thickness of the film (nano φ)]. (5) The cellulose film according to any one of items (1) to (4), which has a water vapor transmission rate of 60 g at 95% RH 24hr at 400 g / m2 · 24hr or more and 2,000 g / m2 · Less than 24hr. (6) The cellulose film according to any one of items (1) to (5), which has an equilibrium water content of 3.0% or less at 25 ° C80% RH and an equilibrium of 80% RH at 25 ° C The ratio of the moisture content to the equilibrium moisture content of 10% RH at 25 ° C is 3 to 10 200526728, which is characterized in that at least one of the protective films is any one of items (1) to (8) The cellulose film of one item. (10) A polarizing plate characterized in that an adhesive layer is provided on the polarizing plate of item (9). (11) The polarizing plate according to item (9), which is provided with an anti-glare layer on the air-side protective film. (12) The polarizing plate according to item (9), which is provided with a reflective layer or a transflective reflective layer on the air-side protective film. (13) The polarizing plate according to item (9), which has a retardation layer or a λ / 4 layer. (14) The polarizing plate according to item (9), which has a viewing angle compensation film (view angle compensation layer). (15) The polarizing plate according to item (9), which has a brightness enhancement layer (16), a liquid crystal display device, which is characterized by a liquid crystal cell and two polarizing plates arranged on both sides thereof, and At least one polarizing plate • One of the polarizing plates according to items (9) to (1 5). In the present invention, the term "delay modifier" means used to change the retardation of a cellulose film. If at least two of these are contained, excellent effects can be obtained, but it is preferable to include a delay-rise agent and a delay-down agent separately. At least one agent. Among them, "delaying rising agent" means adding 0.1 to 30 parts by mass, preferably 1 to 10 parts by mass, to 100 parts by mass of the tritiated cellulose film.値 Comparison 'can delay the tritiated cellulose film 値 -11-

200526728 Compounds that rise by more than 10 nanometers, preferably more than 50 nanometers and less than 250 nanometers. In contrast, the "delay reducing agent" means that 0.1 to 30 parts by mass is added to 100 parts by mass of the cellulose film, and preferably 0.5 to 5 parts by mass, compared with the retardation when not added. It can decrease the delay time of the chemical fiber film by less than 5 nanometers, preferably by 5 nanometers or more by 100 nanometers or less. The ratio (mass ratio) of the retarder to the retarder is preferably 1/10 to 10, and more preferably 1/10 to 1. The delay time is measured in the following manner. The in-plane retardation of the cellulose film was measured at 25 ° C 10% RH using an ellipsometer (M -1 150) (made by Japan Spectroscopy Co., Ltd. (commercial)), and the in-plane retardation was measured. The axis is the shift axis, and the axis is shifted by 4 (Γ 40 ° to measure the delays 値 Re (40) and Re (-40). Then, the refractive index nx of iii and the direction of the late-phase axis are used as parameters to approximate to The 値 Re (〇), Re (40), and Re (-4 0) methods are used to calculate the refractive index ny in the direction of the phase axis and the refractive index nz in the thickness direction to determine the retardation 値. The measurement wavelength is selected. 63 2.8 nm. In addition, the same measurement was performed at 80% RH. [Effect of the invention] According to the present invention, it can provide excellent heat resistance and durability, and is suitable for protection of a polarizing plate. The film or retardation film is a thin film of vitamins, preferably a cellulose film. In addition, according to the present invention, it is possible to provide a meter with a superior quality (~ 10 dimensional factors and a more rounded name) 1 Re And-film thickness measurement in and out: polarizing plate with Rth 2 5 ° C fibrous heat, -12- 200526728 humidity durability. The polarizing plate has optical compensation function, and is suitable for TN (Twisted Nematic) type, OCB (Optically Compensated Bend) type, ECB (Electrically Controlled Birefringence) type, VA (Vertically Aligned) type, IPS (In-Plane Switching) type of liquid crystal display device. [The best form of implementing the invention] # The inventors have carefully discussed the results and found that if the high planarity When both a discotic compound and a compound having an aromatic ring but low planarity are added to the tritiated cellulose film at the same time, the water permeability of the tritiated cellulose film can be significantly reduced, and The humidity dependence of the optical properties of the tritiated cellulose film becomes small. Furthermore, it has been found that by adjusting the ratio of the disc-shaped compound to the low-planarity compound, the humidity dependence of the moisture permeability and optical properties can be maintained The optical characteristics can be adjusted in a wide range under natural conditions. The former has the effect of increasing the delay time, such as: Represented by the general formula (I), which has the effect of reducing the delay time, such as those represented by the general formula (II), (III), or (IV). However, it has also been found that When the cellulose film is triturated, it is unexpectedly possible to obtain an effect far superior to that expected when each compound is added individually. That is, it is possible to obtain an excellent tritiated cellulose film having a function of lowering the moisture permeability lower than the effect that can be expected by adding it alone, and at the same time the temperature dependence of the optical characteristics is small. The film system can be used as a phase Poor film. -13- 200526728 In the present invention, 'both the above-mentioned delayed rising agent and delayed falling agent are added to the tritiated cellulose film, whereby the above-mentioned unexpectedly excellent effects can be achieved by the complementary effects of these. In other words, the present invention uses a combination of a delay-increasing agent and a delay-decreasing agent which exhibit a combination of alternate effects. First, the compound having a 1,3,5-triazine ring represented by the above general formula (I) used in the present invention is described as follows: [Chemical Formula 5]

In the formula, X1 is a single bond, —NR4-, —〇—, or —S—; X2 is a single bond, —NR5 —, — 〇—, or —S—; X3 is a single bond, —NR6 —, —〇 —, Or one S —; Ri, R2, and R3 each independently represent a radical, alkenyl, aryl, or composite ring group; and R4, R5, and R6 each independently represent a hydrogen atom, alkyl, or alkenyl , Aryl, or composite ring. The compound represented by the formula (I) is particularly preferably a melamine compound. In the melamine compound, X1, X2 and X3 in the formula (I) are each —NR4 φ —, —NR5 —, and NR6 —, or X], X2 and X3 are single bonds, and W'R2 And R3 is a complex ring group having a free atomic valence on a nitrogen atom. -X1-R1,-X2-R2 and -X3-R3, preferably the same substituent. R1, R2 and R3 are particularly preferably an aryl group. R4, R5 and R6 are particularly preferably a hydrogen atom. The alkyl group is preferably a chain alkyl group than a cyclic alkyl group. The branched chain alkyl group is preferably a linear alkyl group. The number of carbon atoms of the alkyl group is preferably -14-200526728 1 to 30, more preferably 1 to 20, even more preferably 丨 to 10, and further advancement is more preferably 1 to 8, most preferably 丨 to 6 . The alkyl system may have a substituent. Examples of the substituent include a halogen atom, an alkoxy group (for example, a methoxy group, an ethoxy group, an epoxy ethoxy group), and a fluorenyl group (for example, an acrylfluorenyl group, a methyl propionateoxy group). The alkenyl group is preferably a cyclic alkenyl group, and a chain alkenyl group is preferred. Compared with branched alkenyl groups, linear alkenyl groups are preferred. The carbon number of the alkenyl group is preferably from 2 to 30, more preferably from 2 to 20, even more preferably from 2 to 10, still more preferably from 2 to 8, most preferably from 2 to 6. The alkenyl system may have a substituent. Examples of the substituent include a halogen atom, an alkoxy group (for example, a methoxy group, an ethoxy group, and an epoxy ethoxy group), and a fluorenyl group (for example, acrylfluorenyl group, methacrylfluorenyloxy group). The aryl group is preferably a phenyl group or a naphthyl group, and particularly preferably a phenyl group. The aryl system may 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 alkenyl group, an aryloxy group, a fluorenyl group, an alkoxycarbonyl group, Alkenyloxycarbonyl, aryloxycarbonyl, aminesulfonyl, aminesulfonyl substituted with alkyl, aminesulfonyl substituted with alkenyl, aminesulfonyl substituted with aryl, sulfamino , Carbamoyl, carbamoyl substituted with alkyl, carbamoyl substituted with alkenyl, carbamoyl substituted with aryl, carbamoyl, alkylthio, alkenylthio , Sulfur-based and fermented. The above-mentioned colleges and universities have the same definition as the above-mentioned colleges and universities. Alkoxy, alkoxy, alkoxycarbonyl, aminesulfonyl substituted with alkyl, sulfaminyl, carbamoyl substituted with alkenyl, fluorenyl, alkylthio, and sulfanyl alkane The base portion is also the same as the above-mentioned alkyl group. The aforementioned radical has the same definition as the aforementioned radical. Anthoxy, fluorenyl • 15- 200526728, oxycarbonyl, aminesulfonyl substituted with alkenyl, sulfaminyl, carbamoyl substituted with alkenyl, fluorenylamino, alkenylthio, and The alkenyl group of a fluorenyl group is also the same as the said alkenyl group. Examples of the above-mentioned aryl include naphthyl, / 3-naphthyl, 4-methoxyphenyl, 3,4-diethoxyphenyl, 4-octyloxyphenyl, and 4-dodecane Oxyphenyl. Aryloxy, fluorenyloxy, aryloxycarbonyl, aminesulfonyl substituted with aryl, sulfaminyl, carbamoyl substituted with aryl, fluorenylamino, arylthio, and fluorenyl Examples of parts are the same as those of the above-mentioned aryl group. φ χΐ, χ2 is a compound ring group when NR—, — 〇 — or —S —, and it is preferred to have aromaticity. The aromatic composite ring system is generally an unsaturated composite ring, preferably a composite ring having the most double bonds. The compound ring is preferably 5 rings, 6 rings, or 7 rings, more preferably 5 rings or 6 rings, and most preferably 6 rings. The heteroatom of the compound ring is preferably N, S or O, and particularly preferably N. The aromatic ring is particularly preferably a pyridine ring (as a 2-pyridyl group or a 4-pyridyl group). The composite ring group system may have a substituent. Examples of the substituent of the composite ring group are the same as those of the substituent of the aryl portion described above. When X1, X2 or X3 is a single bond, it is preferably a composite ring group having a free atomic valence in the nitrogen atom. The nitrogen atom has a free ring valence complex ring group, preferably 5 rings, 6 rings, or 7 rings, more preferably 5 rings or 6 rings, and most preferably 5 rings. The complex ring system may have several nitrogen atoms. In addition, the composite ring group system may have a hetero atom (for example, 0, S) other than a nitrogen atom. The composite ring group system may have a substituent. Examples of the substituent of the composite ring group are the same as the examples of the substituent of the aryl portion described above. Examples of composite ring groups having a free atomic valence at the nitrogen atom are shown below. -16200526728

(Hc-l)

H3C (Hc ^ 2) (Ho3)

〔Chem 7〕

(Hc-9) H3C-o

(Hc-10)

(Hc-12)

(Hc‘n)

n-C4H8—〇-CO

The molecular weight of the compound having a 1,3,5-triazine ring represented by the general formula (1) is preferably 300 to 2,000. 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, Seiko Electronics Industry Co., Ltd.). Specific examples of the compound having a 1,3,5-triazine ring represented by the above-mentioned general formula (I) are shown below. In addition, the several R shown in each example means the same base. The definition of R will be shown with the specific instance number -17- 200526728 after the formula. 〔Chem 1〕

(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-furyl

〔Chem 1 2〕

-18- 200526728 (14) phenyl (15) 3-ethoxycarbonylphenyl (16) 3-butoxybenzyl (17) m-biphenyl (18) 3-phenylthiophenyl (19) 3-chlorophenyl (20) 3-benzyloxyphenyl (21) 3-ethoxyloxyphenyl φ (22) 3-benzyloxyphenyl (23) 3-phenoxycarbonylbenzene (24) 3 -methoxyphenyl (25) 3 -anilinophenyl (26) 3 -isobutylaminophenyl (27) 3 -phenoxy · carbonylaminophenyl (28) 3 -(3-ethylureido) phenyl (29) 3-(3,3-diethylureido) phenyl • (30) 3-methylphenyl (31) 3-phenoxyphenyl ( 32) 3-hydroxyphenyl (33) 4-ethoxy-based phenyl (34) 4-butoxyphenyl (35) p-biphenyl (36) 4-phenylthiophenyl (37) 4-chlorophenyl

-19- 200526728 (38) 4-benzyloxyphenyl (39) 4-ethoxyloxyphenyl (40) 4-benzyloxyphenyl (41) 4-phenoxycarbonylphenyl ( 42) 4-methoxyphenyl (43) 4-anilinylphenyl (44) 4-isobutylfluorenylaminophenyl (45) 4-phenoxycarbonylaminophenyl φ (46) 4- (3 -Ethylureido) phenyl_ (47) 4-(3, 3 -diethylureido) phenyl (48) 4 -methylphenyl (49) 4 -benzylphenyl (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-dibenzophenylphenyl (57) 3,4-diethoxyloxyphenyl (58) 3,4-Dibenzophenoxyphenyl (59) 3, 4-diphenoxycarbonylphenyl (60) 3, 4-dimethoxyphenyl (61) 3, 4-diphenylaminophenyl Base-20- 200526728

(62) (63) (64) (65) (66) (67) (68) (69) (70) (71) (72) (73) (74) (7 5) (76) (77) (77) 78) (79)

3,4- _. Methylbenzyl 3,4-diphenoxyphenyl 3,4-dihydroxyphenyl 2-naphthyl 3, 4, 5-triethoxycarbonylphenyl 3, 4, 5- Tributoxyphenyl 3,4,5-triphenylphenyl 3,4,5-triphenylthiophenyl 3,4,5-trichlorophenyl 3,4,5-triphenylmethylphenyl Phenyl 3, 4, 5-triethoxyloxyphenyl 3,4,5-tribenzyloxyphenyl 3,4,5-triphenoxycarbonylphenyl 3, 4, 5-trimethoxy 3,4,5-triphenylaminophenyl3,4,5-trimethylphenyl3,4,5-triphenoxyphenyl3,4,5-trihydroxyphenyl (80) -(145) R

(80) Phenyl (81) 3-ethoxyminephenyl> 21-200526728 (82) 3-butoxyphenyl (83) m-biphenyl (84) 3-phenylthiophenyl (85) 3-chlorophenyl (86) 3-benzyloxyphenyl (87) 3-ethoxyloxyphenyl (88) 3-benzyloxyphenyl (89) 3-phenoxy Carbonylphenyl φ (90) 3 -methoxyphenyl (91) 3 -anilinophenyl (92) 3 -isobutylfluorenylaminophenyl (93) 3 -phenoxycarbonylaminophenyl (94 ) 3-(3-ethylureido) phenyl (95) 3-(3,3-diethylureido) phenyl (96) 3 -methylphenyl (97) 3 -phenoxyphenyl φ (98) 3-hydroxyphenyl- (99) 4-ethoxycarbonylphenyl (100) 4-butoxyphenyl (101) p-biphenyl (102) 4-phenylthiophenyl ( 103) 4-chlorophenyl (104) 4-benzyloxyphenyl (105) 4-ethoxyloxyphenyl-22-200526728 (106) 4 -benzyloxyphenyl (107) 4- Phenoxycarbonylphenyl (108) 4-methoxyphenyl (109) 4-anilinylphenyl (no) 4-isobutylfluorenylaminophenyl (111) 4-phenoxycarbonylaminophenylphenyl ( 1 12) 4-(3-ethylureido) phenyl (1 13) 4- (3,3-diethylureido ) Phenyl (114) 4 -methylphenyl (1 15) 4 -phenoxyphenyl (116) 4 -hydroxyphenyl (1 17) 3, 4-diethoxycarbonylphenyl (1 18 ) 3,4-dibutoxyphenyl (I 1 9) 3,4-diphenylphenyl (120) 3,4-diphenylthiophenyl (121) 3, 4-dichlorophenyl (122) 3, 4-Dibenzophenoxyphenyl (123) 3, 4-diethoxymethoxyphenyl (124) 3, 4- dibenzophenoxyphenyl (125) 3, 4- Diphenoxycarbonylphenyl (126) 3, 4-dimethoxyphenyl (127) 3, 4-diphenylaminophenyl (128) 3, 4-dimethylphenyl (129) 3, 4 -Diphenoxyphenyl-23- 200526728

(130) (131) (132) (133) (134) (135) (136) (137) (138) (139) (140) (141) (142) (143) (144) (145) (Chemistry) 14 3,4-dihydroxyphenyl 2-naphthyl 3, 4, 5-triethoxycarbonylphenyl 3, 4, 5-tributoxyphenyl 3, 4, 5-triphenylphenyl 3 , 4,5 -triphenylthiophenyl 3, 4,5 -trichlorophenyl 3,4,5-tribenzylidenephenyl 3, 4, 5 -triethoxyloxyphenyl 3,4 , 5 -tribenzyloxyphenyl 3, 4,5 -triphenoxycarbonylphenyl 3, 4,5 -trimethoxyphenyl 3, 4, 5-triphenylaminophenyl 3, 4, 5-trimethylphenyl 3,4,5-triphenoxyphenyl 3, 4, 5-trihydroxyphenyl

(146)-(164)

(146) (147) (148) (149) Phenyl 4-ethoxycarbonylphenyl 4-butoxyphenyl p-biphenyl-24- 200526728 (150) 4-benzene (151) 4-chloro (152) 4-benzene (153) 4-ethyl (154) 4-benzene (155) 4-benzene (156) 4-methyl (157) 4-benzene # (158) 4-iso (159) 4-benzene ( 160) 4-((161) 4-((162) 4 -methyl (163) 4 -benzene (164) 4 -hydroxy Methoxymethylmethoxyphenyl • ^ 甘 甘 # Glyoxylic acid ft Ben S oxyphenylaminophenylphenylbutanylaminophenyloxycarbonylaminophenyl 3-ethylureido) phenyl 3, 3-diethylureido) phenylphenyloxyphenylphenyl

(165) phenyl (166) 4-ethoxycarbonylphenyl (167) 4-butoxyphenyl (168) p-biphenyl (169) 4-phenylthiophenyl-25- 200526728 (170 ) 4-Chlorophenyl (171) 4-benzyloxyphenyl (172) 4-ethoxyloxyphenyl (173) 4-benzyloxyphenyl (174) 4-phenoxycarbonylbenzene (17 5) 4-methoxyphenyl (176) 4-anilinophenyl (177) 4-isobutylfluorenylaminophenyl φ (I78) 4 -phenoxycarbonylaminophenyl (179) 4 -(3-ethylureido) phenyl (180) 4- (3,3-diethylureido) phenyl (181) 4-methylphenyl (18 2) 4-phenoxyphenyl ( 183) 4-Hydroxyphenyl

[Chem. 16 • (184) phenyl (185) 4-ethoxycarbonylphenyl (186) 4-butoxyphenyl (187) p-biphenyl (18 8) 4-phenylthiophenyl ( 189) 4-chlorophenyl-26- 200526728

(190) 4-benzyloxyphenyl (191) 4 -ethynyloxyphenyl (192) 4-benzyloxyphenyl (193) 4-phenoxycarbonylphenyl (194) 4- Methoxyphenyl (195) 4-anilinophenyl (196) 4-isobutylfluorenylaminophenyl (197) 4-phenoxycarbonylaminophenyl (198) 4-(3-ethylureido ) Phenyl (199) 4- (3,3-diethylureido) phenyl (200) 4-methylphenyl (201) 4-phenoxyphenyl (202) 4-hydroxyphenyl 17] (203)-(221) RHV Y% N YN (203) phenyl (204) 4-ethoxyminylphenyl (205) 4-butoxyphenyl (206) p-biphenyl (207) 4-phenylthiophenyl (208) 4-chlorophenyl (209) 4-benzylphenyl

-27- 200526728 (210) 4-Ethyloxyphenyl (211) 4-benzyloxyphenyl (212) 4-phenoxycarbonylphenyl (213) 4-methoxyphenyl (214 ) 4-anilinophenyl (215) 4-isobutylfluorenylaminophenyl (216) 4-phenoxycarbonylaminophenyl (217) 4- (3-ethylureido) phenyl φ (218) 4-(3, 3 -diethylureido) phenyl · (219) 4 -methylphenyl (220) 4 -phenoxyphenyl (221) 4 -hydroxyphenyl

(222)-(419) R HN (222) phenyl # (223) 4-butylphenyl (224) 4- (2-methoxy-2-ethoxyethyl) phenyl (225) 4- (5-nonenyl) phenyl (226) p-biphenyl (227) 4-ethoxycarbonylphenyl (228) 4-butoxyphenyl (229) 4-methylphenyl- 28- 200526728 (23 0) 4 -chlorophenyl (231) 4-phenylthiophenyl (2 3 2) 4 -benzylidenephenyl (233) 4 -ethoxyphenyl (234) 4 -Benzyloxyphenyl (23 5) 4 -phenoxycarbonylphenyl (236) 4 -methoxyphenyl (237) 4 -anilinophenyl φ (238) 4-isobutyridinylaminobenzene (239) 4-phenoxycarbonylaminophenyl (240) 4- (3-ethylureido) phenyl (241) 4- (3,3-diethylureido) phenyl (242) 4-phenoxyphenyl (243) 4-hydroxyphenyl (244) 3-butylphenyl (2 4 5) 3-(2-methoxy-2-ethoxyethyl) benzyl • ( 246) 3-(5 -nonenyl) phenyl (247) m-biphenyl (248) 3 -ethoxycarbonylphenyl (249) 3 -butoxyphenyl (250) 3 -methylbenzene (251) 3-chlorophenyl (252) 3-phenylthiophenyl (253) 3-benzylidenephenyl-29- 200526728 (254) 3- Methoxyphenyl (25 5) 3 -benzyloxyphenyl (256) 3 -phenoxyminephenyl (25 7) 3 -methoxyphenyl (258) 3 -anilinophenyl (259) 3-isobutylfluorenylaminophenyl (260) 3-phenoxycarbonylaminophenyl (261) 3- (3-ethylureido) phenyl

(262) 3- (3,3-diethylureido) phenyl (263) 3-phenoxyphenyl (264) 3-hydroxyphenyl (265) 2-butylphenyl (2 6 6) 2- (2-methoxy-2-ethoxyethyl) phenyl (2 6 7) 2 · (5-nonenyl) phenyl (26 8) o-biphenyl (269) 2 -ethyl Oxyphenyl

(270) 2-butoxyphenyl (271) 2-methylphenyl (272) 2-chlorophenyl (273) 2-phenylthiophenyl (274) 2-benzylidenephenyl (275 ) 2 -ethoxyphenyl (276) 2-benzyloxyphenyl (277) 2 -phenoxycarbonylphenyl-30- 200526728 (278) 2 -methoxyphenyl (2 7 9 ) 2 -anilinophenyl (2 80) 2 -isobutylfluorenylaminophenyl (281) 2 -phenoxycarbonylaminophenyl (282) 2-(3-ethylureido) phenyl (283) 2- (3, 3-diethylureido) phenyl (2 8 4) 2 -phenoxyphenyl (2 85) 2-hydroxyphenyl

(286) 3,4-dibutylphenyl (287) 3,4-bis (2-methoxy-2-ethoxyethyl) phenyl (2 88) 3,4-diphenylphenyl (289) 3, 4-diethoxycarbonylphenyl (290) 3, 4-di-dodecyloxyphenyl (2 9 1) 3, 4-dimethylphenyl (292) 3, 4 -Dichlorophenyl (293) 3,4-dibenzophenylphenyl

(294) 3,4-Diethoxyphenyl (295) 3, 4-dimethoxyphenyl (296) 3, 4-Di-N-methylaminophenyl (297) 3, 4 -Isobutylfluorenylaminophenyl (298) 3,4-diphenoxyphenyl (299) 3, 4-dihydroxyphenyl (3 00) 3, 5-dibutylphenyl (301) 3, 5 -Bis (2-methoxy-2-ethoxyethyl) phenyl-31-200526728 (3 02) 3,5-diphenylphenyl (3 03) 3, 5-diethoxycarbonylbenzene (304) 3,5-di-dodecyloxyphenyl (3 05) 3,5-dimethylphenyl (3 06) 3,5-dichlorophenyl (3 07) 3,5- Dibenzyl phenyl (3 08) 3,5-diethoxyphenyl (3 09) 3,5-dimethoxyphenyl φ (3 10) 3, 5 -di-N -methyl Aminoaminophenyl (311) 3,5-diisobutylfluorenylaminophenyl (312) 3,5-diphenoxyphenyl (313) 3,5-dihydroxyphenyl (314) 2,4 -Dibutylphenyl (3 15) 2, 4-bis (2-methoxy-2-ethoxyethyl) phenyl (316) 2,4-diphenylphenyl (317) 2, 4 -Diethoxycarbonylphenyl • (318) 2, 4 -di-dodecyloxyphenyl # (319) 2,4-dimethylphenyl (320) 2, 4-dichlorophenyl ( 321) 2, 4- Benzamylphenyl (322) 2, 4-diethoxyphenyl (3 2 3) 2, 4-dimethoxyphenyl (324) 2, 4-di-N-methylamino Phenyl (325) 2, 4-diisobutyridinylaminophenyl-32- 200526728 (3 26) 2,4-diphenoxyphenyl (3 27) 2, 4-dihydroxyphenyl (3 2 8 ) 2, 3-monobutylbenzyl (3 29) 2,3-mono ^ (2-methoxy-2-ethoxyethyl) benzyl (3 3 0) 2, 3-diphenylphenyl (331) 2,3-monoethoxycarbylphenyl (3 3 2) 2,3-di-dodecyloxyphenyl (3 3 3) 2,3-dimethylphenyl φ (334 ) 2, 3-Dichlorophenyl (3 3 5) 2, 3-Dibenzyl phenyl (3 3 6) 2, 3-Diethoxyphenyl (3 3 7) 2, 3- Dimethoxyphenyl (3 3 8) 2, 3 -di-N-methylaminophenyl (3 3 9) 2, 3 -diisobutylfluorenylaminophenyl (340) 2,3-diphenyl Oxyphenyl (341) 2,3-dihydroxyphenyl • (342) 2,6-dibutylphenyl (343) 2,6- _. (2-methoxy-2-ethoxyethyl ) Phenyl (344) 2,6-diphenylphenyl (345) 2,6-monoethoxyfluorenylphenyl (346) 2, 6-di-dodecyloxyphenyl (347) 2, 6- Methylphenyl (348) 2,6-dichlorophenyl (349) 2,6-dibenzophenylphenyl-33- 200526728 (3 5 0) 2,6-diethoxyloxyphenyl ( 351) 2,6-dimethoxyphenyl (352) 2,6-di-N-methylaminophenyl (353) 2,6-diisobutylfluorenylaminophenyl (3 54) 2,6 -Diphenoxyphenyl (355) 2 ^ 6-dihydroxyphenyl (356) 3,4,5-tributylphenyl (357) 3,4,5-tri (2-methoxy-2 -Ethoxyethyl) phenyl • (3 5 8) 3, 4, 5 -triphenylphenyl (359) 3, 4,5-triethoxycarbonylphenyl (360) 3, 4, 5 -tri-dodecyloxyphenyl (361) 3,4,5-trimethylphenyl (3 62) 3,4,5-trichlorophenyl (3 6 3) 3,4,5- Tribenzylidenephenyl (3 64) 3,4,5-triethoxymethoxyphenyl (3 6 5) 3,4,5-trimethoxyphenyl • (3 66) 3, 4, 5 -Tri-N-methylaminophenylphenyl (367) 3, 4, 5-triisobutylfluorenylaminophenyl (3 68) 3, 4, 5-triphenoxyphenyl (3 69) 3, 4, 5-trihydroxyphenyl (3 70) 2, 4, 6-tributylphenyl (371) 2,4, 6-tri (2-methoxy-2-ethoxyethyl) phenyl (3 72) 2, 4, 6-triphenylphenyl (373) 2, 4 , 6-triethoxycarbonylphenyl-34- 200526728 (374) 2, 4, 6-tri-dodecyloxyphenyl (3 7 5) 2,4,6-trimethylphenyl (3 76) 2,4,6-trichlorophenyl (377) 2,4,6-tribenzylidenephenyl (378) 2, 4,6-triethoxyphenyl (3 79) 2, 4, 6-trimethoxyphenyl (380) 2, 4, 6-tri-N-methylaminophenyl (381) 2, 4, 6-triisobutylfluorenylaminophenyl (3 82) 2, 4,6-triphenoxyphenyl (383) 2,4,6-trihydroxyphenyl (3 84) pentafluorophenyl (3 8 5) pentachlorophenyl (3 86) pentamethoxybenzene (387) 6-N -methylamine ortho group-8 -methoxy-2-Zeyl (388) 5-N-methylaminosulfonyl-2-naphthyl (389) 6-N- Phenylaminesulfonyl-2-naphthyl (390) 5-ethoxy-7-N-methylaminesulfonyl-2-naphthyl # (391) 3 -methoxy-2 -naphthyl ( 3 92) 1-ethoxy-2 -naphthyl (393) 6-N-phenylaminesulfonyl-8-methoxy-2-naphthyl (394) 5 -methoxy-7-N- Phenylaminesulfonyl-2-naphthyl (3 95) 1-(4-methyl) -2 -naphthyl (3 96) 6, 8 -di-N -methylaminosulfonyl-2 -naphthalene (397) 6-N-2-Ethyloxyethylaminesulfonyl-8-methoxy-2-2-35-20052672 8 Naphthyl (398) 5 -Ethyloxy- 7- N-phenylaminesulfonyl-2-naphthyl (3 99) 3 -Benzyloxy-2 -naphthyl (400) 5 -ethyl Fluorenylamino-1 -naphthyl (401) 2 -methoxy-1 -naphthyl (402) 4 -phenoxy-1 -naphthyl (403) 5 -1 ^ -methylaminesulfonyl- 1-naphthyl (4 04) 3 -N-methylaminomethylamidino-4 -hydroxy-1 -naphthyl (405) 5-methoxy-6-N-ethylaminesulfonyl-1-naphthalene (406) 7-tetradecyl-1-naphthyl (407) 4- (4-methylphenoxy) -1-naphthyl (408) 6-N-methylaminesulfonyl-1 -Naphthyl (409) 3 -N, N-dimethylaminomethylmethyl-4-methoxy-1-naphthyl (410) 5-methoxy-6-N-benzylaminosulfonyl 1-naphthyl (411) 3, 6-di-N-phenylaminesulfonyl-1-naphthyl (412) methyl (413) ethyl φ (414) butyl (415) octyl (416 ) Dodecyl (417) 2-butoxy-2-ethoxyethyl (418) benzyl (419) 4-methoxybenzyl-36- 200526728

(424) methyl (425) phenyl (426) butyl -37- 200526728 (chemical 2 2) (427) (428) (429)

(Hua 23)

(430)-(437) R R

(43 0) methyl (431) ethyl (432) butyl (43 3) octyl (434) dodecyl (435) 2-butoxy-2-ethoxyethyl (43 6) benzoyl Group # (43 7) 4 -methoxybenzyl-38- 200526728 [Chem. 24]

(Hua 25)

-39- 200526728 〔Chem 26〕

The substance represented by the general formula (I) can also be synthesized by using a melamine polymer represented by the following formula (IA). Yes, the combination of 3,5 -trinitrogen trap rings. The melamine polymer is preferably a polymer compound and a carbonyl compound.

In the formula, R, R, R13, R14, R] 5 and R] 6 each independently represent a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, or a composite ring group. The definitions and substituents of the above-mentioned alkyl group, alkyl group, aryl group, and composite ring group are the same as the definitions and substituents of each group described in the above formula (1). The polymerization reaction of the melamine compound and the carbonyl compound is the same as the synthesis method of a general melamine resin (such as a melamine formaldehyde resin). Commercial grade melamine polymers (melamine resins) can also be used. The molecular weight of the melamine polymer is preferably from 2,000 to 400,000. Examples of repeating units of the melamine polymer are shown below. -40- 200526728 〔Chem 2 8〕 (MP-1HMP-50)

MP — 1 MP — 2 MP- 3 MP- 4 MP- 5 Μ P — 6

mj 1 1} 1 1 RRRRRR 5 5 5 5 5 5 1 mj u 1 TJ RRRRRR 4 4 4 4 4 4 1 ij 1 1 mj 1X RRRRRR CH2OH CH2OCH3 CH2O + C4H9 CH2〇-n ~ C4H9 CH2NHCOCH = CH2 CH2NHCO (CH2) ? CH = CH (CH2) 7CH3

MP-7 Ri ^ Ri5: CH2OH; R16: CH2〇CH3 MP — 8: R! 3, Ri4, Ri6: cH2〇H; Ri5: CH2〇CH3 MP — 9: R] 3, Ri4: CH20H; Ri5, R ] 6: CH2〇CH3 MP — 1 0: R] 3, R] 6: CH2〇H; RW, R15: ch2 0 CH3 MP — 1 1: R] 3: CH20H; R] 4, R15, .ri6: ch2〇CH3 MP— 1 2: RW, Rm, rj6: ch2OCH3; R] 5: CH2〇H MP—1 3: R] 3, R] 6: cH2〇CH3; R] 4, R] 5: CH20H 4 5 6 7 8 9 0 I—i 1 · —1 1 ~ I i ~ i 1 OQ IIII II I ppppppp

: K] 3, RM, RJ5: CH2〇H; R] 6: CH2〇 + C4H9: R] 3, R] 4, R16: CH20H; R15: CH20-i-C4H9: R! 3, rm: cH2. H; R] 5, R16: CH2〇-i-C4H9: R] 3, R! 6: ch20H; R] 4, R] 5: CH2〇-i-C4H9: R] 3: cH2〇H; R] 4.Ru, ri6: CH2〇 + C4H9: R] 3, R] 4, r! 6: ch2 (H-C4H9; R15: CH2〇H: R] 3, r] 6: ch2 (H-c4H9; R ] 4, R] 5: CH2OH MP — 2 1 MP- 2 2 MP — 2 3 MP- 2 4 MP- 2 5 MP- 2 6 MP — 2 7 MP- 2 8 Μ P — 2 9 Μ P-3 0 Μ P-3 1 Μ P — 3 2 Μ P — 3 3 Μ P-3 4 Μ P — 3 5 Μ P — 3 6 Μ P — 3 7

R] 3, R14, R] 5: CH2〇H; R] 6: CH2 (Hl-C4H9 R] 3, RM, r] 6: Ch2〇h; R] 5: ch20-n-UH9 R] 3, R] 4: cH20H; R] 5, R] 6: CH20-iH: 4H9 R] 3, R] 6: ch20H; R] 4, R] 5: CH2〇-h-C4H9 R] 3: CH2〇H ; R] 4 'R] 5, R] 6: CH2〇-n-C4H9 R] 3, R] 4, R] 6: CH2〇-n-C4H9; R] 5: CH2〇H Ri6; CH20-n -C4H9; R] ^ R15: CH20H: R] 3, R] 4: R] 3, R14: KA R16: R] 3 CH20H: R] 5 CH20H; R] 5 CH2〇H; R ^ CH2〇H; R] 4 'R] 5 CH20H; R] 4, R] 6 CH2〇CH3; R] 6: CH2 (Hi-C4H9 CH2〇-nC Meaning: R] 6: CH20CH3 R] 5: CH2CH] -C4H9 R] 6: CH2 (HHUH9 RJ5: CH20-n-CziH9

CH2OCH3 CH2OCH3: R] 3: CH2〇H; R] 4, R] 6: CH2〇CH3: R ^; CH2OH; R ^: CH2〇CH3; R15 > R16: CH20-nC, jH9: R] 3: CH2 〇H; P4, RI5: CH2 (Hi-bH9; R) 6: CH2〇CH3: RJ3, Rh; ch2OCH3; Rj5: CH2〇H; R ^: CH2〇-] K < iH9: R] 3, R] 6: CH2〇CH3: Rw: CH2〇H; R] 5: CH2〇-n-C4H9: RJ3: CH2〇CH3; R ^ > RJ5: CH2〇H; RJ6: CH2〇-nC, jHg -41- 200526728 Μ P — 3 8 Μ P-3 9 MP- 4 0 Μ P-4 1 Μ P — 4 2 Μ P ~ 4 3 Μ P-4 4 Μ P — 4 5 CH2 MP — 4 6 CHa MP — 4 7 CHa MP-4 8: CH2 MP ~ 4 9 CHa MP — 5 0 ·· CHa R 丨 3, R! 6. CH2O-: CH2OCH3; R] 5: CH2OH CH2OCH3; R3 5: CHaO-nC ^ Hs; RJ 6: CH2NHCOCH = CH2 CH2〇CH3; K15: CH2NHCOCH = CH2; R16: CH2〇-Ji * O ^ 9 ΓΗ〇ϋΗ · Λ- CH2〇 ^ C4H9; RJ5: CH2NHCOCH = CH2; R16: CH2〇CH3 · R14 · R14 · CH2OH; R15: CH2 [Hi-C4H9; R] 6: CH2NHC0CH = CH2 t = CH3: R] 4: CH2〇H; R] 5: C_HC0CH = CH2; R] 6: CH20t C4H9 CH2 (H) -kH9; K] 4: CH2OCH3; Ris: CH2〇H; R] 6: CH2NHCOCH = CH2: Ri3; CH2OH; RJ4: CH2〇CH3; RJ5: CH2NHCO (CH2) 7CH = CH (CH2) 7CH3; R16: CH2NHC0 CH =: R13; CH20H; R14: CH20CH3; R15: CH2NHC0CH = CH2; R16: CH2NHC0 (CH2)? CH-CH (CH2) 7: Ri3; CH2〇H; R14: CH2NHCO (CH2)? CH = CH (CH2 ) 7CH3: R15: CH2NHCOCH = CH2; R16: CH2; Ri3: CH2OCH3; R14: CH2OH; R15: CH2NHCO (CH2)? CH = CH (CH2) 7CH3; R] 6: CH2NHC0CH =: R13: cH2OCH3; Rh : CH2〇H; RJ5: CH2NHCOCH = CH2; R16: CH2NHCO (CH2) 7CH = CH (CH2) 7 R13; CH2NHC0 (CH2) 7CH = CH (CH2) 7CH3; RI4: CH2〇CH3; R15: CH2〇H; Rj6: CH2NHCOCH = R13 R13 R13 RI3 R] 3 R] 3 ch2oh; k] 4 ch2〇h; k] 4 ch2oh; r] 4 29] (MP-5I)-(MP-100)

MP— 5 1 MP— 5 2 Μ P — 5 3 Μ P — 5 4 MP— 5 5 MP ~ 5 6

--I 1% J 1 I * 1 R R R R R R

mj 1J mj u 1 1 R R R R R R 4 4 4 4 4 4 mj J 1 1 1 R R R R R R

J u J 1 1J Ti R R R R R R CH2〇H CH20CH3 CH20-I-C4H9 〇Η2〇 ~ π " 〇4Η9 CH2NHC0CH = CH2 CH2NHC0 (CH2)? CH = CH (CH2) 7CH3

MP-5 7: Ri3, Ri5: CH2〇H; R16: CH2〇CH3 MP— 5 8: R] 3, R] 4, R] 6: cH2 OH; R15: CH2 0 CH3 MP— 5 9: R ] 3, R] 4: CH2〇H; R] 5, R] 6: CH2〇CH3 MP-6 0: R] 3, R] 6: CH2〇H; R] 4, R] 5: CH2〇CH3 MP— 6 1: R] 3: CH20H; R] 4, R] 5, R16: CH2〇CH3 MP— 6 2: R] 3, R] 4, r16: CH2〇CH3; r] 5: CH2〇H MP- 6 3: K] 3, R] 6: ch2〇ch3; Rh, Rj5: CH2〇H MP-6 4: R13, R] 4, R] 5: ch2OH; R] 6: CH2〇-Bu LH9 MP-6 5 R16: CH2〇H; R15: CH2〇-i-C4H9 MP-6 6: R13, R] 4: CH2〇H; R] 5, R] 6: cH2〇-Bu C4H9 MP-6 6 7 : R] 3, Ri6: CH2〇H; R] 4, R] 5: CH2〇-Bu C4H9 MP-6 6: R] 3: CH2〇H; R] < i, κ] 5, r] 6 : cH2〇-Bu Cdb -42- 200526728 MP-6 9: Ri3, r14, RJ6.CH2〇 + c4H9; Ri5: CH2〇] ·]

MP_7 0: R] 3, r] 6: CH2〇-Bu C4Hg; RH, Ri5: CH2 0H MP-7 1: R] 3, rm, r] 5.CH2 0h; Ri6: cH2 (HK4H9 MP- 7 2 RM ^ R16: CH2〇H; R, 5: CH2〇-n-C4H9

MP — 7 3: R] 3, Ri4: cH2〇H; R15, R16: CH2 0-n-C4H9 MP_7 4: R] 3, r] 6: ch2 0H; R] 4, R] 5: CH2. -n-C4H9 MP-7 5: R] 3: CH2〇HR] 4, R15, R16: CH2 (H) -C4H9 MP-7 7: R] 3, R] 4, 'R] 6.CH2〇_ n_C4H9; R] 5: CH2〇H MP-7 7: R] 3, r16: CH2 (H) _C4H9; Ri4, ri5: CH2〇H MP-7 8 Ri4: cH2〇H; Ri5: cH2〇CH3; R16 : CH2〇-n-C4H9 MP-7 9 RM.cH2OH; R15: CH2〇-n-C4H9; R16-CH2〇CH3

MP—8 0: R] 3, R16.CH2〇h: Ri4: CH2〇Ch3; R15: CH2 (Hi-C4H9 MP-8 1: R13: CH2〇H-Ri ^ Ri5: CH2〇CH3; R16: CH2 〇-n-C4H9 MP-8 2: R13: CH2〇H; R ^, Ri6: CH2〇CH3; R15: CH2〇 ~ n ~ C4H9 MP-8 3 *. R13: CH2〇H; Ri4: CH2〇CH3 R15 > R36: CH2〇-n-C4H9 MP-8 4: RJ3: CH2〇H-Ri ^ RJ5: CH20-n-C4H9; RJ6: CH2〇CH3 MP-8 8: R] 3, Ri4jH2〇CH3; K] 5: CH2〇H; R16: CH2〇-n-C4H9 MP-8 6: R] 3, R16: CH2〇CH3; R] 4: CH2〇H; Ri5: cH2 (HH: 4H9 MP-8 7 : R13: CH2〇CH3; R14 >Ri5;cH2〇H; R16: CH2〇-n-C4H9

MP-8 8: Rj3> Ri6: CH2〇 >n-c4H9; R14: CH2〇CH3; R15: CH2〇H MP-8 9: K13: CH2〇H; R ^: CH2〇CH3; R15: CH2 -n-C4H9; RJ6: CH2NHCOCH = CH2 MP-9 0: R13: CH2〇H; Ri4: CH2〇CH3; R15: CH2NHCOCH = CH2; RJ6: CH2〇-n-C4H9 MP-9 1: R13: CH2. H; RJ4: CH2〇-n-C4H9; R15: CH2NHCOCH = CH2; R16: CH2〇CH3 MP-9 2: R13: CH2〇CH3; R34: CH2〇H; R] 5: CH2〇 ~ n-C4H ' 9; R16: CH2NHCOCH = CH2 MP-9 3: K13; CH2〇CH3; R ^: CH2〇H; R15: CH2NHCOCH = CH2; R16: CH2〇-n-C4H9 MP ^ 9 4: Ri3: CH2〇_n .C4Hg; R] 4: cH2OCH3; R15: CH2OH; R16: CH2NHCOCH = CH2 MP-95: Ri3: CH2OH; RJ4: CH2OCH3; R15: CH2NHCO (CH2)? CH-CH (CH2) 7CH3; R16: CH2NHC0CH = CH2MP-96: R13: CH2OH; R ^: CH2OCH3; R15: CH2NHCOCH = CH2; R16: CH2NHCO (CH2)? CH = CH (CH2) 7 CH3 UP-9 7: R13: CH2OH; R ^: CH2NHCO (CH2) 7CH = CH (CH2) 7CH3; R15: CH2NHCOCH = CH2; R16: CH2.

ch3 MP— 9 8: R13: CH2〇CH3; R] 4: CH2〇H; Ri5: CH2NHCO (CH2) 7CH = CH (CH2) 7CH3; R] hCH2NHCOCH = CH2 MP ^ 9 9: Ri3: CH2〇CH3; R14: CH2〇H; R ^: CH2NHCOCH = CH2; R16: CH2NHCO (CH2) 7CH = CH (CH2) 7 ch3

MP-1 0 0: R13: CH2NHC0 (CH2) 7CH = CH (CH2) 7CH3; R14: CH2〇CH3; R15: CH2〇H * Ri6 * CH2NHC0C h = ch2 * -43- 200526728

pppppp MMMMM M 12 3 4 5 6 000000 i—_ 1 1—_ 1—i one ~ _ 1

6 6 6 6 6 6 1) 1Λ 1 1i u RRRRRR 5 5 5 5 5 5 1 1i-1J 2 1 RRRRRR 4 4 4 4 4 4 mj lx 11 TJ 3 mj RRRRRR rrrrf, 3 3 3 3 3 3 1 1 1 1 li 1 RRRRRR CH2OH CH2OCH3 CH2O-i-C4H9 CH2〇 ~ Tl ~ C4H9 CH2NHCOCM2 CH2NHC0 (CH2) 7CH = CH (CH2) 7CH3

MP- 1 MP — 1 MP — 1 MP- 1 MP — 1 MP— 1 MP-1 12 3 4 5 6 7 2 2 2 2 2 2 2 MP— 10 7 ..R13, R14, r] 5: ch2OH; R16: CH2〇CH3 MP— 1 0 8: rm, k] 6: CH2 0H; R15: CH2 0 CH3 MP— 1 0 9: M3, r] 4: cH2 0H; R] 5, R] 6: ch20CH3 MP-1 10: R] 3, R16: Ch2〇H; Rh, R] 5: cH2〇CH3 MP-1 1 1: R13: ch2〇H; R] < », R] 5, RM: CH2 〇Ch3

MP-1 12: R] 3, R] 4, Ri6: ch2〇CH3; R] 5: CH2〇H MP-1 1 1: RU, ri6: Ch2〇CH3; Rm, r] 5: Ch2〇H

MP-1 14: Rn, R] 4, p5: CH2OH; Ri6: CH2〇 + C4H9 MP-1 1 5: R] 3K R] 6: ch2OH; R] 5: CH2 0-Bu C4H9 MP-1 1 1 6 : R] 3, Rm: ch2〇H; R] 5, R] 6: CH20-i-C4H9 MP-1 17: R] 3, r] 6: CH2 0h; r] \ R] 5: CH2. -i-C4H9 MP— 1 1 8: R] 3: CH2〇H; Rj4, R] 5, R] 6: CH20-i-C4H9 MP — 1 1 9: R] 3, Ri4, ri6: ch2〇- Bu C4H9; R] 5: CH2〇H MP-1 2 0: RU, R16: ch2〇 + C4H9; R14, R] 5: CH2〇HK] 3, R] (R) 5: CH2〇H; R] 6: CH2 (Hl-C4H9 R) 3, R] 4, R16: CH2 OH; R] 5: CH2 (Hl-C < lH9 R] 3, RH: CH2 0H; Ri5, R] 6: ch20- n-C4H9 Ris, RJ6: CH2〇H; Ri ^ RJ5: CH20-n-C4H9 R] 3: CH20H; R] 4, R] 5, R] 6: ch2〇-n-C4H9

RU, Rw, r] 6: ch2〇ten C4H9; R15: CH2〇H

R] 3, R] 6: CH2 (Hi_C4H9; R14, R] 5: CH2〇H MP-1 2 8: R] 3, R] 4: ch2〇H; R] 5: CH2〇CH3; R] 6 : CH2 (H) -C4H9 MP—1 2 9: R! 3, Rh: ch2〇H; R] 5: CH2CHi-C4H9; R] 6: CH2〇CH3 MP— 1 3 0 ·· K] 3, R ] 6: CH2〇H; R] 4: CH2〇CH3; RJ5: CH2〇tC4H9 MP-1 3 1: R] 3: CH2〇H: Rm, R] 5: CH2〇CH3: K] 6: CH2tH] -C4H9 MP— 1 3 2: R] 3: CH2〇H; R] 4, R] 6: CH2〇CH3; R] 5: CH2 (Hi-C4H9 MP— 1 3 3: R] 3: CH2〇H ; R] 4: CH2〇CH3; K] 5, R] 6: CH2 (Hi-C < jH9 MP— 1 3 4: RU: CH2〇H; R] \ R] 5: CH2〇-ibu LH9; R] 6: CH2〇CH3 MP — 1 3 5: R] 3, Rm: ch2〇CH3: R] 5: CH2〇H; R] 6: CH2〇-n-CdlfD MP— 1 3 6: R] 3 , Ri6: CH2〇CH3; R14: CH2〇H: R] 5: CH2 (Hb Cd9 MP-1 37: R] 3: CH2 0 CH3: R] 4, R] 5: CH2 0 H: R] 6: CH2〇- 11-WI9 -44- 200526728 MP— 1 3 8: RJ3, R]

6.rH, 〇 ^ C, H9; R14--CH2〇CH3; R ^: CH2〇H

ppppp p MMMMMM u 1 1J —J 1- 1 > RRRRRR 9 0 12 3 4 3 4 4 4 4 ΓΗ ΠΗ.rM · CH2OCH3; R] 5: CH2〇-n-C4H9; R16: CH2NHC0CH = CH2 γη! πη · Ii ^; CH2OCH3; R15: CH2NHC0CH = CH2; R ^: CH20-11-C4H9 ΓΗ ^ ΩΗ: R ^: CH2〇 ^ -C4H9; R15: CH2NHCOCH = CH2; RJ 6: CH2OCH3 rH9〇CH, · CH2OH ; R15: CH20-n-C4H9; 6: CH2NHCOCH = CH2 CH2〇CH3: R ^: CH2〇H; R15: CH2NHC0CH = CH2; Ri ^ -CH2〇 ^ C4H9 CH2〇-h-C4H9 * R14: CH2OCH3; R15 : CH2OH; RJ 6: CH2NHC0CH = CH2

MP ~ 1 H = CH2 MP— 1) tCH3 MP-1 2OCH3 MP- 1 M2 MP — 1)? CH3 MP — 1 H = CH2

4 5: R) 3; ch2OH; R ^: CH2〇CH3; Rj5: CH2NHCO (CH2) 7CH = CH (CH2) 7CH3; R16: CH2NHCOC 4 6: R13; CH20H; R ^: CH20CH3; R15: CH2NHC0CH = CH2 ; R16: CH2NHC0 (CH2) 7CH = CH (CH2 4 7: R) 3: CH20H: R] 4: CH2NHC0 (CH2) 7CH = CH (CH2) 7CH3; R] 5: CH2NHC0CH = CH2; R16: CH 4 8 : R13: CH2〇CH3; R ^: CH2〇H; R ^: CH2NHC0 (CH2) 7CH = CH (CH2) 7CH3; RJ6: CH2NHC0C 4 9: R13: CH2〇CH3; R ^: CH2〇H; Ri5: CH2NHCOCH = CH2; R16: CH2NHCO (CH2) 7CH = CH (CH2 5 〇: RU: CH2NHC0 (CH2) 7CH = CH (CH2) 7CH3; R14: CH2OCH3; R] 5: CH2OH; R] 6: CH2NHCOC 31 (MP-151HMP-200)

J 1 J 3 u JRR υη RRR 5 5 5 5 5 5 J 1 1] 1 JRRRRRRJ 1 u 1 —i 1 RRRRRR 3 3 3 3 3 3 -J 1 3 1 * i 1 RKRRRR 12 3 4 5 6 5 5 5 5 5 5 CH2OH CH2OCH3 CH2〇-i ~ C < iH9 CH2O-H-C4H9 CH2NHC0CH = CH2 CH2NHCO (CH2) 7CH = CH (CH2) 7CH3

P -P — P — 15 7 1 5 8 15 9 16 0 16 1 16 2 16 3

: Hs Jl5: CH2〇H; R ^: CH2〇CH3: i] 3, 5M, nR16: CH20H: R] 5: CH20CH3: 5) 3, L .: J? 2〇H: R] 5, R] 6: CH2〇CH3: L'r5 nuCS2〇H; R14 'R35-CH2〇CH3 r] 5, r] 6: CH2〇CH3: L'? 16 'fl6: CH2OCH3; R15: CH2〇H

ppppp MMMM M 6 5 6 5 6 RRRRR Η H 、, 0 0 5 4 5 2 2 JJ i-Η HRRK c rv · ·: :: Η H ， 5 6 πυ nv] J 2 2 3 RR Η HR cc; \% ·· · · nn o J tj J 1J RRRRH c 3 3 3 3 3 RRR RRJ 4 5 6 7 8 6 6 6 6 6 邙 2〇- 卜葛 CkO + C 』9 CH2O-bu. Qu CH20-i ^ H9 CH2〇-i ^ < jH9-45- 200526728 pp PPPPPPP Μ Μ Μ Μ Μ Μ Μ Μ ρρρρρρρρρρρρΜΜΜΜΜΜΜΜΜΜΜΜΜΜ

1 6 9: RJ3, Ri4% Rj6: cH2〇-i-C <iH9; RJ5: CH2〇H

1 70: R] 3, r] 6: cH2 0—Bu C4H9; Rm, R] 5: CH2 0H 1 7 1: R] 3, rm, Ri5: CH2 0H; R] 6: CH2 0-n -C4H9 1 72: R] 3, RM, R] 6: cH2〇H; R] 5: CH2〇-n-C4H9 1 73: R! 3, ru: ch2〇H; R] 5, R] 6: CH2〇-n-C4Hs 1 74 ri6: ch20H; R] 4, R] 5: CH2〇-n-C4H9 1 75: R] 3: CH20H: R] 4, Ris, Ri6: CH2 (Hi-C4H9

176: RJ3% Ri4% Ri6: cH20-n-C4H9; R15: CH2〇H 1 77: R] 3, R] 6: CH2〇-n-C4H9; R] 4, R] 5: CH2〇H 1 78 : R] 3, RM: CH2〇H: R] 5: CH2〇CH3; R] 6: CH2〇-n-C4jj9 179: Ri3, ri4: ch2〇H; R15: CH2〇 "H-C4H9; R16 : CH2〇CH3 1 8 0: Ri3% Ri6; cH2OH; R34: CH2〇CH3; RJ5: CH2〇-n-C4H9 181: R] 3: CH2 0H; R] 4, R] 5: CH2 0 CH3; R] 6: CH2〇-n-C4H9 182: Ri3; CH20H; R ^, Rie: CH2〇CH3; EJ5: CH2〇-n-C4H9 183: Ri3: cH2〇H; R] 4: CH2〇CH3; R15 , Li) 6: CH2 (Hi-C4H9 1 84: R) 3: CH20H; R] 4, Ri5: CH2〇-]]-C4H9: Ri6: CH2〇CH3

1 8 5: Ri3, Ri4; cH2OCH3; R15: CH2〇H; R16: CH2〇-n-C4H9 186: RJ3% RJ6: cH2OCH3; R14: CH2〇H; R15: CH2〇-n-C4H9 1 87: Ri3 : ch2〇CH3; R] 4, R] 5: CH2OH; R] 6: CH2〇-n-C4H9 1 8 8: RJ3> RJ6: cH20-n-C4H9; R14: CH2〇CH3; R15: CH2〇H ρ ρ ρ ρ ρ ρ ΜΜΜΜΜΜ 9 0 12 3 4 8 9 9 9 9 9

JJJ mj J ΊΛ RRRRRR CH2〇H; R ^: CH2〇CH3; RJ5: CH2〇-n-C4H9; RI6: CH2NHCOCH = CH2 CH2OH; R14: CH2OCH3; R15: CH2NHC0CH = CH2; R] 6: CHzO-nC ^ Hg CH2OH; R] 4: CH2〇-n-UH9; R15: CH2NHC0CH = CH2; R] 6: CH2OCH3 CH2〇CH3; R] 4: CH2〇H; R] 5: CH2〇-n- (UH9; R16 : CH2NHCOCH = CH2 CH2OCH3: R] 4: CH2OH; R] 5: CH2NHC0CH = CH2; R16: CH2O-11-C4H9 CH2〇-n-C4H9; R14: CH2〇CH3; R15: CH2〇H; R16: CH2NHCOCH = CH2

MP ~ 1 9 5: Ri3: CH2〇H; R ^: CH2〇CH3; R15: CH2NHCO (CH2) 7CH = CH (CH2) 7CH3; K16: CH2NHCOC h = ch2 MP-1 9 6: R13: CH20H; R ^: CH20CH3; RJ5: CH2NHC0CH = CH2; R36: CH2NHC0 (CH2) 7CH = CH (CH2) 7CH3 MP— l 9 7: K] 3: cH2〇H; R] 4: CH2NHCO (CH2) 7CH = CH (CH2 ) 7CH3; R) 5: CH2NHCOCH = CH2; Ri6: CH 2OCH3

MP— 1 9 8: R] 3: CH2〇CH3; Rw: CH2〇H; R] 5: CH2NHCO (CH2) 7CH = CH (CH2) 7CH3: R] 6: CH2NHCOC h = ch2 MP— 1 9 9: R] 3: CH2OCH3; R] 4: CH2〇H: R] 5: CH2NHCOCH = CH2: Rj6: CH2NHCO (CH2) 7CH: CH (CH2)? CH3

MP- 2 0 0: R] 3: ch2NHCO (CH2) 7CH = CH (CH2) 7CH3; R] 4: CH2〇CH3; R] 5: CH2〇H; K] 6: CH2NHCOC h = ch2 Combinations can also be used A copolymer of two or more repeating units. It is also possible to use two or more homopolymers or copolymers. It is also possible to use two or more compounds having a 1,3,5-triazine ring represented by the general formula (I) described above. Two or more discoid compounds (for example, a compound having a 1,3,5-triazine ring and a compound having a porphyrin skeleton represented by the above general formula (I)) can also be used. 200526728 Next, the compounds represented by the general formula (II) used in the present invention will be described in detail as follows. General formula (π) [Chemical 3 2]

In the above general 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, ethyl, propyl, and isopropyl). , Butyl, pentyl, isopentyl); particularly preferred is 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).乂 21 is preferably selected from the group consisting of: a single bond, a 0—, a CO—, an alkylene (preferably 1 to 6 carbon atoms, more preferably 1 to 3, for example: methylene, Ethyl, propyl), or aryl (preferably 6 to 24 carbon atoms, more preferably 6 to 12. For example: phenylene, phenylene, and naphthyl) A divalent linking group formed by one or more of these groups; particularly preferred is a divalent linking group formed by one or more groups selected from the group consisting of: 10-, alkylene, or arylene. Y21 is a hydrogen atom or an alkyl group (preferably one having 2 to 25 carbon atoms, and more preferably 2 to 20. For example: ethyl, isopropyl, tertiary-butyl, hexyl, 2-ethyl Hexyl, tertiary-octyl, dodecyl, cyclohexyl, dicyclohexyl, adamantyl), -47- 200526728 aryl (preferably 6 to 24 carbon atoms, more preferably 6 to 1 8 For example: phenyl, biphenyl, bitriphenyl, naphthyl, or aralkyl (preferably those having 7 to 30 carbon atoms, more preferably 7 to 20). For example: benzyl Group, cresol group, tertiary-butylphenyl group, diphenylmethyl group, triphenylmethyl group): Particularly preferred is an alkyl group, an aryl group, or an aralkyl group. The combination of —X21-Y21, preferably a total of X21 — γ21 has a carbon number of 0 to 40 ′, more preferably 1 to 3 0, and particularly preferably 1 to 2 5 °. These general formulas (II) Preferred examples of the represented compounds are shown below, but the present invention is not limited to these specific examples

-48- 200526728

-49- 200526728 〔Chem 34〕

PL-28 PL-29 PL-30 PL-3 1 〇

Next, the compounds represented by the general formula (III) used in the present invention will be described in detail below. Formula (III) -50- 200526728 [Chemical 3 5] 0 R33

1 I R31-S-N-R32 0 In the above general 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 R, R, and R3 3 is 10 or more. Substituent groups are preferably a fluorine atom, an alkyl group, an aryl group, an alkoxy group, a sulfonic acid group, I, and a sulfonyl group; particularly preferred are an alkyl group, an aryl group, an alkoxy group, a sulfonyl group, and a sulfonyl group. In addition, the college system can be linear, branched, or cyclic. The number of carbon atoms is preferably 1 to 25, more preferably 6 to 25, and particularly preferably 6 to 20 (for example: methyl, Propyl, propyl, isopropyl, butyl, isobutyl, tertiary-butyl, pentyl, isopentyl, tertiary-pentyl, hexyl, cyclohexyl, heptyl, octyl, bicyclooctyl, Nonyl, adamantyl, decyl, tertiary-octyl, undecyl, twelve, thirteen, fourteen, fifteen, sixteen, seventeen, eighteen, nineteen Base, didecyl). Aryl is preferably 6 to 30 carbon atoms, particularly 6 to 24 (eg, phenyl, biphenyl, bitriphenyl, naphthyl, binaphthyl, triphenylphenyl) . R31 and R32 series can also be connected to each other to form a ring. In addition, the amount of the modifier to be added in the present invention is preferably 2 to 30% by mass, more preferably 2 to 25% by mass, and particularly preferably 2 to 20% by mass relative to the tritiated cellulose. Hereinafter, preferred examples of the compound represented by the general formula (III) will be described below -51-200526728, but the present invention is not limited to these specific examples. (Chemical 3 6) P〆

-52- 200526728 〔Chemical 3 8〕

A—3 0 Next, the compounds represented by the general formula (IV) used in the present invention will be described in detail as follows: General formula (IV) • 53- 200526728 [Chemical 40] r4〇 42 / R50, 42 R60

[In the formula, X42 represents B, C— (R7〇 represents a hydrogen atom or a substituent), N, P, or P = 0. R40, r50, and r6G each independently represent an aryl group (such as phenyl), a cycloalkyl group (such as cyclohexyl), or a composite ring group (such as 4-pyridyl). The composite ring base system may have a substituent on the ring. R4G and R5G can also be connected to each other to form a __ ring. 〕. The compound of the above general formula (IV) used in the present invention is preferably a compound represented by the following general formula (IVA): General formula (IVA) [Chem. 40-1]

[In the formula, X42 represents B, C — R7 () (R70 represents a hydrogen atom or a substituent.), N, P, or p = 0. r41, R42, R43, R44, R45, R51, -54- 200526728

R 5 2

R 5 3 5 4

R 5 5 6 1

R 6 2

R 63 and R65 each independently represent a hydrogen atom or a substituent. If possible, the two groups R4! ~ R65 φ & above (for example, R41 and R51) can also be connected to each other to form a ring. 〕. In the general formulae (IV) and (IVA), X42 represents b, c — R7〇 (r70 represents a hydrogen atom or a substituent.), N, P, P = 〇; χ42 is preferably β, c-rm ( R7Q is preferably: aryl, substituted or unsubstituted amine,

Oxo, oxo, fluorenyl, oxo, aryloxy, oxo, oxo, oxamido, alkoxycarbonylamino, aryloxycarbonylamino, sulfoamido, meridian , Hydrogen thio group, halogen atom (such as fluorine atom, chlorine atom, molybdenum atom, iodine atom), carboxyl group; more preferably aryl, alkoxy, aryloxy, meridian, halogen atom; more preferably, it is a hospital Oxygen and hydroxy are particularly preferred. ), N, P = 〇; further more preferred are c- R7G, N; and particularly preferred are R7〇R4i, R42, R43, R44, R45, R5〗, R52, r53, r54, r55, R6 1, R62, r63, R64, and R65 represent a hydrogen atom or a substituent, and the substituent T described later can be applied. R41, R42, R43, R44, r45, r51, R52, R53, R ", R", and R. , R63, R "and r65 are preferably: φ alkyl, alkenyl, alkynyl, aryl, substituted or unsubstituted amine, alkoxy, aryloxy, fluorenyl, alkoxycarbonyl, Aryloxycarbonyl, fluorenyloxy, sulfonylamino, alkoxycarbonylamino, aryloxycarbonylamino, sulfonamido, sulfamomidino, carbamoyl, alkylthio, arylthio, sulfonamido Group, sulfenyl group, urea group, phosphoamidino group, hydroxyl group, hydrogen thio group, halogen atom (such as fluorine atom, chlorine atom, bromine atom, iodine atom), cyano group, sulfonic acid group, carboxyl group, nitrate Group, hydroxamic acid group, sulfinyl group, hydrazino group, imine-55-200526728 group, heterocyclic group (preferably 1 to 30 carbon atoms, more preferably 1 to 12, The heteroatom system includes, for example, a nitrogen atom, an oxygen atom, and a sulfur atom. Specifically, the system includes, for example, imidazolyl, pyridyl, quinolinyl, furyl, piperidinyl, benzo Df, oxazolyl, and N-morpholino. Benzoflfazolyl, benzimidazolyl, benzothiazolyl, etc.), silyl; more preferably alkyl, aryl, substituted or unsubstituted amine, alkoxy, aryloxy Is more preferably an alkyl group, an aryl group, or an alkoxy group. These substituents may be further substituted. In addition, if there are two or more substituents, they may be different. If possible, they may be different. They are connected to each other to form a ring. The aforementioned substituent T is described below. The "substituent τ" includes, for example, "alkyl" (preferably, the number of carbon atoms is 1 to 20, and more preferably the number of carbon atoms It is 1 ~ 12, and it is particularly preferable that the number of carbon atoms is 丨 ~ 8, including, for example, methyl, ethyl, isopropyl, tertiary-butyl, n-octyl, n-decyl, n-ten Hexyl, cyclopropyl, cyclopentyl, cyclohexyl, etc.); "flammable" (preferably 2 to 20 carbon atoms, more preferably 2 to 12 carbon atoms, particularly preferred is The number of carbon atoms is 2 to 8, including, for example, vinyl, aryl, 2-butenyl, 3-pentenyl, etc.); "alkynyl" (preferably 2 to 20 carbon atoms, More preferably, the number of carbon atoms is 2 to 12, particularly preferably, the number of carbon atoms is 2 to 8, including, for example, propargyl, 3-pentenyl, etc.); "aryl" (preferably carbon The number of atoms is 6 ~ 30, It is preferred that the number of carbon atoms is 6 to 20 '. Particularly preferred is that the number of carbon atoms is 6 to 12, including, for example, phenyl, p-methylphenyl, naphthyl, etc.); "substituted or unsubstituted "Amine group" (preferably having a carbon number of 0 to 20 ', more preferably a carbon number of 0 to 10, especially -56-200526728 {ϋ's carbon atom number of 0 to 6, including, for example, ·· Amine, methylamino, dimethylamino, monoethylamino, benzhydrylamino, etc.); "alkoxy" (preferably 1 to 20 carbon atoms, more preferably The number of carbon atoms is 1 to 12 ′, and the number of carbon atoms is preferably i to 8, including, for example, methoxy, ethoxy, butoxy, etc.); "Methoxy" (preferably The number of carbon atoms is 6 to 20 ′, more preferably, the number of carbon atoms is 6 to 16, and particularly preferably, the number of carbon atoms is 6 to I2. Examples include phenoxy, 2-naphthyloxy, and the like. ); "Fluorenyl" (preferably 1 to 20 carbon atoms, more preferably 1 to 16 carbon atoms, particularly preferably 1 to 12 carbon atoms, for example: ethenyl, Benzamyl, formamyl, trimethylethenyl, etc.); "alkoxycarbonyl" (preferably 2 to 20 carbon atoms, more preferably 2 to 16 carbon atoms) It is particularly preferred that the number of carbon atoms is 2 to 12, including, for example, methoxycarbonyl, ethoxycarbonyl, etc.); "Methoxycarbonyl" (preferably 7 to 20 carbon atoms, more preferably The number of carbon atoms is 7 to 16, particularly preferably, the number of carbon atoms is 7 to 10, including, for example, phenoxycarbonyl and the like.); "Methoxy" (preferably 2 to 20 carbon atoms) , More preferably, the number of carbon atoms is 2 to 16, particularly preferably, the number of carbon atoms is 2 to 10, for example, ethoxyl, benzyl fluorenyl, etc.); The number of carbon atoms is 2 to 20, more preferably the number of carbon atoms is 2 to 16, and the most preferred number is 2 to 10 carbon atoms, for example: acetamido, benzamidine and the like.) ; "Alkoxycarbonylamino" (preferably carbon The number of children is 2 to 20, more preferably 2 to 16, the number of carbon atoms is particularly preferred, and the number of carbon atoms is 2 to 12, including, for example, a methoxycarbonylamino group.); (The number of carbon atoms is preferably 7 to 20 ′, more preferably, the number of carbon atoms is 7 to 16, and particularly preferably, the number of carbon atoms is 7 to 12 ′. Example -57- 200526728 Such as: phenoxycarbonylamino group and the like. ); "Sulfonamido" (preferably 1 to 20 carbon atoms, more preferably 1 to 16 carbon atoms, particularly preferably 1 to 12 carbon atoms, for example: methanesulfonamide Group, benzenesulfonylamino group, etc.); "aminesulfonyl group" (preferably carbon number of 0 to 20 ', more preferably carbon number of 0 to 16, particularly preferably carbon number of 0 to 12 For example, it includes: sulfamoyl, methylsulfamoyl, dimethylsulfamoyl, phenylsulfamoyl, etc.); "aminomethylsulfonyl" (preferably carbon number 1 ~ 20, more preferably 1 to 16 carbon atoms, particularly preferably 1 to 12 carbon atoms, for example, carbamoyl, methylaminomethyl, diethylaminomethyl, phenyl φ Aminomethyl, etc.); "Alkylthio" (preferably carbon The number of children is 1 to 20, more preferably 1 to 16 carbon atoms, particularly preferably 1 to 12, carbon atoms, for example: methylthio, ethylthio, etc.); "arylthio" (more than Preferably, the number of carbon atoms is 6 to 20, more preferably, the number of carbon atoms is 6 to 16 ', particularly preferably, the number of carbon atoms is 6 to 12, including, for example, phenylthio and the like.); Preferably, the number of carbon atoms is 1 to 20, more preferably, the number of carbon atoms is 1 to 16, particularly preferably, the number of carbon atoms is 1 to 12, including, for example, methanesulfonyl, tosylsulfonyl and the like.); "Sulfinyl" (preferably 1 to 20% of carbon atoms, more preferably 1 to 16 carbon atoms, particularly preferably 1 to 12 carbon atoms, for example, methylsulfinyl, Benzenesulfenyl and the like. ); "Ureido" (preferably 1 to 20 carbon atoms, more preferably 1 to 16 carbon atoms, particularly preferably 1 to 12 carbon atoms, for example: ureido, methylurea, Phenylureido, etc.); "phosphonium amino" (preferably 1 to 20 carbon atoms, more preferably 1 to 16 carbon atoms, particularly preferably 1 to 12 carbon atoms, including, for example, · · Diethylphosphonium phosphate, phenylphosphonium phosphate; hydroxyl, hydrogen-58- 200526728 sulfur group, halogen atom (such as fluorine atom, chlorine atom, bromine atom, iodine atom), cyano group, sulfonic acid group , Carboxyl, nitro, hydroxamic acid, sulfinic, hydrazino, imino; "heterocyclic" (preferably 1 to 30 carbon atoms, more preferably 1 to 12. The heteroatom system includes, for example, a nitrogen atom, an oxygen atom, and a sulfur atom. Specifically, the system includes, for example, imidazolyl, pyridyl, quinolinyl, furyl, piperidinyl, morpholinyl, and benzofluorene. Azolyl, benzimidazolyl, benzothiazolyl, etc.); "silyl" (preferably 3 to 40 carbon atoms, more preferably 3 to 30 carbon atoms, particularly preferably carbon atoms) The number is 3 to 24, for example, including trimethylsilyl group, triphenylsilyl group, etc.). These substituents may be further substituted. In addition, if there are two or more substituents, they may be The same or different. If possible, they can also be connected to each other to form a ring. The compounds represented by the general formula (IV) are described below with specific examples, but the present invention is not limited to these specific examples. .

-59- 200526728 〔Chem 4 1〕 F-1 F— 6

F— 2

F— 3 F— 8

OCH3

F

F — 5 F-10

-60- 200526728 〔Chem 42〕 F —16 F One 1 1

61 200526728

-62- 200526728

B — 2 B — 7 OCHo h3co

/ -〇ch3

B-8 B — 3 CH〇

OCHq

och3

B — 9

B —10

• CH〇

-63- 200526728 〔Chem 45〕 Β -Π

Β- 1 6 CH ^

巳 一 12 巳 1 17

Yi 13

巳 1 14

Β -15

-64 200526728

-65- 200526728

Compounds represented by the general formula (I) and compounds represented by the general formula (II), (III)

Or the compound represented by (IV) is used in an amount of 0.01 to 20 parts by mass, more preferably 0.5 to 10 parts by mass, with respect to 100 parts by mass of the cellulose ester. By using the above compounds within this range, 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 the retardation and water permeability will be insufficient. If it is used in an amount exceeding 20 parts by mass, the additive will not be compatible with the cellulose ester and may crystallize in the film. The compound represented by the general formula (I) is used in an amount of 0.1 to 30 parts by mass, and preferably 1 to 10 parts by mass, based on 100 parts by mass of the cellulose ester. The compound represented by the general formula (II), (III), or (IV) is used in an amount of 0.1 to 10 parts by mass, and more preferably 0.5 to 7 parts by mass, with respect to 100 parts by mass of the cellulose ester. Next, a cellulose film suitable for use in the present invention is described below. The cellulose that can be used in the cellulose film of the present invention is a cellulose compound and a compound having a cellulose skeleton prepared by using cellulose as a raw material and biologically or chemically introducing functional groups. Among them, cellulose esters are preferred, and tritiated cellulose is more preferred. The halogenated cellulose film used in the present invention is described below. [Manufacturing of Tritiated Cellulose and Tritiated Cellulose Film] Although the triphenyl group of the tritiated cellulose film is not particularly limited, it is preferred to use ethenyl, propionyl, butyryl, and particularly preferred is to use ethyl醯 基. The degree of substitution of the perfluorenyl group is preferably 2.7 to 3.0, and more preferably 2.8 to 2.95. If • cellulose acetate having an allyl group as the ethyl group is used, the degree of substitution of the ethyl group φ is preferably 2.7 to 2.95, more preferably 2.8 to 2.95, and most preferably 2.84 to 2.89. In addition, those described in Japanese Patent Laid-Open No. 1 3-3 562 1 No. 2.50 to 2.86 or below, or those described in Japanese Patent Laid-Open No. 1 3-226495 No. 2.75 to 2.86 Also suitable for use. If it is too low, Re tends to become larger than desired due to the transport tension during the flow delay, and it also has the problem of causing in-plane unevenness. The degree of substitution of the fluorenyl group at the 6-position is preferably 0.9 or more. When the degree of substitution is 0.9 * or less, unevenness of Re and Rth is likely to be caused. In addition, Φ, the degree of substitution of the fluorenyl group in the present invention is calculated using AS TM D8 17 In the present invention, it is preferred to use cellulose acetate having a degree of acetylation of 59.0 to 6 1.5%. "Ethyl acetate" means the combined amount of acetic acid per cellulose unit mass. The degree of acetylation is obtained by measuring and calculating the degree of acetylation in ASTM: D-817-91 (test method of cellulose acetate and the like). -67- 200526728 The viscosity average polymerization degree (DP) of tritiated cellulose is preferably more than 250 and more preferably more than 290. In addition, the tritiated cellulose used in the present invention has a narrow molecular weight distribution based on the molecular weight distribution of Mw / Mn (Mw is mass average molecular weight and Mη is number average molecular weight) of gel permeation chromatography. The range of Mw / Mn is preferably 1.0 to 1.7, more preferably 1.3 to 1.65, and most preferably 1.4 to 1.6. The cellulose acetate of the present invention can be synthesized as described in Paragraph Nos. 0043 to 0044 of Japanese Patent Laid-Open Publication No. 1 1-5 8 5 and Synthesis Examples 1 described in Paragraph Nos. 0043 to 0044. 2, and cellulose acetate prepared by the synthesis method of Synthesis Example 3 described in paragraph numbers 005 1 to 00S2. [Production of tritiated cellulose film] The tritiated cellulose film of the present invention is preferably produced by a solvent casting method. In the solvent casting method, the film is produced using a solution (coating solution: dope) in which tritiated 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 halogenation having 1 to 6 carbon atoms. Ethers, ketones, and esters in the group consisting of hydrocarbon solvents may have a cyclic structure. Compounds having any two or more of the functional groups of ethers, ketones, and esters (i.e., -0-, -C0-, and -c00-) can also be used as organic solvents. The organic solvent may have other functional groups like an alcoholic group. In the case of an organic -68-200526728 solvent having two or more functional groups, the number of carbon atoms is preferably a solvent having any one of the functional groups within the above-mentioned preferred carbon number range. Examples of ethers having 3 to 12 carbon atoms include: diisopropyl ether, dimethoxymethane, dimethoxyethane, 1,4-dioxane, 1,3-dioxopentane Alkanes, tetrahydrofuran, methoxybenzene, and phenylethyl ether. Examples of ketones having 3 to 12 carbon atoms include: acetone, methyl ethyl ketone, diethyl ketone, diisobutyl ketone, cyclohexanone, and methyl cyclohexanone.

Examples of the ester 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 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 halogenated hydrocarbons is preferably chlorine. The ratio of the hydrogen atom of the halogenated hydrocarbon to the halogen is preferably 25 to 75 mole%, more preferably 30 to 70 mole%, still more preferably 35 to 65 mole%, and most preferably 40 to 60 mol%. Dichloromethane is a representative halogenated hydrocarbon. It is also possible to mix two or more organic solvents. A general method consisting of processing at the above temperature (normal temperature or high temperature) can prepare a tritiated cellulose solution. The preparation of the solution can be carried out by a method and apparatus for preparing a coating solution using a general solvent casting method. In addition, if a general method is used, a halogenated hydrocarbon (especially dichloromethane) is preferably used as the organic solvent. The amount of tritiated cellulose should be adjusted to contain 10 to 40% by mass in the resulting solution. The amount of tritiated cellulose is more preferably 10 to 30% by mass. An organic solvent (main solvent) may be added with any of the additives described later (plasticizer, anti-deterioration agent, etc.). The solution can be prepared by stirring tritiated cellulose and an organic solvent at normal temperature (0 to 40 ° C). High concentration solutions can be stirred under pressure and heat. Specifically, the tritiated 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 does not boil, at the same time as Stir. The heating temperature is usually 4 ° C. or higher, preferably 60 to 20 ° C., and more preferably 80 to 1100 ° C. The components can also be coarsely mixed in advance and then put into a container. Alternatively, they can be gradually added to the container. The container must have a structure capable of being stirred. An inert gas such as nitrogen can be injected to pressurize the container. In addition, the increase in the pressure of the solvent vapor caused by heating can also be used. Add the ingredients below. • When heating, it should be heated from the outside of the container. For example, a jacket-type heating device can be used. In addition, a plate heater can be installed outside the container and the pipe can be circulated to heat the liquid. The method of the entire container. It is preferable to set a stirring blade inside the container and use it for stirring. The stirring blade is preferably a length that can reach the vicinity of the container wall. It is preferable to provide a scraping blade at the end of the stirring blade. In order to update the liquid film on the container wall, instruments such as pressure gauges and thermometers can be installed in the container. Each component is dissolved in the solvent in the container. The coating liquid prepared by the preparation After cold-70-200526728, it is taken out of the container, or after it is taken out, it is cooled by a heat exchanger. The solution can also be prepared by the cooling dissolution method. The cooling dissolution method can dissolve the tritiated cellulose in In organic solvents that are difficult to dissolve according to the usual dissolving method. In addition, even if it is a solvent that can dissolve tritiated cellulose according to the usual dissolving method, if the cooling dissolving method is adopted, a uniform solution can be quickly prepared efficacy.

In the cooling and dissolving method, tritiated cellulose is slowly added at room temperature under stirring in an organic solvent. The amount of H tritiated cellulose is preferably adjusted to contain 10 to 40% by mass in the mixture. The amount of tritiated cellulose is more preferably 10 to 30% by mass. In addition, any of the additives described below may be added to the mixture in advance.

Next, the mixture is cooled to -100 to -10 ° C (preferably -80 to -10 ° C, more preferably -50 to -20 ° C, and most preferably -50 to -30 ° C). The cooling system can be implemented in, for example, a dry ice • methanol bath (-75 ° C) or a cooled diethylene glycol solution (-30 to -20 ° C). After cooling, the mixture of cellulose and organic solvent will harden. The cooling rate is preferably 4 ° C / min or more, more preferably 8 t / min or more, and most preferably 12 ° C / min or more. The faster the cooling rate, the better, but 10,000 ° C / second is the theoretical upper limit, 1,000 ° C / second is the technical upper limit, and 100t / second is the practical upper limit. In addition, the 'cooling rate is the difference between the temperature at the beginning of cooling and the last cooling temperature divided by the time from the start of cooling to the time required to reach the last cooling temperature 値 ° -71-200526728, then when it is heated to 0 To 200 ° c (preferably 0 to 150 ° C, more preferably 0 to 120 ° C, and most preferably 0 to 50T :), the tritiated cellulose is about to be dissolved in the organic solvent. The temperature rise system may be left alone at room temperature, or may be heated 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 speed is as fast as possible, the theoretical upper limit is 10,000 ° C / second, the technical upper limit is 1,000 ° C / second, and 100 ° C / second is practical On the ceiling. Heating rate is the difference between the temperature at the beginning of heating and the last heating temperature divided by the time required from the beginning of heating to the time of reaching the last heating temperature. A uniform solution can be prepared in the manner described above. If the dissolution is insufficient, the cooling and heating operations may be repeated. Whether the dissolution is sufficient is judged by merely visually observing the appearance of the solution.

In the cooling and dissolving method, in order to avoid mixing of water due to dew condensation during cooling, a closed container is preferably used. In addition, during the cooling and heating operation, the dissolution time can be shortened by increasing the pressure during cooling and reducing the pressure during heating. When pressurizing and decompressing, it is preferable to use a pressure-resistant container. In addition, a cellulose acetate (acetic acid degree: 60.9%, viscosity average degree of polymerization: 299) was dissolved in a 20% by mass solution of methyl acetate by a cooling and dissolving method. (DSC) When measured, 'there are pseudo-phase transition points in the sol state and the gel state near 33 ° C', and the gel state is uniform below this temperature. Therefore, the solution must be stored at a temperature higher than the pseudo-phase transfer temperature, preferably at a gel-phase transfer temperature plus 10 ° C left -72-200526728 right. However, the pseudo-phase transfer temperature varies 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. From the prepared tritiated cellulose solution (coating solution), a tritiated cellulose film was produced by a solvent casting method. It is preferable to add the retardation rising agent and the retardation reducing agent to the coating liquid.

The coating solution is cast on a drum or a belt, and the solvent is evaporated to form a thin film. The coating liquid before casting is preferably adjusted to have a solid content of 18 to 35%. The surface of the drum or belt is preferably finished in advance to be a mirror surface. The coating liquid is preferably cast on a drum or belt having a surface temperature of 10 ° C or less. In the present invention, if the coating solution (the cellulose cellulose solution) is cast on the belt, the first half of the drying before peeling is 10 seconds to 90 seconds, preferably 1 second. For 5 seconds to 90 seconds, a step of drying in a substantially windless state is performed. When the coating liquid is cast on the drum, the first half of the drying before stripping is performed within 1 second to 10 seconds, preferably 2 seconds to 5 seconds. The drying step is performed in a substantially windless state. In the present invention, the "drying before peeling" means a drying period after a coating liquid is applied to a belt or a drum until it is peeled off as a film. In addition, the "first half" means a step back to the previous step from one and a half of the total time required from the application of the coating liquid to the peeling. "Essentially no wind" refers to a state in which a wind speed of more than 0.5 meters / second cannot be detected at a distance of less than 200 mm from the surface of the belt or the surface of the drum. -73- 200526728

Half before drying before stripping, in the case of belt, it is usually about 30 ~ 300 seconds, but it is more than 10 seconds and less than 90 seconds, preferably more than 15 seconds and 90 seconds. For periods below 15 minutes, dry in the absence of wind. In the case of a rotating drum, it is usually about 5 to 30 seconds, but in the range of 1 second to 10 seconds, it is preferable that the time is 2 seconds to 5 seconds with strong wind. Allow to dry. The atmosphere temperature is preferably 0 ° C to 180 ° C, and more preferably 4CTC to 150 ° C. The operation of drying without wind may be performed at any stage in the half before drying before stripping, but it is preferably performed immediately after casting. If the drying time without air is shorter than 10 seconds, it is difficult to uniformly distribute the retardation rising agent and the retardation falling agent in the film, and if it is longer than 90 seconds, it will be forced to be stripped under insufficient drying. As a result, the surface shape of the film is deteriorated. In the drying before stripping, except for airless drying, it can be dried by blowing an inert gas. The hot air temperature at this time is preferably 0 ° C to 180 ° C, and more preferably 40 ° C to 150 ° C.

Regarding the drying method in the solvent casting method, in U.S. Invention Patent Nos. 2,3 36,3 1 0, the same as 2,3 67,603, the same as 2,492,078, the same as 2,492,977, the same as 2,492,978, and the same No. 2,607,704, the same as No. 2,739,069, the same as No. 2,73 9,070, the British invention patent No. 64,7; 31, the same specifications as No. 73 6,892, Japanese Patent Publication No. 45-45 54, It is described in the same publications as 49-56 1 4, Japanese Patent Application Laid-Open No. 60-1 76 834, 60-20343 0, and 62-1 11503. Drying on a belt or a drum can be performed by blowing inert gas such as air, nitrogen, or the like. -74- 200526728 The produced film can also be stripped from the drum or belt, and then dried with high hot air that gradually changes the temperature from 100 to 1 60 ° c to evaporate the residual solvent. The above method is described in Japanese Patent Unexamined Patent Publication No. 5-1 7844. According to this method, the time required from casting to stripping can be shortened. To implement this method, the coating solution must be gelled at the surface temperature of the rotating drum or belt. It is also possible to use a conditioned cellulose solution (coating solution) to perform two or more layers of casting to form a thin film. In this case, it is preferable to produce a tritiated cellulose film by a solvent casting method. The coating solution is cast on a drum or a belt, and then the solvent is evaporated to form a thin film. The coating solution before casting is preferably adjusted to a concentration in the range of 10 to 40% by solid content. The surface of the drum or belt is preferably finished in advance to be a mirror surface. When casting more than two layers of tritiated cellulose solution, it is also possible to cast several tritiated cellulose solutions, that is, several casts provided at intervals from the direction toward the support may be taken. The method of casting the solution containing tritiated cellulose separately, and forming a film on one side and one side. For example, the respective publications of the Japanese Patent Publication No. 6 1-1 5 84 1 4, the same Patent Publication No. U 1 224 1 9, and the Japanese Patent Publication No. 1 1-1 9 8 2 8 5 can be used. Method described in. It is also possible to cast the tritiated cellulose solution from two casting ports to form a thin film. For example, Japanese Patent Publication No. 60-27562, Japanese Patent Publication No. 6 1-94724, Japanese Patent Publication No. 6 1-947245, Japanese Patent Publication No. 61-1 (H813, Japanese Patent Publication No. The method described in the respective gazettes of Kaisho No. 6 1-1 5 84 1 3, and the same Japanese Unexamined Patent Publication No. 6-1 3 493 3. Also, it can be used in the same Japanese Unexamined Patent No. 5 6- 1 626 1 The high viscosity and low viscosity tritiated cellulose solutions are simultaneously squeezed while the fluid substance of the high viscosity tritiated cellulose-75- 200526728 solution is covered with the low viscosity tritiated cellulose solution, as described in JP 7 Casting method of the tritonated cellulose film. In addition, it is also possible to use two casting openings, peel off the film formed on the support through the first casting opening, and then contact the surface of the supporting surface. A second casting is applied on one side to produce a film. For example, the method described in Japanese Patent Publication No. 44-2023 5 can be used. The same cellulose solution used for casting can also be used. It is also possible to use different tritiated cellulose solutions. In order to make the tritiated cellulose layer have several functions, it is suitable It is sufficient to extrude the tritiated cellulose solution according to its function from the respective casting mouth. Furthermore, the tritiated cellulose solution of the present invention can also be used with other functional layers (such as adhesive layer, dye layer, anti- Electrostatic agent, anti-halation layer, ultraviolet absorbing layer, polarizing layer, etc.) are simultaneously cast. In the previous single-layer liquid, in order to make the required film thickness, it is necessary to extrude a high viscosity compound at a high concentration. Cellulose solution. At this time, the stability of the tritiated cellulose solution is not good, resulting in the formation of solid matter and the formation of small bumps, or the flatness becomes poor and most of them will become problematic. For φ this problem As a solution, if several kinds of tritiated cellulose solutions are delayed from the casting mouth, the high-viscosity solution can be extruded onto the support at the same time. In this way, not only can the planarity be made, but also the quality can be improved and it has Excellent planar film, and the use of concentrated tritiated cellulose solution can reduce the drying load to increase the production rate of the film. For tritiated cellulose films, the following plasticizers can be used to improve its mechanical properties. Phosphate or carboxylic acid ester can be used as the agent. Examples of phosphate esters are -76-200526728, including: triphenyl phosphate (TPP) and tricresyl phosphate (TCP). Residual acid esters are phthalic acid. Acid esters, and citrate [citrate esters are shown in Table 4. Examples of phthalates include: o-phthalate; phthalic acid. Dimethyl formate (DMP) 'diethyl phthalate (DEP), Phthalate: dibutyl dicarboxylate (DBP), dioctyl phthalate (DOP), phthalate, diphenyl dicarboxylate (DPP), and diethylhexyl phthalate (dehp). Examples of the citrates include: 0-ethyl ethyl triethyl citrate (OACTE), and 0-ethyl ethyl triethyl citrate (OACTB). Examples of other carboxylic acid esters include: butyl oleate, methyl ethyl ricinoleate, dibutyl sebacate, and various 1,2,4-trimelates. Phthalate plasticizers (DMP, DEP, DBP, DOP, DPP, DEHP) are suitable for use. Among them, DEP and DPP are particularly preferred. The amount of the plasticizer to be added is preferably 0.1 to 25 mass% of the amount of tritiated cellulose, more preferably 1 to 20 mass%, and most preferably 3 to 15 mass%. Anti-deterioration agents (such as antioxidants, peroxide decomposers, free radical inhibitors, metal inerts, acid trapping agents, amines) can also be added to tritiated cellulose films. As for the anti-deterioration agent, it is described in Japanese Patent Laid-Open No. 3-199201, the same as No. 5-1907073, the same as No. 5-194789, the same as No. 5-27 1 47 1 and the same as No. 6- 1 07854 It is described in each bulletin. The addition amount of the anti-deterioration agent is preferably from 0.01 to 1% by mass, more preferably from 0.01 to 0.2% by mass, of the target solution (coating solution) to be prepared. When the added amount is less than 0.001% by mass, the effect of the anti-deterioration agent is hardly seen. If the added amount is more than 1% by mass, there may be a phenomenon that the anti-deterioration agent bleeds on the surface of the film. Examples of particularly desirable anti-deterioration agents are butylated-77-200526728 hydroxytoluene (BHT), and tritylamine (TB A). The steps from casting to post-drying can be carried out in an air atmosphere or under an inert gas atmosphere such as nitrogen. The winding machine system that can be used for the production of tritiated cellulose film of the present invention can also be used by general users, that is, it can be a fixed tension method, a constant torque method, a conical torque method, and a program with constant internal stress. Take-up method such as tension control method. [Surface treatment of tritiated cellulose film] The tritiated cellulose film is preferably subjected to a surface treatment. Specific methods include corona discharge treatment, glow discharge treatment, flame treatment, acid treatment, alkali treatment, or ultraviolet irradiation treatment. Alternatively, as described in Japanese Patent Application Laid-Open No. 7-3 3 343 3, an undercoat layer may be provided. From the viewpoint of maintaining the flatness of the film, during such processing, the temperature of the tritiated cellulose film is set to Tg (glass transition temperature) or less. Specifically, it is preferably set to 150 t or less. When it is used as a transparent protective film for a polarizing plate, it is particularly preferable to perform an acid treatment or an alkali treatment from the viewpoint of the adhesion with the polarizing film, that is, it is particularly preferable to perform a saponification treatment on the rhenium fiber. The surface energy is preferably 55 mN / m or more, more preferably 60 mN / m or more and 75 mN / m or less. Here is an example of empirical test treatment. The alkaline alkalizing treatment of the fermented cellulose film is preferably performed by a cycle in which the surface of the film is immersed in the stomach & liquid solution 'and neutralized with an acidic solution, and then washed with water and dried. -78- 200526728 The alkaline solution includes a prescribed concentration of potassium hydroxide solution, sodium hydroxide solution, and hydroxide ions, preferably in the range of 0.1 to 3.0 N, and more preferably in the range of 0.5 to 2.0 N. The temperature of the alkaline solution is preferably in the range of room temperature to 90, and more preferably in the range of 40 to 70 ° C. The surface energy of a solid can be obtained by contact angle method, moist heat method, and adsorption method as described in the book "Basics and Applications of Wetting" (Realize, published on December 10, 1989). In the case of the tritiated cellulose film of the present invention, the contact angle method is preferably used.

Specifically, the two solutions whose surface energy is known are dropped on the triton fiber film, and the intersection between the surface of the droplet and the surface of the film is used to draw the corner formed by the connection of the droplet and the surface of the film, and The angle of the droplet is defined as the contact angle, and the surface energy of the film can be calculated by calculation. [Water vapor transmission rate] The water vapor transmission rate is measured in accordance with the method described in JIS Z 0 2 0 8 for each sample, and the amount of water (g) evaporated in an area of 24 hours per 1 m2 is calculated.

The moisture permeability of the tritiated cellulose film can be adjusted in various ways. Hydrophobic compounds can be added to the tritiated cellulose film to reduce the water absorption of the tritiated cellulose film to reduce the moisture permeability. In this case, it is preferable to use an additive with low compatibility with tritiated cellulose and a small plasticizing effect. The compounds represented by the above general formulae (I) to (IV) are suitable for use as a water repellent. The water absorption of tritiated cellulose film can be evaluated by measuring the equilibrium moisture content under a certain temperature and humidity. The equilibrium moisture content of the tritiated cellulose film at 251-279-200526728 8 0% R is preferably 5% by mass or less, more preferably 3% by mass or less. The equilibrium moisture content is determined by Karl Fischer analysis after 24 hours of standing at the above temperature and humidity, and then calculating the moisture content of the sample that has reached equilibrium, and then dividing the moisture content (g) by the mass (g) of the sample. . In addition, the moisture permeability can also be reduced by extending the orientation of the tritiated cellulose molecular chains to be dense by extending in the transport direction and / or width direction during film formation. # Extension can be implemented in either the uniaxial extension method or the biaxial extension method. Although the biaxial stretching method includes two types 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 is removed, the film is peeled off by a belt or a drum, extended in the width direction (length direction), and then extended in the length direction (width direction). The method of extending in the width direction has been described in, for example, Japanese Patent Laid-Open No. 62- 1 1 503 5, Japanese Unexamined Patent Publication No. 4- 1 5 2 1 25, the same as No. 4-2842 1 No. 1, the same as No. In various publications such as No. 4-298310 and No. 11-48271. The stretching 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 stretched by a treatment in drying ', which is particularly effective when a solvent remains. When extending in the length direction, for example, the speed of the film transport roller can be adjusted so that the film can be stretched when the film winding speed is faster than the film peeling speed. When stretched in the width direction, the tenter is used to keep the width of the film while being transported, and the method of slowly expanding the width of the tenter -80-200526728 tenter can also stretch the film. It is also possible to stretch the film using a stretcher after drying (preferably uniaxial stretching using a long stretcher). The stretch ratio of the film (the ratio of the original length to the increase by extension) is preferably in the range of 5 to 50%, more preferably in the range of 10 to 40%, and most preferably in the range of 15 to 35%. . In addition, by treating the tritiated cellulose film at a high temperature to increase the degree of crystallinity, the water permeability can also be reduced. The above treatment must be performed at a temperature and time at which the volatilization of the low molecular compounds and the thermal cracking of the tritiated cellulose film itself do not cause problems. The processing temperature is preferably 160 ° C or more and 260 ° C or less, more preferably 180 ° C or more and 24 ° C or less. The processing time is preferably 5 minutes or more and 2 hours or less, and more preferably 10 minutes or more and Less than 1 hour. [Hygroscopic expansion coefficient] "Hygroscopic expansion coefficient" refers to the amount of change in sample length when the relative humidity is changed at a certain temperature. To prevent the frame-like transmittance from increasing, the absorption of tritiated cellulose film The wet expansion coefficient is preferably 30 X 1 0_ 5 /% R or less, more preferably 15 X 1 0.5 ·% /% RH or less, and most preferably 10 × 1 (T5 /% RH In addition, although the coefficient of hygroscopic expansion is preferably the smaller one, it is usually 1. χχ 〇 · 5 /% r Η or more. The method for measuring the coefficient of hygroscopic expansion is described below. Polymer thin fe (phase retardation plate) cut out a sample with a width of 5 mm and a length of 20 mm, fix one end, and then suspend it in an atmosphere of 20% rH (R0). Hang on the other end Lift a 0.5-gram weight and leave it for ～ 0 minutes to measure -81 ~ 200526728 疋 length (L0). Then the temperature is still below 25 The humidity was changed to 80% rh (R1) to measure the length (L · 1). The coefficient of hygroscopic expansion was calculated from the following formula. The measurement was performed on the same sample for 10 times, and then the average absorption was used. Wet expansion coefficient [/% RH] = {(LI-L0) / L0} / (Rl _ R〇) In order to reduce the dimensional change caused by the above moisture absorption, it is preferable to reduce the amount of residual solvent during film formation And make the free volume in the polymer film smaller. The general method to reduce the residual solvent is to dry at high temperature and for a long time, but if it is too long, the productivity will of course decrease. Therefore, the amount of residual solvent for the tritiated cellulose film is preferably in the range of 0.001 to 1% by mass, more preferably in the range of 0.02 to 0.07% by mass, and most preferably in the range of 0.03 to 0.05 Range of mass%. By controlling the amount of the residual solvent, a polarizing plate with optical compensation energy can be produced inexpensively and with high productivity. The amount of residual solvent is a certain amount of sample dissolved in chloroform, and the gas phase is used. Measured by chromatography (GC 1 8 A, manufactured by Shimadzu Corporation). The solution casting method uses a solution (coating solution) prepared by dissolving a polymer material in an organic solvent to produce a thin film. The drying method in the solution casting method can be divided into a drum (or belt) surface as described later. Drying on the surface and during film transport. When drying on the surface of the drum (or belt), it is preferred not to exceed the boiling temperature of the solvent used (if higher than the boiling point, it will become a bubble ) Is slowly dried. As for the drying during the transport of the film, the glass transition point of the polymer material is preferably 30 ° C, and more preferably at -20-200526728 at 20 ° C. Furthermore, "another method for reducing the dimensional change caused by the moisture absorption" is to add a compound having a hydrophobic group. The material having a hydrophobic group is not particularly limited as long as it has a hydrophobic group such as an alkyl group or a phenyl group in the molecule, but it is preferably a plasticizer or Materials that can meet the requirements of anti-deterioration agents. Examples of such preferred materials include: triphenyl phosphate (TPP), tritylamine (TB A), and the like.

• The addition amount of the compound having these hydrophobic groups is preferably in the range of 0.01 to 30% by mass, and more preferably in the range of 0.1 to 20% by mass relative to the H solution (coating solution) to be adjusted. . [Delay of the film] Re retardation 値 (nano) and Rth retardation 値 (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 formulas (A) and (B), nx is the direction of the late phase axis in the film plane (The fold φ emissivity will become the direction of maximum). In equations (A) and (B), ny is the refractive index in the direction of the phase advance axis (the direction in which the refractive index will become the smallest) in the plane of the film. In Formula (B), nz is the refractive index in the thickness direction of the thin film. In the formulae (A) and (B), d is the thickness of the film in nanometers. The halogenated cellulose film of the present invention is suitable for use as a retardation film corresponding to the liquid crystal mode > 83-200526728. The ideal optical characteristics of the tritiated cellulose film vary depending on the liquid crystal mode. For OCB mode users, Re is preferably 10 to 100, and more preferably 20 to 70. Rth is preferably 50 ~ 300, more preferably 100 ~ 250. For VA mode users, Re is preferably 20 to 100, more preferably 30 to 70. Rth is preferably 50 to 25 0, more preferably 80 to 180. In addition, for TN users, Re is preferably 0 to 50, and more preferably 2 to 30 mm. Rth is preferably 10 to 200, more preferably 30 to 150. Among them, in the OCB mode and the TN mode, an optically anisotropic layer can be coated on the halogenated cellulose film having the above-mentioned retardation and used as an optical compensation film. The birefringence (Δn: nx-ny) of the tritiated cellulose film is preferably in the range of 0.00 to 0.002. The birefringence {(nx + ny) / 2-nz} in the thickness direction of the support film and the opposing film is preferably in the range of 0.00 to 0.04. • As for the thickness (dry film thickness) of the tritiated cellulose film, it is 1 to 20 microns, preferably 20 to 110 microns, and more preferably 40 to 100 microns. [Photoelasticity] The photoelastic coefficient of the protective film of the present invention is preferably 60xl 0_8 cm2 / N or less, and more preferably 20x1 (Γ8 cm2 / N or less. The photoelastic coefficient can be obtained by an ellipse meter. [Glass transition temperature ] The glass transition temperature of the protective film of the present invention is preferably above 1 20 ° C, more preferably -84-200526728, more preferably 14 (TC or higher. The glass transition temperature is measured by differential scanning calorimetry (DSC). When measuring at a speed of 10 ° C / min, the average of the temperature at which the baseline of the glass transition originating from the film will change and the temperature of returning to the baseline again is obtained. 1. Structure of the polarizing plate First, here is A protective film and a polarizing film constituting the polarizing plate of the present invention are described below.

The polarizing plate of the present invention may include an adhesive layer, a release film, and a protective film as constituent elements in addition to a polarizing film or a protective film. (1) Protective film The polarizing plate of the present invention has a protective film totaling two pieces on each side 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 norbornene resin, polyethylene terephthalate (PET), polyethylene naphthalate, polycarbonate, polystyrene 'polyarylate, polyfluorene, Among the polymer films produced by tritiated cellulose and the like, the aforementioned tritiated cellulose is most preferred. (2) Polarizing film Although the polarizing film of the present invention is preferably composed of polyvinyl alcohol (PVA) and dichroic molecules, it can also be used as disclosed in Japanese Patent Laid-Open No. 丨 1 _ 24 8 93 7 It is described that a polyvinylene-based polarizing film is formed by dehydrating and dechlorinating PVA or polyvinyl chloride to generate a polyene structure and aligning it. PVA is a polymer material obtained by testing polyvinyl acetate, -85- 200526728, but it can also contain unsaturated carboxylic acid, unsaturated sulfonic acid, olefins, vinyl ethers and vinyl acetate. Copolymerized ingredients. Alternatively, a modified PVA containing an ethylamidine group, a sulfonic acid group, a carboxyl group, an olefin oxide, or the like may be used. Although there is no particular limitation on the degree of saponification of P v A, from the viewpoint of solubility and the like, it is preferably 80 to 100 mol%, and particularly preferably 90 to 100 mol%. In addition, although the polymerization degree of PVA is not particularly limited, it is preferably 1,000 to 10,000, and particularly preferably 1,500 to 5,000. # PVA's antiquated (stereo) regularity is as described in Invention Patent No. 2,978,2 19, and it is better to improve the durability by more than 55%, but it is the same as Invention Patent No. 3,3 17,4 94 45 ~ 52.5% described in No. can also be used. After the PVA is thinned, it is preferable to introduce a dichroic molecule to form a polarizing film. As a method for manufacturing a PVA film, a method in which a PVA-based resin is dissolved in water or an organic solvent and cast to form a film is generally used. The concentration of the polyvinyl alcohol-based resin in the dope is usually 5 to 20% by mass. By forming the dope into a film by a casting method, a PVA film # having a film thickness of 10 to 200 microns can be obtained. For the production of PVA film, please refer to the invention patent No. 3,342,5 1 6; JP-A No. 09-3 2 85 93; JP-A No. 1 3-3028 1 7; JP-A No. 14-1 4 4 4 0 1 Method described in. Although there is no particular limitation on the crystallinity of the PVA film, the average crystallinity (XO 50 to 75 mass%) described in Invention Patent No. 3,251,073, or to reduce the variability of in-plane hue The PVA film described in Japanese Patent Application Laid-Open No. 14-2 362 14 has a crystallinity of 38% or less. The birefringence (△ η) of the PVA film is preferably the smaller one. Invention Patent No.-86-200526728

A PVA film having a birefringence of 10 < < 10-3 or less as described in No. 3,342,5 16 is suitable for use. However, as described in Japanese Patent Application Laid-Open No. 1 4-228 8 3 5, in order to avoid the cutting of the PVA film during stretching and to obtain a high degree of polarization, the birefringence of the PVA film can also be set to be greater than 0.02 and 0.01. Hereinafter, as described in Japanese Patent Application Laid-Open No. 14-060505, the 値 of {(nx + ny) / 2-nz} may be set to 0.0003 or more and 0.001 or less. The retardation (in-plane) of the PVA film is preferably from 0 nm to 100 nm, and more preferably from 0 nm to 50 nm. The Rth (thickness direction) of the PVA thin film is preferably 0 nm or more and 500 nm or less, and more preferably 0 nm or more and 300 nm or less.

In addition, the polarizing plate of the present invention is also suitable for using a PVA film having a 1,2-glycol bond content of 1.5 mol% or less as described in Invention Patent No. 3,021,494, Japanese Patent Laid-open No. 1 3 -3 1 The number of optical foreign matter of 5 micrometers or more per 100 cm2 as described in No. 6492 is PVA film of 500 or less, and the hot water in the TD direction of the film described in Japanese Patent Application Laid-Open No. 1 4-030 1 63 PVA film with cut-off temperature variability of 1.5 ° C or less, and polyhydric alcohols of 3 to 6 yuan mixed with 1 to 100 parts by mass of glycerin, etc., or JP-A No. 06-289225 mixed with 15 mass% or more PVA film made from the solution of the plasticizer described. Although there is no particular limitation on the film thickness of the PVA film before stretching, from the viewpoint of maintaining the stability of the film and the homogeneity of stretching, it is preferably 1 micron to 1 mm, and particularly preferably 20 to 200. Microns. It can also be used as described in Japanese Patent Laid-Open No. 1 4-2362 1 No. 2-4 to 6 times in water when the stress generated will be less than 10 N -87- 200526728 Thin PVA film. For dichroic molecules, 13_ or 15 'or higher order iodine ions or dichroic dyes can be used. In the present invention, iodine ion, which is the next highest order, is particularly suitable for use. High-order iodine ions can be immersed in PVA by dissolving iodine in an aqueous solution of potassium iodide as described in "Applications of Polarizing Plates", edited by Nagata, CMC Publishing or Industrial Materials, Volume 28, No. 7, pages 39-45. The liquid and / or the boric acid aqueous solution are produced in a state of being adsorbed and aligned with PVA. When a dichroic molecule uses a dichroic dye, an azo-based pigment is preferable, and a diazo-based and a quinoid-based pigment is particularly preferable. A dichroic dye is preferably a water-soluble one, so a hydrophilic substituent such as a sulfonic acid group, an amine group, or a hydroxyl group is introduced into a dichroic molecule for use as a free acid, or an alkali metal salt, an ammonium salt, or an amine. Of salt. Specific examples of dichroic dyes as described above include: CI Direct Red 37, Congo Red (CI Direct Red 28), CI Direct Purple 12, CI Direct Blue 90, CI Direct Blue 22, CI Direct Blue 1, c. I · direct blue 1 5 1, C · I · direct green 1 and other benzidine series; C · I. direct yellow 44, C · I. direct red 23, C · I · direct red 79 and other diphenyls Biuret series; C. I. Direct Yellow 12 and other stilbene series; CI Direct Red 31 and other dinaphthylamine series; C. I. Direct Red 81, C. I. Direct Violet 9, CI Direct Blue 7 8 Etc. J acid. In addition, CI Direct Yellow 8, CI Direct Yellow 28, C. I. Direct Yellow 86, C. I. Direct Yellow 87, C. I. Direct Yellow 142, C, I. Direct Orange 26, CI Direct Orange 39, C · I. Direct Orange 72, CI -88- 200526728 Direct Orange 106, CI Direct Orange 107, C · I. Direct Red 2, CI Direct Red 3 9, CI Direct Red 8 3, CI Direct Red 8 9, C. I · Direct Red 240, CI Direct Red 242, CI Direct Red 247, C · I · Direct Violet 48, CI Direct Violet 51, CI Direct Violet 98, CI Direct Blue 15, CI Direct Blue 67, CI Direct Blue 71, CI Direct Blue 98, CI Direct Blue 168, CI Direct Blue 202, C. I. Direct Blue 236, C I Direct Blue 249, CI Direct Blue 270, CI Direct Blue 59, CI Direct Green 85, CI Direct Brown 44, C · I. Direct Brown 106, C · I. Direct Brown 195, CI Direct Brown 210, C · I. Direct Brown 223, C · I · Direct Brown 224, CI Direct Black 1, CI Direct Black 17, CI Direct Black 19, CI Direct Black 54, etc .; and Japanese Patent Laid-Open No. 62-7 0 802, Japanese Patent Laid-Open No. 1-1 6 1202, Japanese Patent Laid-Open No. 1-1 72906, JP-A No. 1-1 7290 No. 7, JP-A No. 1-1 8 3 602, JP-A No. 1-248 1 05, JP-A No. 1-265205, JP-A No. 7-26 1 024 Wait. In order to produce dichroic molecules having various hue, the dichroic dye may be mixed with two or more kinds. When a dichroic dye is used, the absorption thickness may be 4 m or more as described in JP-A No. M-082222. If the content of the dichroic molecules in the film is too small, the polarization degree will be low. If the content of the dichroic molecule is too large, the transmission of the veneer will soon decrease. Therefore, the polyvinyl alcohol system constituting the matrix of the film is usually used. The polymer is adjusted to a range of 0.01% by mass to 5% by mass. The preferred film thickness of the polarizing film is 5 to 40 microns, and more preferably 10 to 30 microns. The ratio of the thickness of the polarizing film to the thickness of the protective film described later is set to -89- 200526728 as described in Japanese Patent Application Laid-Open No. 14-174727, which is 0.001 $ A (polarizing film film thickness) / Β (protective film Thick) ^. The range of i 6 is also available. Although the crossing angle of the retardation axis of the protective film and the absorption axis of the polarizing film can be any arbitrary angle, it is preferably parallel or 45 ± 20. Azimuth. 2. Manufacturing steps of polarizing plate Next, the manufacturing steps of the polarizing plate of the present invention are described below. The manufacturing steps of the polarizing plate of the present invention are preferably composed of a swelling step, a dyeing step, a solid film step, an extension step, a drying step, a protective film bonding step, and a drying step after bonding. The order of the dyeing step, the solid film step, and the extending step can be arbitrarily changed, or several steps can be combined to be implemented simultaneously. Alternatively, as described in Invention Patent Nos. 3, 3 3 1, 6 1 5, it may be washed with water after the film-fixing step. In the present invention, the swelling step, the dyeing step, the film-fixing step, the stretching step, the drying step, the protective film bonding step, and the drying step after bonding are preferably performed one after the other in the order described. However, in the above steps or after, a surface inspection step on the line may be provided. The swelling step is preferably performed using water only, but as described in Japanese Patent Laid-Open No. 10- 1 5 3 709, in order to stabilize the optical performance and avoid the production of polarizer substrates in the production line, The striated pattern can also swell the polarizing plate substrate with an aqueous boric acid solution to manage the degree of swelling of the polarizing plate substrate. Although the temperature and time of the swelling step can be arbitrarily set, it is preferably 10 ° C to 60 ° C, and 5 seconds to 2,000 seconds. For the dyeing step, the method described in Japanese Patent Laid-Open No. 2002-86554 can be used. In addition, the dyeing method is not only a dipping method, but any method such as coating or spraying iodine or a dye solution may be used. Also, as described in Japanese Patent Laid-Open No. 13-290025, a method of simultaneously dyeing by adjusting the concentration of iodine, the temperature of the dyeing bath, the extension ratio in the bath, and the bath liquid in the stirring bath can be used.

When dichroic molecules use higher-order iodine ions, in order to obtain polarizing plates with high contrast, the dyeing step is preferably a solution in which iodine is dissolved in an aqueous potassium iodide solution. In this case, the preferable content range of the iodine-potassium iodide aqueous solution is 0.05 to 20 g / liter of iodine, 3 to 200 g / liter of potassium iodide, and the 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 60 ° C. Even more preferably, the iodine is 0.5 to 2 g / L, the potassium iodide is 30 to 120 g / L, the mass ratio of iodine to potassium iodide is 3 0 to 120, the dyeing time is 30 to 600 seconds, and the liquid temperature It is 20 to 50 ° C. In addition, as described in Invention Patent No. 3, 1 45,747, boron-based compounds such as boric acid and borax may be added to the dyeing solution.

The film-fixing step is preferably a method of dipping in the cross-linking agent solution or including the cross-linking agent in the coating solution. It may also be implemented by dividing the solid film step into several times as described in Japanese Patent Laid-Open No. 11-5 2 130. As the cross-linking agent, those described in U.S. Republished Invention Patent No. 232,8 97, or as described in Invention Patent No. 3,3 5 7,1 09, can be used as a cross-linking agent to improve dimensional stability. Polyaldehyde, but the best is to use boric acid. When the cross-linking agent used in the film-fixing step is boric acid, metal ions can be added to the boric acid and potassium iodide aqueous solution. As the metal ion, zinc chloride-91-200526728 is preferably used. However, as described in Japanese Patent Laid-Open No. 2 0 0-3 5 5 1 2, halogenation of zinc iodide or the like may be used instead of zinc chloride. Zinc salts of zinc, zinc sulfate, zinc acetate, etc. In the present invention, it is preferable to adopt a method in which a boric acid-potassium iodide aqueous solution to which zinc chloride is added is first produced, and then the PVA film is immersed therein to solidify the film. Preferably, boric acid is 1 to 100 g / L, potassium iodide is 1 to 120 g / L, zinc chloride is 0.01 to 10 g / L, solid film time is 10 to 1,200 seconds, and the liquid temperature is 10 ~ 60 ° C. More preferably, boric acid is 10 to 80 g / liter, potassium iodide is 5 to 100 g / liter, zinc chloride is 0.02 to 8 g / liter, and the solidification time is 30 to 600 seconds, and The liquid temperature is 20 ~ 50 ° C. The stretching step is suitable for using the longitudinal uniaxial stretching method described in US Patent No. 2,454,5 1 5 or the like, or the tenter described in Japanese Patent Laid-Open No. 2 0 2 · 8 6 5 54 the way. The preferable stretching ratio is 2 times or more and 12 times or less, and more preferably 3 times or more and 10 times or less. In addition, the relationship between the stretching magnification, the original reflection thickness, and the thickness of the polarizing film is also suitable to be set as described in Japanese Patent Application Laid-Open No. Hei (Polarizing film thickness after protective film bonding / original film thickness) χ (full Stretch ratio) > 0.17, the relationship between the width of the polarizing film at the time of the last bath and the width of the polarizing film when the protective film is bonded is also suitable for use in the same as described in Japanese Patent Application No. 14_〇4〇247 0 · 8 0 $ (The width of the polarizing film when the protective film is bonded / the width of the polarizing film when it comes out from the last bath) SO.95. The drying step can use the method described in Japanese Patent Laid-Open No. 2000-8 6 5 5 4, but the preferred temperature range is 30 ° ~ 10 (rc, drying time is 30 Seconds to 60 minutes. In addition, as described in the invention patent No. 3, 1 4 8, 5 1 3 -92- 200526728, it is also suitable to apply heat treatment to set the temperature of discoloration in water to 50 ° C or higher, or like Japan According to National Patent Publication No. 07-3252 1 No. 5 or No. 07-3 2 52 1 No. 8, aging treatment is applied in an atmosphere subjected to temperature and humidity management. The protective film bonding step is to protect two pieces. The film is bonded to both sides of the above-mentioned polarizing film after the drying step. The method is to use a method of supplying a bonding solution immediately before bonding, and then bonding the polarizing film and the protective film by a pair of rollers. In addition, as described in Japanese Patent Laid-Open Nos. 200 1 -296426 and 2002-865 54, it is preferable to also adjust the moisture content of the polarizing film to suppress the recording produced by the polarizing film due to extension. Groove-like unevenness. In the present invention, it is suitable to use a moisture content of 0.1 to 30% Although there is no particular limitation on the adhesive of polarizing film and protective film, it is preferable to use PVA-based resin (including modified PVA such as acetamidine, sulfonate, carboxyl, oxyalkylene, etc.) or boron. Among them, aqueous solutions of compounds are preferred. Among them, PVA-based resins are preferred. The thickness of the adhesive layer is preferably 0.01 to 5 microns after drying, and more preferably 0.05 to 3 microns. In addition, it is also suitable to apply a protective film to the surface first. After the treatment is performed to make it hydrophilic, an adhesion method is performed to improve the adhesion between the polarizing film and the protective film. The surface treatment method is not particularly limited, and any method such as a method of saponification using an alkali solution, a corona treatment method and the like can be adopted. In addition, after the surface treatment, an easy-adhesive layer such as a base coat can be provided. As described in Japanese Patent Laid-Open No. 14-26783 9, the contact angle between the surface of the protective film and water is 50. The following is preferred. The combined drying conditions can be determined according to the method described in JP 2002-865 54-93-200526728, but the preferred temperature range is 30 ° C ~ 100 ° C, and the preferred drying time is 30 seconds. Minutes ~ 60 minutes. Alternatively, According to Japanese Patent Laid-Open No. 07-325 220, the aging treatment is performed in an atmosphere with temperature and humidity management. The content of the element in polarized light S, preferably 0.1 to 3.0 g / m2, boron It is 0.1 to 5.0 g / m2, potassium is oi to 2.0 g / m2, and zinc is 0 to 2.0 g / m2. In addition, the potassium content can also be described in Japanese Patent Laid-Open No. 13-1 66 1 43, When the content is set to 0.2% by mass or less, the zinc content in the polarizing film # may be set to 0 · 0 4% by mass to 0 · 5% by mass as described in JP-A No. 1 2-03 5 5 1 2. In order to improve the dimensional stability of the polarizing plate, as described in the invention patent No. 3, 3, 23, 25, 5, an organic titanium compound and / or The chromium compound contains at least one compound selected from an organic titanium compound and an organic rhenium compound. In addition, in order to adjust the hue of the polarizing plate, a dichroic dye may be added. 3. Characteristics of polarizing plate • (1) Transmittance and polarization degree 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 49.0% the following. A preferred range of the degree of polarization defined by Equation 4 is 99.9% or more and 99.999% or less, more preferably 99.940% or more and 99.995% or less. A preferable range of the parallel transmittance is 36% or more and 42% or less. A preferable range of the orthogonal transmittance is 0.001% or more and 0.05% or less. The better range of the dichroism ratio defined by Equation 5 is 48 or more and 1,215 or less, but more preferably 53 or more and -94- 200526728 5 2 5 under transmission on_

The rate system can be defined by JIS Z8701 as follows:

r (λ) is as follows: where [Number 2

Κ 100 ρ (λ) γ (λ) άλ

S (Λy (λ λ% j is the spectroscopic distribution of standard light used to display color. Isometric parameters in the xyz system; spectroscopic transmittance; [number of wavelengths (nm)

(Mar 4) [Number 4] Polarization (%) = 100

Parallel transmittance-orthogonal transmittance Parallel transmittance + orthogonal transmittance

Dichroism ratio (Rd) = log 'transmittance of single board h polarized light, 1 100 1 100 J log t transmittance of single board "—polarized light 1 100 J 100

The transmittance of the veneer can also be in the range described in Japanese Patent Laid-Open No. 14-95-200526728 2 5 8 0 51. The parallel transmittance is as described in Japanese Patent Laid-Open No. 13-0 8 3 3 2 8 or the same as Japanese Patent Laid-Open No. 14-2022295, and the wavelength dependency may also be small. The optical characteristics when the polarizing plate is arranged to cross Nicols can also be within the range described in JP-A No. 1 3 -09 1 7 3 6 and the relationship between the parallel transmittance and the orthogonal transmittance can also be Within the range described in Japanese Patent Application Laid-Open No. 1 4- 1 7472 8. As described in Japanese Patent Application Laid-open No. 14-221618, the wavelength of light is φ between 420 and 700 nanometers, and every 10 nanometers is parallel. The standard deviation of the transmittance can be 3 or less, and the wavelength of the light is between 42 0 to 700 nm. The minimum 値 per 10 nm (parallel transmittance / orthogonal transmittance) can be 3,000 or more. The polarizing plate can have parallel transmittance and orthogonal transmittance and parallel transmittance at a wavelength of 440 nm, parallel transmittance and orthogonal transmittance at a wavelength of 550 nm, and parallel transmittance and positive transmittance at a wavelength of 610 nm. The cross transmittance is set to the range described in Japanese Patent Laid-Open No. 1 4-258042 or the same as Japanese Patent Laid-Open No. 14- # 25 8 (M3.) (2) Hue The hue of the polarizing plate of the present invention can be used as The lightness index and chromaticity indices a * and b * in the L * a * b * chromaticity system deduced from the C1E equal perception space To evaluate. L *, a *, b * system using the above X, Y, Z and are as defined (formula 6)

-96-200526728 I * = ll6 (y / y0) ^ -16 (Eq. 6) α * = 500 (Χ / Χ0) ^-(Υ / Υ0) Ϊ ^ = 2〇 [(y / y0) i- (2 / z0) i 'where XQ, ΥQ, and ZQ represent the three stimulus 照明 of the illumination light source. In the case of standard light C, X〇 = 98.072, Y〇 = 100, Zo = 118.225, in In the case of standard light E > 65, X〇 = 95.045, Y〇 = 1〇〇, z〇 = 108.892 ο The preferred range of a * for a single polarizer is -2.5 or more and 0.2 or less, more preferably- 2.0 or more and 0 or less. The preferable b * of the polarizer single sheet is 1.5 or more and 5 or less, and more preferably 2 or more and 4.5 or less. The preferable range of a * of the parallel transmitted light of the two polarizing plates is -4.0 or more and 0 or less', and more preferably -3.5 or more and _0_5 or less. The preferred range of b * for the parallel transmitted light of the rain film polarizing plate is 2 · 0 or more and 8 or less, and more preferably 2.5 or more and 7 or less. A preferable range of a * of orthogonally transmitted light of the two polarizing plates is -0.5 or more and 2 or less, and more preferably 0 or more and 1.0 or less. A preferred range of b * of orthogonal transmitted light of the two polarizing plates is -2 · 〇 or more and 2 or less, and more preferably -1.5 or more and 0.5 or less. The hue system can also be evaluated from the chromaticity coordinates (χ, y) calculated by the above X, Y, and Z. For example, the chromaticity (&, yp) of the parallel transmitted light of two polarizing plates and the color of the orthogonal transmitted light The degree (xe, ye) can be set to the range described in Japanese Patent Laid-open No. 14 "1 4436, Japanese Patent Laid-open No. 1 or the same as -97- 200526728 Japanese Patent Laid-open No. 1 4 -1 6 9 0 2 4 , Or set the relationship between hue and absorbance within the range described in JP-A No. 1 3-3 1 1 8 2 7. (3) Viewing angle characteristics When the polarizing plate is configured to be orthogonal Nicols, and when light with a wavelength of 5500 nm is incident, it can also be made to be incident with vertical light from 45 degrees to the polarization axis. The transmittance ratio or xy chromaticity difference when the azimuth is incident to the normal at an angle of 40 degrees is set to Japanese Patent Laid-open No. 13-166135 or the same as Japanese Patent Laid-open No. 13-166135. Documented range. In addition, as described in Japanese Patent Application Laid-Open No. 10-0688 17, the vertical light transmittance (T0) of a polarizing plate laminated body configured as a crossed Nicols can also be normalized by the laminated body. The ratio (T6G / T〇) of the light transmittance (τ6〇) inclined at 60 ° is set to 10,000 or less, or as described in Japanese Patent Application Laid-Open No. I 4- 1 39625. When natural light is incident at any angle of 80 degrees, the transmission spectrum is set to 6% or less in the wavelength range of 520 to 640 nanometers, and the transmittance difference of the transmitted light in the wavelength range of 20 nanometers is set to 6% or less. The brightness difference of the transmitted light on the film described in Kaiping No. 08-248201 at an arbitrary distance of 1 cm is set to within 30%. (4) Durability (4-1) The wet heat durability is described in Japanese Patent Laid-Open No. 1 3-1 1 6922. When it is left in an atmosphere of 60 ° C '90% RH for 500 hours, The change rate of the light transmittance and the degree of polarization before and after it is preferably 3% or less in absolute terms. In particular, the change rate of the light transmittance is 2% or less, or the change rate of the polarization degree is preferably 1.0% or less in absolute terms, and more preferably 0.1% or less -98 ** 200526728. In addition, as described in Japanese Patent Application Laid-Open No. 07-07 760 8, it is preferred that the polarized light after being left for 500 hours at 80%, 90%, and 1111 is 95% or more, and the monomer transmittance is 38% or more. (4-2) Dry durability When left at 80 ° C in a dry atmosphere for 500 hours, the change rate of the light transmittance and polarization before and after it is preferably 3% or less in absolute terms. In particular, the change rate of the light transmittance is 2% or less, and the change rate of the degree of polarization is preferably 1.0% or less, and more preferably 0.1% or less in absolute terms. # (4-3) For other durability, as described in Japanese Patent Laid-Open No. 06- 1 676 1 No. 1, the shrinkage rate after being left at 80 ° C for 2 hours can be set to 0.5% or less. Or set the polarizing plate laminates with crossed Nicols on both sides of the glass plate and place them in an atmosphere of 69 ° C for 75 hours. X 値 and y 値 are set to the same as JP-A No. 1 0-06 8 In the range described in No. 8 1 or after being left in an atmosphere of 80 ° C and 90% RH for 200 hours, the spectral intensity ratios of 105 cnT1 and 157 cnT1 by Raman spectrometry are compared. The change is set to the range described in Japanese Patent Application No. 08-094834 or Japanese Patent Application No. 09-197127. (5) Degree of alignment Although the higher the degree of alignment of PVA, the better the polarization performance can be obtained, but the order parameters calculated by methods such as polarized Raman scattering or polarized FT-IR are preferably 0.2 to 1.0. In addition, as described in Japanese Patent Laid-Open No. 5 9- 1 3 3 5 09, the difference between the alignment coefficient of the polymer portion of the fully amorphous domain of the polarizing film and the alignment coefficient of the occupying molecule (above 0.75) can also be used. Set to at least 0_15 'or set the non-99-200526728 crystal domain alignment coefficient of the polarizing film to 0 · 65 ~ 0.85 as described in JP-A-04-204907, or a higher order of I3 · or I5 · For the degree of orientation of the iodine ion, set its order parameter to 0.8 to 1.0. (6) For other characteristics, as described in Japanese Patent Laid-Open No. 1 4-006 1 3 3, the shrinkage force per unit width in the absorption axis direction when heated at 80 ° C for 30 minutes is set to 4.0 N / cm or less, or as described in Japanese Patent Application Laid-Open No. 1 4-23 62 1 3 'After placing the polarizer under heating at 70 ° C for 120 hours, the dimensional change rate in the absorption axis direction of the polarizer and The dimensional change rates in the direction of the polarizing axis are all set within ± 0.6%, or the moisture content of the polarizing plate is set to 3% by mass or less as described in JP @ 平 第 11090546. Furthermore, as described in Japanese Patent Application Laid-Open No. 1 2-249832, the surface roughness in a direction perpendicular to the extension axis may be set to 0.04 micrometers or less as a center line average roughness, or like Japanese Patent Application Laid-Open No. 10- As described in 268294, the refractive index no in the transmission axis direction is set to be greater than 1.6, or the relationship between the thickness of the polarizing plate and the thickness of the protective film is set to the range described in Japanese Patent Application Laid-Open No. 10-111411.

4. Functionalization of polarizing plate The polarizing plate of the present invention is suitable for use as an λ / 4 plate with a viewing angle expansion film having an LCD, suitable for reflective LCD, and anti-reflection required for improving the visibility of a display Optical films such as thin films, brightness-enhancing films, or functional layers such as hard coatings, forward scattering layers, and anti-glare layers are combined into composite functional polarizing plates. A schematic sectional view of an example of a composite structure of the polarizing plate of the present invention and the above-mentioned functional optical film is shown in Fig. 1. As shown in Figure 1, it can also be used as -100- 200526728

For the protective film 1 on one side of the polarizing plate, the functional optical film 3 and the polarizing film 2 are bonded via an adhesive (FIG. 1 (A)), and the functional optical film 3 can also be bonded to the polarizing film via the adhesive layer 4. Polarizing plates with protective films la, lb are provided on both sides of 2 (Fig. 1 (B)). In the former case, any transparent protective film can be used for the other protective film. The peel strength between layers such as a functional layer or a protective film may be set to 4.0 N / 25 mm or more as described in Japanese Patent Laid-Open No. 1 4-3 1 1 23 8. The functional optical film is preferably arranged on the liquid crystal module side according to the intended function or on the opposite side from the liquid crystal phase group, that is, on the display side or the backlight side. The functional optical film for use in combination with the polarizing plate of the present invention will be described below. (1) Viewing angle widening film (optical auxiliary film) The polarizing plate of the present invention can be used in combination with, for example, TN (Twisted Nematic type), IPS (In-plane cutting)

Type change: In-Plane Switching type), OCB (Optically Compensatory Bend type), VA (Vertically Aligned type), ECB (Electric Field Controlled Birefringence: Electrically Controlled Birefringence type) display mode The viewing angle widens the film. The viewing angle widening film for TN mode can be used in Japanese Journal of Printing Society Vol. 36, No. 3 (1999) pages 40-44, Monitor Monthly August (2002) pages 20-24, Japan The WV film described in Patent Publication No. 4-229828, Patent Publication No. 6-75115, Patent Publication No. 6-214116, Patent Publication No. 8-50206, etc. (Fujizhao-101-200526728 Photographic Film (Share) system). The preferred structure of the viewing angle expansion film for the TN mode is one in which an alignment layer and an optically anisotropic layer are laminated in this order on the transparent polymer film described above. Although the viewing angle-enlarging film can be used for bonding to a polarizing plate through an adhesive, as described in SID '00 Dig., Page 551 (2000),' think from the viewpoint of thinness, It is particularly preferable to also serve as one of the protective films of the above-mentioned 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 micro grooves. In addition, there is known an alignment layer that is to be provided with an electric field, a magnetic field, or by irradiation with light, but an alignment layer formed by a rubbing treatment of a polymer is particularly preferred. The rubbing treatment is accomplished by rubbing the surface of the polymer layer in a certain direction several times with paper or cloth. The direction of the absorption axis of the polarizing film and the direction of rubbing are preferably substantially parallel. Examples of the polymer used as the alignment layer include polyimide, polyvinyl alcohol, and a polymer having a polymerizable group described in Japanese Patent Application Laid-Open No. 9-1 525 09 and the like. The thickness of the alignment layer is preferably 0.01 to 5 μm, and more preferably f is 0.05 to 2 μm. The optically anisotropic layer 'preferably contains a liquid crystal compound. The liquid crystalline compound which can be used in the present invention is particularly preferably a compound having a dish-like compound (dish-like liquid crystal). The dish-like liquid crystal molecule is like a triphenylene derivative of D_1 having a disc-shaped core, and the side chain is a structure in which the side chain extends radially. In addition, in order to impart diachronic stability ', a group capable of reacting with heat, light, or the like may be introduced. A preferred example of the above-mentioned dish-shaped liquid crystal is described in Japanese Patent Laid-Open No. 102-200526728

The dish-like liquid crystal molecules are aligned approximately parallel to the film plane at a pre-tilt angle with respect to the rubbing direction in the vicinity of the alignment layer, and the dish-like liquid crystal molecules on the opposite side of the air surface are aligned vertically near the plane. The entire system of the disc-shaped liquid crystal layer forms a hybrid alignment, whereby the layer angle of the TN mode TFT-LCD (thin-film transistor-liquid crystal display device) can be used to expand the viewing angle. And other compounds (and further, for example, a polymerizable monomer and a photopolymerization initiator) are dissolved in a solvent, the solution is prepared, coated on the alignment layer, dried, and then heated to a dish-like nematic phase formation temperature, It can be produced by irradiating UV (ultraviolet) light to polymerize it, and then cooling it. The dish-like nematic liquid crystal phase-solid phase transition temperature for the dish-like liquid crystalline compound used in the present invention is preferably 70 to 30 ° C., and particularly preferably 70 to 170 ° C. In addition, it can be added to the above-mentioned optical Any compound other than the dish-like compound of the directional layer can be used as long as it has compatibility with the dish-like compound and can impart a change in oblique angle to the front face of the liquid-crystalline dish-like compound or does not hinder the alignment Among these, a polymerizable monomer -103-

200526728 Body (for example, compounds with vinyl, vinyloxy, acryl, and archyloxy), fluorine-containing trinitrogen trap compounds, and other two-sided side orientation control additives, cellulose acetate, cellulose Esters, hydroxypropyl cellulose, and cellulose acetate butyrate; etc .; The amount of these compounds added to the dish-like compound is usually C% by mass, preferably 0.1 to 30% by mass. The thickness of the optically anisotropic layer is preferably 0.1 to 10 micrometers and 0.5 to 5 micrometers. A preferred embodiment of the viewing angle-enlarging film is an optical anisotropy composed of a cellulose film as a transparent film, an alignment layer provided thereon, and a dish-like liquid crystal on the alignment layer. Hiroto / The optically anisotropic layer is crosslinked by irradiating UV light. In addition, in addition to the above, when the viewing angle widening film is combined with the plate of the present invention, for example, as described in Japanese Patent Laid-Open No. 1 98942, a light refraction in a direction crossing the surface of the plate may appear. The method of laminating anisotropic retardation plates, or the method described in Zetekaihei 1 4-25 8052, sets the dimensional change rate of the protective film and the optical layer to be substantially the same. In addition, as described in Japanese Patent Application Laid-Open No. 1 2-25 863 2, the moisture content of the polarizing plate to be attached to the visual field film is set to 2.4% or less, or described in Japanese Patent Application Laid-Open No. 1 4-267839. , The method of setting the contact angle with water with an enlarged viewing angle to 70 ° or less. IP S mode liquid crystal cell viewing angle expansion film is used to improve the propylene, airborne acrylic polymer aligned in parallel to the substrate surface in the field-free black display, 1 ~ 50 and better substrate thin Formed in the structure, the polarized light is 07-, and in the double direction, it can be taken in different directions. It can be enlarged and thin. The surface of the film is electro-optical liquid crystal-104- 200526728, and the angle of view of the polarizing plate's orthogonal transmittance. The IP S mode is displayed in black when no electric field is applied, and the transmission axes of the upper and lower polarizing plates are orthogonal. However, when viewed from an oblique direction, the crossing angle of the transmission axis is no longer 90 °, so that light leakage occurs and the contrast decreases. When the polarizing plate of the present invention is used in an IPS-mode liquid crystal cell, the in-plane phase difference from that described in Japanese Patent Application Laid-Open No. 10-54982, such as to reduce light leakage, is close to 0, and it is in the thickness direction. Combination of viewing angle expansion film with retardation. • The viewing angle expansion film for liquid crystal cells of 〇CB mode is used to optically compensate the liquid crystal layer that becomes vertical alignment at the center of the liquid crystal layer and becomes oblique alignment near the substrate interface due to the application of a φ electric field to improve black display. Field of view characteristics. When the polarizing plate of the present invention is used in an OCB mode liquid crystal cell, the polarizing plate of the present invention can be suitably used in combination with a viewing angle-enlarging film in which the discotic liquid crystal compound described in US Patent No. 5,805,253 is mixed and aligned. The viewing angle expansion film for liquid crystal cells in the VA mode is used to improve the viewing angle characteristics of black display when liquid crystal molecules are vertically aligned on the substrate surface in the absence of an applied electric field. Such a viewing angle-enlarging film can be a film having a phase difference close to 0 and having a phase difference in the thickness direction described in Invention Patent No. 2,866,3 72, or a disc-shaped compound system and a substrate. Films that are arranged in parallel, or stretched films with the same in-plane retardation, are laminated to configure the film so that the retardation axis becomes orthogonal, or to prevent the orthogonal transmittance of the oblique direction of the polarizer from deteriorating. Films made of molecular rod-like compounds are used in combination. -105- 200526728 (2) λ / 4 plate The polarizing plate of the present invention can be used as a circular polarizing plate laminated with a λ / 4 plate. The circular polarizing plate has a function of converting incident light into circularly polarized light, and is suitable for use in a reflective liquid crystal display device, a semi-transmissive liquid crystal display device such as an ECB mode, or an organic EL (electrically excited light element) element. The λ / 4 plate used in the present invention, in order to obtain substantially complete circularly polarized light in the range of visible light wavelengths, preferably has a retardation (Re) which is substantially 1/4 of the wavelength in the range of visible light wavelengths. Retardation film. The so-called "# delay in the range of visible light wavelength is generally 1/4", which means that the longer the wavelength from 400 to 700 nm, the longer the delay is, and it can meet the 4 The delay chirp (re 4 5 0) measured at a wavelength of 50 nm is 80 to 125 nanometers, and the delay chirp (Re5 90) measured at a wavelength of 590 nanometers is a relationship of 120 to 160 nanometers. However, it is more preferably Re590-Re45025 nm, and particularly preferred is Re590-Re4502 10 nm. The λ / 4 plate used in the present invention is not particularly limited as long as it can meet the above conditions, but it can be used in, for example, Japanese Patent Laid-Open No. 5-# 271 18, and Japanese Patent Laid-Open No. 10- Laminated λ / 4 plates in which several polymer films are laminated, as disclosed in Japanese Patent Publication No. 688 16 and Japanese Patent Application Laid-Open No. H 10-90521, World Patent No. WO 00/653 84, and World Patent No. WO0 0/2 6 7 0 5 A sheet of polymer film extended by a polymer sheet / 4 sheet is described in Japanese Patent Application Laid-Open No. 2000-284 1 26 and Japanese Patent Application Laid-Open No. 2002-31717. Any one of an λ / 4 plate or the like having at least one optically anisotropic layer on the polymer film; an I / 4 plate. In addition, the polymer phase is aligned with the retardation axis direction or the alignment direction of the optically anisotropic layer. In the circular polarizing plate, the retardation axis of the λ / 4 plate and the transmission axis of the polarizing film can be crossed at any angle, but it is preferably 45. Tu 20. Range to make it cross. However, the retardation axis of the λ / 4 plate and the transmission axis system of the polarizing film may cross each other in a range other than the above. When the λ / 4 plate is composed of a laminated λ / 4 plate and a λ / 2 plate, for example, the invention patent number 3,23 6,3 04 or the Japanese Patent Laid-open No. 10-ό 8 8 1 6 According to the publication, it is preferable to attach the Λ / 4 plate and the / 2 plate so that the angle formed by the retardation axis of the Λ / 4 plate and the transmission plate of the polarizing plate is substantially 75 ° and 15 °. (3) Anti-reflection film The polarizing plate of the present invention can be used in combination with an anti-reflection film. The antireflection film can be a thin film having a reflectance of about 1.5%, such as a fluoropolymer that gives only a single layer, or a thin film having a multilayer reflection of 1% or less. Either. In the present invention, it is preferable to use a layer having at least one of a low refractive index layer and a layer having a higher refractive index than the low refractive index layer (that is, a high refractive index layer, a medium refractive index layer) on a transparent support. ) Structure to be laminated. In addition, it is also suitable to use the anti-reflection described in Nitto Gazette Vol. 38, No. 1, May 2000, pages 26-28, or Japanese Patent Laid-Open No. 2 002-3 0 1 783. film. The refractive index of each layer satisfies the following conditions. The refractive index of the high refractive index layer > the refractive index of the intermediate refractive index layer > the refractive index of the transparent support > the refractive index of the low refractive index layer can be used as a transparent support of the anti-reflection film, which can be used for the above- 107- 200526728 Transparent polymer film for protective film of polarizing layer. The refractive index of the low refractive index layer is from 1.20 to 1.55, preferably from 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 abrasion resistance, a material containing polysiloxy and fluorine may be used to impart lubricity to the surface. Compounds containing fluorine can be used, for example, in paragraph numbers [0018] to [0026] in the specification of Japanese Patent Laid-Open No. 9-222503, as in paragraph numbers [0019] to [0030] in the specification of Japanese Patent Publication No. 11-38202. The compounds described in Japanese Patent Application Publication No. 200 1-402 84, paragraph numbers [0027] to [0028], and Japanese Patent Application Publication No. 2000-284 102. The compound containing polysiloxane is preferably a compound having a polysiloxane structure, but a reactive polysiloxane (such as Sairaplein (made by nitrogen)) or a polysiloxane containing a silanol group at both ends may also be used. (Japanese Patent Laid-Open Publication No. 1 1-25 84403), etc. It is also possible to condense an organometallic compound such as a silane coupling agent and a specific silane coupling agent containing a fluorine-containing hydrocarbon group in the presence of a catalyst. Reaction hardens (Same as JP 58- • 1 42 9 5 8; S. 5 8-1 47483; S. 5 8-1 47484 0; S. JP 9- 1 5 75 82, same as 1-11 06704, same as JP 2000-1 1 7902, same as 200-48590, and compounds described in 2002-53 804) For low-refractive-index layers, in addition to additives other than those described above, other additives (such as silicon dioxide (si 1 ica), fluorine-containing particles (magnesium fluoride, calcium fluoride, barium fluoride), etc.) Low-refractive index inorganic compound with a primary particle average diameter of 1 ~ 150 nm, Japan National Institute of Technology Japanese Unexamined Patent Publication No. i-38 20-108-200526728 paragraphs [0020] to [003 8] organic fine particles, etc.), silane coupling agents, lubricants, surfactants, etc. Low refractive index layer system It can also be formed by a vapor phase method (vacuum evaporation method, sputtering method, ion plating method, plasma CVD method, etc.), but it is preferably formed by a coating method from the viewpoint that it can be manufactured at low cost. A dipping method, an air knife coating method, a curtain coating method, a roll coating method, a wire rod coating method, a photogravure coating method, and a microphotogravure coating method can be used.

The film thickness of the low refractive index layer is preferably 30 to 200 nm, more preferably 50 to 150 nm, and most preferably 60 to 120 nm. The medium-refractive index layer and the high-refractive index layer preferably have a structure in which ultrafine particles of an inorganic compound with a high refractive index having an average particle diameter of 1000 nm or less are dispersed in a matrix material. For inorganic particles with high refractive index, inorganic compounds with a refractive index of 1.65 or more, such as oxides of Ti, Zn, Sb, Sn, Zr, Ce, Ta, La, and In, can be used. Compound oxides and so on. These ultrafine particles can be treated on the surface of the particles with a surface treatment agent (silane coupling agent, etc .: JP-A No. 1 1-295 5 03, same as JP-A No. 1-1 5 3 703 φ, JP-A 2000- 9908, anionic compounds or organometallic coupling agents: JP-A No. 2001 -3 1 0432, etc.), core-sheath structures with high refractive index particles as cores (JP-A No. 200 1-1 66 1 04, etc.),倂 Use a specific dispersant (for example, Japanese Patent Application Laid-Open No. 11-1 53 703, invention patent number US Patent No. 6,2 1 0,85 8 B1, Japanese Patent Application Laid-Open No. 2002-2776069, etc.) use. As the material for the substrate, any thermoplastic resin, (thermo) curing, or 109 · 200526728 resin film can be used, but JP-A-2000-47004, Japanese Patent Publication No. 2001-315242, and Japanese Patent Publication No. 2001-31871 can also be used. The polyfunctional materials described in Bulletin No. 2964〇1 and the like, and the hardening film composed of metal alkoxides described in Bulletin No. 2001-293 8 1 and the like. The refractive index of the high refractive index layer is preferably from 1.70 to 2.20. The thickness is preferably 5 nm to 10 m, and more preferably 10 nm. # The refractive index of the medium refractive index layer should be adjusted to be between the low refractive index and the high refractive index layer. The middle refractive index is preferably from 1.50 to 1.70. The haze of the anti-reflection film is preferably 5% or less, more preferably, the strength of the film is based on: The pencil hardness of TIS K5400 is preferably Η or more, more preferably 2H or more, and most preferably 3H or more (4) Brightness-improving film The polarizing plate of the present invention can be combined with a brightness-improving film to make it. • The enhancement film has the function of separating circularly polarized light or linearly polarized light. Between the polarizer and the backlight module, one of the circularly polarized light Or make a back reflection or back scattering towards the backlight side. From the backlight part, the polarization state can be changed locally, and when it is incident on the bright film and polarizing plate, it can be transmitted locally, and the light utilization rate can be repeatedly increased, which can increase the front brightness by about 1.4 times. It is known that a high-thin film has an anisotropic reflection method and an anisotropic scattering, etc., and can be used in combination with the polarizing plate of the present invention. Bulletin No. R, the same as the first or JP-L products, the refractive index layer m ~ 1 micrometer layer, the refraction of 0 layer is less than 3%. Degree test, on. use. Brightness is used to configure f linearly polarized light and then reflect light to increase the thickness. This process is based on. Brightness improvement method, its -110-200526728 In the aspect of the isotropic reflection method, it is known to laminate a uniaxially stretched film and an unstretched film into multiple layers to increase the refractive index difference in the extension direction to have reflectivity and transmission. Film with enhanced isotropic brightness and a multilayer film system using the principle of a dielectric mirror (documented in World Invention Patent No. WO 95/1 769 1; same as WO 95/1 7692; same as WO 9 5/1 7 699) or a cholesteric liquid crystal system (described in European Invention Patent No. 606940 A2, Japanese Patent Laid-Open No. 8-27 1 73 1). Multi-layer method using the principle of dielectric mirror # The brightness-improving films include DBEF-E, DBEF-D, and DBEF-M (all manufactured by 3M) Suitable for use in the present invention, the brightness of the cholesteric liquid crystal method is improved As the film, NIPOCS (manufactured by Nitto Denko Corporation) is suitable for use in the present invention. Regarding NIP OCS, you can refer to Nitto Gazette Vol. 38, No. 1, May 2000, pages 19-21. Furthermore, in the present invention, the specifications of World Invention Patent No. WO 97/32223, the same as WO 97/32224, the same as WO 97/3 2225, the same as WO 97/3 2226, and Japan National Patent Publication No. 9- • 2? 4! 〇8, as described in each of the publications Nos. 1 to 1 7423 1 is a blend of a positive intrinsic f birefringent polymer and a negative intrinsic birefringent polymer. , And used in combination with the brightness enhancement film of unidirectionally extending anisotropic scattering method. The anisotropic scattering method brightness improving film is preferably DRPF-H (manufactured by 3M Corporation). The polarizing plate and the brightness-improving film of the present invention are preferably used in the form of bonding through an adhesive, or one of the protective films of the polarizing plate is used as an integrated type of the brightness-improving film. -111- 200526728 (5) Other functional optical films The polarizing plate of the present invention can also be used with hard coating, front scattering layer, anti-glare layer, gas barrier layer, lubricating layer, antistatic layer, base coating or setting A functional optical film such as a protective layer is used in combination. In addition, these functional layers may be used in combination with each other or in the same layer as the above-mentioned antireflection layer or optically anisotropic layer. (5-1) Hard coating The polarizing plate of the present invention is to provide mechanical strength such as abrasion resistance. Compared with Lujia, it adopts a "hard coating" and a functional φ optical film provided on the surface of a transparent support. Combination method. When a hard coat is applied to the above-mentioned anti-reflection film, it is particularly 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 hardening functional group is preferably a photopolymerizable functional group, and the organometallic compound containing a hydrolyzable functional group is preferably an organic alkoxysilyl compound. The specific structure of the hard coating # The composition can be used, for example, in Japanese Patent Laid-Open No. 2002- 1 449 1 3 φ, the same as 2000-9908, and the World Invention Patent No. WO 0/466 1 7 Those listed in the bulletin. The film thickness of the hard coating layer is preferably 0.2 to 100 microns. The strength of the hard coating layer is preferably Η or more in a pencil hardness test according to JIS K5400, more preferably 2H or more, and most preferably 3H or more. In addition, according to the results of the Taber abrasion test according to JIS K5400, the lesser the abrasion amount of the test piece before and after the test, the better. -112 · 200526728 The materials that can be used to form the hard coating layer are compounds containing ethylenically unsaturated groups and compounds containing ring-opening polymerizable groups. These compounds can be used alone or in combination. Preferred examples of the compound containing an ethylenically unsaturated group include ethylene glycol diacrylate, trimethylolpropane triacrylate, di-trimethylolpropane tetraacrylate, neopentyl tetraol triacrylate, Polyacrylates of polyhydric alcohols such as neopentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate; diacrylates of bisphenol A diglycidyl ether, hexanediol Glycidyl ether diacrylates and other epoxy acrylates; urethane acrylates and the like made by the reaction of polyisocyanate with hydroxyl-containing acrylates such as hydroxyethyl acrylate. In addition, commercially available compounds include: EB-600, EB-40, EB-140, EB-1150, EB-1 2 9 0 K, IRR2 1 4, EB-2 2 2 0, TMPTA, TMPTMA ( The above are made by DAICEL · UCB (stock), UV-6300, UV-1700B (the above are made by Japan Synthetic Chemical Industry (stock)) (all are trade names), and so on.

In addition, preferable examples of the compound containing a ring-opening polymerizable group include: Glycidyl ethers include ethylene glycol diglycidyl ether, bisphenol A diglycidyl ether, and trimethylolethane Glycidyl ether, trimethylolpropane triglycidyl ether, glycerol triglycidyl ether, triglycidyl trihydroxy ether isotricyanate, sorbitol tetraglycidyl ether, neopentyl Alcohol tetraglycidyl ether, polyglycidyl ether of cresol novolac resin; polyglycidyl ether of phenol novolac resin, etc .; alicyclic epoxy are: Seloxide 2021P, Seloxide 2081, Epolead GT-301 , Epolead GT-401, E HP E 3 1 5 0 CE (the above are all DAICEL -113- 200526728 manufactured by Chemical Industry Co., Ltd. (both trade names)); polycyclohexyl epoxy methyl group of phenol novolac resin Ethers, etc .; oxetanes are: oxetane-121, OXT-221, OX-SQ, PNOX-1009 (the above are all manufactured by East Asia Synthetic (stock) (both trade names)). It is also possible to use a polymer of (meth) acrylic acid glycidyl ester or a copolymer of a monomer copolymerizable with glycidyl acrylate as a hard coating. For the hard coating, in order to reduce the hardening shrinkage of the hard coating, improve the adhesion with the substrate, and reduce the curl of the hard coating treated article of the present invention

It is also suitable to take silicon oxide, titanium, hafnium, aluminum and other oxide particles, or φ polyethylene, polystyrene, poly (meth) acrylates, polydimethylsiloxane and other cross-linked particles (Styrene-butadiene rubber), NBR (

A method of crosslinking microparticles such as organic microparticles such as rubber microparticles such as nitrile rubber). The average particle diameter of these crosslinked fine particles is preferably 1 nm to 20,000 nm. In addition, the shape of the crosslinked fine particles is not particularly limited to a spherical shape, a rod shape, a needle shape, a plate shape, and the like. The amount of micro particles added is 60 volume of the hard coating after hardening. /. The following is preferable, and more preferably 40% by volume or less. When the above-mentioned inorganic fine particles are added, generally, since the affinity with the binder polymer is not good, it is also suitable to use a metal containing silicon, aluminum, titanium, etc., and having an alkoxide group, A surface treatment agent for a functional group such as a carboxylic acid group, a sulfonic acid group, or a phosphonic acid group to perform a surface treatment. The hard coating layer is preferably hardened by heat or active energy rays. Among them, radiation, gamma rays, α-rays, electron rays, purple-114-200526728 outer lines, etc. are preferred. ≪ For safety and productivity, the use of electron beams and ultraviolet rays is particularly preferred. When hardened by heat, from the viewpoint of the heat resistance of the plastic itself, the heating temperature is preferably 140 ° C or lower, and more preferably 100 ° C or lower. (5-2) The forward scattering layer "forward scattering layer" is used to improve the viewing angle characteristics (hue and brightness distribution) in the vertical, horizontal, and leftward directions when the polarizing plate of the present invention is applied to a liquid crystal display device. The fine particles with different ratios are preferably dispersed with a binder. For example, it can be used: the date when the forward scattering coefficient is specified φ Japanese Patent Laid-Open No. 1 1-3 8 2 0 8 and the relative refraction of transparent resin and fine particles Rate is defined as a specific range of Japanese Patent Laid-Open Publication No. 2000_19 9 809, Japanese Patent Laid-Open Publication No. 2002- 1 075 75, etc., with a haze 値 stipulated of 4 or more. The structure. In addition, in order to control the viewing angle characteristic of the haze, the polarizing plate of the present invention may be used in combination with the "Lumisuty" described on pages 3 1 to 39 in the "Light Functional Film" of the technical report of Sumitomo Chemical Industries, Ltd. .

The "anti-glare layer" is used to scatter the reflected light to prevent image reflection. The anti-glare function is obtained by forming unevenness on the outermost surface (display side) of the liquid crystal display device. The haze of the anti-glare optical film is preferably 3 to 30%, more preferably 5 to 20% ', and most preferably 7 to 20%. The method for forming unevenness on the film surface can be, for example, a method of adding fine particles to form unevenness on the film surface (for example, Japanese Patent Laid-Open No. 2000-271878), and a small amount (〇 · ι ~ 50% by mass) ) A method for forming a concave-convex film with particles larger than (-115- 200526728) in particle size (0.5 to 2 microns) (for example, Japanese Patent Laid-Open Nos. 2000- 2 8 1 4 1 0, The same as in Japanese Patent Publication No. 2000-95893, Japanese Patent Publication No. 2001-100004, Japanese Patent Publication No. 2001-2 8 1 407, etc.), and a method of physically transferring an uneven shape on a film surface (for example, Japanese Patent Laid-Open No. Shokai 6 3-2 7 8 8 3 9 (including those disclosed in Japanese Patent Application Laid-Open No. 11-183710, Japanese Patent Application Laid-Open No. 2000-275401).

These functional layers may be provided on one or both sides of the polarizing film side and the opposite side of the polarizing film. 5. Liquid crystal display device using polarizing plate Next, a liquid crystal display device using the polarizing plate of the present invention will be described below. FIG. 2 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 includes a liquid crystal cell (15 to 19), and an upper polarizing plate 11 and a lower polarizing plate 22 arranged through the liquid crystal cell (15 to 19). The polarizing plate sandwiches a polarizing film and a pair of transparent protective films, but in FIG. 2 it is shown as an integrated polarizing plate and its detailed f structure is omitted. The "liquid crystal cell" includes an upper substrate 15 and a lower substrate 18, and a liquid crystal layer formed by the liquid crystal molecules 17 held by the substrates. Liquid crystal cell lines can be classified into TN (Twisted Nematic), IPS (In-Plane Switching; In-Plane Switching; In-Plane Switching; In-Plane Switching; (Switching)), OCB (Optically Compensatory Bend), VA (Vertically Aligned), ECB (Electricallyly -116- 200526728

(Controlled Birefringence) display mode, but the polarizing plate of the present invention can be used in any display mode regardless of the transmission type and reflection type.

An alignment film (not shown) is formed on the surface of the liquid crystal molecules 17 in contact with the substrates 15 and 18 (hereinafter also referred to as the "inner surface"). The liquid crystal molecules are in an unapplied or low-applied electric field state. The alignment of 17 is controlled by applying a rubbing treatment or the like on the alignment film. In addition, transparent electrodes (not shown) capable of applying an electric field to a liquid crystal layer made of liquid crystal molecules 17 are formed on the inner surfaces of the substrates 15 and 18. The friction direction of the TN mode is applied in a direction orthogonal to each other on the upper and lower substrates, and the inclination angle can be controlled by the strength and the number of frictions. The alignment film is formed by coating a polyimide film and firing it. The twist angle of the liquid crystal layer depends on the intersection angle of the rubbing directions of the upper and lower substrates and the chiral agent added to the liquid crystal material. In this example, palmitizers with a pitch of about 60 microns are added so that the twist angle becomes 90 °. In addition, when the twist angle is in the case of a notebook computer, a personal computer monitor, or a liquid crystal display device for a television, it is set to 90. When the vicinity (85 to f95 °) is used as a reflective display device for a portable telephone or the like, it is set to 0 to 70 °. In IPS mode or ECB mode, the twist angle will be 0 °. In the IPS mode, the electrode system is arranged only on the lower substrate i 8 to apply an electric field parallel to the substrate surface. As for the OCB mode, there is no twist angle and the tilt angle is set to be larger. In the VA mode, the liquid crystal molecules 17 are aligned perpendicular to the upper and lower substrates. However, due to the product of the thickness d of the liquid crystal layer and the refractive index anisotropy Δ η Δ nd -117- 200526728, the brightness changes during white display. Therefore, in order to obtain the maximum brightness, the range is set for each display mode.

The parent prong angle 'of the absorption axis 12 of the upper polarizing plate 11 and the absorption axis 23 of the lower polarizing plate 22 is generally made to be approximately orthogonal to each other, thereby obtaining high contrast. The intersection angle of the rubbing axis 12 of the upper polarizing plate 11 of the liquid crystal cell and the rubbing direction of the upper substrate 15 varies depending on the liquid crystal display mode, but in the TN and IPS modes, it is generally set in parallel or perpendicular. 〇cb, ECB

The mode is mostly set to 45. . However, in order to adjust the hue or viewing angle of the display color, the optimum mode differs in each display mode, so it is not limited to these ranges.

The liquid crystal display device in which the polarizing plate of the present invention can be used is not limited to the structure shown in FIG. 2 and may include other components. For example, a color filter may be disposed between the liquid crystal cell and the polarizing film. In addition, the above-mentioned viewing angle widening films 1 3 and 20 may be disposed between the liquid crystal cell and the polarizing plate. The polarizing plates 1 1, 2 2 and the viewing angle expansion film 1 3, 2 0 can be arranged through the laminated form of the adhesive, and can also be used as one of the liquid crystal cell-side protective films for viewing angle expansion. The so-called integrated elliptical polarizer is arranged. In the case of a transmissive type, a backlight having a cold-cathode or hot-cathode fluorescent tube, a light-emitting diode, a field emission element, or an electroluminescence element as a light source can be disposed on the back surface. In addition, the liquid crystal display device for using the polarizing plate of the present invention may also be a reflective type. In this case, the polarizing plate may be arranged only on the observation side and in the substrate on the back of the liquid crystal cell or on the lower side of the liquid crystal cell. The surface is provided with a reflective film. Of course, the light module can also be set on the liquid crystal cell observation side before using the light source. -118- 200526728 [Embodiments] [Examples] The present invention will be described in more detail based on examples below, but the present invention is not limited to these. [Example 1] (Production of tritiated cellulose film (1)) The following composition was charged into a mixing tank and stirred while heating to dissolve each component to prepare tritiated cellulose solution A.

<Composition of tritiated cellulose solution A> 100 mass parts of cellulose acetate having a degree of acetylation of 60.9% triphenyl phosphate (plasticizer) 7.8 mass parts of diphenyl diphenyl phosphate (plasticizer) 3.9 mass Parts methylene chloride (first solvent) 300 parts by mass methanol (second solvent) 54 parts by mass 1-butanol 11 parts by mass

The following composition was charged into another mixing tank, and the components were dissolved while heating to dissolve the components to prepare additive solutions B-1 to B-6.

<Composition of Additive Solution B-1 to B-6> Table 1 Coating Solution 1 * Chloroform methanol methanol ultraviolet ultraviolet compound compound absorbent absorbent (446) (F-7) (mass parts) (mass parts) (A ) (Parts by mass) (B) (parts by mass) (parts by mass) (parts by mass) B- 1 80 20 2 4 j \\\ No B-2 80 20 2 4 30 Ατττ No B-3 80 20 2 4 No 30 B-4 80 20 2 4 10 20 B-5 80 20 2 4 20 10 B-6 80 20 2 4 15 15 (Chemical 49) -119- 200526728

UV absorber A uv absorber B <cellulose acetate film (manufacturing of n)>

To 4 to 4 parts by mass of the tritiated cellulose solution A, 40 parts by mass of the additive solution B-1 was added and stirred sufficiently to prepare a coating solution. The coating solution was cast from a casting orifice onto a drum cooled to 0 ° C. The solvent content is 70% by mass, and both ends of the film in the width direction are clamped with a pinch tenter Φ (the needle described in Japanese Patent Application Laid-Open No. 4- 1 009, Figure 3). Clip tenter) is fixed, and the solvent content rate is 3 to 5% by mass, and the horizontal direction (the direction perpendicular to the mechanical direction) is maintained at an interval of 3% while being dried. Thereafter, it was transported between rolls of a heat treatment apparatus and dried again to obtain a cellulose acetate film having a thickness of 80 μm (1 <manufacturing of cellulose acetate film (2) to (8)>

A cellulose acetate film (2) was prepared in the same manner as the cellulose acetate film (1), except that the additive solution and thickness were changed to those shown in Table 2 in the production of the cellulose acetate film (1). )~(8 ). -120-200526728 Table 2 Sample number Additive solution thickness (micron) Additive amount (% by mass, relative to cellulose acetate) Water vapor permeability (g / m2 · 24hr) Remark Compound (446) Compound (F-7) (1 ) B- 1 80 0 0 1,950 Comparative example (2) B-2 80 8.8 0 1,530 Comparative example (3) B-3 80 0 8.8 1,610 Comparative example (4) B-4 80 2.9 5.9 1,100 The present invention (5) B -5 80 5.9 2.9 1,040 The present invention (6) B-6 80 4.4 4.4 810 The present invention (7) B-7 60 4.4 4.4 1,080 The present invention⑻ B-8 40 4.4 4.5 1,340 The present invention [Example 2]

(Alkaliization treatment) The cellulose acetate film (D ~ (8)) was immersed in a 55 ° C, 1.5% sodium hydroxide aqueous solution for 2 minutes. Then, it was washed in a water bath at room temperature and used at 3 It was neutralized with sulfuric acid specified at 0 ° C and 0.1. It was washed again in a water bath at room temperature, and then dried with warm air at 100 ° C. In this way, the surface of the cellulose acetate film was cleaned. Saponification was performed. Furthermore, a WV film made by Fuji Photographic Film Co., Ltd. was alkalized under the same conditions for the production of the following samples. [Example 3] Iodine was adsorbed on the stretched polyvinyl alcohol film to obtain a polarizing film. The cellulose acetate film (1) prepared in Example 1 was attached to one side of the polarizing film using a polyvinyl alcohol-based adhesive, and the transmission axis of the polarizing film and the cellulose acetate film were delayed. The phase axes are arranged in parallel. In addition, the WV film subjected to the alkali treatment in Example 2 was attached to the opposite side of the polarizing film using a polyvinyl alcohol-based adhesive. A polarizing plate (1) was obtained in this manner. -121 -200526728 [Example 4] and Example 3 Plot composition shown in Table 3 for producing a cellulose acetate film of the polarizing plate (2) to (8). [Example 5]

The polarizing plate prepared in this way was attached to the glass plate such that the WV film was on the glass side, and it was allowed to stand at 60 ° C 90% RH for 1,000 hours. The photometer measures the parallel transmittance and the orthogonal transmittance, and then calculates the polarization degree by the above-mentioned (Expression 4). The results are shown in Table 3. According to the results in Table 3, it was found that the polarization degree of the polarizing plate system of the present invention has a small change in the degree of polarization with respect to heat and humidity, and therefore has excellent durability.

Table 3 Polarization remarks of the protective film on the air interface side of the polarizing plate (1) Tritonized cellulose film (1) 97.4 Comparative example (2) Tritonized cellulose film (2) 98.1 Comparative example (3) Tritonized cellulose film (3 ) 98.4 Comparative Example (4) Tritiated cellulose film (4) 99.1 The present invention (5) Tritiated cellulose film (5) 99.3 The present invention (6) Tritiated cellulose film (6) 99.7 Tritiated fiber of the present invention Plain film (7) 99.0 The present invention (8) Tritiated cellulose film (8) 98.9 The present invention [Example 6]

One of the 20-inch liquid crystal display devices (LC-20V1, manufactured by Sharp Corporation) using a TN-type liquid crystal cell was peeled off from the polarizing plate and replaced with an adhesive. The obtained polarizing plate was attached to the observer side and the backlight side so that the optical compensation sheet was positioned on the liquid crystal cell side. The polarizer transmission axis on the viewer side and the polarizer transmission axis on the backlight side are arranged orthogonally. Then, under the ambient conditions of a temperature of 25 t and a phase of -122- 200526728 and a humidity of 60%, the backlight module was continuously turned on for 100 hours' and the full black display state was visually observed in a dark room to evaluate light leakage. As a result, the polarizing plate of the comparative example observed a picture-frame-shaped light leakage in the display image of the liquid crystal display device, while the liquid crystal display device using the polarizing plate of the present invention did not observe these cases. [Example 7] (Preparation of cellulose acetate solution) The following composition was charged into a mixing tank and stirred to dissolve each component to prepare a cellulose acetate solution. Composition of cellulose acetate solution A1-cellulose acetate with a degree of acetic acid of 60.9% 100.0 parts by mass of dichloromethane (first solvent) 402.0 parts by mass of methanol (second solvent) 60.0 parts by mass (matting agent solution) Preparation) The following composition was charged into a disperser and stirred to dissolve each component to prepare a matting agent solution. The composition of the matting agent solution has an average particle diameter of 16 nanometers of silica particles (AEROSIL R972, trade name, manufactured by Japan Aerosil Corporation) 2.0 parts by mass of dichloromethane (first solvent) 76.3 parts by mass of methanol (second solvent ) U.4 parts by mass of cellulose acetate solution A1 10.3 parts by mass

(Preparation of Additive Solution) The following composition was charged into a mixing tank and stirred while heating to dissolve each component to prepare an additive (delayed ascending agent) solution. -123- 200526728 ¥ Composition of dosing solution-Additive (446) 19.8 parts by mass of monochloromethane (first solvent) 58.4 parts by mass of methanol (first solvent) 8.7 parts by mass of flavison acetate solution αΊ-12.8 parts by mass (0268)

(446)

(Manufacture of cellulose acetate film (1 1))

94. 6 parts by mass of the above cellulose acetate solution A 1, 1.3 parts by mass of the matting agent solution and 4.1 parts by mass of the delayed rising agent solution were filtered, mixed, and then cast using a belt casting machine . The mass ratio of the delayed rising agent to the cellulose acetate was 4.6%. When the residual solvent content is 30%, the film is peeled from the casting belt. At 130 ° C, the film with the residual solvent content of 13% by mass is drawn with a tenter at a draw ratio of 28%. Extend laterally, and still hold the stretched width at 14 ° C for 30 seconds. Then remove the jig and dry at 14 ° C for 40 minutes to obtain a cellulose acetate film. The obtained cellulose acetate film The amount of residual solvent is 0.2% -124-200526728, and the film thickness is 92 microns. Except changing the type and quantity of additives in the additive solution to the content not shown in Table 4, the cellulose was prepared by the same method. Acetate films (1 2) to (1 8). (Measurement of optical properties) With respect to the obtained cellulose acetate film, the retardation 値 was measured by the following method.

Determination of Rth Delay

• In-plane retardation 値 Re (〇) was measured using an ellipsometer (150, manufactured by JASCO Corporation) at 25 ° C 10% RH. And, using the in-plane late phase axis as the shift axis, the axis is shifted by 40. And -40. To determine the delays 値 Re (40) and Re (-40). Taking the film thickness and the refractive index ηχ in the direction of the late phase axis as parameters, the approaching phase direction can be calculated by approximating these measurements 値 Re (〇), Re (40), and Re (−40). The refractive index ny and the refractive index nz in the thickness direction determine the Rth retardation 値. The measurement wavelength was selected to be 632.8 nm. In addition, the same measurement was performed at 25 t 8 0% RH. The results φ are shown in Table 5. In addition, "Rth will increase when compound 446 and compound 25 are added", and when A-4, PL-29, and F-2 are added, Rth will decrease -125- 200526728 Table 4 Sample No. 1 _ Agent Remarks Number of types (% by mass) Number of types (% by mass) Cellulose acetate film (11) (446) 4.6-0 Comparative example cellulose acetate film (12) (250) 7-0 Comparative example cellulose acetate film ( 13) (250) J 3-0 Comparative Example Cellulose Acetate Film (14) (250) 5 (A-4) 2 Cellulose Acetate Film of the Present Invention (15) (250) 6 (A-4) 3 Sheets Invention cellulose acetate film (16) (250) 7 (A · 4) 2 Invention cellulose acetate film (17) (446) 7 (PL-29) 2 Invention cellulose acetate film (18) ( 446) 7 (F-2) 2 Table 5 of the present invention The sample number is measured at 25 ° C 10% RH; measured at 25 ° C 80% RH; measured at 25 ° C 80% RH; and at 25 ° C 10% RH The ratio of the measurement 値 Re (nano) Rth (nano) Re (nano) Rth (nano) Rth / Re Re ratio Rth ratio cellulose acetate mm do 46 210 39 176 4.5 0.61 0.65 Cellulose acetate mm cm 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 Fiber of the present invention Plain acetate film (15) 51 159 43 156 3.6 0.72 0.73 The cellulose acetate film (16) 55 170 47 150 3.2 0.77 0.78 The cellulose acetate film (Π) 53 177 48 162 3.4 0.78 0.75 The invention Cellulose acetate film (18) 54 173 48 153 3.2 0.75 0.73 This _1 ~ According to the results in Table 5, it is known that the halogenated cellulose film of the present invention can achieve a wide range of optical characteristics, and the humidity dependence of the optical characteristics Small, so it is an ideal retardation film. [Example 8] (Alkaline treatment) -126- 200526728 The cellulose acetate film (n) obtained in Example 7 was coated with a solution of the following composition at 5.2 ml / m2, and dried at 6 (TC). 10 seconds. After washing the film surface with running water, blow dry the film surface with air at 25 ° C. Composition of test solution isopropyl alcohol 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 film (1 1), a coating solution with a composition of 24 ml / m 2 as shown below was applied using a wire rod coater # 1 4. Dry at 60 ° C for 60 seconds, then at 90 ° C for 150 seconds. Then, the formed film is extended toward the cellulose acetate film (transparent support). The rubbing treatment is performed at a direction of 45 ° (approximately coincides with the late phase axis). Composition of the alignment coating liquid The modified polyvinyl alcohol 20 parts by mass of water 360 parts by mass methanol 120 parts by mass glutaraldehyde (crosslinking agent) 1.0 parts by mass [Chem. 5 1]

Modified polyvinyl alcohol

1 (CH2-CH) 12.〇- 〇 Let = 0 CHa 0 (CH2) 40C0CH = CH2

— (CHj—CH) b7.8 — OH 200526728 (Formation of optically anisotropic layer (optical compensation sheet))

On the alignment film, a wire rod coater of # 3.6 was used to coat 9 1 parts by mass of 6.2 ml / m2 of dish-like liquid crystalline molecules (I) of the following formula, and 9 parts by mass of modified ethylene oxide. Trimethylolpropane triacrylate (V # 3 60, trade name, manufactured by Osaka Organic Chemical Co., Ltd.), 1.5 parts by mass of cellulose acetate butyrate (CAB 53 1-1, trade name, Eastman ( (Eastman) Chemical Co., Ltd.), 3 parts by mass of a photopolymerization initiator (Irgacure-907, trade name, manufactured by Ciba-Geigy), and 1 part by mass of a sensitizer (Kayacure-DETX, trade name, Nippon Kayaku Co., Ltd.) )), 1.0 part by mass of a citrate mixture represented by the following formula β is dissolved in 2 1 4 · 2 parts by mass of a methyl ethyl ketone coating solution. It was attached to a metal frame and heated in a thermostatic bath at 140 ° C for 2 minutes to align the dish-like liquid crystal molecules. Then, at 90 ° F: a 120 W / cm high-pressure mercury lamp was irradiated with UV (ultraviolet rays) for 1 minute to polymerize the discotic liquid crystalline compound, and then allowed to cool to room temperature. (Hua 52)

R R

Dish-shaped liquid crystal molecules (I) 〔Chemical 5 3〕 0 H2C-C-0-R! Ho-c-co2r2 h2c-co-r3 〇 -128- 200526728 R] = Η or C2H5 = η or C2h5 R3 = η Or C2H5 citrate mixture (manufactured by a polarizing plate) The iodine is adsorbed on the stretched polyvinyl alcohol film to obtain a polarizing film.

A polyvinyl alcohol-based adhesive was used to attach the transparent support side of the obtained optical compensation sheet to one side of the polarizing film. The late phase axis of the transparent support is arranged parallel to the transmission axis of the polarizing film. φ

A commercially available cellulose triacetate film (Fujitac TD80UF "Fuji Photographic Film Co., Ltd.") was subjected to a saponification treatment in the same manner as in Example 2 and then attached to the opposite side of the polarizing film using a polyvinyl alcohol adhesive ( The side where the optical compensation sheet is not attached). A 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 is provided as an alignment film, and a rubbing treatment is applied to the alignment film. The two glass substrates of # produced were oppositely arranged so that the rubbing treatment directions became parallel, and the lattice gap was set to 5.7 μm. A liquid crystal compound (ZLI1132, trade name, manufactured by Merk) with a Δη of 0.1 396 was injected into the interstices of the crystal lattice to obtain a curved alignment liquid crystal cell. (Manufacturing of a liquid crystal display device) The two polarizing plates produced were attached by sandwiching the obtained curved alignment lattices. Its configuration is such that the optically anisotropic layer of the polarizing plate is antiparallel to the lattice -129- 200526728 substrate, so that the rubbing direction of the liquid crystal cell and the rubbing direction of the opposite optical anisotropic layer are antiparallel. [Example 9] A polarizing plate (1 2) was prepared in the same manner except that the tritiated cellulose film was changed to (1 2) to (1 8) in the polarizing plate (1 1) of Example 8. ~ (1 8) 〇 Under ambient conditions of 25t temperature and relative humidity of 60%, the backlight module was continuously turned on for 5,000 hours, and the full black display state was visually observed in a dark room to evaluate light leakage. As a result, the polarizing plate of the comparative example observed a picture-frame-shaped light leakage in the display image of the liquid crystal display and reference display device. In contrast, the liquid crystal display device using the polarizing plate of the present invention did not observe such a situation. Example 1 〇] One of the 22-inch liquid crystal display devices (made by Sharp Corporation) using a VA-type liquid crystal cell was peeled off from the polarizing plate and replaced with an adhesive. The obtained polarizing plate was attached to each of the observer side and the β backlight side so that the tritiated cellulose film prepared in Example 7 could be located on the liquid crystal cell side. The polarizer transmission axis on the observer side and the polarizer transmission axis on the backlight side are arranged orthogonally. As a result, it was found that the polarizing plate of the present invention is a super-optimal polarizing plate having a wide viewing angle. [Brief description of the drawings] Figure 1 is an explanatory diagram showing a structural example of a composite polarizing plate and a functional optical film according to the present invention, showing the functional optical film-130-200526728 and a polarizing film being bonded as a polarizing plate through an adhesive, respectively. Example (A) of a single-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 the polarizing film via an adhesive.

Fig. 2 is an explanatory view showing an example of a liquid crystal display device &amp; stomach using the polarizing plate of the present invention. [Description of main component symbols] 1. La, lb Protective film 2 Polarizing film 3 Functional optical film 4 Adhesive layer 11 Upper polarizing plate 12 Upper polarizing plate absorption axis 13 Optical anisotropic layer (view angle expanding film) 14 Upper optics Anisotropic layer alignment control direction 15 LCD cell upper electrode substrate 16 Upper substrate alignment control direction 17 Liquid crystal layer 18 Liquid crystal cell lower electrode substrate 19 Lower substrate alignment control direction 20 downward Optical anisotropic layer (view angle expanding film) 2 1 down Optical anisotropic layer alignment control direction 22 lower polarizer 23 lower polarizer absorption axis

-131-

Claims (1)

200526728 10. Scope of patent application: 1. A cellulose film, which is characterized by containing at least two types of retardation modifiers 2. As for the cellulose film in the scope of patent application item 1, it contains at least one type of delay rising agent and delay Descending agent. 3. A cellulose film characterized by containing at least one of the compounds represented by the following general formula (I) and among the compounds represented by the following general formula (II), (III) or (IV) At least one: Formula (I) [Chemical Formula 1] [In the formula, X1 is a single bond, an NR4 —, — 〇 —, or an s —; X2 is a single bond, —NR5 —, 10 —, or —S —; X3 is a single bond, — NR6 —, — Q—, or —S—; R1, R2, and R3 each independently represent an alkyl, alkenyl, aryl, or composite ring group; and R4, R5, and R6 each independently represent a hydrogen atom, alkyl, Alkenyl, aryl, or composite ring groups, and each of the alkyl, alkenyl, aryl, and composite ring groups may have a substituent] General formula (Π) -132- 200526728 [Chemical 2] [In the formula, 'R21, R22, and R23 each independently represent a hydrogen atom or a radical; X2 1 represents a divalent linking group formed by one or more bases φ selected from the linking group 1; Y2 1 represents Hydrogen atom, alkyl group, aryl group or aralkyl group; (linking group 1) single bond, one zero one, —CO —, — NR24 —, alkylene group and alkylene group; R24 represents hydrogen atom, alkyl group , Aryl, or aralkyl]; general formula (IΠ) [Chemical Formula 3]] r33 · R31—S—N—R32 II 0 [wherein R31 represents an alkyl group or an aryl group, and R32 and R33 are independent of each other Ground represents a hydrogen atom, an alkyl group, or an aryl group, and the total number of carbon atoms of R31, R32, and R33 is 10 or more, and each alkyl and aryl system may have a substituent, and R31 and R32 may be linked to form a ring. ] -133- 200526728 Formula (IV) [Chemical Formula 4] R4〇 / R50 \ χ42〆R60 [wherein, X42 represents B, C—r7q (r7. Represents a hydrogen atom or a substituent), N, P or P = 0 ′ r4〇, r50, and r6g each independently represent an aryl group, a cycloalkyl group, or a composite ring group 'and each of the aryl group, the ring group, and the composite ring group system may also be Substituent, and may be attached r4〇 junction to form a ring]. 4 · If the cellulose film in the scope of patent application No. 1 or 2, its Rth (nano) and ^ (nano) as defined by the following formula (A) and (B) are 30 nm $ RthS 3 00 Nanometers, 2 nanometers SRe $ 80 nanometers, and Rth / Re ratio is 1 or more and 6 or less: (A) Formula Re (nanometer) = (nx-ny) xd (B) Formula Rth (nanometer) = { (nx + ny) / 2-nz} xd [where 'nx is the refractive index in the direction of the retardation axis in the film plane; ny is the refractive index in the direction of the advance axis in the film plane; nz is the thickness direction of the film Refractive index; and d is the thickness (nanometer) of the film]. 5 · If the cellulose film of item 1 or 2 of the patent application scope, its moisture permeability at 60 ° C 9 5% RH 24hr is 400 g / m2 · 24hr or more and 2,000 g / m2 · 24hr or less. 200526728 6 · If the cellulose film has an equilibrium moisture content of 80% RH or less of 3.0%, and the equilibrium moisture content of the cellulose film at 25 to 10% RH is 3 or more and 10 or less . 7. If the cellulose film of item 1 or 2 of the patent application applies, the Rth of 10% RH is higher than the Rth of 25 ° C 80% RH. 8 · If the cellulose film in item 1 or 2 of the patent application scope is above 10 ° C, Re at 25 ° C and above 80% RH. 9. A polarizing plate, which is bonded on both sides of a polarizing film, and is characterized in that at least one of the protective films is a cellulose film as described in item 1 or 2. 10. The polarizing plate according to item 9 of the scope of patent application, wherein at least one of an anti-glare layer, a reflective layer, a transflective reflective layer, a phase difference compensation layer, and a brightness enhancement layer is provided. 11. The polarizing plate such as the 10th in the scope of patent application, and its phase layer. 1 2. A liquid crystal display device, which is composed of a liquid crystal cell and two polarizing plates on the side, and at least one polarizing plate of the 9th scope of the patented polarized light. The ratio of 80% RH at 25 ° C 25 ° C is 0.6 5 at 25t, and the ratio is 0.6 5 at 25. The protective film is composed of an adhesive layer, a layer, and a viewing angle difference layer. Configure λ / 4 on its rainboard as applied &gt; 135-