TW200535179A - Cellulose acylate composition and cellulose acylate film - Google Patents

Abstract

The present invention provides a cellulose acylate film having small Rth and wavelength dispersion of Rth, and less process pollution, and also provides a polarizing plate and image display device using the said cellulose acylate. The said cellulose acylate composition has the degree of substitution for acyl group is satisfying the all requirements of the following equations (I)-(III), and the molecular weight is more than 250 and less than 1,000, and is a compound represented by the following general formula (1): (I) 2.3 ≤ SA+SB ≤ 3.0 (II) 1.5 ≤ SA ≤ 3.0 (III) 0 ≤ SB ≤ 0.8 wherein the SA and SB represent the substitution of hydroxy group for acyl group, the SA is the degree of substitution of acetyl group, and the SB is the degree of substitution of acyl group having carbon number from 3 to 22.

Description

200535179 9. Description of the invention: [Technical field to which the invention belongs] The present invention relates to a halogenated cellulose composition, a halogenated cellulose film, a polarizing plate, and an image display device having superior optical characteristics. [Prior art] Hitherto, in the production of the halogenated cellulose used in silver halide photographic photosensitive materials or liquid crystal image display devices, the organic solvent of the halogenated cellulose solution used has always been using chlorine-containing chloride such as dichloromethane. Hydrocarbons. In particular, methylene chloride (boiling point is about 40 ° C) has been used as a good solvent for tritiated cellulose, and because of its low boiling point, it has the advantages of being easy to dry during film formation and drying steps in the process, so it is widely used. use. From the viewpoint of environmental preservation, chlorine-based organic solvents, which are low boiling points, have now evolved to the point where leakage in the processing steps can be significantly reduced even under closed equipment. For example, the adoption of a thorough sealing To prevent leakage from the system, and also set up a gas absorption tower before exhausting to the outside, in order to prevent the method of adsorbing organic solvents and processing in case of leakage. In addition, measures such as the use of firepower or the decomposition of chlorine-based organic solvents that have been irradiated with electron rays have been adopted to make the discharge of organic solvents almost disappear. However, if it is to be completely non-discharged, Further research is needed. On the other hand, the search for halogenated cellulose solvents other than dichloromethane, which is a chlorine-based organic solvent, is also underway. It is known that organic solvents that exhibit solubility in cellulose trioxide, especially cellulose triacetate, are known. There are acetone (boiling point at 56 ° C), methyl acetate (boiling point at 56 ° C), tetrahydrofuran (boiling at 200535179 point at 65 ° C), 1,3-dioxanium (boiling point at 75. (:), : L, 4-dioxolane (boiling point is 010 ° C), etc. Among them, ethyl acetate has excellent solubility and film-forming properties. Ethyl acetate is currently being reviewed in detail. A solvent is used to produce a coating solution, which is then stripped off from a casting mold, and then transported and dried to form a film, etc. Generally, a tritiated cellulose film is used as a phase difference for a liquid crystal display device. When the film is used, the front retardation (Re, the thickness direction retardation) (hereinafter referred to as ^ Rth) and the wavelength dispersion characteristics are very important. When using a non-chlorine organic solvent, it takes a lot of time to change the solvent. Investment cost of new manufacturing equipment Therefore, efforts should be made to integrate with existing materials (cotton, plasticizer, etc.). However, if non-chlorine organic solvents are compared with chlorine organic solvents, they lack the ability to dissolve tritiated cellulose. Solubility, it is indispensable to change the fluorenyl substituent of tritiated cellulose. Therefore, even if the plasticizer is a phosphate ester plasticizer used in a chlorine-based organic solvent, the polymer and solvent The main reason for this has been changed so that it is no longer possible to make the same optical characteristics as those of films made with previous chlorine-based organic solvents, that is, specifically, films made with non-chlorine-based solvents Compared with films made with chlorine-based solvents, it has the disadvantage that Rth will increase. Therefore, if you want to obtain the same optical characteristics as films made with chlorine-based organic solvents, you must add In addition, compounds that cause Rth to rise (can reduce or maintain it). On the other hand, regardless of the type of solvent, TAC thin-film Rth has a large wavelength dispersion, so it is also desirable to add Compounds with reduced wavelength dispersion. In a halogenated cellulose film made with a non-chlorine solvent, a compound containing a diphenyl ketone system as an ultraviolet absorber is known (see Non-Invention Patent Document 1). It has gradually become clear that these compounds have the effect of reducing the wavelength dispersion of Rth. However, due to their small molecular weight and high volatility, the compounds disclosed in these compounds will cause The volatilization of these compounds will cause the disadvantage of contaminating the manufacturing machine. In other words, it is being requested to develop a tritiated cellulose film, which has a low volatility of the compound itself, and can reduce the wavelength dispersion of Rth in terms of optical properties. (Specifically, do not cause a change in Rth at a wavelength of 600 nm or more, and increase only Rth below 600 nm), and add a compound that does not cause an increase in Rth. [Non-Inventive Patent Literature 1] Japanese Invention Association Publication Techniques (Public Technical Number 2001-1 745) Pages 17 to 18 [Content of the Invention] [Technical Problems to Be Solved] The object of the present invention is to provide Chlorine-based solvent, but the wavelength dispersion of Rth and Rth is small, and the tritiated cellulose composition and tritiated cellulose film with less process pollution are provided. A polarizing plate and an image display device using the tritiated cellulose film are also provided. [Technical method to solve the problem] These objects can be achieved by the methods of (1) to (7) below. (1) A tritiated cellulose composition comprising a tritiated fiber 200535179 having a degree of substitution with a trityl group that satisfies all the following formulae (I) to (ΙΠ), and a molecular weight of 250 or more and 1,000 or less And represented by the following general formula (1): 2.3 ^ SA + SB ^ 3.0 (II) 1.5 ^ SA ^ 3.0 (III) 0 S SB S 0.8 [In the formula, SA and SB represent substitutions in cellulose The degree of substitution of the fluorenyl group of the hydroxyl group, SA represents the degree of substitution of the ethenyl group, and SB represents the degree of substitution of the fluorenyl group having 3 to 22 carbon atoms. ] General formula (1) [Chemical formula 2]

[In the formula, Q1 and Q2 each independently represent an aromatic ring; X represents NR (R represents a hydrogen atom or a substituent), an oxygen atom, or a sulfur atom. 〕. (2) The tritiated cellulose composition according to the above item (1), wherein the compound represented by the general formula (1) has a volatility of 1% or less when heated at 13 3 ° C for 1 hour. (3) The tritiated cellulose composition of items (1) and (2) as described above, wherein the degree of substitution of the tritiated cellulose group to tritiated cellulose is in accordance with all the conditions of the following formulae (I) to (III): 200535179 2.80 ^ SA + SB ^ 2.95 (I) (II) 2.80 ^ SA ^ 2.95 (III) SB ^ 0.1 [In the formula, SA and SB represent the degree of substitution of the fluorenyl group substituted with cellulose, SA is Degree of substitution of ethenyl, and sB is the degree of substitution of fluorenyl having 3 to 22 carbon atoms. 〕. As described above, the tritiated cellulose composition according to items (1) to (3), which contains a group selected from ethers having 3 to 12 carbon atoms, ketones having 3 to 12 carbon atoms, and a carbon number of At least one of the non-chlorine organic solvents in the group consisting of 3 to 12 esters. The tritiated cellulose composition according to item (4) above, which contains at least three solvents. A tritiated cellulose film is composed of a tritiated cellulose composition as described in any one of items (1) to (5) above. For example, the tritiated cellulose film of the scope of application for the patent No. 5 is to set the tritiated cellulose film containing the above-mentioned compound (1) at a wavelength of 6 3 2.8 nm in the Rth retardation ratio defined by the following formula (IV). The measured 値 is Rth (a), and the 値 obtained by subtracting the minimum 値 from the maximum 値 of the Rth 以 measured at a wavelength of 400 to 700 nm is Rth (A), and will not contain only the general formula (1) When the Rth retardation measured by a halogenated cellulose film of a representative compound at a wavelength of 632.8 nm is Rth (b), then all the conditions of the following formulas (V) and (VI) are met: -10-200535179 (IV) Rth = {(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 advancement axis in the film plane; nz: refraction in the thickness direction of the film Rate; d: film thickness. ]; (V) -20 ^ Rth (a)-Rth (b) <40; (VI) OS Rth (A) ^ 15. (8) A retardation film, which is a halogenated cellulose film having the item (6) or (7) as described above. (9) A polarizing plate comprising a halogenated cellulose film as described in (6) or (7) above. (10) An image display device using the polarizing plate of the item (9) as described above. [Effect of the Invention] According to the present invention, even if a non-chlorine-based solvent is used, a wavelength-dispersed Rth and Rth wavelength dispersion is small, the process pollution is small, and the degraded cellulose film with little degradation over time, and A polarizing plate and an image display device using the halogenated cellulose film. [Best Mode for Carrying Out the Invention] First, the compound represented by the general formula (1) of the present invention will be described in detail as follows. Formula (1): [Chemical Formula 3] -11-200535179 〇 Q1

Q2

XH [where Q1 and Q2 each independently represent an aromatic ring; X represents NR (R represents a hydrogen atom or a substituent.), An oxygen atom, or a sulfur atom. The aromatic ring system represented by Q1 and Q2 may be an aromatic hydrocarbon ring or an aromatic heterocyclic ring. Alternatively, it may be a single ring, or may further form a condensed ring with another ring. The aromatic hydrocarbon ring represented by Q1 and Q2 is preferably a monocyclic or bicyclic aromatic hydrocarbon ring having 6 to 30 carbon atoms (for example, a benzene ring, a naphthalene ring, etc.); more preferably a carbon An aromatic hydrocarbon ring having 6 to 20 atoms; more preferably an aromatic hydrocarbon ring having 6 to 12 carbon atoms. ), Further more preferably a benzene ring. The aromatic heterocyclic ring represented by Q1 and Q2 is preferably an aromatic heterocyclic ring containing at least any one of an oxygen atom, a nitrogen atom, or a sulfur atom. Specific examples of the "heterocyclic ring" include, for example, furan, pyrrole, thiophene, imidazole, pyrazole, pyridine, pyridine, dagen, triazole, triazole, indole, indazole, purine, thiazoline, thiazole , Thiadiazole, oxazoline, oxazole, Df diazole 'quinoline, isoquinoline, phthaloline, pyridine, quinoxaline, quinazoline, octyline, pyridine, acridine, morphine, Brown farming, tetrazole, benzimid 11 seat, benzopyrene 11 seat, benzothiazole, benzotriazole, tetrazindene, and the like. The aromatic heterocyclic ring is preferably pyridine, trinitrogen trap, or quinoline. -12- 200535179 The aromatic rings represented by Q1 and Q2 are preferably aromatic hydrocarbon rings, more preferably aromatic hydrocarbon rings having 6 to 10 carbon atoms, and even more preferably substituted or unsubstituted. The benzene ring. Q1 and Q2 may contain a substituent, preferably a substituent τ as described later, and if possible, the substituents may be connected to each other to form a ring structure. However, the substituents will not contain carboxylic acid, sulfonic acid, or quaternary ammonium salt. These hydrophilic groups have low solubility and may cause deterioration of water permeability. X represents NR (R represents a hydrogen atom or a substituent. The substituent is a substituent T as described later), an oxygen atom, or a sulfur atom, and X is preferably NR (R is preferably a fluorenyl group or a sulfo group. Amidino, these substituents may be substituted again.), Or an oxygen atom, particularly preferably an oxygen atom. The "substituent T" includes, for example, "alkyl" (preferably 1 to 20 carbon atoms, more preferably 1 to 12 carbon atoms, particularly preferably 1 to 8 carbon atoms, Examples include: methyl, ethyl, isopropyl, tertiary-butyl, n-octyl, n-decyl, n-hexadecyl, cyclopropyl, cyclopentyl, cyclohexyl, etc.); "Alkenyl" (preferably 2 to 20 carbon atoms, more preferably 2 to 12 carbon atoms, and most preferably 2 to 8 carbon atoms, for example, vinyl, aryl, 2 -Butenyl, 3-pentenyl, etc.); "alkynyl" (preferably 2 to 20 carbon atoms, more preferably 2 to 12 carbon atoms, particularly preferably carbon atoms) It is 2 to 8 and includes, for example, propargyl, 3-pentenyl, etc.); "aryl" (preferably 6 to 30 carbon atoms, more preferably 6 to 20 carbon atoms, Particularly preferred are 6 to 12 carbon atoms, including, for example, phenyl, p-methylphenyl, naphthyl, etc.); "substituted or unsubstituted amino" (preferably carbon atoms The number is 0 ~ 2 0, more preferably -13-200535179. The number of carbon atoms is preferably 0 ~ 10. Preferably, the number of carbon atoms is 0 to 6, including, for example, amino, methylamino, dimethylamino, diethylamino, benzhydrylamino, etc.); "alkoxy" ( Preferably, the number of carbon atoms is 1 to 20 ′, more preferably, the number of carbon atoms is 1 to 12, and particularly preferably, the number of carbon atoms is 1 to 8, including, for example, fluorenyloxy, ethoxy, and butoxy. Radicals, etc.); "Methoxy" (preferably 6 to 20 carbon atoms, more preferably 6 to 16 carbon atoms, particularly preferably 6 to 12 carbon atoms, for example: Phenoxy, 2-naphthyloxy, etc.); "fluorenyl" (preferably 1 to 20 carbon atoms, more preferably 1 to 16 carbon atoms, particularly preferred is carbon number is 1 ~ 12, for example: ethylamyl, benzamyl, formamyl, trimethylacetate, etc.); "Sinoxyl" (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 12, including, for example, methoxycarbonyl, ethoxycarbonyl, etc.); "Methoxycarbonyl" (preferably 7 to 20 carbon atoms, more preferably 7 carbon atoms 16. Particularly preferred is a carbon number of 7 to 10, including, for example, phenoxycarbonyl and the like.); "Methoxy" (preferably carbon number of 2 to 20, more preferably carbon number It is 2 to 16, particularly preferably 2 to 10 carbon atoms, including, for example, ethoxyl, benzamyl and the like.); "Fluorenylamino" (preferably 2 to 20 carbons) More preferably, the number of carbon atoms is 2-16, and particularly preferably, the number of carbon atoms is 2-10, including, for example, acetamido, benzamido, etc.); "alkoxycarbonylamino" (Preferable is 2 to 20 carbon atoms, more preferably 2 to 16 carbon atoms, particularly preferred is 2 to 12 carbon atoms, for example: methoxycarbonylamino group, etc.); "Methoxycarbonylamino" (preferably having 7 to 20 carbon atoms, more preferably -14 to 200535179, more preferably 7 to 16 carbon atoms, and particularly preferably 7 to 12 carbon atoms, for example Including: phenoxycarbonylamino and so on. ); "Sulfonamido" (preferably 1 to 20 carbon atoms, more preferably 1 to 6 carbon atoms, particularly preferably 1 to 12 carbon atoms, for example: methanesulfonate Sulfonylamino, benzenesulfonylamino, etc.); "sulfinosulfonyl" (preferably carbon number is 0-20; more preferably, carbon number is 0-16; particularly preferred is carbon atom; The number is 0 to 12 and includes, for example, sulfamoyl, methylsulfamoyl, dimethylsulfamoyl, phenylsulfamoyl, etc.); "aminomethylsulfonyl" (preferred It is 1 to 20 carbon atoms, more preferably 1 to 16 carbon atoms, and particularly preferably 1 to 12 carbon atoms, for example, carbamoyl, methylaminomethyl, diethyl Aminomethylamino, phenylaminomethyl, etc.); "alkylthio" (preferably 1 to 20 carbon atoms, more preferably 1 to 16 carbon atoms, particularly preferred is The number of carbon atoms is 1 to 12, for example: methylthio, ethylthio, etc.); "Arylthio" (preferably 6 to 20 carbon atoms, and more preferably 6 to 6 carbon atoms) 16. Particularly preferred are 6 to 12 carbon atoms, including, for example: Sulfhydryl, etc.); "sulfofluorenyl" (preferably 1 to 20 carbon atoms, more preferably 1 to 16 carbon atoms, particularly preferably 1 to 12 carbon atoms, for example Including: methanesulfonyl, tosylsulfonyl, etc.); r sulfinyl "(preferably 1 to 20 carbon atoms, more preferably 1 to 16 carbon atoms, particularly preferred is The number of carbon atoms is ι ~ 12, for example: methylsulfinyl, benzenesulfinyl and the like.); "Ureido" (preferably carbon number is 1 to 20, more preferably carbon number It is 丨 ~ 16, particularly preferably, the number of carbon atoms is 1-12, including, for example, urea group, methylurea group, phenylurea group, etc.); "Phosphorus-15-200535179 acid acid female group" (preferably疋 The number of carbon atoms is 1 to 20, more preferably the number of carbon atoms is 1 to 16, and the most preferred is the number of carbon atoms to 1 to 12, for example: diethylphosphonium amino group, phenylphosphonium amino group .); Hydroxyl, hydrogen sulfide, halogen atom (such as fluorine atom, chlorine atom, bromine atom, iodine atom), cyano group, sulfonic acid group, carboxyl group, nitro group, hydroxamic acid group, sulfinic acid group, Hydrazine, imino; "Cyclo group" (preferably 1 to 30 carbon atoms, more preferably 1 to 12, heteroatom systems include, for example, nitrogen, oxygen, and sulfur atoms, and specifically, systems include, for example, imidazolyl and pyridyl , Quinolinyl, furyl, piperidinyl, morpholinyl, benzoxazolyl, benzimidazolyl, benzothiazolyl, etc.); "silyl" (preferably 3 carbon atoms ~ 40 'is more preferably 3 to 30 carbon atoms, and particularly preferably 3 to 24 carbon atoms, such as: trimethylsilyl, triphenylsilyl, etc.). These substituents can also be further substituted. When 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 general formula (1) is preferably a compound represented by the following general formula (1-A). Formula (1-A): 200535179 〔Chem 4〕

[Wherein Ri, R2, RW, R5, M, r7, r8, and r9 each independently represent a hydrogen atom or a substituent. 〕. φ RW, RW, R5, R6, R7, R8, and r9 each independently represent a hydrogen atom or a substituent '. The substituent T is applicable to the above-mentioned substituent T. In addition, these substituents may be substituted by other substituents, or the substituents may be condensed with each other to form a ring structure. R1, R3, R4, R5, R6, R8 and R9 are preferably a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, a substituted or unsubstituted amine group, an alkoxy group, an aryloxy group, a hydroxyl group , Halogen atom; more preferably a hydrogen atom, an alkyl group, an aryl group, a compound oxygen group, a square oxygen group, a dentin atom, and further a step is more preferably an ammonia atom, an alkyl group having 1 to 12 carbon atoms; particularly preferred Hydrogen atom, methyl group; hydrogen atom is the most preferred. R2 is preferably a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, a substituted or unsubstituted amine group, an alkoxy group, an aryloxy group, a hydroxyl group, or a halogen atom; more preferably a hydrogen atom or a carbon atom Alkyl group having 1 to 20, amine group having 0 to 20 carbon atoms, alkoxy group having 1 to 12 carbon atoms, aryloxy group having 6 to 12 carbon atoms, and hydroxyl group; further preferred It is -17-200535179 alkoxy group having 1 to 20 carbon atoms; particularly preferred is alkoxy group having 1 to 12 carbon atoms. < R7 is preferably a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, a substituted or unsubstituted amine group, an alkoxy group, an aryloxy group, a hydroxyl group, a halogen atom; more preferably a hydrogen atom, Alkyl group having 1 to 20 carbon atoms, amine group having 0 to 20 carbon atoms, alkoxy group having 1 to 12 carbon atoms, aryloxy group having 6 to 12 carbon atoms, and hydroxyl group; further more Preferred is a hydrogen atom and an alkyl group having 1 to 20 carbon atoms (preferably 1 to 12 carbon atoms, more preferably 1 to 8 carbon atoms, and even more preferably a methyl group); particularly preferred Is a methyl group or a hydrogen atom. The general formula (1) is more preferably a compound represented by the following general formula (1-B). Formula (1-B): [Chemical Formula 5]

Ο OH ^^^ OR10 · [In the formula, r1g represents a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted alkynyl group, a substituted or Unsubstituted aryl. 〕. R1 () represents a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted alkynyl group, a substituted or unsubstituted aryl group, a substituent The substituent τ as described above is applicable. R1 Q is preferably a substituted or unsubstituted alkyl group; more preferred is a substituted or unstolen & substituted alkyl group having a carbon number of -18-200535179 of 5 to 20; further preferred is carbon Pick-up or unsubstituted alkyl groups with 5 to 12 atoms (n-, hexyl, 2-ethylhexyl, n-octyl, n-yigan r # stop-decyl, n-twelve Alkyl, Benshenyl, etc.); Especially preferred are substituted or unsubstituted alkyls having 6 to 2 carbon atoms (2-ethylhexyl, n-octyl, n-decyl, n _Dodecyl, benzyl). The compound represented by the general formula (1) can be synthesized by a conventional method disclosed in Japanese Patent Application Laid-Open No. 1 1 -1 22 1 9.

Specific examples of the compound represented by the general formula (1) are shown below, but the present invention is not limited to the following specific examples. 〔Chem 6〕 UV-1

UV- 2

UV-3

Ο OH

-19- 200535179 〔Chem 7〕

〇 PH

/ -5

UV-11

-20- 200535179

O OH

UV-21

-21-200535179 〔Chem 9〕 UV-22

H3CO UV-27

⑻〇5Η "0

UV-28

HN-SO2-Q-CH3

H3CO

In the present invention, from the viewpoint of volatility, among the compounds represented by the general formula (1) shown above, those having a molecular weight of 250 to 1,000 are used, preferably those having a molecular weight of 260 to 800, more The molecular weight is preferably 270 to 700, and the molecular weight is particularly preferably 3,000 to 600. The volatile system was heated to 20 ° C / min to 25 ° C under a nitrogen atmosphere (flow rate 200 ml / min) using an EXTER6000 TG / DTA manufactured by Seiko Instruments Co., Ltd. under a nitrogen atmosphere (flow rate 200 ml / min). ~ 133 ° C, after reaching 133 ° C, 値 0 calculated by the method represented by formula (VII) according to the mass after 10 minutes and 70 minutes after reaching 133 ° C Formula (VII)- 22- 200535179 Volatility (% by mass) = 100 x [(mass after 10 minutes after reaching 13 3 ° C)-(mass after 70 minutes after reaching 133 ° C)] / mass before heating is 13 3. When C is heated for 1 hour, the volatility of the compound represented by the general formula (1) is preferably 1% by mass or less, more preferably 0.6% or less, still more preferably 0.4% or less, and particularly preferably 0.2% or less. . In addition, the volatility can be reduced by mixing a plurality of compounds, and may be the volatility of one compound of the present invention or the volatility of a plurality of compounds of the present invention. In the tritiated cellulose composition of the present invention, the content of the compound represented by the general formula (1) shown above is based on 100 parts by mass of the tritiated cellulose, and the preferred content is 0.001 to 20% by mass. , More preferably 0.001 to 5% by mass, even more preferably 0.01 to 5% by mass, particularly preferably 0.1 to 5% by mass, and most preferably 0.5 to 3% by mass. / 〇. Next, the optical characteristics of the tritiated cellulose film formed by the tritiated cellulose composition of the present invention are described below. The tritiated cellulose film of the present invention is obtained by subtracting the minimum value from the maximum value of Rth (measured at 400 to 700 nm) with Rth (a) measured at a wavelength of 63 2.8 nm. When 値 is Rth (A), and Rth retardation 测定 measured at a wavelength of 6 3 2 · 8 nm of a tritiated cellulose film not containing only the compound represented by the general formula (1) above is Rth (b), Then all the conditions of the following formulas (V) and (VI) are met: (V) -20 ^ Rth (a)-Rth (b) < 40 (VI) 0 $ Rth (A) ^ 15

Preferably -15SRth (a)-Rth (b) < 35, 0 $ Rth (A) S 200535179 13; more preferably -10 $ Rth (a)-Rth (b) < 30, OS Rth (A ) $ 1 〇. Where Rth 値 is defined by the following formula. (IV) Rth = {(nx + ny) / 2-nz} xd [nx: refractive index in the direction of the retardation axis in the film plane; ny: refractive index in the direction of the advancement axis in the film plane; nz: in the thickness direction of the film Refractive index; d: thickness of film. 〕. The tritiated cellulose film of the present invention is characterized in that, because it contains a compound represented by the general formula (1), Rth will exhibit an increase or decrease effect as represented by the formula (V), and, as shown in the formula (VI) The effect of the 'threated cellulose film itself on the dispersion of Rth wavelength is that the wavelength of 400 to 700 nanometers will soon become smaller. However, the content of the compound of the general formula (1) that can meet the requirements of the formulae (V) and (VI) is preferably the above-mentioned content relative to tritiated cellulose. If it is added too much, it will cause precipitation and make it mandatory. The change in diachronic optical characteristics under the conditions becomes significant. The Rth of the tritiated cellulose film of the present invention is preferably 5 to 400 nm, more preferably 8 to 350 nm, and even more preferably in the range of 10 to 300 nm when the film thickness is 60 microns. . In addition, the front delay Re 値 defined by the following formula Re = (nx -ny) x d is preferably 0 to 100 nm, more preferably 0.1 to 80 nm, and even more preferably 0.2 to 70 nm. Next, the tritiated cellulose suitable for use in the present invention is described in detail below. The tritiated cellulose which can be used in the present invention is one having substitution degree to the hydroxyl group of cellulose which satisfies all the conditions of the general formulae (I) to (III) shown below. (I) 2.3S SA + SBS 3.0 (II) 1.5 ^ SA ^ 3.0 -24- 200535179 (III) 0 ^ SB ^ 0.8 [In the formula, SA and SB represent fluorenyl groups substituted at the hydroxyl position of cellulose The degree of substitution, SA is the degree of substitution of ethenyl, and SB is the degree of substitution of fluorenyl having 3 to 22 carbon atoms. 〕. The 3-1,4-bonded glucose units constituting cellulose have free hydroxyl groups at the 2-, 3-, and 6-positions. Tritiated cellulose is a polymer (polymer) in which some or all of these hydroxyl groups are substituted (i.e., esterified) with a tritiated group. The "degree of substitution with a fluorenyl group" means the ratio of esterification at the 2-, 3-, and 6-positions of cellulose (100% esterification has a degree of substitution of 1). In the present invention, the The total substitution degree of SB is preferably 2.7 to 2.96, and particularly preferably 2.80 to 2.95. In addition, SA is preferably 2.5 to 2.95, and more preferably 2.80 to 2.95. SB is preferably 0 to 0.6, particularly preferably 0 to 0.4, and most preferably 0 to 0.1. In addition, although the ratio at which the 6-position hydroxyl group is substituted in SB is 28% or more, it is more preferably 30% or more, even more preferably 31% or more, and particularly preferably 32% or more. In addition, the total degree of substitution of SA and SB at the 6th position of the tritiated cellulose is 0.8 or more, preferably 0.85 or more, and particularly preferably a tritiated cellulose film of 0.90 or more. The synthesis of these 6-position tritiated celluloses is disclosed in Japanese Patent Laid-Open Nos. 1 1-5 8 51, Japanese Patent Laid-Open No. 2002-2 1 233 8 or Japanese Patent Laid-Open No. 2002- No. 338601 and so on. The above-mentioned tritiated cellulose film can be used to prepare a solution with good solubility, especially when a non-chlorine-based organic solvent is used. 200535179 The halogenated cellulose of the present invention has a carbon number of 3 to 22 carbon atoms, which is not particularly limited, and may be an aliphatic group or an allyl group. These are, for example, alkane carbonyl esters, alkenyl carbonyl esters or aromatic carbonyl esters, aromatic alkano esters of cellulose, and the like, and each may further contain a substituted group. Preferred examples of these include: propanyl, butanyl, heptyl, hexyl, octyl, decyl, dodecyl, tridecyl, tetradecyl, hexadecyl, ten Octafluorenyl, isobutylfluorenyl, trimethylethylfluorenyl, cyclohexylcarbonyl, oleyl, benzamyl, naphthylcarbonyl, cinnamyl and the like. Among these, propionyl, butylfluorenyl, decylfluorenyl, octadecyl, trimethylethylfluorenyl, oleyl, benzyl, naphthylcarbonyl, cinnamyl, and the like are preferred. The basic principles of the synthetic method of tritiated cellulose are disclosed on pages 180 to 190 of the book "Wood Chemistry" by Kume (Kyoritsu Publishing, 1 968). A more representative synthesis method is a liquid-phase dehydration method using a formic anhydride-acetic acid-sulfuric acid catalyst. Specifically, the cellulose raw materials such as cotton wool or wood pulp are pretreated with an appropriate amount of acetic acid, and then added to a previously cooled carboxylic acid mixture to be esterified to synthesize fully tritiated cellulose ( The total fluorenyl substitution degrees at the 2-, 3-, and 6-positions are approximately 3.00). The carboxylic acid mixed liquid contains acetic acid generally as a solvent, carboxylic anhydride as an esterifying agent, and sulfuric acid as a catalyst. Generally, the carboxylic anhydride is used in a stoichiometric method in excess of the total amount of cellulose and the water present in the system. After the completion of the tritiation reaction, in order to hydrolyze excess carboxylic anhydride remaining in the system and neutralize some esterification catalysts, a neutralizing agent (such as calcium, magnesium, iron, aluminum or zinc carbonate, acetic acid) is added. Salt or oxide). Next, in the presence of a small amount of tritiated reaction catalyst (generally -26-200535179 is residual sulfuric acid), the fully tritiated cellulose is maintained at 50 ~ 90t for saponification and maturation, and it is changed to have the same as ours. Desired cellulose with a desired degree of substitution and polymerization. When the desired tritiated cellulose is obtained, the neutralizing agent as described above is used to completely neutralize the catalyst remaining in the system, or the tritiated cellulose solution is added to water without neutralization or A method of diluting sulfuric acid (or adding water or dilute sulfuric acid to a tritiated cellulose solution) to separate tritiated cellulose, and to obtain tritiated cellulose by washing and stabilizing. The tritiated cellulose film of the present invention is preferably composed of tritiated cellulose having the above-mentioned definition as a polymer component. The "essential" means that the content of the polymer is 55% by mass or more (preferably 70% by mass or more, and more preferably 80% by mass or more). As a raw material for manufacturing a film, particles of tritiated cellulose are preferably used. The particles used are preferably 90% by mass or more and have a particle diameter of 0.5 to 5 mm. In addition, 50% by mass or more of the particles used have a particle diameter of 1 to 4 mm. The tritiated cellulose particles preferably have a shape as near spherical as possible. The degree of polymerization of the tritiated cellulose suitable for the present invention has a viscosity average polymerization degree of 200 to 700, preferably 250 to 550, more preferably 250 to 400, and a particularly good viscosity average polymerization degree of 250 to 350. . The average degree of polymerization can be measured by the limiting viscosity method of Uda et al. (Uda Kazuo, Hideo Saito, The Journal of the Japan Fiber Association, Vol. 18, No. 1, pp. 105-120, 1962). In addition, it is disclosed in Japanese Patent Laid-Open No. 9-9553 8. In addition, in the present invention, removal of low-molecular components corresponding to a viscosity average polymerization degree of -27 to 200535179 1 00 or less is preferably performed. Once the low-molecular components are removed, the average molecular weight (degree of polymerization) will become higher, but the viscosity will become lower than that of normal cellulose, so it has a positive effect. Tritiated cellulose with less low-molecular components can be obtained by removing low-molecular components from tritiated cellulose synthesized by a common method. Removal of low-molecular components can be achieved by washing the tritiated cellulose with a suitable organic solvent. In addition, if it is desired to produce tritiated cellulose with low low-molecular components, it is preferred to adjust the amount of sulfuric acid catalyst during the tritiation reaction to 0.5 to 25 parts by mass based on 100 mass of cellulose. When the amount of the sulfuric acid catalyst is set within the above range, tritiated cellulose having a uniform molecular weight distribution can be synthesized. The moisture content of the tritiated cellulose of the present invention is preferably 2% by mass or less, more preferably 1% by mass or less, and particularly preferably 0.7% by mass or less. In general, it is known that the content of tritiated cellulose-based water is high and is 2.5 to 5% by mass. In the present invention, if the moisture content of the tritiated cellulose is to be the above-mentioned preferred moisture content, a drying step is required. The method is not particularly limited as long as the desired moisture content can be achieved. The tritiated cellulose of the present invention has been disclosed in detail in the Japanese Technical Association Public Technical Bulletin (public technical number 2001-1745, issued on March 15, 2001, Japanese Invention Association). In pages 7 to 12, the tritiated cellulose film of the present invention is a tritiated cellulose solution (coating solution) prepared by dissolving the tritiated cellulose and the compound represented by the general formula (1) in an organic solvent described later. ) To make. In the tritiated cellulose film of the present invention, various additives (for example, plasticizer, anti-ultraviolet agent, anti-deterioration agent, optical anisotropy control agent, fine particles, Release agent, infrared absorber, etc.), these can be solid or oily. That is, there is no particular limitation on the melting point or boiling point. For example, anti-violet agents below 20 ° C and above 20 ° C, or plasticizers (such as those disclosed in Japanese Patent Laid-Open No. 2 001-151901, etc.) are similarly mixed. As the infrared absorbing agent, for example, an infrared absorbing dye disclosed in Japanese Patent Laid-Open No. 2001-1 94522 can be used. The timing of the addition may be implemented at any time during the manufacturing process of the coating solution (dope), but it may also be implemented by adding an additive at the final preparation step of the coating solution preparation step. In addition, the amount of each additive is not particularly limited as long as it exhibits functions. In addition, when the tritiated cellulose film is formed of a plurality of layers, the types or amounts of additives in the respective layers may be different from each other. The same is true for the compound represented by the general formula (1). For example, although it has been disclosed in Japanese Patent Laid-Open No. 2001-1 5 1 902, etc., it is a technology that has been known so far. In addition, it is preferable to use materials disclosed on pages 16 to 22 of the Japan Invention Association's published technical bulletin (public technical number 2001-1745, issued March 15, 2001, Japan Invention Association). The organic solvents used to dissolve the tritiated cellulose of the present invention are described below. First, a non-chlorine-based organic solvent which is suitable for use in the production of the tritiated cellulose solution of the present invention is described below. In the present invention, the non-chlorine-based organic solvent is not particularly limited as long as the purpose is achieved within a range where the tritiated cellulose can be dissolved and a cast film is applied. The non-chlorine-based organic solvents which can be used in the present invention are preferably -29-200535179 organic solvents selected from the group consisting of esters, ketones and ethers having 3 to 12 carbon atoms. The ester, ketone, and ether systems may include a cyclic structure. Ester, ketone, and ether functional groups (ie, 10-, -CO-, and -C 00-) each having more than two compounds can also be used as the main solvent, in addition, for example, can also contain alcohol Other functional groups of sex hydroxyl. When the main solvent contains two or more functional groups, the number of carbon atoms may be within a predetermined range of a compound containing any functional group. Examples of the esters having 3 to 12 carbon atoms include ethyl formate, propyl formate, pentyl formate, methyl acetate, ethyl acetate, and pentyl acetate. Examples of ketones having 3 to 12 carbon atoms include: acetone, methyl ethyl ketone, diethyl ketone, diisopropyl ketone, cyclopentanone, cyclohexanone, and methyl cyclohexanone. Examples of ethers having 3 to 12 carbon atoms include diisopropyl ether, dimethoxymethane, dimethoxyethane, alkane such as 1,4-difluorene, and 1,3-difluorene. Alkanes, tetrahydrofuran, anisole, and phenylethyl ether. Examples of the organic solvent having two or more functional groups include 2-ethoxyethyl acetate, 2-methoxyethanol, and 2-butoxyethanol. The above-mentioned non-chlorine-based organic solvents suitable for tritiated cellulose can be selected from various viewpoints as described above, but are preferably as follows. That is, the preferred solvents of the tritiated cellulose of the present invention are three or more mixed solvents different from each other, preferably four or more mixed solvents, that is, the first solvent is selected from methyl acetate and ethyl acetate. At least one of methyl acetate, ethyl formate, ethyl formate, acetone, dioxane, dioxane, or a mixture thereof; the second solvent is selected from ketones or acetamidine acetates having 4 to 7 carbon atoms -30- 200535179; the third solvent is selected from alcohols having 1 to 10 carbon atoms or hydrocarbons, and more preferably the alcohols having 1 to 8 carbon atoms; and the fourth solvent is selected from carbon atoms Among alcohols or hydrocarbons having a number of i to 10, 'alcohols having 1 to 8 carbon atoms are more preferable. In addition, if the first solvent is a mixed solution of two or more solvents, the second solvent may be omitted. The first solvent is more preferably methyl acetate, acetone, methyl formate, ethyl formate, or a mixture thereof, and the second solvent is preferably methyl ethyl ketone, cyclopentanone, cyclohexanone, or ethyl acetate. Ester can also be a mixture of these. These alcohols, which are the third and fourth solvents, are preferably linear, branched, or cyclic, and among them, saturated aliphatic hydrocarbons are preferred. The hydroxy group of the alcohol may be any one of the first to third stages. Examples of alcohols include methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, tertiary-butanol, 1-pentanol, 2-methyl-2-butanol Alcohol, and cyclohexanone. In addition, as the alcohol, a fluorine-based alcohol may be used, and examples thereof include 2-fluoroethanol, 2,2,2-trifluoroethanol, 2,2,3,3-tetrafluoro-1 -propanol, and the like. In addition, the hydrocarbons belonging to the third and fourth solvents may be linear, branched, or cyclic. Either an aromatic hydrocarbon or an aliphatic hydrocarbon may be used. The aliphatic hydrocarbon system may be saturated or unsaturated. Examples of hydrocarbons include cyclohexane, hexane, benzene, toluene, and xylene. These alcohols and hydrocarbons which are the third and fourth solvents may be singular, or a mixture of two or more, and are not particularly limited. The third and fourth solvents of -31-200535179 are preferred specific compounds. In terms of alcohols, they include methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, and cyclohexanol, Cyclohexane, hexane, especially methanol, ethanol, 1-propanol, 2-propanol, 1-butanol. When three kinds of mixed solvents are used, one of the third and fourth solvents can be used. The above four kinds of mixed solvents are preferably ratios of the first solvent containing 20 to 95% by mass, the second solvent containing 2 to 60% by mass, the third solvent containing 2 to 30% by mass, and the fourth solvent containing 2 to 30% by mass. And more preferably the first solvent contains 30 to 90% by mass, the second solvent contains 3 to 50% by mass, and the third and fourth solvents contain 3 to 25% by mass of the alcohol. In addition, it is more preferable that the first solvent contains 30 to 90% by mass, the second solvent contains 3 to 30% by mass, and the third and fourth solvents are both alcohols and contain 3 to 15% by mass. In addition, if the first solvent is a mixed solution and the second solvent is not used, it is preferable that the first solvent contains 20 to 90% by mass, and the third and fourth solvents contain 5 to 30% by mass; more preferably One solvent contains 30 to 86% by mass, and the third and fourth solvents contain 7 to 25% by mass, respectively. In addition, in the case of the three mixed solvents, it is preferable that the first solvent contains 20 to 95% by mass, the second solvent contains 20 to 60% by mass, and the solvent of either the third or the fourth contains 4 to 60%. Ratio by mass. The above-mentioned non-chlorine-based organic solvents used in the present invention have been disclosed in more detail in the Japanese Technical Association's published technical bulletin (public technical number 2001-1 745, issued on March 15, 2001, Japan Invention Association) No. 12 Go to page 16. Although preferred combinations of the non-chlorine-based organic solvents of the present invention are exemplified below, they are not limited thereto. -32- 200535179 • Methyl acetate / acetone / methanol / ethanol / butanol (75/10/5/5/5, parts by mass) • Methyl acetate / acetone / methanol / ethanol / propanol (75/10/5 / 5/5 'mass parts', • Methyl acetate / acetone / methanol / butanol / cycloethane (75/10/5/5/5, parts by mass)' • methyl acetate / acetone / ethanol / butanol (81/8/7/4 'parts by mass), • Methyl acetate / acetone / ethanol / butanol (82/10/4/4, parts by mass), • Methyl acetate / acetone / ethanol / butanol (80 / 10/4/6, parts by mass), • methyl acetate / methyl ethyl ketone / methanol / butanol (80/10/5/5, parts by mass) • methyl acetate / acetone / methyl ethyl ketone / Ethanol / isopropanol (75/10/10/5/7, parts by mass), • methyl acetate / cyclopentanone / methanol / isopropanol 8 0/10/5/8, parts by mass), • acetic acid Methyl ester / acetone / butanol (85/5/5, parts by mass), • methyl acetate / cyclopentanone / acetone / methanol / butanol (60/15/15/5/6, parts by mass), • Methyl acetate / cycloethyl ketone / methanol / hexane (70/20/5/5, parts by mass), • methyl acetate / methyl ethyl ketone / acetone / methanol / ethanol (50/20/20/5 / 5, parts by mass), • methyl acetate / 1,3-two噚 pentane / methanol / ethanol (70/20/5/5, parts by mass) '• ethyl acetate / dioxane / acetone / methanol / ethanol (6 0/2 0/1 0/5/5, parts by mass ), -33- 200535179 • methyl acetate / acetone / cyclopentanone ethanol / isobutanol / cyclohexane (65/10/10/5/5/5, parts by mass), • methyl formate / fluorenyl ethyl Ketone / acetone / methanol / ethanol (50/20/20/5/5, parts by mass), • methyl formate / acetone / ethyl acetate / ethanol / butanol / hexane (65/10/10/5 / 5/5, parts by mass), • Acetone / methyl ethyl acetate / methanol / ethanol (65/20/1 0/5, parts by mass), • Acetone / cyclopentanone / ethanol / butanol (65/20 / 1 0/5, parts by mass), • Acetone / 1,3-dioxopentane / ethanol / butanol (65/20/1 0/5, parts by mass) • 1,3-dioxopentane / cycloethyl Ketone / methyl ethyl ketone / methanol / butanol (5 5/20/1 0/5/5/5, parts by mass), etc. In addition, the tritiated cellulose solution can be used in the following method. • Methyl acetate / acetone / ethanol / butanol (81/8/7/4, parts by mass) is used to make a tritiated cellulose solution. After filtering and concentrating, add 2 parts by mass of butanol. • Using methyl acetate / Acetone / ethanol / butanol (81/10/4/2, parts by mass) to produce a tritiated cellulose solution, filtered and concentrated, and then added 4 parts by mass of butanol. • Methyl acetate / acetone / ethanol ( 84/10/6, parts by mass) to produce a tritiated cellulose solution, after filtering and concentrating, and then 5 parts by mass of butanol in a coating solution (tritiated cellulose solution) used in the present technology, in addition to the above-mentioned present technology In addition to the non-chlorine-based organic solvent, dichloromethane may be contained in an amount of 10% by mass or less of the total organic solvent. -34- 200535179 In the production of the tritiated cellulose solution of the present invention, a chlorine-based organic solvent may be used as the main solvent. In the present invention, there is no particular limitation on the chlorine-based organic solvent in the garden where the tritiated cellulose can be dissolved for casting and film processing. The chlorine-based organic solvents are preferably dichloromethane and chloroform. Especially dichloromethane is preferred. In addition, there is no particular problem in mixing organic solvents other than chlorine-based organic solvents. At this time, at least 50% by mass of methylene chloride must be used. When using a chlorine-based organic solvent as the main solvent, the non-chlorine-based organic solvents that can be used are described below. That is, the preferred non-chlorine organic solvents are selected from the group consisting of esters having 3 to 12 carbon atoms, ketones having 3 to 12 carbon atoms, ethers having 3 to 12 carbon atoms, alcohols, hydrocarbons, and the like. Of solvents. These esters, ketones, ethers, alcohols, and hydrocarbon systems may have a cyclic structure. In addition, a compound having two or more of functional groups (i.e., -0-, -CO-, -COO-, and -OH) of-, ketone, ether, and alcohol may also be used as the solvent. In the case of a solvent having two or more functional groups, the number of carbon atoms may be within a prescribed range of a compound having any functional group. Examples of the esters having 3 to 12 carbon atoms include methyl acetate, ethyl acetate, methyl formate, ethyl formate, acetamyl acetate and pentyl acetate. Examples of ketones having 3 to 12 carbon atoms include: acetone, methyl ethyl ketone, diethyl ketone, diisobutyl ketone, cyclopentanone, cyclohexanone, and methyl cyclohexanone. Examples of ethers having 3 to 12 carbon atoms include: diisopropyl_, dimethoxymethane, dimethoxyethane, 1,4-dioxane, 1,3_dioxopentane , Tetrahydrofuran, anisole and phenylethyl ether. Alcohols that can be used with chlorine-based organic solvents can be straight-chain, branched or cyclic 200535179, of which saturated aliphatic hydrocarbons are preferred. The hydroxyl group of the alcohol may be any of the first to third stages. Examples of alcohols include methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, tertiary-butanol, 1-pentanol, 2-methyl-2-butanol, and Cyclohexanol. As the alcohol, a fluorine-based alcohol can also be used. For example, 2-fluoroethanol, 2, 2, 2-trifluoroethanol, 2, 2, 3, 3-tetrafluoro-1 -propanol, and the like. Hydrocarbons can be linear, branched or cyclic. Also, any of aromatic hydrocarbons and aliphatic hydrocarbons may be used. The aliphatic hydrocarbon system may be saturated or unsaturated. Examples of hydrocarbons include the cyclohexyl compound, the compound, benzene, toluene, and xylene. Examples of the organic solvent having two or more functional groups include 2-ethoxyethyl acetate, 2-methoxyethanol, and 2-butoxyethanol. In the tritiated cellulose solution when a chlorine-based organic solvent is used as the main solvent, the non-chlorine-based organic solvent that can be used is not particularly limited, but it is preferably selected from methyl acetate and ethyl acetate. , Methyl formate, ethyl formate, acetone, 1,3-diospentane, 1,4-dioxane, ketones with 4 to 7 carbon atoms or acetamyl acetate, with 1 to 3 carbon atoms 10% of alcohol or hydrocarbon. In addition, more suitable non-chlorine-based organic solvents include: methyl acetate, acetone, methyl formate, ethyl formate, methyl ethyl ketone, cyclopentanone, cyclohexanone, and ethyl acetate. Methyl esters, methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, and cyclohexanol, cyclohexane, and hexane. Although the preferred combination in the case where a non-chlorine-based organic solvent is used as the main solvent in the present invention is exemplified below, it is not limited thereto. • Dichloromethane / methanol / ethanol / butanol (75/10/5/5/5, parts by mass), 200535179 • Dichloromethane / acetone / methanol / propanol (80/10/5/5, parts by mass) , • Dichloromethane / methanol / butanol / cyclohexane (75/10/5/5/5, parts by mass), • Dichloromethane / methyl ethyl ketone / methanol / butanol (80/10/5 / 5, parts by mass)% • Dichloromethane / acetone / methyl ethyl ketone / ethanol / isopropanol (75/10/10/5/7, parts by mass), • Dichloromethane / cyclopentanone / 曱Alcohol / isopropanol (80/10/5/8, parts by mass), • dichloromethane / methyl acetate / butanol (80/10/10, parts by mass), • dichloromethane / cycloethyl ketone / methanol / Hexane (70/20/5/5, parts by mass), • methylene chloride / methyl ethyl ketone / acetone / methanol / ethanol (5 0/2 0/2 0/5/5, parts by mass), • Dichloromethane / 1, 3 dioxane pentane / methanol / ethanol (70/20/5/5, parts by mass) '• Dichloromethane / dioxane / acetone / methanol / ethanol (60/20/10 / 5/5, parts by mass), • dichloromethane / acetone / cyclopentanone / ethanol / isobutanol / cyclohexane (65/10/10/5/5/5, parts by mass), • dichloromethane / Methyl ethyl ketone / acetone / methanol / ethanol (7 0/10 / 10/5/5, parts by mass), • dichloromethane / acetone / ethyl acetate / ethanol / butanol / hexane (65/10/10/5/5/5, parts by mass), • dichloromethane / Acetyl methyl acetate / methanol / ethanol (65/20/1 0/5, parts by mass) > • Dichloromethane / cyclopentanone / ethanol / butanol (65/20/1 0/5, parts by mass) 20052005179 The tritiated cellulose solution of the present invention is a solution prepared by dissolving 10-30 mass% tritiated cellulose in an organic solvent, but it is more preferably 1 to 27% by mass, and particularly preferably 1 5 to 25% by mass. To make the tritiated cellulose meet these concentration conditions, it can also be adjusted to the desired concentration during the dissolution stage, or another feasible method is to prepare a low concentration solution (for example, 9 to 14% by mass) in advance. It is then adjusted to a high-concentration solution in a concentration step described later. In addition, a high-concentration tritiated cellulose solution may be prepared in advance, and various additives may be added to prepare a low-concentration tritiated cellulose solution as desired, that is, as long as the tritiated fiber of the present invention can be prepared There is no particular limitation on any method for the concentration of the vegan solution. Next, as for the preparation of the tritiated cellulose solution (coating liquid) of the present invention, the dissolving method is not particularly limited, and it can be performed at room temperature, or it can be further cooled by the dissolution method or by the high temperature dissolution method, or a combination And so on. The preparation method of these tritiated cellulose solutions has been disclosed in, for example, Japanese Patent Laid-Open No. 5-1 63 301, Japanese Patent Laid-Open No. 61-1 06628, and Japanese Patent Laid-Open No. 5 8- 1 27737. JP-A No. 9-95544, JP-A No. 1 0-95854, JP-A No. 1 0-45950, JP-A No. 2000-53 784, JP-A No. 1 1-322946, and JP-A No. n-322947 Japanese Patent Application No. 2-276 830, Japanese Patent Application No. 2000-273239, Japanese Patent Application No. 1-71 463, Japanese Patent Application No. 04-2595 1, Japanese Patent Application No. 2000-273 1 84, Japanese Patent Application No. Kaiping No. 1 1-32301 7 and JP-A No. ii-3〇23 8 8 and other publications. The above-disclosed method of dissolving the tritiated cellulose in an organic solvent in the present invention may appropriately apply these techniques if it is within the scope of the present invention. For details about these, especially for non-chlorine solvents, it is published in the Technical Bulletin of the Invention Association of 200535179 (public technical number 2001-1745, issued on March 5th, 2001, Japan Invention Association) Nos. 22 to 25 The methods described in detail on the page are used to implement them. In addition, the coating liquid solution of the tritiated cellulose of the present invention is usually subjected to solution concentration and filtration, and it is also disclosed in detail in the Japanese Technical Association Publication Technical Bulletin (Public Technology Number 2000-1745, March 2001). Issued on the 15th, Japan Invention Association) p. 25. In the case of dissolving at a high temperature, the temperature is usually higher than the boiling point of the organic solvent used. In this case, it is carried out under pressure. In the tritiated cellulose solution of the present invention, the viscosity and dynamic storage elasticity of the solution are preferably within a specific range. One milliliter of the sample solution was measured in a rheometer (CLS 500) using a steel cone (both manufactured by TA Instruments) having a diameter of 4 cm / 2 °. The measurement conditions are in the Oscillation Step / Temperature Ramp mode, and the temperature is changed at 2 ° C / min in the range of 40 ° C to -10 ° C to obtain the static state of 40. Non-Newtonian viscosity n * (Pa · s) and -5. (: Storage elastic modulus G, (Pa). In addition, the sample solution is measured after the measurement start temperature is maintained until the liquid temperature becomes constant. In the present invention, it is 40. (: The viscosity below is 1 to 400 Pa · S, the dynamic storage elastic modulus at 15 ° C is preferably 500 Pa or more; more preferably, the viscosity at 40 ° C is 10 ~ 200 Pa. S, and the dynamic storage elastic modulus at 15 ° C is preferably 1 ~ 1 million. And the greater the dynamic storage elasticity at low temperature, the better. For example, when the casting support is -5 ° C, the dynamic storage elasticity is preferably 10,000 to 1 million at -5 ° C. Pa; When the support is -50 ° C, the dynamic storage elasticity at -50 ° C is preferably 10,000 to 5 million pa. 200535179 Next, the production of a film using the tritiated cellulose solution of the present invention will be described. The method is as follows. The method and equipment for manufacturing the tritiated cellulose film of the present invention are a solution casting film forming method and a solution casting film forming device for traditionally manufacturing cellulose triacetate film. ) The prepared coating solution (the tritiated cellulose solution) is temporarily stored in a storage kettle, and then Defoaming the bubbles contained in the coating solution for final preparation. The coating solution is discharged from the coating solution outlet and sent to the pressurized die through a pressurized fixed-quantity gear pump that can, for example, perform high-precision quantitative liquid feeding with a number of revolutions. Head, the coating liquid is uniformly cast from the die nozzle (gap) of the pressurized die on the metal support of the casting part which continuously advances in a ring shape, and the peeling point of the metal support is moved about one circle , Peel the semi-dry coating liquid film (also called "base film") from the metal support. Hold both ends of the prepared base film with a jig, keep its width while transporting it with a tenter, and dry it. It is transported by the roller group of the drying device, and is wound to a specific length by the winder after the drying. The combination of the tenter and the roller group of the drying device varies depending on the purpose. It is used in silver halide photographic photosensitive materials or electronic displays. With the use of a solution casting film forming method for a functional protective film, in addition to the solution casting film forming device, it is mostly for the surface processing of the base film, antistatic layer, anti-halation layer, protective layer, etc. applied to the film. Additional coating device is attached. These are described in detail in pages 25 to 30 of the Japan Invention Association's published technical bulletin (public technical number 2001-1 74 5, issued on March 15, 2001, Japan Invention Association), which is classified as cast ( Including co-casting), metal support, drying, peeling, stretching, etc. Although the space temperature of the casting part in the present invention is not particularly limited, it is preferably -50 to 50 ° C, more preferably- 30 ~ 40 ° C, especially -20 200535179 ~ 30 ° C. Especially the tritiated cellulose solution cast out at low temperature in the space temperature will be instantly cooled on the support to increase its gel. 'Strength' can hold the organic solvent-containing film. Therefore, it can be stripped from the support for high-speed casting without causing the organic solvent from tritiated cellulose to evaporate. In addition, the method of cooling the space is not particularly limited, and ordinary air may be used, and nitrogen, argon, or helium may also be used. In addition, the humidity at that time is preferably 0 to 70% RH, and more preferably 0 to 50% RH. In addition, in the present invention, the temperature of the support used as the casting portion of the cast cellulose solution is -50 to 130 ° C, preferably -3 0 to 25 ° C, and more preferably -20 to 15 . In order to maintain the casting portion at the temperature of the present invention, a gas may be introduced into the casting portion, or a cooling device may be provided in the casting portion to cool the space. At this time, it is important to prevent moisture from adhering, and a method such as drying a gas may be used for this purpose. In the present invention, the contents and casting of each layer are particularly preferably the following. That is, at 25 ° C, the tritiated cellulose solution is preferably a tritiated cellulose solution characterized by the following items and a tritiated cellulose film prepared therefrom: at least one liquid Or a solid plasticizer containing 0.1 to 20% by mass of the tritiated cellulose solution relative to the tritiated cellulose; and / or at least one liquid or solid ultraviolet absorbent 'comprising the tritiated cellulose' 0.001 to 5% by mass of tritiated cellulose solution; and / or at least one kind of micropowder powder that is solid and has an average particle diameter of 5 to 3,000 m, and contains 0.5% of tritiated cellulose. 1 to 5% by mass of the tritiated cellulose solution 'and / or at least one fluorine-based surfactant containing 0.001 200535179 to 2% by mass of the tritiated cellulose solution, and / or at least A peeling agent containing 0. 0 0 0 1 to 2% by mass of a tritiated cellulose solution with respect to tritiated cellulose, and / or at least one anti-degradation agent containing 0.0001 to 2 Mass% of tritiated cellulose solution, and / or An optical anisotropy control agent contains 0.1 to 15% by mass of tritiated cellulose, and / or at least one infrared absorber contains 0.1 to 5% by mass of tritiated cellulose relative to tritiated cellulose Solution. In the casting step, one type of tritiated cellulose solution may be cast as a single layer, or two or more types of tritiated cellulose solution may be cast simultaneously and / or stepwise. When having a casting step consisting of two or more layers, among the tritiated cellulose solution and tritiated cellulose film produced, the tritiated cellulose solution and The tritiated cellulose film made from the solution, that is, the chlorine solvent composition of each layer, the concentration of additives in the solution, the molecular weight of the aggregates in each layer, the coating amount of each layer, the viscosity of each layer, the solution temperature of each layer, each layer The physical properties and the film thickness of each layer after drying must be either the same or different; the additives for each layer must be any one or a mixture of two or more; the location of addition to each layer must be the same layer Or any of different layers; the additives to each layer must be in the same layer or in different layers; the materials existing in each layer must be in the same state or distribution or different states; and the physical properties of each layer must be the same or Any of different distributions of physical properties. Among them, the "physical properties" means the physical properties described in detail on pages 6 to 7 of the Japan Gazette's Public Technical Bulletin (Public Technology Number 2001-1 745, issued March 15, 2001, Japan Institute of Inventors). Such as haze, transmittance, spectral characteristics, retardation 値 Re, same as -42- 200535179

Rth, molecular alignment axis, axis offset, tear strength, flexural strength, tensile strength, poor Rt inside and outside of curl, rough feel, dynamic friction, alkaline hydrolysis, curling, moisture content, residual solvent content, heat shrinkage rate, high Wet size evaluation, moisture permeability, flatness of substrate, dimensional stability, thermal shrinkage onset temperature, elastic modulus, and measurement of bright spot foreign matter, etc., also include impedance and planarity for substrate evaluation. In addition, it also includes the yellow index of tritiated cellulose as disclosed in detail on page 11 of the Japanese Technical Association's published technical bulletin (public technical number 2 001-174 5, issued on March 15, 2001, Japan Invention Association). Transparency, thermal properties (Tg, heat of crystallization), etc. The φ tritiated cellulose film can also be used to improve the adhesion between the tritiated cellulose film and various functional layers (such as the base coat and back layer) by applying a surface treatment. For example, a glow discharge treatment, an ultraviolet irradiation treatment, a corona treatment, a flame treatment, an acid or alkali treatment can be used. The so-called “glow discharge treatment” here may be a low-temperature plasma generated under a low-pressure gas of 1 (Γ3 to 20 Torr), and may also be a plasma treatment at atmospheric pressure. The so-called “plasma excitation "Gas gas" is a gas that can be excited into plasma under the conditions described above. It includes gases such as argon, helium, gas, krypton, neon, nitrogen, carbon dioxide, and tetrafluoromethane. Fluorocarbons and their mixtures, etc. The details of these systems are disclosed in the Japan Invention Association's published technical bulletin (Public Technology Number 2001-1 74 5, issued March 15, 2001, Japan Invention Association) Nos. 30 to 32 In addition, plasma treatment systems under atmospheric pressure that have attracted attention in recent years, for example, use irradiation energy of 20 to 500 Kgy at 10 to 10,000 Kev, and more preferably 20 to 500 Kev. Irradiation energy of 300 Kgy. Among these, alkaline alkaline treatment is particularly preferred, which is an extremely effective treatment method on the surface treatment of cellulose cellulose film-43-200535179. The alkaline alkaline treatment is applied by coating The method of cloth alkalizing solution is implemented. The coating method includes a dip coating method, a curtain Coating method, extrusion coating method, rod coating method, and E-type coating method. The solvent of the experimental alkalizing treatment coating liquid is preferably selected because the alkalizing liquid is applied to the transparent support. Solvent that has good wettability and does not cause unevenness on the surface of the transparent support due to the solvent of the alkalizing solution, and can keep the surface shape in a good state. Specifically, an alcohol-based solvent is particularly preferred It is isopropanol. In addition, an aqueous solution of a surfactant can also be used as a solvent. The alkali of the alkaline alkalizing coating liquid is preferably an alkali that will dissolve in the solvent as described above, and more preferably KOH and NaOH. The pH of the cloth liquid is preferably 10 or more, more preferably 12 or more. The reaction conditions when performing alkaline alkalization are preferably at room temperature for 1 second or more and 5 minutes or less, more preferably 5 More than seconds and less than 5 minutes, particularly preferably more than 20 seconds and less than 3 minutes. It is preferable to wash the coated surface of the alkalizing solution with water or acid washing after the alkaline alkalizing reaction. , The coating-type alkalization treatment can be continuously performed with the orientation film uncoating described later. Reduce the number of process steps. In addition, if the tritiated cellulose film of the present invention is used as a protective film of a silver halide photographic photosensitive material, in order to achieve the adhesion between the film and the emulsion layer, the surface activation treatment may be applied directly after A method of coating a functional layer on a tritiated cellulose film to obtain adhesion, and after applying some surface treatment or without surface treatment, a base coating (adhesive layer) is provided and the functional layer is coated thereon. The details of these base coatings are disclosed in the Japanese Invention Association's published technical bulletin (public technical number 2001-1 745, 2001 200535179 March 15, 179, Japan Invention Association) page 32. In addition With regard to the functional layer of the tritiated cellulose film of the present invention, its various functional layers are also disclosed in detail in the Japanese Technical Association's published technical bulletin (public technical number 200 1 -1 745, issued March 15, 2001, Japanese invention Association) Pages 32 to 45. First, the use of tritiated cellulose produced by the present invention is briefly described as follows. The optical film of the present invention is particularly suitable for use as a protective film for a polarizing plate. When used as a protective film for a polarizing plate, the manufacturing method of the polarizing plate is not particularly limited, and it can be manufactured by a general method. For example, an alkali-treated cellulose film prepared by alkali treatment may be used, and then a completely saponified A method in which a polyvinyl alcohol film is bonded to both sides of a polarizing film prepared by dipping and stretching in an iodine solution. Instead of alkali treatment, it can also be processed easily as disclosed in Japanese Patent Laid-open Nos. 6-949 15 and 6-1 1 823 2. Adhesives which can be used as an adhesive for bonding a protective film-treated surface to a polarizing film include polyvinyl alcohol-based adhesives such as polyvinyl alcohol and polyvinyl butyral, and vinyl latexes such as butyl acrylate. The polarizing plate is composed of a polarizing film and a protective film for protecting both sides thereof, and a protective film is bonded on one side of the polarizing plate and a separation film is bonded on the opposite side. The protective film and separation film are used for the purpose of protecting the polarizing plate during the process of shipping the polarizing plate and inspecting the product. In this case, the laminating protective film is used for the purpose of protecting the surface of the polarizing plate, and is used on the side opposite to the surface where the polarizing plate is attached to the liquid crystal panel. The separation film is used for covering the adhesive layer of the liquid crystal panel, and is used for attaching the polarizing plate to the front side of the liquid crystal panel. In a liquid crystal display device, a base plate containing a liquid crystal -45-200535179 is usually disposed between two polarizing plates. However, a polarizing plate protective film to which the optical film of the present invention is applied can be arranged at any position to obtain excellent display properties. Especially, since the polarizing plate protective film on the display surface of the liquid crystal display device is provided with a transparent hard coating, an anti-glare layer, an anti-reflection layer, etc., it is particularly preferable to use the polarizing plate protective film in this portion. Although the tritiated cellulose film of the present invention can be used in various applications, it is particularly effective when used as an optical compensation sheet for a liquid crystal display device as a retardation film. The tritiated cellulose film of the present invention can be used in liquid crystal cells in various display modes. Proposed like TN (Twisted Nematic), IPS (In-Plane Switching), FLC (Ferroelectric Liquid Crystal; Ferroelectric Liquid Crystal), AFLC (Anti-Ferroeletric Liquid Crystal), OCB (Optical Compensation) Bend type), STN (Super Twisted Nematic), VA (Vertical Alignment), and HAN (Mixed Component Nematic) display modes. Also, a display mode in which the above display mode is divided into directions has been proposed, but the tritiated cellulose film of the present invention is effective in a liquid crystal display device in any display mode. It is also effective in any liquid crystal display device of a transmissive type, a reflective type, or a transflective type. The tritiated cellulose film of the present invention can also be used as a support for an optical compensation sheet of a TN type liquid crystal display device having a TN mode cell. The tritiated cellulose film of the present invention can also be used as a support for an optical compensation sheet of an STN type liquid crystal display device having an STN mode cell. Generally speaking, in the STN type liquid crystal display device, the rod-like liquid crystal molecules in the liquid crystal cell are twisted into a range of 90 to 360 degrees. The 200535179 refractive index anisotropy (△ η) of the rod-like liquid crystal molecules and the crystal The product (△ nd) of the cell gap (d) is in the range of 3 00 ~ 1,500 nanometers. (The optical compensation sheet used in STN type liquid crystal display devices is disclosed in Japanese Patent Laid-Open No. 2000-1 05 3 1 6). The tritiated cellulose film of the present invention is particularly advantageous when it is used as a support for an optical compensation sheet of a VA type liquid crystal display device having a VA mode liquid crystal cell. The halogenated cellulose film of the present invention is also advantageous when it is used as a support for an OCB type liquid crystal display device having an OCB mode liquid crystal cell or an optical compensation sheet having a HAN mode liquid crystal cell and an AN type liquid crystal display device. The tritium cellulose film is also advantageous when it is used as an optical compensation sheet for a reflective liquid crystal display device of the TN type, the STN type, the ΗAN type, or the GH (host-guest type; Guest-Host) type. These display modes have been known so far. The TN-type reflective liquid crystal display device is disclosed in various publications of Japanese Patent Laid-Open Nos. 10-1 2 3 4 7 8, World Invention Patent No. WO 98832280, and Invention Patent No. 3022477. The optical compensation sheet used in a reflective liquid crystal display device is disclosed in World Invention Patent No. WO 00-653 84. It is also advantageous when the tritium cellulose film of the present invention is used as a support for an optical compensation sheet of an ASM-type liquid crystal display device having an ASM (Axially Symmetric Aligned Microcell) mode liquid crystal cell. The liquid crystal cell of the ASM mode has the characteristic that the thickness of the liquid crystal cell is maintained by the resin spacer whose position can be adjusted. Other properties are the same as those of the TN mode liquid crystal cell. Regarding the ASM mode liquid crystal cell and the ASM type liquid crystal display device, 200535179 Yu Tian et al. (Uda et al., SID 98 Digest 1,089 (1998)) is disclosed. The use of the above-mentioned detailed tritiated cellulose film is disclosed in detail in the Japan Inventor's Technical Publication (publication number 200 1-1 745, issued March 15, 2001, Japan Inventor's Association) No. 45 [Embodiment] to page 59 The following describes specific embodiments of the tritiated cellulose of the present invention, but the present invention is not limited to these. [Examples] · [Example 1] <Evaluation of Volatility> The volatility was determined by using EXTER6000 TG / DTA manufactured by Seiko Instruments Inc., and compounds 1 to 7 under a nitrogen atmosphere (flow rate 200 ml / min) at 20 ° C / The rate of minutes is heated to 25 ° C ~ 133 ° C, reaching 133. (: Later, it is calculated by the method represented by formula (VII) based on the mass after 10 minutes and 70 minutes. Formula (vii) · Volatility (mass) = 100 × [(10 minutes after reaching 133 ° C After mass)-(mass after 70 minutes after reaching 133 ° C)] / mass before heating. -48- 200535179

Number Compound Volatile Molecular Weight Remarks 1 UVT-1 2.8% 228.2 Comparative Example 2 UVT-2 2.3% 244.2 Comparative Example 3 UV-11 0.73% 304.3 The present invention 4 UV-1 1.10% 284.4 The present invention 5 UV-2 0.86% 298.4 This Invention 6 UV-5 0.43% 326.4 The present invention 7 UV-6 0.14% 326.4 The present invention 8 UV-7 0.13% 354.5 The present invention 9 UV-8 0.1% or less 382.5 The present invention [Chemical formula 1] can be obtained from the results of Table 1 It is known that the compounds of the present invention are less volatile. [Example 2] In each example, the chemical and physical properties of the tritiated cellulose in the film state were measured and calculated in the following manner. (1) Evaluation of optical characteristics After the obtained film was humidity-conditioned at 25 ° C and 60% RH for more than 2 hours, the retardation 、 Re and Rth were measured using an ellipsometer (M-15 0, manufactured by JASCO Corporation). Samples were taken at ten equally spaced intervals in the width direction of the film and averaged. (2) Changes in UV (ultraviolet) absorption characteristics under mandatory conditions. The prepared film was left alone at 60 ° C and 90% RH at a constant temperature of -49- 200535179 in a constant humidity chamber. After 500 hours, the spectrometer was used. A photometer (uv_3150) measures the absorption spectrum at a wavelength of 190 nm to 780 nm, and determines the difference from the absorption spectrum of the sample before the thermal duration 'as the delta transmittance (before and after the heat). The evaluation criteria are as follows: A: △ Transmittance is less than 0.2%; B: △ Transmittance is 0.2% or more and less than 0.4%; C: △ Transmittance is 0.4% or more and less than 0.6%; D: △ Transmission The rate is above 0.6%. (3) Removal residue of film: Observe visually the surface of the support when peeling the produced film from the support, and evaluate the remnants of the tritiated cellulose film based on the following criteria: A: No peeling residue was seen; B: slightly peeling residue was seen on the support; C: quite a lot of peeling residue was seen on the support; D: a lot of peeling residue was seen on the support. (4) Inhomogeneity of the horizontal section of the film Observe the produced film visually, and evaluate the defects of the transverse inhomogeneity on the basis of the following criteria: A: No transverse inhomogeneity is seen in the film B: A little horizontal unevenness is seen in the film; C: Quite a lot of unevenness in the horizontal line is seen in the film; D: A lot of unevenness in the horizontal line is seen in the film. (5) Concavo-convex particles of the film 200535179 Observing the produced film visually and evaluating the concavo-convex particles on the surface according to the following criteria: A: No concavo-convex particles were seen on the surface of the film; B: Slightly uneven grains are seen on the surface of the film = C: Quite a few uneven grains are seen on the film 〃 D: A large number of uneven grains are seen on the film. (6) Haze of the film was measured using a haze meter (type 1001DP, manufactured by Nippon Denshoku Industries, Ltd.). (7) Exudation The resulting film was visually observed and evaluated on the basis of the following criteria: X: The film was white and turbid and crystals were attached; ○: No white turbidity was observed; ◎: No white turbidity was observed at all. (2-1) Production of tritiated cellulose solution <Sample 1 -1 Solution> In a 400-liter stainless steel dissolution tank with a stirring blade and circulating with cooling water on the periphery, slowly add the solution with sufficient stirring and dispersion. The cellulose triacetate powder described below (flaky: ethanoyl substitution degree is 2.82, viscosity average polymerization degree is 320, water content is 0.4% by mass, and viscosity of 6% by mass in dichloromethane solution is 305 mPa · s, powder with an average particle diameter of 1.5 mm and standard deviation of 0.5 mm, residual acetic acid content of 0.1% by mass or less, Ca of 0.05% by mass, Mg of 0.007% by mass, Fe of 5 ppm 200535179, and 6-position acetamidine as 0.95 and 33% of the total substituents, the ratio of weight average molecular weight to number average molecular weight is 0.5, haze is 0.08, transparency is 93.5%, Tg is 160 ° C, and crystallization calorific value is 6.2 J / g) The additives described in Table 2 and the following solvent mixed solution were adjusted to 200 kg as a whole. In addition, 0.5 6 kg of the compound (UV-1) of the present invention was added thereto. In addition, as the solvents, methyl acetate, butanol, acetone, methanol, and ethanol were all used in which the moisture content was 0.2% by mass or less. First, the powder of cellulose triacetate was charged into a dispersion tank, and then the pressure in the tank was reduced to 1,300 Pa. At the time of stirring and shearing, the initial speed was 15 meters / second (shear stress). 5xl04 kgf / m / sec2), an eccentric stirring shaft of a rotary disc type stirring machine that performs stirring at a peripheral speed, and an anchor wing on the central axis and a peripheral speed of 1 m / s (shear stress lxlO4 kgf / m / sec2) With stirring, dispersion was performed for 30 minutes. The starting temperature of dispersion is 25 ° C. Cooling water is caused to flow to a final temperature of 35 ° C. After the dispersion was completed, the high-speed stirring was stopped, the peripheral speed of the anchor wing was reduced to 0.5 m / s, and the stirring was continued for another 100 minutes to swell the cellulose triacetate sheet. Until the end of swelling, the inside of the tank was pressurized to 0 "2 MPa with nitrogen. The oxygen concentration in the tank at this time is less than 2% by volume, which is in a state where there is no problem in explosion protection. It was also confirmed that the amount of water in the coating liquid was 0.2% by mass or less. In addition, the coating solution was made to contain additives such as plasticizers as shown in Table 2. The test sample 1 to 1-cellulose cellulose solution prepared by the above method had the following composition. 200535179 Yi 2: Composition of sample 1 -1 Solution composition of tritiated cellulose solution Part by mass of cellulose acetate (degree of substitution of ethyl acetate: 2.82) 100 triphenyl phosphate (plasticizer) 8.0 diphenyl phosphate Biphenyl ester (plasticizer) 4.0 Methyl acetate 476.3 Acetone 47.0 — Ethanol 41.2 Butanol 23.5 Ethyl citrate 0.04 Silica particles (20 m) 0.05 UV-1 2.0 The resulting non-uniform The gel-like solution is pumped by a screw pump heated at the center of the shaft to 30, and passed through the cooling section by cooling the screw peripheral part to -75 ° C for 3 minutes. Cooling is performed using a -8 ° C refrigerant which is cooled by a freezer. And the solution obtained after cooling is heated to 35 C in a spiral chestnut feeding solution and transferred to a container made of stainless steel. Stir at 50 ° C for 2 hours to make it a homogeneous solution. 'Filter with a filter paper with absolute filtration accuracy of 0.0 1 mm (manufactured by Toyo Filter Paper Co., Ltd., # 63), and then filter paper with absolute filtration accuracy of 2.5 microns. (Manufactured by Pole, FH025). Then, 'the pressure part of the heating part of the liquid feeding pipe is heated to 110 ° C, 1 MPa, and then released at normal pressure (about 0.1 MPa) to volatilize the organic solvent', and then cooled to obtain a temperature of 40 ° C, Cellulose triacetate solution at a concentration of 2 2 · 1%. While the solution was sufficiently stirred, 2% by mass of butanol was slowly added to the solid content of cellulose triacetate to obtain a uniform solution. The viscosity (40 ° C) of the solution was 103 Pa · -53- 200535179 s, and the dynamic storage elastic modulus (〗 5 〇) was 850 Pa. · <Comparative sample 0-1 solution> Except that the compound (UV-D) was not added to the production of the above-mentioned sample 1-1 solution, a comparative sample 0-1 was prepared in the same manner. In addition, 'except in sample 1-1 Except for changing the type of the compound of the present invention, the type of the comparative compound, and the addition amount thereof in the production of the solution, the sample solutions 1-2 to 1-9 and the comparative sample solutions 0-2 and 0- were prepared by the same method. 3 (Refer to Table 3) (2-3) Manufacturing of cellulose triacetate film Φ The above-mentioned filtered 50 ° C cellulose triacetate solution was cast on a 3 m diameter drum by a casting geyser. On the mirror stainless steel support (the temperature of the support is set to -5.0. The Geyser used is similar to the type disclosed in Japanese Patent Laid-Open No. i i_3 1 4233. The casting rate is set to 75 m / Min. And its coating width is 200 cm. The temperature of the whole space part of the casting part is set to 15 ° C. The cast part is peeled and turned back at a distance of 50 meters from the casting part. The cellulose film, and clamp both ends with a pin tenter. The tritium cellulose film held by β held by the pin clip tenter is transported to the drying area. The initial drying is a drying air of 45 ° C. Then it is dried at 110 ° C for 5 minutes, and then 145 ° C for 10 minutes. (The film temperature is about 140 ° C) to obtain a cellulose triacetate film (film thickness is 60 microns). The obtained sample was cut off at both ends by 3 cm and at a distance of 2 cm from the end. A part with a size of ~ 10 mm was subjected to a centrifugal cooling with a height of 100 microns, and then rolled into a roll shape to obtain a cellulose triacetate film sample 1 -1 film. -54- 200535179 〇3 solution and sample u ~ i Sample 〇- 丨 ~ ο-3 Films and tests On the other hand, Comparative Samples 0_1 to 9 solutions were used to prepare Comparative Materials I-2 to 1-9 films in the same way. The film thickness of these films is The results are shown in Table 3. The evaluation results of the obtained cellulose triacetate film are shown in Table 3.

-55- 200535179 Thin film I ooze out! 1_ 〇XX 〇〇 ◎ ◎ ◎ ◎ ◎ ◎ ◎ Haze 〇inch mdm cn omd ΓΟ d cn 〇〇 (N d (N d rq d concave-convex prison &lt; &lt; PQ &lt; &lt; C &lt; &lt; &lt; &lt; &lt; d &lt; &lt; uneven PQ &lt; &lt; &lt; &lt; C &lt; &lt; &lt; &lt; &lt; &lt; stripping residue &lt; &lt; &lt; &lt; C &lt; &lt; &lt; &lt; &lt; &lt; &lt; change over time △ transmittance (before and after heat) UUU PQ &lt; &lt; &lt; &lt; &lt; &lt; &lt; &lt; Nanometer) Ό Inch v〇u- &gt; Ό Ό VO VO VO Rth (A) (Nano) 18.6 m uS (N rH 00 inch · iri 00 rn VO inch · H iri o (N Rth (a) -Rth (b) (nano) 〇 inch OS od od od O rH 〇 \ vd bl ON bl od od On 10.0 Addition amount of the compound of the present invention 〇〇CN o cs ο (N 〇 (N o CN o (N o CN 〇 &lt; N o (N 〇rH o »〇Type 壊 τ-Η 1 UVT-2 UV-1 UV-2 UV-5 UV-6 UV-7 UV-8 rH 1 UV-6 UV-6 Content comparison Compare the present invention, the present invention, the present invention, the present invention 1, the present invention I, the present invention, the present invention, the sample r- ^ ό S r〇0 1—ί I (NT—H cn TH wo rH v〇τ * Η 00 1— ^ On r— &lt; Song Ru ^^^^ (I) ^^^^^^^. 0 ^^. ^ 5 ^^ 1 ^^^^ 00.29 ^ 2) 5 ^ -0) 5 ^ .3 .Article Φ_ SW% _ _001 We have forgotten 鼗 筚 _ 运 腾 · ___: 锟 銮 .μ } 轵 ^ 忉 忉 海海 账 °° &lt; Νε9 ^^ ί · inch. Back ^ #》 跎 Touched "/« Avoid ^ 1!} 4 &lt; «^ Touch} 115 鲣 窸 钜 ¥ 鲣 窸 钜 米 账 00 卜-0017 ^ Button skimmer ^^ (55 ^. £ ._Μι? ΔΜΜΪΉ Chain fine 矻 200535179 When comparing the cellulose triacetate sample film (samples 1-1 to 1-9) of the present invention with the comparison sample film (comparative sample 0 -1 to 0-3), it is known that the thin film having the wavelength dispersion represented by Rth (A) after adding the compound of the present invention is small. In addition, the rise in Rth represented by Rth (a)-Rth (b) is also small, and it is apparent that Rth is excellent so as not to cause rise in Rth. Like the compound of the general formula (1) whose molecular weight is in the range of 250 or more in the present invention, if a compound with a large molecular weight is added, it will exhibit UV absorption characteristics even after 500 hours under the mandatory condition of 60 ° C 90% RH. Good condition with little deterioration. In addition, when a film of a compound represented by the general formula (1) is added, it has a superior surface shape with small residues, unevenness, and uneven particles. [Example 3] Except in Example 2 of Japanese Patent Laid-Open No. 1 1 -3 1 6378, the first transparent support was changed to the sample solution 1-8 prepared in Example 2 of the present invention. Except for the cellulose triacetate film having a thickness of 60 micrometers, the rest was carried out in exactly the same manner as in Example 3 of JP-A No. 1 1 -3 1 6378 to obtain a round circular polarizing plate. As a result, the obtained circularly polarized plate system exhibited superior optical characteristics. Therefore, it is apparent that even if the halogenated cellulose film of the present invention is used for an optical polarizing plate, it is an ideal method without problems. [Example 4] Except that the cellulose triacetate made from Fuji photographic film (stock) of Example 1 of Japanese Patent Laid-Open No. 7-3 3343 3 was changed to the sample 1_2 ~ 1- of the present invention in Example 2 Except for the cellulose triacetate film of No. 8, the rest is exactly the same as in Example 1 of Japanese Patent Application Laid-Open No. 7-333433, and an optical compensation 200535179 color filter film sample is manufactured. As a result, the films obtained have excellent viewing angles from left to right. Therefore, it was found that the cellulose triacetate film of the present invention is excellent in optical applications. [Example 5] In order to review the further optical properties of the film of the present invention, the sample films 1-2 to 1-8 of the present invention were used in Example 1 of Japanese Patent Laid-Open No. 10-4 8 420, for example. The disclosed liquid crystal display device, the optically anisotropic layer containing dish-like liquid crystal molecules disclosed in Example 1 of JP-A-9-26572, the alignment film coated with polyvinyl alcohol, and JP-A-2000- The VA type liquid crystal display device disclosed in Figs. 2 to 9 of No. 154261 and the OCB type liquid crystal display device disclosed in Figs. 10 to 15 of JP 2000-15 42 610 have good performance. Therefore, it was found that the cellulose triacetate film of the present invention is excellent in optical applications. [Example 6] Except for changing cellulose triacetate in the solution of samples 1-8 of the present invention in Example 2 to this cellulose triacetate (10 parts by mass) and cellulose acetate propionate (acetamidine) The degree of substitution is 2.44, the degree of propionate substitution is 0.26, the degree of total substitution is 2.70, the average viscosity is 318, the water content is 0.4% by mass, and the viscosity of 6% by mass in a dichloromethane solution is 2 7 7 mP a · s, powder with an average particle size of 1.3 mm and standard deviation of 0.4 mm, the amount of residual acetic acid and propionic acid are all 0.06 mass% or less, Ca is 0.011 mass%, Mg is 0.08 mass%, and Fe is 0 54 ppm, 6-position ethenyl and propionyl groups are 0.70 and 0.17, respectively, which is 33% of the total substituents, acetone extraction is 7% by mass, and the ratio of weight average molecular weight to number average molecular weight is 3.5 , Yellow 200535179 index is 1.3, haze is 0.2, transparency is 93.3%, Tg is 157 ° C, crystallization heat value is 4.3 J / g) (5 parts by mass) 'and cellulose acetate butyrate (ethyl The degree of substitution with fluorenyl is 2.39, the degree of substitution with butyrate is 0.45, the degree of total substitution is 2.84, and the average degree of polymerization of viscosity 340. Powder with a water content of 0.4% by mass, a viscosity of 6% by mass in a dichloromethane solution of 295 mPa · s, an average particle size of 1.3 mm and a standard deviation of 0.4 mm, the amount of residual acetic acid and the amount of butyric acid All are 0.03% by mass or less, Ca is 0.005% by mass, Mg is 0.004% by mass, Fe is 5 ppm, 6-ethenyl and propionyl groups are 0.72 and 0.20, respectively, and 32% of the total substituents , 14 mass% acetone extraction, 1.3 weight average molecular weight to number average molecular weight ratio, yellow index 0.9, haze 0.5, transparency 92.9%, Tg 153 ° C, crystallization calorific value 3.9 J / g) (5 parts by mass), except that a solvent equivalent to 1/5 parts by mass of the solvent used in Example 2 was used, and the remainder was prepared in the same manner as in Examples 1 and 2.素 膜。 Thin film. As a result, Rth (a)-Rth (b) of the film was -7 · 8, and Rth (A) was -4.5. In addition, the peeling residue was A, the unevenness was A, the uneven grains were A, and the haze was 0.4, which were excellent in all the test items. Therefore, in the present invention, even if two or more kinds of tritiated cellulose are used in combination, an excellent tritiated cellulose film can be obtained. [Industrial Applicability] According to the present invention, even if a non-chlorine-based solvent is used, the wavelength dispersion of Rth and Rth is small, the process pollution is small, and the degraded cellulose film with little degradation over time is provided. The film of the present invention is suitable for use as a retardation film, a protective film for a polarizing plate, and an image display element.

Claims (1)

200535179 X. Scope of patent application: 1. A tritiated cellulose composition, which contains tritiated cellulose with a degree of substitution of a tritium group that meets all the requirements of the following formulae (I) to (ΙΠ), and has a molecular weight of 250 or more. And less than 1,000 and represented by the following general formula (1): (I) 2.3 ^ SA + SB ^ 3.0 (II) 1.5 S SAS 3.0 (III) OS SBS 0.8 [wherein SA and SB Is the degree of substitution of the fluorenyl group substituted for the hydroxyl group of cellulose, SA is the degree of substitution of the ethenyl group, and SB is the degree of substitution of the fluorenyl group having 3 to 22 carbon atoms]; General formula (1) [ Chemistry 1] [In the formula, Q1 and Q2 each independently represent an aromatic ring; X represents a NR (R represents a hydrogen atom or a substituent), an oxygen atom, or a sulfur atom]. 2. For example, the tritiated cellulose composition of the scope of patent application, wherein the degree of substitution of the tritiated cellulose with tritiated cellulose is in accordance with all the conditions of the following formulas (I) to (III): 2.80 ^ SA + SB ^ 2.95 -60- 200535179 (II) 2.80 ^ SA ^ 2.95 (III) SB ^ 0.1 [In the formula, SA and SB are substituents of the fluorenyl group substituted on the hydroxyl group of cellulose, and SA is the degree of substitution of the ethenyl group And SB represents the degree of substitution of a fluorenyl group having 3 to 22 carbon atoms]. 3. The tritiated cellulose composition according to item 1 or 2 of the scope of the patent application, which contains an ether selected from the group consisting of 3 to 12 carbon atoms, a ketone having 3 to 12 carbon atoms, and a carbon number of At least one of the non-chlorine organic solvents in the group consisting of 3 to 12 esters. 4. For example, the tritiated cellulose composition of the scope of patent application No. 3, which contains at least three solvents. 5. A tritiated cellulose film comprising a tritiated cellulose composition as described in item 1 of the patent application. 6. The tritiated cellulose film according to item 5 of the scope of patent application, in the Rth retardation 値 defined by the following formula (IV), set the tritiated cellulose film containing the compound (1) as shown above to 63 2.8 The (measured at the nanometer wavelength is Rth (a), and the 値 obtained by subtracting the minimum 値 from the largest 波长 of the Rth 测定 measured at a wavelength of 400 to 700 nanometers is Rth (A), and will only contain the same as shown above. When the Rth retardation of the tritiated cellulose film of the compound represented by formula (1) measured at a wavelength of 632.8 nm is Rth (b), then all the conditions of the following formulas (V) and (VI) are met: (IV) Rth = {(nx + ny) / 2-nz} xd [wherein, nx: refractive index in the direction of the retardation axis in the film plane; ny: thin -61- 200535179 emissivity; d: film thickness]; (V) -20 ^ Rth (a) -Rth (b) &lt;40; (VI) 0 ^ Rth (A) S 1 5. 7. A polarizing plate having a tritiated cellulose film as described in item 5 or 6 of the patent application. 8. An image display device having a polarizing plate as in item 7 of the scope of patent application. • 62- 200535179 7. Designated Representative Map: (1) The designated representative map in this case is: None. (2) A brief description of the component representative symbols of this representative map: Μ. j \ \\ 8. If there is a chemical formula in this case, please disclose the chemical formula that can best show the characteristics of the invention: 4FR1 〇 / \ \\