TW201219464A - Cellulose acylate film and method for manufacturing the same, polarizing plate and liquid crystal display - Google Patents

Abstract

A cellulose acylate film is provided, which comprises cellulose acylate with total acyl substitution degree of 2.1 to 2.8, is characterized in that the elastic modulus in the direction of membrane delivering is more than 3200 MPa, the unevenness of the elastic modulus in the direction of membrane width is no more than 0.5 GPa, and the following formulae (1) to (3) are satisfied. Formula (1) OARe 15.0 (in the formula, ARe represents a value obtained fromthe delay value of in-plane direction at a wavelength of 630nm minus the delay value of in-plane direction at awavelength of 450 nm (the unit is nm). ) Formula (2) 2*10<SP>-3</SP> ≤ Rth/d ≤ 6*1 0<SP>-3</SP> (in the formula, Rth represents a value obtained fromthe delay value of the membrane thickness direction at awavelength of 550 nm (the unit is nm), and d representsmembrane thickness (the unit is nm).) Formula (3) 1.0 ≤ E'(TD)/E'(MD) ≤ 1.43 (in the formula, E'(MD) represents the elastic modulusI in the direction of membrane delivering (the unit is MPa), and E'(TD) represents the elastic modulus in the direction of membrane width (the unit is MPa).)

Description

201219464r VI. Description of the Invention: [Technical Field of the Invention] The present invention relates to a cellulose-deposited film and a method for producing the same. More specifically, it relates to a method comprising a deuterated cellulose, a wavelength dispersion of reverse dispersion, a large Rth per unit film thickness, and a uniform display in the plane when attached to the panel after the polarizing plate is processed. Cellulose film and its method of manufacture. Further, it relates to a polarizing plate and a liquid crystal display device using the deuterated cellulose film. [Prior Art] The liquid crystal display of the VA (Vertically Aligned) mode has a high contrast ratio and a high manufacturing yield, and has attracted attention as a liquid crystal display device for televisions. In order to widen the angle of view of the VA mode liquid crystal display device, the fluorinated cellulose film has been used as an optical compensation film, such as an optical compensation film, in recent years, in recent years, in the optical film for VA, the color tone when viewing the display from the self-improving self-slanting orientation From the viewpoint of change, it is required to exhibit a reverse dispersion film in which the retardation Re in the in-plane direction increases as the wavelength becomes larger. Further, at the same time, the thin film formation trend of the panel is made thinner in order to reduce the manufacturing cost (4) to increase the retardation in the thickness direction of each early film thickness. On the other hand, the size of the liquid crystal display device is increased, and an optical film having a suitable physical property that can achieve the uniformity of the curvature of the panel is required. In the Japanese Patent Laid-Open Publication No. 2-6-_62, the method of formulating the method or the method of coating the film does not reveal the performance of the front and film thickness retardation. 201219464 Excellent, due to humidity, etc. An optical film and a polarizing plate having a small variation in delay value caused by environmental changes. In this document, it is disclosed that the wavelength dispersion can be controlled by stretching, and an example of the use of materials such as CAP (cellulose acetate propionate) or cab (cellulose acetate butyrate) is disclosed in the examples of the document. In the solution film forming method, the film which is peeled off in the form of a residual volatile component of 25 wt% to 35 Wt/ί) is biaxially stretched in the film transport direction and the film width direction. Further, in the Japanese Patent Laid-Open Publication No. 2009-263619, the use of a solvent and a specific thiol-substituted degree of deuterated cellulose resin to control the water content or the SP value reveals that the haze and the surface are good. Cellulose film. An example of the literature is disclosed in the film forming method in which the film is peeled off in a state in which the residual volatile component is 25 wt% to 35 wt%, and is 1% to 5 in the film width direction. The range of 〇% is extended. However, the current situation is that it is difficult to balance the performance of reverse dispersion with the improvement of Rth per unit film thickness, having to sacrifice productivity, or sacrifice cost due to the use of expensive additives. In addition, the inventors of the present invention have studied the addition of a method for adding optical properties to control the optical performance, and the results are clear = using previously known additives, after the polarizing plate is processed, the surface is unevenly displayed after being attached to the panel. Becomes all--, the residue is unsatisfactory. Further, it has also been clarified that the change of the member on the support when casting the film is carried out as a result of the conventionally known length, which is similarly applied to the panel. Therefore, it is very difficult to improve the in-plane display of the panel in addition to the reverse dispersion and the Rth which improves the maternal film thickness. 201219464 -rlt. Therefore, in addition to the above-mentioned optical characteristics, it is necessary to change the film physical properties to the extent that the in-plane display uniformity can be improved, in addition to the above-mentioned optical characteristics. The film condition is improved by the method. SUMMARY OF THE INVENTION The subject of the present invention is to provide a material for the production of deuterated cellulose and the like, wherein the (four) fiber is inversely dispersed in the shape of the filament, and the Rth of the mother film thickness is large, and the polarized light is polarized. When the board is processed and attached to the panel, it is not uniform in the plane. ^Under normal circumstances, the more the extension ratio in the TD direction (the film transfer direction Si, that is, the film width direction), the more 2 ^ (refer to the film obtained from the Japanese lions _62) In the middle or (10) (cellulose acetate butyrate == cellulose acetate propionate) ==:; in terms of in-plane uniformity, there is still a problem.伸 respective |=#&quot;Factory, regarding the manufacturing method, the county has a special study on the vertical extension and the horizontal extension and the residual volatile components, and in this case in the direction of the rush / by the special = even if it is described in the second document Real two === Solvent residual amount or drying condition, and there is no combination of 201219464t w〆aw, /b 11 for different extensions. Therefore, a combination of different solutions of T:: acidified cellulose. The formulation and manufacturing quantity and reverse dispersion of the unevenness in the S hair; the performance of the target Rth 罝 and the film of the sister b, the biliary direction above, the TD/M ^ number of the elastic modulus ^ to the special value

The direction of the elastic 楹壑々 仏 amp amp amp 疋 、 、 、 、 、 TD TD TD TD TD TD TD TD TD TD TD TD TD TD TD TD TD TD TD TD TD TD TD TD TD TD TD TD TD TD TD TD TD TD TD In addition, the display unevenness in the in-plane is remarkably lowered. In addition, the present inventors have found that the film of the present invention can be completed by providing various types of cellulose-dyed films which can be used in combination with the specific elongation conditions of the brewing. Specifically, the above problems are solved by the following means. The bismuth cellulose film is characterized in that the elastic modulus of the direction of the brewing cellulose film containing the total thiol group of 111 is 3200 MPa μ, which is below the weft of the woven material, and satisfies the following formula (1)~式〇): Formula (1) OnmSARe$15.〇nm (wherein, she represents the value obtained by subtracting the in-plane retardation value at a wavelength of 450 rnn from the retardation value in the in-plane direction of the wavelength 63〇nmT (Unit: nm)) Equation (2) 2xl〇-3SRth/d$6&gt;&lt;10-3 Punching (wherein Rth represents the retardation value in the film thickness direction at a wavelength of 550 nm (in nm)'d" Film thickness (unit: 〇11)) 201219464 1 VV/pif type (3) 1.0SE' (TD) /E'(MD) S1.43 (where E, (MD) indicates the elastic modulus of the film transport direction (The unit is MPa), and E'(TD) indicates the elastic modulus (in MPa) in the film width direction. [2] The cellulose-deposited film according to [1], wherein the film has a direction of elasticity of 3500 MPa or more. [3] The cellulose-deposited film according to [1] or [2], wherein the retardation value Re of the in-plane direction at a wavelength of 59 〇 nm and the retardation value Rth of the film thickness direction at a wavelength of 590 nm satisfy the lower Description: 35 nm$Re$80 nm, 100 nm$Rth$300 nm. [4] The cellulose-degraded cellulose film according to any one of [1] to [3] wherein the cellulose deuterated cellulose is cellulose acetate. [5] The cellulose-degraded cellulose film according to any one of [1] to [4], which comprises a polycondensed ester. [6] The cellulose-deposited film according to any one of [1] to [5], wherein a less than 3 wt% of Re manifest is contained with respect to the deuterated cellulose. [7] The cellulose-deposited film according to any one of [1] to [6], which contains the organic acid represented by the following formula (1): Formula (1) (in the formula ( In 1), X represents a substituent having an acidic group having an acid dissociation constant of 5 5 or less, L represents a single bond or a divalent or higher linking group, and Ri represents an alkyl group having a carbon number of 6 to 30 and a carbon number of 6 to 6. An alkenyl group of 3, an alkynyl group having a carbon number of 6 to 30, an aryl group having a carbon number of 6 to 30, or a heterocyclic 201219464t ring group having a carbon number of 6 to 30, and further having a substituent; n is at L In the case of a single bond, it is 1, and when L is a linking group of two or more valences, it is (the valence of L, 丨)). [8] The cellulose-deposited film according to [7], wherein R1 in the formula (1) represents an alkyl group having a carbon number of 6 to 24, a carbon group having a carbon number of 6 to 24, or carbon The number is an alkynyl group of 6 to 24 (wherein 'may further have a substituent). [9] The cellulose-deposited film according to [7] or [8], wherein X in the formula (1) has at least one member selected from the group consisting of a carboxyl group, a sulfonic acid group, a sulfonic acid group, and an acid-filling group. At least one group consisting of a group consisting of an imine group and an ascorbate group. [10] The cellulose-deposited film according to any one of [7], wherein L in the formula (1) is a single bond or is selected from the group of the following a linking group having a valence or higher or a linking group obtained by combining two or more units selected from the group of the following units; a unit: -0-, -CO-, -N(R2)- (the R2 represents a carbon number of 1-4 alkyl), -OH, -CH = CH-, -CH(OH)-, -CH2-, -S02-,

HCI

[11] The cellulose-degraded cellulose film according to any one of [7], wherein the organic acid represented by the general formula (1) is bonded to one molecule of a fatty acid on one molecule of the polyol. It is made with 1 molecule of dicarboxylic acid and has at least one unsubstituted thiol derived from polycarboxylic acid. [12] The cellulose-deposited film according to any one of [7], wherein the organic acid represented by the formula (1) has a molecular weight of 200 to 1,000. The bismuth cellulose film according to any one of [1] to [12], wherein 'the average total of the deuterated cellulose contained in each layer' has a laminated structure of two or more layers. The degree of substitution of the base is different from each other. [14] The cellulose-deposited film according to any one of [1] to [13] wherein the standard deviation (?) of the unevenness of the retardation axis direction at the end portion in the film width direction is 0.10 or less. [15] A method for producing a cellulose-deposited cellulose film, comprising: doping a solution containing a cellulose acetate having a total thiol substitution degree of 2.1 to 2.8 on a metal support a step of obtaining a film; a step of peeling the film from the metal support by satisfying the residual volatile component Η1 of the following formula (i); and removing the film from the residual volatilization satisfying the following formula (ii) a step of extending 5% to 1% by weight in the film transport direction in the state of the component H2; and the peeled film is orthogonal to the film transport direction in a state in which the residual volatile component H3 of the following formula (i) is satisfied. The step of extending the direction from 20% to 15%; the extension step satisfies the following formula (iv); (i) 20%$H1S60%, formula (ii) 10%$H2S60%, formula (iii) 5%^H3 ^45% Formula (iv) (MD stretching ratio + 100%) / (TD extension bait + 100%) 20.70 ° (In the formula, MD stretching ratio indicates the stretching ratio in the film conveying direction (unit: %), TD The stretching ratio is expressed by the stretching ratio (unit: %) in the direction orthogonal to the film conveying direction. [16] A method for producing a bismuth cellulose film, characterized in that the package 11 201219464 includes a dopant comprising a cellulose butyrate or a cellulose propionate having a total thiol substitution degree of 2.1 to 2.8. a step of performing solution casting on the support to obtain a film; a step of peeling the film from the metal support by satisfying the residual volatile component H1 of the following formula (i); and the peeled film is satisfied a step of extending 20% to 100% in the film transport direction in the state of the residual volatile component H2 of the above formula (;); and the peeled film is conveyed in the direction of the film in a state in which the residual volatile component H3 of the following formula is satisfied a step of extending from 35% to 150% in the direction of orthogonality; the extending step satisfies the following formula (iv); Formula (i) 20%^HI^60% Formula (ii) 10%$H2S60% Formula (iii) 5 %^H3^45% Formula (iv) (MD stretching ratio + 100%) / (td stretching ratio + 100%) ^0.70 (In the formula, the MD stretching ratio indicates the stretching ratio in the film conveying direction (unit: %) ''Drawing magnification ratio is expressed as a stretching ratio in a direction orthogonal to the film conveying direction (unit is %. [17] Deuterated cellulose as described in [15] or [16] In the manufacturing method, the stretching in the film transport direction is performed while controlling the variation of the tensile force (tensi〇n) to less than 1〇N/m. The living room is as in [15] to [17]. The method for producing a brewing cellulose film according to any one of the preceding claims, wherein the dopants are replaced by a total of two different dopants of the deuterated cellulose, and the dopants are [12] The method for producing a fluoridated cellulose film according to any one of [15] to [18], wherein the stripping step to the extending In the transition portion of the step, the film passes through at least three path rolls having a wrap angle of 60 or more. [20] As described in any one of [15] to [19] The method for producing a cellulose film according to any one of [15] to [20], wherein the method of producing a cellulose film according to any one of [15] to [20] Wherein, from both the back surface and the surface of the metal support body, the dopants cast on the metal branch body are blown dry air. [22] [15]~[21] In the method for producing a cellulose-degraded cellulose film according to any one of the preceding claims, wherein the stretching in a direction orthogonal to the film transporting direction is performed by a tenter, the following formula (v) is satisfied; Wx302L2Wx2 (where L represents the distance from the stripping step to the tenter (in mm), and W represents the width (in mm) of the stripped film.) [23] A cellulose film produced by the method for producing a cellulose oxime according to any one of [22]. [24] A polarizing plate comprising a polarizing element, such as the cellulose oxide film according to any one of [14] to [14] or [23]. [25] A liquid crystal display device comprising: [丨]~. The cellulose-deposited film according to any one of [23], or the polarizing plate according to [24]. [Effect of the Invention] A deuterated cellulose film and a method for producing the same can be provided. The wavelength dispersion of the deuterated cellulose film is inversely dispersed, and the Rth per unit film thickness is large, and is attached to the panel after processing on the polarizing plate 13 201219464. The display on the top becomes uniform in the plane. Further, the liquid crystal display device using the cellulose-degraded cellulose film of the present invention has a good front surface contrast even in the case of an enlarged size. [Embodiment] Hereinafter, the contents of the present invention will be described in detail. The description of the constituent elements recited below is based on a representative embodiment of the present invention, but the present invention is not limited to such an embodiment. In addition, "the so-called "~" in the specification is used as follows: the numerical value described later is included as the lower limit and the upper limit. In the present specification, the film transport direction is referred to as a longitudinal direction, a film longitudinal direction, or a ^0 direction, and a direction orthogonal to the film transport direction is referred to as a lateral direction, a film width direction, or a td direction. [Silified cellulose film] The cellulose-degraded cellulose film of the present invention (hereinafter also referred to as the film of the present invention) comprises a cellulose having a total thiol substitution degree of 2.1 to 2.8, which is characterized in that: The modulus of elasticity is 32 〇〇Mpa or more, and the modulus of elasticity in the film width direction is not more than 0.5 GPa, and the following formulas (1) to (3) are satisfied. Equation (1) OSAReg 15.0 (wherein ARe represents the value obtained by subtracting the in-plane retardation value at a wavelength of 450 nm from the retardation value in the in-plane direction at a wavelength of 630 nm (in nm).) 2xUT3SRth/dS6xlO·3 (In the formula, Rth indicates the retardation value in the film thickness direction at a wavelength of 55 〇 nm 201219464. J^iuupif (unit: nm)' ^ shows the film thickness (unit is leg).) (3) 1.0SE· (TD) /E, (MD) $1·43 (where E, (MD) represents the elastic modulus of the film transport direction (unit: 2 MPa), and E| (TD) represents the elastic mode of the film width direction MPa). Further, the film of the present invention can be produced by the method for producing a film of the present invention. Hereinafter, the film of the present invention will be described. &lt;Film characteristics&gt; (Delay) In the specification, Re(1)* Rth(1)* does not indicate the retardation in the plane at the wavelength λ and the retardation in the thickness direction. In the case of this manual, the wavelength λ is 550 Μ &lt; λ) is measured by K〇BRA 21 wrapped or generous (manufactured by Oji Scientific Instruments Co., Ltd.) = light is measured in the direction of the normal line. In the case of selecting the measurement, the amount can be manually determined or converted by the program to measure the measured value.于 When the _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _

Rth (λ) is determined from the normal phase of the in-plane Η or W as the tilting direction from the normal direction, from the normal direction to the one-sided 5Q degree, the incident wavelength is λ nm every other direction of the tilt. Light, ReU), based on the measured retardation value =:= 15 , if the film thickness value entered in 201219464 is calculated by KOBRA21ADH or WR. In the above-mentioned order, when the retardation axis with the in-plane is the rotation axis, the direction in which the delay value becomes zero at a certain inclination angle is opened _ the more oblique angle of the inclination angle larger than the inclination angle If the K0BRA h ADH or the failure is calculated, the H phase change 2 can also be used. The late phase _ can also be the tilt axis (when the axis of the rotation axis is used, 'any direction in the film plane is used as the rotation axis). The retardation value was measured in two directions of inclination, and based on the value and the average refractive index = 疋 value and the input film thickness value, Rth was calculated by the following equation. Chinese style U2) (11)

Re^)* The delay represents the value in the direction of the inclination angle θ from the normal direction. η 式 in the formula (11) indicates that the retardation axis in the plane represents the refractive index in the direction orthogonal to η 面 in the plane, the refractive index in the direction in which η is orthogonal, and 廿 is the film thickness. No /, nx (12)

Rth= {(nx + ny) /2-nz} xd The film measured cannot be uniaxially or biaxially folded. *: Rth (λ) is calculated by the method of expanding the optical axis (0ptlcaxis). ). The straw is as follows 201219464

Rth (λ) is the in-plane retardation axis (determined by k〇BRa2iadH4 WR) as the tilt axis (rotation axis), every 1〇 from -50 degrees to +50 degrees with respect to the normal direction of the film. Degreely measuring the light of the wavelength ληηι from the oblique direction and measuring the U point, based on the measured retardation value and the assumed value of the average refractive index and the input film thickness value, by KOBRA 21ADH or Calculated by WR. In the above measurement, the assumed value of the average refractive index can be used as a catalogue value of various optical films in the polymer handbook (JOHN WILEY &amp; SONS, INC). The value of the average refractive index is not known and can be measured by an Abbe refractometer. The values of the average refractive index of the main optical film are shown below: brewing cellulose (1.48), cycloolefin polymer (152), polycarbonate (1.59), polymethyl methacrylate 49), polystyrene (159). By inputting the assumed values of the average refractive indices and the film thickness, nx, ny, and nz can be calculated from KOBRA 21ADH or WR. Further, Nz = ( nx - nz) / ( nx - ny ) is calculated by the calculated nx, ny, and nz.

Re is preferably 35 nm$Re$70 nm, more preferably 40 nm$Re$60 nm 〇 and Rth preferably satisfies 60 nm$RthS300 nm, and more preferably satisfies 80 nm SRthg 150 nm. By setting such Rth, it is possible to produce a retardation film for VA having less color shift. (Wavelength dispersion) The film of the present invention has a retardation Re (630) in the in-plane direction at a wavelength of 630 nm and a retardation Re (450) in the in-plane direction at a wavelength of 450 nm (that is, ARe = Re (630) -Re (450)) The inverse dispersion film of the following formula (1) 17 201219464t is satisfied, and the change in the color tone of the viewing angle when incorporated in the liquid crystal display device can be improved. Formula (1) 0nm^ARe^l5_0nm (wherein ARe represents the value obtained by subtracting the in-plane retardation value at a wavelength of 450 nm from the in-plane retardation value at a wavelength of 630 nm (in nm) ° ) More preferably, the film of the invention has an ARe of 0.5 rim to 10 nm, and particularly preferably 1.0 nm to 9.0 nm. (Rth/d) The film of the present invention is a film satisfying the following formula (2), which can achieve both film thinning and sufficient Rth performance, and can reduce the raw material cost of the film. Formula (2) 2xl〇-3SRth/dS6xlO·3 (wherein Rth represents a retardation value (unit: nm) in the film thickness direction at a wavelength of 550 nm] d represents a film thickness (unit: nm).) The Rth/ d is preferably 2.0ΧΚΓ3~5·〇χ1〇·3, more preferably 2·5χ1 (Γ3~4.5χ1〇-3〇 (standard deviation of the azimuth direction of the longitudinal direction of the film σ6〇〇 and σ) -600) The film of the present invention preferably has a film width and a standard deviation (σ) of the unevenness of the retardation axis direction of the end portion is 010 or less. The film width direction end portion means from the center portion in the film width direction. In the film width direction, it is separated from the end portion by a distance of 600 mm to 1 mm, and any portion that is apart from the end portion in the film width direction by more than 100 mm varies depending on the width of the film. In the case of using the liquid crystal display device, the effect of the present invention can be sufficiently achieved. The film thickness of the film of the present invention is lye mm or more and satisfies the following formula (4) and formula ( 5), more preferably, the following formula (4') and formula (5·) are satisfied. Formula (4) σ600$0.13ο Equation (5) σ-600$0.13ο (in equations (4) and (5) ' Σ6〇〇 represents the rod difference of the azimuth of the slow phase axis when the direction of the longitudinal axis of the film is detected from the center line in the width direction of the film in the direction of one of the film ends. The standard deviation of the azimuth direction of the slow phase axis when the direction of the longitudinal axis of the film is detected from the center line in the width direction of the film from the center line in the film width direction is detected.) (4,) σ600 (0') σ·600$〇.ΐ〇 Here, the σ600 and σ_600 are preferably in the longitudinal direction of the film, lasting 2000 m, and satisfying the formula (4) and the formula when measured. (5), more preferably, it is 400 〇m in the longitudinal direction of the film and satisfies the formula (4) and the formula (5) in the measurement. The standard deviation σ6 〇〇 and σ of the azimuth direction of the longitudinal direction of the film in the longitudinal direction The off-line measurement can also be determined in-line, and it is better to measure the balance from the balance when the cutting is cut off. It is better to measure in the line. ~ And 'if the film is shaken up and down When the line in the long-side direction is implemented, then the delay of each of the slow-phase axes is detected more than the actual size. The measurement is carried out under the condition that the sloshing of the film is suppressed to 2 Å or less. As a branch for suppressing the sloshing of the film up and down, for example, the film-surface-remaining roll of the present invention can be transported by 201219464 ivrupif. The standard deviation σ600 and σ_6〇〇 of the azimuth direction of the longitudinal direction of the film in the longitudinal direction of the film are measured in parallel within 0.5 mm. 昧, # is not particularly limited, and may be separated by any speed or detection time. It was measured by 2 = m / leg into 2 = =. In the present invention, when the micro-transport is used, the data of 2000 m is continuously measured every 0.1 seconds at intervals of 0.1 second, and the respective deviations of the azimuth direction of the longitudinal direction of the film are calculated. The other measurement conditions of σ_ and σ-600 were set as follows, and detection and calculation were performed by the following methods. ^ Placement: High-speed extension wire set R_Scale Electronics Co., Ltd. Manufactured length: 2000 m Measurement pitch: continuous measurement every 20 seconds/min, for approximately 20,000 points of data, by X , &amp; is the late phase (four) degree uneven, order 20 201219464 jyioopif

n /«1 and calculate the dispersion σ. (Elastic Modulus) The elastic modulus E (MD) of the film transport direction of the film of the present invention is 32 MPa or more, and the elastic modulus E in the film width direction is equal to or less than (TD) GPa, and the following formula (1) is satisfied. . ^〇·5 Equation (3) 1.0SF (TD) /E,(MD) $1.43 , (where E'(MD) represents the elastic modulus of the film transport direction (in MPa), E'(TD) Elastic modulus (MPa) in the width direction of the film.) »; r.. Mooncake J (by using a film that satisfies such physical properties, unevenness in the surface when attached to the panel after processing the polarizing plate The details of the reason for the significant reduction are not clear. Although it is not limited to any reason, in fact, in the extension of the remnant-transfer component including the solution-forming method, the result can be improved by the value of the number of modules. The uneven modulus of the modulus of the enemy film is considered to be due to the low modulus of elasticity. On the other hand, when the film of the present invention is applied as a partial protective film and attached to a polarizing element, it is added to the polarizing plate. (4) _ f One side enters (four). However, the characteristics of the crepe (four) filaments are caused by the difference in the width direction and the long side direction which are applied during the working hours, resulting in the occurrence of the previous sag in the broad side and the long side direction. In the film of the present invention in which the number of the films is also improved, it is possible to suppress the unevenness of the wide side and the long side direction of the tensile force applied to the polarizing plate by the addition of the polarizing plate = 21 201219464 '. The elastic modulus of the film transport direction is MPa to MPa, and more preferably 33_ is 3500 MPa to 4000 MPa. υ MPa, excellent knife back θ elastic modulus of the mantle moving direction £, (TD) better 疋 3200 hall ~ bribe, better is smooth ~ side MPa, especially good 4 〇〇 〇MPa~47〇〇MPa. Further, 'e'(tD)/e, (md) is preferably 1〇5~14, preferably U0~丨.35, and particularly preferably 1.15~1.30. The elastic modulus E in the width direction, (TD) is not all below Q 5 , preferably 〇.4 GPa or less, and particularly preferably 〇3 coffee or less. (Thickness) The thickness of the film of the present invention is suitably determined by the type of the polarizing plate to be used, etc., preferably 30 μm to 60 μm, more preferably 35 μm to 55 μm. By making the thickness of the film 60 μm or less, the cost can be reduced and it is preferable. (Layer structure of deuterated cellulose film) The film of the present invention may be a single layer film or may have a laminated structure of two or more layers. In particular, the degree of substitution in the cellulose of bismuth is 2 6 to 2, preferably a single layer, and in the case where the degree of substitution is 2. 2.6, it is 2 or more. In this case, it is preferred that the film of the present invention has a laminated structure of two or more layers, and the average total thiol group substitution degree of the cellulose-deposited cellulose contained in each layer is different from each other. (Film width) 22 201219464 The film of the present invention preferably has a film width of 1 mm or more, 1500 mm or more, and particularly preferably 18 mm or more.疋&lt;Deuterated cellulose&gt; (raw material) (10) The cellulose to be used is not particularly limited, except for the cellulose of .1 to 2.8 which contains at least one type of total alumina. It is preferred that the cellulose is deuterated, and the cellulose used as the raw material for deuteration is used in cotton wool or nucleus (broadwood pulp, needle paper, etc.), and the cellulose derived from the raw material cellulose can be used. It is also possible to use it in a mixed manner. For this kind of raw material _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ Cellulose planted in the Inventor's Association of Public Technical Report No. 200M745 (pages 7 to 8). First, the cellulose deuterated cellulose preferably used in the present invention is described in detail. The glucose units constituting the β_1,4 linkage of cellulose have free hydroxyl groups at the 2, 3 and 6 positions. Deuterated cellulose is a polymer obtained by partially or completely esterifying one of these hydroxyl groups with a mercapto group having 2 or more carbon atoms. The thiol substitution degree indicates the ratio of the hydroxyl group esterification of the cellulose at the 2, 3, and 6 positions (100% esterification to degree of substitution i). The total thiol substitution degree of the deuterated cellulose of the film of the present invention, that is, DS2 + DS3 + DS6 is 2.1 to 2.8' is preferably 2.2 to 2.7, more preferably 疋2.3 to 2.7, particularly preferably 2.4 to 2.6. Moreover, DS6/(DS2 + DS3 + DS6) is preferably 〇~0.66, more preferably 〇15~〇6〇, further into 23 201219464 lVJVJplf step is preferably 0.20~0.45. Here, DS2 is the thiol substitution degree of the hydroxyl group at the 2-position of the glucose unit (hereinafter also referred to as "the thiol substitution degree of the 2-position"). DS3 is the thiol substitution degree of the hydroxyl group at the 3 position (hereinafter also referred to as " The thiol substitution degree of the 3 position is "), and DS6 is the thiol substitution degree of the 6-position hydroxy group (hereinafter also referred to as "6-position thiol substitution degree"). Further, DS6/(DS2 + DS3 + DS6) is a ratio of the thiol substitution degree of the 6-position to the total thiol substitution degree, and is hereinafter referred to as the "6-position thiol substitution rate". The mercaptan group used in the film of the present invention may have only one type of mercapto group, or two or more kinds of mercapto groups may be used. When two or more kinds of fluorenyl groups are used, it is preferred that one of them is an ethyl group, and as the fluorenyl group having a carbon number of 2 to 4, a propyl group or a butyl group is preferred. If the sum of the degree of substitution of the ethyl group of the hydroxyl groups at the 2, 3, and 6 positions is DSA, and the sum of the substitution degrees of the propyl group or the butyl group of the 2, 3, and 6 hydroxyl groups is referred to as DSB, The value of DSA + DSB is preferably 1.5 to 2.7. The value of DSB is preferably 0 1.70 'better 疋〇~1.2, especially 〇~〇5. In the present invention, it is particularly preferred that G' is the cellulose which is acetic acid. Cellulose. By setting the values of DSA and DSB to a range, it is preferable to obtain a film having a small change in Re value and Rth value due to environmental humidity. ... In addition, as DSB, 28% or more of them are substituted for 6 health bases, and more preferably 3G% or more are substituents of 6 health bases, and _ 2曰, the above is a substituent of 6 base groups, especially More than 32% is 6 digits: , = the base is also better. By using these membranes, it is possible to produce a solution of a solution, especially in a non-gasoline organic solvent, which can be produced well, and can be made into a solution having a low viscosity and good filterability. another

24 201219464 2 is a fluorenyl group having a carbon number of 2 or more in the cellulose of the present invention, and may be an allyl group for the gambling silk, and is limited in formation. These compounds are, for example, cellulose alkyl esters, alkenyl vinegars or aromatic groups s 曰 曰 aromatic alkyl vinegars, etc. and may also have further substituted groups, respectively. Preferred examples of the bases include a fluorenyl group, a butyl fluorenyl group, a fluorenyl group, a hexyl fluorenyl group, a surface group, a fluorenyl group, a decyl group, a tetradecyl group, a hexadecanyl group, and an octadecyl group. , Isobutyl fluorenyl, tert-butyl fluorenyl, cyclohexylmethyl fluorenyl, naphthyl, benzoyl, naphthalene, phenyl, cinnamyl and the like. More preferably, the propyl group, the τ fluorenyl group, the fluorenyl group, the octadecyl group, the third butyl group, the oil fluorenyl group, the benzamidine group, the naphthyl group, the cinnamyl group, etc. The best is Bingyin and Dingji. In the case of the use of an acid anhydride or ruthenium chloride as a oximation agent, an organic acid (e.g., acetic acid), dioxane or the like can be used as the organic solvent for the reaction solvent. As the catalyst, in the case where the oximation agent is an acid anhydride, a protonic catalyst such as sulfuric acid can be preferably used, and in the case where the oximation agent is helium (e.g., CH3CH2C0C1), a basic compound can be used. The most common industrial synthesis method of mixed fatty acid esters of cellulose is by mixing organic acids containing fatty acids (acetic acid, propionic acid, valeric acid, etc.) corresponding to ethyl hydrazino groups and other brewing groups or anhydrides of the same. A method of deuterating cellulose by a component. The deuterated cellulose used in the present invention can be synthesized, for example, by the method described in JP-A-10-45804. &lt;Additives&gt; 25 201219464 ^yivupif &quot;XinTeng' knife is called containing various additives.辛膜ΐΓΓ,ΐΓΓ: For the addition of a sword, a high molecular weight additive and a low molecular weight which are well known as an additive for a brewing fiber: film can be widely used. In the film of the present invention, the additive is preferably J wt%~ 3 ^ mesh is better for knowing the weight % of fibrin. 'Better is 4 wt% ~ 30 詈Λ丨 price 25 Wt%. If the additive is added = two = ft to change the temperature and humidity, if the amount added is here, the physical properties of the present invention are also excellent. A component added for the purpose of functions and the like. Also: or a residual solvent or the like is not an additive in the present invention. ο miscellaneous shells Two or more additives can be used in the middle and lower. Due to the optical characteristics, the advantages of the film elastic mold, and the adaptability of each additive. , film brittleness, or web operation (web late expression agent and ί::: if possible, polycondensation of polyester; delay adjuster (such as plasticizer; degradation (associated with phthalate, phosphate ester) The compound which can be used in the film of the present invention is described in detail (polyester). The polycondensation of the heart of the present month is preferably made of at least one of the two aromatic compounds having a ring of 26 201219464 carboxylic acid (also known as silky a mixture of a group of dicarboxylic acids and at least a species of a linalic acid (for example, an average of 5 s or more of carbon atoms) and at least an average carbon number of 2.5 or more and 7 () or less The aliphatic diol is obtained. The level of one aliphatic dinucleus residue is calculated in detail from the second residue and the one alcohol residue. μ Multiply the composition ratio (mole fraction) of the dicarboxylic acid residue The value of the nose is taken as the average carbon number. For example, when the adipic acid residue is 50 mol% and the o-dibenzoic acid hetero 5G mol% is composed, the average carbon number becomes and the diol is In the case of the residue, the average carbon number of the aliphatic diol residue is the composition ratio of the aliphatic diol residue (mole fraction). The value calculated by constituting the carbon number. For example, when the ethylene glycol residue 5 () mol% and the propylene-alcohol residue 5 G mol% are used, the average carbon number is 2 5 . The number average molecular weight is preferably a leak of ~ 诵, more preferably = 600 〜 I ·, and even more preferably a period of ~. If the average amount of knives in the condensed vinegar is 6 〇〇 or more, the volatility becomes low and becomes It is difficult to produce fiber-fiber riding, and it is difficult to produce film formation when the film is volatilized under high reading. The exudation plate when heating is extended; § The average molecular weight of the number 4 can be evaluated by the gel permeation layer =: and, when the terminal is not blocked (4), it can also be reduced by the unit weight. The amount (hereinafter referred to as the value of the value) 27 201219464 after the second two. The mixture of the middle and excess diacid and the lipid thief two New York acid 2 good ^ ^ number of 8 = 5.5 or more below the two light plate. If the above is used, the durability can be excellent, and Us can be used as a plasticizer. =. One. "Formation = two: base ratio (four) secret j: wide one. 1% 'in the best step is 5. One. You can get excellent partial silk 1 and, if it is 95 and it is For the longness ==: in the cellulose system _=:=

28 201219464 -7^1 uupif acid, ^Ϊ: ί : make f]if $ two slow acid widely enumerated o-phthalic acid 酉夂, 1,5-methyl dicarboxylic acid, 1 4-guana one ' 2ί^ ^ ^: ί ^ Hao Ben - h S this - formic acid, 2,6 • naphthalene dicarboxylic acid, more preferably a dicarboxylic acid, terephthalic acid, better step-by-step terephthalic acid. The group II is formed by mixing aromatic diwei to form an aromatic. Specifically, the 'aromatic dicarboxylic acid residue preferably contains an phthalic acid residue, a terephthalic acid residue, and an isophthalic acid residue. At least one species, more preferably at least one of an o-dicarboxylic acid residue and a terephthalic acid residue, more preferably a terephthalic acid residue. That is, in the mixing of the formation of the polycondensation, by using terephthalic acid as the aromatic dicarboxylic acid, the compatibility with the cellulose ester is more excellent, even when the cellulose ester film is formed and A cellulose ester film which is less likely to cause bleed out can also be formed by heating and stretching. Further, the aromatic dicarboxylic acid may be used in combination of two or more kinds. In the case of using two kinds, it is preferred to use phthalic acid and terephthalic acid. By using a combination of two kinds of aromatic dicarboxylic acids, phthalic acid and terephthalic acid, the polyester can be softened at room temperature, and the dicarboxylic acid residue of the polyester is reduced in terms of ease of handling. The content of the stearic acid residue in the medium is preferably 40 mol% to 95 mol%, preferably 45 mol% to 70 m〇i〇/〇, preferably 50 mol% to 70 mol%. . By making the terephthalic acid residue ratio 40 mol% or more, an optically anisotropic cellulose ester film which does not show a singularity of 29 201219464 1 can be obtained. Further, when it is at most % mol%, it is excellent in compatibility with cellulose vinegar, and it is difficult to cause bleed out even during film formation of the cellulose ruthenium film and during heating and stretching. 9 The aliphatic two-nuclear residue is contained in a polycondensed vinegar obtained by decaging a diol with one containing an aliphatic group. - In the present specification, the residue is a partial structure having a characteristic of a monomer forming a polycondensation vine in a partial knot of polycondensed vinegar. For example, the dicarboxylic acid HOOC-R-COOH and the pseudo-acid-residue formed by the 屮-OC-R-CO- 〇 are the aliphatic two ships of the present type, such as Bismuth, malonic acid, _acid, maleic acid, fumaric acid, glutaric acid, hydrazine, pimelic acid, softwood acid, sebacic acid, sebacic acid, dodecane or M-cyclohexane Acid, etc. A 酉 = = = 酉 = = 酉 酉 酉 ’ ’ ’ 由 由 由 由 由 由 由 由 由 由It is better that the average carbon number is 5.5 or more and 10.0 or less, and the more 疋5·5~8.0 ’ step is more preferably 5 5 to 7 G. If the [^ thousand carbon number is less than 7.0", the compound can be reduced: the occurrence of a two-sided surface failure (the reason for the planar failure)

The step of contamination caused by exudation when the web is dry. Further, when the L number is 2·5 or more, the compatibility is excellent, and it is difficult to precipitate the polycondensation polyester. It is preferable to include the amber axis and the own I in the case of the body 5'. It is preferable to include the amber axis and the own I: one of the two types of 201219464 uupif, and two or more types can be used. The use is the use of succinic acid and adipic acid. In the case of this, it is preferable to use amber. When the disk of the diol residue can be cleared, the value is preferably 'the compatibility with the cellulose is the same as that of the present invention, and the second meaning is better. Preferably. In the case of two types, fat or three types must be used. For each type, when three types are used, ^ 夂 方 香 二 二 与 与 与 与 与 与 与 与 与 与 与 与 与 与 与 与 与 与 与 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 The reason is that the content of the di-acid and the one aromatic can increase the content of the stremator St, which is a preferred one. It is a diol residue which has a polydidiol Ηα_ which forms a monomer which forms a polycondensation vine in the structure of a polycondensation gambling, and is formed by the diol which is a diol which forms a polycondensation, for example. At least the aliphatic two is listed as an aromatic diol and an aliphatic group containing an average carbon number of 2.5 or more and 7.0 or less. Preferred are genomic aliphatic diol residues having an average carbon number of 2.5 or more and 4.0 or less. If the compatibility of the aliphatic diol residual 3 is not reduced, it becomes difficult to produce * and the heating loss of the δ is not too large, and it is difficult to produce 31 201219464 jyiuupif planar failure (considered The reason (4) the steps of chemical fiber are stricken. &amp; a, 矣: day 7th, 1st, when the web is dry, the heart is Zheng Qiaomu). Moreover, it is difficult to synthesize the synthesis of the right-handed aliphatic diol residue. The number of extinctions is an aliphatic diol used in the present invention, and the alicyclic diols are, for example, ethylene glycol, 1, propylene glycol, i, di or 1,2-butanediol, α-butanediol, 2•methyl_丨, 3_propanediol, hydrazine, 4-butanediol, 1,5-pentanediol, 2,2-dimercapto-1,3-propanediol (neopentylene glycol), 2 2_ Diethyl-1,3·propanediol (3,3·dihydroxydecylpentane), 2 n-butyl 2-ethylpropanediol (3,3-dihydroxydecylheptane), 3-mercapto-1 , 5-pentanediol, [6_hexane'diol, 2,2,4-trimethylpentanediol, 2_ethyl_1&gt;3-hexanediol, '2-I--1, 8_octanediol, iota, 9-decanediol, u〇_nonanediol, hydrazine, 12-octadecanediol diethylene glycol, cyclohexane dimethanol, etc., preferably these compounds One type or a mixture of two or more types may be used together with ethylene glycol. The preferred aliphatic diol is at least one selected from the group consisting of ethylene glycol, i.2-propylene glycol, and hydrazine, and 3-propylene glycol. Particularly preferred are at least one of ethylene glycol and 12-propylene glycol. In the case of using two kinds, it is preferred to use ethylene glycol and 12-propylene glycol. Crystallization of the condensed polyester can be prevented by using 1,2-propanediol or hydrazine, 3-propylene glycol. The diol residue is formed from the diol used in combination in the polycondensation. The diol residue preferably contains at least one of an ethylene glycol residue, a 12-propylene glycol residue, and a 1,3-diol diol residue, more preferably an ethylene glycol residue or 1,2-propane. Leaven residue. Preferably, the ethylene glycol residue is from 20 mol% to 100 mol%, more preferably from 0.01 mol%/0 to 1 〇〇 m〇l〇/0 中.

32 201219464 The end of the polycondensate of t-month can be kept as a diol or hydrazine without blocking, and it can be further reacted with a monocarboxylic acid or a monoalcohol to carry out the end capping. 2 is a monocarboxylic acid used in the capping, preferably acetic acid, propionic acid, or hydrazine, more preferably acetic acid or propionic acid, and most preferably acetic acid. As the monoalcohol used for the capping, it is preferably decyl alcohol, ethanol, propanol, isopropanol, butyl, iso-alcohol, etc., and the best is the case. When the number of carbon atoms in the early carboxylic acid used in the end of the polycondensation s is 3 or less, the heating loss of the compound does not become large, and no planar failure occurs. Preferably, the end of the polycondensation of the invention is not sealed and remains as a diol residue, or more preferably terminated with acetic acid or propionic acid. Both ends of the polyester of the present invention can be terminated or unsealed. In the case where both ends of the condensed body are not blocked, it is preferred that the polycondensation condensate is a polyhydric alcohol. The mountain is one of the aspects of the polycondensation of the present invention, and the inverse number of the aliphatic diol residue is 2.5 or more. 7. G. The condensate is a polyester which is not blocked at both ends of the condensate. In the case where both ends of the condensed body are blocked, it is preferred to make it opposite to the monocarboxylic acid. At this time, the two ends of the county S are single residues. In the specification sheet, the portion of the structure based on the shrinkage (four) has a partial structure in which the characteristics of the monomer of the polycondensation are formed. For example, the monocarboxylic acid residue formed from the monocarboxylic acid R-COOH is R_c〇_. Preferably, the aliphatic single lining female 'more (four) is a single Wei residue having a carbon number of 22 or less, a single-nuclear residue, and the carbon number is 3 or less. 33 201219464 -Jp χ υν/ An aliphatic monocarboxylic acid residue of pif. Further, an aliphatic monocarboxylic acid residue having a carbon number of 2 or more is preferred, and an aliphatic monocarboxylic acid residue 7 having a carbon number of 2 is particularly preferred as one of the polycondensed vinegars of the present invention. The carbon number of the residue is more than 2.5 and 7.0 or less, and the polycondensate of the dicarboxylic acid residue is condensed. When the carbon number of the monocarboxylic acid residue at both ends of the right-polyester is 3 or less, the volatility is lowered, and the reduction of the polycondensation due to heating does not become large, thereby reducing the occurrence of step contamination or surface failure. produce. That is, as the monocarboxylic acid used for the capping nail, a fat = a monocarboxylic acid is preferred. More preferably, the monocarboxylic acid is an aliphatic monocarboxylic acid having a carbon number of 2 to 22, more preferably an aliphatic monocarboxylic acid having a carbon number of 2 to 3, particularly preferably an aliphatic having 2 carbon atoms. Monocarboxylic acid residue. For example, acetic acid, propionic acid, butyric acid, benzoic acid and derivatives thereof and the like are preferred, and acetic acid or propionic acid is more preferred, and acetic acid is most preferred. The monocarboxylic acid used for the capping may be mixed in two or more kinds. Preferably, the ends of the polyester of the present invention are blocked with acetic acid or propionic acid. The most preferred is to terminate the ends by acetic acid to form the ends of the vinegar residue (sometimes referred to as acetamidine). Base residue). In the case where the both ends are blocked, it is possible to obtain a cellulose ester film which is difficult to be in a solid state at a normal temperature and which is excellent in handling, and which is excellent in humidity stability and polarizing plate durability. Specific examples of the polycondensation ester of the present invention are described in Table 1 below, but are not limited to these specific examples.

34 201219464 J-a99l6£ 〔! &lt;] number average molecular weight 750 750 750 750 800 800 850 850 1500 1200 1200 1000 1 750 1800 〇〇〇750 750 750 750 1800 1200 1000 terminal ethyl decyl ester residue ethyl decyl ester residue ethyl ketone residue Ethyl decyl ester residue ethyl decyl ester residue ethyl ketone residue ethyl decyl ester residue ethyl decyl ester residue ethyl decyl ester residue ethyl decyl ester residue ethyl decyl ester residue acetamidine residue Ester residue acetal ester residue ethyl decyl ester residue ethyl decyl ester residue hydroxy hydroxy group 1 hydroxy hydroxy hydroxy hydroxy group average C number 2.55 2.55 2.55 2.55 ! 1 2·75 | 2.90 I | 2.55 I | 2.55 1 1 2.55 1 | 2.55 | | 2.55 | Γ 2.55 1 | 2.55 1 3.50 ; 6.50 2.55 2.55 2.55 2.55 2.75 2.90 2.75 diol diol ratio (mol%) 45/55 45/55 45/55 45/55 25/75 10/90 | 45/55 | | 45/55 | | 45/55 I | 45/55 | 45/55 45/55 45/55 25/75 25/75 45/55 45/55 45/55 45/55 25/75 10/90 25/75 diol 2 propylene glycol propylene glycol propylene glycol propylene glycol propylene glycol propylene glycol propylene glycol propylene glycol propylene glycol propylene glycol propylene glycol propylene glycol propylene glycol butanediol cyclohexane dinonanol i propylene glycol Propylene glycol propylene glycol propylene glycol propylene glycol propylene glycol propylene glycol diol 1 ethylene glycol glycol ethylene glycol glycol ethylene glycol 1 ethylene glycol 1 ethylene glycol | 1 ethylene glycol | 1 ethylene glycol | ethylene glycol | | Glycol | Ethylene Glycol Ethylene Glycol Ethylene Glycol Ethylene Glycol Ethylene Glycol Ethylene Glycol Ethylene Glycol Dicarboxylate η) Average C Number 5.80 6.00 6.20 丨6.60 S | 6.20 1 1 6.20 JI 8.00 I 9.00 6.00 6.00 | 6.40 I 1 6.60 1 7.00 6.20 1 1 6.20 I 5.80 1 6.00 6.20 6.60 6.20 6.20 8.00 Dicarboxylic acid ratio (mol%) 45/55 50/50 55/45 65/35 55/45 55/45 50/50 50/50 45/5/50 40/10/50 50/30/20 50/20/30 i 50/50 ! 55/45 55/45 45/55 50/50 55 /45 65/35 55/45 55/45 50/50 Aliphatic acid 2 SA/AA SA/AA Aromatic dicarboxylic acid ΤΡΑ ΤΡΑ ΤΡΑ ΤΡΑ I ΤΡΑ ΤΡΑ 2,6-ΝΡΑ 2,6-ΝΡΑ ΤΡΑ/ PA ΤΡΑ ΡΑ ΡΑ ΤΡΑ ΤΡΑ ΤΡΑ ΤΡΑ ΤΡΑ TPA TPA TPA TPA TPA TPA 2,6-ΝΡΑ &lt; Α-2 Α-3 Α-4 Α-5 Α-6 Α-7 Α-8 Α-9 Α-10 Α -11 Α-12 Α-13 Α-14 Α-15 A-16 A-17 A-18 A-19 A-20 A-21 Α-22 201219464 J-a99l6e 850 Ο οο Ο Ον 750 I 900 1800 850 750 850 900 750 850 1200 Ο 850 750 450 2500 Hydroxyhydroxyhydroxyhydroxyhydroxyhydroxyhydroxypropyl propyl ester residue Ethyl ester residue Ethyl ester residue Ethyl decyl ester residue ethyl decyl ester residue ethyl decyl ester residue hydroxy hydroxy hydroxy hydroxy group 1 2.75 1 L 2-75 I 1 — 2.75 1 2.75 L 2.75 I |_2.75 — I 3.50 1 6.50 1 1 2.55 I | 2.55 I | 2.55 | | 2.55 I | 2.55 1 | 2.55 ] 4.00 1 8.00 I 2.00 1 2.55 1 2.55 25/75 25/75 25/75 25/75 | 25/75 1 25/75 25/75 1 25/75 1 | 45/55 I | 45/55 | 45/55 45/55 | 45/55 1 45/55 ο ο 〇1 45/55 45/55 Propylene Glycol Propylene Glycol Propylene Glycol Propylene Glycol Propylene Glycol Propylene Glycol Butanediol Alkane dimethanol propylene glycol propylene glycol propylene glycol propylene glycol propylene glycol propylene glycol butanediol cyclohexane dinonol propylene glycol | propylene glycol glycol 1 ethylene glycol ι 1 glycol ι 1 glycol ι l glycol ι 1 glycol ι 1 Ethylene glycol ι I glycol | 1 glycol ι 1 glycol ι 1 ethylene glycol I 1 glycol ι ethylene glycol I glycol ι glycol 1 ethylene glycol | | 9.00 1 6.00 1 1 6.00 1 1 6.40 1 6.60 7.00 6.20 | 6.20 I | 6.20 I 5_40 | | 5.20 1 | 6.70 I | 8.00 1 10.20 6.20 6.20 6.20 | 6.20 I 6.20 50/50 45/5/50 40/10 /50 50/30/20 50/20/30 50/50 55/45 55/45 55/45 35/65 30/70 35/65 50/50 70/30 55/45 55/45 55/45 55/ 45 55/45 1 SA/AA I | SA/AA I ί 3 3 2,6-ΝΡΑ ΤΡΑ/ΡΑ ΤΡΑ/ΡΑ TPA TPA TPA TPA TPA TPA TPA TPA TPA 2,6-ΝΡΑ 2,6-ΝΡΑ TPA TPA TPA TPA TPA 1 Α-23 1 1 Α-24 1 1 Α-25 1 | A-26 | A-27 1 A-28 | A-29 丨A·30 1 丨A-31 | Lb-u B--2 B-3 Β·4—Β-5 Β-6 B-7 B-8 1 B-9 | B-10 Key®-M 姝-9CN: vdN-9ri Helmets? VS, key 4ΙΓΟ: W, Wglffi-M Igg: Vd!, key lB-Mu4l^:vdl, l^IB-uu4l^:vICLI(I&gt; 201219464 j Mingzhi, synthesis can be melted by condensation 5; 2, using the conventional method to make the diol and the diwei to carry out the polystyrene S human fS exchange reaction) 'or the acid chloride and the three sides of the boundary ΐΪΐ arbitrary method and easy to synthesize Moreover, regarding the invention Ϊ Ϊ 酉 ' 于 于 村 村 村 村 村 村 村 村 村 村 村 村 村 村 村 村 村 村 村 村 村 村 村 村 村 村 村 村 村 村 村 村 村 村 村 村 村 村 村 村 村 村 村 村 村 村 村 村Kaiping 05-155810, Sakamoto Patent No. 5-197073, Japanese Patent Special Open Separation %, Nikhan Kaiping 07-330670, Japanese Patent Special Opening 2〇〇6_34222 = Patent Special Opening - Na 79 The material described in the publication, etc. The content of the polycondensate in the cellulose vinegar film is relative to ^^i^5wt〇/〇.40 wt〇/〇wt% 'optimally 10 wt% to 25 wt. The content of the aliphatic diol, the diacid ester, or the diol ester of the raw material contained in the polycondensate of the present invention is preferably less than 1 wt% in the cellulose ester film. More preferably, it is less than 〇5. Wt%. Examples of diesters include dinonyl phthalate, di(p-ethyl) phthalic acid, dimethyl phthalate t-di(10)-ethyl phthalate, adipic acid. Di(transethyl) vinegar, bis(hydroxyethyl) ester, and the like. Examples of the glycol ester include ethylene glycol diacetate and diol diacetate. The type and ratio of each residue of the dicarboxylic acid residue and the diol residue mono-acid-acid residue contained in the polycondensation used in the present invention can be measured by a usual method using a leg. Under normal circumstances, it can be used as a solvent. The number average molecular weight of the polycondensed vinegar can be measured by a usual method using GPC (Gel Permeation Chromatography), and polystyrene can usually be used as a standard material. The measurement of the hydroxyl value of the polycondensation ester can be carried out by the acetic anhydride method described in Japanese Industrial Standard JIS K3342 (obsolete). In the case where the polycondensate is a polyester polyol, the hydroxyl value is preferably 50 or more and 190 or less, more preferably 50 or more and 130 or less. (Delayed Expression Agent) The film of the present invention preferably does not contain 3 wt% or more of Re Reagent with respect to the cellulose deuterated cellulose. On the other hand, in order to exhibit a retardation value, a retardation agent may be contained, but it is preferred that the content of the Re agent is less than 3 wt% with respect to the deuterated cellulose. The retardation agent is not particularly limited, and examples thereof include a delayed expression agent comprising a rod-shaped or disk-shaped compound. As the rod-like or disc-shaped compound, it is preferred to use a compound having at least two aromatic rings as a retardation agent. The amount of the delayed expression agent containing the rod-like compound is preferably 0.1 part by weight or more and less than 3 parts by weight, more preferably 0.5 part by weight or more and less than 2 parts by weight based on 100 parts by weight of the deuterated cellulose component. . The discotic compound contained in the delayed expression agent is preferably 〇] by weight or more and less than 3 parts by weight, more preferably 0.5 parts by weight or more, based on 100 parts by weight of the fluorinated cellulose. It is less than 2 parts by weight, and particularly preferably 0 to 5 parts by weight or more and less than 1 part by weight. Disk-like compounds are more rod-like in terms of Rth delay performance

38 201219464 f is excellent, so it is especially good when it is necessary to have a large Rth delay. It is also possible to use two or more kinds of delayed expression agents in combination. Preferably, the delayed expression agent has a maximum absorption at 250 nm to side n 2 and preferably does not substantially describe the discotic compound in the visible region. As the discotic compound, a compound having at least two aromatic rings can be used. In addition to the aromatic hydrocarbon ring, the "aromatic ring" is also a 6-membered ring (ie, a benzene ring). The group heterocyclic ring is usually an unsaturated heterocyclic ring. Aromatic = ring, 6-membered ring or 7-membered ring, more preferably a 5-membered ring or a 'good-side aromatic heterocyclic ring usually having the most double bonds. As a smock, a nitrogen atom is particularly preferred. Aromatic = ^ Seton, heterogeneous ring, gamma ring, ring correction, two Qin] two kiss ring, 哒. Qinhuan, pyrimidine, °biazine ring and u,5-special, =benzene ring, and stupid. : Use Japanese patent special _; No.:;:= 39

Af 201219464 6 Case, (b) is (a) the formation of a condensed ring and the bonding of the 12-bond bond and (4) via the linked base (four) = fang! family = two sub-fused tetraphenyl ring, Blessing Ring, ^ ring == two benzophenone rings. Heart (four) ring, stupid (four)" open bite ring, microphone ring, benzotrisole ring, = ro this ring, stupid and drip ring, different bell ring, two _ ^ benzopyrene ring, 喧Pyridazine ring, bite ring, sigma kawake ring, long time, day, f, ten evil ring, ring, scent ring, squama ring, die dibenzophenone, stupid and scorpion Ring, toward. Preferably, the bond between the carbon atoms of the two aromatic faces is bonded to the two aromatic rings by a single bond, and the axis is a fatty ring or a non-aromatic heterocyclic ring between the two. (c) The linking group is also preferably 岐 环 较佳 较佳 较佳 较佳 较佳 较佳 较佳 较佳 较佳 较佳 较佳 较佳 较佳 较佳 较佳 较佳 较佳 较佳 较佳 较佳 较佳 较佳 较佳 较佳 较佳 较佳 较佳 较佳 较佳 较佳 较佳 较佳 较佳 较佳 较佳 较佳 较佳 较佳 较佳 较佳 较佳 较佳 较佳 较佳 较佳 较佳 较佳An example in which the combined base is combined indicates that the left-right relationship of the example of the base may be reversed. Cl . -CO-0- 201219464, c2 : -CO-NH- c3 : _ 亚烧!基_0_ c4 : -NH-CO-NH- c5 : -NH-CO-O- c6 : -O-CO- O- c7 : -0-alkylene group -0 · c8 : -CO-sub-base - c9 : -CO-alkenylene-NH- cio : -CO-alkenylene-〇-

Cll :-alkylene-CO-O-alkylene-Ο-co.alkylene- cl2 : -O-alkylene-CO-O-alkylene-O-CO-alkylene-O- Cl3 : -O-CO-alkylene-CO-O- cl4 : -NH-CO-alkenylene- cl5 : -O-CO-alkenylene- The aromatic ring and the linking group may have a substituent. Examples of the substituent include a halogen atom (F, (Br, I), a mercapto group, a mercapto group, a cyano group, an amine group, an anthrace group, a thiol group, an amine group, an amine group, a urea group, and a burn group. Base, dilute base, fast base, aliphatic base, aliphatic oxy, alkoxy, chlorpyrifos, silky kilin, shouting base, burnt base, aliphatic guanamine, aliphatic sulfonate An amidino group, an aliphatically substituted amine group, an aliphatic substituted amine carbenyl group, an aliphatic substituted amine sulfonyl group, an aliphatic substituted ureido group, and a non-aromatic heterocyclic group. The number of carbon atoms is preferably 8. The chain-like group is more preferred than the ring-shaped group, and particularly preferably is a linear group. The group may further have a substituent 41 201219464 (for example, a hydroxyl group, a carboxyl group, Examples of alkoxy groups, alkyl-substituted amino groups). Alkyl groups (including substituted alkyl groups) include mercapto, ethyl, n-butyl, n-hexyl, 2-hydroxyethyl, 4-carboxybutyl The base of 2-methoxyethyl and 2-diethylaminoethyl. The number of carbon atoms of the alkenyl group is preferably 2 to 8. The chain alkenyl group is better than the cyclic alkenyl group. Straight The alkenyl group may further have a substituent. Examples of the alkenyl group include a vinyl group, an allyl group and a fluorene-hexenyl group. The number of carbon atoms of the fast group is preferably 2 to 8. The chain alkynyl group is more preferred. The cyclic alkynyl group is more preferably a linear alkynyl group. The alkynyl group may further have a substituent. Examples of the alkynyl group include an ethynyl group, a 1-butynyl group and a 1-hexynyl group. The number of carbon atoms is preferably 1 to 1 Å. Examples of the aliphatic fluorenyl group include an ethyl fluorenyl group, a propyl fluorenyl group and a butyl fluorenyl group. The aliphatic methoxy group preferably has 1 to 1 Å of carbon atoms. Examples of the decyloxy group include an ethoxy group. The number of carbon atoms of the alkoxy group is preferably from 1 to 8. The alkoxy group may further have a substituent (for example, an alkoxy group). The alkoxy group (including a substituted group) Examples of the alkoxy group include a methoxy group, an ethoxy group, a butoxy group, and a decyloxy group. The number of carbon atoms of the alkoxycarbonyl group is preferably 2 to 1 Å. Examples of the alkoxycarbonyl group include Methoxycarbonyl and ethoxycarbonyl. The number of carbon atoms of the alkoxycarbonylamino group is preferably 2 to 1 Å. Examples of the alkoxyamino group include methoxy The amine group and the ethoxy group of the amine group. The number of carbon atoms of the alkylthio group is preferably 丨~. Examples of the alkylthio group include an oximethio group, an ethylthio group and an octylthio group. The number of carbon atoms is preferably 42 19 卜 卜 2012 2012 2012 2012 2012 2012 2012 2012 2012 2012 2012 2012 2012 2012 2012 2012 2012 2012 2012 2012 2012 2012 2012 2012 2012 2012 2012 2012 2012 2012 2012 2012 2012 2012 2012 2012 2012 2012 2012 2012 2012 2012 2012 2012 2012 2012 2012 2012 2012 2012 2012 2012 2012 2012 2012 2012 2012 2012 2012 2012 2012 2012 2012 2012 2012 2012 2012 2012 2012 2012 2012 2012 2012 2012 2012 2012 2012 2012 2012 2012 2012 2012 2012 2012 2012 2012 Examples of the amine group include an ethenamine group. The aliphatic sulfonamide group preferably has 1 to 8 carbon atoms.

Examples of the amidino group include a methyl hydrazino group, a butyl hydrazine group, a positive = sulfonamide group. The number of carbon atoms of the amine group substituted with an aliphatic group is preferably 丨10. Examples of the aliphatic substituted amino group include a dimercaptoamine group, a diethylamino group and a benzylethylamine group. The number of carbon atoms of the aliphatically substituted amine sulfhydryl group is preferably from 2 to 10. Examples of the aliphatic substituted aminic acid group include a methylamine methyl sulfonyl group and a diethylamine methyl fluorenyl group. The number of carbon atoms of the aliphatic substituted aminoxime group is preferably 8. Examples of the aliphatically substituted aminoximino group include a methylamine sulfonyl group and a diethylamine sulfonyl group. The number of carbon atoms of the aliphatic substituted ureido group is preferably 2 to 1 Å. Examples of the aliphatic substituted ureido group include a methylureido group. Examples of the non-aromatic heterocyclic group include a butyl group and a N morpholinyl group. The molecular weight of the delayed expression agent is preferably from 3 〜 to 800. As the discotic compound, a triazine compound represented by the following formula (j) is preferably used. Formula (I) 43

201219464 «y ✓ A V/V/mII

N

X201_r201 X201 R201 In the above formula (I): 201 R each independently represents an aromatic ring or a heterocyclic ring having at least an arbitrary position in the ortho, meta and para positions. X201 independently represents a single bond or _NR2G2_. Here, R2〇2 is independently expressed as a money, a teacher or a non-generational, a dilute base or a heterocyclic group.

The aromatic ring represented by R β — is preferably a phenyl group or a naphthyl group, and particularly preferably an anthracenephenyl group. The aromatic ring represented by R may be in any of the substitution positions and may have one substituent. The substituents include (iv) atom, thiol, nitro, silk, silk, county, aryl, alkoxy, diloxy, decyloxy, occupational county, occupational group, aryloxy, a base Si sulfhydryl group, a dilute-substituted amine, an amine-based amine base, a trans-substituted amine methyl sulfhydryl group, a substituting base, a hydrazine, a _, a material

44 201219464 is a ring that is preferably a 5-member ring, a 6-member ring or a 7-member. It is: or 6-member ring, the best is 6-member ring. The heterocyclic ring = more preferably has a sub, a sulfur atom or an oxygen atom, and particularly preferably a nitrogen atom is preferably an aromatic heterocyclic ring, particularly preferably atb A. As a base with 4 or 4). The heterocyclic group may also be an example of a 2-mercapto group and an example of a substituent with an upper aryl moiety. The substituent of the % group is preferably a heterocyclic group of a free radical having a 5-membered ring in the nitrogen atom. # ^% f 疋5 members shouted 6-member ring, the best can also 罝 right ϋ can also ~ ❹ (4) child. Moreover, the heterocyclic group is suffocated by the county (example (4), s). The following is an example of a heterocyclic group of η^η. Here, -C4H9n means

One N

One N

COOC4H9n 45 201219464 The alkyl group represented by R2G2 may be a cyclic alkyl group or a chain alkyl group, preferably a chain alkyl group, and more preferably a linear chain than a branched chain group. Shaped base. The number of carbon atoms of the alkyl group is preferably 1 to 3 Å, more preferably 1 to 20, still more preferably 丨~(7), still more preferably 丨8, and most preferably 1-6. The alkyl group may also have a substituent. Examples of the substituent include a halogen atom, an alkoxy group (e.g., methoxy group, ethoxy group), and a decyloxy group (e.g., acryloxy group, methacryloxy group). The alkenyl group represented by R202 may be a cyclic alkenyl group or a chain alkenyl group, preferably a chain alkenyl group, and more preferably a linear chain than a branched chain alkenyl group having a branch. Alkenyl. The number of carbon atoms of the alkenyl group is preferably 2 to 3 Å, more preferably 2 to 2 G', more preferably 2 to 1 (), further preferably 2 to 8, and most preferably 2 ~6. The alkenyl group may also have a substituent. The % of the substituents are the same as the substituents of the above-mentioned alkyl group. The aromatic ring group and the heterocyclic group represented by R202 are the same as those of r201, and the preferred range is also the same. Aromatic ring group and miscellaneous in No. 2,344,655: in the case of Ϊ;; the details of the case can be found in the open technical report: where the molecular compound is also the same as the polymer used for the vinegar Description: 46 if 201219464 is a polymer-based delayed expression agent which may also be present in the polythene towel, preferably the aromatic private polyester-based polymer and the aromatic polyester-based polymer and other resins Copolymer. From the viewpoint of efficiently representing Re and achieving an appropriate Nz factor, it is more preferable that the extension of the present invention is a Re-table. Examples of the retardation agent in the retardation agent include a discotic compound and a rod compound. (Reducing agent) A known compound "In the present invention, as a retardation reducing agent, a heterocyclic ruthenium compound or a ruthenium hydride film can be widely used as a polymer system or a retardation reducing agent. It is selected from the group consisting of a dish-acid type polyester-based polymerized Μ 物 及 and an acid-based polymer, and the like, and the 'surface is a olefinic acid polymer and a styrene (tetra) polymer. The styrene polymer and the acrylic polythene have a rhodium-based birefringent polymer. The human Hit molecular weight retardation reducing agent may, for example, be exemplified by the following compounds. For its lion or boiling point material; for example: thief below and 2g °c above the ultraviolet absorption.. /fc 〇 or the same deterioration of the inhibitor mixture, etc. In addition, for the report, for example, Japanese Patent Special Open 2 ·-194522 liquid (doped with ΐ ° * and 'the addition period can be added in the step of sulfonating cellulose = step by step, arbitrarily added, # can be added to the lion preparation after the preparation step, adding additives to the step of preparation进47 201219464 ^ A VVfplf No specific restrictions The addition amount of each material is not particularly limited as long as it can exhibit a function, and is described in detail. In [K6 GW272177] [_6] to [_5], there is A. Patent Publication No. 2007_272177 [〇〇66]~[〇〇85] 11 ', ', the compound of the formula (1) can be produced by the following method. - The compound of the formula (1) in Hawthorn A can be derived from the chlorine. The compound described in the general formula (2) can be obtained by using a condensing agent (for example, dicyclohexylcarbodiimide (DCC), etc.). It is obtained by a dehydration condensation reaction of a carboxylic acid with an amine, or a substitution reaction of a carboxyxanthene derivative with an amine derivative, etc. (Plasticizer) As a plasticizer used in the present invention, it can also be usefully used as A variety of compounds known as plasticizers for deuterated cellulose. As a plasticizer, a phosphate or a carboxylate is used. Examples of the phosphate include triphenyl phosphate (TPP) and tri-f-phenyl phosphate (TCP). The acid ester is represented by phthalic acid ester and citrate ester. Examples of esters include dimethyl phthalate (DMP), diethyl phthalate (DEP), dibutyl phthalate (DBP), dioctyl phthalate (D0P), ortho-benzene. Diphenyl dicarboxylate (DPP) and diethylhexyl phthalate (DEHP). Examples of twisted acid vinegar include ethyl acetate-based diacetic acid (〇ACTE) and 0-acetamido citric acid. Tributyl vinegar (0ACTB). Examples of other resorcinic vinegars 48 201219464 oil, 1 from the purpose 1 linoleic acid thioglycolate, dibutyl sebacate, various benzoic acid®. Preferably, phthalic acid g is used as a plasticizer (DMP DEP, DBP, DOP, DPP, DEHP). Particularly good are DEP and DPP. (Deterioration Inhibitor) In the present invention, a known deterioration (oxidation) inhibitor such as 2,6-di-t-butyl-4-methylphenol, 4, 4 may be added to the deuterated cellulose solution. _ thiobis-(6-tert-butyl-3-indolyl benzene), u, bis(4-phenylphenyl)cyclohexene, 2,2 2-indenyl bis (4-ethyl) 6_T-butylbenzene), 2,5-di-t-butyl-p-phenylene, pentaerythritol-tetrakis[3-(3,5-di-t-butyl-4-phenylphenyl)酉 酉 ]] S 曰 曰 曰 曰 曰 曰 曰 曰 曰 曰 曰 曰 曰 曰 曰Further, it is preferably a sub-potassic acid bis(4.methoxy-3,5-diphenyl)p, a tris(mercaptophenyl) sulfite, or a tris(2,4-phosphite). Di-t-butylphenyl) ester, bis(2,6-di-t-butyl-4-indolylphenyl)pentaerythritol diphosphite, bis(2,4-di-tert-butylbenzene A phosphorus-based antioxidant such as pentaerythritol diphosphite. The amount of the deterioration inhibitor added is 0.05 parts by weight to 5% by weight based on 100 parts by weight of the cellulose resin. (Ultraviolet absorbing agent) In the present invention, the ultraviolet absorbing agent is preferably used in the deuterated cellulose solution from the viewpoint of suppressing deterioration of the polarizing plate or the liquid crystal. As the external and external absorbents, it is preferable to use an ultraviolet absorber having a small absorption of visible light having a wavelength of 4 〇〇 nm or more from the viewpoint of excellent absorption of ultraviolet rays having a wavelength of 370 nm or less and good liquid crystal display properties. Specific examples of the ultraviolet absorber to be preferably used in the present invention include, for example, a hindered 49 201219464 jy loopif (-) phenolic compound, a hydroxydibenzophenone compound, a triterpenoid compound, and a salicylic acid compound. A diclosan compound, a cyanoacrylic acid S compound, an error salt compound, or the like. As an example of the hindered compound, there may be mentioned 2,6-di-t-butyl. p-prepared, pentaerythritol-tetrakis [3-(3,5-mono-t-butyl-4-yl-phenyl) Propionic acid], hexamethylene bis (3,5-mono-t-butyl-4-hydroxy-phenylpropanamide), & trimethyl-2,4,6-di(3,5- 1. Tributyl-4--4-benzylbenzyl)benzene, tris-5-di-2-butyl-4-hydroxybenzyl)-isocyanurate, and the like. Examples of the benzotriazole-based compound include 2-(2,-hydroxy-5,-nonylphenyl)benzotriazole and 2,1 methylenebis (4_(1,1,3,3). -tetramethylbutyl)_6-(2H-benzotriazin-2-yl)phenol), 2,4-bis(n-octylthio)-6-(4-hydroxy-3,5-di- Tert-butylanilino)-1,3,5-triazine, triethylene glycol-bis[3-(3-tert-butyl-5-fluorenyl-4-cyclophenyl)propanoic acid] ester , N,N,-hexamethylene bis(3,5-di-t-butyl-4-hydroxy-benzamide), 1,3,5-trimethyl-2,4,6-three (3,5-di-t-butyl-4-ylhydroxybenzyl)benzene, 2(2·-hydroxy-3·,5'-di-t-butylphenyl)-5-gas benzotriazole , 2(2'-trans-based _3',5'-di-t-pentylphenyl)-5-gas benzotriene 1, 2,6-di-t-butyl-p-nonylphenol, Pentaerythritol-tetrakis[3-(3,5-di-t-butyl 4-hydroxyphenyl)propanoate]. The amount of the ultraviolet inhibitor to be added is preferably from 1 ppm to 3% by weight, more preferably from 10 ppm to 1,000 ppm, based on the total mass of the bismuth cellulose hydride. (Matting agent) From the viewpoint of film slidability and stable production, it is preferred that the film of the present invention contains a matting agent. The matting agent may be a matting agent for an inorganic compound or a matting agent for an organic compound. 201219464 jyioopif θ as a preferred specific example of the matting agent of the inorganic compound, preferably containing Shishi no Wei compound (for example, dioxane, machine Wei @, hydrated Shixi acid dance, Qian Ming, gift) , titanium oxide, zinc oxide, oxidation Ming: oxygen oxide, oxygen oxide, oxidation, tin oxide, tin oxide, calcium carbonate, talc, clay, calcined kaolin and calcium phosphate, etc., more preferably The inorganic compound or zirconia can particularly preferably use cerium oxide because the turbidity of the fluorinated cellulose film can be reduced. As the fine particles of the cerium oxide, for example, it is possible to use a product name of Aerotech R972, R974, R812, 2(8), 3〇〇, R202, OX50, TT600 (the above is a Japanese company). Commercial products. As the oxidized fine particles, for example, those commercially available under the trade names of Aerotech R976 and R811 (above, manufactured by Aer〇sil Co., Ltd., Japan) can be used. As preferred examples of the matting agent for the organic compound, for example, a polymer such as a silicone resin, a fluororesin or an acrylic resin is preferable, and a silicone resin can be preferably used. In the epoxy resin, particularly a silicone resin having a three-dimensional network structure, for example, T〇spearl 1〇3, Tospearl 105 &gt; Tospearl 108 ^ Tospearl 120 ^ Tospearl 145 &gt;

Commercial products such as Tospearl 3120 and Tospearl 240 (made by Toshiba Silicone Co., Ltd.) are commercially available. In the case where the matting agents are added to the deuterated cellulose solution, there is no problem particularly if the desired deuterated cellulose solution can be obtained by any method which does not limit the method. For example, in the stage of mixing the deuterated cellulose with the solvent, an additive may be contained, and after the mixed solution is prepared by deuterated cellulose and a solvent, an additive may be added. In addition, 201219464 ^^ιυυρίί may be added and mixed before casting the dopant, that is, a so-called direct addition method, and the mixing is on-line setting of the spiral mixing - specifically, preferably A static mixer such as an in-line mixer, and a mixture of, for example, an in-line mixer such as static; a kneading machine cm and a SWJ (manufactured by Toray Static In-Tube Mixer Twisting Co., Ltd.) machine. In addition, regarding the in-line addition, the degree, the uniformity, and the particle aggregate, the Japanese Patent Laid-Open Patent Application: In the method for producing a cellulose film, the addition of the g-end end and the in-line mixer The distance L at the starting end portion is set to be less than 5 times the inner diameter 4 of the main raw material pipe, and the agglomeration can be eliminated. The above-mentioned addition nozzle is mixed in the main raw material doping. The same, and the addition of liquid. As a better aspect, the additive liquid of different composition is supplied to the front end of the nozzle and the = (1) is set to be mixed in the front tube of the supply nozzle = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = ; liquid ^ =::==; rr. In addition, in the invention of the = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = The solution is added to the second == (4) to reduce the compatibility, so it is better to find the static mixing machine ί

52 201219464 ^yioopif Mixer 檇:. (organic acid) acid. Preferably, the film of the present invention comprises an organic formula (1) represented by the following formula (1): x 叱乂矣 if if if 'X' indicates an acid dissociation constant of 5.5 or less and an acidity A = Linking group, Rl is a heterocyclic group having a carbon number of 6 to 3: 6% of which is burned, and has a carbon number of 6 to 3 Å, and a carbon number of 4, which is 3G. - In the case where m is a single bond, it is 〖, in the case where L is a j-bonding group, it is (the valence of L)].) The organic acid represented by the above is the acid A. The second-generation film-forming device (the dopant is ionized and blocked) is on the metal surface of the support, and thus is compared with the organic acid of the hydrophobic group of the R: corrosion. Hereinafter, the peeling accelerator which can be used in the film of the present invention is referred to in the formula (1), and X represents an acid having an acid dissociation constant of 5 5 or less, preferably a ruthenium, a ruthenium group or a propargyl group. , hetero-base, gammine ^, 53 201219464 jyioopif ascorbic acid base, better base, two base, the most honest. In the case of the ascorbic acid group, it is preferred that the hydrogen atoms at the 5-position and the 6-position in the wind atom of ascorbic acid fall off and are linked to 1. In this specification, the acid dissociation constant is stated in the journal of Chemical Society. ^ In the formula (1) +, R1 represents a hydrogen atom, a carbon group having 6 to 30 carbon atoms (which may have a substituent), an alkenyl group (which may also have a substituent), a block = a substituent, and an aryl group. (may also have a substituent), a heterocyclic group can be: there is =). Examples of the substituent include a dentate atom, an aryl group, a hetero ring, a pit oxy group, an aryloxy group, a thiol group, an arylthio group, a fluorenyl group, a thiol group, a aryl group, an amine group, and an alkoxy group. , mercaptoamine, oxymethyl, amine, sulfonyl, sulfonyl, sulfonyl, sulfo, carboxy, and the like. More preferably, the alkyl group having a carbon number of 8 to 24 and the fluorenyl group are preferably a linear alkyl group or an alkenyl group having a carbon number of 10 to 24. L in the general formula (1) is preferably a single bond, or a linking group of two or more valences selected from the group of the following groups, or a combination of two or more units selected from the group of the following groups. Linkage above the price. Unit: -0- '-CO-, -N(-R2)- (the R2 is a radix with a carbon number of i~5), -CH=CH-, -CH(OH)-, -CHr·, -S02-, -C-- L is particularly preferred in the general formula (1), which has a single bond and is derived from an ester group. 54 201219464 j^ioopif base group (-COO-, -OCO-), or derived from A linking group of amidino groups (-C0Nr2-, -NR2CO-) is used as a partial structure. Further, the L may further have a substituent, and the substituent is not particularly limited, and examples thereof include a substituent which the r1 may have, and among them, an -OH group is preferred. In these, it is more preferred that the 1 is a linking group containing a group derived from glycerin. As the L, specifically, the following structure is preferable. In the following, p, q, and r each represent an integer of 1 to 40, preferably 1 to 20, more preferably 1 to 10, and particularly preferably 1 to 6. Further, it is further preferable that q is 2 to 4. -(CH2)p-CO-0-(CH2)q-〇- · -(CH2)p-C0-0-(CH2)q-(CH(0H))-(CH2)r-0-; -( CH2)p-C0-0-(CH2)q-(CH(0C0-R3))-(CH2)r-0-; -(CH2)p-CO-O-(CH2)q-(CH(OH) )-(CH2)r-0-C0-; -(CH2)p-C0-0-(CH2)q-(CH(0C0-R3))-(CH2)r-0-C0_. Further, R3 contained in the above specific example of L is synonymous with R1 in the above formula (1), that is, a linking group -(CH2)p-C0-0-(CH2)q-(CH( R3 in 0C0-R3)HCH2)r-0- is only described in the interior of L for the sake of convenience, and the linking group L indicates a portion in which R3 is removed. That is, in this case, L is 3 valence. If expressed by the general formula (1), δ can be carried as X-LJR1)], [10, L represents -(CH2)p-C0-0-(CH2)q-(CH(0C0-))- (CH2)r-0-], that is, the linking group L at this time becomes a trivalent linking group. 55 201219464 jyiOopif The L and the X are preferably bonded by an ester bond or a guanamine bond, and more preferably by an ester bond. Moreover, it is preferred that no acetal or guanamine bond is present in said X. Preferably, the L and the R1 are bonded by an ester bond, an ether bond or a guanamine bond, more preferably an ester bond or a amide bond, and particularly preferably an ester bond. . Moreover, it is preferred that no ester bond or ether bond or guanamine bond is present in said R1. Hereinafter, preferred specific examples of the organic acid represented by the above formula (1) are listed below. "Fatty Acids" Nutmeg, palmitic acid, stearic acid, oleic acid, linoleic acid, sub-linoleic acid, simianic acid, undecanoic acid. "Soda-based sulfuric acid" meat beans, sulphuric acid, sixteen silk, sulfuric acid. "Como-benzoic acid" eleven-burning benzene continued acid, fifteen-burning benzene continued acid. "Alkylnaphthalenesulfonic acid" sesquibutyl acid, diisobutyl phthalic acid. "Dialkyl sulfosuccinic acid" Dioctyl succinyl sulphate, dihexyl sputum, dicyclohexyl ruthenium, diastah succinct _, two (thirteen silk) ring a _. "Partial Derivative of Polybasic Organic Acid" The partial derivative represented by the above formula (1). In the present specification, the organic acid is preferably a partial derivative of a so-called polybasic organic acid of a polybasic organic acid.

56

201219464 refers to a structure having a structure in which a molecular weight fatty acid and a polybasic organic acid are bonded to one molecule of a polyol, and has at least one unsubstituted acidic group derived from a plural ship. In addition, in this book, the fatty acid means Lin 2 acid. That is, the acid of the (4) acid of the present invention is not limited to the so-called r% fat (4), and includes a lower fatty acid having a carbon number of 12 or less such as acetic acid or propionic acid. Preferably, the partial derivative of the polybasic organic acid is a multi-component flavonoid derivative. That is, the organic acid represented by the formula (1) preferably has a bond on the one molecule of the polyol. The structure of the molecular acid and the molecular polybasic acid, and having at least one unsubstituted slow group derived from the polycarboxylic acid. As a multi-component of the multi-component, the multi-repulsive acid used in the multi-injection does not have a specific setting, for example, a relatively small sage, a lemon acid, a tartaric acid, an acetyl tartaric acid, a malic acid, and p as the plurality of The polyhydric alcohol used in the partial derivative of the organic acid may, for example, betaxel (ad() nitG1), arabitol, ethylene glycol, diethylene glycol, triethylene glycol or tetraethylene glycol. , propylene glycol, 13-butanediol, 1,4-butanediol, dibutyl glycol,! , 2, butyl triol, π pentanediol, hexane diol, hexane triol, galactitol, mannitol, methyl pentane H, 3, 5 _ dip, pinacol (Pinacol), sorbitol, three It is made of methyl propyl ketone, trimethyl ketone, wood (four), and golden material. It is difficult to use glycerin, and it is preferred that the ship of the formula (1) is a so-called organic acid glycerin. = the organic acid represented by the above formula (1), preferably the mono-substance X of the organic acid is bonded to the hydrophobic portion R via a linking group 1 containing a glycerol-based group, and the organic acid glycerol Organic acid vinegar). 57 201219464 Here 'in the present specification> Compound: Three gastric organic acid glycerides of glycerol means that the following structure is derived from the acidity of the multi-it organic acid/organic _ fine key, and佳# θ is particularly good for organic acid monoglycerol § or organic acid diglycerin vinegar, oil vinegar refers to the following structure of the so-called organic acid mono-glycolic acid to form 酉 键 key, and with Γ or 2 And the acidic group of the so-called organic acid acid in the plural organic book. 2 of the three radicals of the present specification: Γ曰疋 means a compound having a structure in which glycerin forms a s-bond with a polybasic organic acid; the remaining one is via a base. Eight, the original acidity of the multi-organic acid from the 5 hai: The further step-by-step structure is the following structure and == one is the unsubstituted base, and the other one is based on the base. Hemp ^ ^ 酉 酉 9 bond ' and has the acidity derived from the polybasic organic acid, set (the position of the α-monoglyceride of the stomach), and compared with the ==, _ single Ganguan and polymorphic acid The same is true for the asymmetric position (so-called (the position of X monoglycerol). Heart. Organic acid monoglycerol is preferred. The preferred structure is an unsubstituted hydroxyl group and fatty acid. The carbon bismuth and the shirt element which are directly bonded by the ester-bonded hydroxy jin jin have the _

58 201219464 J^ioopif The carbon atoms directly bonded by the base are not adjacent. Further among the organic acid monoglycerides, a monoglyceride of a polyvalent carboxylic acid is further preferable. The monoglyceride of the polyvalent carboxylic acid means an organic acid having at least one unsubstituted carboxyl group in the polyvalent carboxylic acid and the other carboxyl group substituted by the monoglyceride. That is, it is particularly preferable to use a carboxyl group-containing organic acid monoglycerol in which a molecular fatty acid and a monovalent polycarboxylic acid are bonded to a molecular glycerin. The polybasic decanoic acid used in the monoglyceride of the polyvalent carboxylic acid is not particularly limited, and for example, succinic acid, citric acid, tartaric acid, diterpene tartaric acid, malic acid, adipic acid is preferred. . The fatty acid used in the monoglyceride of the polycarboxylic acid is not limited, and preferably a saturated or unsaturated fatty acid having a carbon number of 8 to 22, specifically, lycosyl octanoic acid, citric acid, orthorium , peas, palmitic acid, stearic acid, behenic acid, oleic acid, etc. Hereinafter, the organic acid monoglyceride containing a carboxyl group which can be used in the present invention will be described in detail. The organic acid monoglyceride which can be used in the present invention can be made into an acid of a polybasic organic acid according to the method described in Japanese Patent Laid-Open No. Hei No. 97-1995, Japanese Patent No. 3823524, and the like. Obtained by reaction with fatty acid monoglyceride. The reaction is usually carried out in the absence of a solvent, for example, in the reaction of amber and a number of 18% fatty acid monoglyceride at a temperature of 120. (:^ The secret of the clock should be. The acid monoglyceride obtained as the surface | Tongwei becomes a mixture containing organic acid, unreacted monoglycerol §, diglycerin 59 201219464f ^ A w^/11. In the present invention, the mixture may be used as it is. In the case where the purity of the thiol-containing organic acid monoglycerol is desired to be increased, the drum base is contained in the mixture as described above by distillation or the like. The organic acid monoglyceride may be purified, and a high-purity carboxyl group-containing organic acid monoglyceride may be used as a distilled monoglyceride. As the carboxyl group-containing organic acid monoglyceride market Examples of the product to be sold include POEM K-37V (glycerol citrate oleate), STEP SS (glycerol stearic acid/palmitic acid carboxylic acid ester) manufactured by Kao Corporation, and the like. The amount of the organic acid represented by the above formula (1) is from 0.1% by weight to 2% by weight relative to the cellulose deuterated cellulose, and particularly preferably from 0.5% by weight to 10% by weight. Further particularly preferred is 〇·6 wt%~5 wt% 'further extra is 1.5 wt%~5 wt%. When the amount is 0.1% or more, the effect of improving the durability of the polarizing element and the effect of improving the peeling property are sufficient. Further, when the amount is 2% by weight or less, the organic acid is hard to bleed out during the south temperature and the wet period. It is preferable that the orthogonal transmittance of the polarizing plate is difficult to rise. The molecular weight of the organic acid represented by the general formula (1) is preferably from 2 to 1000 Å (sugar ester compound) - sugar residue - the sugar The ester compound is a compound in which at least one of a substitutable group (for example, a hydroxyl group or a carboxyl group) constituting the compound is acetylated with at least one substituent, that is, the so-called sugar ester compound is also included. 201219464 i uujjif A generalized sugar derivative, for example, also contains a compound containing a sugar residue as a structure such as gluconic acid. That is, the above-mentioned compound also includes an ester of glucose and a carboxylic acid, gluconic acid and an alcohol. The ester group is preferably a hydroxyl group which is a substituent in the polysaccharide of the sugar ester compound. The sugar ester compound contains a structure derived from a polysaccharide constituting the sugar ester compound (hereinafter also referred to as a sugar residue). Description The structure of each monosaccharide of the sugar residue is referred to as a structural unit of the sugar ester compound. The structural unit of the sugar ester compound preferably contains a pyranose structural unit or a furanose structural unit, and more preferably all sugar residues. All of them are pyranose structural units or furanose structural units. Further, in the case where the sugar ester is composed of a polysaccharide, it is preferred to include a gulycan structural unit or a furanose structural unit together. The sugar residue may be derived from 5 monosaccharides or 6 monosaccharides. Preferably, it is derived from 6 monosaccharides. The number of structural units contained in the sugar ester compound is preferably 2 to 4'. It is 2 to 3' particularly preferable. That is, the sugar constituting the sugar ester compound is preferably 2 saccharides to 4 saccharides, more preferably 2 saccharides to 3 saccharides, and particularly preferably 2 saccharides. In the present invention, the sugar ester compound is more preferably at least one of the hydroxyl group-containing sugar ester compounds containing 2 to 4 pyranose structural units or furanose structural units, more preferably a hydroxyl group. At least one esterified sugar ester compound comprising two pyranose structural units or furanose structural units. Examples of the monosaccharide or a saccharide containing two to four monosaccharide units include erythrose, hetero-erythroside (thre〇se), 61 201219464 jyioopif ribose, arabinose, xylose , sorbitol, allose, altrose, glucose, fructose, gulose, idose, galactose, talose, trehalose, trehalose , new trehalose, trehalose, kojibiose, niger〇se, maltose, wheat “sugar alcohol, isomaltose, sucrose, kelp disaccharide, cell disaccharide, gentian Lactose lactose, lactosamine, lactitol, lactulose, melibiose, primrose, sucrose, scillabiose, sucrose, sucralose, pine disaccharide, sugar, fiber trisaccharide , potato trisaccharide, gentian trisaccharide, isomaltotriose exoglucose maltose, maltotriose, mannose trisaccharide, pine trisaccharide, panose, car sugar, raffinose, eggplant trisaccharide, Umbelliferous sugar, oligosaccharide, maltotetraose, 'stachyose, malto-pentose, six hexagrams', one malt hexaose, xylose Pearitol, etc. Preferred are ribose, arabinose, xylose, lyxose, glucose fructose: mannose, galactose, (iv) sugar, wheat miscellaneous, cellobiose, recommendation sugar, glycoside, wood Sugar alcohol, sucrose, more preferably adisaccharide, xylose, glucose, fructose, mannose, galactose, maltose, disaccharide, sucrose, especially good is xylose, glucosamine, silk, mannose Galactose, maltose, cellobiose, neotium, xylitol, sorbitol: preferred examples of the substituent of the vinegar compound, the alkyl group having a ruthenium number of the alkyl group is preferably 22, more preferably the carbon number The silk of h is 'excellent is the burning base of carbon number 8, such as thiol, ethyl, base, minus ethyl, propyl, 2-cyano, hydrazine, etc.), ^ (more) Preferably, the carbon number is 6 to 24 aryl groups, more preferably 6 to 18 soils, especially the 6 to 12 filaments, such as phenyl, Li), Ming (better soil 62 201219464 ^yioopif is a fluorenyl group having a carbon number of 1 to 22, more preferably a fluorenyl group having a carbon number of 2 to 12, particularly preferably a fluorenyl group having a carbon number of 2 to 8, such as an ethyl group, a propyl group, a butyl group, a butyl group醯基,己醯Base, octyl decyl, benzhydryl, tolylmethyl, phthalic acid, etc.), guanamine group (preferably a ruthenium group having a carbon number of 1 to 2. 2 2, more preferably a carbon number) It is a 2 to 12 decylamino group, particularly preferably a decylamino group having a carbon number of 2 to 8, such as a carbamide group, an etidamine group, or the like, and a quinone imine group (preferably having a carbon number of 4) Preferably, the imine group is a group having a carbon number of 4 to 12, and particularly preferably an anthranylene group having a carbon number of 4 to 8, such as amber quinone imine or phthalate. More preferably, it is a pyridyl group or a fluorenyl group, more preferably a methyl group, an ethyl fluorenyl group or a benzoinyl group, and particularly preferably a benzamidine group and an acetamidine group. At least one of them is further preferably a benzoquinone group. Hereinafter, specific examples of the sugar ester compound which can be used in the present invention are listed, but the present invention is not limited thereto. Further, the specific degree of ester substitution of each of the sugar ester compounds is not described in the following specific examples. However, as long as the main components of the present invention are not infringed, the sugar-based compound of the degree of substitution may be used. Sugar, a mixture of compounds used. 1 63 201219464 jyioopif Compound 1

R1 a c-ch3

Compound 3

Ο u R3= —C Compound 4

ο R4= —C-C2Hs 64 201219464 jyioopif compound 5

R5=—C-CHS Compound 6

R6= Ο II -C-CH3 Compound 7

R7= — C-CH3

O

II Compound 8

R8= 0 II -c-ch3 Compound 9

Compound 10

〇II c—ch3 o ch3II I —C—CH3 65 201219464 j^ioopif Compound 11 CH2OR11 CH2ORl1 H R11. , s?R11 R Che XH2OR11 A L L l R11 Compound 12

R12= Compound 13

CH2OR13 CH2OR13 R13〇\?^3 H

CH2OR13 OR13 H R13 = Compound 14

R14= ?ch3

〇ch3 〇ch3 compound 15

Compound 16

66 201219464 ^yioopif In the following structural formula, R each independently represents an arbitrary substituent, and a plurality of R may be the same or different. Ch2〇r ~ 6r ^**···^ 丫_1面·&quot;y ch2〇r H OR OR Η [Table 2] Compound Substituent 1 Substituent 2 Molecular Weight Kind Substitution Degree Substitution Degree 101 Ethyl 7 Benzyl 1 727 102 Ethyl 6 benzyl 2 775 103 Ethyl 7 Benzopyridyl 1 741 104 Ethyl 6 Benzopyridin 2 802 105 Benzyl 2 No 0 523 106 Benzyl 3 No 0 613 107 Benzyl 4 No 0 702 108 Ethylene 7 Styrene 1 Styrene 1 771 109 Ethyl 6 Styyl Ethyl 2 847 110 Stupid 1 N - 446 111 Clumky 2 No - 550 112 Stupid甲基基3 无 - 654 113 笨甲醯基4 无- 758 114 苯甲醯基5 无 - 862 115 苯甲醯基6 无 - 966 116 苯甲醯基7 无 - 1070 117 苯甲醯基8 - 1174

H OR 67 201219464 i uwplt [Table 3] Compound Substituent 1 Substituent 2 Molecular Weight Kind Substitution Degree Substitution Degree 301 Ethyl 6 Benzomethyl 2 803 302 Ethyl 6 Benzyl 2 775 303 Ethyl 6 Benzene Ethyl hydrazide 2 831 304 Stupid thiol 2 No 0 551 305 Benzyl 2 No 0 522 306 Stupyl acetyl 2 No 0 579 [Table 4] Compound substitution 3 Substituent 2 Molecular weight species Substitution degree Substitution degree 401 Ethyl group 6 phenyl group 2 803 402 acetyl group 6 benzyl 2 775 403 acetyl group 6 phenyl acetyl group 2 831 404 曱醯 曱醯 2 2 0 551 405 benzyl 2 no 0 523 406 Vinegar 2 is not 0 579. Further, as the sugar ester compound, Japanese Patent Laid-Open Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. 2, No. Hei. The sugar ester compound described in Japanese Laid-Open Patent Publication No. Hei 9/ou. The method for obtaining the glycoside compound can be commercially obtained in the form of a commercial product by the Tokyo Chemicals Co., Ltd., 68 201219464 ^yioopif Co., Ltd., Aldrich, etc., or by a known wall of commercially available carbohydrates. A street biochemical method (for example, the method described in JP-A-8-245678) is synthesized. The number average molecular weight of the sweet and sour compound is preferably from 2 〇〇 to 3,500, more preferably from 420 to 3 Å, and particularly preferably from 45 Å to 2 Å. The sugar ester compound preferably contains 2 wt% to 30 wt%, more preferably 5 wt% to 20 wt%, relative to the deuterated cellulose. [Manufacturing Method of Film] The film of the present invention can be produced by the method for producing a film of the present invention (hereinafter also referred to as the production method of the present invention) as described below, depending on the case where cellulose acetate is used as the brewing cellulose, Different from the film forming conditions in the case of using cellulose butyrate or cellulose propionate as the cellulose halide, it can be efficiently produced. In the case of using cellulose acetate as the cellulose deuterated, the production method of the present invention comprises: carrying out a solution flow on a metal support by using a dopant containing cellulose acetate having a total thiol substitution degree of 2 i~2 8 a step of obtaining a film; a step of peeling the film from the metal support by satisfying the residual volatile component H1 of the following formula (i); and peeling off the film to satisfy the following (ii) a step of extending 5/〇 to 100% in the film transport direction in the state of the residual volatile component H2; and the peeled film is orthogonal to the film transport direction in a state in which the residual volatile component H3 of the following formula (丨) is satisfied. The step of extending the direction by 20% to 150%; characterized in that the extending step satisfies the following formula (iv).

S 69 201219464 j^ioopif Formula (i) 20%SH1S60% Formula (ii) 10%SH2^60% Formula (iii) 5%^H3^45% +二二〇(TM rate + 1〇〇%)/(10) In the case of the retardation ratio j, the MD stretching ratio indicates the stretching ratio (unit: %) in the film conveying direction, and the TD stretching ratio indicates the stretching ratio (unit: %) in the direction orthogonal to the film conveying direction. In the case of using cellulose butyrate or cellulose propionate as the cellulose deuterated, it comprises: blending a cellulose containing a total thiol group with a degree of substitution of 21 to 28 or a cellulose propionate a step of obtaining a film by casting a solution on a metal support; and removing the film from the metal support by satisfying the residual volatile component H1 of the following formula (i); a step of extending 20% to 100% in the film transport direction in a state in which the film satisfies the residual volatile component H2 of the following formula (ii); and peeling the film on the residual volatile component H3 satisfying the following formula (i) The step of extending 35% to 150% in a direction orthogonal to the film transport direction in the state; wherein the extending step satisfies the following formula (iv). Formula (i) 20% SH1$60% Formula (ii) 10% SH2S60〇/o Formula (iii) 5%^H3^45% Formula (iv) (MD stretching ratio + 100%) / (TD stretching ratio 4-100 %) ^〇·7〇 (wherein the MD stretching ratio is expressed as the stretching ratio in the film conveying direction 201219464 jyioopif rate (unit: %), and the TD stretching ratio is expressed as the extension material in the film moving direction (unit is %) The manufacturing method of the present invention will be described below. &lt;Step of Forming Deuterated Cellulose into a Film Form> In the production method of the invention, the cellulose deuterated film is formed into a film shape, and the bath can be formed by a bath casting method, or a film can be formed by using a film. law. It is more preferable to use a method of casting a film by a solution casting method, and it is more preferable to use a method in which a doped stream of a 3-dimensional vitamin and an agent is produced on a support. In the manufacturing method of ΐ二本 =, it is particularly preferable to extend the doping stream onto the branch bud and evaporate the solvent to form a bismuth cellulose film. (Production of dopant) In the production method of the present invention, preferred embodiments of the dopant are described. The towel is not included in the relative surface of the film, and is not particularly limited in the range exemplified by the day of the film of the present invention. In the dopant prepared by the present invention, it is preferable to contain 〇10 wt% to 30 wt% of 〇 纤 纤 素 杂 杂 杂 更 更 更 更 更 丑 丑 丑 丑 丑 丑 丑 wt wt wt wt wt /. . The solvent used in the dopant in the dopant is considered to be silent (4), which is known from the viewpoint of reducing the haze, and preferably comprises a carbon ray selected from 3 to 12 A solvent of a halogenated hydrocarbon having a ketone, a carbon atom number of 3 to 12, and a halogen counter atomic number of 1 to 6 in the south. Ether, g and ester 71 201219464 ^yioopif may also have a cyclic structure. A compound having two or more ethers, g and vinegar, or any of "-CO- and -COO-", may be used as a solvent. The solvent may have other such as an alcoholic hydroxyl group. In the case of a solvent having two or more functional groups, the carbon atom may be within a predetermined range of the compound having a functional group. Examples of the ether having 3 to 12 carbon atoms include Diisopropyl ether, dimethoxy oxime, dimethoxy ethane bromide, bismuth-bis oxalate, ye oxolane tetrahydrofuran, anisole and phenyl ethyl ether. Carbon number is 3~12 Examples of the ketones include acetone, methyl ethyl ketone, diethyl ketone, diisobutyl ketone, cyclohexanone, and decyl cyclohexanone. Examples of the ester having 3 to 12 carbon atoms include ethyl formate and formic acid. Propyl ester, amyl decanoate, methyl acetate, ethyl acetate, and amyl acetate. Examples of the organic solvent having two or more functional groups include acetic acid 2-ethoxyethoxy group, 2-methoxyethanol and 2-butoxyethanol. The number of carbon atoms of the halogenated hydrocarbon is preferably 1 or 2. Most preferably, the halogen of the halogenated hydrocarbon is preferably a gas. The ratio of the sub-substituted to dentate is preferably 25 mol% to 75 mol%, more preferably 3 mol%, still more preferably 35 mol% to 65 mol%, optimal; I: 40 mol %〜60 mol%. Examples of the halogenated hydrocarbons include methylene chloride, gas imitation, methane, carbon tetrachloride, trichloroacetic acid, methyl bromide, iodide/millimeter, and tris(tetra)vinyl chloride. It is preferred to include at least two gas smelting. In the present invention, it is further preferred to include a poor solvent in the case of 3 wt% to 30 wt ° / ,, more preferably 5 The ratio of wt ° / 〇 - 2 〇 wt% contains a poor solvent, because the above range contains no osmosis

72 201219464 It is better to prefer T: the compatibility with brewed cellulose is improved, and the service is further reduced. The door θ 4Π. Poor > The boiling point of the granule is preferably 12 〇 ° C or less, and more preferably. The boiling point of the borrowed money is below 12G °C, which can further accelerate the dryness and better. As such a poor solvent, methanol, butanol, and water are mentioned as a preferable example, and a sterol is more preferable. The table θ is modulated by the method of pass 7. The so-called normal side ~=& is not treated at a temperature above 〇c (normal temperature or high temperature). ^ Modulation can be carried out using the usual solvent method ("the method and device for the preparation of dopants in casting". The dopant can be used to disturb the brewing cellulose and solvent at "warm (0 °c ~ 40 °c)). Mixing. The solution of the concentration of I ^ can also be stirred under pressure and heating conditions. The cellulose and the solvent are placed in a pressurized container and the force is sealed and heated under pressure. Stirring is carried out until the solvent is at a temperature above the boiling point at normal temperature. The heating temperature is usually ^Cw_L' is preferably 6 (rc~20 (rc, more preferably 8 (rc~ id C 〇) The knives can also be coarsely mixed in advance and then placed in a container (storage tank, etc.) and can be sequentially fed into the hopper. The container must be constructed in a detachable manner. The container can be pressurized by injecting an inert gas such as nitrogen. And , 'the vapor pressure by heating the solvent may be increased. Alternatively, the container may be sealed and the components may be added under pressure. For the reading of the city, the age is added to the outside of the container. For example, a jacket type heating device can be used. And, 73 201219464 ^ yioopif externally set the heating plate 'to carry out the piping to circulate the liquid, and to hunt this to heat the whole container. The clothes are preferably provided inside the mixing wing, = the length of the mixing wall near the mixing To = In order to update the liquid film on the container wall, it is better to set the test tube 温度计 Γ! You can set the gauges such as pressure gauges and thermometers. Yu Rong = dissolve the ingredients in the spray. After the heat exchanger or the like is used, the dopant may be prepared by a cooling dissolution method. (Film forming step): This is preferably a solvent washing method, doping. (7) Modulation of the method and apparatus for producing the film of the present invention can be made by the same solution casting method and film device of the same manufacturer. The prepared dopant solution is temporarily stored in the storage dad, and the n-bubble contained in the dopant is finally prepared. The surface is a Kana mold, which is easy to make the film thickness uniform and the pressure die spray == Any one can be preferably used. Table n of the metal support increases the film forming speed Alternatively, a metal support may be provided with a plurality of layers for doping the amount of dopants, or a co-casting method of a plurality of dopants of the upper force σ stamper to obtain a laminated structure. 201219464 3yi66pif preferably. And 擦 擦 擦 擦 自 自 自 自 自 自 自 自 自 自 自 自 自 自 自 自 自 自 自 自 自 自 自 自 自 自 自 自 自 自 自 自 自 自 自 自 自 自 自 自 自 自 自 自The support body is roughly turned on the metal support of the casting portion of the transfer, and the gold is the web. From the gold point, the semi-dry doping film (also known as the clipped, buried by the *-bud body) The two ends of the obtained web are moved by the machine of the clamp device, and the drying is carried out by the drying of the t. The winding is taken up by the coiler. 'Electronic 2: The combination of the drying device of the roll group can be changed as needed, and the film can be changed. 4) The solution casting used for the functional protective film t is used for the undercoat layer. The surface processing of the film such as the static Z layer, the anti-military layer, and the protective layer is described in the following, and the manufacturing steps are simply described below, but are not limited thereto. The doped dopant is preferably cast on a non-edge metal branch body such as a metal drum or a metal slab (belt or belt). The solvent is evaporated to form a film. The dopant before casting is preferably adjusted in such a manner that the fiber becomes 10 wt% to 35 wt%. Preferably, the drum or belt is pre-finished to have a mirrored state. Regarding the casting and viewing method of the melt-casting method, it is disclosed in U.S. Patent No. 233,631, ', US Patent No. 2,367,603, U.S. Patent No. 2,492,78, U.S. Patent No. 2,977, U.S. Patent No. 2,492,978, U.S. Patent No. No. 4, US Patent No. 2739069, US Patent No. 2739〇7〇, British Patent 75 201219464 ^yioopif 640731, British Patent No. 736892, each side of the description, side number, 曰本专利特公昭=书特特开开昭6〇 Ϊ́7^ίΜ &amp; It ) 614 5 Tiger, Japanese Patent This patent I, Japanese Specialist Kai Chong 6~2G343G, and Japanese 1 Kai Zhao 62_n5G35 are published in each bulletin. No., Japan straight ^ Fa Cai can apply Japanese patent special opening 2_-301555 7 This patent special opening 2000-301558, Sakamoto special thorns turn 7_03239!, 曰本 patent special open flat 3_193 this 2 special open flat 5 - 嶋 buckle No., Japan Correction _ Day 3, special f temple open two == this = r55 her number, two each reported in the brewing cellulose film technology. Preferably, the belt is contacted after casting:::==dry wind.

The obtained film can be changed from the drum or the red heart to the ruthenium, and θ π g is emitted from iOOC to 160 〇C. The above method is carried out in a special dish and dried/dryed, and the residual solvent is steamed. According to this method, the second extension can be shortened by the following: No. 844: = must be at the surface temperature of the roller or the belt at the time of the flow = the green wei of the present invention is two or more different _ degrees of substitution The dopant is co-cast on the support as the doped 76 201219464 dopant. Secondary flow = hair; low birth and minus First, when each layer is made of two rows, '*TT, each layer' is self-supporting at a suitable time and dried to form a film casting method. The upper stripping and casting method is performed by casting the dopant with a dopant from a casting machine with or without drying, and then casting the second crucible by a molding machine, and laminating the layer to The first ==== The stripping process is performed by drying the doping stream to form a film. The method is to form a core film by diluting the solution onto the film, and modulating the film using a suitable coating. a cloth machine, coated with a coating liquid on each single side or two cloths, and dried to form a film of a laminated structure; the film is peeled off on the film (the peeling) to evaporate the solvent on the metal branch body Into the web ^. The stripped web is sent to the subsequent step. # The residual volatile component of the web at the time of stripping (the following formula) is too large. 77 if 201219464

l UUP is difficult to peel off. · Conversely, if it is peeled off too much on the metal support, it will cause the film to be behind the film on the way.仃 仃 而 8 制 制 制 制 制 制 制 制 ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° Method; a method of reducing gelation by 3 temperatures = and the like. By increasing the strength of the film at the time of peeling due to gelation of the metal branch, the peeling can be accelerated to increase the film forming speed. Fortunately, the father is better than the strength of the drying conditions, the length of the metal branch body, etc., the amount of residual solvent in the metal stalks of Weishang is 5 sense ~ =% within the range of peeling, the amount of residual solvent is more When the time is left, the amount of solvent in the case of peeling is determined by taking into consideration the economic speed and quality. In the present invention, it is preferable to set the temperature of the metal support body to a position of _5 (rc~thief, more preferably a post-thief, and a good one is 15 ° C to 3 〇ΐ. The manufacturing method of the invention is a step of peeling the film from the metal ruthenium support by the residual volatile component m satisfying the following formula (1) regardless of the meaning of the fluorinated cellulose. Formula (i) 20% SH1$60o The HI is preferably 22% to 55%, particularly preferably 25% to 45%. The amount of residual solvent can be expressed by the following formula: Residual solvent amount (wt%) = {(MN) / N} Χίοο Here, Μ is the weight of the web at any point in time, and N is the weight when the weight is 201219464 μ when dried under iurc for 3 hours. (DaneeFmeehanism) Tension Control) The orientation of the self-improving film long side The direction of the late phase axial flow (4) county, between the control of the film from the mechanism before the film stretching step, using the beating and then = by jumping with _da a) The tension is maintained at a fixed amount. The tension control of the following ir-type moiré mechanism is not particularly limited to the manufacturing method of the present invention, and the preferred S is to be dried on the drum or the second, and the test (film) is described later. The roll group arranged as shown in Fig. 1 or Fig. 2 in the extending step is variably driven, and the number of the specific center value of the tension applied by the moving mechanism is not large, and the surface is transported. Moreover, the tension of the type of the beating mechanism is more than that of the device, and can be read after the drying step. In the post-Syrian extension, it is better to use the tenter to extend the step-by-step. The face is held by the tenter and the face is m-turned, and the -φ is used to make the film, that is, After the film is peeled off from the roll or belt of the cast film forming apparatus, the tension control portion of the beating mechanism is used in the state of the film soft film before the drying step. As such a bounce mechanism, a known device can be used, and in particular, the bounce mechanism 1A shown in Figs. 1 and 2 can be used. Fig. 2 is a schematic view of a pulsating mechanism 1G which can be preferably used in the present invention. Bounce mechanism 1 bag x contains. 79 201219464 Bounce roller 11, guide roller 17a π dry ratio ν peach 郓 昆 昆 11 11 load load control _ load control device (jumping load control unit) (1) = jump roller Π The angle detector at the position (the pulsation device position detection sense = η (4) moves up and down in the up and down direction between the guide roller 2 and the guide roller 17b. And 'the peeled off the self-peeling roller 21, j belly ^) The magnitude of the tension applied by the soft film 24 is determined by the magnitude of the load carried by the beating pro. Plus:! The film (web) peeled off on the lower drum 21 is preferably applied in the range of 0 N to 300 N. Further, it is preferable that the magnitude of the tension applied to the film (web) which is peeled off is the center value of the set tension, and the following method of controlling the cylinder weight may be as follows. Any method: (1) Using the load weight: ground 2: load (the opposite side bearing on the side where the film is connected) the straw is detected by the angle 11 (the position detection sensing 11 ^ and the 'being as the position based on the position The method for controlling the response of the roller 11 may be any of the following methods: the device for increasing or decreasing the amplitude of the tenter drive when the device is raised or lowered, or by the method of loading the device. For example, the jump extension step + The conveyance speed in the step after the movement mechanism (for example, the conveyance is performed while the extension 3 2r tenter is holding the grip film, and the rotation roller 11 is held at the machine drive speed) is controlled to increase and decelerate to control the intermediate position. 〜1, when between the upper limit position and the lower limit position of the movable position, for example, 'when the dancer roller 11 moves from the neutral position to the lower limit direction 201219464', the bounce roller η can be returned to neutral by speeding up the tenter drive speed Position as a self-flowing film The film which is peeled off on the drum or the belt is softened as the temperature is higher. Therefore, in the present invention, it is preferred that the temperature of the beating device portion is in the range of 25 ° C to 10 ° C. In the temperature range, it is preferable that the magnitude of the tension applied to the film (web) soft film 24 peeled off from the peeling roller 21 becomes the center value of the set tension ± 30 The size of the load to be loaded by the bouncer is set in a range of N or less. The surface temperature of the film (web) film 24 peeled off by the peeling roller 21 can be disposed on the peeling roller 21 and the bounce mechanism. Between 10 and 10, the temperature sensor 14 connected to the temperature measuring probe for measuring the surface temperature of the film is used for measurement. Further, as the temperature measuring probe, if the surface of the film is not damaged, The probe of any shape and material is used. In the present invention, the position of the temperature sensor 14 of Fig. 2 is not limited thereto, and the case is also disposed at another position on the upstream side of the pulsating mechanism 10. Controlling the various parts of the tension control unit of the beating mechanism, It is carried out (not shown). As a system controller, the "system controller" of the "System of the Japanese Patent Laid-Open No. 2, No. 3_19" can collectively control the operation of the film manufacturing equipment. The upper part is connected with, for example, a drive motor (not: the angle detector 12, for the board (not shown), the temperature sensor 14, the operation surface is not). The system controller can adjust the tenter 81 as follows. 201219464 Driving speed of the device 23: based on the load of the load on the operating surface, and based on the position detecting drive motor (not shown) of the angle detector 12, the beat view 11 is maintained as a better temperature system (4) The control unit (not shown) for controlling the temperature of the wind can be controlled based on the film surface of the temperature sensor 14 = Γ = , and the air blower (not shown) can be blown out. In addition, the tension control unit using the pulsating mechanism is provided in the 臈, the way of the ,, and the i is provided in the drawing, but the present invention is not limited to this aspect, and may also be the length of the transport path. Two or more are set correspondingly. Further, as described in Japanese Laid-Open Patent Publication No. 2005-306019, the jumper mechanism can also be used in combination with a suction drum. The method of drying the web which is dried and peeled off on a drum or a conveyor belt is described. Preferably, the web which is peeled off at the peeling position before the drum or the belt is rotated one week is conveyed by: a method of carrying the conveyance by the roller group arranged in the form of a mineral tooth or holding the holder by a jig or the like A method of transporting both ends of the peeled web, not by contact. In the production method of the present invention, in the transition portion from the stripping step to the stretching step, it is preferred that the film passes through at least three or more of the angles of 60. Preferably, the path roller above passes through more than 5 path rollers, and particularly preferably passes through 7 to 51 path rollers. Indeed, in the manufacturing method of the present invention, as described above, it is preferable that the wrap angle is 60. The above path roller comprises at least one bouncer, preferably the bouncer is 82 201219464 iyibOpif l root. In addition, the term "bounce device" as used herein also includes the guide roller described in i7a or m of Fig. 2, preferably in Fig. 2 and Fig. 2, between the self-guided m and the extension device 23, through the above-mentioned number The above at least the corner angle is 6 〇. The road above is Wei. In addition, the so-called limbs in this book indicate that the film is connected to the roller in the arc area around the roller. The size of the corners, for example, 180 degrees when the film passes through a fully configured (four) toothed roll. The drying can be carried out by a method of blowing a wind at a predetermined temperature on the web (film) in the conveyance, or a heating means such as a Laibo. Rapid drying damages the film's planarity. Therefore, the ruthlessness of the ruthenium is better than the temperature at which the solvent does not foam. Dry down. Lai Bucai after the self-supplement of the body, from the evaporation of the solvent / in the direction of the long side or width (four). The higher the temperature, the lower the drying and the shrinkage. In view of the fact that the planarity of the film to be formed is good, it is preferable to dry while suppressing the shrinkage as much as possible. In view of this, it is preferable to maintain the width of both ends of the wide side of the web by a jig or a pin in the width direction as shown in Japanese Laid-Open Patent Publication No. Sho 62-46625, for example. The method of performing the entire step of drying or part of the step (triangulation). In the above drying step, the drying temperature is preferably nc~145. The drying temperature, the drying air amount, and the drying time vary depending on the solvent to be used, and can be appropriately selected depending on the type and combination of the solvent to be used. As a manufacturing method of the present invention, the retardation axis 83 from the long side direction of the film is reduced by the tenter and satisfies the following formula (V) Wx30$LgWx2 (罝^中\L indicates from the above The stripping step to the tenter is too long. The length of the film is 7 (the unit is mm).) The method of making the heart from the ^ is better to satisfy Wx28^L^Wx2 5 It is especially good to satisfy Wx25-L2Wx3. (Extension step) The step of producing the film of the invention includes the step of stretching the film which is peeled off from the support. (1) The use of B g-vitamin as a preferred embodiment of the chemical fiber, the elemental decoration, and (2) (4) the age-preserving or (4) cellulose as the cellulose-defluorinated material is described below. (1) In the case where cellulose acetate is used as the deuterated cellulose, the production method of the present invention, when cellulose acetate is used as the deuterated cellulose, includes: the film to be peeled off satisfies the following formula (ii) The step of extending the volatile component H2 in the film transport direction by 5% to 100%; and the peeled film is in a direction orthogonal to the film transport direction in a state in which the residual volatile component H3 of the crucible is satisfied. a step of extending from 20% to 150%; characterized in that the extension step satisfies the following formula (iv): Formula (ϋ) 10%^H2^60% Formula (iii) 5%^H3^45°/ Formula (iv) (MD stretching ratio + 100%) / (TD stretching ratio 201219464 jyioopif + 100%) ^0.70 ... (wherein, MD stretching magnification indicates the stretching ratio in the film conveying direction (unit: %)' The TD stretching ratio is expressed as a stretching ratio (unit: %) in a direction orthogonal to the film conveying direction.) When the cellulose acetate is used as the cellulose hydride, the stretching ratio in the film conveying direction is extended. Preferably, it is 5% to 25%, more preferably 8% to 22%. In addition, here, the "stretch ratio" %)" means the one obtained by the following formula: Extension ratio (%) = l〇〇x {(length after extension) _ (length of extension)} / length before extension extends in the film transport direction The method is not particularly limited, and for example, a method in which a difference in the speed of the closing of the roller is applied to the circumferential speed difference of the heating roller in the longitudinal direction is performed, and the both ends of the web are fixed by S1 or the pin. a method of widening the ridge or the interval in the traveling direction and extending in the longitudinal direction; or a method of expanding in the longitudinal direction and the transverse direction in the case of the vertical stretching, etc. Of course, the methods may be used in combination. In the case of the so-called Lai Law, if the fixture part is driven by the linear driving method, the extension of the financial operation can reduce the risk of breaking, etc., and the extension in the vertical direction is more It is preferable to extend the deuterated fiber in the conveying direction (longitudinal direction) by using a device having two light means 'the rotation speed of the nip roller on the σ side is faster than the rotation speed of the nip roller on the inlet side. This extension can also adjust the performance of the delay 85 201219464 j^iuupif Moreover, at this time, H2 is preferably 20% to 55%, more preferably 25% to 50%. If there are too many residual volatile components in the web, the effect of stretching cannot be obtained, and if If the amount is too small, the elongation becomes difficult, and there is a case where the web is broken. The method of the present invention is preferably to control the film transport direction while controlling the tensile force variation value to less than 10 N/m. Preferably, the control is less than 8 N/m, and the control is preferably 〇N/m~6 N/m. When using cellulose acetate as the cellulose hydride, the film is transported. The stretching ratio of the extension in the direction orthogonal to the direction is preferably from 5% to 60%', more preferably from 20% to 5%. It is not necessary to extend the abdomen in the direction orthogonal to the direction of transport (4). (疋. The list σ can be listed as: fixing the ends of the web by clamps or pins or expanding the width in the horizontal direction. The direction is extended &gt; 夕古 L*, or Saki at the same time, the vertical and horizontal two financial upwards are extended by 1 μμ, etc. § 然 'These methods can also be combined. Also, in the 3 section 'If the injection of the material (4) Loss; In the extension of this cup, it can reduce the risk of breakage, etc., and it is better, in the middle of the month, as a method in the direction orthogonal to the direction of transport of the crucible, it is better to use the deletion置 = 顺 〇 此时 此时 此时 此时 此时 此时 此时 为 为 为 为 为 为 为 为 为 为 为 为 为 为 为 为 为 为 为 为 为 为 为 为 为 为 为 为 为

86 201219464 jyioopif , and, if too little, the extension becomes obviously difficult, and there is a situation in which the web is broken. The manufacturing method of the present invention can improve the film elastic modulus by controlling the stretching ratio ratio so that the MD stretching ratio and the TD stretching ratio satisfy the following formula (iv). Formula (iv) (MD stretching ratio + i〇0%) / (TD extension + 100%) ^〇.7〇 In the case of A, the MD stretching ratio indicates the stretching ratio in the film conveying direction (unit The % TD stretching ratio is expressed as a stretching ratio (unit: ❶/.) in a direction orthogonal to the film conveying direction. Further, in the case of extending in the film width direction, there is a case where the refractive index is distributed on the wide side. This phenomenon can be seen, for example, when the tenter method is used, and it is generally considered that this is caused by the fact that the extension in the width direction causes the contraction force at the central portion of the film, and the end portion is deprecated. The phenomenon of b〇wing. In this case, by extending in the casting direction, the meandering phenomenon can be suppressed, and the improvement can be made so that the phase difference distribution of the wide sides is small. In addition, it is possible to reduce the thickness variation obtained by the extension of the biaxial directions which are orthogonal to each other. If the film thickness of the brewing cellulose film changes by A, the _ position difference (four) is uneven. The film thickness of the deuterated cellulose film is preferably a dynamic range of ± 3%, more preferably ± 1%. For the purpose as described above, the method of extending in the biaxial directions of the mutually positive fathers in a manner satisfying the formula (iv) is also effective. . In the manufacturing method # of the present invention, it is preferred that the extension temperature is

Te + 30 ° C or less, of which 87 201219464 ^vioopif extended temperature STe + 30 ° C (I)

Te=T[tan5]-ATm (II) ΔTm = Tm (0) -Tm (x) (in) (In the formula (II), Τ〇ηδ] is expressed when the residual solvent amount is 〇%. When the dynamic viscoelasticity of cellulose is tanS, tan5 shows the peak temperature, Tm(0) represents the crystal melting temperature of the deuterated cellulose when the residual solvent amount is 0%, and Tm(X) represents the deuterated fiber. Residue of the compound ^ The crystal melting temperature of the deuterated cellulose at a dose of X%.). Hereinafter, the extension of such a temperature range is also referred to as low temperature extension. By low-temperature stretching of the film formed into a film shape, Rth performance can be improved without increasing the film thickness of the present invention, and Rth (55 Å) and /d' can be further improved. Although not limited to any theory, in the low-temperature extension, it is difficult to increase the elongation of the polymer or the added ruthenium when it is extended at a relatively high temperature, so that Re can be expressed without lowering Rth. The extension temperature is more than Te thief ~ Te ° C. In the case where the extending direction of the hard-to-feed direction is extended in the film width direction, the preferred range is also the same. (2) The case where the acid-aged or the (IV) cellulose is used as the cellulose-deposited cellulose. The use of cellulose butyrate or cellulose propionate includes: stretching the film to a residue satisfying the formula (5), and extending the film in the direction of H2 by 2% to 1% (%). The film peeled off by the step satisfies the step of extending the residual volatile component H3 to the lower edge of the formula (1) in a direction orthogonal to the film transport direction by 2G% to 丨5〇%. The 201219464 jyioopif step is characterized in that the lightening is performed. Steps are full of foot (5). (4) In the case of acid cellulose or cellulose propionate as the cellulose hydride, the stretching ratio of the elongation in the direction of the transport is preferably 6% by weight, more preferably 25% to 45%. (4) 使用38/°~8G%, more preferably 使用38/°~8G%, which is better than the extension of the direction in which the orientation direction of the st film is orthogonal to the use of T-acid cellulose* propionate as the cellulose hydride. 4G%~60〇/〇. The outer range of the use of cellulose butyrate or cellulose propionate as the deuterated fiber is the same as that in the case of using cellulose acetate as the deuterated cellulose. (Heat treatment step) The method for producing the film of the present invention may also be subjected to a heat treatment as described in the above after the completion of the drying step. The heat treatment of the treatment step can be carried out at the end of the drying step, and can be carried out immediately after the extension/drying of the material, or after the dry end of the method is temporarily taken over by the method described later, and only the heat treatment step is provided. The heat treatment can be carried out by a method of blowing a wind of a predetermined temperature to the film being conveyed or a method of using a heating means such as a microwave. The s heat treatment is preferably carried out at 15 (TC to 20 (TC temperature, more preferably, at a temperature of 160 C to 180 ° C.), and heat treatment is preferably carried out for 1 minute to 2 minutes. More preferably, it is carried out for 5 minutes to 1 minute. (Winding) The coiler that winds up the film to be fed can use the conventionally used coiler's by the constant tension method, the constant torque method, Taper tension (taper tensi〇n) 89 201219464 jyioopif method, internal stress fixed program tension control method transfer method for coiling. The cellulose halide film roll obtained as described above is preferably the retardation axis of the film The direction is in the range of ±2 degrees with respect to the winding direction (longitudinal direction of the film). More preferably, it is in the range of ±1 degree. Or, preferably, relative to the winding direction, with respect to the right angle direction. (the width direction of the film) is in the range of ±2 degrees, more preferably in the range of ±1 degree. Particularly preferably, the retardation axis direction of the film is relative to the winding direction (longitudinal direction of the film) Within ±01 degrees, or, particularly preferably, within ±01 degrees with respect to the broad side of the film. Volatile component) As the cellulose-deposited film obtained by the above-described method for producing a film of the present invention, in terms of obtaining a film having good dimensional stability, it is preferred that the residual volatile component of the final finished film is I wt% or less, more preferably 0.2 wt% or less. Further, in the manufacturing method of the present invention, the step of producing a film on one side of the retardation axis orientation of the long-hand method of detecting the film in one line may be included. The preferred aspect is the same as the standard deviation of the retardation axis orientation of the film long hand method for determining the film of the present invention in the line. &lt;Polarizing Plate&gt; The polarizing plate of the present invention is characterized by comprising a polarizing element. The film of the present invention has a good optical property of the film and a good modulus of elasticity of the film. Therefore, it can be preferably used in a protective film for a polarizing plate. The shape is good, and the film surface is observed under the orthogonal polarized light of the polarizing plate. The film is suitable for the protective film for polarizing plates. The polarizing plate can be laminated with at least one surface of the 201219464 ^yioopif polarizing element. As the polarizing element, a previously known polarizing element can be used, for example, a hydrophilic polymer film such as a polyvinyl alcohol film is treated with a dichroic dye such as a moth and extended. The bonding with the polarizing element is not particularly limited and can be carried out by using an adhesive containing an aqueous solution of a water-soluble polymer. The water-based polymer adhesive can preferably be a completely purified aqueous polyvinyl alcohol solution. Further, the polarizing plate using the film of the present invention can provide a liquid crystal display device having less unevenness in the distribution of the slow phase axis and good display performance. Further, in the case where the film of the present invention is a wide-width preferred embodiment When the polarizing plate is produced by bonding the film of the present invention to the polarizing element, the so-called polarizing plate can be divided into two equal parts and three equal parts in the film width direction, and the manufacturing cost of the polarizing plate can be reduced. Further, in the case where the σ6 〇〇 and σ_6 〇〇 in the film width direction are also good, the performance of the polarizing plate which is further divided into two equal parts and three equal parts can be improved. &lt;Liquid Crystal Display Device&gt; The liquid crystal display device of the present invention is characterized by comprising a cellulose oxide film or a polarizing plate of the present invention. ▲ The film of the present invention can be preferably used as follows: a protective film for a polarizing plate / a polarizing element / a protective film for a polarizing plate / a liquid crystal cell / a film of the present invention / a polarizing 7G piece / a protective film for a polarizing plate The protective film/polarizing element of the polarizing plate, the film/liquid crystal cell of the present invention, the protective film for a polarizing plate of the present invention, the polarizing element, and the protective film for a polarizing plate. In particular, it can be used by being bonded to liquid crystal cells such as ΤΝ, VA, and 0CB, and it is possible to provide a liquid crystal display device which is excellent in viewing angle, has excellent visibility, and has excellent in-plane uniformity. Further, the polarizing plate using the film of the present invention has less deterioration under high temperature and high humidity conditions, and can maintain stable performance for a long period of time, that is, the durability of the liquid crystal display device of the present invention is also good. [Examples] Hereinafter, the present invention will be more specifically described by way of examples. The materials, the amounts used, the ratios, the contents of the treatment, the order of treatment, and the like shown in the following examples can be appropriately changed without departing from the gist of the present invention. Therefore, the scope of the present invention is not limited to the specific examples shown below. [Example 1: Film formation of bismuth cellulose film] (2) Preparation of dopants The following composition was put into a mixing tank and stirred to dissolve the components. After heating at 90 ° C for about 10 minutes, it was filtered through a filter paper having an average pore diameter of 34 μΐ and a sintered metal filter having an average pore diameter of 10 μm. Deuterated cellulose solution ----- 100.0 parts by weight 403.0 parts by weight 60.2 parts by weight of bismuth chemical fiber dichloromethane methanol as described in Table 6 &lt;: U2&gt; matting agent dispersion 92 201219464 ^yioopxf Next, the following composition containing the brewed cellulose produced by the above method was placed in a dispersing machine to prepare a matting agent dispersion. Matting agent dispersion *------______ cerium oxide particles with an average particle diameter of 16 nm - 72.4 parts by weight, 10 parts by weight, 1 part by weight, 3 parts by weight, 〇sll R972, manufactured by Japan Aerosil Co., Ltd. The dioxane methanol brewing cellulose solution &lt; 1-3 &gt; the solution solution tank is put into the cellulose solution, and the mixture is stirred and heated to be dissolved in the heat Additives, Modification Additives, and the following additives are described. Additive A~Additive. ^ Mix

C is the composition shown below in the following table. In addition, in Table 5, EG represents ethylene propylene glycol, BG represents τ - γ ethyl alcohol, PG is not represented by _, and TPA means that formic acid represents formic acid, fluorene is phthalic acid, and bismuth is not present. Acid 'S Α means broken shot acid 5 shows 93 201219464 J-a99l6e

1 1 Molecular weight 1000 ο ο σ ο ο ο ο ο 〇 ( ( ( ( ( - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - - $ ο csi ο CN ^Τ) Γ- (Ν BG (mol% ) ο Ο Ο Ο PG PG (mol% ) ο Ο JO * Ί EG (mol% ) ο ο ο CN Chu € ο ο ο Ο Additive A Additive Β Additive C

201219464 ^ A. W

Compound D represents a delayed expression agent of the following structure. Compound D

Compound E represents POEM K-37V manufactured by Riken Vitamin Co., Ltd. as a release promoter. Compound U represents a delayed expression agent of the following structure.

Compound U

The compound T represents TPP/BDP (1/1, weight ratio) ° Further, in the case of Example 6 using CAP, the compound X of the above-described structure was used as an additive. 95 201219464 j^ioopif compoundχ

100 parts by weight of the above-described deuterated cellulose solution, 1.35 parts by weight of the matting agent dispersion, and the additive solution were mixed to prepare a film-forming dopant. Further, the deuterated cellulose and various additives used as a raw material of the dopant were dried by using a silo manufactured by Nara Machinery Co., Ltd. in advance at i2〇t for 2 hours. Here, 'fp describes the table 6 towel, the letter indicates the type of each additive π plus 1 ° and the 'addition ratio of the additive solution is; the amount of each additive force when the amount is set to 100 parts by weight" becomes the following Table 6 The ratio of the values stated. (casting) by using Figure 7, Example 7, and Comparison 1 - Function = 11 = In ==

96 201219464 jyioopif The temperature is 75ΐ~12^ The gas supply temperature is 8〇°C~130°C (the exhaust gas composition is as shown in the following table 6 J = dry air and then dried after the 'remaining wave 2! When the H1 (Wt%) is removed from the belt, the bounce mechanism of the temperature is lowered by the extension device 23 before the longitudinal extension and the lateral extension. - The surface is controlled so that the temperature of the tension sensing portion is 5 叱, and the film is formed by the tension of the film + 2 〇 0, and the tension of the load of 1 制 is made. The method controls the load by the jumper manufacturing device and the angle detector 12, and reads the butterfly (four) corners; the road back roller 18 guides the film to the extension device 23. (4), peeling, and then to the tenter The distance B of the machine is 15 mm, and the width is 19 mm and satisfies Wx30gl^Wx2. (Extension) When the residual solvent concentration in the following Table 6 is h2, MD ό ό ό § MD MD MD MD MD MD MD MD MD MD MD MD MD MD MD MD MD MD MD MD MD MD MD MD MD MD MD MD MD MD MD MD MD MD MD MD MD MD MD MD MD MD MD MD MD MD MD MD MD MD MD MD MD MD MD MD MD MD MD MD MD MD MD MD MD MD MD MD MD MD MD MD MD MD MD MD MD The hunting force is measured by the tension sensor to measure the variation of the tensile force when the SMD is extended, and is described in the following Table 6. 4 When the residual solvent concentration is Η3, the TO stretching ratio of the following Table 6 is used. In the film width direction, the uniaxial stretching in the film width direction is carried out in the tenter region to produce the deuterated fiber ', 臈. And 'determine the MD/TD stretching ratio, which is described below. Table 6 97 201219464 jyioopif t. At this time, the cast film thickness was adjusted so that the film thickness after stretching and drying became the film thickness described in the following Table 7. The film of the composition shown in the following Table 6 was produced. In order to judge the manufacturing adaptability, a minimum of 24 rolls of a roll width of 1980 m and a roll length of 2000 m were produced by the above conditions. One of the 24 rolls continuously manufactured was cut at intervals of 1 μm. A sample of 1 m (width: 1980 mm) was used as the cellulose film of Example 1. [Example 2 to Example 1 and Comparative Example 1 to Comparative Example I] The contents were changed as described in Table 6 below. In addition to the use of the deuterated cellulose resin and the crucible production conditions, in the same manner as in Example 1, various examples and ratios were obtained. Examples of the acylated cellulose film. Further, examples other than the u 'branched from the feed-side layer with a dopant / core made of doped impurities of the order for three-layer co-casting. Physical / outer shield with #

98 201219464 JU9916£ [94] Film thickness after film formation conditions (μηι) m 〇\ ο § o &lt; ms § o SS stretch ratio ratio MD/TD 1 0.86 0.79 0.77 0.77 0.77 0.83 0.83 0.80 00 o 0.80 | 0.79 I ! 0.77 :0.79 0.85 0.79 0.69 1 TD stretching ratio (%) Ο (S m ο $ 00 m 吞〇〇mv〇ο JTl ο Volatile component at the beginning of TD extension Η3 (%) 0\ 00 00 inch ( Ν »«Η OS 00 〇〇o 卜CN CN ^Τί Ο CS rH CS Tensile force variation during MD extension (N/m) CS (Ν ι〇CN fS trj &lt;N (N in yn (N CN »r&gt; IT) oo ο (Ν νη SQ 峤m «•Ή ο Η ο ο Ο 宕〇〇 Ο ψ ^ ^ ^ ^ ^ Η Η Η Η Η Η Η Η Η Η Η Η Η Η Η Η Η Η Η Η Η Η Η Η Η Η Η Η Η Η Η Η Η Η Η Η Η Η Η Η Η Η Η Η m ΓΛ CN ΓΛ 00 00 00 cS fS CN Volatile component HI (%) when peeled off $ 妄苳oo 00 &lt;N (N CO CN Additive Additive 2 ο D Ο Ο ο 寸 Q 1 D: 0.8 I | U :0.8 I o 〇oo 1 U:4_5 I 1 U:4.5 | Ο CN ω ο ο Additive 1 ο Η 1 Τ:11.3 1 ο Another 0\ On On r*H ON FH 〇\ v-&gt; X 〇\ Ψ—4 〇 〇 \ σ \ &lt; P3 CQ m C &lt; UHH Ό ο &lt;&lt; Deuterated cellulose total base substitution A + B 1 2.66 1 2.66 1 2.65 1 丨 2.42 1 2.42 2.42 2.42 2.42 2.42 2.42 1— 2.42" 2.65 00 01 00 oi 2.05 2.42 1 2·42 1 '2.42 Degree of substitution B ν〇ν〇ν〇丨2.47 I 1 1 1 1 1 1 1 2.47— 1 1 1 II 1 Bu/Pr ; _] CQ 0Q £ 1 1 1 1 1 1 1 1 £ 1 1 1 1 1 1 Substitution degree A 〇·18 —2丄42— 2.42 2_42 | 2.42 1 丄42” 2_—42 2.42 2.42 0.18 I 00 CN 00 CN 1 2.05 1 2.42 1 2.42 2.42 υ &lt; ο &lt; ο C ο &lt; Ο υ &lt; o &lt; O &lt; 〇 &lt; 〇 &lt; o &lt; υ &lt; υ &lt; 〇 &lt; ο &lt; Ο &lt; ο C ο &lt; Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Comparative Example 5 Comparative Example 6 Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Comparative Example 7 Comparative Example 8 Comparative Example 9 Example 7 Comparative Example 10 Comparative Example 11 201219464

JU9916E Breaking CS Both sides are 2 0.80 0.80 0.80 0.80 0.79 00 m 〇〇m 〇〇m 〇〇〇〇 inch (Ν o ο m ^T) CA ο Ο *-Η 〇〇ON σ\ tT) cn Os 〇〇&lt;Ν CN V) in CN v〇OO (N ο Ο o 〇〇ο 〇\ 0\ Os 〇\ as ψ-^ U (Ν Ο Ο υ o U 2.42 1 2.42 1 2.42 2.42 2.42 2.81 1 1 1 1 1 ί 1 1 1 1 1 1 2.42 12·421 丨 2.42 1 12·421 2.42 2.81 υ &lt; ο &lt; 〇 &lt; O &lt; O &lt; ο &lt; Comparative Example 12 Example 8 Example 9 Comparative Example 13 Example l〇_ Core layer example 1〇_ Outer layer 201219464 j^iuupif &lt;Measurement method&gt; (Optical properties of film) King

By the above method, the J-dimensional birefringence measurement is performed at a wavelength of 550 nm using an automatic birefringence meter kobra_wr (manufactured by Sub-Measurer Co., Ltd.), and the surface-dependent Re is obtained, and the retardation Rth in the film thickness direction can be borrowed. It was determined by measuring Re by changing the inclination angle. Further, the measurement wavelength was changed to 45 〇 111]: 1 and 63 〇 nm, and the values of Re (450) and Re (63 〇) were measured, and the wavelength dispersion &amp; ((4)) - Re (450) = was calculated. Further, the value of Rth (unit: nm) obtained was divided by the film thickness d (unit: nm) of each film, and Rth Rth/d per unit thickness of the film was determined. These results are described in Table 7 below. (Standard of the retardation of the retardation axis at the end in the longitudinal direction of the film σ-600)) The deviation of the retardation of the end portions in the longitudinal direction of the film is measured by the following method to show the deviations σ600 and σ-600. The path in which the two sides are fed in parallel within 0.5 mm is controlled to control the unevenness of the film in the up-and-down direction to 2 mm, and the sample 4 is transported at 20 m/min on the side of ίγ σ η. In the direction of the width of the film from the + center line to the side of the film in the direction of the end of the film, the __ line is Γ) in the film transport direction (long side two counts of 60000 points of each of the late phase axis orientation. Find the second The kinematic value is calculated by calculating the slow phase axes σ600 and σ-600. The drought deviation of the 101101 201219464 loopif The other standard deviation σ6〇〇 and σ-600 of the azimuth axis direction of the long side direction of the film The other measurement conditions were set as follows, and the detection and calculation were performed by the following methods. Apparatus: High-speed retardation measuring apparatus Rel〇〇 Dayuan Electric Co., Ltd. Manufacturing page limit Measurement length: 2000 m Measurement pitch: 20 m/ Min into the rod 、,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,, X分散'n is 60000) and the dispersion σ is calculated. The obtained result is evaluated by the following criteria: σ600 or σ-600 is 〇〇8 or less. 〇: σ600 or σ-600 is 〇 or less. △ : σ600 or σ -600 is 〇13 or less ▲ : σ600 or σ-600 is 〇μ or less 1 02 201219464 jyioopif χ : σ600 or σ-600 is greater than 0.15. The results obtained are shown in the following Table 7. (Elastic modulus of the film) The sample is 10 mm x 150 mm (TDxMD) at 25. (:, relative humidity is 65 The humidity of 2 hours was controlled under %, and the universal tensile tester STM T50BP manufactured by TOYO BALDWIN CO., LTD. was used to measure the initial sample length of 5 环境 in an environment of 23 ° C and a relative humidity of 60%. The stress-strain curve was measured in the MD direction at l〇%/min, and the elastic modulus E (MD) of the film in the MD direction was determined (unit: MPa). Similarly, the sample mmxl〇 was used. (tdxmd) and extending the TD direction under the same conditions, and obtaining the elastic modulus E, (TD) (unit: MPa) of the film in the TD direction, and calculating based on the obtained elastic modulus in each direction. E, (TD) / E, (MD). Further, in 19 samples, TD was measured every 1 mm in the wide side. The average value of these samples was determined by the following method. Membrane width ς = elastic modulus (4), (TD) standard deviation σ (unit: which). For the 19 data obtained, by γ* «Ο ·» •Λ» *^· η varies (here, by the following formula

Xi is the unevenness of each E' (TD), and η is 19). 103 201219464 jyioopif σ2= -x)2 η /=ι Calculate the dispersion σ. The results obtained are shown in Table 7 below. (Panel performance) [Manufacturing of polarizing plate] A polarizing element was produced by adsorbing an angstrom on an extended ethylene glycol film. The cellulose-deposited film of Example i subjected to the alkalization treatment was attached to one side of the polarizing element using a polyvinyl alcohol-based adhesive. The commercially available cellulose diacetate film (FUjitac TD80UF, manufactured by Fujifilm Co., Ltd.) was subjected to the same alkalization treatment, and a polyvinyl alcohol-based adhesive was used, and a polarizing plate protective film was attached to the prepared example 101. The surface of the polarizing element on the opposite side of the side is attached with a cellulose triacetate film after the chemical treatment. At this time, the transmission axis of the polarizing element was arranged in parallel with the retardation axis of the polarizing plate protective film of the example. Further, the transmission axis of the polarizing element is arranged orthogonally to the late phase axis of the commercially available cellulose triacetate film. The polarizing plate of Example 1 was produced in this manner. [Manufacturing of Liquid Crystal Display Device] The following bonding to the panel was applied to the polarizing plate to be applied. The evaluation was made by removing the polarizing plates on the front and rear sides of the LC-42DS6 liquid crystal display from Sharp Corporation, Inc. (hereinafter also referred to as panels) using the above polarizing plates in the respective examples and comparative examples. LCD display device. In addition, the size of the panel is 1025 mm x 673 mm. 104 201219464 jyioopif (1) Viewing color tone (contrast in oblique direction) Using a measuring device (BM5A' TOPCON), in the dark room, the polar angle of the front of the device is measured at 60 degrees, and the azimuth direction is 0 degrees and 45 degrees. The luminance values of the black display and the white display in three directions of 90 degrees were calculated, and the viewing angle contrast (the whitest brightness/blackest brightness) was calculated, thereby evaluating the viewing angle characteristics of the liquid crystal display device. 〇: The corner contrast is 60 or more, and the light leakage cannot be recognized. △: The minimum value of the corner contrast is less than 6 〇 and is 30 or more, and light leakage is slightly recognized, but it is tolerable. X: The minimum value of the viewing angle contrast is less than 30, and a large leak is recognized and cannot be tolerated. The column showing the evaluation results of the viewing angle contrast in the following table is based on the above criteria to evaluate the above three directions, and the average results are shown. The results were not shown in Table 7 below. (2) Financial durability evaluation Each liquid crystal display device was 50. (:, when the relative humidity is 95%, it is placed in a hot state for 500 hours.) After it is taken out, it is turned on. After that, the measuring instrument (manufactured by Lanyi ON Co., Ltd.) is used, and the direction of the polar angle is 60 degrees. And the viewing angle contrast of 45 degrees in the azimuth direction. The contrast of the viewing angles before and after the continuous point is compared, and the financial durability is evaluated by the following criteria. ◎: The difference in viewing angle contrast is less than 5. 〇 The difference in viewing angle contrast is 5 or more. Less than 1 〇 (slightly leaking light after continuous lighting, to the extent that it is tolerable) 105 rll 201219464 χ : The difference in viewing angle contrast is 胄10 or more (may be a larger leak after continuous party, and cannot be allowed). The results are shown in the following Table 7. (3) In-plane uniformity of the panel _ In the respective examples and comparative examples, the panel of the wave crystal display device was white-displayed, and the BM-5 luminance meter manufactured by TOPCON Corporation was used. The brightness was measured every 10 mm in the plane. Next, the black display 'Using!' 0: 01^ manufactured by the company's 3]^-5 luminance meter was used to measure the brightness every 1〇111«1 in the plane. Set the brightness of the above white display to T white, and display the black when The brightness was set to T black 'T white/Ding black was defined as the contrast. The uniformity of the panel was evaluated by the following criteria. ◎: The contrast in the panel surface was not within 3%. 〇: Contrast in the panel surface Not all of them are within 5%. △: The contrast ratio in the panel surface is not within 10%. ▲: The contrast in the panel surface is not within 15%. X: The contrast in the panel surface is not the same (4) The results obtained by the above evaluation are shown in Table 7 below.

106 201219464 J-a99l6e 斗崦】 Evaluation panel performance in-plane uniformity XXXXXX 〇〇&lt; ◎ 〇XXX ◎ XX Broken 〇〇X ◎ Durability〇〇〇〇〇〇〇〇〇〇〇〇〇〇X ◎ 〇〇 〇〇〇〇 〇〇〇〇 π 轺 轺 a a a a a a a 〇〇〇〇 〇〇〇〇 〇〇〇〇 〇〇〇〇 〇〇〇〇 〇〇〇〇 〇〇〇〇 〇〇〇〇 〇〇〇〇 〇〇〇〇 之 之 之 之 之 之 之 之 之 之 之 之 之 之 之 之(GPa) TH oo o r- o VO o oo oaoo tr&gt; 〇o cs o CO 〇d in d 00 o CO 〇ο dd Broken inch 卜 οο cs o E' (TD) / F (MD) ( N 〇\ 〇gg VO CN om rn AA On FH ON IT) ON (S 2 〇\ cs $ CN On 破 Breaking 〇〇CN ν〇CN 〇\ CN vH E' (TD) (MPa) 2300 2220 2400 4800 3500 3600 | 4200 4250 3800 4200 4150 3800 4000 4100 4000 4250 4600 2950 Breaking 4600 4100 4000 4250 F (MD) (MPa) 2500 2130 2200 3800 2500 2700 3300 3400 3200 3400 3500 3300 3100 3600 3100 ! 3500 3100 3200 Breaking 3600 3250 3100 3550 ϋgw 柃ίΓ Q VA XXX &lt;&lt;&lt;&lt;&lt;&lt;&lt;&lt;1 ◎ 〈 &lt;; ο 〇〇&lt;] ◎ Optical properties of the film Rth/d xlO·3 CN CN Ό CN cn v〇CN 00 Γ-» (N u·) rn CN (N (N oi inch rn ri cs (N 00 ( N 卜 ri (Ν ( oi 卜 Ν (Ν CN (N Ο) inch CN CO (N rn οό CN OO rji »T| in v〇vd tT) ^T) iri t cs 00 ΓΊ yn (Ν νο CN broken \〇vd rvi II s CN 〇§ ON ooo 00 cs 1 &lt; ON (N 00 o CO o PO Ο cn •Τ) Breaking 〇&lt;r*H &lt;N TH s 〇\ V_/ CN s ζ (N 9 Qj o Bu I break α; Bu inch Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Comparative Example 5 Comparative Example 6 Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Comparative Example 7 Comparative Example 8 Comparative Example 9 Example 7 Comparative Example 10 Comparative Example 11 Comparative Example 12 Example 8 Example 9 Comparative Example 13 Example 10 201219464 According to Table 7, the cellulose film of the present invention is inversely/long dispersed. 'Every single reliance on the rich side (4) of the performance of the excellent eight '臈's long-side elastic modulus is large, the redundancy of the redundant side of the elastic modulus is small, the surface is built on the polarizing plate and combined with the panel The internal uniformity becomes good. The liquid crystal display using the film of the present invention has a good viewing angle and durability. On the other hand, in Comparative Example 1 and Comparative Example 10, the TD extension was not performed, and it was found that the obtained film had poor heterogeneity and was uniform in the panel surface, which was problematic. Comparative Example 2 and Comparative Example 3 are aspects similar to the configuration of the example of Japanese Laid-Open Patent Publication No. 2006-030962. Comparative Example 2 is to make the acid fiber _ 岐 plus 5 swim. Material retardation table = additive U, the MD stretching ratio and the TD stretching ratio are outside the range specified in the method of the present invention, and it is understood that the elastic modulus is not inferior to the reverse wavelength dispersion, and is contained in the liquid crystal display. In the device, there is a problem in the viewing angle hue and the in-plane uniformity of the panel. In Comparative Example 3, in Comparative Example 2, the addition of the addition amount was added to increase the td stretching ratio to the dry circumference of the present invention, but the MD stretching ratio exceeded the range specified by the manufacturer of the present invention. The retardation in the film thickness direction of the unit film thickness is poor, and the elasticity is also poor. (4) When the liquid crystal display device is used, there is a problem in the uniformity of the panel surface. Comparative Example 4 t 匕 乂 Example 6 is a configuration similar to the example of Japanese Patent Publication No. 2009-26^619, and neither of which is extended in the direction, it is known that the optical properties of the film or the film elasticity Modulus

108 201219464 jyioopif is poor, and when it is installed in a liquid crystal display device, there is a problem in the uniformity of the panel surface. Comparative Example 7 and Comparative Example 8 are examples in which 5 wt% of the additive U as a retardation agent was used, and it was found that the total thiol substitution degree and the MD stretching ratio of the deuterated cellulose were outside the range of the production method of the present invention. In the case of Comparative Example 7, the expression of the retardation in the film thickness direction per unit film thickness is inferior to the elastic modulus in the MD direction, and when it is incorporated in the liquid crystal display device, there is a problem in the in-plane uniformity of the panel. Further, it is understood that the case where the stretching ratio is within the range of the production method of the present invention and the total thiol substitution degree of the deuterated cellulose is outside the range of the production method of the present invention does not become a reverse The wavelength is dispersed, and when it is incorporated in a liquid crystal display device, there are problems in viewing angle hue and in-plane uniformity. Comparative Example 9 is an aspect of the cellulose deuterated cellulose having a total substitution degree of less than the range of the total degree of substitution of the deuterated cellulose of the present invention, and it is understood that the retardation of the film thickness direction per unit film thickness is inferior to the film elastic modulus. When it is incorporated in a liquid crystal display device, there is a problem in the uniformity of the panel surface. In Comparative Example 11, the stretch ratio of the MD extension and the TD extension was outside the range of the production method of the present invention, and it was found that the film had a poor film elastic modulus and was incorporated in the liquid crystal display device. There is a problem with the uniformity of the panel surface. In Comparative Example 12 and Comparative Example 13, the residual volatile component at the time of film formation was outside the range of the production method of the present invention, and in Comparative Example 12, the film was broken. Further, it is understood that the film obtained in Comparative Example 13 has a poor retardation in the film thickness direction per unit film thickness and is inferior to the film elastic modulus, and is contained in the liquid layer 109 201219464 crystal display device in the panel surface. There is a problem with homogeneity. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a schematic view showing a state in which a deuterated cellulose film of the present invention is produced by using a beating mechanism. Fig. 2 is a schematic view showing the details of a bounce mechanism which can be used in the method for producing a cellulose-deposited cellulose film of the present invention. [Description of main component symbols] 10: Bounce mechanism 11. Bounce device (as a path roller for the hopping movement. Freedom of movement, non-motion) / Bounce 12: Angle detector 13: Load control device 14 · Temperature sensor 15: Tension Sensor 16: film conveying direction 17a, 17b: guide roller (one part of the path roller) 18: path roller 20: belt casting machine 21: peeling roller 22: #杂物23: extension device 24: film (belly Board) soft film

110

Claims (1)

201219464 jyioopif VII. Patent application scope: 1. A deuterated cellulose film, characterized in that: a deuterated cellulose having a total thiol substitution degree of 2.1 to 2.8, the elastic modulus of the film transport direction is 3200 MPa or more, film The modulus of elasticity in the width direction is not more than 〇5 〇pa, and satisfies the following formula (1) to formula (3): Formula (1) 0 nmSAReS15.0 nm (wherein ARe represents the surface at a wavelength of 630 nm The value of the retardation in the inner direction minus the in-plane retardation value at a wavelength of 450 nm (in nm)) (2) 2xl (T3SRth/dS6xl〇-3 (wherein Rth represents the film at a wavelength of 550 nm) The retardation value in the thickness direction (in nm) 'd indicates the film thickness (in nm)) Equation (3) lO^E'(TD) /E' (MD) $1.43 (wherein F(MD) indicates the above The modulus of elasticity (in MPa) 'E' (TD) in the direction in which the film is conveyed indicates the modulus of elasticity (in MPa) of the film width direction. ' 2. The deuteration as described in item 1 of the patent application. a cellulose film, wherein the film has a modulus of elasticity of 35 MPa or more. 3. The cellulose film according to claim 1 Wherein, the retardation value Rth of the retardation value of the in-plane direction at a wavelength of 590 nm and the film thickness direction under the wavelength of 59 〇ηηη satisfies the following formula: 35 nm $ Re $ 80 nm, 100 nm $ Rth S 300 nm. The cellulose-degraded cellulose film according to the above-mentioned item 1, wherein the deuterated cellulose film is a cellulose acetate according to the above-mentioned claim 1, wherein the deuterated cellulose film contains polycondensation from 6. The cellulose-deposited film according to claim 1, wherein the deuterated cellulose comprises less than 3 wt% of Re-representing agent relative to the deuterated cellulose. The 酉 化 纤维素 纤维素 纤维素 ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' In the above formula (1), 'X represents a substituent having an acid group having an acid dissociation constant of 5 5 or less, L represents a single bond or a divalent or higher linking group, and R represents a carbon group having a carbon number of 6 to 30, and carbon. a fluorenyl group having 6 to 30 decyl groups, an alkynyl group having 6 to 30 carbon atoms, an aryl group having 6 to 30 carbon atoms or a heterocyclic group having 6 to 3 carbon atoms, and Further having a substituent; n is 1 in the case where L is a single bond, and is (a price of L) when L is a linking group having a valence of 2 or more. 8. The fluorene fiber as described in claim 7 a film of the formula (1) wherein R1 represents an alkyl group having a carbon number of 6 to 24, a base having a carbon number of 6 to 24, or a radical having a slave number of 6 to 24 (wherein In-; with a substituent). 9. The cellulose-deposited film according to claim 7, wherein X in the formula (1) has at least one member selected from the group consisting of a carboxyl group, a acid group, a sulfonic acid group, and a carboxylic acid group. And continuing at least one group of the group consisting of an imido group and an anti-fail acid group. 112 201219464 jyioopif 10. The brewing cellulose film according to claim 7, wherein the formula (1)_L is a single bond or a unit group selected from the group consisting of two or more a linking group obtained by combining two or more units selected from the group of τ; a group of early 兀: -Ο-, -CO-, -N(R2)- (the R2 represents a carbon number of 1 to 5) a thiolated cellulose film according to claim 7 of the patent application, wherein the The organic acid represented by the formula (1) is obtained by binding one molecular fatty acid to the i molecule poly-acid on the molecular polyol, and has at least one unsubstituted slow group derived from the polycarboxylic acid. 12. The cellulose-degraded cellulose film according to item 7 of the patent application, wherein the molecular weight of the organic acid represented by the formula (1) is 200 to 1 〇〇〇〇 13' as claimed in the patent scope 帛 1 The cellulose-deposited film according to any one of the items 6 to claim 6, which has a laminated structure of two or more layers, and the average total thiol substitution degree of the cellulose-deposited cellulose contained in each of the layers is mutually different. The bismuth cellulose film according to any one of the preceding claims, wherein the standard deviation (σ) of the unevenness of the azimuth direction of the end portion in the film width direction is Below 0.10. 15. A method of producing a brewed cellulose film, characterized in that the package 113 201219464 ^yioopif comprises: a total thiol substitution degree of 2 丨~? a step of obtaining a film by doping a solution of cellulose acetate of 8 on a metal support; peeling the film from the metal support by satisfying a residual volatile component H1 of the following formula (丨) a step of extending the peeled film in the film transport direction by 5% to 1% by weight in a state in which the residual volatile component H2 of the following formula (ii) is satisfied; a step of extending the film in a direction orthogonal to the film transport direction by 2% to 150% in a state in which the residual volatile component H3 of the following formula (i) is satisfied; the extending step satisfies the following formula (iv); Formula (i) 20% SH1$60% Formula (ii) 10% SH2S60% Formula (iii) 5%^H3^45% Formula (iv) (MD stretching ratio + 100%) / (TD stretching ratio + 100%) ^ 〇.7〇 (wherein the MD stretching magnification is expressed by the stretching ratio (unit: %) in the film conveying direction, and the TD stretching magnification is expressed in the direction orthogonal to the film conveying direction Magnification (in %)). 16. A method for producing a bismuth cellulose film, comprising: constituting a cellulose acylate or a cellulose acylate containing a total thiol substitution degree of 2.1 to 2.8 The step of delaying the film; 114 201219464f a step of peeling the film from the metal support by satisfying a residual volatile component HI of the following formula (i); and peeling the film on a residue satisfying the following formula (ii) a step of extending 20% to 100% in the film transport direction in the state of the volatile component H2; and the peeled film is in a state in which the film is conveyed in a state in which the residual volatile component H3 is satisfied a step of extending from 35% to 150% in the direction of intersection; the extension step satisfies the following formula (iv); (i) 20% SH1$60%, formula (ii) 10% SH2$60%, formula (iii) 5%^H3 ^45% Formula (iv) (MD stretching ratio + 100%) / (Td stretching ratio + 100%) ^〇.7〇 (wherein the MD stretching ratio is expressed as the stretching ratio in the film conveying direction ( The unit is %), and the TD stretching ratio is expressed by a stretching ratio (unit: %) in a direction orthogonal to the film conveying direction. 17) As described in claim 15 or claim 16, a method for producing a cellulose film of bismuth, wherein - The surface changes the tension force into a state of ^ 1G N/m, and the surface extends in the direction in which the film is conveyed. 18. For example, in the scope of the patent application, the method for producing the vegan film, wherein the total thiol substitution degree of the bismuth cellulose of the sulphated cellulose of the 16th item is different from each other. And each of the two or more types of tamers is 115 201219464. It is cast on the support. 19. The method for producing a cellulose-deposited cellulose film according to Item 15, wherein the film passes through at least three of the transition portions from the stripping step to the extending step. At least the corner angle is 60. The above path roller. 20. The method of producing a cellulose channel according to claim 15 or claim 16, wherein the path roller comprises at least a root bounce device. The method for producing a cellulose-deposited cellulose film according to Item 15 or Item of the present invention, wherein the metal support body is flown from both the back surface and the surface of the metal branch body The method of manufacturing the brewed vegetal film according to claim 15 or claim 16, wherein the stretching is performed by the towel The direction in which the difficult-to-feed direction is orthogonal satisfies the following formula (v); Formula (v) Wx30^l^Wx2 (wherein, L represents mm)) 23·--------- The method for producing a first fluorinated cellulose film is characterized by the method described in any one of items 15 to 22. 201219464 ^ Λ. W 24. A polarizing plate characterized by comprising: a polarizing element, such as The bismuth cellulose film according to any one of the items 1 to 14 and 23, wherein the liquid crystal display device is characterized in that: The cellulose-deposited cellulose film according to any one of the items 23, or as described in claim 24 Polarizer. 117