JP2011027898A - Method for manufacturing optical film, optical film, and polarizing plate and liquid crystal display device using the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method for manufacturing an optical film suitably used as a retardation film in a large-sized liquid crystal display device. <P>SOLUTION: In the method for manufacturing an optical film, a composition containing cellulose nano fibers which have a modified group expressed by general formula (1): -(L)<SB>n</SB>-R<SP>1</SP>and have an average fiber length of 2.0 to 100 μm, and a thermoplastic resin is formed into a film and is stretched in at least one direction. In the formula, L represents a linking group, and n represents an integer 0 or 1, and R<SP>1</SP>represents a cycloalkyl group, an aryl group, or a heterocyclic group and they may have a substituent furthermore. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

  The present invention relates to an optical film manufacturing method, an optical film, a polarizing plate using the same, and a liquid crystal display device.

  Liquid crystal display devices are widely used as display devices for liquid crystal TVs, personal computers, and the like because they can be directly connected to an IC circuit with low voltage and low power consumption, and can be particularly thin. The liquid crystal display device has a basic configuration in which, for example, polarizing plates are provided on both sides of a liquid crystal cell. In such a liquid crystal display device, from the viewpoint of contrast or the like, a conventional liquid crystal display device using a twisted nematic (TN) with a twist angle of 90 degrees and a super twisted nematic (STN) with a twist angle of 160 degrees or more are used. A liquid crystal display device has been developed. Recently, for example, a vertical alignment (vertical alignment, VA for short) and a VA type liquid crystal display device disclosed in Japanese Patent Laid-Open No. 2-176625 have been recently developed. It has been developed. The VA type liquid crystal display device uses a so-called vertical alignment mode liquid crystal cell and has a feature that black is displayed firmly as black, has high contrast, and has a wider viewing angle than TN and STN type. Yes.

  However, as the liquid crystal screen becomes larger as in a large TV, there is a growing demand for further widening the viewing angle. In these cases, retardation films have been used to expand the viewing angle. Accordingly, with the enlargement of the liquid crystal screen, the phase difference film is also increasingly widened.

  Conventionally, application of a thermoplastic resin film, particularly a triacetyl cellulose film, has been studied for the retardation film, but a triacetyl cellulose (TAC) film usually has a constant retardation value (Rt) in the thickness direction. However, only a very small phase difference value (Ro) is developed in the in-plane direction, which is not always suitable for the purpose of improving the viewing angle of the VA liquid crystal display device described above, for example.

  In order to produce a retardation film having a slow axis in the width direction (also a polarizing plate protective film), a cellulose ester film such as TAC is stretched in the width direction during film formation, and the slow axis in the width direction. It is necessary to use a retardation film having However, when attempting to produce a wide retardation film for large displays that has recently been demanded, stretching unevenness tends to occur and the uniformity of the retardation value tends to be lost. It is.

  In addition, these cellulose ester films are usually wound on a core to form a film original, which is stored and transported. For this reason, the film may be stored for a long time in the state of the film roll wound on the core. At this time, the so-called “horse spine” failure or the film core is wound around the core. It has been found that there is a problem called core transfer and a problem that the film tends to wrinkle when starting to roll.

  The horse's back failure is a failure in which the original film is deformed into a U shape like the horse's back, and a belt-like convex part is formed at a pitch of about 2 to 3 cm near the center, and the film remains deformed. If processed into a polarizing plate, the screen will appear distorted. Until now, the back failure of horses has been reduced by reducing the coefficient of dynamic friction between the film surfaces or adjusting the height of the knurling (embossing) on both sides of the film. In addition, the core transfer is a failure due to film deformation caused by unevenness of the core or film.

  These failures have not been a problem so far, but as the film becomes wider, the width of the film becomes wider and the winding length tends to be longer, so the film load tends to increase. These situations are more likely to occur, and countermeasures have become necessary.

  On the other hand, the technique which improved the mechanical strength with the cellulose-ester composition containing a cellulose nanofiber or crystalline cellulose is also proposed (for example, refer patent document 1, 2 or 3). However, these techniques, when a wide retardation film is produced, are insufficient to satisfy the optical performance, the uniformity of the retardation value, and the film deformation suppression at the same time.

JP 2008-208231 A JP 2008-209595 A JP 2009-52016 A

  The present invention has been made in view of the above problems, and its purpose is to control the retardation within a suitable range and at the same time suppress the fluctuation of the retardation, and further improve the failure due to film deformation, and the method thereof. It is providing the optical film manufactured by this, the polarizing plate using the same, and the liquid crystal display device using the said polarizing plate. In particular, an object of the present invention is to provide a method for producing an optical film suitably used as a retardation film in a large liquid crystal display device.

  The present invention has been made to solve the above-mentioned problems, and as a result of intensive studies, the present inventors have conducted research on stretching conditions using a composition comprising cellulose nanofibers modified with a specific substituent and cellulose ester. By manufacturing an optical film, we have found a manufacturing method that can control the retardation within a suitable range by the action of the modified cellulose nanofibers and at the same time suppress the fluctuation of the retardation, and further improve the failure due to film deformation. It is.

  If the production method of the present invention is used, the optical film can be widened, and the polarizing plate using the optical film and the liquid crystal display device (liquid crystal display) using the polarizing plate can also be widened.

  The above object of the present invention is achieved by the following configurations.

(1)
After forming a composition containing cellulose nanofibers having a modifying group represented by the following general formula (1) and an average fiber length of 2.0 μm to 100 μm and a thermoplastic resin, at least in one direction A method for producing an optical film, which comprises performing a stretching treatment.

General formula (1)
-(L) _n -R ¹
(In the formula, L represents a linking group, n represents an integer of 0 or 1. R ¹ represents a cycloalkyl group, an aryl group, or a heterocyclic group, and these may further have a substituent. .)
(2)
The method for producing an optical film according to (1), wherein the cellulose nanofiber is crushed after the introduction of the modifying group.

(3)
The method for producing an optical film according to (1) or (2), wherein the thermoplastic resin is a cellulose ester.

(4)
In any one of (1) to (3), the stretching treatment is performed to form a retardation film having an in-plane retardation Ro of 20 to 200 nm and a retardation Rt in the thickness direction of 70 to 400 nm. The manufacturing method of the optical film of description.

(5)
The method for producing an optical film according to any one of (1) to (4), wherein the optical film is formed by a solution casting method.

(6)
The method for producing an optical film according to any one of (1) to (4), wherein the optical film is formed by a melt extrusion method.

(7)
An optical film manufactured by the method for manufacturing an optical film according to any one of (1) to (6).

(8)
A polarizing plate using the optical film according to (7) on at least one surface.

(9)
A liquid crystal display device using the polarizing plate according to (8).

  According to the present invention, the retardation can be controlled within a suitable range and at the same time the fluctuation of the retardation can be suppressed, and further, the production method for improving the failure due to film deformation, the optical film produced by the method, the polarizing plate using the same, In addition, a liquid crystal display device using the polarizing plate can be provided.

  In particular, it is possible to provide an optical film that is suitably used as a retardation film used in a large liquid crystal display device.

Schematic flow block diagram showing one form of an apparatus for carrying out the method for producing an optical film (cellulose ester film) according to the present invention Fig. 1 is an enlarged flow diagram of the main part of the manufacturing apparatus of Fig. 1. (A) is the external view of the principal part of a casting die, (b) is sectional drawing of the principal part of a casting die. Sectional drawing of 1st Embodiment of a pinching rotary body Sectional drawing in the plane perpendicular | vertical to the rotating shaft of 2nd Embodiment of a pinching rotary body Sectional drawing in the plane containing the rotating shaft of 2nd Embodiment of a pinching rotary body Exploded perspective view schematically showing the configuration of a liquid crystal display device The figure explaining the preservation | save method of the cellulose ester film original fabric sample wound up

  Hereinafter, the best mode for carrying out the present invention will be described in detail, but the present invention is not limited thereto.

[Optical film]
In the present invention, the “optical film” is a functional film used for various display devices such as a liquid crystal display, a plasma display, and an organic EL display, and more specifically, a polarizing plate protective film and a retardation film for a liquid crystal display device. , An antireflection film, a brightness enhancement film, a hard coat film, an antiglare film, an antistatic film, an optical compensation film for expanding the viewing angle, and the like.

  The optical film of the present invention is preferably used for a polarizing plate protective film (including a polarizing plate protective film provided with a functional layer) and a retardation film.

[Cellulose Nanofibers of the Present Invention]
The cellulose nanofiber used in the present invention is obtained by introducing a modifying group (hereinafter also referred to as a substituent) into the cellulose fiber described later. The step of introducing the modifying group may be any step after the raw pulp removal step, after the step of defibration to some extent, or after the step of crushing to nanofibers, but after the raw pulp removal step or the average fiber diameter is 1 It is preferable to perform the modifying group introduction step after defibration to the extent that it falls within the range of -100 μm. Then, after introducing the modifying group, by further pulverizing until the average fiber diameter becomes 1 μm or less, cellulose nanofibers that hardly cause aggregation are obtained by the dispersibility improving action of the introduced modifying group.

  Cellulose nanofibers are known to be obtained by applying a strong mechanical shearing force to cellulose fibers such as paper pulp, and many production methods have been proposed. For example, in Japanese Examined Patent Publication No. 60-19921, a suspension of fibrous cellulose is passed through a small-diameter orifice, and the suspension is given a high speed with a pressure difference of at least 20.7 MPa, and then is made to collide with the suspension. A process of causing a cutting action by rapidly decelerating and a process of repeating this process so that the cellulose suspension becomes a substantially stable suspension. Has proposed.

  Japanese Patent Laid-Open No. 4-82907 proposes a method for producing fibrillated natural cellulose by crushing short fibers of natural cellulose fibers in a dry state. Further, in JP-A-06-10286, a suspension of fibrous cellulose is obtained by a vibration mill crusher using beads or balls made of glass, alumina, zirconia, zircon, steel, titania or the like as a crushing medium. A method for producing fine fibrous cellulose subjected to wet pulverization is disclosed.

  The cellulose nanofibers of the present invention are preferably refined using a plurality of crushing means. The crushing means is not limited, but a strong shearing force such as a high-pressure homogenizer, a media mill, a grindstone rotary crusher, or a stone mill grinder can be obtained for fine crushing to a particle size suitable for the purpose of the present invention. A method is preferably used.

  A high-pressure homogenizer is a device that grinds by shear force due to accelerated high flow velocity, rapid pressure drop (cavitation), and impact force caused by high-velocity particles colliding face-to-face within a fine orifice, and is commercially available. As the device, a nanomizer (manufactured by Nanomizer Co., Ltd.), a microfluidizer (manufactured by Microfluidics) or the like can be used.

The degree of cellulose fibrillation and homogenization by the high-pressure homogenizer depends on the pressure fed to the high-pressure homogenizer and the number of passes (number of passes) passed through the high-pressure homogenizer. The pumping pressure is usually in the range of about 500 to 2000 kg / cm ^2, which is suitable for ultrafine processing, but 1000 to 2000 kg / cm ² is more preferable in consideration of productivity. The number of passes is, for example, about 5 to 50 times, preferably about 10 to 40 times, particularly about 20 to 30 times.

  The medium mill is a wet vibration mill, a wet planetary vibration mill, a wet ball mill, a wet roll mill, a wet coball mill, a wet bead mill, a wet paint shaker, or the like. Among these, for example, a wet bead mill is a device in which a metal or ceramic medium is built in a container and this is subjected to wet grinding by forcibly stirring it. A mill (manufactured by Kotobuki Giken Kogyo Co., Ltd.), a pearl mill (manufactured by Ashizawa Co., Ltd.), a dyno mill (manufactured by Shinmaru Enterprises Co., Ltd.), or the like can be used.

  The grindstone rotary type crusher is a kind of colloid mill or mortar type crusher. For example, a grindstone made of abrasive grains having a particle size of 16 to 120 is rubbed, and the aqueous dispersion is passed through the rubbed portion. That is, the device to be crushed. You may perform a process in multiple times as needed. It is one of the preferred embodiments that the grindstone is appropriately changed. The grindstone rotary type crusher has both “short fiber” and “miniaturization” effects, but the effect is influenced by the grain size of the abrasive grains. For the purpose of shortening the fiber length, a # 46 or less grindstone is effective. For miniaturization purposes, a # 46 or greater grindstone is effective. No. 46 has both functions. Specific examples of the apparatus include a pure fine mill (grinder mill) (Kurita Machinery Co., Ltd.), a serendipeater, a super mass collider, and a super grinder (above, Masuko Sangyo Co., Ltd.).

  In the present invention, the obtained cellulose nanofiber is added to the cellulose ester directly or as a dispersion, and the content thereof is preferably in the range of 0.1 to 50% by mass. More preferably, it is 5-50 mass%, and especially 5-30 mass% is preferable.

  When the content of the cellulose nanofiber is less than 0.1% by mass, the retardation control of the optical film, the retardation fluctuation suppression, and the effect of improving the failure due to film deformation tend to be insufficient, and exceeds 50% by mass. In addition, the transparency and surface flatness may be reduced.

[Modifying group of cellulose nanofiber]
In the general formula (1), L represents a linking group, and n represents an integer of 0 or 1.

R ¹ represents a cycloalkyl group, an aryl group, or a heterocyclic group, and these may further have a substituent.

  Specifically, examples of the cycloalkyl group include a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, and a cyclooctyl group.

  Examples of the aryl group include a phenyl group, a biphenyl group, a naphthyl group, an indenyl group, an azulenyl group, a fluorenyl group, a phenanthryl group, an anthryl group, an acenaphthenyl group, a naphthacenyl group, and a pyrenyl group.

  Examples of the heterocyclic group include a furyl group, a thienyl group, a thiazolyl group, an isothiazolyl group, a pyrrolyl group, a pyridyl group, a pyrazolyl group, a pyranyl group, a pyridazinyl group, a pyrimidinyl group, a pyrazinyl group, a furazanyl group, a triazolyl group, an oxazolyl group, Isoxazolyl, imidazolyl, indolyl, isoindolyl, indolizinyl, indazolyl, benzofuranyl, benzothienyl, benzothiazolyl, benzoxazolyl, benzoimidazolyl, benzotriazolyl, purinyl, chromenyl, quinolyl Group, isoquinolyl group, quinolidinyl group, quinoxalinyl group, quinazolinyl group, cinnolinyl group, phthalazinyl group, pteridinyl group, carbazolyl group, acridinyl group, phenanthridinyl group, xanthenyl group Phenazinyl group, phenothiazinyl group, phenoxathiinyl group, phenoxazinyl group, and a thianthrenyl group.

  These modifying groups may further have a substituent. Examples of the substituent include a halogen atom, an alkyl group (for example, a methyl group, an ethyl group, an isopropyl group, a tert-butyl group), an aryl group ( Preferably it has 6 to 30 carbon atoms, more preferably 6 to 15 carbon atoms; for example, phenyl group, biphenyl group, naphthyl group and the like, alkoxy group (preferably 1 to 30 carbon atoms, more preferably 1 to 12 carbon atoms; For example, methoxy group, ethoxy group, isopropoxy group and the like), acyl group (preferably having 2 to 36 carbon atoms, more preferably 2 to 18 carbon atoms; for example, acetyl group, propionyl group, butyryl group and the like), acylamino group ( Preferably 1 to 36 carbon atoms, more preferably 1 to 18 carbon atoms; for example, formylamino group, acetylamino group, etc.), aryloxy (Preferably 6 to 36 carbon atoms, more preferably 6 to 18 carbon atoms; for example, phenoxy group), acyloxy group (preferably 2 to 36 carbon atoms, more preferably 2 to 18 carbon atoms; for example, acetyloxy group , Propionyloxy group, butyryloxy group, etc.), cyano group, hydroxyl group, nitro group and the like.

  In the general formula (1), L represents a linking group, and preferred specific examples are illustrated below, but are not limited thereto.

  Among these, from the viewpoint of easy formation of bonds, (1), (2), (3), (5), (6), (7), (9), (10), (14), (15 ), (16), (17), (18), and (20) are preferred. (1), (3), (5), (6), (14 ) And (20) are more preferable, and a linking group represented by either (1) or (3) is more preferable.

(10) ^R 2 in represents ^R 3, (16) in the ^R 4, (20) ^{R 5} is an organic substituent independently in in (12).

  Although the preferable specific example of the modification group represented by the said General formula (1) below is illustrated, it is not limited to these.

  In the present invention, the modifying group represented by the general formula (1) is preferably a substituent capable of controlling optical anisotropy due to birefringence. As a feature of the substituent capable of controlling the optical anisotropy, there is a bias of electron distribution caused by the type of chemical bond forming the substituent-containing molecule, that is, anisotropy with a large polarizability. . In general, a molecule has a direction in which the polarizability is maximum and minimum, and a compound having a large difference between the polarizability in the maximum direction and the polarizability in the minimum direction has a large polarizability anisotropy.

  Substituents that control optical anisotropy are preferably those having a ring structure such as aromatic compounds and alicyclic compounds. The ring structure may be an allocyclic compound formed only from carbon atoms, or a heterocyclic compound in which two or more atoms are incorporated, such as a pyridine ring formed from a carbon atom and a nitrogen atom It may be. Among these compounds, those having a ring structure of an aromatic compound can be used particularly preferably because the polarizability is increased by π electrons.

For example, in the case of a benzene ring, the polarizability in the parallel direction of the ring per molecule is 123.1 × 10 ⁻²⁵ cm ³ and 63.5 × 10 ⁻²⁵ cm ³ in the vertical direction, and the difference in polarizability is large. Other aromatic ring structures include naphthalene structure, biphenyl structure, anthracene structure, trans-stilbene structure, diphenylacetylene structure, benzylidenephenylamine structure, N, N'-dibenzylidenehydrazine structure, fluorene structure Etc. Since the π-electron conjugated system spreads over the entire ring structure, the polarizability in the major axis direction of the ring structure increases, and the ring structure having a large polarizability anisotropy is suitable for the present invention.

  Furthermore, in the present invention, one or two or more ring structures selected from the group consisting of a phenyl group, a naphthyl group, and a biphenyl group having little steric hindrance upon introduction into cellulose nanofibers and having no absorption in the ultraviolet region are used. What has is especially preferable. A naphthyl group and a biphenyl group are more preferable because they have a larger polarizability anisotropy than a phenyl group.

  The modifying group represented by the general formula (1) is modified into a part of an alicyclic compound, an aromatic compound, a heterocyclic compound, etc. to form an acid, an alcohol, a halide, and an acid anhydride. It is preferable to introduce a cycloalkyl group, an aryl group, or a heterocyclic group by chemically modifying the hydroxyl group of cellulose nanofibers with one or two or more compounds selected from the group consisting of. When making it react with the hydroxyl group of cellulose nanofiber, in order to make modification control easy, the compound is preferably monofunctional, but may be bifunctional or higher. These are introduced by a chemical bond such as an ether bond or an ester bond by a known method.

  In particular, by reacting the cellulose nanofiber with a compound modified at the 1-position (α-position) of the naphthyl group and the 2-position or 3-position of the biphenyl group, the long side of the ring structure is aligned with the fiber axis of the cellulose nanofiber. Thus, the anisotropy of the cellulose nanofiber is increased, the birefringence of the obtained composite material is increased, and a retardation imparting composite material is obtained.

As the structure of the group represented by R ¹ in the general formula (1) in the present invention, the following rod-like compound structure or 1,3,5-triazine ring structure is preferable, and these structures are monovalent groups. R ¹ is preferred.

(Bar-shaped compound structure)
The rod-like compound structure is preferably a trans-1,4-cyclohexanedicarboxylic acid ester structure represented by the following general formula (B-1).

Formula (B-1)
Ar ¹ -L ^B1 -Ar ²
In General Formula (B-1), Ar1 and Ar2 each independently represent an aryl group or a heterocyclic group, and these may further have a substituent. Specific examples are the same as the aryl group and heterocyclic group in the general formula (1). In the general formula (B-1), L ^B1 is a divalent group selected from the group consisting of an alkylene group, an alkenylene group, an alkynylene group, a divalent saturated heterocyclic group, —O—, —CO—, and combinations thereof. It is a linking group. The alkylene group may have a cyclic structure. As the cyclic alkylene group, cyclohexylene is preferable, and 1,4-cyclohexylene is particularly preferable. As the chain alkylene group, a linear alkylene group is more preferable than a branched alkylene group. The number of carbon atoms of the alkylene group is preferably 1-20, more preferably 1-15, still more preferably 1-10, still more preferably 1-8, 6 is most preferred.

  Preferable specific examples of the rod-like compound represented by the general formula (B-1) include, for example, the structures described in paragraphs 57 to 61 of JP-A-2006-154760.

(1,3,5-triazine ring structure)
The structure having a 1,3,5-triazine ring is preferably a structure represented by the following general formula (T).

In the general formula (T), X ^T1 is a single bond, —NR ^T4 —, —O—, or —S—; X ^T2 is a single bond, —NR ^T5 —, —O—, or —S—; X ^T3 is a single bond, —NR ^T6 —, —O— or —S—; R ^T1 , R ^T2 and R ^T3 are alkyl groups, alkenyl groups, aryl groups or heterocyclic groups; and R ^T4 , R ^T5 and R ^T6 are a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, or a heterocyclic group. The compound represented by the general formula (T) is particularly preferably a melamine compound. Preferable specific examples of the structure having a 1,3,5-triazine ring represented by the general formula (T) include, for example, the structures described in paragraphs 93 to 115 of JP-A-2006-154760.

  The structure having a 1,3,5-triazine ring may be a melamine polymer structure. Preferable specific examples of the melamine polymer structure include, for example, the structures described in paragraphs 122 to 129 of JP-A-2006-154760.

In the present invention, the structure of the group represented by R ¹ in the general formula (1) is preferably a benzoic acid phenyl ester structure represented by the general formula (B-2).

(In the formula, R ^B1 , R ^B2 , R ^B3 , R ^B4 , R ^B5 , R ^B6 , R ^B7 , R ^B8 , R ^B9 and R ^B10 each independently represent a hydrogen atom or a substituent, and R ^B1 , R ^B2 , R ^B3 , R ^B4 and R ^B5 each represents an electron donating group.)
In general formula (B-2), R ^B1 , R ^B2 , R ^B3 , R ^B4 , R ^B5 , R ^B6 , R ^B7 , R ^B8 , R ^B9 and R ^B10 each independently represent a hydrogen atom or a substituent. , For example, an alkyl group (preferably having 1 to 20 carbon atoms, more preferably 1 to 12 carbon atoms, particularly preferably 1 to 8 carbon atoms, such as methyl, ethyl, iso-propyl, tert-butyl, and n-octyl, n-decyl, n-hexadecyl, cyclopropyl, cyclopentyl, cyclohexyl, etc.), an alkenyl group (preferably having 2 to 20 carbon atoms, more preferably 2 to 12 carbon atoms, and particularly preferably carbon number). 2 to 8, for example, vinyl, allyl, 2-butenyl, 3-pentenyl, etc.), an alkynyl group (preferably having 2 to 2 carbon atoms) , More preferably 2 to 12 carbon atoms, particularly preferably 2 to 8 carbon atoms, such as propargyl, 3-pentynyl, etc.), aryl groups (preferably 6 to 30 carbon atoms, more preferably carbon atoms). 6 to 20, particularly preferably 6 to 12 carbon atoms, such as phenyl, p-methylphenyl, naphthyl, etc.), substituted or unsubstituted amino groups (preferably having 0 to 20 carbon atoms, more preferably The number of carbon atoms is 0 to 10, particularly preferably 0 to 6 carbon atoms, and examples thereof include amino, methylamino, dimethylamino, diethylamino, dibenzylamino, and the like, and alkoxy groups (preferably having 1 to 20 carbon atoms. Preferably it has 1 to 12 carbon atoms, particularly preferably 1 to 8 carbon atoms, and examples thereof include methoxy, ethoxy, butoxy and the like. An aryloxy group (preferably having 6 to 20 carbon atoms, more preferably 6 to 16 carbon atoms, and particularly preferably 6 to 12 carbon atoms, such as phenyloxy and 2-naphthyloxy), an acyl group ( Preferably it has 1 to 20 carbon atoms, more preferably 1 to 16 carbon atoms, particularly preferably 1 to 12 carbon atoms, and examples thereof include acetyl, benzoyl, formyl, pivaloyl and the like, and an alkoxycarbonyl group (preferably carbon). 2 to 20, more preferably 2 to 16 carbon atoms, particularly preferably 2 to 12 carbon atoms, such as methoxycarbonyl, ethoxycarbonyl, etc.), an aryloxycarbonyl group (preferably 7 to 20 carbon atoms). More preferably 7 to 16 carbon atoms, particularly preferably 7 to 10 carbon atoms, such as phenyloxy Examples include carbonyl. ), An acyloxy group (preferably having 2 to 20 carbon atoms, more preferably 2 to 16 carbon atoms, particularly preferably 2 to 10 carbon atoms such as acetoxy and benzoyloxy), an acylamino group (preferably 2-20 carbon atoms, more preferably 2-16 carbon atoms, particularly preferably 2-10 carbon atoms, and examples thereof include acetylamino, benzoylamino, and the like, and an alkoxycarbonylamino group (preferably having 2-2 carbon atoms). 20, more preferably 2 to 16 carbon atoms, particularly preferably 2 to 12 carbon atoms, such as methoxycarbonylamino and the like, aryloxycarbonylamino group (preferably 7 to 20 carbon atoms, more preferably 7 to 16 carbon atoms, particularly preferably 7 to 12 carbon atoms, such as phenyloxycarbonyl And sulfonylamino groups (preferably having 1 to 20 carbon atoms, more preferably 1 to 16 carbon atoms, and particularly preferably 1 to 12 carbon atoms, such as methanesulfonylamino and benzenesulfonylamino). ), A sulfamoyl group (preferably having 0 to 20 carbon atoms, more preferably 0 to 16 carbon atoms, particularly preferably 0 to 12 carbon atoms, such as sulfamoyl, methylsulfamoyl, dimethylsulfamoyl, phenyl Sulfamoyl, etc.), a carbamoyl group (preferably having 1 to 20 carbon atoms, more preferably 1 to 16 carbon atoms, particularly preferably 1 to 12 carbon atoms, such as carbamoyl, methylcarbamoyl, diethylcarbamoyl, Phenylcarbamoyl etc.), alkylthio group ( Preferably it has 1 to 20 carbon atoms, more preferably 1 to 16 carbon atoms, particularly preferably 1 to 12 carbon atoms, such as methylthio, ethylthio, etc.), an arylthio group (preferably 6 to 20 carbon atoms). , More preferably 6 to 16 carbon atoms, particularly preferably 6 to 12 carbon atoms, such as phenylthio, and the like, a sulfonyl group (preferably 1 to 20 carbon atoms, more preferably 1 to 16 carbon atoms, Especially preferably, it is C1-C12, for example, a mesyl, tosyl etc. are mentioned), a sulfinyl group (Preferably C1-C20, More preferably C1-C16, Most preferably C1-C12 For example, methanesulfinyl, benzenesulfinyl, etc.), ureido group (preferably having 1 to 20 carbon atoms, more preferably carbon It has 1 to 16 primes, particularly preferably 1 to 12 carbons, and examples thereof include ureido, methylureido and phenylureido. ), Phosphoric acid amide groups (preferably having 1 to 20 carbon atoms, more preferably 1 to 16 carbon atoms, particularly preferably 1 to 12 carbon atoms, such as diethyl phosphoric acid amide and phenylphosphoric acid amide. ), Hydroxy group, mercapto group, halogen atom (eg fluorine atom, chlorine atom, bromine atom, iodine atom), cyano group, sulfo group, carboxyl group, nitro group, hydroxamic acid group, sulfino group, hydrazino group, imino group, Heterocyclic group (preferably having 1 to 30 carbon atoms, more preferably 1 to 12 carbon atoms, and examples of the hetero atom include a nitrogen atom, an oxygen atom, a sulfur atom, specifically, for example, imidazolyl, pyridyl, quinolyl, furyl, piperidyl , Morpholino, benzoxazolyl, benzimidazolyl, benzthiazolyl, etc.), Group (preferably, 3 to 40 carbon atoms, more preferably 3 to 30 carbon atoms, particularly preferably 3 to 24 carbon atoms, e.g., trimethylsilyl, etc. triphenylsilyl and the like) and the like. These substituents may be further substituted.

At least one of R ^B1 , R ^B2 , R ^B3 , R ^B4 and R ^B5 represents an electron donating group. More preferably, one of R ^B1 , R ^{B3 and} R ^B5 is an electron donating group, and R ^B3 is more preferably an electron donating group. An electron donating group is one having a Hammett σp value of 0 or less. Rev. 91, 165 (1991). Those having a Hammett's σp value of 0 or less are preferably applicable, and those having −0.85 to 0 are more preferably used. Examples thereof include an alkyl group, an alkoxy group, an amino group, and a hydroxyl group.

  Preferable specific examples of the benzoic acid phenyl ester structure represented by the general formula (B-2) include, for example, the structures described in paragraphs 183 to 190 of JP-A-2006-154760.

[Cellulose nanofibers]
The cellulose nanofiber according to the present invention refers to a cellulose-based fiber having an average fiber diameter of 4 to 200 nm as a fiber. The fibers may be composed of single fibers that are sufficiently spaced and so as to enter each other. In this case, the average fiber diameter is the average diameter of single fibers. Further, the fiber according to the present invention may be one in which a plurality of (may be many) single fibers are gathered into a bundle to form one yarn. The fiber diameter is defined as the average value of the diameter of one yarn.

  In the present invention, when the average fiber diameter of the fibers exceeds 200 nm, the wavelength approaches the wavelength of visible light, and refraction of visible light tends to occur at the interface with the cellulose ester, resulting in a decrease in transparency. The upper limit of the average fiber diameter of the fibers used is preferably 200 nm.

  Since it is difficult to produce fibers having an average fiber diameter of less than 4 nm, the lower limit of the average fiber diameter of the fibers used in the present invention is preferably 4 nm. The average fiber diameter of the fiber used in the present invention is preferably 4 to 100 nm, more preferably 4 to 60 nm.

  In addition, as long as the fiber used by this invention has an average fiber diameter in the range of 4-200 nm, the thing of the fiber diameter out of the range of 4-200 nm may be contained in the fiber, The ratio is 30. Preferably, the fiber diameter of all the fibers is 200 nm or less, particularly 100 nm or less, particularly 60 nm or less.

  The fiber length of the cellulose nanofiber of the present invention is 2.0 μm or more and 100 μm or less in average length. When the average length of the fibers is shorter than 2.0 μm, the retardation fluctuation suppressing effect and the failure improving effect due to film deformation are reduced. When the fiber length is longer than 100 μm, the dispersibility deteriorates, the fiber distribution becomes uneven, the composition distribution in the fiber composite material becomes uneven, and the improvement effects are all reduced. Furthermore, the transparency as an optical film may be insufficient. In addition, although a fiber length less than 2.0 micrometers may be contained in the fiber, it is preferable that the ratio is 30 mass% or less. More preferably, it is 2.0 μm or more and 50 μm or less. More preferably, it is 2.0 μm or more and 10 μm or less.

  The measurement of the said fiber diameter and fiber length can be measured with a commercially available microscope and an electron microscope.

  For example, by taking a photograph of cellulose nanofibers magnified 2000 times with a scanning electron microscope, and then analyzing the photographic image using “SCANNING IMAGE ANALYZER” (manufactured by JEOL Ltd.) based on this photograph It was measured. Under the present circumstances, the average value of a fiber diameter and fiber length can be calculated | required using 100 cellulose nanofibers.

  Cellulosic fibers refer to cellulose microfibrils constituting the basic skeleton of plant cell walls or the like, or constituent fibers thereof, and are usually aggregates of unit fibers having a fiber diameter of about 4 nm. In order to obtain high strength and low thermal expansion, it is preferable that this cellulose fiber contains a crystal structure of 40% or more.

  In the present invention, the cellulosic fiber to be used can be suitably used whether it is separated from a plant or bacterial cellulose produced by bacterial cellulose, but is preferably separated from a plant.

  The pulp used as the raw material of the cellulose nanofiber of the present invention is a pulp obtained by a mechanical method (eg, groundwood pulp, refiner ground pulp, thermomechanical pulp, semichemical pulp, chemiground pulp), or a chemical method. Pulp (craft pulp, sulfite pulp, etc.) obtained in (1) can be used. As the pulp, wood pulp, linter pulp, waste paper pulp and the like are usually used. In addition, materials containing cellulose can be widely used, for example, refined pulp subjected to delignification treatment such as bamboo pulp and bagasse pulp, or cellulose type such as cotton fiber, cotton linter and hemp fiber Natural fibers, or refined natural fibers that have been delignified, or regenerated cellulose moldings such as viscose, rayon, tencel, polynosic fibers, or dietary fibers derived from grains or fruits (For example, wheat bran, oat bran, corn hulls, rice bran, beer lees, soybean meal, pea fiber, okara fiber, apple fiber, etc.) or lignocellulosic materials such as wood and rice straw It may be.

  Further, non-wood fibers such as kenaf, shiogusa, esparto, cocoon, cocoon, cocoon, ramie, etc. may be used, and microbially produced cellulose, valonia cellulose, squirt cellulose, etc. may also be used.

  In the above, it is preferable to use wood pulp as a main raw material, and synthetic pulp such as polypropylene may be added as necessary. Inorganic-supported pulp is preferably used, and cellulose pulp used for this production is, for example, sulfite pulp (SP), alkali pulp (AP), kraft pulp (KP), etc. obtained from hardwood and softwood. Chemical pulp, semi-chemical pulp, semi-mechanical pulp, mechanical pulp, and the like. Further, the pulp can be used without distinction between unbleached pulp, bleached pulp and beating, and unbeaten. Hardwood bleached kraft pulp (hereinafter also referred to as LBKP) or softwood bleached kraft pulp is most suitable due to its quality and cost. As wood pulp, any of LBKP, LBSP, NBKP, NBSP, LDP, NDP, LUKP, and NUKP can be used, but it is preferable to use more LBKP, NBSP, LBSP, NDP, and LDP with a short fiber content. However, the ratio of LBSP and / or LDP is preferably 10% by mass or more and 70% by mass or less. The freeness of the pulp used in the present invention is preferably 200 to 500 ml as defined by CSF, and the fiber length after beating is 24 mesh residual mass and 42 mesh residual mass specified in JIS-P-8207. When the cellulose nanofiber is produced, a sum of 30% to 70% is preferable. In addition, it is preferable that 4 mesh residual mass% is 20 mass% or less. Bamboo pulp is also preferably used, but it is not particularly limited. However, it is preferable to use true bamboo to make cellulose nanofibers because the fiber diameter is smaller (15 μm or less) than 孟宗竹.

  In addition, water-soluble gums such as xanthan gum, karaya gum, carrageenan, pectin, and sodium fibrin glycolate, and hydrophilic substances such as starch hydrolysates and dextrins can be appropriately blended with the cellulose-based material. These water-soluble gums and hydrophilic substances may be added to the fine cellulose after grinding.

  In the present invention, a dispersion aid can be blended. The content is usually up to 1 part by mass, but as a dispersion aid, glucose, glucose, sucrose, fructose, lactose, maltose, cellobiose, cellotriose, cellotetraose, maltotriose, fructose, xylose, various Water-soluble substances such as oligosaccharides, sorbit, dextrins, starches, sorbose, gum degradation products, various gums, pullulan, curdlan, agar, pectin, dextran, gelatin, cellulose derivatives, alginic acid, farseleran, quince, and water Swellable substances can be used.

  Moreover, the process by a phosphate etc. can be used, This weakens the bond strength between cellulose fibers by phosphoric esterifying the surface of a plant cell wall etc., Then, a refiner process is performed and fiber is made. This is a treatment method for obtaining cellulose fibers in pieces. For example, a plant cell wall from which lignin and the like have been removed is immersed in a solution containing 50% by mass urea and 32% by mass phosphoric acid, and the solution is sufficiently soaked between cellulose fibers at 60 ° C. and then heated at 180 ° C. To promote phosphorylation. After washing this with water, it is hydrolyzed in a 3% by mass hydrochloric acid aqueous solution at 60 ° C. for 2 hours and washed again with water. Then, phosphorylation is completed by processing for about 20 minutes at room temperature in 3 mass% sodium carbonate aqueous solution. And a cellulose fiber is obtained by defibrating this processed material with a refiner.

〔Thermoplastic resin〕
Examples of the thermoplastic resin constituting the optical film used in the present invention include polyethylene, polypropylene, ABS resin, PMMA (polymethyl methacrylate), polystyrene, polycarbonate, polycycloolefin (Zeon Corporation, Zeon Corporation, Arton manufactured by JSR Corporation, Polyplastics) TOPAS, Mitsui Chemicals' Appel, etc.), polylactic acid, cellulose ester, polyethersulfone, polyetherimide, polyetheretherketone, polyphenylene sulfide, polyphenylene oxide, polycaprolactone, polyethylene terephthalate, polyethylene naphthalate, polybutylene terephthalate , Polypropylene terephthalate, polybutylene succinate, poly-3-hydroxybutyrate, polyarylate, nylon, alla De, thermoplastic elastomers, such as silicone. Of these, cellulose ester, polyethylene terephthalate, and polycycloolefin are preferable.

(Cellulose ester (CE))
The cellulose ester constituting the optical film preferably used in the present invention (hereinafter also referred to as CE) is preferably a cellulose ester having an average substitution degree of 2.0 to 3.0. For example, an aromatic carboxylic acid ester or the like is also used. However, in view of the characteristics of the obtained film such as optical characteristics, it is preferable to use a lower mixed fatty acid ester of cellulose. Lower fatty acid means a fatty acid having 6 or less carbon atoms, such as cellulose acetate, cellulose propionate, cellulose acetate propionate, cellulose butyrate, cellulose acetate butyrate, cellulose pivalate, cellulose caproate, cellulose Acetate caproate and the like are preferable as the lower fatty acid ester of cellulose. In a cellulose ester substituted with a fatty acid having 7 or more carbon atoms, the mechanical properties of the resulting cellulose ester film tend to be low.

  Among the cellulose esters, cellulose acetate, cellulose acetate propionate, cellulose acetate butyrate, and cellulose acetate caproate are preferable. Among these, cellulose diacetate, cellulose triacetate or cellulose acetate propionate is preferable, and cellulose diacetate is particularly preferable.

  Next, the substitution degree of the acyl group of the cellulose ester used for this invention is demonstrated.

  Cellulose has a total of three hydroxyl groups, one at the 2nd, 3rd, and 6th positions of 1 glucose unit. The degree of substitution is the average number of acyl groups bonded to 1 glucose unit. Is a numerical value indicating Therefore, the maximum substitution degree is 3.0. These acyl groups may be substituted on the 2nd, 3rd and 6th positions of the glucose unit on average, or may be substituted with a distribution.

  A preferable substitution degree is a cellulose ester that simultaneously satisfies the following formulas (I), (II), and (III) when the substitution degree of the acetyl group is X and the substitution degree of other acyl groups is Y. In addition, the substitution degree of an acetyl group and the substitution degree of other acyl groups are determined by the method prescribed in ASTM-D817-96.

Formula (I) 1.5 ≦ X + Y ≦ 3.0
Formula (II) 1.5 ≦ X ≦ 3.0
Formula (III) 0 ≦ Y ≦ 1.5
Moreover, the cellulose ester from which the substitution degree of an acyl group differs may be blended, and the cellulose ester film whole may be in the said range. The part not substituted with the acyl group is usually present as a hydroxyl group.

  The cellulose ester used in the present invention preferably has a number average molecular weight (Mn) of 50,000 to 150,000, more preferably a number average molecular weight of 55,000 to 120,000, and a number average molecular weight of 60000 to 100,000. Most preferred.

  Further, the cellulose ester used in the present invention preferably has a weight average molecular weight (Mw) / number average molecular weight (Mn) ratio of 1.3 to 5.5, particularly preferably 1.5 to 5.0. More preferably, it is 1.7-4.0, More preferably, the cellulose ester of 2.0-3.5 is used preferably.

  Mn and Mw / Mn were calculated by gel permeation chromatography in the following manner.

  The measurement conditions are as follows.

Solvent: Tetohydrofuran Equipment: HLC-8220 (manufactured by Tosoh Corporation)
Column: TSKgel SuperHM-M (manufactured by Tosoh Corporation)
Column temperature: 40 ° C
Sample concentration: 0.1% by mass
Injection volume: 10 μl
Flow rate: 0.6 ml / min
Calibration curve: Standard polystyrene: PS-1 (manufactured by Polymer Laboratories)
A calibration curve with 9 samples from Mw = 2,560,000 to 580 was used.

  The cellulose ester raw material cellulose used in the present invention may be wood pulp or cotton linter, and the wood pulp may be softwood or hardwood, but softwood is more preferred. A cotton linter is preferably used from the viewpoint of peelability during film formation. The cellulose ester made from these can be mixed suitably or can be used independently.

  For example, the ratio of cellulose ester derived from cellulose linter: cellulose ester derived from wood pulp (coniferous): cellulose ester derived from wood pulp (hardwood) is 100: 0: 0, 90: 10: 0, 85: 15: 0, 50:50: 0, 20: 80: 0, 10: 90: 0, 0: 100: 0, 0: 0: 100, 80:10:10, 85: 0: 15, 40:30:30.

  The cellulose ester can be obtained, for example, by substituting the hydroxyl group of the raw material cellulose with acetic anhydride, propionic anhydride and / or butyric anhydride in the usual manner using an acetyl group, propionyl group and / or butyl group within the above range. . The method for synthesizing such a cellulose ester is not particularly limited. For example, the cellulose ester can be synthesized with reference to the method described in JP-A-10-45804 or JP-A-6-501040.

  The alkaline earth metal content of the cellulose ester used in the present invention is preferably in the range of 1 to 50 ppm. If it exceeds 50 ppm, lip adhesion stains increase or breakage tends to occur at the slitting part during or after hot stretching. Even if it is less than 1 ppm, it tends to break, but the reason is not well understood. In order to make it less than 1 ppm, since the burden of a washing | cleaning process will become large too much, it is unpreferable also in that point. Furthermore, the range of 1-30 ppm is preferable. The alkaline earth metal as used herein refers to the total content of Ca and Mg, and can be measured using an X-ray photoelectron spectrometer (XPS).

  The residual sulfuric acid content in the cellulose ester used in the present invention is preferably in the range of 0.1 to 45 ppm in terms of elemental sulfur. These are considered to be contained in the form of salts. If the residual sulfuric acid content exceeds 45 ppm, the deposits on the die lip during heat melting increase, such being undesirable. Moreover, since it becomes easy to fracture | rupture at the time of slitting at the time of hot drawing or after hot drawing, it is not preferable. A smaller amount is preferable, but if it is less than 0.1, it is not preferable because the load of the cellulose ester washing process becomes too large, and it is not preferable because it may easily break. This is not well understood, although an increase in the number of washings may affect the resin. Furthermore, the range of 1-30 ppm is preferable. The residual sulfuric acid content can be measured by a method prescribed in ASTM-D817-96.

  The free acid content in the cellulose ester used in the present invention is preferably 1 to 500 ppm. If it exceeds 500 ppm, deposits on the die lip will increase and breakage will easily occur. It is difficult to make it less than 1 ppm by washing. Furthermore, it is preferable that it is the range of 1-100 ppm, and also it becomes difficult to fracture | rupture. A range of 1 to 70 ppm is particularly preferable. The free acid content can be measured by the method prescribed in ASTM-D817-96.

  By washing the synthesized cellulose ester more sufficiently than when it is used in the solution casting method, the residual acid content can be within the above range, and a film is produced by the melt casting method. In this case, adhesion to the lip portion is reduced and a film having excellent flatness can be obtained, and a film having good dimensional change, mechanical strength, transparency, moisture resistance, Rt value and Ro value described later can be obtained. . In addition to washing with water, cellulose ester can be washed with a poor solvent such as methanol or ethanol, or as a result, a mixed solvent of a poor solvent and a good solvent can be used as a poor solvent. Low molecular organic impurities can be removed. Furthermore, washing of the cellulose ester is preferably performed in the presence of an antioxidant such as a hindered amine or a phosphite, which improves the heat resistance and film forming stability of the cellulose ester.

  In order to improve the heat resistance, mechanical properties, optical properties, etc. of cellulose ester, it can be dissolved in a good solvent of cellulose ester and then reprecipitated in a poor solvent to remove low molecular weight components and other impurities of cellulose ester. it can. At this time, it is preferable to carry out in the presence of an antioxidant as in the case of washing the cellulose ester.

  Furthermore, another polymer or a low molecular weight compound may be added after the cellulose ester reprecipitation treatment.

  Moreover, it is preferable that the cellulose ester used by this invention is a thing with few bright spot foreign materials when it is made into a film. A bright spot foreign material is an arrangement in which two polarizing plates are arranged orthogonally (crossed Nicols), a cellulose ester film is arranged between them, light from the light source is applied from one side, and the cellulose ester film is applied from the other side. This is the point where the light from the light source appears to leak when observed. At this time, the polarizing plate used for the evaluation is desirably composed of a protective film having no bright spot foreign matter, and preferably a glass plate is used for protecting the polarizer. One of the causes of bright spot foreign matter is the unacetylated or low acetylated cellulose contained in the cellulose ester. Use a cellulose ester with less bright spot foreign matter (use a cellulose ester with a small dispersion degree of substitution). And filtering the melted cellulose ester, or removing the bright spot foreign matters through the filtration process in the same way once in the solution state in at least one of the process of synthesizing the cellulose ester and the process of obtaining the precipitate You can also. Since the molten resin has a high viscosity, the latter method is more efficient.

As the film thickness decreases, the number of bright spot foreign matter per unit area decreases, and as the cellulose ester content in the film decreases, the bright spot foreign matter tends to decrease. 0.01 mm or more is preferably 200 pieces / cm ² or less, more preferably 100 pieces / cm ² or less, further preferably 50 pieces / cm ² or less, and 30 pieces / cm ² or less. More preferably, it is more preferably 10 pieces / cm ² or less, but most preferably none. Moreover, it is preferable that it is 200 pieces / cm < ² > or less also about the bright spot of 0.005-0.01 mm or less, It is more preferable that it is 100 pieces / cm < ² > or less, It is 50 pieces / cm < ² > or less. Even more preferred is 30 / cm ² or less, still more preferred is 10 / cm ² or less, and most preferred is none.

  When removing bright spot foreign matter by melt filtration, filtering the cellulose ester composition to which a plasticizer, a deterioration inhibitor, an antioxidant, etc. are added and mixed is more effective than filtering the melted cellulose ester alone. It is preferable because the removal efficiency of point foreign matters is high. Of course, the cellulose ester may be dissolved in a solvent during the synthesis and reduced by filtration. What mixed the ultraviolet absorber and other additives suitably can be filtered. Filtration is preferably performed at a viscosity of a melt containing cellulose ester of 10,000 Pa · s or less, more preferably 5000 Pa · s or less, even more preferably 1000 Pa · s or less, and even more preferably 500 Pa · s or less. . As the filter medium, conventionally known materials such as glass fibers, cellulose fibers, filter paper, and fluorine resins such as tetrafluoroethylene resin are preferably used, and ceramics, metals and the like are particularly preferably used. The absolute filtration accuracy is preferably 50 μm or less, more preferably 30 μm or less, still more preferably 10 μm or less, and even more preferably 5 μm or less. These can be used in combination as appropriate. The filter medium can be either a surface type or a depth type, but the depth type is preferably used because it is relatively less clogged.

  In another embodiment, a cellulose ester obtained by dissolving the raw material cellulose ester at least once in a solvent and then drying the solvent may be used. In that case, a cellulose ester which is dissolved in a solvent together with at least one of a plasticizer, an ultraviolet absorber, a deterioration inhibitor, an antioxidant and a matting agent and then dried is used. As the solvent, a good solvent used in a solution casting method such as methylene chloride, methyl acetate or dioxolane can be used, and a poor solvent such as methanol, ethanol or butanol may be used at the same time. You may cool to -20 degrees C or less in the process of dissolution, or you may heat to 80 degrees C or more. When such a cellulose ester is used, each additive in a molten state can be easily made uniform, and optical characteristics can be made uniform.

〔Additive〕
Among the three additives (1) to (3) described below, the optical film of the present invention has the purpose of further improving the performance of a polarizing plate produced using the optical film and a liquid crystal display device. It is preferable to add at least one or more. Particularly preferably, all three types are added.
(1) Carbon radical scavenger (2) Primary antioxidant having hydrogen radical donating ability to peroxy radical (3) Secondary antioxidant additive having reducing action on peroxide (Carbon radical scavenger)
The optical film of the present invention preferably contains at least one carbon radical scavenger.

  In the present invention, the “carbon radical scavenger” has a group (for example, an unsaturated group such as a double bond or a triple bond) that allows a carbon radical to rapidly undergo an addition reaction, and is followed by polymerization or the like after the addition of the carbon radical. It means a compound that gives a stable product in which no reaction takes place.

  Examples of the carbon radical scavenger include compounds having a radical polymerization inhibitory ability such as a group (unsaturated group such as (meth) acryloyl group and aryl group) that reacts quickly with a carbon radical in the molecule, and a phenolic or lactone based compound. The compound represented by the following general formula (AD-1) or general formula (AD-2) is particularly preferable.

In the general formula (AD-1), R ₁₁ represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, particularly preferably a hydrogen atom or a methyl group. It is.

R ₁₂ and R ₁₃ each independently represent an alkyl group having 1 to 8 carbon atoms, and may be linear or have a branched structure or a ring structure.

R ₁₂ and R ₁₃ are preferably a structure represented by “* —C (CH ₃ ) ₂ —R ′” containing a quaternary carbon (* represents a connecting site to an aromatic ring, and R ′ represents a carbon number of 1 Represents an alkyl group of ˜5).

R ₁₂ is more preferably a tert-butyl group, a tert-amyl group or a tert-octyl group. R ₁₃ is more preferably a tert-butyl group or a tert-amyl group. Examples of commercially available compounds represented by the above general formula (AD-1) include “Sumilizer GM, Sumilizer GS” (both trade names, manufactured by Sumitomo Chemical Co., Ltd.) and the like.

  Specific examples (I-1 to I-18) of the compound represented by the general formula (AD-1) are illustrated below, but the present invention is not limited thereto.

In the general formula (AD-2), R _{22 to} R ₂₅ each independently represent a hydrogen atom or a substituent, and the substituent represented by R _{22 to} R ₂₅ is not particularly limited. An alkyl group (for example, methyl group, ethyl group, propyl group, isopropyl group, t-butyl group, pentyl group, hexyl group, octyl group, dodecyl group, trifluoromethyl group, etc.), cycloalkyl group (for example, cyclopentyl group, Cyclohexyl group etc.), aryl group (eg phenyl group, naphthyl group etc.), acylamino group (eg acetylamino group, benzoylamino group etc.), alkylthio group (eg methylthio group, ethylthio group etc.), arylthio group (eg , Phenylthio group, naphthylthio group, etc.), alkenyl group (for example, vinyl group, 2-propenyl group) 3-butenyl group, 1-methyl-3-propenyl group, 3-pentenyl group, 1-methyl-3-butenyl group, 4-hexenyl group, cyclohexenyl group, etc.), halogen atom (for example, fluorine atom, chlorine atom, Bromine atom, iodine atom etc.), alkynyl group (eg propargyl group etc.), heterocyclic group (eg pyridyl group, thiazolyl group, oxazolyl group, imidazolyl group etc.), alkylsulfonyl group (eg methylsulfonyl group, ethylsulfonyl) Group), arylsulfonyl group (eg phenylsulfonyl group, naphthylsulfonyl group etc.), alkylsulfinyl group (eg methylsulfinyl group etc.), arylsulfinyl group (eg phenylsulfinyl group etc.), phosphono group, acyl group ( For example, acetyl group, pivaloyl group, benzoyl group, etc. Carbamoyl group (for example, aminocarbonyl group, methylaminocarbonyl group, dimethylaminocarbonyl group, butylaminocarbonyl group, cyclohexylaminocarbonyl group, phenylaminocarbonyl group, 2-pyridylaminocarbonyl group, etc.), sulfamoyl group (for example, aminosulfonyl group) Group, methylaminosulfonyl group, dimethylaminosulfonyl group, butylaminosulfonyl group, hexylaminosulfonyl group, cyclohexylaminosulfonyl group, octylaminosulfonyl group, dodecylaminosulfonyl group, phenylaminosulfonyl group, naphthylaminosulfonyl group, 2-pyridylamino Sulfonyl groups, etc.), sulfonamide groups (eg methanesulfonamide groups, benzenesulfonamide groups etc.), cyano groups, alkoxy groups (eg For example, methoxy group, ethoxy group, propoxy group, etc.), aryloxy group (eg, phenoxy group, naphthyloxy group, etc.), heterocyclic oxy group, siloxy group, acyloxy group (eg, acetyloxy group, benzoyloxy group, etc.) Sulfonic acid group, sulfonic acid salt, aminocarbonyloxy group, amino group (for example, amino group, ethylamino group, dimethylamino group, butylamino group, cyclopentylamino group, 2-ethylhexylamino group, dodecylamino group, etc.) , Anilino group (eg, phenylamino group, chlorophenylamino group, toluidino group, anisidino group, naphthylamino group, 2-pyridylamino group, etc.), imide group, ureido group (eg, methylureido group, ethylureido group, pentylureido group) , Cyclohexylureido group, octyl Raid group, dodecylureido group, phenylureido group, naphthylureido group, 2-pyridylaminoureido group, etc.), alkoxycarbonylamino group (eg, methoxycarbonylamino group, phenoxycarbonylamino group, etc.), alkoxycarbonyl group (eg, methoxycarbonyl) Group, ethoxycarbonyl group, phenoxycarbonyl, etc.), aryloxycarbonyl group (eg, phenoxycarbonyl group, etc.), heterocyclic thio group, thioureido group, carboxyl group, carboxylic acid salt, hydroxyl group, mercapto group, nitro group, etc. Each group is mentioned. These substituents may be further substituted with the same substituent.

In the general formula (AD-2), R ₂₆ represents a hydrogen atom or a substituent, and examples of the substituent represented by R ₂₆ include the same groups as the substituents represented by R _{22 to} R _25. it can.

  In the general formula (AD-2), n represents 1 or 2.

In the general formula (AD-2), when n is 1, R ₂₁ represents a substituent, and when n is 2, R ₂₁ represents a divalent linking group. When R ₂₁ represents a substituent, examples of the substituent include the same groups as the substituents represented by R _{22 to} R ₂₅ .

When R ₂₁ represents a divalent linking group, examples of the divalent linking group include an alkylene group that may have a substituent, an arylene group that may have a substituent, an oxygen atom, a nitrogen atom, and a sulfur atom. Or a combination of these linking groups.

  In the general formula (AD-2), n is preferably 1.

  Next, although the specific example of a compound represented by the said general formula (AD-2) in this invention is shown, this invention is not limited by the following specific examples.

  The carbon radical scavenger can be used alone or in combination of two or more thereof, and the amount of the carbon radical scavenger is appropriately selected within a range that does not impair the object of the present invention, but the total mass of the resin that forms the optical film. On the other hand, it is preferable to add 0.001-10.0 mass parts normally, More preferably, it is 0.01-5.0 mass parts, Most preferably, it is 0.1-1.0 mass part.

(Primary antioxidant)
The optical film of the present invention preferably contains at least one primary antioxidant having a hydrogen radical donating ability for peroxy radicals.

  In the present invention, the “primary antioxidant having the ability to donate a hydrogen radical to a peroxy radical” is a compound having at least one hydrogen atom in the molecule that is rapidly extracted by the peroxy radical, and is a hydroxyl group or a primary or An aromatic compound substituted with a secondary amino group or a heterocyclic compound having a sterically hindered group is preferable, and a phenol compound or a hindered amine compound having an alkyl group at the ortho position is more preferable.

(Phenolic compounds)
The phenolic compounds preferably used in the present invention include 2,6-dialkylphenol derivative compounds such as those described in US Pat. No. 4,839,405, columns 12-14. Such a compound includes a compound represented by the following general formula (AD-3).

  In formula, R31-R36 represents a hydrogen atom or a substituent. Examples of the substituent include a halogen atom (eg, fluorine atom, chlorine atom), an alkyl group (eg, methyl group, ethyl group, isopropyl group, hydroxyethyl group, methoxymethyl group, trifluoromethyl group, t-butyl group, etc.), A cycloalkyl group (eg, cyclopentyl group, cyclohexyl group, etc.), an aralkyl group (eg, benzyl group, 2-phenethyl group, etc.), an aryl group (eg, phenyl group, naphthyl group, p-tolyl group, p-chlorophenyl group, etc.), alkoxy Groups (eg methoxy, ethoxy, isopropoxy, butoxy), aryloxy (eg phenoxy), cyano, acylamino (eg acetylamino, propionylamino), alkylthio (eg methylthio) Group, ethylthio group, butylthio group, etc.), aryl O group (for example, phenylthio group), sulfonylamino group (for example, methanesulfonylamino group, benzenesulfonylamino group, etc.), ureido group (for example, 3-methylureido group, 3,3-dimethylureido group, 1,3-dimethylureido) Group), sulfamoylamino group (dimethylsulfamoylamino group etc.), carbamoyl group (eg methylcarbamoyl group, ethylcarbamoyl group, dimethylcarbamoyl group etc.), sulfamoyl group (eg ethylsulfamoyl group, dimethylsulfamoyl group) Moyl group etc.), alkoxycarbonyl group (eg methoxycarbonyl group, ethoxycarbonyl group etc.), aryloxycarbonyl group (eg phenoxycarbonyl group etc.), sulfonyl group (eg methanesulfonyl group, butanesulfonyl group, phenylsulfonyl group) Group), acyl group (eg, acetyl group, propanoyl group, butyroyl group, etc.), amino group (methylamino group, ethylamino group, dimethylamino group, etc.), cyano group, hydroxy group, nitro group, nitroso group, amine oxide Group (for example, pyridine-oxide group), imide group (for example, phthalimide group, etc.), disulfide group (for example, benzene disulfide group, benzothiazolyl-2-disulfide group, etc.), carboxyl group, sulfo group, heterocyclic group (for example, pyrrole group, Pyrrolidyl group, pyrazolyl group, imidazolyl group, pyridyl group, benzimidazolyl group, benzthiazolyl group, benzoxazolyl group, etc.). These substituents may be further substituted.

  A compound in which R31 is a hydrogen atom and R32 and R36 are t-butyl groups is preferable. Specific examples of the phenol compound include n-octadecyl 3- (3,5-di-t-butyl-4-hydroxyphenyl) -propionate, n-octadecyl 3- (3,5-di-t-butyl-4 -Hydroxyphenyl) -acetate, n-octadecyl 3,5-di-t-butyl-4-hydroxybenzoate, n-hexyl 3,5-di-t-butyl-4-hydroxyphenylbenzoate, n-dodecyl 3,5 -Di-t-butyl-4-hydroxyphenylbenzoate, neo-dodecyl 3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate, dodecyl beta (3,5-di-t-butyl-4 -Hydroxyphenyl) propionate, ethyl α- (4-hydroxy-3,5-di-t-butylphenyl) isobutyrate, octadecyl α- (4-hydroxy-3,5-di-t-butylphenyl) isobutyrate, octadecyl α- (4-hydroxy-3,5-di-t-butyl-4-hydroxyphenyl) propionate, 2- (n- Octylthio) ethyl 3,5-di-t-butyl-4-hydroxy-benzoate, 2- (n-octylthio) ethyl 3,5-di-t-butyl-4-hydroxy-phenylacetate, 2- (n-octadecyl) Thio) ethyl 3,5-di-t-butyl-4-hydroxyphenyl acetate, 2- (n-octadecylthio) ethyl 3,5-di-t-butyl-4-hydroxy-benzoate, 2- (2-hydroxy Ethylthio) ethyl 3,5-di-t-butyl-4-hydroxybenzoate, diethyl glycol bis- (3,5-di-t-butyl-4- Droxy-phenyl) propionate, 2- (n-octadecylthio) ethyl 3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate, stearamide N, N-bis- [ethylene 3- (3,5 -Di-t-butyl-4-hydroxyphenyl) propionate], n-butylimino N, N-bis- [ethylene 3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], 2- ( 2-stearoyloxyethylthio) ethyl 3,5-di-tert-butyl-4-hydroxybenzoate, 2- (2-stearoyloxyethylthio) ethyl 7- (3-methyl-5-tert-butyl-4-hydroxy) Phenyl) heptanoate, 1,2-propylene glycol bis- [3- (3,5-di-t-butyl-4-hydroxypheny ) Propionate], ethylene glycol bis- [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], neopentyl glycol bis- [3- (3,5-di-t-butyl-4) -Hydroxyphenyl) propionate], ethylene glycol bis- (3,5-di-t-butyl-4-hydroxyphenylacetate), glycerin-ln-octadecanoate-2,3-bis- (3,5 -Di-t-butyl-4-hydroxyphenyl acetate), pentaerythritol tetrakis- [3- (3 ', 5'-di-t-butyl-4'-hydroxyphenyl) propionate], 3,9-bis- { 2- [3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionyloxy] -1,1-dimethylethyl -2,4,8,10-tetraoxaspiro [5.5] undecane, 1,1,1-trimethylolethane-tris- [3- (3,5-di-t-butyl-4-hydroxyphenyl) Propionate], sorbitol hexa- [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], 2-hydroxyethyl 7- (3-methyl-5-tbutyl-4-hydroxyphenyl) propionate 2-stearoyloxyethyl 7- (3-methyl-5-t-butyl-4-hydroxyphenyl) heptanoate, 1,6-n-hexanediol-bis [(3 ', 5'-di-t-butyl- 4-hydroxyphenyl) propionate], pentaerythritol tetrakis (3,5-di-t-butyl-4-hydroxyhydrocinnamate) Be turned. The phenol compound of the above type is commercially available from Ciba Japan Co., Ltd. under the trade names “Irganox 1076” and “Irganox 1010”, for example.

  The above phenol compounds can be used alone or in combination of two or more thereof, and the blending amount thereof is appropriately selected within a range not impairing the object of the present invention, but with respect to the total mass of the resin forming the optical film, Usually, it is preferable to add 0.001-10.0 mass part, More preferably, it is 0.05-5.0 mass part, Most preferably, it is 0.1-2.0 mass part.

(Hindered amine compounds)
The hindered amine compound preferably used in the present invention is preferably a hindered amine compound represented by the following general formula (AD-4).

  In formula, R41-R47 represents a substituent. As a substituent, it is synonymous with the substituent represented by R31-R36 of the said general formula (AD-3). R44 is preferably a hydrogen atom and a methyl group, R47 is preferably a hydrogen atom, and R42, R43, R45 and R46 are preferably a methyl group. Specific examples of hindered amine compounds include bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis (2,2,6,6-tetramethyl-4-piperidyl) succinate, bis (1 , 2,2,6,6-pentamethyl-4-piperidyl) sebacate, bis (N-octoxy-2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis (N-benzyloxy-2,2) , 6,6-tetramethyl-4-piperidyl) sebacate, bis (N-cyclohexyloxy-2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis (1,2,2,6,6- Pentamethyl-4-piperidyl) 2- (3,5-di-t-butyl-4-hydroxybenzyl) -2-butylmalonate, bis (1-acryloyl-2,2,6,6- Tramethyl-4-piperidyl) 2,2-bis (3,5-di-tert-butyl-4-hydroxybenzyl) -2-butylmalonate, bis (1,2,2,6,6-pentamethyl-4- Piperidyl) decanedioate, 2,2,6,6-tetramethyl-4-piperidyl methacrylate, 4- [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionyloxy] -1- [ 2- (3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionyloxy) ethyl] -2,2,6,6-tetramethylpiperidine, 2-methyl-2- (2,2, 6,6-tetramethyl-4-piperidyl) amino-N- (2,2,6,6-tetramethyl-4-piperidyl) propionamide, tetrakis (2,2,6,6-tetramethyl-4-piperidyl) 1,2,3,4-butane tetracarboxylate, tetrakis (1,2,2,6,6-pentamethyl-4-piperidyl) 1,2,3,4-butane tetracarboxylate, and the like.

  Further, it may be a polymer type compound. As specific examples, N, N ′, N ″, N ″ ′-tetrakis- [4,6-bis- [butyl- (N-methyl-2,2,6, 6-tetramethylpiperidin-4-yl) amino] -triazin-2-yl] -4,7-diazadecane-1,10-diamine, dibutylamine and 1,3,5-triazine-N, N′-bis ( 2,2,6,6-tetramethyl-4-piperidyl) -1,6-hexamethylenediamine and N- (2,2,6,6-tetramethyl-4-piperidyl) butylamine polycondensate, di Polycondensate of butylamine, 1,3,5-triazine and N, N′-bis (2,2,6,6-tetramethyl-4-piperidyl) butylamine, poly [{(1,1,3,3 -Tetramethylbutyl) amino-1,3,5-tri Gin-2,4-diyl} {(2,2,6,6-tetramethyl-4-piperidyl) imino} hexamethylene {(2,2,6,6-tetramethyl-4-piperidyl) imino}], Between 1,6-hexanediamine-N, N'-bis (2,2,6,6-tetramethyl-4-piperidyl) and morpholine-2,4,6-trichloro-1,3,5-triazine Polycondensate, poly [(6-morpholino-s-triazine-2,4-diyl) [(2,2,6,6-tetramethyl-4-piperidyl) imino] -hexamethylene [(2,2,6 , 6-tetramethyl-4-piperidyl) imino]], etc., high molecular weight HALS in which a plurality of piperidine rings are bonded via a triazine skeleton; dimethyl succinate and 4-hydroxy-2,2,6,6-tetramethyl- 1-piperidine ester Polymer with diol, 1,2,3,4-butanetetracarboxylic acid, 1,2,2,6,6-pentamethyl-4-piperidinol and 3,9-bis (2-hydroxy-1,1-dimethyl) (Ethyl) -2,4,8,10-tetraoxaspiro [5,5] undecane and the like, and the like are exemplified by compounds in which a piperidine ring is bonded through an ester bond, but the present invention is not limited thereto. It is not a thing.

  Among these, polycondensates of dibutylamine, 1,3,5-triazine and N, N′-bis (2,2,6,6-tetramethyl-4-piperidyl) butylamine, poly [{(1, 1,3,3-tetramethylbutyl) amino-1,3,5-triazine-2,4-diyl} {(2,2,6,6-tetramethyl-4-piperidyl) imino} hexamethylene {(2 , 2,6,6-tetramethyl-4-piperidyl) imino}], a polymer of dimethyl succinate and 4-hydroxy-2,2,6,6-tetramethyl-1-piperidineethanol, etc. Those having a molecular weight (Mn) of 2,000 to 5,000 are preferred.

  The hindered amine compound of the above type is commercially available from Ciba Japan Co., Ltd. under the trade names “Tinuvin 144” and “Tinuvin 770” and from ADEKA Co., Ltd. under the name “ADK STAB LA-52”.

  The above hindered amine compounds can be used alone or in combination of two or more thereof, and the blending amount thereof is appropriately selected within a range not impairing the object of the present invention, but with respect to the total mass of the resin forming the optical film, Usually, it is preferable to add 0.001-10.0 mass part, More preferably, it is 0.05-5.0 mass part, Most preferably, it is 0.1-2.0 mass part.

(Antioxidant secondary agent)
The optical film of the present invention preferably contains at least one secondary antioxidant having a reducing action on peroxide.

  In the present invention, the “secondary antioxidant having a reducing action on peroxide” means a reducing agent that rapidly reduces peroxide to convert it to a hydroxyl group.

  The secondary antioxidant having a reducing ability for peroxide is preferably a phosphorus compound or a sulfur compound.

(Phosphorus compounds)
The phosphorus compound preferably used in the present invention is preferably a phosphorus compound selected from the group consisting of phosphite, phosphonite, phosphinite, or tertiary phosphane. Is a partial structure represented by the following general formula (AD-5-1), (AD-5-2), (AD-5-3), (AD-5-4), (AD-5-5) Are preferred in the molecule.

In the formula, Ph ₁ and Ph ′ ₁ represent a substituent. As a substituent, it is synonymous with the substituent represented by R31-R36 of the said general formula (AD-3). More preferably, Ph ₁ and Ph ′ ₁ represent a phenylene group, and the hydrogen atom of the phenylene group is a phenyl group, an alkyl group having 1 to 8 carbon atoms, a cycloalkyl group having 5 to 8 carbon atoms, or 6 to 12 carbon atoms. Or an alkyl cycloalkyl group or an aralkyl group having 7 to 12 carbon atoms. Ph ₁ and Ph ′ ₁ may be the same as or different from each other. X represents a single bond, a sulfur atom or a —CHR— group. R represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, or a cycloalkyl group having 5 to 8 carbon atoms. These may be substituted with a substituent having the same meaning as the substituents represented by R31 to R36 in the general formula (AD-3).

Wherein, Ph ₂ and Ph _'2 each represent a substituent. As a substituent, it is synonymous with the substituent represented by R31-R36 of the said general formula (AD-3). More preferably, Ph ₂ and Ph ′ ₂ represent a phenyl group or a biphenyl group, and the hydrogen atom of the phenyl group or biphenyl group is an alkyl group having 1 to 8 carbon atoms, a cycloalkyl group having 5 to 8 carbon atoms, or a carbon number. It may be substituted with a 6-12 alkylcycloalkyl group or an aralkyl group having 7-12 carbon atoms. Ph2 and Ph′2 may be the same as or different from each other. These may be substituted with a substituent having the same meaning as the substituents represented by R31 to R36 in the general formula (AD-3).

In the formula, Ph ₃ represents a substituent. As a substituent, it is synonymous with the substituent represented by R31-R36 of the said general formula (AD-3). More preferably, Ph ₃ represents a phenyl group or a biphenyl group, and the hydrogen atom of the phenyl group or biphenyl group is an alkyl group having 1 to 8 carbon atoms, a cycloalkyl group having 5 to 8 carbon atoms, or a 6 to 12 carbon atom. It may be substituted with an alkylcycloalkyl group or an aralkyl group having 7 to 12 carbon atoms. These may be substituted with a substituent having the same meaning as the substituents represented by R31 to R36 in the general formula (AD-3).

In the formula, Ph ₄ represents a substituent. As a substituent, it is synonymous with the substituent represented by R31-R36 of the said general formula (AD-3). More preferably, Ph ₄ represents an alkyl group having 1 to 20 carbon atoms or a phenyl group, and the alkyl group or phenyl group is a substituent having the same meaning as the substituent represented by R31 to R36 in the general formula (AD-3). It may be substituted by a group.

In the formula, Ph ₅ , Ph ′ ₅ and Ph ″ ₅ represent substituents. The substituents have the same meaning as the substituents represented by R 31 to R 36 in the general formula (AD-3). More preferably, Ph ₅ , Ph ′ ₅ and Ph ″ ₅ represent an alkyl group having 1 to 20 carbon atoms or a phenyl group, and the alkyl group or phenyl group is a substituent represented by R 31 to R 36 in the general formula (AD-3). It may be substituted with a substituent having the same meaning as

  Specific examples of phosphorus compounds include triphenyl phosphite, diphenylisodecyl phosphite, phenyl diisodecyl phosphite, tris (nonylphenyl) phosphite, tris (dinonylphenyl) phosphite, tris (2,4-di-). t-butylphenyl) phosphite, 10- (3,5-di-t-butyl-4-hydroxybenzyl) -9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 6- [ 3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propoxy] -2,4,8,10-tetra-tert-butyldibenz [d, f] [1,3,2] dioxaphosphine Monophosphite compounds such as pin and tridecyl phosphite; 4,4'-butylidene-bis (3-methyl-6-t-butyl) Diphosphite compounds such as phenyl-di-tridecyl phosphite), 4,4'-isopropylidene-bis (phenyl-di-alkyl (C12-C15) phosphite); triphenylphosphonite, tetrakis (2,4- Di-tert-butylphenyl) [1,1-biphenyl] -4,4'-diylbisphosphonite, tetrakis (2,4-di-tert-butyl-5-methylphenyl) [1,1-biphenyl]- Phosphonite compounds such as 4,4'-diylbisphosphonite; phosphinite compounds such as triphenylphosphinite and 2,6-dimethylphenyldiphenylphosphinite; triphenylphosphine and tris (2,6-dimethoxyphenyl) Phosphine compounds such as phosphine; and the like.

  Phosphorus compounds of the above type are, for example, from Sumitomo Chemical Co., Ltd. “Sumilizer GP”, from ADEKA Co., Ltd. “ADK STAB PEP-24G”, “ADK STAB PEP-36” and “ADK STAB 3010”, from Ciba Japan “IRGAFOS P-EPQ”, commercially available from Sakai Chemical Industry Co., Ltd. under the trade name “GSY-P101”.

  The above phosphorus compounds can be used alone or in combination of two or more, and the blending amount thereof is appropriately selected within a range not impairing the object of the present invention, but with respect to the total mass of the resin forming the optical film. Usually, it is preferable to add 0.001-10.0 mass parts, More preferably, it is 0.05-5.0 mass parts, Most preferably, it is 0.05-2.0 mass parts.

(Sulfur compounds)
The sulfur compound preferably used in the present invention is preferably a sulfur compound represented by the following general formula (AD-6).

Formula (AD-6) R61-S-R62
In the formula, R61 and R62 each represents a substituent. As a substituent, it is synonymous with the substituent represented by R31-R36 of the said general formula (AD-3).

  Specific examples of the sulfur compound include dilauryl 3,3-thiodipropionate, dimyristyl 3,3'-thiodipropionate, distearyl 3,3-thiodipropionate, lauryl stearyl 3,3-thiodipropioate. And pentaerythritol-tetrakis (β-lauryl-thio-propionate), 3,9-bis (2-dodecylthioethyl) -2,4,8,10-tetraoxaspiro [5,5] undecane and the like. .

  The above-mentioned type of sulfur-based compound is commercially available from Sumitomo Chemical Co., Ltd. under the trade names “Sumilizer TPL-R” and “Sumilizer TP-D”, for example.

  The above sulfur-based compounds can be used alone or in combination of two or more thereof, and the blending amount thereof is appropriately selected within a range not impairing the object of the present invention, but with respect to the total mass of the resin forming the optical film. Usually, it is preferable to add 0.001-10.0 mass parts, More preferably, it is 0.05-5.0 mass parts, Most preferably, it is 0.05-2.0 mass parts.

[Other additives]
In the optical film of the present invention, additives such as an acid scavenger, an ultraviolet absorber, a plasticizer, a mat agent, an optical anisotropy control agent and an antistatic agent may be used in combination as other additives.

(Acid scavenger)
Since decomposition is accelerated by an acid in a high temperature environment where melt film formation is performed, the optical film of the present invention preferably contains an acid scavenger as a stabilizer. Any acid scavenger useful in the present invention can be used without limitation as long as it is a compound that reacts with an acid to inactivate the acid, and is described in U.S. Pat. No. 4,137,201. A compound having an epoxy group is preferred. Epoxy compounds as such acid scavengers are known in the art and are derived by condensation of various polyglycol diglycidyl ethers, particularly about 8 to 40 moles of ethylene oxide per mole of polyglycol. Glycol, diglycidyl ether of glycerol, etc., metal epoxy compounds (such as those conventionally used in and with vinyl chloride polymer compositions), epoxidized ether condensation products, diphenols of bisphenol A Glycidyl ether (ie, 4,4'-dihydroxydiphenyldimethylmethane), epoxidized unsaturated fatty acid ester (especially an ester of an alkyl of about 4 to 2 carbon atoms of a fatty acid of 2 to 22 carbon atoms (for example, Butyl epoxy stearate) And epoxidized vegetable oils and other unsaturated natural oils (sometimes epoxies) that may be represented and exemplified by compositions of various epoxidized long chain fatty acid triglycerides and the like (eg, epoxidized soybean oil, epoxidized linseed oil, etc.) Natural fatty glycerides or unsaturated fatty acids, which generally contain 12 to 22 carbon atoms). Further, as a commercially available epoxy group-containing epoxide resin compound, EPON 815C and other epoxidized ether oligomer condensation products of the following general formula (AD-7) can also be preferably used.

  In formula, n is an integer of 0-12. Other acid scavengers that can be used include those described in paragraphs 87 to 105 of JP-A-5-194788.

  The acid scavenger can be used singly or in combination of two or more, and the amount of the acid scavenger is appropriately selected within a range not impairing the object of the present invention, but is usually based on the total mass of the resin forming the optical film. It is preferable to add 0.001-10.0 mass parts, More preferably, it is 0.05-5.0 mass parts, Most preferably, it is 0.05-2.0 mass parts.

  In addition, although an acid scavenger may be called an acid scavenger, an acid capture agent, an acid catcher etc. with respect to resin, in this invention, it can use without a difference by these names.

(UV absorber)
In the optical film of the present invention, from the viewpoint of preventing deterioration of the polarizer or the display device with respect to ultraviolet rays, the optical film is excellent in the ability to absorb ultraviolet rays having a wavelength of 370 nm or less, and from the viewpoint of liquid crystal display properties, visible light having a wavelength of 400 nm or more It is preferable to contain an ultraviolet absorber that absorbs little. Examples of the ultraviolet absorber used in the present invention include oxybenzophenone compounds, benzotriazole compounds, salicylic acid ester compounds, benzophenone compounds, cyanoacrylate compounds, nickel complex compounds, triazine compounds, and the like. However, benzophenone compounds, less colored benzotriazole compounds, and triazine compounds are preferable. Further, ultraviolet absorbers described in JP-A Nos. 10-182621 and 8-337574, and polymer ultraviolet absorbers described in JP-A Nos. 6-148430 and 2003-113317 may be used.

  Specific examples of the benzotriazole ultraviolet absorber include 2- (2′-hydroxy-5′-methylphenyl) benzotriazole, 2- (2′-hydroxy-3 ′, 5′-di-tert-butylphenyl) benzo Triazole, 2- (2'-hydroxy-3'-tert-butyl-5'-methylphenyl) benzotriazole, 2- (2'-hydroxy-3 ', 5'-di-tert-butylphenyl) -5 Chlorobenzotriazole, 2- (2′-hydroxy-3 ′-(3 ″, 4 ″, 5 ″, 6 ″ -tetrahydrophthalimidomethyl) -5′-methylphenyl) benzotriazole, 2,2-methylenebis (4- (1,1,3,3-tetramethylbutyl) -6- (2H-benzotriazol-2-yl) phenol), 2- (2'-hydroxy- '-Tert-butyl-5'-methylphenyl) -5-chlorobenzotriazole, 2- (2'-hydroxy-3'-tert-butyl-5'-(2-octyloxycarbonylethyl) -phenyl) -5 -Chlorobenzotriazole, 2- (2'-hydroxy-3 '-(1-methyl-1-phenylethyl) -5'-(1,1,3,3-tetramethylbutyl) -phenyl) benzotriazole, 2 -(2H-benzotriazol-2-yl) -6- (linear and side chain dodecyl) -4-methylphenol, octyl-3- [3-tert-butyl-4-hydroxy-5- (chloro-2H- Benzotriazol-2-yl) phenyl] propionate and 2-ethylhexyl-3- [3-tert-butyl-4-hydroxy-5- (5-chloro-2) - can be exemplified mixtures of benzotriazol-2-yl) phenyl] propionate, and the like.

  As commercially available products, TINUVIN 171, TINUVIN 900, TINUVIN 928, TINUVIN 360 (all manufactured by Ciba Japan), LA31 (manufactured by ADEKA Corporation), RUVA- 100 (manufactured by Otsuka Chemical).

  Specific examples of benzophenone compounds include 2,4-dihydroxybenzophenone, 2,2'-dihydroxy-4-methoxybenzophenone, 2-hydroxy-4-methoxy-5-sulfobenzophenone, bis (2-methoxy-4-hydroxy- 5-benzoylphenylmethane) and the like, but are not limited thereto.

  The above ultraviolet absorbers can be used alone or in combination of two or more, and the blending amount thereof is appropriately selected within a range not impairing the object of the present invention, but with respect to the total mass of the resin forming the optical film. Usually, it is preferable to add 0.1-5 mass parts, More preferably, it is 0.2-3 mass parts, Most preferably, it is 0.5-2 mass parts.

  The benzotriazole structure or triazine structure may be part of the polymer, or may be regularly pendant to the polymer, and part of the molecular structure of other additives such as plasticizers, antioxidants, and acid scavengers. May be introduced.

  Although it does not specifically limit as a conventionally well-known ultraviolet absorptive polymer, For example, the polymer which homopolymerized RUVA-93 (made by Otsuka Chemical), the polymer which copolymerized RUVA-93, and another monomer, etc. are mentioned. . Specific examples include PUVA-30M obtained by copolymerization of RUVA-93 and methyl methacrylate at a ratio (mass ratio) of 3: 7, and PUVA-50M obtained by copolymerization at a ratio of 5: 5 (mass ratio). It is done. Furthermore, the polymer etc. which are described in Unexamined-Japanese-Patent No. 2003-113317 are mentioned.

(Plasticizer)
In the optical film of the present invention, at least one plasticizer may be added to the film.

  A plasticizer is generally an additive that has the effect of improving brittleness or imparting flexibility by being added to a polymer. In this case, a plasticizer is added in order to lower the melting temperature than the melting temperature alone, and to lower the melt viscosity of the film constituent material containing the plasticizer than the resin alone at the same heating temperature. Moreover, since it adds also in order to improve the hydrophilic property of a cellulose ester and to improve the water vapor transmission rate of an optical film, it has a function as a moisture permeation prevention agent.

  Here, the melting temperature of the film constituent material means a temperature at which the material is heated and fluidity is developed. In order to melt and flow the resin according to the present invention, it is necessary to heat at least a temperature higher than the glass transition temperature. Above the glass transition temperature, the elastic modulus or viscosity decreases due to heat absorption, and fluidity is exhibited. However, in the resin according to the present invention, the molecular weight of the cellulose ester is reduced due to thermal decomposition at the same time as melting at a high temperature, which may adversely affect the mechanical properties of the resulting film. Therefore, the resin is melted at a temperature as low as possible. There is a need. In order to lower the melting temperature of the film constituting material, it can be achieved by adding a plasticizer having a melting point or glass transition temperature lower than the glass transition temperature of the resin according to the present invention.

  The above plasticizers can be used alone or in combination of two or more, and the amount of the plasticizer is appropriately selected within a range not impairing the object of the present invention, but is 0 with respect to the total mass of the resin forming the optical film. 0.1 to 20% by mass is preferably added, and more preferably 0.2 to 10 parts by mass.

  In the present invention, an ester plasticizer comprising a polyhydric alcohol and a monovalent carboxylic acid, and an ester plasticizer comprising a polyvalent carboxylic acid and a monohydric alcohol are preferred.

  Examples of polyhydric alcohols that are raw materials for ester plasticizers include the following, but the present invention is not limited to these. Adonitol, arabitol, ethylene glycol, glycerin, diglycerin, diethylene glycol, triethylene glycol, tetraethylene glycol, 1,2-propanediol, 1,3-propanediol, dipropylene glycol, tripropylene glycol, 1,2-butanediol 1,3-butanediol, 1,4-butanediol, dibutylene glycol, 1,2,4-butanetriol, 1,5-pentanediol, 1,6-hexanediol, hexanetriol, galactitol, mannitol, 3-methylpentane-1,3,5-triol, pinacol, sorbitol, trimethylolpropane, ditrimethylolpropane, trimethylolethane, pentaerythritol, dipentaerythritol, xyl Mention may be made of the toll and the like. In particular, ethylene glycol, glycerin, and trimethylolpropane are preferable.

  Specific examples of ethylene glycol ester plasticizers that are one of the polyhydric alcohol esters include ethylene glycol alkyl ester plasticizers such as ethylene glycol diacetate and ethylene glycol dibutyrate, and ethylene glycol dicyclopropyl. Examples thereof include ethylene glycol cycloalkyl ester plasticizers such as carboxylate and ethylene glycol dicyclohexylcarboxylate, and ethylene glycol aryl ester plasticizers such as ethylene glycol dibenzoate and ethylene glycol di4-methylbenzoate. These alkylate groups, cycloalkylate groups, and arylate groups may be the same or different, and may be further substituted. Further, it may be a mix of alkylate group, cycloalkylate group and arylate group, and these substituents may be covalently bonded. Further, the ethylene glycol part may be substituted, and the ethylene glycol ester partial structure may be part of the polymer or regularly pendant, and may be an antioxidant, an acid scavenger, an ultraviolet absorber, etc. It may be introduced into a part of the molecular structure of the additive.

  Specific examples of the glycerin ester plasticizer that is one of the polyhydric alcohol esters include glycerol alkyl esters such as triacetin, tributyrin, glycerol diacetate caprylate, glycerol oleate propionate, and glycerol tricyclopropylcarboxylate. Glycerol glycerol esters such as glycerol tricyclohexyl carboxylate, glycerol aryl esters such as glycerol tribenzoate and glycerol 4-methylbenzoate, diglycerol tetraacetylate, diglycerol tetrapropionate, diglycerol acetate tricaprylate, diglycerol Tetralaurate, diglycerin alkyl ester, diglycerin tetracyclobutylcarboxylate, diglycerin tet Diglycerol cycloalkyl esters such as cyclopentyl carboxylate, diglycerin tetrabenzoate, diglycerin aryl ester such as diglycerin 3-methylbenzoate or the like. These alkylate groups, cycloalkylcarboxylate groups, and arylate groups may be the same or different, and may be further substituted. Further, it may be a mixture of alkylate group, cycloalkylcarboxylate group, and arylate group, and these substituents may be bonded by a covalent bond. Furthermore, the glycerin and diglycerin part may be substituted, the partial structure of the glycerin ester and the diglycerin ester may be part of the polymer or regularly pendant, and the antioxidant, acid scavenger, You may introduce | transduce into a part of molecular structure of additives, such as a ultraviolet absorber.

  As other polyhydric alcohol ester plasticizers, specifically, polyhydric alcohol ester plasticizers described in paragraphs 30 to 33 of JP-A-2003-12823, paragraphs 64- of JP-A-2006-188663. 74 polyhydric alcohol ester plasticizer.

  These alkylate groups, cycloalkylcarboxylate groups, and arylate groups may be the same or different, and may be further substituted. Further, it may be a mixture of alkylate group, cycloalkylcarboxylate group, and arylate group, and these substituents may be bonded by a covalent bond. Furthermore, the polyhydric alcohol part may be substituted, and the partial structure of the polyhydric alcohol may be part of the polymer or regularly pendant, and may be an antioxidant, an acid scavenger, an ultraviolet absorber. May be introduced into a part of the molecular structure of the additive.

  Among the ester plasticizers composed of the polyhydric alcohol and the monovalent carboxylic acid, alkyl polyhydric alcohol aryl esters are preferable. Specifically, the ethylene glycol dibenzoate, glycerin tribenzoate, diglycerin tetrabenzoate, penta Examples include erythritol tetrabenzoate, exemplified compound 16 described in paragraph 31 of JP-A No. 2003-12823, and exemplified compound 48 described in paragraph 71 of JP-A No. 2006-188663.

  Specific examples of the dicarboxylic acid ester plasticizer that is one of the polyvalent carboxylic acid esters include alkyl dicarboxylic acid alkyl ester plasticizers such as didodecyl malonate, dioctyl adipate, and dibutyl sebacate. Alkyl dicarboxylic acid cycloalkyl ester type plasticizers such as cyclopentyl succinate and dicyclohexyl adipate, alkyl dicarboxylic acid aryl ester type plasticizers such as diphenyl succinate and di4-methylphenyl glutarate, dihexyl-1,4-cyclohexane Cycloalkyl dicarboxylic acid alkyl ester plasticizers such as dicarboxylate and didecylbicyclo [2.2.1] heptane-2,3-dicarboxylate, dicyclohexyl-1,2-cyclobutanedicarboxylate, dicis Cycloalkyldicarboxylic acid cycloalkyl ester plasticizers such as ropropyl-1,2-cyclohexyldicarboxylate, diphenyl-1,1-cyclopropyldicarboxylate, di2-naphthyl-1,4-cyclohexanedicarboxylate, etc. Cycloalkyldicarboxylic acid aryl ester plasticizers such as diethyl phthalate, dimethyl phthalate, dioctyl phthalate, dibutyl phthalate, di-2-ethylhexyl phthalate, and other aryl dicarboxylic acid alkyl ester plasticizers, dicyclopropyl phthalate, dicyclohexyl phthalate, etc. Aryl dicarboxylic acid cycloalkyl ester plasticizers, and aryl dicarboxylic acid aryl ester plasticizers such as diphenyl phthalate and di-4-methylphenyl phthalate And the like. These alkoxy groups and cycloalkoxy groups may be the same or different, may be mono-substituted, and these substituents may be further substituted. The alkyl group and cycloalkyl group may be mixed, and these substituents may be bonded together by a covalent bond. Furthermore, the aromatic ring of phthalic acid may be substituted, and a multimer such as a dimer, trimer or tetramer may be used.

  Also, the partial structure of phthalate ester may be part of the polymer or regularly pendant to the polymer, and it may be part of the molecular structure of additives such as antioxidants, acid scavengers, and UV absorbers. It may be introduced.

  Examples of other polycarboxylic acid ester plasticizers include alkyl polycarboxylic acid alkyl esters such as tridodecyl tricarbarate and tributyl-meso-butane-1,2,3,4-tetracarboxylate. Plasticizers, alkylpolycarboxylic acid cycloalkyl ester plasticizers such as tricyclohexyltricarbarate, tricyclopropyl-2-hydroxy-1,2,3-propanetricarboxylate, triphenyl 2-hydroxy- Alkyl polyvalent carboxylic acid aryl ester plasticizers such as 1,2,3-propanetricarboxylate, tetra-3-methylphenyltetrahydrofuran-2,3,4,5-tetracarboxylate, tetrahexyl-1,2, 3,4-cyclobutanetetracarboxylate, tetrabu Cycloalkyl polycarboxylic acid alkyl ester plasticizers such as ru-1,2,3,4-cyclopentanetetracarboxylate, tetracyclopropyl-1,2,3,4-cyclobutanetetracarboxylate, tricyclohexyl- Cycloalkyl polycarboxylic acid cycloalkyl ester plasticizers such as 1,3,5-cyclohexyl tricarboxylate, triphenyl-1,3,5-cyclohexyl tricarboxylate, hexa-4-methylphenyl-1,2, Cycloalkyl polycarboxylic acid aryl ester plasticizers such as 3,4,5,6-cyclohexylhexacarboxylate, tridodecylbenzene-1,2,4-tricarboxylate, tetraoctylbenzene-1,2,4 , 5-tetracarboxylate and other aryl polyvalent Rubinoic acid alkyl ester plasticizers, tricyclopentylbenzene-1,3,5-tricarboxylate, tetracyclohexylbenzene-1,2,3,5-tetracarboxylate and other aryl polyvalent carboxylic acid cycloalkyl esters Plasticizers of aryl polyvalent carboxylic acid aryl esters such as plasticizers triphenylbenzene-1,3,5-tetracarboxylate, hexa-4-methylphenylbenzene-1,2,3,4,5,6-hexacarboxylate Agents. These alkoxy groups and cycloalkoxy groups may be the same or different, and may be mono-substituted, and these substituents may be further substituted. The alkyl group and cycloalkyl group may be mixed, and these substituents may be bonded together by a covalent bond. Furthermore, the aromatic ring of phthalic acid may be substituted, and a multimer such as a dimer, trimer or tetramer may be used. Also, the partial structure of phthalate ester may be part of the polymer or regularly pendant into the polymer, and introduced into part of the molecular structure of additives such as antioxidants, acid scavengers, UV absorbers, etc. May be.

  Among the ester plasticizers composed of the polyvalent carboxylic acid and the monohydric alcohol, alkyl dicarboxylic acid alkyl esters are preferable, and specific examples include the dioctyl adipate.

  Examples of other plasticizers used in the present invention include phosphate ester plasticizers, carbohydrate ester plasticizers, and polymer plasticizers.

  Specific examples of the phosphoric acid ester plasticizer include phosphoric acid alkyl esters such as triacetyl phosphate and tributyl phosphate, phosphoric acid cycloalkyl esters such as tricyclopentyl phosphate and cyclohexyl phosphate, triphenyl phosphate, tricresyl phosphate, Examples thereof include phosphoric acid aryl esters such as cresylphenyl phosphate, octyl diphenyl phosphate, diphenyl biphenyl phosphate, trioctyl phosphate, tributyl phosphate, trinaphthyl phosphate, trixylyl phosphate, tris ortho-biphenyl phosphate. These substituents may be the same or different, and may be further substituted. Moreover, the mix of an alkyl group, a cycloalkyl group, and an aryl group may be sufficient, and substituents may couple | bond together by the covalent bond.

  Also, alkylene bis (dialkyl phosphate) such as ethylene bis (dimethyl phosphate), butylene bis (diethyl phosphate), alkylene bis (diaryl phosphate) such as ethylene bis (diphenyl phosphate), propylene bis (dinaphthyl phosphate), phenylene bis (dibutyl) Phosphate), arylene bis (dialkyl phosphate) such as biphenylene bis (dioctyl phosphate), phosphate esters such as arylene bis (diaryl phosphate) such as phenylene bis (diphenyl phosphate) and naphthylene bis (ditoluyl phosphate). These substituents may be the same or different, and may be further substituted. Moreover, the mix of an alkyl group, a cycloalkyl group, and an aryl group may be sufficient, and substituents may couple | bond together by the covalent bond.

  Furthermore, the partial structure of the phosphate ester may be part of the polymer or may be regularly pendant, and may be introduced into part of the molecular structure of additives such as antioxidants, acid scavengers, and UV absorbers. It may be. Among the above-mentioned compounds, phosphoric acid aryl ester and arylene bis (diaryl phosphate) are preferable, and specifically, triphenyl phosphate and phenylene bis (diphenyl phosphate) are preferable.

  Next, the carbohydrate ester plasticizer will be described. The carbohydrate means a monosaccharide, disaccharide or trisaccharide in which the saccharide is present in the form of pyranose or furanose (6-membered ring or 5-membered ring). Non-limiting examples of carbohydrates include glucose, saccharose, lactose, cellobiose, mannose, xylose, ribose, galactose, arabinose, fructose, sorbose, cellotriose and raffinose. The carbohydrate ester refers to an ester compound formed by dehydration condensation of a carbohydrate hydroxyl group and a carboxylic acid, and specifically means an aliphatic carboxylic acid ester or an aromatic carboxylic acid ester of a carbohydrate. Examples of the aliphatic carboxylic acid include acetic acid and propionic acid, and examples of the aromatic carboxylic acid include benzoic acid, toluic acid, and anisic acid. Carbohydrates have a number of hydroxyl groups depending on the type, but even if a part of the hydroxyl group reacts with the carboxylic acid to form an ester compound, the whole hydroxyl group reacts with the carboxylic acid to form an ester compound. Also good. In the present invention, it is preferable that all of the hydroxyl groups react with the carboxylic acid to form an ester compound.

  Specific examples of the carbohydrate ester plasticizer include glucose pentaacetate, glucose pentapropionate, glucose pentabtylate, saccharose octaacetate, saccharose octabenzoate and the like. Among these, saccharose octaacetate, saccharose Octabenzoate is more preferred, and sucrose octabenzoate is particularly preferred.

  Examples of these compounds are listed below, but the present invention is not limited thereto.

Monopet SB: manufactured by Daiichi Kogyo Seiyaku Co., Ltd. Monopet SOA: manufactured by Daiichi Kogyo Seiyaku Co., Ltd. Specific examples of the polymer plasticizer include aliphatic hydrocarbon polymers, alicyclic hydrocarbon polymers, and ethyl polyacrylate. , Acrylic polymers such as polymethyl methacrylate, copolymers of methyl methacrylate and 2-hydroxyethyl methacrylate (eg, any ratio between 1:99 and 99: 1), polyvinyl isobutyl Ethers, vinyl polymers such as poly N-vinyl pyrrolidone, styrene polymers such as polystyrene and poly 4-hydroxystyrene, polybutylene succinates, polyesters such as polyethylene terephthalate and polyethylene naphthalate, polyethers such as polyethylene oxide and polypropylene oxide , Polyamide, polyureta , And a polyurea or the like. The number average molecular weight is preferably about 1,000 to 500,000, particularly preferably 5,000 to 200,000. If it is 1000 or less, a problem arises in volatility, and if it exceeds 500000, the plasticizing ability is lowered, and the mechanical properties of the optical film are adversely affected. These polymer plasticizers may be a homopolymer composed of one type of repeating unit or a copolymer having a plurality of repeating structures. Two or more of the above polymers may be used in combination.

(Matting agent)
In the optical film according to the present invention, a matting agent can be added in order to impart slipperiness, optical and mechanical functions. Examples of the matting agent include inorganic compound fine particles and organic compound fine particles.

  The shape of the matting agent is preferably a spherical shape, a rod shape, a needle shape, a layer shape, a flat shape or the like. Examples of the matting agent include silicon dioxide, titanium dioxide, aluminum oxide, zirconium oxide, calcium carbonate, kaolin, talc, calcined calcium silicate, hydrated calcium silicate, aluminum silicate, magnesium silicate, and calcium phosphate. Examples thereof include inorganic fine particles such as oxides, phosphates, silicates, and carbonates, and crosslinked polymer fine particles. Among these, silicon dioxide is preferable because it can reduce the haze of the film. These fine particles are preferably surface-treated with an organic substance because the haze of the film can be reduced.

  The surface treatment is preferably performed with halosilanes, alkoxysilanes, silazane, siloxane, or the like. The larger the average particle size of the fine particles, the greater the sliding effect, and the smaller the average particle size, the better the transparency. The average primary particle size of the fine particles is in the range of 0.01 to 1.0 μm. The average particle size of the primary particles of preferable fine particles is preferably 5 to 50 nm, more preferably 7 to 14 nm. These fine particles are preferably used for generating irregularities of 0.01 to 1.0 μm on the optical film surface.

  As the fine particles of silicon dioxide, Aerosil 200, 200V, 300, R972, R972V, R974, R202, R812, OX50, TT600, NAX50, etc. manufactured by Nippon Aerosil Co., Ltd. P10, KE-P30, KE-P100, KE-P150 and the like can be mentioned, and Aerosil 200V, R972V, NAX50, KE-P30 and KE-P100 are preferable. Two or more kinds of these fine particles may be used in combination.

  When using 2 or more types together, it can mix and use in arbitrary ratios. Fine particles having different average particle sizes and materials, for example, Aerosil 200V and R972V can be used in a mass ratio of 0.1: 99.9 to 99.9: 0.1.

  These matting agents are preferably added by kneading. Further, as another form, after mixing and dispersing a matting agent dispersed in a solvent in advance with a resin and / or a plasticizer and / or an antioxidant and / or an ultraviolet absorber, a solid material obtained by volatilizing or precipitating the solvent is obtained. It is preferable to use this in the process of producing the resin melt from the viewpoint that the matting agent can be uniformly dispersed in the resin.

  The matting agent can also be added to improve the mechanical, electrical and optical properties of the film.

  The slipperiness of the resulting film improves as the fine particles are added, but the haze increases as the fine particles are added, so the blending amount is appropriately selected within the range not impairing the object of the present invention. It is preferable to add 0.001-5 mass parts with respect to the total mass of resin which forms a film, More preferably, it is 0.005-1 mass part, More preferably, it is 0.01-0.5 mass part. is there.

(Optical anisotropy control agent)
A retardation increasing agent for controlling optical anisotropy is optionally added. Since these adjust the retardation of an optical film, it is preferable to use an aromatic compound having at least two aromatic rings as a retardation increasing agent. The aromatic compound is used in the range of 0.01 to 20 parts by mass with respect to the total mass of the resin forming the optical film. And it is preferable to use in 0.05-15 mass parts, and it is still more preferable to use in 0.1-10 mass parts. Two or more aromatic compounds may be used in combination. The aromatic ring of the aromatic compound includes an aromatic hetero ring in addition to the aromatic hydrocarbon ring. The aromatic hydrocarbon ring is particularly preferably a 6-membered ring (that is, a benzene ring). The aromatic heterocycle is generally an unsaturated heterocycle. The aromatic heterocycle is preferably a 5-membered ring, 6-membered ring or 7-membered ring, more preferably a 5-membered ring or 6-membered ring. Aromatic heterocycles generally have the most double bonds. As the hetero atom, a nitrogen atom, an oxygen atom and a sulfur atom are preferable, and a nitrogen atom is particularly preferable. Examples of aromatic heterocycles include furan ring, thiophene ring, pyrrole ring, oxazole ring, isoxazole ring, thiazole ring, isothiazole ring, imidazole ring, pyrazole ring, furazane ring, triazole ring, pyran ring, pyridine ring , Pyridazine ring, pyrimidine ring, pyrazine ring and 1,3,5-triazine ring. Details thereof are described in JP-A No. 2004-109410, JP-A No. 2003-344655, JP-A No. 2000-275434, JP-A No. 2000-1111914, JP-A No. 12-275434, and the like.

[Method for producing optical film]
Although the example of the manufacturing method of the optical film of this invention is demonstrated, this invention is not limited to this.

  As a method for forming the optical film of the present invention, a production method such as an inflation method, a T-die method, a calendar method, a cutting method, a casting method, an emulsion method, or a hot press method can be used. From the viewpoints of suppression and suppression of optical defects such as die lines, solution casting by casting is preferred. However, since the solvent casting method must remove the solvent remaining in the film, it is also preferable to produce the solution by melt casting from the viewpoint of production costs such as capital investment for the drying line.

(Solution casting method)
The production of the optical film by the solution casting method is a step of preparing a dope by dissolving cellulose esters and cellulose nanofibers and the above various additives in a solvent, a step of casting the dope on a belt-like or drum-like metal support It is performed by a step of drying the cast dope as a web, a step of peeling from the metal support, a step of stretching or maintaining the width, a step of further drying, and a step of winding up the finished film.

  The process for preparing the dope will be described. The concentration of cellulose ester in the dope is preferably higher because the drying load after casting on the metal support can be reduced. However, if the concentration of cellulose ester is too high, the load during filtration increases and the filtration accuracy increases. Becomes worse. The concentration for achieving both of these is preferably 10 to 35% by mass, and more preferably 15 to 25% by mass.

  The solvent used in the dope may be used alone or in combination of two or more, but it is preferable from the viewpoint of production efficiency that the good solvent and poor solvent of the cellulose ester are mixed and used. A larger amount is preferable in terms of solubility of the cellulose ester. The preferable range of the mixing ratio of the good solvent and the poor solvent is 70 to 98% by mass for the good solvent and 2 to 30% by mass for the poor solvent. With a good solvent and a poor solvent, what dissolve | melts the cellulose ester to be used independently is defined as a good solvent, and what poorly swells or does not melt | dissolve is defined as a poor solvent. Therefore, depending on the acyl group substitution degree of the cellulose ester, the good solvent and the poor solvent change. For example, when acetone is used as a solvent, cellulose acetate ester (acetyl group substitution degree 2.4), cellulose acetate propionate is a good solvent. Thus, cellulose acetate (acetyl group substitution degree 2.8) is a poor solvent.

  Although the good solvent used for this invention is not specifically limited, Organic halogen compounds, such as a methylene chloride, dioxolanes, acetone, methyl acetate, methyl acetoacetate, etc. are mentioned. Particularly preferred is methylene chloride or methyl acetate.

  Moreover, although the poor solvent used for this invention is not specifically limited, For example, methanol, ethanol, n-butanol, cyclohexane, cyclohexanone, etc. are used preferably. Moreover, it is preferable that 0.01-2 mass% of water contains in dope.

  As a method for dissolving the cellulose ester when preparing the dope described above, a general method can be used. When heating and pressurization are combined, it is possible to heat above the boiling point at normal pressure. It is preferable to stir and dissolve while heating at a temperature that is equal to or higher than the boiling point of the solvent at normal pressure and that the solvent does not boil under pressure, in order to prevent the generation of massive undissolved materials called gels and mamacos. Moreover, after mixing a cellulose ester with a poor solvent and making it wet or swell, the method of adding a good solvent and melt | dissolving is also used preferably.

  The pressurization may be performed by a method of injecting an inert gas such as nitrogen gas or a method of increasing the vapor pressure of the solvent by heating. Heating is preferably performed from the outside. For example, a jacket type is preferable because temperature control is easy.

  A higher heating temperature with the addition of a solvent is preferable from the viewpoint of the solubility of the cellulose ester, but if the heating temperature is too high, the required pressure increases and the productivity deteriorates. A preferable heating temperature is 45 to 120 ° C, more preferably 60 to 110 ° C, and still more preferably 70 ° C to 105 ° C. The pressure is adjusted so that the solvent does not boil at the set temperature.

  Alternatively, a cooling dissolution method is also preferably used, whereby the cellulose ester can be dissolved in a solvent such as methyl acetate.

  In the present invention, the method for adding the cellulose nanofibers to the cellulose ester solution is not particularly limited, but it is preferable to add the cellulose nanofibers as a dispersion in which cellulose nanofibers are dispersed in advance.

  The method for preparing the dispersion containing the cellulose nanofibers is not particularly limited, but the cellulose nanofibers are added in a solvent or binder having an affinity for the cellulose nanofibers, and dispersed by a known dispersing machine or method. be able to.

  Solvents include water, methylene chloride, methyl acetate, ethyl acetate, amyl acetate, methyl acetoacetate, acetone, tetrahydrofuran, 1,3-dioxolane, 1,4-dioxane, cyclohexanone, ethyl formate, 2,2,2-triate. Fluoroethanol, 2,2,3,3-tetrafluoro-1-propanol, 1,3-difluoro-2-propanol, 1,1,1,3,3,3-hexafluoro-2-methyl-2-propanol 1,1,1,3,3,3-hexafluoro-2-propanol, 2,2,3,3,3-pentafluoro-1-propanol, nitroethane, 1,3-dimethyl-2-imidazolidinone Organic halogen compounds such as methylene chloride, dioxolane derivatives, methyl acetate, ethyl acetate, Ton, methyl acetoacetate and the like are preferable. These solvents may be used alone or as a mixed solvent of two or more.

  As the binder, the presence of a water-soluble polymer during dispersion improves dispersibility and can reduce haze. The water-soluble polymers here include starches, mannans, seaweeds such as galactan and sodium alginate, plant mucilages such as tragacanth gum, gum arabic and dextran, proteins such as gelatin and casein, methylcellulose, hydroxycellulose and carboxymethylcellulose. Celluloses, polyvinyl alcohol, sodium polyacrylate, polyethylene oxide, polyvinyl pyrrolidone, polyacrylamide, and other synthetic polymers.

  If the molecular weight of these water-soluble polymers is too small, an effect for improving dispersibility is not recognized. Therefore, the molecular weight is preferably 10,000 or more, more preferably 30,000 to 200,000. The molecular weight can be measured by a viscosity method, a diffusion method, a light scattering method, a gel filtration method, a high performance liquid chromatography method or the like, and particularly a gel filtration method or a high performance liquid chromatography method is preferably applied.

  The water-soluble polymer is preferably added in a mass ratio of 0.05 to 30 times with respect to the cellulose nanofibers to be dispersed, and the aqueous solution is preferably in the range of 1 to 20% by mass.

  It is also a useful method to use various surfactants for dispersion. As the surfactant, any of anionic, cationic, amphoteric, nonionic and the like can be used, but anionic and nonionic surfactants are preferable, and anionic surfactants are particularly preferable. In addition, when adjusting the pH, a general acid-alkali aqueous solution such as sodium hydroxide, potassium hydroxide, acetic acid, citric acid, phosphoric acid, sulfuric acid or the like, preferably a buffer solution is used.

  Examples of the disperser used in the present invention include a centrifugal disperser (flow jet mixer, fine flow mill, etc.), a media type disperser (ball mill, sand mill, etc.), an ultrasonic disperser, a homogenizer, and a high pressure homogenizer. Of these, a centrifugal disperser and a media disperser are preferable.

  Next, the cellulose ester solution to which the cellulose nanofibers are added is filtered using an appropriate filter medium such as filter paper. As the filter medium, it is preferable that the absolute filtration accuracy is small in order to remove insoluble matters and the like. However, if the absolute filtration accuracy is too small, there is a problem that the filter medium is likely to be clogged. For this reason, a filter medium with an absolute filtration accuracy of 0.008 mm or less is preferable, a filter medium with 0.001 to 0.008 mm is more preferable, and a filter medium with 0.003 to 0.006 mm is more preferable.

  There are no particular restrictions on the material of the filter medium, and ordinary filter media can be used. However, plastic filter media such as polypropylene and Teflon (registered trademark), and metal filter media such as stainless steel do not drop off fibers. preferable. It is preferable to remove and reduce impurities, particularly bright spot foreign matter, contained in the raw material cellulose ester by filtration.

  The dope can be filtered by a normal method, but the method of filtering while heating at a temperature not lower than the boiling point of the solvent at normal pressure and in a range where the solvent does not boil under pressure is the filtration pressure before and after filtration. The increase in the difference (referred to as differential pressure) is small and preferable. A preferred temperature is 45 to 120 ° C, more preferably 45 to 70 ° C, and even more preferably 45 to 55 ° C.

  A smaller filtration pressure is preferred. The filtration pressure is preferably 1.6 MPa or less, more preferably 1.2 MPa or less, and further preferably 1.0 MPa or less.

  Here, the dope casting will be described.

  The metal support in the casting (casting) step preferably has a mirror-finished surface. As the metal support, a stainless steel belt or a drum whose surface is plated with a casting is preferably used. The cast width can be 1 to 4 m. The surface temperature of the metal support in the casting step is set to −50 ° C. to a temperature at which the solvent boils and does not foam. A higher temperature is preferable because the web can be dried faster, but if it is too high, the web may foam or the flatness may deteriorate. A preferable support temperature is appropriately determined at 0 to 100 ° C, and more preferably 5 to 30 ° C. Alternatively, it is also a preferable method that the web is gelled by cooling and peeled from the drum in a state containing a large amount of residual solvent. The method for controlling the temperature of the metal support is not particularly limited, and there are a method of blowing hot air or cold air, and a method of contacting hot water with the back side of the metal support. It is preferable to use warm water because heat transfer is performed efficiently, so that the time until the temperature of the metal support becomes constant is short. When using warm air, considering the temperature drop of the web due to the latent heat of vaporization of the solvent, while using warm air above the boiling point of the solvent, there may be cases where wind at a temperature higher than the target temperature is used while preventing foaming. . In particular, it is preferable to efficiently dry by changing the temperature of the support and the temperature of the drying air during the period from casting to peeling.

  In the present invention, it is also preferable to cast the cellulose ester solution by dividing it into two or more times. By dividing the cast in this way, it becomes possible to easily control the distribution state of cellulose nanofibers in the film membrane, and to control the tear strength, elastic modulus, and degree of film dimensional change of the film as required. Can do.

  In order for the optical film to exhibit good flatness, the residual solvent amount when peeling the web from the metal support is preferably 10 to 150% by mass, more preferably 20 to 40% by mass or 60 to 130% by mass. Yes, particularly preferably 20 to 30% by mass or 70 to 120% by mass.

  In the present invention, the amount of residual solvent is defined by the following formula.

Residual solvent amount (% by mass) = {(MN) / N} × 100
Note that M is the mass of a sample collected during or after the production of the web or film, and N is the mass after heating M at 115 ° C. for 1 hour.

  In the drying step of the optical film, the web is peeled off from the metal support, and further dried, so that the residual solvent amount is preferably 1% by mass or less, more preferably 0.1% by mass or less. Preferably it is 0-0.01 mass% or less.

  In the film drying process, generally, a roll drying method (a method in which a plurality of rolls arranged on the upper and lower sides are alternately passed through and dried) or a method of drying while transporting the web by a tenter method is adopted.

  The optical film of the present invention can be stretched in the transport direction where the amount of residual solvent of the web immediately after peeling from the metal support is large, and further stretched in the width direction by a tenter system that grips both ends of the web with clips or the like. preferable.

  In order to stretch in the machine direction immediately after peeling, it is preferable to stretch by peeling tension and subsequent transport tension. For example, it is preferable to peel at a peeling tension of 210 N / m or more, and particularly preferably 220 to 300 N / m.

  The means for drying the web is not particularly limited, and can be generally performed with hot air, infrared rays, a heating roll, microwave, or the like, but it is preferably performed with hot air in terms of simplicity.

  The drying temperature in the web drying step is preferably increased stepwise from 30 to 200 ° C, and more preferably stepwise increased from 50 to 180 ° C in order to improve dimensional stability.

  Although the film thickness of an optical film is not specifically limited, 10-200 micrometers is used preferably. The film thickness is particularly preferably 10 to 80 μm, and more preferably 20 to 80 μm. An optical film having a multilayer structure by a co-casting method can also be preferably used.

  The optical film of the present invention has a width of 1 m or more and preferably has a width of 1.4 to 4 m. Especially preferably, it is 1.4-3 m. If it exceeds 4 m, conveyance becomes difficult. The center line average roughness (Ra) of the optical film surface is preferably in the range of 0.001 to 1 μm.

  The optical film of the present invention is useful as a polarizing plate protective film, and can be preferably used as a retardation film that is used for viewing angle expansion having a desired retardation.

  When producing the optical film of the present invention as a retardation film, and further as a retardation film combined with the function of a polarizing plate protective film, it is necessary to perform refractive index control, the refractive index control is the type of cellulose ester, The degree of acyl group substitution, the type and content of cellulose nanofibers, the type and content of additives, the film thickness, the stretching operation, and the like can be controlled, but the stretching operation is preferably performed.

(Melt casting method)
As described above, the optical film of the present invention is also preferably produced by melt casting from the viewpoint of production cost. The molding method by melt casting, which is heated and melted without using the solvent used in the solution casting method (for example, methylene chloride, etc.), more specifically, melt extrusion molding method, press molding method, inflation method, injection molding method And can be classified into blow molding, stretch molding and the like. Among these, in order to obtain a polarizing plate protective film having excellent mechanical strength and surface accuracy, the melt extrusion method is excellent.

  Hereinafter, the manufacturing method of the optical film of the present invention will be described by taking the melt extrusion method as an example.

  FIG. 1 is a schematic flow sheet showing the overall configuration of an apparatus for carrying out the method for producing an optical film according to the present invention, and FIG. 2 is an enlarged view of a cooling roll portion from a casting die.

  1 and 2, the method for producing an optical film according to the present invention comprises mixing film materials and then extruding from a casting die 4 onto a first cooling roll 5 by using an extruder 1 to produce a first cooling roll. 5, and is further circumscribed in order by a total of three cooling rolls of the second cooling roll 7 and the third cooling roll 8, and is cooled and solidified to form a film 10. Next, the film 10 peeled off by the peeling roll 9 is then stretched in the width direction by holding both ends of the film by the stretching device 12 and then wound by the winding device 16. In addition, a touch roll 6 is provided that clamps the molten film on the surface of the first cooling roll 5 in order to correct the flatness. The touch roll 6 has an elastic surface and forms a nip with the first cooling roll 5. Details of the touch roll 6 will be described later.

  In the method for producing an optical film according to the present invention, the conditions for melt extrusion can be carried out in the same manner as the conditions used for other thermoplastic resins such as polyester. The material is preferably dried beforehand. It is desirable to dry the moisture to 1000 ppm or less, preferably 200 ppm or less by using a vacuum or reduced pressure drier or a dehumidifying hot air drier.

  For example, resin dried under hot air, vacuum or reduced pressure is melted at an extrusion temperature of about 200 to 300 ° C. using the extruder 1, filtered through a leaf disk type filter 2, and the like to remove foreign matters.

  When introducing into the extruder 1 from a supply hopper (not shown), it is preferable to prevent oxidative decomposition or the like under vacuum, reduced pressure, or inert gas atmosphere.

  When additives such as a plasticizer are not mixed in advance, they may be kneaded in the middle of the extruder. In order to add uniformly, it is preferable to use a mixing apparatus such as a static mixer 3.

  In the present invention, the resin and other additives that are added as necessary are preferably mixed before melting, and more preferably the resin and the additive are mixed before heating. Mixing may be performed by a mixer or the like, or may be performed in the resin preparation process as described above. When a mixer is used, a general mixer such as a V-type mixer, a conical screw type mixer, a horizontal cylindrical type mixer, a Henschel mixer, or a ribbon mixer can be used.

  After the film constituent materials are mixed as described above, the mixture may be directly melted using the extruder 1 to form a film. Once the film constituent materials are pelletized, the pellets are extruded. The film may be melted by the machine 1 to form a film. When the film constituent material includes a plurality of materials having different melting points, a so-called braided semi-melt is once produced at a temperature at which only the material having a low melting point is melted, and the semi-melt is supplied to the extruder 1. It is also possible to form a film by introducing it. If the film component contains a material that is easily pyrolyzed, in order to reduce the number of times of melting, a method of directly forming a film without producing pellets, or after making a paste-like semi-molten material as described above A method of forming a film is preferred.

  As the extruder 1, various commercially available extruders can be used, but a melt-kneading extruder is preferable, and a single-screw extruder or a twin-screw extruder may be used. When forming a film directly without producing pellets from film constituent materials, it is preferable to use a twin-screw extruder because an appropriate degree of kneading is necessary, but even with a single-screw extruder, the screw shape is a Maddock type. By changing to a kneading type screw such as a unimelt type or a dull mage, moderate kneading can be obtained, so that it can be used. When a pellet or braided semi-melt is once used as a film constituent material, it can be used in either a single screw extruder or a twin screw extruder.

  In the extruder 1 and the cooling step after extrusion, it is preferable to reduce the oxygen concentration by replacing with an inert gas such as nitrogen gas or by reducing the pressure.

  The preferable conditions for the melting temperature of the film constituent material in the extruder 1 vary depending on the viscosity and discharge amount of the film constituent material, the thickness of the sheet to be manufactured, etc., but generally the glass transition temperature Tg of the film Tg to Tg + 100 ° C., preferably Tg + 10 ° C. to Tg + 90 ° C. The melt viscosity at the time of extrusion is 1 to 10000 Pa · s, preferably 10 to 1000 Pa · s. Further, the residence time of the film constituting material in the extruder 1 is preferably short, and is within 5 minutes, preferably within 3 minutes, more preferably within 2 minutes.

  The residence time depends on the type of the extruder 1 and the extrusion conditions, but can be shortened by adjusting the material supply amount, L / D, screw rotation speed, screw groove depth, and the like. is there.

  The shape, rotation speed, and the like of the screw of the extruder 1 are appropriately selected depending on the viscosity, the discharge amount, and the like of the film constituent material. In the present invention, the shear rate in the extruder 1 is 1 / second to 10000 / second, preferably 5 / second to 1000 / second, more preferably 10 / second to 100 / second.

  The extruder 1 that can be used in the present invention is generally available as a plastic molding machine.

  The film constituent material extruded from the extruder 1 is sent to the casting die 4 and extruded from the slit of the casting die 4 into a film shape. The casting die 4 is not particularly limited as long as it is used for producing a sheet or a film. The material of the casting die 4 is sprayed or plated with hard chromium, chromium carbide, chromium nitride, titanium carbide, titanium carbonitride, titanium nitride, super steel, ceramic (tungsten carbide, aluminum oxide, chromium oxide), etc. Processing such as buffing, lapping using a # 1000 or higher grinding wheel, plane cutting using a # 1000 or higher diamond grinding wheel (the cutting direction is perpendicular to the resin flow direction), electrolytic polishing, electrolytic composite polishing, etc. And the like. A preferred material for the lip portion of the casting die 4 is the same as that of the casting die 4. The surface accuracy of the lip is preferably 0.5S or less, and more preferably 0.2S or less.

  The slit of the casting die 4 is configured so that the gap can be adjusted. This is shown in FIG. Of the pair of lips forming the slit 32 of the casting die 4, one is a flexible lip 33 having low rigidity and easily deformed, and the other is a fixed lip 34. A large number of heat bolts 35 are arranged at a constant pitch in the width direction of the casting die 4, that is, in the length direction of the slits 32. Each heat bolt 5 is provided with a block 36 having an embedded electric heater 37 and a cooling medium passage, and each heat bolt 35 penetrates each block 36 vertically. The base of the heat bolt 35 is fixed to the die body 31, and the tip is in contact with the outer surface of the flexible lip 33. While constantly cooling the block 36, the input to the embedded electric heater 37 is increased or decreased to increase or decrease the temperature of the block 36, thereby causing the heat bolt 35 to thermally expand and contract, thereby displacing the flexible lip 33 and thereby increasing the film thickness. adjust. Thickness gauges are installed at the required locations in the wake of the die, and the web thickness information detected by this is fed back to the control device. This thickness information is compared with the set thickness information by the control device, and corrections coming from the device It is also possible to control the power or ON rate of the heat bolt heating element by a control amount signal. The heat bolt preferably has a length of 20 to 40 cm and a diameter of 7 to 14 mm, and a plurality of, for example, several tens of heat bolts are preferably arranged at a pitch of 20 to 40 mm. Instead of the heat bolt, a gap adjusting member mainly composed of a bolt for adjusting the slit gap by manually moving back and forth in the axial direction may be provided. The slit gap adjusted by the gap adjusting member is usually 200 to 1000 μm, preferably 300 to 800 μm, more preferably 400 to 600 μm.

  The first to third cooling rolls are made of seamless steel pipe having a wall thickness of about 20 to 30 mm, and the surface is finished to a mirror surface. Inside, a pipe for flowing a coolant is arranged so that heat can be absorbed from the film on the roll by the coolant flowing through the pipe. Of the first to third cooling rolls, the first cooling roll 5 corresponds to the rotary support according to the present invention.

  On the other hand, the touch roll 6 in contact with the first cooling roll 5 has an elastic surface and is deformed along the surface of the first cooling roll 5 by the pressing force to the first cooling roll 5. A nip is formed between the two. The touch roll 6 is also called a pinching rotary body. As the touch roll 6, a touch roll disclosed in registered patent 3194904, registered patent 3422798, Japanese Patent Application Laid-Open No. 2002-36332, Japanese Patent Application Laid-Open No. 2002-36333, or the like can be preferably used. These can also use what is marketed. These will be described in more detail below.

  FIG. 4 is a cross-sectional view showing an example of the pinching rotator. (The 1st example of touch roll 6 (henceforth, outline section of touch roll A)) is shown. As shown in the drawing, the touch roll A has an elastic roller 42 disposed inside a flexible metal sleeve 41.

  The metal sleeve 41 is made of stainless steel having a thickness of 0.3 mm and has flexibility. If the metal sleeve 41 is too thin, the strength is insufficient, whereas if it is too thick, the elasticity is insufficient. For these reasons, the thickness of the metal sleeve 41 is preferably 0.1 to 1.5 mm. The elastic roller 42 is formed in a roll shape by providing a rubber 44 on the surface of a metal inner cylinder 43 that is rotatable via a bearing. When the touch roll A is pressed toward the first cooling roll 5, the elastic roller 42 presses the metal sleeve 41 against the first cooling roll 5, and the metal sleep 41 and the elastic roller 42 have the shape of the first cooling roll 5. It deforms corresponding to the familiar shape, and forms a nip with the first cooling roll. Cooling water 45 flows in a space formed between the metal sleeve 41 and the elastic roller 42.

  FIG. 5 is a cross-sectional view taken along a plane perpendicular to the rotation axis, showing a second example (hereinafter referred to as touch roll B) of the pinching rotator.

  FIG. 6 is a cross-sectional view showing an example of a plane including the rotation axis of the second example (touch roll B) of the pinching rotator.

  5 and 6 show a touch roll B which is another embodiment of the pinching rotator. The touch roll B includes a flexible, seamless stainless steel pipe (thickness 4 mm) outer cylinder 51, and a highly rigid metal inner cylinder 52 arranged on the same axis as the inner side of the outer cylinder 51. It is roughly composed. A coolant 54 flows in the space 53 between the outer cylinder 51 and the inner cylinder 52. Specifically, in the touch roll B, outer cylinder support flanges 56a and 56b are attached to the rotation shafts 55a and 55b at both ends, and a thin metal outer cylinder 51 is attached between the outer peripheral portions of the both outer cylinder support flanges 56a and 56b. Yes. A fluid supply pipe 59 is disposed in the same axial center in a fluid discharge hole 58 formed in the axial center portion of one rotary shaft 55a and forming a fluid return passage 57. The fluid supply pipe 59 is thin-walled. It is connected and fixed to a fluid shaft cylinder 60 arranged at the axial center in the metal outer cylinder 51. Inner cylinder support flanges 61a and 61b are attached to both ends of the fluid shaft cylinder 60, respectively, and a thickness of about 15 to 20 mm between the outer periphery of the inner cylinder support flanges 61a and 61b and the other end side outer cylinder support flange 56b. A metal inner cylinder 52 having a thickness is attached. A cooling liquid flow space 53 of, for example, about 10 mm is formed between the metal inner cylinder 52 and the thin metal outer cylinder 51, and the metal inner cylinder 52 has a flow space 53 and an inner space near both ends. An outlet 52a and an inlet 52b are formed to communicate with the intermediate passages 62a and 62b outside the cylinder support flanges 61a and 61b, respectively.

  Further, the outer cylinder 51 is thinned within a range in which the thin cylinder theory of elastic mechanics can be applied in order to have flexibility, flexibility, and resilience close to rubber elasticity. The flexibility evaluated by the thin-walled cylinder theory is expressed by the thickness t / roll radius r, and the flexibility increases as t / r decreases. In this touch roll B, the flexibility is the optimum condition when t / r ≦ 0.03. Usually, the touch roll generally used has a roll diameter R = 200 to 500 mm (roll radius r = R / 2), a roll effective width L = 500 to 1600 mm, and a horizontally long shape with r / L <1. is there. As shown in FIG. 6, for example, when the roll diameter R = 300 mm and the roll effective width L = 1200 mm, the appropriate range of the wall thickness t is 150 × 0.03 = 4.5 mm or less, but the molten sheet width is 1300 mm. On the other hand, when the average linear pressure is clamped at 98 N / cm, the equivalent spring constant is equal by setting the wall thickness of the outer cylinder 51 to 3 mm compared to the rubber roll of the same shape. The nip width k in the roll rotation direction of the nip is also about 9 mm, which is almost the same as the nip width of this rubber roll of about 12 mm. The deflection amount at the nip width k is about 0.05 to 0.1 mm.

  Here, t / r ≦ 0.03. However, in the case of a general roll diameter R = 200 to 500 mm, flexibility is sufficiently obtained especially in the range of 2 mm ≦ t ≦ 5 mm. Thinning by processing can be easily performed, and it is an extremely practical range. If the wall thickness is 2 mm or less, high-precision processing cannot be performed due to elastic deformation during processing.

  The converted value of 2 mm ≦ t ≦ 5 mm is 0.008 ≦ t / r ≦ 0.05 with respect to a general roll diameter, but in practical use, the roll diameter under the condition of t / r≈0.03. The wall thickness should be increased in proportion to For example, when roll diameter: R = 200, t = 2 to 3 mm, and when roll diameter: R = 500, t = 4 to 5 mm.

  The touch rolls A and B are urged toward the first cooling roll by urging means (not shown). The urging force of the urging means is F, and the value F / W (linear pressure) obtained by dividing the width of the film in the nip in the direction along the rotation axis of the first cooling roll 5 is 9.8 to 147 N / cm. Set to

  According to the present embodiment, a nip is formed between the touch rolls A and B and the first cooling roll 5, and the flatness may be corrected while the film passes through the nip. Accordingly, since the film is sandwiched over a long time with a small linear pressure compared to the case where the touch roll is formed of a rigid body and no nip is formed between the first cooling roll and the flatness is more reliably corrected. Can do. That is, when the linear pressure is smaller than 9.8 N / cm, the die line cannot be sufficiently eliminated. On the other hand, if the linear pressure is greater than 147 N / cm, the film is difficult to pass through the nip, resulting in unevenness in place of the film thickness.

  Moreover, since the surface of the touch rolls A and B can be made smoother than the case where the surface of the touch rolls is made of rubber, the surface of the touch rolls A and B can be made smoother. Obtainable. In addition, as a material of the elastic body 44 of the elastic roller 42, ethylene propylene rubber, neoprene rubber, silicon rubber, or the like can be used.

  Now, in order to satisfactorily eliminate the die line by the touch roll 6, it is important that the viscosity of the film when the touch roll 6 clamps the film is in an appropriate range. Cellulose esters are known to have relatively large changes in viscosity with temperature. Therefore, in order to set the viscosity when the touch roll 6 clamps the optical film to an appropriate range, it is important to set the temperature of the film when the touch roll 6 clamps the film to an appropriate range. . When the glass transition temperature of the optical film is Tg, it is preferable to set the temperature T of the film immediately before the film is sandwiched between the touch rolls 6 so as to satisfy Tg <T <Tg + 110 ° C. If the film temperature T is lower than Tg, the viscosity of the film is too high and the die line cannot be corrected. On the contrary, if the temperature T of the film is higher than Tg + 110 ° C., the film surface and the roll do not adhere uniformly, and the die line cannot be corrected. Preferably, Tg + 10 ° C. <T2 <Tg + 90 ° C., more preferably Tg + 20 ° C. <T2 <Tg + 70 ° C. In order to set the temperature of the film when the touch roll 6 clamps the optical film to an appropriate range, the first cooling roll starts from the position P1 at which the melt extruded from the casting die 4 contacts the first cooling roll 5. What is necessary is just to adjust the length L along the rotation direction of the 1st cooling roll 5 of the nip of 5 and the touch roll 6. FIG.

  In the present invention, preferred materials for the first roll 5 and the second roll 6 include carbon steel, stainless steel, resin, and the like. The surface accuracy is preferably increased, and the surface roughness is set to 0.3 S or less, more preferably 0.01 S or less. In the present invention, it was discovered that the die line correction effect is more greatly manifested by reducing the pressure from the opening (lip) of the casting die 4 to the first roll 5 to 70 kPa or less. The reduced pressure is preferably 50 to 70 kPa. Although there is no restriction | limiting in particular as a method of keeping the pressure of the part from the opening part (lip | rip) of the casting die 4 to the 1st roll 5 below 70 kPa, Cover the roll periphery from the casting die 4 with a pressure | voltage resistant member, and reduce pressure. There are methods. At this time, the suction device is preferably subjected to a treatment such as heating with a heater so that the device itself does not become a place where the sublimate is attached. In the present invention, if the suction pressure is too small, the sublimate cannot be sucked effectively, so it is necessary to set the suction pressure to an appropriate value.

  In the present invention, a film-like resin in a molten state from the T die 4 is cooled and solidified while being brought into close contact with the first roll (first cooling roll) 5, the second cooling roll 7, and the third cooling roll 8 in order. The unstretched resin film 10 is obtained.

  In the embodiment of the present invention shown in FIG. 1, the cooled and solidified unstretched film 10 peeled from the third cooling roll 8 by the peeling roll 9 is guided to a stretching machine 12 via a dancer roll (film tension adjusting roll) 11. Therefore, the film 10 is stretched in the transverse direction (width direction). By this stretching, the molecules in the film are oriented.

  As a method for stretching the film in the width direction, a known tenter or the like can be preferably used. In particular, it is preferable to set the stretching direction to the width direction because lamination with a polarizing film can be performed in a roll form. By stretching in the width direction, the slow axis of the optical film becomes the width direction.

  On the other hand, the transmission axis of the polarizing film is also usually in the width direction. By incorporating a polarizing plate in which the transmission axis of the polarizing film and the slow axis of the optical film are parallel to each other into the liquid crystal display device, the display contrast of the liquid crystal display device can be increased and a good viewing angle can be obtained. Is obtained.

  The glass transition temperature Tg of the film constituting material can be controlled by varying the material type constituting the film and the ratio of the constituting material. When a retardation film is produced as an optical film, Tg is preferably 120 ° C. or higher, preferably 135 ° C. or higher. In the liquid crystal display device, in the image display state, the temperature environment of the film changes due to the temperature rise of the device itself, for example, the temperature rise derived from the light source. At this time, if the Tg of the film is lower than the use environment temperature of the film, the retardation value derived from the orientation state of the molecules fixed inside the film by stretching and the dimensional shape as the film are greatly changed.

  If the Tg of the film is too high, the temperature is increased when the film constituent material is made into a film, so that the energy consumption for heating is increased, and the material itself may be decomposed when it is made into a film, resulting in coloring. Therefore, Tg is preferably 250 ° C. or lower.

  The stretching step may be performed by known heat setting conditions, cooling, and relaxation treatment, and may be appropriately adjusted so as to have the characteristics required for the target optical film.

(Stretching process)
In order to provide the physical properties of the retardation film and the functionality of the retardation film for expanding the viewing angle of the liquid crystal display device, the stretching step and the heat setting treatment are appropriately selected and performed. When such a stretching step and heat setting treatment are included, the heating and pressurizing step is performed before the stretching step and heat setting treatment.

  When the optical film of the present invention is manufactured as a retardation film, and further as a retardation film in which the functions of a polarizing plate protective film are combined, it is necessary to perform refractive index control, and the refractive index control may be performed by a stretching operation. preferable. Hereinafter, the stretching method will be described.

  In the retardation film stretching process, the required retardation is achieved by stretching 1.0 to 6.0 times in one direction of the film and 1.01 to 6.0 times in the direction perpendicular to the film plane. Ro and Rt can be controlled. Here, Ro indicates in-plane retardation, and Rt indicates thickness direction retardation.

  Retardation Ro and Rt are calculated | required by a following formula.

Formula (i) Ro = (nx−ny) × d
Formula (ii) Rt = ((nx + ny) / 2−nz) × d
(Where nx is the refractive index in the slow axis direction in the film plane, ny is the refractive index in the fast axis direction in the film plane, nz is the refractive index in the thickness direction of the film (refractive index is 23 ° C., 55 (Measured at a wavelength of 590 nm in an environment of% RH), d represents the thickness (nm) of the film.)
The refractive index of the optical film is an Abbe refractometer (4T), the thickness of the film is a commercially available micrometer, and the retardation value is an automatic birefringence meter KOBRA-21ADH (Oji Scientific Instruments). Etc.) can be used for measurement.

  Stretching can be performed, for example, sequentially or simultaneously in the longitudinal direction of the film and the direction orthogonal to the longitudinal direction of the film, that is, the width direction. At this time, if the stretching ratio in at least one direction is too small, a sufficient phase difference cannot be obtained, and if it is too large, stretching becomes difficult and film breakage may occur.

  For example, when stretching in the melt casting direction (longitudinal direction), if the shrinkage in the width direction is too large, the value of nz becomes too large. In this case, it can be improved by suppressing the width shrinkage of the film or stretching in the width direction. When stretching in the width direction, the refractive index may be distributed in the width direction. This distribution may appear when the tenter method is used. By stretching the film in the width direction, a shrinkage force is generated at the center of the film, and the phenomenon is caused by the end being fixed. It is thought to be called the Boeing phenomenon. Even in this case, by stretching in the casting direction, the bowing phenomenon can be suppressed and the distribution of the phase difference in the width direction can be reduced.

  By stretching in the biaxial directions perpendicular to each other, the film thickness variation of the obtained film can be reduced. When the film thickness variation of the retardation film is too large, the retardation becomes uneven, and unevenness such as coloring may be a problem when used in a liquid crystal display.

  The film thickness variation of the optical film is preferably in the range of ± 3%, and more preferably ± 1%. For the purposes as described above, the method of stretching in the biaxial directions perpendicular to each other is effective, and the stretching ratios in the biaxial directions perpendicular to each other are finally 1.01 to 4.0 times in the casting direction, respectively. The width direction is preferably 1.01 to 4.0 times, preferably 1.1 to 3.0 times in the casting direction and 1.2 to 3.0 times in the width direction. It is more preferred to obtain the required retardation value.

  When the absorption axis of the polarizer exists in the longitudinal direction, the transmission axis of the polarizer coincides with the width direction. In order to obtain a long polarizing plate by roll-to-roll bonding, the retardation film is preferably stretched so as to obtain a slow axis in the width direction.

  For example, when a cellulose ester that obtains positive birefringence with respect to stress is used, the slow axis of the retardation film can be provided in the width direction by stretching in the width direction from the above-described configuration.

In this case, in order to improve the display quality, the slow axis of the retardation film is preferably in the width direction, and in order to obtain the desired retardation value,
Formula (stretch ratio in the width direction)> (stretch ratio in the casting direction)
It is necessary to satisfy the following conditions.

  After stretching, after slitting the edge of the film to a product width by the slitter 13, the film is subjected to knurling (embossing) on both ends of the film by a knurling device comprising an embossing ring 14 and a back roll 15. By winding with the winder 16, sticking in the optical film (original winding) F and generation of scratches are prevented. The knurling method can process a metal ring having an uneven pattern on its side surface by heating or pressing. In addition, since the grip part of the clip of the both ends of a film is deform | transforming normally and cannot be used as a film product, it is cut out and reused as a raw material.

  Next, in the film winding process, the film is wound on the take-up roll while keeping the shortest distance between the outer peripheral face of the cylindrical roll film and the outer peripheral face of the mobile transport roll immediately before the roll. It is. In addition, a means such as a static elimination blower for removing or reducing the surface potential of the film is provided in front of the winding roll.

  The winding machine related to the production of the optical film according to the present invention may be a commonly used winding method such as a constant tension method, a constant torque method, a taper tension method, a program tension control method with a constant internal stress, etc. Can be rolled up. In addition, it is preferable that the initial winding tension at the time of winding of a polarizing plate protective film is 90.2-300.8 N / m.

  In the film winding step in the method according to the present invention, the film is preferably wound under environmental conditions of a temperature of 20 to 30 ° C. and a humidity of 20 to 60% RH. Thus, the tolerance of the humidity change of thickness direction retardation (Rt) improves by prescribing | regulating the temperature and humidity in the winding-up process of a film.

  If the temperature in the winding process is less than 20 ° C., wrinkles are generated and the film winding quality is deteriorated, which is unpractical. If the temperature in the film winding process exceeds 30 ° C., wrinkles are also generated, and the film winding quality is deteriorated, so that it cannot be put into practical use.

  Moreover, if the humidity in the film winding process is less than 20% RH, it is not preferable because it is easily charged and cannot be put into practical use due to deterioration in film winding quality. If the humidity in the film winding process exceeds 60% RH, the winding quality, sticking failure, and transportability deteriorate, which is not preferable.

  When winding the polarizing plate protective film in a roll shape, the winding core may be any material as long as it is a cylindrical core, but is preferably a hollow plastic core, as a plastic material May be any heat-resistant plastic that can withstand the heat treatment temperature, and examples thereof include phenol resins, xylene resins, melamine resins, polyester resins, and epoxy resins. A thermosetting resin reinforced with a filler such as glass fiber is preferred. For example, a hollow plastic core: a wound core made of FRP and having an outer diameter of 6 inches (hereinafter, inch represents 2.54 cm) and an inner diameter of 5 inches is used.

  The number of windings to these winding cores is preferably 100 windings or more, more preferably 500 windings or more, the winding thickness is preferably 5 cm or more, and the width of the film substrate is 80 cm or more. It is preferably 1 m or more.

  Although the film thickness of the optical film according to the present invention varies depending on the purpose of use, the finished film is preferably 10 to 500 μm. In particular, the lower limit is 20 μm or more, preferably 35 μm or more. The upper limit is 150 μm or less, preferably 120 μm or less. A particularly preferable range is 25 to 90 μm. When the retardation film also serves as a polarizing plate protective film, if the film is thick, the polarizing plate after polarizing plate processing becomes too thick, especially for liquid crystal displays used in notebook computers and mobile electronic devices for thin and lightweight purposes. Not suitable. On the other hand, if the film is thin, it is difficult to develop retardation as a retardation film. In addition, the moisture permeability of the film increases, and the ability to protect the polarizer from humidity decreases, which is not preferable.

  The slow axis or the fast axis of the retardation film exists in the film plane, and θ1 is −1 to + 1 °, preferably −0.5 to + 0.5 °, where θ1 is an angle formed with the film forming direction. To be.

  This θ1 can be defined as an orientation angle, and the measurement of θ1 can be performed using an automatic birefringence meter KOBRA-21ADH (manufactured by Oji Scientific Instruments).

  When each θ1 satisfies the above relationship, it contributes to obtaining high luminance in a display image, suppressing or preventing light leakage, and contributing to faithful color reproduction in a color liquid crystal display device.

  When the retardation film is used for the multi-domain VA mode, the retardation film is arranged in the above region with the fast axis of the retardation film being θ1, which contributes to the improvement of display image quality. When the plate and the liquid crystal display device are in the MVA mode, for example, the configuration shown in FIG. 7 can be adopted.

  In FIG. 7, 21a and 21b are protective films, 22a and 22b are retardation films, 25a and 25b are polarizers, 23a and 23b are slow axis directions of the film, 24a and 24b are transmission axis directions of the polarizer, 26a, Reference numeral 26b denotes a polarizing plate, 27 denotes a liquid crystal cell, and 29 denotes a liquid crystal display device.

  The retardation Ro distribution in the in-plane direction of the optical film is preferably adjusted to 5% or less, more preferably 2% or less, and particularly preferably 1.5% or less. Further, the retardation Rt distribution in the thickness direction of the film is preferably adjusted to 10% or less, more preferably 2% or less, and particularly preferably 1.5% or less.

  In the retardation film, the retardation value distribution variation is preferably small. When a polarizing plate including a retardation film is used in a liquid crystal display device, the retardation distribution variation is preferably small from the viewpoint of preventing color unevenness and the like. .

  The retardation film is adjusted to have a retardation value suitable for improving the display quality of the VA mode or TN mode liquid crystal cell, and is preferably used for the MVA mode by dividing the retardation film into the above multi-domain as the VA mode. In order to achieve this, it is required to adjust the in-plane retardation Ro to 20 nm to 200 nm and the thickness direction retardation Rt to 70 nm to 400 nm.

  The in-plane retardation Ro was observed obliquely from the normal line of the display surface when the two polarizing plates were arranged in crossed Nicols and the liquid crystal cell was arranged between the polarizing plates, for example, as shown in FIG. It mainly compensates for light leakage due to the deviation of the polarizing plate from the crossed Nicols state. The retardation Rt in the thickness direction mainly compensates for the birefringence of the liquid crystal cell similarly observed when viewed from an oblique direction when the liquid crystal cell is in the black display state in the TN mode or VA mode, particularly in the MVA mode. To contribute.

  As shown in FIG. 7, in the liquid crystal display device, when two polarizing plates are arranged above and below the liquid crystal cell, 22a and 22b in the figure select the distribution of the thickness direction retardation Rt. It is preferable that the total value of both of the above-mentioned ranges and the thickness direction retardation Rt be larger than 140 nm and 500 nm or less. In this case, in-plane retardation Ro and thickness direction retardation Rt of 22a and 22b are preferably the same for improving productivity of an industrial polarizing plate. Particularly preferably, the in-plane retardation Ro is 35 nm or more and 95 nm or less, and the thickness direction retardation Rt is 90 nm or more and 180 nm or less, which is applied to the liquid crystal cell of the MVA mode with the configuration of FIG.

  In the liquid crystal display device, for example, a TAC film having an in-plane retardation Ro = 0 to 4 nm and a thickness direction retardation Rt = 20 to 50 nm and a thickness of 35 to 85 μm as one commercially available polarizing plate protective film, for example, When used at the position 22b in FIG. 7, the polarizing film disposed on the other polarizing plate, for example, the retardation film disposed on 22a in FIG. 7, has an in-plane retardation Ro of 20 nm to 300 nm. In addition, when a film having a thickness direction retardation Rt of 70 nm or more and 400 nm or less is used, the display quality is improved and the production of the film is preferable.

  The production effect obtained by the present invention becomes more remarkable particularly in a long roll of 100 m or more, and the longer the length is 1500 m, 2500 m, or 5000 m, the more the production effect of polarizing plate production is obtained.

  For example, in the production of a polarizing plate protective film, the roll length is 10 to 5000 m, preferably 50 to 4500 m in consideration of productivity and transportability. At this time, the width of the film is the width of the polarizer or the production line. A suitable width can be selected. A film with a width of 0.5 to 4.0 m, preferably 0.6 to 3.0 m, may be wound into a roll shape and used for polarizing plate processing. After being manufactured and wound on a roll, it may be cut to obtain a roll having a desired width, and such a roll may be used for polarizing plate processing.

  In the production of the polarizing plate protective film, functional layers such as an antistatic layer, a hard coat layer, a slippery layer, an adhesive layer, an antiglare layer, and a barrier layer may be coated before and / or after stretching. At this time, various surface treatments such as corona discharge treatment, plasma treatment, and chemical treatment can be performed as necessary. Specific examples include the method described in paragraphs 225 to 349 of JP-A-2008-209595.

  In the film forming process, the clip holding portions at both ends of the cut film are crushed as described above, or after granulating as necessary, and then used as film raw materials of the same type or different types. It can be reused as a raw material for film.

  Moreover, the optical film of a laminated structure can also be produced by coextruding compositions having different additive concentrations such as the above-mentioned plasticizer, ultraviolet absorber and matting agent.

  For example, an optical film having a structure of skin layer / core layer / skin layer can be produced. For example, the matting agent can be contained in the skin layer in a large amount or only in the skin layer. The plasticizer and the ultraviolet absorber can be contained in the core layer more than the skin layer, and may be contained only in the core layer. In addition, the type of plasticizer and ultraviolet absorber can be changed between the core layer and the skin layer. For example, the skin layer contains a low-volatile plasticizer and / or an ultraviolet absorber, and the core layer has excellent plasticity. It is also possible to add a plasticizer or an ultraviolet absorber excellent in ultraviolet absorption.

  The glass transition temperature of the skin layer and the core layer may be different, and the glass transition temperature of the core layer is preferably lower than the glass transition temperature of the skin layer. At this time, the glass transition temperatures of both the skin and the core can be measured, and an average value calculated from these volume fractions can be defined as the glass transition temperature Tg and similarly handled. Moreover, the viscosity of the melt at the time of melt casting may be different between the skin layer and the core layer, and the viscosity of the skin layer> the viscosity of the core layer or the viscosity of the core layer ≧ the viscosity of the skin layer may be used.

  The optical film according to the present invention has a dimensional stability of ± 2.0 when measured at 80 ° C. and 90% RH, based on the dimensions of the film left at 23 ° C. and 55% RH for 24 hours. %, Preferably less than 1.0%, more preferably less than 0.5%.

  When the optical film according to the present invention is used for a polarizing plate protective film as a retardation film, the retardation film itself has a variation within the above range, and the retardation has an absolute value and an orientation angle as the initial values. This is preferable because it does not deviate from the setting and does not cause deterioration in display quality.

〔Polarizer〕
The polarizing plate of the present invention will be described.

  The polarizing plate can be produced by a general method. The back side of the optical film of the present invention is subjected to alkali saponification treatment, and the treated optical film is bonded to at least one surface of a polarizing film prepared by immersing and stretching in an iodine solution using a completely saponified polyvinyl alcohol aqueous solution. It is preferable. The optical film of the present invention may be used on the other surface, or another polarizing plate protective film may be used. With respect to the optical film of the present invention, a commercially available cellulose ester film can be used as the polarizing plate protective film used on the other surface. For example, as a commercially available cellulose ester film, KC8UX2M, KC4UX, KC5UX, KC4UY, KC8UY, KC12UR, KC8UCR-3, KC8UCR-4 (above, manufactured by Konica Minolta Opto Co., Ltd.) and the like are preferably used. Alternatively, it is also preferable to use a polarizing plate protective film that also serves as an optical compensation film having an optical anisotropic layer formed by aligning liquid crystal compounds such as discotic liquid crystal, rod-shaped liquid crystal, and cholesteric liquid crystal. For example, the optically anisotropic layer can be formed by the method described in JP-A-2003-98348. By using in combination with the optical film of the present invention, a polarizing plate having excellent flatness and a stable viewing angle expansion effect can be obtained.

  The polarizing film, which is the main component of the polarizing plate, is an element that transmits only light having a polarization plane in a certain direction. A typical polarizing film known at present is a polyvinyl alcohol polarizing film, which is a polyvinyl alcohol film. There are one in which iodine is dyed on a system film and one in which dichroic dye is dyed. As the polarizing film, a polyvinyl alcohol aqueous solution is formed and dyed by uniaxially stretching or dyed, or uniaxially stretched after dyeing, and then preferably subjected to a durability treatment with a boron compound. On the surface of the polarizing film, one side of the optical film of the present invention is bonded to form a polarizing plate. It is preferably bonded with an aqueous adhesive mainly composed of completely saponified polyvinyl alcohol or the like.

  Instead of the alkali treatment, polarizing plate processing may be performed by performing easy adhesion processing as described in JP-A-6-94915 and JP-A-6-118232.

  Since the polarizing film is stretched in a uniaxial direction (usually the longitudinal direction), when the polarizing plate is placed in a high-temperature and high-humidity environment, the stretching direction (usually the longitudinal direction) shrinks, and the direction perpendicular to the stretching (usually the width direction) ) Will grow. As the thickness of the polarizing plate protective film decreases, the expansion / contraction ratio of the polarizing plate increases, and in particular, the amount of contraction in the stretching direction of the polarizing film increases. Usually, since the stretching direction of the polarizing film is bonded to the longitudinal direction (MD direction) of the polarizing plate protective film, it is particularly important to suppress the stretching ratio in the longitudinal direction when the polarizing plate protective film is thinned. Since the optical film of the present invention is extremely excellent in dimensional stability, it is suitably used as such a polarizing plate protective film.

  That is, even when the durability test is performed at 60 ° C. and 90% RH, the wavy unevenness does not increase, and even if the polarizing plate has an optical compensation film on the back side, the viewing angle characteristics fluctuate after the durability test. Good visibility can be provided without doing so.

  The polarizing plate can be constructed by further bonding a protective film on one surface of the polarizing plate and a separate film on the opposite surface. The protective film and the separate film are used for the purpose of protecting the polarizing plate at the time of shipping the polarizing plate and at the time of product inspection. In this case, the protect film is bonded for the purpose of protecting the surface of the polarizing plate, and is used on the side opposite to the surface where the polarizing plate is bonded to the liquid crystal plate. Moreover, a separate film is used in order to cover the contact bonding layer bonded to a liquid crystal board, and is used for the surface side which bonds a polarizing plate to a liquid crystal cell.

  In the polarizing plate of the present invention, a polarizing plate protective film of a cellulose derivative is used on the surface opposite to the retardation film as viewed from the polarizer, and a general-purpose TAC film or the like can be used. The polarizing plate protective film located on the side far from the liquid crystal cell can be provided with another functional layer in order to improve the quality of the display device.

  For example, it may be affixed to a film containing a known functional layer as a constituent for display in order to prevent reflection, anti-glare, scratch resistance, dust adhesion prevention, brightness improvement, or the polarizing plate surface of the present invention. It is not limited to.

  In general, a retardation film is required to obtain stable optical characteristics that the fluctuation of Ro or Rt is small as the above-mentioned retardation value. In particular, in a liquid crystal display device in a birefringence mode, these fluctuations may cause image unevenness.

  Since the long optical film or the long retardation film produced by the melt casting film forming method according to the present invention is mainly composed of cellulose resin, it is subjected to alkali treatment by utilizing saponification inherent to cellulose resin. There is an advantage that the process can be utilized. When the resin which comprises a polarizer is polyvinyl alcohol, it can be bonded with the said elongate film using complete saponified polyvinyl alcohol aqueous solution similarly to the conventional polarizing plate protective film. For this reason, the present invention is excellent in that the conventional polarizing plate processing method can be applied as it is, and particularly excellent in that a long roll polarizing plate can be obtained.

  The production effect obtained by the present invention becomes more remarkable particularly in a long roll of 100 m or more, and the longer the length is 1500 m, 2500 m, or 5000 m, the more the production effect of polarizing plate production is obtained.

  For example, in the retardation film production, the roll length is 10 m or more and 5000 m or less, preferably 50 m or more and 4500 m or less in consideration of productivity and transportability. The width of the film at this time is the width of the polarizer or the production. A width suitable for the line can be selected. A film is produced with a width of 0.5 m or more and 4.0 m or less, preferably 0.6 m or more and 3.0 m or less, wound into a roll, and may be used for polarizing plate processing. After a film is manufactured and wound on a roll, the film may be cut to obtain a roll having a desired width, and such a roll may be used for polarizing plate processing.

  In the film forming process, the clip gripping portions at both ends of the cut film are pulverized or granulated as necessary, and then used as a film material of the same product type or as a film material of a different product type. It may be reused.

  An optical film having a laminated structure can be produced by co-extrusion of a composition containing a cellulose resin having different additive concentrations such as the plasticizer, the ultraviolet absorber, and the matting agent. For example, an optical film having a structure of skin layer / core layer / skin layer can be produced. For example, the matting agent can be contained in the skin layer in a large amount or only in the skin layer. The plasticizer and the ultraviolet absorber can be contained in the core layer more than the skin layer, and may be contained only in the core layer. In addition, the type of plasticizer and ultraviolet absorber can be changed between the core layer and the skin layer. For example, the skin layer contains a low-volatile plasticizer and / or an ultraviolet absorber, and the core layer has excellent plasticity. It is also possible to add a plasticizer or an ultraviolet absorber excellent in ultraviolet absorption. The glass transition temperature of the skin layer and the core layer may be different, and the glass transition temperature of the core layer is preferably lower than the glass transition temperature of the skin layer. At this time, the glass transition temperatures of both the skin and the core can be measured, and an average value calculated from these volume fractions can be defined as the glass transition temperature Tg and similarly handled. Also, the viscosity of the melt containing the cellulose ester during melt casting may be different between the skin layer and the core layer, and the viscosity of the skin layer> the viscosity of the core layer or the viscosity of the core layer ≧ the viscosity of the skin layer may be used.

[Liquid Crystal Display]
The polarizing plate including the optical film of the present invention can exhibit high display quality as compared with a normal polarizing plate.

  The polarizing plate of the present invention includes an MVA (Multi-domain Vertical Alignment) mode, a PVA (Patterned Vertical Alignment) mode, a CPA (Continuous Pinweal Alignment-Pensitive Intensive) mode, an OCB (Optical Compensated InP mode, and an OCB (Optical Compensated InP mode). Can be used.

  Liquid crystal display devices are being applied as devices for colorization and moving image display, and the display quality is improved by the present invention, and the improvement of contrast and the resistance of polarizing plates improve the display of moving images that are less fatigued and faithful. It becomes possible.

  By incorporating the polarizing plate bonded with the optical film of the present invention into a liquid crystal display device, it is possible to produce various liquid crystal display devices with excellent visibility, but particularly outdoors such as large liquid crystal display devices and digital signage. It is preferably used for a liquid crystal display device for use.

  In a liquid crystal display device including at least a polarizing plate including a retardation film, one polarizing plate including a retardation film is disposed with respect to the liquid crystal cell, or two polarizing plates are disposed on both sides of the liquid crystal cell. At this time, it can contribute to improvement in display quality by using the retardation film side included in the polarizing plate so as to face the liquid crystal cell of the liquid crystal display device. In FIG. 7, the films 22a and 22b face the liquid crystal cell of the liquid crystal display device.

  In such a configuration, the retardation film can optically compensate the liquid crystal cell. When the polarizing plate of the present invention is used in a liquid crystal display device, at least one polarizing plate in the liquid crystal display device may be the polarizing plate of the present invention. By using the polarizing plate of the present invention, a liquid crystal display device with improved display quality and excellent viewing angle characteristics can be provided.

  EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited to these examples.

Example 1
[Modified cellulose nanofiber]
(Production of modified cellulose nanofiber (SCNF-1))
10 g of powdered cellulose NP fiber W-10MG2 (average particle size 10 μm) manufactured by Nippon Paper Chemical Co., Ltd. and 5.0 g of pyridine were added to 100 ml of toluene and stirred at room temperature to obtain a dispersion. Thereto, 8.0 g of benzoyl chloride was added dropwise and reacted at 50 ° C. for 1 hour. After cooling the reaction solution to room temperature, it was poured into 200 ml of methanol and filtered to obtain 9.8 g of modified cellulose fiber (SCF-1) according to the present invention.

  Disperse this modified cellulose fiber in water, and use a grinder ("KM1-10" manufactured by Kurita Kikai Seisakusho Co., Ltd.) to place the aqueous suspension between the disks rotating at 1200 rpm in a substantially contacted state from the center to the outside. The operation of passing through was performed 30 times (30 pass). Further, the dispersion treatment was performed with a bead disperser using zirconia beads having an average particle diameter of 2 μm. The zirconia beads were removed by centrifugation and filtration and then dried to obtain a cotton-like modified cellulose nanofiber (SCNF-1).

  A part of the suspension before drying was taken out and water was evaporated. Then, 100 cellulose nanofibers were observed with an electron microscope, and the average fiber diameter was 55 nm and the average fiber length was 2.05 μm.

(Production of modified cellulose nanofiber (SCNF-2))
Powdered cellulose NP fiber W-10MG2 (average particle size: 10 μm) manufactured by Nippon Paper Chemical Co., Ltd. was dispersed in water, and this water suspension was approximately mixed with a grinder (“KM1-10” manufactured by Kurita Machinery Co., Ltd.). The operation of passing between the disks rotating at 1200 rpm in contact with each other from the center to the outside was performed 30 times (30 passes). Further, the dispersion treatment was performed with a bead disperser using zirconia beads having an average particle diameter of 2 μm. The zirconia beads were removed by centrifugation and filtration and then dried to obtain cotton-like cellulose nanofibers.

  10 g of this cellulose nanofiber (CNF-2) and 5.0 g of pyridine were added to 100 ml of toluene and stirred at room temperature to obtain a dispersion. Thereto, 8.0 g of benzoyl chloride was added dropwise and reacted at 50 ° C. for 1 hour. After cooling the reaction solution to room temperature, it was put into 200 ml of methanol and filtered to obtain 9.0 g of the modified cellulose fiber (SCNF-2) of the present invention.

  A part of the suspension before drying was taken out and water was evaporated. Then, 100 cellulose nanofibers were observed with an electron microscope, and the average fiber diameter was 75 nm and the average fiber length was 2.1 μm.

(Production of modified cellulose nanofiber (SCNF-3))
10 g of powder freeze-dried from microfibrous cellulose serish KY-100G (solid content 10%) manufactured by Daicel Chemical Industries, Ltd. and 5.0 g of pyridine were added to 100 ml of toluene and dispersed by stirring at room temperature. A liquid was used. 1-naphthoyl chloride 10.0g was dripped there and it was made to react at 50 degreeC for 1 hour. After cooling the reaction solution to room temperature, it was put into 200 ml of methanol and filtered to obtain 8.5 g of modified cellulose fiber (SCF-3) according to the present invention.

  Disperse this modified cellulose fiber in water, and use a grinder ("KM1-10" manufactured by Kurita Kikai Seisakusho Co., Ltd.) to place the aqueous suspension between the disks rotating at 1200 rpm in a substantially contacted state from the center to the outside. The operation of passing through was performed 30 times (30 pass). Further, the dispersion treatment was performed with a bead disperser using zirconia beads having an average particle diameter of 2 μm. The zirconia beads were removed by centrifugation and filtration and then dried to obtain a cotton-like modified cellulose nanofiber (SCNF-3).

  A part of the suspension before drying was taken out and water was evaporated. Then, 100 cellulose nanofibers were observed with an electron microscope, and the average fiber diameter was 55 nm and the average fiber length was 2.5 μm.

(Production of modified cellulose nanofiber (SCNF-4))
Daicel Chemical Industries Co., Ltd. microfibrous cellulose serish KY-100G was dispersed in water, and this water suspension was almost brought into contact with a grinder ("KM1-10" manufactured by Kurita Kikai Seisakusho). The operation of passing between the discs rotating at 1200 rpm outward from the center was performed 30 times (30 passes). Further, the dispersion treatment was performed with a bead disperser using zirconia beads having an average particle diameter of 2 μm. The zirconia beads were removed by centrifugation and filtration and then dried to obtain cotton-like cellulose nanofibers. 10 g of this cellulose nanofiber (CNF-4) and 5.0 g of pyridine were added to 100 ml of toluene and stirred at room temperature to obtain a dispersion. 1-naphthoyl chloride 10.0g was dripped there and it was made to react at 50 degreeC for 1 hour. After cooling the reaction solution to room temperature, it was poured into 200 ml of methanol and filtered to obtain 8.4 g of the modified cellulose nanofiber (SCNF-4) of the present invention.

  A part of the suspension before drying was taken out and water was evaporated, and then 100 cellulose nanofibers were observed with an electron microscope and measured to have an average fiber diameter of 85 nm and an average fiber length of 3.2 μm.

(Production of modified cellulose nanofiber (SCNF-5))
10 g of powder freeze-dried from microfibrous cellulose serish KY-100G (solid content 10%) manufactured by Daicel Chemical Industries, Ltd. and 5.0 g of pyridine were added to 100 ml of toluene and dispersed by stirring at room temperature. A liquid was used. Thereto, 10.0 g of 2-naphthalenecarbonyl chloride was added dropwise and reacted at 50 ° C. for 1 hour. After cooling the reaction solution to room temperature, it was put into 200 ml of methanol and filtered to obtain 8.5 g of modified cellulose fiber (SCF-5) according to the present invention.

  Disperse this modified cellulose fiber in water, and use a grinder ("KM1-10" manufactured by Kurita Kikai Seisakusho Co., Ltd.) to place the aqueous suspension between the disks rotating at 1200 rpm in a substantially contacted state from the center to the outside. The operation of passing through was performed 30 times (30 pass). Further, the dispersion treatment was performed with a bead disperser using zirconia beads having an average particle diameter of 2 μm. The zirconia beads were removed by centrifugation and filtration and then dried to obtain a cotton-like modified cellulose nanofiber (SCNF-5).

  A part of the suspension before drying was taken out and water was evaporated. Then, 100 cellulose nanofibers were observed with an electron microscope, and the average fiber diameter was 50 nm and the average fiber length was 9.6 μm.

(Production of modified cellulose nanofiber (SCNF-6))
10 g of powder freeze-dried from microfibrous cellulose serish KY-100G (solid content 10%) manufactured by Daicel Chemical Industries, Ltd. and 5.0 g of pyridine were added to 100 ml of toluene and dispersed by stirring at room temperature. A liquid was used. Anisoyl chloride 8.0g was dripped there and it was made to react at 50 degreeC for 1 hour. After cooling the reaction solution to room temperature, it was poured into 200 ml of methanol and filtered to obtain 8.0 g of modified cellulose fiber (SCF-6) according to the present invention.

  Disperse this modified cellulose fiber in water, and use a grinder ("KM1-10" manufactured by Kurita Kikai Seisakusho Co., Ltd.) to place the aqueous suspension between the disks rotating at 1200 rpm in a substantially contacted state from the center to the outside. The operation of passing through was performed 30 times (30 pass). Further, the dispersion treatment was performed with a bead disperser using zirconia beads having an average particle diameter of 2 μm. The zirconia beads were removed by centrifugation and filtration and then dried to obtain a cotton-like modified cellulose nanofiber (SCNF-6).

  A part of the suspension before drying was taken out and water was evaporated, and then 100 cellulose nanofibers were observed with an electron microscope and measured to have an average fiber diameter of 40 nm and an average fiber length of 11.5 μm.

(Production of modified cellulose nanofiber (SCNF-7))
10 g of powder freeze-dried from microfibrous cellulose serish KY-100G (solid content 10%) manufactured by Daicel Chemical Industries, Ltd. and 5.0 g of pyridine were added to 100 ml of toluene and dispersed by stirring at room temperature. A liquid was used. Thereto, 12.0 g of 3,4,5-trimethoxybenzoyl chloride was added dropwise and reacted at 50 ° C. for 1 hour. After cooling the reaction solution to room temperature, it was poured into 200 ml of methanol and filtered to obtain 8.8 g of modified cellulose fiber (SCF-7) according to the present invention.

  Disperse this modified cellulose fiber in water, and use a grinder ("KM1-10" manufactured by Kurita Kikai Seisakusho Co., Ltd.) to place the aqueous suspension between the disks rotating at 1200 rpm in a substantially contacted state from the center to the outside. The operation of passing through was performed 30 times (30 pass). Further, the dispersion treatment was performed with a bead disperser using zirconia beads having an average particle diameter of 2 μm. The zirconia beads were removed by centrifugation and filtration and then dried to obtain a cotton-like modified cellulose nanofiber (SCNF-7).

  A part of the suspension before drying was taken out and the water was evaporated. Then, 100 cellulose nanofibers were observed with an electron microscope and measured to have an average fiber diameter of 55 nm and an average fiber length of 8.4 μm.

(Production of modified cellulose nanofiber (SCNF-8))
10 g of powder freeze-dried from microfibrous cellulose serish KY-100G (solid content 10%) manufactured by Daicel Chemical Industries, Ltd. and 5.0 g of pyridine were added to 100 ml of toluene and dispersed by stirring at room temperature. A liquid was used. 2-Ethoxynaphthoyl chloride 12.0g was dripped there and it was made to react at 50 degreeC for 1 hour. After cooling the reaction solution to room temperature, it was poured into 200 ml of methanol and filtered to obtain 8.2 g of modified cellulose fiber (SCF-8) according to the present invention.

  Disperse this modified cellulose fiber in water, and use a grinder ("KM1-10" manufactured by Kurita Kikai Seisakusho Co., Ltd.) to place the aqueous suspension between the disks rotating at 1200 rpm in a substantially contacted state from the center to the outside. The operation of passing through was performed 30 times (30 pass). Further, the dispersion treatment was performed with a bead disperser using zirconia beads having an average particle diameter of 2 μm. The zirconia beads were removed by centrifugation and filtration and then dried to obtain a cotton-like modified cellulose nanofiber (SCNF-8).

  A part of the suspension before drying was taken out and the water was evaporated. Then, 100 cellulose nanofibers were observed with an electron microscope and measured to have an average fiber diameter of 55 nm and an average fiber length of 51.5 μm.

(Production of modified cellulose nanofiber (SCNF-9))
10 g of powder freeze-dried from microfibrous cellulose serish KY-100G (solid content 10%) manufactured by Daicel Chemical Industries, Ltd. and 5.0 g of pyridine were added to 100 ml of toluene and dispersed by stirring at room temperature. A liquid was used. Biphenyl-3-carbonyl chloride 12.0g was dripped there, and it was made to react at 50 degreeC for 1 hour. After the reaction solution was cooled to room temperature, it was poured into 200 ml of methanol and filtered to obtain 7.8 g of modified cellulose fiber (SCF-9) according to the present invention.

  Disperse this modified cellulose fiber in water, and use a grinder ("KM1-10" manufactured by Kurita Kikai Seisakusho Co., Ltd.) to place the aqueous suspension between the disks rotating at 1200 rpm in a substantially contacted state from the center to the outside. The operation of passing through was performed 30 times (30 pass). Further, the dispersion treatment was performed with a bead disperser using zirconia beads having an average particle diameter of 2 μm. The zirconia beads were removed by centrifugation and filtration and then dried to obtain a cotton-like modified cellulose nanofiber (SCNF-9).

  A part of the suspension before drying was taken out and water was evaporated. Then, 100 cellulose nanofibers were observed with an electron microscope, and the average fiber diameter was 55 nm and the average fiber length was 82.0 μm.

(Production of modified cellulose nanofiber (SCNF-10))
10 g of powder obtained by mechanically pulverizing softwood kraft pulp NDP-T from Nippon Paper Chemical Co., Ltd. and 5.0 g of pyridine were added to 100 ml of toluene, and stirred at room temperature to obtain a dispersion. Thereto, 8.0 g of benzoyl chloride was added dropwise and reacted at 50 ° C. for 1 hour. After cooling the reaction solution to room temperature, it was put into 200 ml of methanol and filtered to obtain 9.8 g of modified cellulose fiber (SCF-10) according to the present invention.

  Disperse this modified cellulose fiber in water, and use a grinder ("KM1-10" manufactured by Kurita Kikai Seisakusho Co., Ltd.) to place the aqueous suspension between the disks rotating at 1200 rpm in a substantially contacted state from the center to the outside. The operation of passing through was performed 30 times (30 pass). Further, the dispersion treatment was performed with a bead disperser using zirconia beads having an average particle diameter of 2 μm. The zirconia beads were removed by centrifugation and filtration and then dried to obtain a cotton-like modified cellulose nanofiber (SCNF-10).

  A part of the suspension before drying was taken out and water was evaporated. Then, 100 cellulose nanofibers were observed with an electron microscope, and the average fiber diameter was 60 nm and the average fiber length was 96.0 μm.

(Production of modified cellulose nanofiber (SCNF-11))
10 g of powder freeze-dried from microfibrous cellulose serish KY-100G (solid content 10%) manufactured by Daicel Chemical Industries, Ltd. and 5.0 g of pyridine were added to 100 ml of toluene and dispersed by stirring at room temperature. A liquid was used. Thereto, 11.0 g of cyclohexanecarbonyl chloride was added dropwise and reacted at 50 ° C. for 1 hour. After the reaction solution was cooled to room temperature, it was put into 200 ml of methanol and filtered to obtain 6.8 g of modified cellulose fiber (SCF-11) according to the present invention.

  Disperse this modified cellulose fiber in water, and use a grinder ("KM1-10" manufactured by Kurita Kikai Seisakusho Co., Ltd.) to place the aqueous suspension between the disks rotating at 1200 rpm in a substantially contacted state from the center to the outside. The operation of passing through was performed 30 times (30 pass). Further, the dispersion treatment was performed with a bead disperser using zirconia beads having an average particle diameter of 2 μm. The zirconia beads were removed by centrifugation and filtration and then dried to obtain a cotton-like modified cellulose nanofiber (SCNF-11).

  A part of the suspension before drying was taken out and the water was evaporated. Then, 100 cellulose nanofibers were observed with an electron microscope and measured to have an average fiber diameter of 55 nm and an average fiber length of 62.0 μm.

(Production of modified cellulose nanofiber (SCNF-12))
10 g of powder freeze-dried from microfibrous cellulose serish KY-100G (solid content 10%) manufactured by Daicel Chemical Industries, Ltd. and 5.0 g of pyridine were added to 100 ml of toluene and dispersed by stirring at room temperature. A liquid was used. Thereto, 15.0 g of carbazole-N-carbonyl chloride was added dropwise and reacted at 50 ° C. for 1 hour. After cooling the reaction solution to room temperature, it was put into 200 ml of methanol and filtered to obtain 5.3 g of modified cellulose fiber (SCF-12) according to the present invention.

  Disperse this modified cellulose fiber in water, and use a grinder ("KM1-10" manufactured by Kurita Kikai Seisakusho Co., Ltd.) to place the aqueous suspension between the disks rotating at 1200 rpm in a substantially contacted state from the center to the outside. The operation of passing through was performed 30 times (30 pass). Further, the dispersion treatment was performed with a bead disperser using zirconia beads having an average particle diameter of 2 μm. The zirconia beads were removed by centrifugation and filtration and then dried to obtain a cotton-like modified cellulose nanofiber (SCNF-12).

  A part of the suspension before drying was taken out and the water was evaporated. Then, 100 cellulose nanofibers were observed with an electron microscope, and the average fiber diameter was 60 nm and the average fiber length was 75.0 μm.

  For comparison, the following materials were manufactured.

(Manufacture of unmodified cellulose nanofiber (UNSCNF-1))
Nippon Paper Chemicals Co., Ltd.'s softwood kraft pulp NDP-T is dispersed in water, and this water suspension is rotated at 1200 rpm in a substantially contacted state with a grinder ("KM1-10" manufactured by Kurita Kikai Seisakusho). The operation of passing between the disks to be performed outward from the center was performed 30 times (30 passes). Further, the dispersion treatment was performed with a bead disperser using zirconia beads having an average particle diameter of 2 μm. The zirconia beads were removed by centrifugation and filtration and then dried to obtain cotton-like unmodified cellulose nanofibers (UNSCNF-1).

  A part of the suspension before drying was taken out and water was evaporated. Then, 100 cellulose nanofibers were observed with an electron microscope, and the average fiber diameter was 75 nm and the average fiber length was 5.3 μm.

(Production of modified cellulose nanofiber (SSCNF-1) having a short fiber length)
10 g of powder obtained by mechanically pulverizing softwood kraft pulp NDP-T from Nippon Paper Chemical Co., Ltd. and 5.0 g of pyridine were added to 100 ml of toluene, and stirred at room temperature to obtain a dispersion. Thereto, 8.0 g of benzoyl chloride was added dropwise and reacted at 50 ° C. for 1 hour. After cooling the reaction solution to room temperature, it was poured into 200 ml of methanol and filtered to obtain 9.8 g of modified cellulose fiber (SCF-10). Disperse this modified cellulose fiber in water, and use a grinder ("KM1-10" manufactured by Kurita Kikai Seisakusho Co., Ltd.) to place the aqueous suspension between the disks rotating at 1200 rpm in a substantially contacted state from the center to the outside. The operation of passing through was performed 30 times (30 pass). Further, the dispersion treatment was performed with a bead disperser using zirconia beads having an average particle diameter of 2 μm. The zirconia beads were removed by centrifugation and filtration and then dried to obtain a cotton-like modified cellulose nanofiber (SSCNF-1). A part of the suspension before drying was taken out and water was evaporated. Then, 100 cellulose nanofibers were observed with an electron microscope and measured to have an average fiber diameter of 85 nm and an average fiber length of 1.88 μm (1880 nm).

(Manufacture of modified cellulose nanofiber (LSCNF-1) having a long fiber length)
10 g of powder obtained by mechanically pulverizing softwood kraft pulp NDP-T from Nippon Paper Chemical Co., Ltd. and 5.0 g of pyridine were added to 100 ml of toluene, and stirred at room temperature to obtain a dispersion. Thereto, 8.0 g of benzoyl chloride was added dropwise and reacted at 50 ° C. for 1 hour. After cooling the reaction solution to room temperature, it was poured into 200 ml of methanol and filtered to obtain 9.8 g of modified cellulose fiber (SCF-10).

  Disperse this modified cellulose fiber in water, and use a grinder ("KM1-10" manufactured by Kurita Kikai Seisakusho Co., Ltd.) to place the aqueous suspension between the disks rotating at 1200 rpm in a substantially contacted state from the center to the outside. The operation of passing through was performed 20 times (20 passes). After separating water, it was dried to obtain a cotton-like modified cellulose nanofiber (LSCNF-1).

  A part of the suspension before drying was taken out and water was evaporated. Then, 100 cellulose nanofibers were observed with an electron microscope, and the average fiber diameter was 110 nm and the average fiber length was 110 μm or more.

(Production of surfactant-adsorbed cellulose crystal (WA-1))
Surfactant-adsorbed cellulose crystals (WA-1) were produced by the method described in Production Example 12 of JP-A-2009-52016. After removing a part of the suspension before drying and evaporating water, 100 cellulose crystals were observed with an electron microscope. The size of the cellulose crystals was 10 nm in average minor axis length and 160 nm in average major axis length. there were.

(Production of butyryl cellulose crystals (W13))
Butyryl cellulose crystals (W13) were produced by the method described in Production Example 19 of JP-A-2009-52016. After removing a part of the suspension before drying and evaporating the water, 100 cellulose crystals were observed with an electron microscope. The size of the cellulose crystals was 10 nm as the average minor axis length and 162 nm as the average major axis length. there were.

[Cellulose ester (CE)]
The following cellulose esters CE-1 to CE-5 were prepared by known methods.

CE-1: cellulose acetate propionate (acyl group total substitution degree 2.6, acetyl group substitution degree 1.9, propionyl group substitution degree 0.7, molecular weight Mw = 200000)
CE-2: Cellulose acetate propionate (acyl group total substitution degree 2.8, acetyl group substitution degree 0.1, propionyl group substitution degree 2.7, molecular weight Mw = 200000)
CE-3: cellulose acetate propionate (acyl group total substitution degree 2.5, acetyl group substitution degree 1.3, propionyl group substitution degree 1.2, molecular weight Mw = 200000)
In addition, the following commercially available cellulose esters and polycycloolefins were used.

CE-4: Cellulose diacetate L-20 (Daicel Chemical Industries, Inc., acetyl group substitution degree 2.41)
CE-5: Cellulose triacetate LT-35 (manufactured by Daicel Chemical Industries, Ltd., acetyl group substitution degree 2.87)
COP-1: Polycycloolefin “Zeonor # 1600” (manufactured by Nippon Zeon Co., Ltd.)
Example 2
[Manufacture of optical films]
(Production of optical film (F-1) (solution casting method))
(Preparation of additive solution A)
The following compounds were used at the following mixing ratios.

CE-4 5 parts by mass Methylene chloride 80 parts by mass The above material was put into a sealed container and completely dissolved and filtered while heating and stirring. To this, 15 parts by mass of cellulose nanofiber (SCNF-1) was added with stirring, and the mixture was further stirred for 30 minutes, followed by ultrasonic dispersion treatment to prepare additive solution A.

(Preparation of dope A)
Triphenyl phosphate 20 parts by mass Methylene chloride 640 parts by mass Ethanol 120 parts by mass CE-4 220 parts by mass The above materials were sequentially put into a sealed container while stirring, and completely dissolved and mixed while heating and stirring. Additive solution A is added to this dope solution so that the cellulose nanofibers in the film are 5% by mass, thoroughly mixed, lowered to the casting temperature and allowed to stand overnight, and after defoaming operation Azumi filter paper No. manufactured by Azumi Filter Paper Co., Ltd. Filtration using 244 gave Dope A.

  Using the prepared dope A, an optical film was produced as follows.

  After the dope A was filtered, it was uniformly cast on a stainless belt support having a dope temperature of 35 ° C. and a temperature of 30 ° C. using a belt casting apparatus. Then, after drying to the peelable range, the web was peeled from the stainless steel belt support body. At this time, the residual solvent amount of the web was 80%.

  After peeling from the stainless steel belt support and drying while roll transporting the 85 ° C. drying zone, when the residual solvent amount is less than 35% by mass, the biaxially stretched tenter is used in the TD direction (width direction) and The film was dried at 90 ° C. while being stretched in the MD direction (film forming direction), and was further dried in a 125 ° C. drying zone while being conveyed by a roll. The draw ratio in the MD direction of the film was 1.2, the draw ratio in the TD direction was 1.3, and the film thickness was 80 μm. The residual solvent amount at the time of winding was less than 0.1% by mass. The finished film width was slit to 1430 mm width and wound up. The winding core had an inner diameter of 152 mm, an outer diameter of 165 to 180 mm, and a length of 1550 mm. A prepreg resin obtained by impregnating glass fibers and carbon fibers with an epoxy resin was used as the core material for the core. The surface of the core was coated with an epoxy conductive resin, the surface was polished, and the surface roughness Ra was finished to 0.3 μm. The winding length was 2500 m. Let this film original fabric sample of this invention be an optical film (F-1).

(Production of optical film (F-2 to 25) (solution casting method))
In the production of the optical film 1, except that the type of cellulose ester, the type and concentration of cellulose nanofiber, and the stretching conditions were changed as shown in Table 1, the optical film (F-1) was produced in the same manner as in the production method. Films (F-2 to 25) were produced.

(Manufacture of optical film (F-26) (melt casting method))
An optical film (F-26) was produced by the melt casting method using the following materials.

Cellulose ester CE-4 75 parts by weight Diethyl phthalate 20 parts by weight Modified cellulose nanofiber SCNF-1 5 parts by weight After drying the cellulose ester and modified cellulose nanofiber at 70 ° C. under reduced pressure for 3 hours and cooling to room temperature, diethyl phthalate Were mixed. The above mixture was melt-mixed at 220 ° C. using a twin-screw extruder and pelletized.

  Using this pellet, it was melted at 245 ° C. in a nitrogen atmosphere, extruded from the casting die 4 onto the first cooling roll 5, and formed by pressing the film between the first cooling roll 5 and the touch roll 6. .

  The heat bolt was adjusted so that the gap width of the casting die 4 was 0.5 mm within 30 mm from the end in the width direction of the film and 1 mm at other locations. The touch roll A was used as the touch roll, and 80 ° C. water was poured as cooling water therein.

  From the position P1 at which the resin extruded from the casting die 4 contacts the first cooling roll 5 to the position P2 at the upstream end in the rotation direction of the first cooling roll 5 in the nip between the first cooling roll 5 and the touch roll 6. 1 The length L along the peripheral surface of the cooling roller 5 was set to 20 mm. Thereafter, the touch roll 6 was separated from the first cooling roll 5, and the temperature T of the melted part immediately before being sandwiched between the first cooling roll 5 and the touch roll 6 was measured. In the present embodiment, the temperature T of the melted part immediately before being sandwiched between the nips of the first cooling roll 5 and the touch roll 6 is 1 mm upstream from the nip upstream end P2, and a thermometer (an independent meter). It was measured by HA-200E manufactured by Co., Ltd. As a result of the measurement in this example, the temperature T was 141 ° C. The linear pressure of the touch roll 6 against the first cooling roll 5 was 14.7 N / cm. Furthermore, after introduction into a biaxial stretching tenter, stretching at 160 ° C in the MD direction (film forming direction) 1.3 times and in the TD direction (width direction) 1.5 times, the width is relaxed by 3%. The film was then cooled to 30 ° C, then released from the clip, the clip gripping part was cut off, the film was knurled at a width of 10 mm and a height of 5 μm, and wound around a winding core with a winding tension of 220 N / m and a taper of 40%. I took it. In addition, the extrusion amount and the take-up speed were adjusted so that the film had a thickness of 80 μm, and the finished film width was slit and wound up so as to have a width of 1430 mm. The winding core had an inner diameter of 152 mm, an outer diameter of 165 to 180 mm, and a length of 1550 mm.

  A prepreg resin obtained by impregnating glass fibers and carbon fibers with an epoxy resin was used as the core material for the core. The surface of the core was coated with an epoxy conductive resin, the surface was polished, and the surface roughness Ra was finished to 0.3 μm. The winding length was 2500 m. Let this film original fabric sample of this invention be an optical film (F-26).

(Production of optical film (F-27 to 42) (melt casting method))
In the production of the optical film (F-26), the same method as the production method of the optical film (F-26) except that the types and concentrations of cellulose esters and modified cellulose nanofibers and the stretching conditions were changed as shown in Table 1. Thus, optical films (F-27 to 42) were produced.

〔Evaluation methods〕
The following evaluation was implemented about the obtained optical film (F-1 to 42). The results are shown in Table 2.

(Evaluation of retardation and retardation distribution)
For the retardation distribution, the coefficient of variation (CV) shown below was obtained and used as an index.

  About the produced cellulose-ester film sample, the refractive index of the three-dimensional direction was measured at 1 cm intervals in the width direction. The in-plane retardation average value (Ro), retardation direction average value (Rt), and coefficient of variation (CV) obtained from the following formula were determined.

  The measurement was performed using an automatic birefringence meter KOBURA 21ADH (manufactured by Oji Scientific Instruments Co., Ltd.) in an environment of 23 ° C. and 55% RH at a wavelength of 590 nm. Substituting into a) and (b), in-plane retardation Ro and thickness direction retardation Rt were determined.

Formula (a) In-plane retardation Ro = (nx−ny) × d
Formula (b) Thickness direction retardation Rt = ((nx + ny) / 2−nz) × d
Where d is the thickness (nm) of the film, nx is the maximum refractive index in the plane of the film, and the refractive index in the slow axis direction, ny is the refractive index in the direction perpendicular to the slow axis in the film plane. , Nz is the refractive index of the film in the thickness direction. The standard deviation by the (n-1) method was calculated | required, respectively for the obtained thickness direction retardation. The variation coefficient (CV) of retardation in the thickness direction was determined from the following formula. n was set to 130-140.

Retardation coefficient (CV) of retardation (thickness direction) = standard deviation of retardation Rt / average value of retardation Rt Retardation distribution from the obtained variation coefficient (CV) of retardation (Rt) in the thickness direction Evaluation was based on the evaluation criteria.

7: (CV) is less than 1.5%, a practically excellent level 6: (CV) is 1.5% or more and less than 2.0%, a practically excellent level 5: (CV) Is not less than 2.0% and less than 5.0%, and there is no problem in practical use. 4: (CV) is not less than 5.0% and less than 6.0%, and is the minimum allowable range in practical use. 3: (CV) Is 6.0% or more and less than 8.0%, which is a level at which practical problems may occur. 2: (CV) is 8.0% or more and less than 10%, which may cause practical problems. It is a certain level 1: (CV) is 10% or more, and it is a level that causes practical problems (horse spine failure, core transfer)
The wound cellulose ester film original sample is wrapped twice with a polyethylene sheet and stored for 30 days under conditions of 25 ° C. and 50% by the storage method as shown in FIGS. 8 (a), (b) and (c). saved. Then, it was taken out from the box, the polyethylene sheet was opened, and the fluorescent lamp tube lit on the surface of the film original film sample was reflected and imaged. The distortion or fine disturbance was observed, and the horse back failure was ranked to the following level.

A: Fluorescent lamps appear straight B: Fluorescent lamps appear to be bent partially C: Fluorescent lamps appear to be mottled In addition, the original film sample after storage is rewound to form a spot-like deformation of 50 μm or more, Alternatively, it was measured how many meters of the core transfer, in which the strip-shaped deformation in the width direction was clearly visible, from the core portion, and was ranked according to the following levels.

A: Less than 15 m from the core part B: Less than 15 to 30 m from the core part C: Less than 30 to 50 m from the core part D: 50 m or more from the core part (winding wrinkle)
An operation of winding the original film on the core was performed, and when wrinkles occurred at the beginning of the winding and it became defective, the original film was removed from the core and the operation of rewinding was performed. The number of defects at this time was counted. This operation was averaged 10 times and ranked to the following levels.

A: 0 times or more and less than 1 time B: 1 time or more and less than 3 times C: 3 times or more and less than 5 times D: 5 times or more [Characteristic evaluation as a liquid crystal display device]
A liquid crystal display device was produced from the obtained optical film (F-1 to 42) by the following method, and the following evaluation was performed. The results are shown in Table 2.

(Preparation of polarizing plate)
A polarizing plate using each optical film was prepared as follows.

  A 120 μm-thick long roll polyvinyl alcohol film was immersed in 100 parts by mass of an aqueous solution containing 1 part by mass of iodine and 4 parts by mass of boric acid, and stretched in the transport direction 5 times at 50 ° C. to prepare a polarizing film.

  Next, the optical film F-1 of the present invention that had been subjected to alkali saponification treatment on one side of the polarizing film was bonded using a polyvinyl alcohol aqueous solution as an adhesive. Furthermore, KC8UX2M manufactured by Konica Minolta Opto Co., Ltd., which is a polarizing plate protective film subjected to alkali saponification treatment, was bonded to the other surface of the polarizing film and dried to prepare a polarizing plate (P-1). Similarly, polarizing plates (P-2 to 42) were produced using optical films F-2 to 42.

  The polarizing plate using the optical film of the present invention was excellent in film cutting property and easy to process as compared with the polarizing plate using the comparative optical film.

(Production of liquid crystal display device)
Using each of the produced polarizing plates (P-1 to 42), the display characteristics of the optical film were evaluated.

  The polarizing plates on both sides of the 32-inch television AQ-32AD5 manufactured by Sharp Corporation were peeled off in advance, and the produced polarizing plates (P-1 to 42) were optical films (F-1 to 42), respectively. The liquid crystal display devices (D-1 to 42) were produced by bonding so that the absorption axis was in the same direction as the polarizing plate previously bonded so as to be on the glass surface side of the liquid crystal cell. .

(Viewing angle fluctuation evaluation)
The following evaluation was performed using the liquid crystal display devices (D-1 to 42) produced as described above.

  The viewing angle of the liquid crystal display device was measured using EZ-Contrast 160D manufactured by ELDIM in an environment of 23 ° C. and 55% RH. Subsequently, the polarizing plate treated at 60 ° C. and 90% RH for 1000 hours was measured in the same manner, and the viewing angle fluctuation was evaluated in four stages according to the following criteria.

A: No viewing angle variation B: Slight viewing angle variation is observed C: Viewing angle variation is observed D: Viewing angle variation is large (color shift evaluation)
Regarding the produced liquid crystal display devices (D-1 to 42), the display was displayed in black in an environment of 23 ° C. and 55% RH, and observed from an oblique angle of 45 °. Subsequently, the polarizing plate treated at 60 ° C. and 90% RH for 1000 hours was observed in the same manner, and the color change was evaluated in four stages according to the following criteria.

A: No color change B: Color change is slightly observed C: Color change is recognized D: Color change is large Table 2 shows the results of the above evaluation.

  As can be seen from Table 2 above, according to the production method of the present invention, it was possible to control the retardation within an appropriate range, to suppress the occurrence of retardation fluctuations, and to simultaneously improve the failure due to film deformation. Moreover, the polarizing plate and the liquid crystal display device produced using the optical film produced by the production method of the present invention showed excellent properties in visibility and color shift.

Example 3
Table 3 shows the types and concentrations of cellulose esters and modified cellulose nanofibers, stretching conditions, types and amounts of additives, types and amounts of plasticizers replaced with diethyl phthalate, and types and amounts of UV absorbers. Optical films (F-43 to 49) were produced in the same manner as in the production method of the optical film (F-26) except that the changes were made. Further, using the optical films (F-43 to 49), polarizing plates (P-43 to 49) and liquid crystal display devices (D-43 to 49) were produced in the same manner as in Example 2, and the same as in Example 2. Evaluation was performed. The results are shown in Table 4.

  The following was used as an additive.

(AD-1) -A: Sumilizer GS (manufactured by Sumitomo Chemical Co., Ltd.)
(AD-1) -B: Sumilizer GM (manufactured by Sumitomo Chemical Co., Ltd.)
(AD-3) -A: IRGANOX 1010 (manufactured by Ciba Japan)
(AD-3) -B: IRGANOX 1076 (manufactured by Ciba Japan)
(AD-4) -A: ADK STAB LA-52 (manufactured by ADEKA Corporation)
(AD-5) -A: ADK STAB PEP-36 (manufactured by ADEKA Corporation)
(AD-5) -B: GSY-P101 (manufactured by Sakai Chemical Industry Co., Ltd.)
The following were used as plasticizers.

  KA-1: Exemplified compound 48 described in paragraph 71 of JP-A-2006-188663 was used as an ultraviolet absorber. The following were also used.

UV-1: TINUVIN 928 (manufactured by Ciba Japan)
UV-2: ADK STAB LA-31 (manufactured by ADEKA Corporation)

  As can be seen from Tables 3 and 4, according to the production method of the present invention, even when an additive is contained, the retardation is controlled within an appropriate range, and the occurrence of retardation fluctuation is suppressed, and at the same time, the failure due to film deformation is improved. We were able to. Moreover, the polarizing plate and the liquid crystal display device produced using the optical film produced by the production method of the present invention are further improved in visibility and color shift.

DESCRIPTION OF SYMBOLS 1 Extruder 2 Filter 3 Static mixer 4 Casting die 5 Rotating support body (1st cooling roll)
6 Nipping pressure rotating body (touch roll)
7 Rotating support (second cooling roll)
8 Rotating support (3rd cooling roll)
9, 11, 13, 14, 15 Transport roll 10 Cellulose ester film 12 Stretcher 16 Winding device 21a, 21b Protective film 22a, 22b Retardation film 23a, 23b Film slow axis direction 24a, 24b Polarizer transmission axis Direction 25a, 25b Polarizer 26a, 26b Polarizing plate 27 Liquid crystal cell 29 Liquid crystal display device 31 Die body 32 Slit 41 Metal sleeve 42 Elastic roller 43 Metal inner cylinder 44 Rubber 45 Cooling water 51 Outer cylinder 52 Inner cylinder 53 Space 54 Cooling Liquid 55a, 55b Rotating shaft 56a, 56b Outer cylinder support flange 60 Fluid shaft cylinder 61a, 61b Inner cylinder support flange 62a, 62b Intermediate passage 110 Core body 117 Support plate 118 Base 120 Cellulose ester film original

Claims (9)

After forming a composition containing cellulose nanofibers having a modifying group represented by the following general formula (1) and an average fiber length of 2.0 μm to 100 μm and a thermoplastic resin, at least in one direction A method for producing an optical film, which comprises performing a stretching treatment.
General formula (1)
-(L) _n -R ¹
(In the formula, L represents a linking group, n represents an integer of 0 or 1. R ¹ represents a cycloalkyl group, an aryl group, or a heterocyclic group, and these may further have a substituent. .)   The method for producing an optical film according to claim 1, wherein the cellulose nanofiber is crushed after the introduction of the modifying group.   The method for producing an optical film according to claim 1, wherein the thermoplastic resin is a cellulose ester.   The stretching process is performed to form a retardation film having an in-plane retardation Ro of 20 to 200 nm and a thickness direction retardation Rt of 70 to 400 nm. Manufacturing method of optical film.   The method for producing an optical film according to claim 1, wherein the optical film is formed by a solution casting method.   The method for producing an optical film according to claim 1, wherein the optical film is formed by a melt extrusion method.   The optical film manufactured by the manufacturing method of the optical film of any one of Claims 1-6.   A polarizing plate using the optical film according to claim 7 on at least one surface.   A liquid crystal display device using the polarizing plate according to claim 8.

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