JP2012045882A - Cellulose acylate laminated film, polarizing plate, and liquid crystal display device - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a cellulose acylate laminated film which is excellent in adhesiveness with a polarizer and which is small in the change of a measure by humidity and a polarizing plate having high reliability using it and a liquid crystal display device.SOLUTION: In the cellulose acylate laminated film made by laminating and film forming a skin B layer including cellulose acylate satisfying formula (1) and a core layer including the cellulose acylate satisfying formula (2), at least one of the skin B layer and the core layer includes a retardation regulator. Formula (1): 2.0<Z<2.7. Formula (2): 2.7<Z<3.0. (In formulae, the Zand the Zexpress the total acyl group substitution degree of the cellulose acylate).

Description

  The present invention relates to a cellulose acylate laminated film, a polarizing plate using the same, and a liquid crystal display device. More specifically, the present invention relates to a laminated film, a polarizing plate and a liquid crystal display device in which a cellulose acylate having a low substitution degree and a cellulose acylate having a high substitution degree are co-cast.

  Conventionally, a retardation film having a specific retardation value and a combination thereof have been used in order to improve the viewing angle and color change of a liquid crystal display device.

  As a main raw material for such a retardation film, it is known that cellulose acylate is advantageous and that the optical properties of the film depend on the acyl group substitution degree of cellulose acylate. In particular, since cellulose acylate having a low degree of substitution has a high intrinsic birefringence, it is possible to achieve high optical expression suitable as a retardation film for VA by reducing the degree of acyl group substitution. It is considered.

  Moreover, as described in Patent Documents 1 to 4, the surface can be directly bonded to a polarizer mainly composed of polyvinyl alcohol by saponifying and hydrophilizing the surface with an alkaline aqueous solution. For this reason, it is utilized as a protective film (hereinafter referred to as a protective film) to which a phase difference compensation function of a polarizer is added.

  The polarizer bonded with the protective film is incorporated together with the liquid crystal cell when the liquid crystal display device is manufactured. At this time, since the protective film is disposed between the polarizer and the liquid crystal cell, the optical characteristics of the protective film greatly affect the visibility of the liquid crystal display device. For this reason, the protective film is required to exhibit stable optical characteristics against environmental changes such as humidity changes. However, the cellulose acylate film has a problem that its dimensions are likely to fluctuate particularly with respect to changes in humidity. In recent years, with the wide viewing angle and high image quality of liquid crystal display devices, it has been required to further improve the compensation of phase difference, and improvement has been demanded.

  In order to improve the stability against humidity change, a film made of a more hydrophobic polycarbonate or cyclooff olefin polymer has been proposed (see, for example, Patent Document 5). Such a film is also sold as ZEONOR (manufactured by ZEON Corporation) or ARTON (manufactured by JSR Corporation). However, these films are improved in change with respect to humidity, but have a problem that it is difficult to adhere to a polarizer mainly composed of polyvinyl alcohol. For this reason, the further improvement was calculated | required.

  Thus, in the film directly bonded to the polarizer, the bonding property with the polarizer and the dimensional stability against humidity change have a trade-off relationship.

  In order to improve this relationship, it has been proposed to use a cellulose acylate film having a low water contact angle (for example, Patent Document 6). In addition, the degree of acyl group substitution in the skin layer (surface layer) in a laminated structure is proposed. It has been proposed to use a cellulose acylate having a low molecular weight (for example, Patent Document 7).

  However, the cellulose acylate film having a low contact angle is likely to cause elution of the film surface in the process of saponifying and hydrophilizing the surface by immersing the surface in an alkaline aqueous solution, and it is necessary to weaken the immersing process. Adhesion was not obtained, and the relationship was in conflict with dimensional stability against humidity changes. In addition, when cellulose acylate having a low acyl group substitution degree (1.8 to 2.2) is used without passing through a saponification treatment step, the viscosity when dissolved in a halogenated solvent such as dichloromethane is high, and solution casting is performed. There arises a problem that the surface condition after film formation deteriorates.

JP 7-151914 A JP-A-8-94838 JP 2001-166146 A JP 2001-188130 A JP 2001-318233 A JP 2006-215535 A Japanese Patent No. 4279178

  The present invention has been made in view of the above-described problems and situations, and the solution to the problem is a cellulose acylate laminated film that is excellent in bonding properties with a polarizer and has a small dimensional change due to humidity, and a reliability using the same. It is to provide a highly polarizing plate and a liquid crystal display device.

  The above-mentioned problem according to the present invention is solved by the following means.

1. A cellulose acylate laminated film in which a skin B layer containing cellulose acylate satisfying the following formula (1) and a core layer containing cellulose acylate satisfying the following formula (2) are laminated and formed, A cellulose acylate laminated film comprising a retardation adjusting agent in at least one of the skin B layer and the core layer.
Formula (1): 2.0 <Z ₁ <2.7
(In formula (1), Z ₁ represents the total acyl group substitution degree of the cellulose acylate of the skin layer.)
Formula (2): 2.7 <Z ₂ <3.0
(In formula (2), Z ₂ represents the total acyl group substitution degree of the cellulose acylate of the core layer.)
2. The cellulose acylate laminated film according to item 1, wherein the core layer contains a retardation developer.

  3. In the said 1st term | claim or the 2nd term | claim characterized by containing the compound represented by the following general formula (A) whose total average substitution degree is in the range of 4.5-6.9 in the said core layer. The cellulose acylate laminated film described.

(Wherein R _{1 to} R ₈ each independently represents a substituted or unsubstituted alkylcarbonyl group or a substituted or unsubstituted arylcarbonyl group, and R _{1 to} R ₈ may be the same) , May be different.)
4). The cellulose acylate laminated film according to any one of Items 1 to 3, wherein the skin B layer contains a compound having negative intrinsic birefringence.

5. The first layer characterized by having a skin A layer containing cellulose acylate satisfying the following formula (1) on a surface opposite to the surface on which the skin B layer of the laminated core layer is provided. The cellulose acylate laminated film according to any one of items 1 to 4.
Formula (1): 2.0 <Z ₁ <2.7
(In formula (1), Z ₁ represents the total acyl group substitution degree of the cellulose acylate of the skin layer.)
6). 6. The cellulose acylate laminated film according to item 5, wherein at least one of the skin A layer and the skin B layer contains a polymer having a cyclic structure in a side chain.

  7). 7. The cellulose acylate laminated film according to item 5 or 6, wherein metal fine particles are contained in at least one of the skin A layer and the skin B layer.

  8). The average layer thickness of the core layer is in the range of 30 to 100 μm, and the average layer thickness of at least one of the skin A layer and the skin B layer is 0.2% or more and less than 25% of the average layer thickness of the core layer. The cellulose acylate laminated film according to any one of Items 5 to 7, which is characterized in that it is present.

  9. 9. The cellulose acylate laminated film according to any one of items 1 to 8, wherein a film width is in a range of 700 to 3000 mm.

10. The cellulose acylate according to any one of items 5 to 9, wherein the cellulose acylate used in the skin A layer and the skin B layer satisfies the following formulas (3) and (4): Rate laminated film.
Formula (3): 1.0 <X ₁ <2.7
(In the formula (3), X ₁ represents a degree of acetyl substitution of the cellulose acylate of the skin layer A and skin layer B.)
Formula (4): 0 ≦ Y ₁ <1.5
(In Formula (4), Y ₁ represents the total substitution degree of acyl groups having 3 or more carbon atoms in the cellulose acylate of the skin A layer and the skin B layer.)
11. The cellulose acylate laminated film according to any one of items 1 to 10, wherein the cellulose acylate used for the core layer satisfies the following formulas (5) and (6).
Formula (5): 1.2 <X ₂ <3.0
(In the formula (5), X ₂ represents a substitution degree of acetyl groups of the cellulose acylate of the core layer.)
Formula (6): 0 ≦ Y ₂ <1.5
(Wherein (in 6), Y ₂ represents a total substitution degree of the cellulose acylate acyl group having 3 or more carbon atoms of the core layer.)
12 The cellulose acylate laminated film according to any one of items 1 to 11, wherein the cellulose acylate has an acyl group having 2 to 4 carbon atoms.

13. Nz coefficient represented by following formula (7) is 7 or less, The cellulose acylate laminated film as described in any one of said 1st term | claim to 12th term | claim characterized by the above-mentioned.
Formula (7): Nz coefficient = Rth / Re + 0.5
14 14. The cellulose acylate laminated film according to any one of items 1 to 13, wherein the cellulose acylate is cellulose acetate.

  15. A polarizing plate using at least one sheet of the cellulose acylate laminated film according to any one of items 1 to 14 above.

  16. A liquid crystal display device comprising at least one cellulose acylate laminated film according to any one of items 1 to 14 above.

  By the above means of the present invention, it is possible to provide a cellulose acylate laminated film which is excellent in bonding property with a polarizer and has a small dimensional change due to humidity, and a highly reliable polarizing plate and liquid crystal display device using the same. .

  ADVANTAGE OF THE INVENTION According to this invention, the cellulose acylate laminated film which has both the adhesiveness with the hydrophilic film which was not realizable with the conventional cellulose acylate film, and the minimum of the fluctuation range by a humidity change can be provided. That is, it is possible to eliminate the need for the conventional treatment of improving the adhesion while maintaining good releasability to obtain the adhesiveness with the hydrophilic film by treating the surface with alkali. Furthermore, according to the preferable aspect of this invention, when it has a skin layer on both surfaces of a core layer, the physical property (curl) of a film can also be controlled suitably. Such a film and a polarizing plate using the film can be preferably used for a liquid crystal display device, and can be particularly preferably used for a VA liquid crystal display device.

Co-casting die and a diagram showing a multi-layered web formed by casting

  The cellulose acylate laminated film of the present invention was formed by laminating a skin B layer containing a cellulose acylate satisfying the formula (1) and a core layer containing a cellulose acylate satisfying the formula (2). A cellulose acylate laminated film comprising a retardation adjusting agent in at least one of the skin B layer and the core layer. This feature is a technical feature common to the inventions according to claims 1 to 16.

  As an embodiment of the present invention, it is preferable that a retardation developer is contained in the core layer from the viewpoint of the effect of the present invention. Furthermore, it is preferable that the said core layer contains the compound represented by the said general formula (A) whose total average substitution degree exists in the range of 4.5-6.9.

  In the present invention, the skin B layer preferably contains a compound having negative intrinsic birefringence. Moreover, it is preferable that it is an aspect which has the skin A layer containing the cellulose acylate which satisfy | fills following formula (1) on the surface on the opposite side to the surface with the skin B layer of the said laminated | stacked core layer. . Furthermore, it is preferable that at least one of the skin A layer and the skin B layer contains a polymer having a cyclic structure in the side chain.

  In the present invention, at the measurement wavelength of 590 nm, the in-plane retardation Re is in the range of 25 nm ≦ | Re | ≦ 100 nm, and the retardation Rth in the thickness direction is in the range of 50 nm ≦ | Rth | ≦ 250 nm. It is preferable that

  In the present invention, it is preferable that at least one of the skin A layer and the skin B layer contains metal fine particles. The average layer thickness of the core layer is in the range of 30 to 100 μm, and the average layer thickness of at least one of the skin A layer and the skin B layer is 0.2% or more and 25% of the average layer thickness of the core layer. It is preferable that it is less than. Furthermore, the film width is preferably in the range of 700 to 3000 mm.

  In the present invention, it is preferable that the cellulose acylate used in the skin A layer and the skin B layer satisfy the formulas (3) and (4). Moreover, it is preferable that the cellulose acylate used for the core layer satisfies the formulas (5) and (6). Furthermore, the number of carbon atoms of the acyl group of the cellulose acylate is preferably in the range of 2-4. Furthermore, it is preferable that the Nz coefficient represented by the formula (7) is 7 or less.

  In the present invention, the cellulose acylate is preferably cellulose acetate.

  The cellulose acylate laminated film of the present invention can be suitably used for polarizing plates and liquid crystal display devices.

  Hereinafter, the present invention, its components, and modes and modes for carrying out the present invention will be described in detail. In addition, in this application, "-" is used in the meaning which includes the numerical value described before and behind that as a lower limit and an upper limit.

  The following terms and symbols used in the present application are defined as follows.

  (1) “nx” is the refractive index in the direction in which the in-plane refractive index is maximum (ie, the slow axis direction), and “ny” is the direction perpendicular to the slow axis in the plane (ie, advance). “Nz” is the refractive index in the thickness direction.

  For example, “nx = ny” includes not only the case where nx and ny are exactly equal, but also the case where nx and ny are substantially equal. In the present application, “substantially equal” is intended to include the case where nx and ny are different within a range that does not practically affect the overall optical characteristics of the liquid crystal panel.

  (2) “In-plane retardation (retardation) Re” refers to a retardation value in a film (layer) plane measured with light having a wavelength of 590 nm at 23 ° C. and 55% RH. Re is a formula when the refractive index in the slow axis direction and the fast axis direction of the film (layer) at a wavelength of 590 nm is nx and ny, respectively, and d (nm) is the thickness of the film (layer): Re = It is calculated by (nx−ny) × d.

  (3) “Thickness direction retardation (phase difference) Rth” refers to a thickness direction retardation value measured with light having a wavelength of 590 nm at 23 ° C. and 55% RH. Rth is the refractive index in the slow axis direction, fast axis direction, and thickness direction of the film (layer) at a wavelength of 590 nm, respectively, nx, ny, nz, and d (nm) is the thickness of the film (layer). Where Rth = {(nx + ny) / 2−nz)} × d.

  (4) “Nz coefficient” is a value calculated by the formula: Rth / Re + 0.5.

  In the present application, the term “retardation modifier” refers to a retardation in the in-plane direction of the film (hereinafter abbreviated as “Re” as appropriate) or a retardation in the thickness direction of the film (hereinafter referred to as “Rth” as appropriate). A compound that increases or decreases at least one of them.

  Further, “retardation enhancer” refers to a compound that increases at least one of Re or Rth, and “retardation reducing agent” refers to a compound that decreases at least one of Re or Rth.

  In the present application, the “core layer” refers to a layer on the inner side of the laminated layers when the cellulose acylate laminated film is composed of three or more laminated layers. The layer thickness is preferably thicker than the skin layer on the outside. When the cellulose acylate laminated film has a two-layer structure, the layer with the thickest layer is defined as a “core layer”.

  On the other hand, the “skin layer” refers to a layer on the outer surface side of the laminated layers when the cellulose acylate laminated film is composed of three or more laminated layers. The layer thickness is preferably thinner than the core layer on the inner side.

  In the present application, the term “skin layer” refers to both “skin A layer” and “skin B layer”.

  The “skin A layer” may be referred to as an “air surface layer”, and the “skin B layer” may be referred to as a “support surface layer”. Furthermore, the “core layer” may be referred to as a “base layer”.

[Cellulose acylate laminate film]
The cellulose acylate laminated film of the present invention (hereinafter also referred to as “the film of the present invention”) includes a skin B layer containing a cellulose acylate satisfying the following formula (1) and a cellulose acyl satisfying the following formula (2). A cellulose acylate laminated film in which a core layer containing a rate is laminated and formed, wherein at least one of the skin B layer and the core layer contains a retardation adjusting agent.

Formula (1): 2.0 <Z ₁ <2.7
(In formula (1), Z ₁ represents the total acyl group substitution degree of the cellulose acylate of the skin layer.)
Formula (2): 2.7 <Z ₂ <3.0
(In formula (2), Z ₂ represents the total acyl group substitution degree of the cellulose acylate of the core layer.)
As a preferred embodiment of the present invention, the core layer preferably contains a retardation developer. Furthermore, it is preferable that the said core layer contains the compound represented by the said general formula (A) whose total average substitution degree exists in the range of 4.5-6.9.

  In the present invention, the skin B layer preferably contains a compound having negative intrinsic birefringence. Moreover, it is preferable that it is an aspect which has the skin A layer containing the cellulose acylate which satisfy | fills following formula (1) on the surface on the opposite side to the surface with the skin B layer of the said laminated | stacked core layer. . Furthermore, it is preferable that at least one of the skin A layer and the skin B layer contains a polymer having a cyclic structure in the side chain.

  It is a preferred embodiment of the present invention to use a low-substitution cellulose acylate satisfying the above formula (1) for the skin A layer and a polymer having a cyclic structure in the side chain to form a laminated film. By taking the configuration, the adhesion between the cellulose acylate laminated film and the hydrophilic film is enhanced.

  Furthermore, it is also a preferred aspect that a retardation adjusting agent is added to at least one of the core layer or the skin layer and stretched, and partial fluctuations in the thickness of the core layer and the skin layer that are technically unavoidable occur in co-casting. Even if it is a case, the influence which the optical characteristic of the whole laminated film receives is suppressed, and the variation of Re and Rth can be suppressed.

  Therefore, compared with the conventional cellulose acylate film, the cellulose acylate laminated film of the present invention has high expression of optical properties and very little variation in optical properties.

  Hereinafter, the features and preferred embodiments of the film of the present invention will be described in detail.

(Cellulosic resin)
The cellulose resin used in the present invention is not particularly defined as long as the total substitution degree of the acyl group satisfies the formulas (1) and (2).

  Cellulose resin is preferably cellulose acylate, and cellulose as acylate raw material includes cotton linter and wood pulp (hardwood pulp, conifer pulp), and any cellulose acylate obtained from any raw material cellulose can be used depending on circumstances. You may mix and use. Detailed descriptions of these raw material celluloses can be found, for example, by Marusawa and Uda, “Plastic Materials Course (17) Fibrous Resin”, published by Nikkan Kogyo Shimbun (published in 1970), and the Japan Institute of Invention and Technology Publication No. 2001 The cellulose described in No.-1745 (pages 7 to 8) can be used.

(Cellulose acylate)
Glucose units having β-1,4 bonds constituting cellulose have free hydroxyl groups (hydroxyl groups) at the 2nd, 3rd and 6th positions. Cellulose acylate is a polymer obtained by acylating part or all of these hydroxyl groups (hydroxyl groups) with an acyl group. The degree of acyl group substitution means the rate at which the hydroxyl groups (hydroxyl groups) of cellulose located at the 2-position, 3-position and 6-position are acylated (100% acylation has a substitution degree of 1).

Z ₁ preferably satisfies 2.1 <Z ₁ <2.6, and particularly preferably satisfies 2.3 <Z ₁ <2.5.

The Z ₂ preferably satisfies 2.75 <Z ₂ <2.95, and particularly preferably satisfies 2.80 <Z2 <2.95.

  In the film of the present invention, the cellulose acylate used for the skin A layer and the B layer preferably satisfies the following formulas (3) and (4) from the viewpoint of improving optical expression.

Formula (3): 1.0 <X ₁ <2.7
(In the formula (3), X ₁ represents a degree of acetyl substitution of the cellulose acylate of the skin layer A and B layers.)
Formula (4): 0 ≦ Y ₁ <1.5
(In formula (4), Y ₁ represents the total substitution degree of acyl groups having 3 or more carbon atoms in the cellulose acylate of the skin A layer and the B layer.)
The X1 more preferably satisfies 1.5 <X ₁ <2.7, and particularly preferably satisfies 2.0 <X ₁ <2.7.

The Y1 preferably satisfies 0 ≦ Y ₁ <1.3, and particularly preferably satisfies 0 ≦ Y ₁ <1.0.

  In the film of the present invention, the cellulose acylate used in the core layer further satisfies the following formulas (5) and (6) from the viewpoint of improving the peelability from the support in addition to the improvement in optical expression. preferable.

Formula (5): 1.2 <X ₂ <3.0
(In the formula (5), _{X 2} represents a substitution degree of acetyl groups of the cellulose acylate of the core layer.) Equation _{(6): 0 ≦ Y 2} <1.5
(Wherein (in 6), Y ₂ represents a total substitution degree of the cellulose acylate acyl group having 3 or more carbon atoms of the core layer.)
The X ₂ more preferably satisfies 1.5 <X ₂ <3.0, and particularly preferably satisfies 1.8 <X ₂ <3.0.

The Y ₂ more preferably satisfies 0 ≦ Y ₂ <1.3, and particularly preferably satisfies 0 ≦ Y ₂ <1.0.

  The film according to the present invention has a skin A layer containing cellulose acylate satisfying the formula (2) on the surface of the core layer opposite to the skin B layer. ) Is more preferable from the viewpoint of suitably controlling.

  The acyl group having 2 or more carbon atoms of cellulose acylate in the present invention may be an aliphatic group or an aryl group, and is not particularly limited. These are, for example, cellulose alkylcarbonyl esters, alkenylcarbonyl esters, aromatic carbonyl esters, aromatic alkylcarbonyl esters, and the like, each of which may further have a substituted group. Preferred examples of these include acetyl group, propionyl group, butanoyl group, heptanoyl group, hexanoyl group, octanoyl group, decanoyl group, dodecanoyl group, tridecanoyl group, tetradecanoyl group, hexadecanoyl group, octadecanoyl group, isobutanoyl group Group, tert-butanoyl group, cyclohexanecarbonyl group, oleoyl group, benzoyl group, naphthylcarbonyl group, cinnamoyl group and the like. Among these, an acetyl group, a propionyl group, a butanoyl group, a dodecanoyl group, an octadecanoyl group, a tert-butanoyl group, an oleoyl group, a benzoyl group, a naphthylcarbonyl group, a cinnamoyl group, and the like are more preferable, and an acetyl group is particularly preferable. A propionyl group and a butanoyl group (when the acyl group has 2 to 4 carbon atoms), more preferably an acetyl group (when the cellulose acylate is cellulose acetate).

  In the acylation of cellulose, when an acid anhydride or acid chloride is used as an acylating agent, an organic acid such as acetic acid or methylene chloride is used as an organic solvent as a reaction solvent.

As the catalyst, when the acylating agent is an acid anhydride, a protic catalyst such as sulfuric acid is preferably used, and when the acylating agent is an acid chloride (for example, CH ₃ CH ₂ COCl), Basic compounds are used.

  The most common industrial synthesis method of mixed fatty acid esters of cellulose is cellulose mixed organics containing fatty acids corresponding to acetyl groups and other acyl groups (acetic acid, propionic acid, valeric acid, etc.) or acid anhydrides thereof. This is a method of acylating with an acid component.

  The cellulose acylate used in the present invention can be synthesized, for example, by the method described in JP-A-10-45804.

  In the film of the present invention, a compound represented by the following general formula (A), a retardation adjusting agent (a retardation developing agent and a retardation reducing agent), a plasticizer such as a phthalate ester and a phosphate ester; An additive such as an agent; an antioxidant; a matting agent may be added.

(Wherein R _{1 to} R ₈ each independently represents a substituted or unsubstituted alkylcarbonyl group or a substituted or unsubstituted arylcarbonyl group, and R _{1 to} R ₈ are the same, May be different.)
Preferable specific examples of the compound represented by the general formula (A) include compounds shown in Table 1. In addition, R described in the following table represents any one of R _{1 to} R ₈ . As the substituent for the alkylcarbonyl group and the arylcarbonyl group, substituents such as a phenyl group and an alkoxy group included in the alkylcarbonyl group and the arylcarbonyl group shown in the following table are preferable.

<Retardation adjuster>
The retardation adjusting agent is not particularly limited other than the above-described properties, and when additives such as the plasticizer, ultraviolet absorber, antioxidant, matting agent are also used as the retardation adjusting agent, these The additive is included in the retardation adjusting agent in the present invention.

(Retardation expression agent)
In this invention, in order to express a retardation value, what consists of a rod-shaped or a disk shaped compound can be mentioned. As the rod-like or discotic compound, a compound having at least two aromatic rings can be preferably used as a retardation developer.

  The addition amount of the retardation developer composed of the rod-shaped compound is preferably 0.1 to 30 parts by mass, and 0.5 to 20 parts by mass with respect to 100 parts by mass of the polymer component containing cellulose acylate. Is more preferable. The disk-shaped retardation developer is preferably used in a range of 0.05 to 20 parts by mass, and in a range of 1.0 to 15 parts by mass with respect to 100 parts by mass of the polymer component containing the cellulose acylate. It is more preferable to use in the range of 3.0 to 10 parts by mass.

  Since the discotic compound is superior to the rod-shaped compound in Rth retardation expression, it is preferably used when a particularly large Rth retardation is required. Two or more types of retardation developing agents may be used in combination.

  The retardation developer preferably has maximum absorption in the wavelength region of 250 to 400 nm, and preferably has substantially no absorption in the visible region.

  The discotic compound will be described. As the discotic compound, a compound having at least two aromatic rings can be used.

  In the present specification, the “aromatic ring” includes an aromatic hetero ring in addition to an 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.

  As the aromatic ring, a benzene ring, a condensed benzene ring, and biphenyls are preferable. In particular, a 1,3,5-triazine ring is preferably used. Specifically, for example, compounds disclosed in JP-A No. 2001-166144 are preferably used.

  The number of carbon atoms in the aromatic ring of the retardation developer is preferably 2-20, more preferably 2-12, further preferably 2-8, and 2-6. Most preferred.

  The bonding relationship between two aromatic rings can be classified into (a) when forming a condensed ring, (b) when directly connecting with a single bond, and (c) when connecting via a linking group (for aromatic rings). , Spiro bonds cannot be formed). The connection relationship may be any of (a) to (c).

  Examples of the condensed ring (a condensed ring of two or more aromatic rings) include an indene ring, a naphthalene ring, an azulene ring, a fluorene ring, a phenanthrene ring, an anthracene ring, an acenaphthylene ring, a biphenylene ring, a naphthacene ring, Pyrene ring, indole ring, isoindole ring, benzofuran ring, benzothiophene ring, indolizine ring, benzoxazole ring, benzothiazole ring, benzimidazole ring, benzotriazole ring, purine ring, indazole ring, chromene ring, quinoline ring, isoquinoline Ring, quinolidine ring, quinazoline ring, cinnoline ring, quinoxaline ring, phthalazine ring, pteridine ring, carbazole ring, acridine ring, phenanthridine ring, xanthene ring, phenazine ring, phenothiazine ring, phenoxathiin ring, phenoxazine ring and thiantole Ring is included. Naphthalene ring, azulene ring, indole ring, benzoxazole ring, benzothiazole ring, benzimidazole ring, benzotriazole ring and quinoline ring are preferred.

  The single bond (b) is preferably a bond between carbon atoms of two aromatic rings. Two aromatic rings may be bonded by two or more single bonds to form an aliphatic ring or a non-aromatic heterocyclic ring between the two aromatic rings.

  The linking group in (c) is also preferably bonded to carbon atoms of two aromatic rings. The linking group is preferably an alkylene group, an alkenylene group, an alkynylene group, —CO—, —O—, —NH—, —S—, or a combination thereof. Examples of linking groups composed of combinations are shown below. In addition, the relationship between the left and right in the following examples of the linking group may be reversed.

c1: -CO-O-
c2: —CO—NH—
c3: -alkylene-O-
c4: —NH—CO—NH—
c5: —NH—CO—O—
c6: —O—CO—O—
c7: -O-alkylene-O-
c8: -CO-alkenylene-
c9: -CO-alkenylene-NH-
c10: -CO-alkenylene-O-
c11: -alkylene-CO-O-alkylene-O-CO-alkylene-
c12: -O-alkylene-CO-O-alkylene-O-CO-alkylene-O-
c13: -O-CO-alkylene-CO-O-
c14: -NH-CO-alkenylene-
c15: -O-CO-alkenylene-
The aromatic ring and the linking group may have a substituent.

  Examples of substituents include halogen atoms (F, Cl, Br, I), hydroxyl groups, carboxyl groups, cyano groups, amino groups, nitro groups, sulfo groups, carbamoyl groups, sulfamoyl groups, ureido groups, alkyl groups, alkenyls. Group, alkynyl group, aliphatic acyl group, aliphatic acyloxy group, alkoxy group, alkoxycarbonyl group, alkoxycarbonylamino group, alkylthio group, alkylsulfonyl group, aliphatic amide group, aliphatic sulfonamido group, aliphatic substituted amino group An aliphatic substituted carbamoyl group, an aliphatic substituted sulfamoyl group, an aliphatic substituted ureido group, and a non-aromatic heterocyclic group.

  It is preferable that the alkyl group has 1 to 8 carbon atoms. A chain alkyl group is preferable to a cyclic alkyl group, and a linear alkyl group is particularly preferable. The alkyl group may further have a substituent (for example, a hydroxy group, a carboxy group, an alkoxy group, an alkyl-substituted amino group). Examples of alkyl groups (including substituted alkyl groups) include methyl, ethyl, n-butyl, n-hexyl, 2-hydroxyethyl, 4-carboxybutyl, 2-methoxyethyl and 2-methoxyethyl. Each group of a diethylaminoethyl group is included.

  The alkenyl group preferably has 2 to 8 carbon atoms. A chain alkenyl group is preferable to a cyclic alkenyl group, and a linear alkenyl group is particularly preferable. The alkenyl group may further have a substituent. Examples of the alkenyl group include a vinyl group, an allyl group, and a 1-hexenyl group.

  The alkynyl group preferably has 2 to 8 carbon atoms. A chain alkynyl group is preferable to a cyclic alkynyl group, and a linear alkynyl group is particularly preferable. The alkynyl group may further have a substituent. Examples of the alkynyl group include ethynyl group, 1-butynyl group and 1-hexynyl group.

  The number of carbon atoms in the aliphatic acyl group is preferably 1-10. Examples of the aliphatic acyl group include an acetyl group, a propanoyl group, and a butanoyl group.

  The number of carbon atoms in the aliphatic acyloxy group is preferably 1-10. Examples of the aliphatic acyloxy group include an acetoxy group.

  The number of carbon atoms of the alkoxy group is preferably 1-8. The alkoxy group may further have a substituent (for example, an alkoxy group). Examples of the alkoxy group (including a substituted alkoxy group) include a methoxy group, an ethoxy group, a butoxy group, and a methoxyethoxy group.

  The number of carbon atoms of the alkoxycarbonyl group is preferably 2-10. Examples of the alkoxycarbonyl group include a methoxycarbonyl group and an ethoxycarbonyl group.

  The number of carbon atoms of the alkoxycarbonylamino group is preferably 2-10. Examples of the alkoxycarbonylamino group include a methoxycarbonylamino group and an ethoxycarbonylamino group.

  The alkylthio group preferably has 1 to 12 carbon atoms. Examples of the alkylthio group include a methylthio group, an ethylthio group, and an octylthio group.

  The alkylsulfonyl group preferably has 1 to 8 carbon atoms. Examples of the alkylsulfonyl group include a methanesulfonyl group and an ethanesulfonyl group.

  The number of carbon atoms in the aliphatic amide group is preferably 1-10. Examples of the aliphatic amide group include acetamide.

  The number of carbon atoms of the aliphatic sulfonamide group is preferably 1-8. Examples of the aliphatic sulfonamido group include a methanesulfonamido group, a butanesulfonamido group, and an n-octanesulfonamido group.

  The number of carbon atoms of the aliphatic substituted amino group is preferably 1-10. Examples of the aliphatic substituted amino group include a dimethylamino group, a diethylamino group, and a 2-carboxyethylamino group.

  The number of carbon atoms in the aliphatic substituted carbamoyl group is preferably 2-10. Examples of the aliphatic substituted carbamoyl group include a methylcarbamoyl group and a diethylcarbamoyl group.

  The number of carbon atoms in the aliphatic substituted sulfamoyl group is preferably 1-8. Examples of the aliphatic substituted sulfamoyl group include a methylsulfamoyl group and a diethylsulfamoyl group.

  The number of carbon atoms in the aliphatic substituted ureido group is preferably 2-10. Examples of the aliphatic substituted ureido group include a methylureido group.

  Examples of the non-aromatic heterocyclic group include a piperidino group and a morpholino group.

  The molecular weight of the retardation developer is preferably 300 to 800.

  As the discotic compound, a triazine compound represented by the following general formula (I) is preferably used.

In the general formula (I), each R ¹ independently represents an aromatic ring or a heterocyclic ring having a substituent in at least one of the ortho position, the meta position, and the para position.

X represents each independently a single bond or NR < ² >-. Here, each R ² independently represents a hydrogen atom, a substituted or unsubstituted alkyl group, an alkenyl group, an aryl group, or a heterocyclic group.

The aromatic ring represented by R ¹ is preferably phenyl or naphthyl, and particularly preferably phenyl. The aromatic ring represented by R ¹ may have at least one substituent at any substitution position. Examples of the substituent include halogen atom, hydroxyl group, cyano group, nitro group, carboxyl group, alkyl group, alkenyl group, aryl group, alkoxy group, alkenyloxy group, aryloxy group, acyloxy group, alkoxycarbonyl group, Alkenyloxycarbonyl group, aryloxycarbonyl group, sulfamoyl group, alkyl-substituted sulfamoyl group, alkenyl-substituted sulfamoyl group, aryl-substituted sulfamoyl group, sulfonamide group, carbamoyl, alkyl-substituted carbamoyl group, alkenyl-substituted carbamoyl group, aryl-substituted carbamoyl group, amide Groups, alkylthio groups, alkenylthio groups, arylthio groups and acyl groups.

The heterocyclic group represented by R ¹ preferably has aromaticity. The heterocycle having aromaticity is generally an unsaturated heterocycle, preferably a heterocycle having the largest number of double bonds. The heterocyclic ring is preferably a 5-membered ring, 6-membered ring or 7-membered ring, more preferably a 5-membered ring or 6-membered ring, and most preferably a 6-membered ring. The hetero atom of the heterocyclic ring is preferably a nitrogen atom, a sulfur atom or an oxygen atom, and particularly preferably a nitrogen atom. As the heterocyclic ring having aromaticity, a pyridine ring (2-pyridyl or 4-pyridyl as the heterocyclic group) is particularly preferable. The heterocyclic group may have a substituent. Examples of the substituent of the heterocyclic group are the same as the examples of the substituent of the aryl moiety.

When X is a single bond, the heterocyclic group is preferably a heterocyclic group having a free valence on the nitrogen atom. The heterocyclic group having a free valence on the nitrogen atom is preferably a 5-membered ring, 6-membered ring or 7-membered ring, more preferably a 5-membered ring or 6-membered ring, and a 5-membered ring. Is most preferred. The heterocyclic group may have a plurality of nitrogen atoms. Further, the heterocyclic group may have a hetero atom other than the nitrogen atom (for example, O, S). Examples of heterocyclic groups having free valences on nitrogen atoms are shown below. Here, _-C 4 _{H 9} n represents a _n-C 4 _{H 9.}

The alkyl group represented by R ² may be a cyclic alkyl group or a chain alkyl group, but a chain alkyl group is preferable, and a linear alkyl group is more preferable than a branched chain alkyl group. preferable. The number of carbon atoms in the alkyl group is preferably 1-30, more preferably 1-20, further preferably 1-10, still more preferably 1-8, and 1-6. Most preferred. The alkyl group may have a substituent. Examples of the substituent include a halogen atom, an alkoxy group (for example, methoxy group, ethoxy group) and an acyloxy group (for example, acryloyloxy group, methacryloyloxy group).

The alkenyl group represented by R ² may be a cyclic alkenyl group or a chain alkenyl group, but preferably represents a chain alkenyl group, and is a straight chain alkenyl group rather than a branched chain alkenyl group. More preferably it represents a group. The number of carbon atoms in the alkenyl group is preferably 2 to 30, more preferably 2 to 20, still more preferably 2 to 10, still more preferably 2 to 8, 6 is most preferred. The alkenyl group may have a substituent. Examples of the substituent are the same as those of the alkyl group described above.

The aromatic ring group and heterocyclic group represented by R ² are the same as the aromatic ring and heterocyclic ring represented by R ¹ , and the preferred range is also the same. The aromatic ring group and the heterocyclic group may further have a substituent, and examples of the substituent are the same as those of the aromatic ring and heterocyclic ring of R ¹ .

  Although the specific example of a compound represented by general formula (I) below is given, it is not limited to this.

  As the discotic compound, a triphenylene compound represented by the following general formula (II) can also be preferably used.

In the general formula (II), R ^{1 to} R ⁶ each independently represents a hydrogen atom or a substituent.

Examples of the substituent represented by each of R ^{1 to} R ⁶ include an alkyl group (preferably an alkyl group having 1 to 40 carbon atoms, more preferably 1 to 30 carbon atoms, and particularly preferably 1 to 20 carbon atoms. Group, ethyl group, isopropyl group, tert-butyl group, n-octyl group, n-decyl group, n-hexadecyl group, cyclopropyl group, cyclopentyl group, cyclohexyl group, etc.), alkenyl group (preferably carbon An alkenyl group having 2 to 40 carbon atoms, more preferably 2 to 30 carbon atoms, particularly preferably 2 to 20 carbon atoms, and examples thereof include a vinyl group, an allyl group, a 2-butenyl group, and a 3-pentenyl group. An alkynyl group (preferably an alkynyl group having 2 to 40 carbon atoms, more preferably 2 to 30 carbon atoms, particularly preferably 2 to 20 carbon atoms, A propargyl group, a 3-pentynyl group, etc.), an aryl group (preferably an aryl group having 6 to 30 carbon atoms, more preferably 6 to 20 carbon atoms, and particularly preferably 6 to 12 carbon atoms. , Phenyl group, p-methylphenyl group, naphthyl group, etc.), substituted or unsubstituted amino group (preferably having 0 to 40 carbon atoms, more preferably 0 to 30 carbon atoms, and particularly preferably 0 to 0 carbon atoms). 20 amino groups such as an unsubstituted amino group, a methylamino group, a dimethylamino group, a diethylamino group, and an anilino group, and an alkoxy group (preferably having 1 to 40 carbon atoms, more preferably 1 carbon atom). To 30 and particularly preferably an alkoxy group having 1 to 20 carbon atoms, and examples thereof include a methoxy group, an ethoxy group, and a butoxy group). A reeloxy group (preferably an aryloxy group having 6 to 40 carbon atoms, more preferably 6 to 30 carbon atoms, particularly preferably 6 to 20 carbon atoms, and examples thereof include a phenyloxy group and a 2-naphthyloxy group. An acyl group (preferably an acyl group having 1 to 40 carbon atoms, more preferably 1 to 30 carbon atoms, and particularly preferably 1 to 20 carbon atoms, such as an acetyl group, a benzoyl group, a formyl group, and a pivaloyl group. Etc.), an alkoxycarbonyl group (preferably an alkoxycarbonyl group having 2 to 40 carbon atoms, more preferably 2 to 30 carbon atoms, particularly preferably 2 to 20 carbon atoms, such as a methoxycarbonyl group, ethoxycarbonyl group, etc. Group), aryloxycarbonyl group (preferably having 7 to 40 carbon atoms, more preferably having carbon number) An aryloxycarbonyl group having 7 to 30 carbon atoms, particularly preferably 7 to 20 carbon atoms, such as a phenyloxycarbonyl group, and an acyloxy group (preferably having 2 to 40 carbon atoms, more preferably 2 to 2 carbon atoms). 30, particularly preferably an acyloxy group having 2 to 20 carbon atoms, such as an acetoxy group and a benzoyloxy group), an acylamino group (preferably having 2 to 40 carbon atoms, more preferably 2 to 30 carbon atoms, Particularly preferred is an acylamino group having 2 to 20 carbon atoms, such as an acetylamino group and a benzoylamino group, and an alkoxycarbonylamino group (preferably having 2 to 40 carbon atoms, more preferably 2 to 30 carbon atoms, Particularly preferred is an alkoxycarbonylamino group having 2 to 20 carbon atoms, for example, methoxy A sulfonylamino group), an aryloxycarbonylamino group (preferably an aryloxycarbonylamino group having 7 to 40 carbon atoms, more preferably 7 to 30 carbon atoms, particularly preferably 7 to 20 carbon atoms, A phenyloxycarbonylamino group), a sulfonylamino group (preferably a sulfonylamino group having 1 to 40 carbon atoms, more preferably 1 to 30 carbon atoms, particularly preferably 1 to 20 carbon atoms, A methanesulfonylamino group, a benzenesulfonylamino group and the like), a sulfamoyl group (preferably a sulfamoyl group having 0 to 40 carbon atoms, more preferably 0 to 30 carbon atoms, and particularly preferably 0 to 20 carbon atoms, , Sulfamoyl group, methylsulfamoyl group, dimethylsulfamo Carbamoyl group (preferably having 1 to 40 carbon atoms, more preferably 1 to 30 carbon atoms, and particularly preferably 1 to 20 carbon atoms). An unsubstituted carbamoyl group, a methylcarbamoyl group, a diethylcarbamoyl group, a phenylcarbamoyl group, and the like, an alkylthio group (preferably having 1 to 40 carbon atoms, more preferably 1 to 30 carbon atoms, and particularly preferably 1 to carbon atoms). 20, for example, methylthio group, ethylthio group, propylthio group, butylthio group, pentylthio group, hexylthio group, heptylthio group, octylthio group, etc.), arylthio group (preferably having 6 to 40 carbon atoms, more preferably 6-30 carbon atoms, particularly preferably 1-20 carbon atoms, e.g. A sulfonyl group (preferably 1 to 40 carbon atoms, more preferably 1 to 30 carbon atoms, particularly preferably 1 to 20 carbon atoms, such as a mesyl group, a tosyl group, etc.) A sulfinyl group (preferably a sulfinyl group having 1 to 40 carbon atoms, more preferably 1 to 30 carbon atoms, particularly preferably 1 to 20 carbon atoms, such as a methanesulfinyl group and a benzenesulfinyl group). Ureido group (preferably a ureido group having 1 to 40 carbon atoms, more preferably 1 to 30 carbon atoms, particularly preferably 1 to 20 carbon atoms, such as an unsubstituted ureido group, a methylureido group, Phenylureido group), phosphoric acid amide group (preferably having 1 to 40 carbon atoms, more preferably having 1 to 30 carbon atoms) Preferably it is a C1-C20 phosphoric acid amide group, for example, a diethylphosphoric acid amide group, a phenylphosphoric acid amide group etc. are mentioned, a hydroxy group, a mercapto group, a halogen atom (for example, a fluorine atom, a 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). A heterocyclic group having a heteroatom such as a nitrogen atom, an oxygen atom or a sulfur atom, such as an imidazolyl group, a pyridyl group, a quinolyl group, a furyl group, a piperidyl group, a morpholino group, a benzoyl group, Examples include an oxazolyl group, a benzimidazolyl group, a benzthiazolyl group, and a 1,3,5-triazyl group. A silyl group (preferably a silyl group having 3 to 40 carbon atoms, more preferably 3 to 30 carbon atoms, particularly preferably 3 to 24 carbon atoms, and examples thereof include a trimethylsilyl group and a triphenylsilyl group. ) Is included. These substituents may be further substituted with these substituents. Moreover, when it has two or more substituents, they may be the same or different. If possible, they may be bonded to each other to form a ring.

The substituent represented by each of R ^{1 to} R ⁶ is preferably an alkyl group, an aryl group, a substituted or unsubstituted amino group, an alkoxy group, an alkylthio group, or a halogen atom. Although the specific example of a compound represented by general formula (II) below is given, it is not limited to this.

  The compound represented by the general formula (I) is, for example, a method described in JP-A No. 2003-344655, and the compound represented by the general formula (II) is, for example, a method described in JP-A-2005-134484. Can be synthesized by a known method.

  In the present invention, rod-like compounds having a linear molecular structure can be preferably used in addition to the above-mentioned discotic compounds. The linear molecular structure means that the molecular structure of the rod-like compound is linear in the most thermodynamically stable structure. The most thermodynamically stable structure can be obtained by crystal structure analysis or molecular orbital calculation. For example, molecular orbital calculation is performed using molecular orbital calculation software (for example, WinMOPAC2000, manufactured by Fujitsu Limited), and a molecular structure that minimizes the heat of formation of a compound can be obtained. The molecular structure being linear means that in the thermodynamically most stable structure obtained by calculation as described above, the angle of the main chain constituting the molecular structure is 140 degrees or more.

  As the rod-shaped compound having at least two aromatic rings, a compound represented by the following general formula (11) is preferable.

Formula (11): Ar ₁ -L ₁ -Ar ₂
In the general formula (11), Ar ₁ and Ar ₂ are each independently an aromatic group.

  In the present specification, the aromatic group includes an aryl group (aromatic hydrocarbon group), a substituted aryl group, an aromatic heterocyclic group, and a substituted aromatic heterocyclic group.

  An aryl group and a substituted aryl group are more preferable than an aromatic heterocyclic group and a substituted aromatic heterocyclic group. The heterocyclic ring of the aromatic heterocyclic group is generally unsaturated. 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 a hetero atom, a nitrogen atom, an oxygen atom or a sulfur atom is preferable, and a nitrogen atom or a sulfur atom is more preferable.

  As the aromatic ring of the aromatic group, a benzene ring, a furan ring, a thiophene ring, a pyrrole ring, an oxazole ring, a thiazole ring, an imidazole ring, a triazole ring, a pyridine ring, a pyrimidine ring and a pyrazine ring are preferable, and a benzene ring is particularly preferable. .

  Examples of the substituent of the substituted aryl group and the substituted aromatic heterocyclic group include a halogen atom (F, Cl, Br, I), a hydroxyl group, a carboxyl group, a cyano group, an amino group, an alkylamino group (for example, methyl Amino group, ethylamino group, butylamino group, dimethylamino group), nitro group, sulfo group, carbamoyl group, alkylcarbamoyl group (for example, N-methylcarbamoyl group, N-ethylcarbamoyl group, N, N-) Dimethylcarbamoyl group), sulfamoyl group, alkylsulfamoyl group (eg, N-methylsulfamoyl group, N-ethylsulfamoyl group, N, N-dimethylsulfamoyl group), ureido Group, alkylureido group (for example, N-methylureido group, N, N-dimethylureido group, N, N, N′-trimethyl group) Each group of a ureido group), an alkyl group (for example, methyl group, ethyl group, propyl group, butyl group, pentyl group, heptyl group, octyl group, isopropyl group, s-butyl group, tert-amyl group, cyclohexyl group, cyclopentyl) Group), alkenyl group (for example, vinyl group, allyl group, hexenyl group), alkynyl group (for example, ethynyl group, butynyl group), acyl group (for example, formyl group, acetyl group, butyryl group, Hexanoyl group, lauryl group), acyloxy group (for example, acetoxy group, butyryloxy group, hexanoyloxy group, lauryloxy group), alkoxy group (for example, methoxy group, ethoxy group, propoxy group, butoxy group) Pentyloxy group, heptyloxy group, octyloxy group), arylo Si group (for example, phenoxy group), alkoxycarbonyl group (for example, methoxycarbonyl group, ethoxycarbonyl group, propoxycarbonyl group, butoxycarbonyl group, pentyloxycarbonyl group, heptyloxycarbonyl group), aryloxycarbonyl group ( For example, phenoxycarbonyl group), alkoxycarbonylamino group (for example, butoxycarbonylamino group, hexyloxycarbonylamino group), alkylthio group (for example, methylthio group, ethylthio group, propylthio group, butylthio group, pentylthio group, heptylthio group, octylthio group) Each group), arylthio group (for example, phenylthio group), alkylsulfonyl group (for example, methylsulfonyl group, ethylsulfonyl group, propylsulfonyl group, butylsulfonyl group) Group, pentylsulfonyl group, heptylsulfonyl group, octylsulfonyl group), amide group (for example, acetamido group, butyramide group, hexylamide group, laurylamide group) and non-aromatic heterocyclic group ( For example, a morpholyl group and a pyrazinyl group) are included.

  Among these, preferable substituents include a halogen atom, a cyano group, a carboxyl group, a hydroxyl group, an amino group, an alkylamino group, an acyl group, an acyloxy group, an amide group, an alkoxycarbonyl group, an alkoxy group, an alkylthio group, and an alkyl group. Can be mentioned.

  The alkyl moiety of the alkylamino group, alkoxycarbonyl group, alkoxy group, and alkylthio group and the alkyl group may further have a substituent. Examples of the alkyl moiety and the substituent of the alkyl group include halogen atom, hydroxyl group, carboxyl group, cyano group, amino group, alkylamino group, nitro group, sulfo group, carbamoyl group, alkylcarbamoyl group, sulfamoyl group, alkylsulfur group. Famoyl group, ureido group, alkylureido group, alkenyl group, alkynyl group, acyl group, acyloxy group, alkoxy group, aryloxy group, alkoxycarbonyl group, aryloxycarbonyl group, alkoxycarbonylamino group, alkylthio group, arylthio group, An alkylsulfonyl group, an amide group and a non-aromatic heterocyclic group are included. As the substituent for the alkyl moiety and the alkyl group, a halogen atom, a hydroxyl group, an amino group, an alkylamino group, an acyl group, an acyloxy group, an acylamino group, an alkoxycarbonyl group, and an alkoxy group are preferable.

  In the general formula (11), L1 is a divalent linking group selected from an alkylene group, an alkenylene group, an alkynylene group, —O—, —CO—, and a combination thereof.

  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, and most preferably 1-6. It is.

  The alkenylene group and the alkynylene group preferably have a chain structure rather than a cyclic structure, and more preferably have a linear structure rather than a branched chain structure.

  The alkenylene group and the alkynylene group preferably have 2 to 10 carbon atoms, more preferably 2 to 8, more preferably 2 to 6, still more preferably 2 to 4, and most preferably 2. (Vinylene group or ethynylene group).

  The arylene group preferably has 6 to 20 carbon atoms, more preferably 6 to 16, and still more preferably 6 to 12.

In the molecular structure of the general formula (11), the angle formed by Ar ₁ and Ar ₂ across L ₁ is preferably 140 degrees or more.

  As the rod-like compound, a compound represented by the following formula (12) is more preferable.

Formula _{(12): Ar 1 -L 2} -X-L 3 -Ar 2
In the general formula (12), Ar ₁ and Ar ₂ are each independently an aromatic group. The definition and examples of the aromatic group are the same as those of Ar ₁ and Ar _{2 in} the general formula (12).

In General Formula (12), L ₂ and L ₃ are each independently a divalent linking group selected from an alkylene group, —O—, —CO—, and a group consisting of a combination thereof.

  The alkylene group preferably has a chain structure rather than a cyclic structure, and more preferably has a linear structure rather than a branched chain structure.

  The alkylene group preferably has 1 to 10 carbon atoms, more preferably 1 to 8, more preferably 1 to 6, still more preferably 1 to 4, and 1 or 2 (methylene group). Or an ethylene group) is most preferable.

L ₂ and L ₃ are particularly preferably —O—CO— or CO—O—.

  In General formula (12), X is a 1, 4- cyclohexylene group, vinylene group, or an ethynylene group.

  Specific examples of the compound represented by the general formula (11) or (12) include compounds described in [Chemical Formula 1] to [Chemical Formula 11] of JP-A No. 2004-109657.

  Two or more rod-shaped compounds whose maximum absorption wavelength (λmax) is longer than 250 nm in the ultraviolet absorption spectrum of the solution may be used in combination.

  The rod-like compound can be synthesized with reference to methods described in literature. As literature, Mol. Cryst. Liq. Cryst. 53, 229 (1979), 89, 93 (1982), 145, 111 (1987), 170, 43 (1989), J. Am. Am. Chem. Soc. 113, p. 1349 (1991), p. 118, p. 5346 (1996), p. 92, p. 1582 (1970). Org. Chem. 40, 420 pages (1975), Tetrahedron, Vol. 48, No. 16, page 3437 (1992).

  Moreover, you may use the rod-shaped aromatic compound of pages 11-14 of Unexamined-Japanese-Patent No. 2004-50516 as said Re expression agent.

  Further, as the retardation developer, one kind of compound can be used alone, or two or more kinds of compounds can be mixed and used. It is preferable to use two or more different compounds as the retardation enhancer because the retardation adjustment range is widened and can be easily adjusted to a desired range.

  0.1-20 mass% is preferable with respect to 100 mass parts of cellulose acylates, and, as for the addition amount of the said retardation expression agent, 0.5-10 mass% is further more preferable. When the cellulose acylate film is produced by a solvent cast method, the retardation developer may be added to the dope. The addition may be performed at any timing, for example, the retardation developer may be dissolved in an organic solvent such as alcohol, methylene chloride, dioxolane, and then added to the cellulose acylate solution (dope), or You may add directly in dope composition.

  In particular, the ratio of the discotic compound is preferably 0.1 to 20%, more preferably 0.5 to 15%, more preferably 1 to 10% based on the total mass of the discotic compound and the rod-shaped compound. % Is particularly preferred.

  In addition, specific examples of preferable compounds of rod-like compounds other than those described in the above-mentioned publications are shown below.

  The specific examples (1) to (34), (41), and (42) have two asymmetric carbon atoms at the 1-position and the 4-position of the cyclohexane ring. However, since the specific examples (1), (4) to (34), (41), and (42) have a symmetrical meso type molecular structure, there are no optical isomers (optical activity), and geometric isomers (trans Type and cis type). The trans type (1-trans) and cis type (1-cis) of specific example (1) are shown below.

  As described above, the rod-like compound preferably has a linear molecular structure. Therefore, the trans type is preferable to the cis type.

  Specific examples (2) and (3) have optical isomers (a total of four isomers) in addition to geometric isomers. As for geometric isomers, the trans type is similarly preferable to the cis type. The optical isomer is not particularly superior or inferior, and may be D, L, or a racemate.

  In specific examples (43) to (45), the central vinylene bond includes a trans type and a cis type. For the same reason as above, the trans type is preferable to the cis type.

  As the retardation developing agent according to the present invention, a polymer additive can be used in the same manner as the low molecular weight compound. The polymer additive is selected from polyester polymers, styrene polymers, acrylic polymers, and copolymers thereof, and aromatic polyesters are preferred.

  The aromatic polyester polymer used in the present invention can be obtained by copolymerizing a monomer having an aromatic ring with the polyester polymer. The monomer having an aromatic ring is at least one monomer selected from aromatic dicarboxylic acids having 8 to 20 carbon atoms and aromatic diols having 6 to 20 carbon atoms.

  Examples of the aromatic dicarboxylic acid having 8 to 20 carbon atoms include phthalic acid, terephthalic acid, isophthalic acid, 1,5-naphthalenedicarboxylic acid, 1,4-naphthalenedicarboxylic acid, 1,8-naphthalenedicarboxylic acid, 2,8- There are naphthalenedicarboxylic acid and 2,6-naphthalenedicarboxylic acid. Among these, preferable aromatic dicarboxylic acids are phthalic acid, terephthalic acid, and isophthalic acid.

  Examples of the aromatic diol having 6 to 20 carbon atoms include, but are not limited to, bisphenol A, 1,2-hydroxybenzene, 1,3-hydroxybenzene, 1,4-hydroxybenzene, and 1,4-benzenedimethanol. Bisphenol A, 1,4-hydroxybenzene and 1,4-benzenedimethanol are preferred.

  In the present invention, the aforementioned polyester is used in combination with at least one of aromatic dicarboxylic acid or aromatic diol, but the combination is not particularly limited, and there is no problem even if several kinds of each component are combined. . In the present invention, as described above, a high molecular weight additive whose end is sealed with an alkyl group or an aromatic group is particularly preferable, and the above-described method can be used for sealing.

  Although the polyester-type polymer used by this invention is described below, this invention is not limited to these.

  The retardation developing agent according to the present invention is more preferably a Re developing agent from the viewpoint of efficiently expressing Re and realizing an appropriate Nz factor. Among the retardation developing agents, examples of the Re developing agent include a discotic compound and a rod-like compound. Among them, triazine compounds having a plurality of aromatic rings, rod-like compounds (1) to (7) Is preferred.

[Compound with negative intrinsic birefringence]
In the present application, the “compound having negative intrinsic birefringence” means a material exhibiting negative intrinsic birefringence in a specific direction of the film in the cellulose acylate film. “Negative intrinsic birefringence” refers to the property of negative birefringence. Whether or not it has a negative intrinsic birefringence can be known, for example, by measuring the birefringence of the film in a system not added with the compound with a birefringence meter and comparing the difference. it can.

  The compound having negative intrinsic birefringence according to the present invention is not particularly limited, and known compounds exhibiting negative intrinsic birefringence can be used.

  Examples of the compound having negative intrinsic birefringence include a polymer having negative intrinsic birefringence, and acicular fine particles having negative intrinsic birefringence (including polymer acicular fine particles having negative intrinsic birefringence). Can be mentioned. Hereinafter, a polymer having negative intrinsic birefringence and acicular fine particles exhibiting negative intrinsic birefringence that can be used in the present invention will be described.

<Polymer having negative intrinsic birefringence>
The polymer having negative intrinsic birefringence means that when light is incident on a layer in which molecules have a uniaxial orientation, the refractive index of light in the orientation direction is perpendicular to the orientation direction. A polymer smaller than the refractive index of light.

  As a polymer having such a negative intrinsic birefringence, as a negative polymer, a polymer having a specific cyclic structure, a styrene polymer such as polystyrene or a styrene-maleic anhydride copolymer (SMA resin), Acrylic polymers such as polymethyl methacrylate, cellulose ester polymers (excluding those having positive birefringence), polyester polymers (excluding those having positive birefringence), polymers having furanose or pyranose structures, acrylonitrile And a multi-component (binary, ternary, etc.) copolymer polymer thereof. These may be used individually by 1 type and may use 2 or more types together. Further, when it is a copolymer, it may be a block copolymer or a random copolymer.

  Among these, a polymer having a specific cyclic structure, a styrene polymer, and an acrylic polymer are more preferable, and polyvinylpyrrolidone, polystyrene, poly α-methylstyrene, polyhydroxystyrene, polyacrylate, polyacrylic ester, and styrene-maleic acid. A copolymer is particularly preferred.

(Polymer having specific cyclic structure in side chain)
As the polymer having negative intrinsic birefringence, a polymer having a cyclic structure represented by the general formula (21) or (22) in the side chain is also preferable.

  It may have only one or a plurality of cyclic structures represented by the general formula (21) or (22), and may have a side chain in addition to that.

(Circular structure represented by general formula (21))
The cyclic structure represented by the general formula (21) will be described.

In the general formula (21), X ¹ represents CR ¹ or a nitrogen atom, and is preferably a nitrogen atom.

R ¹ represents a hydrogen atom or a monovalent substituent, and the monovalent substituent is not particularly limited. Examples of the monovalent substituent include the substituents described immediately after the specific examples c1 to c15 of the linking group (c) in the description of the retardation developer described below.

Y ¹ represents a carbon atom, a nitrogen atom or a sulfur atom, preferably a carbon atom or a sulfur atom, and more preferably a carbon atom.

L ¹ represents a single bond or a connecting group having a connecting chain length of 1 atom, and L ¹ is preferably a single bond. The atom linking group is not particularly limited, and examples thereof include a divalent carbon atom-containing linking group, a divalent nitrogen atom-containing linking group, a sulfur atom, and an oxygen atom.

L ² represents a linking group having a linking chain length of 2 to 6 atoms. The connecting chain length of L ² is preferably 2 to 5 atoms, and more preferably 2 to 4 atoms. The linking group is not particularly limited as long as it is divalent, and examples thereof include a divalent carbon atom-containing linking group and a divalent nitrogen atom-containing linking group. The linking group may further have a substituent. Examples of such a substituent include the substituents described immediately after the specific examples c1 to c15 of the linking group (c) in the description of the retardation developer described later.

L ² is particularly preferably a substituted or unsubstituted alkylene group having 2 to 4 carbon atoms.

  The cyclic structure represented by the general formula (21) may form an aromatic ring, a hetero ring, or an aromatic hetero ring as a whole. Moreover, although the some cyclic structure may be included, it is preferable that it is a single cyclic structure.

As a preferable combination of X ¹ , Y ¹ , L ¹ and L ² , X ¹ is a nitrogen atom, Y ¹ is a carbon atom, L ¹ is a single bond, and L ² has ² to 4 carbon atoms. The case where it is a substituted or unsubstituted alkylene group is preferable, and it is more preferable that it is a structure represented by General formula (23) or (24).

(Circular structure represented by general formula (23) or (24))
First, the cyclic structure represented by the general formula (23) will be described.

In General Formula (23), R ¹⁹ represents a substituted or unsubstituted alkylene group having 2 to 4 carbon atoms, and a substituted or unsubstituted alkylene group having 3 carbon atoms is more preferable.

  Examples of the substituent include the substituents described immediately after the specific examples c1 to c15 of the linking group (c) in the description of the retardation developer described below. In addition, the substituent may or may not have a structure of —C (═O) —, but if it has, —C (═O) — in the general formula (23). It is preferable that the direction is close to the parallel direction.

(Circular structure represented by general formula (24))
Next, the cyclic structure represented by the general formula (24) will be described.

In the general formula (24), R ²⁰ represents a substituted or unsubstituted alkylene group having 1 to 3 carbon atoms. R ²⁰ is more preferably a substituted or unsubstituted alkylene group having 2 carbon atoms.

  As said substituent, the thing similar to what was demonstrated by General formula (23) can be used, and its preferable range is also the same.

  The cyclic structure represented by the general formula (21) is most preferably a pyrrolidone structure.

  Although the specific example of the cyclic structure represented by the said General formula (21), (23) or (24) is given, it is not limited to these.

(Circular structure represented by general formula (22))
The cyclic structure represented by the general formula (22) will be described below.

In the general formula (22), X ² represents CR ¹³ R ¹⁴ , NR ¹⁵ , an oxygen atom or a sulfur atom. X ² is preferably a ^CR 13 ^{R 14, NR 15,} and more preferably CR ¹³ R 14, ^{NR 15.}

Y ² represents a carbon atom, a nitrogen atom or a sulfur atom, preferably a carbon atom or a sulfur atom, and more preferably a carbon atom.

Y ³ represents CR ¹⁶ R ¹⁷ , NR ¹⁸ , an oxygen atom, a sulfur atom, —C (═O) —, —N (═O) — or S (═O) —, and —S (═O) —. , —C (═O) — is preferable, and —C (═O) — is more preferable.

R ^{2 to} R ¹⁸ represent a hydrogen atom or a monovalent substituent, and more preferably a hydrogen atom or a substituted or unsubstituted alkyl group having 1 to 8 carbon atoms.

  k1, m1, and n1 each independently represents an integer of 0-2. k1 is preferably 0 or 1, and more preferably 0. m1 is preferably 0 or 1. n1 is preferably 0 or 1. More preferably, the sum of m1 and n1 is 0 or 1.

  The k1 partial structure, the m1 partial structure, and the n1 partial structure are joined in any order.

  The cyclic structure represented by the general formula (22) may form an aromatic ring, a hetero ring, or an aromatic hetero ring as a whole. Moreover, although the some cyclic structure may be included, it is preferable that it is a single cyclic structure.

As a preferable combination of X ² , Y ² , Y ³ , R ^{2 to} R ¹⁸ , k1, m1 and n1, X ² is NR ¹⁵ , Y ² is a carbon atom, and Y ³ is —C (═O )-, R ^{2 to} R ¹⁸ are hydrogen atoms, k1 is 0, m1 is 0 or 1, and n1 is 0 or 1, and is represented by the general formula (25). A structure is more preferable.

  (Circular structure represented by general formula (25))

In the general formula (25), R ²¹ represents a hydrogen atom, a group represented by the following general formula (25-1), a group represented by the following general formula (25-2), a substitution having 1 to 8 carbon atoms, or An unsubstituted alkyl group is represented.

R ^{31 to} R ⁴⁷ each independently represent a hydrogen atom; a halogen atom; a substituted or unsubstituted carbon atom having 1 to 30 carbon atoms that may have a linking group containing an oxygen atom, a nitrogen atom, a sulfur atom, or a silicon atom. And an atom or group selected from the group consisting of polar groups.

In formula (25-1), the p1 and q1 is 0 or a positive integer, when p1 = q1 = ^{0, R 32} and ^{R 35} or ^{R 35} and ^{R 39} may have a hetero atom bonded to each other A monocyclic or polycyclic group may be formed.

  In general formula (25-2), s is 0 or an integer of 1 or more.

R ^{22 to} R ²⁹ represent a hydrogen atom or a substituted or unsubstituted alkyl group having 1 to 8 carbon atoms, preferably a hydrogen atom or a substituted or unsubstituted alkyl group having 1 to 8 carbon atoms, and more preferably a hydrogen atom.

  m2 and n2 each represents 0 or 1.

  Although the specific example of the cyclic structure represented by the said General formula (22) or (25) is given, it is not limited to these.

  As the polymer having negative intrinsic birefringence, a styrene polymer is also preferable.

  The styrenic polymer is preferably a structural unit obtained from an aromatic vinyl monomer represented by the general formula (31).

In the formula, each of R ^{101 to} R ¹⁰⁴ independently represents a substituted or unsubstituted carbon atom which may have a linking group containing a hydrogen atom, a halogen atom, an oxygen atom, a sulfur atom, a nitrogen atom or a silicon atom. Represents a hydrocarbon group of 1 to 30 or a polar group, and R ¹⁰⁴ may be the same atom or group or different atoms or groups, and may be bonded to each other to form a carbocyclic or heterocyclic ring ( These carbocycles and heterocycles may form a monocyclic structure, or other rings may be condensed to form a polycyclic structure.

  Specific examples of the aromatic vinyl monomer include styrene; α-methylstyrene; β-methylstyrene; alkyl-substituted styrenes such as o-methylstyrene, m-methylstyrene, and p-methylstyrene; 4-chlorostyrene Halogen substituted styrenes such as 4-bromostyrene; o-hydroxystyrene, m-hydroxystyrene, p-hydroxystyrene, α-methyl-p-hydroxystyrene, 2-methyl-4-hydroxystyrene, 3,4-dihydroxy Hydroxystyrenes such as styrene; vinyl benzyl alcohols; alkoxy-substituted styrenes such as p-methoxystyrene, p-tert-butoxystyrene, m-tert-butoxystyrene; 3-vinylbenzoic acid, 4-vinylbenzoic acid, etc. Vinylbenzoic acids; methyl-4-vinyl Vinyl benzoates such as benzoate, ethyl-4-vinylbenzoate; 4-vinylbenzyl acetate; 4-acetoxystyrene; amide styrenes such as 2-butylamidostyrene, 4-methylamidostyrene, p-sulfonamidostyrene; Aminostyrenes such as 3-aminostyrene, 4-aminostyrene, 2-isopropenylaniline and vinylbenzyldimethylamine; Nitrostyrenes such as 3-nitrostyrene and 4-nitrostyrene; 3-cyanostyrene, 4-cyanostyrene Cyanostyrenes such as; vinyl phenylacetonitrile; aryl styrenes such as phenylstyrene; and indenes, but the present invention is not limited to these specific examples. Two or more of these monomers may be used as a copolymerization component. Of these, styrene and α-methylstyrene are preferred because they are easily available industrially and are inexpensive.

(Acrylic polymer)
As the polymer having negative intrinsic birefringence, an acrylic polymer is also preferable.

  The acrylic polymer is preferably a structural unit obtained from an acrylate ester monomer represented by the general formula (32).

In the formula, each of R ^{105 to} R ¹⁰⁸ independently represents a substituted or unsubstituted carbon atom which may have a linking group containing a hydrogen atom, a halogen atom, an oxygen atom, a sulfur atom, a nitrogen atom or a silicon atom. This represents a hydrocarbon group of 1 to 30 or a polar group.

  Examples of the acrylate monomer include, for example, methyl acrylate, ethyl acrylate, propyl acrylate (i-, n-), butyl acrylate (n-, i-, s-, tert-). , Pentyl acrylate (n-, i-, s-), hexyl acrylate (n-, i-), heptyl acrylate (n-, i-), octyl acrylate (n-, i-), acrylic acid Nonyl (n-, i-), myristyl acrylate (n-, i-), acrylic acid (2-ethylhexyl), acrylic acid (ε-caprolactone), acrylic acid (2-hydroxyethyl), acrylic acid (2- Hydroxypropyl), acrylic acid (3-hydroxypropyl), acrylic acid (4-hydroxybutyl), acrylic acid (2-hydroxybutyl), acrylic acid (2-methoxyethyl) Acrylic acid (2-ethoxyethyl) phenyl acrylate, phenyl methacrylate, acrylic acid (2 or 4-chlorophenyl), methacrylic acid (2 or 4-chlorophenyl), acrylic acid (2 or 3 or 4-ethoxycarbonylphenyl), Methacrylic acid (2 or 3 or 4-ethoxycarbonylphenyl), acrylic acid (o or m or p-tolyl), methacrylic acid (o or m or p-tolyl), benzyl acrylate, benzyl methacrylate, phenethyl acrylate, Phenethyl methacrylate, acrylic acid (2-naphthyl), cyclohexyl acrylate, cyclohexyl methacrylate, acrylic acid (4-methylcyclohexyl), methacrylic acid (4-methylcyclohexyl), acrylic acid (4-ethylcyclohexyl), methacrylic acid ( 4-Eth (Lucyclohexyl) and the like, or those obtained by replacing the acrylic ester with a methacrylic ester, but the present invention is not limited to these specific examples. Two or more of these monomers may be used as a copolymerization component. Of these, methyl acrylate, ethyl acrylate, propyl acrylate (i-, n-), butyl acrylate (n-, i-, s-, tert-), pentyl acrylate (n-, i-, s-), hexyl acrylate (n-, i-), or those obtained by replacing the above acrylate esters with methacrylate esters are preferred.

(Copolymer)
The polymer having negative intrinsic birefringence may be a copolymer unless it is contrary to the gist of the present invention. Moreover, when it is a copolymer, it may be a block copolymer or a random polymer. Moreover, a graft copolymer may be sufficient.

  The polymer having the cyclic structure represented by the general formula (21) or (22) in the side chain is a monomer having the cyclic structure represented by the general formula (21) or (22) in the side chain. Even if it is a polymer, it may be a copolymer of a monomer having a cyclic structure represented by two or more of the above general formulas (21) or (22) in the side chain. Or the copolymer of the monomer which has the cyclic structure represented by (22) in a side chain, and another monomer may be sufficient.

  The other monomers are not particularly limited, and examples thereof include acrylic acid, methacrylic acid, alkyl esters of acrylic acid (such as methyl acrylate and ethyl acrylate), alkyl esters of methacrylic acid (such as methyl methacrylate and ethyl methacrylate), and acrylic acid. Hydroxyalkyl esters (such as hydroxyethyl acrylate), hydroxyalkyl esters of methacrylic acid (such as hydroxyethyl methacrylate), aminoalkyl esters of acrylic acid (such as diethylaminoethyl acrylate), aminoalkyl esters of methacrylic acid, monoesters of acrylic acid and glycol Esters, monoesters of methacrylic acid and glycol (such as hydroxyethyl methacrylate), alkali metal salts of acrylic acid, alkali gold of methacrylic acid Salt, ammonium salt of acrylic acid, ammonium salt of methacrylic acid, quaternary ammonium derivative of aminoalkyl ester of acrylic acid, quaternary ammonium derivative of aminoalkyl ester of methacrylic acid, fourth of diethylaminoethyl acrylate and methyl sulfate Quaternary ammonium compounds, vinyl methyl ether, vinyl ethyl ether, alkali metal salts of vinyl sulfonic acid, ammonium salts of vinyl sulfonic acid, styrene sulfonic acid, styrene sulfonate, allyl sulfonic acid, allyl sulfonate, methallyl sulfonic acid, Methallyl sulfonate, vinyl acetate, vinyl stearate, N-vinylimidazole, N-vinylacetamide, N-vinylformamide, N-vinylcaprolactam, N-vinylcarbazole, acrylic Amide, methacrylamide, N- alkylacrylamide, may be mentioned N- methylolacrylamide, N, N- methylenebisacrylamide, glycol diacrylate, glycol dimethacrylate, divinylbenzene, and glycol diallyl ether. Among these, vinyl acetate, acrylic acid, methacrylic acid, and methyl methacrylate are preferable, vinyl acetate and hydroxyalkyl ester of methacrylic acid are more preferable, and hydroxyalkyl ester of methacrylic acid is particularly preferable.

  When the substitution degree of the cellulose acylate resin is high, the hydrophobicity of the cellulose acylate resin increases. Therefore, a monomer having the cyclic structure represented by the general formula (21) or (22) in the side chain as another monomer is used. It is preferable to improve the hydrophobicity and improve the compatibility as the copolymer. On the contrary, when the substitution degree of the cellulose acylate resin is low, the hydrophobicity of the cellulose acylate resin decreases. Therefore, a monomer having the cyclic structure represented by the general formula (21) or (22) in the side chain is included. As a copolymer with other monomers, it is preferable to reduce hydrophobicity and improve compatibility. For example, when a vinylpyrrolidone homopolymer is used as a polymer having a cyclic structure represented by the general formula (21) or (22) in the side chain, the vinylpyrrolidone homopolymer is hydrophilic and thus highly substituted. The compatibility with the cellulose acylate resin is not good. Therefore, for example, by using a copolymer of polyvinyl pyrrolidone and polyvinyl acetate and adjusting the copolymerization ratio, the hydrophilicity / hydrophobicity can be adjusted according to the substitution degree of the cellulose acylate resin. By adjusting the compatibility in this manner, it is possible to suppress crying and whitening of the obtained cellulose acylate laminated film, which is preferable.

  When the monomer having the cyclic structure represented by the general formula (21) or (22) in the side chain is a copolymer with another monomer, the monomer is represented by the general formula (21) or (22). The copolymerization ratio of the monomer having a cyclic structure in the side chain and the other polymer monomer is preferably 3: 7 to 9: 1, more preferably 3: 7 to 7: 3. : 5-7: 3 is particularly preferable.

  When the polymer having negative intrinsic birefringence is a copolymer, the aromatic vinyl monomer represented by the general formula (31) and the acrylate ester represented by the general formula (32) Those containing at least one structural unit obtained from a monomer are also preferred.

In the formula, each of R ^{101 to} R ¹⁰⁴ independently represents a substituted or unsubstituted carbon atom which may have a linking group containing a hydrogen atom, a halogen atom, an oxygen atom, a sulfur atom, a nitrogen atom or a silicon atom. Represents a hydrocarbon group of 1 to 30 or a polar group, and R ¹⁰⁴ may be the same atom or group or different atoms or groups, and may be bonded to each other to form a carbocyclic or heterocyclic ring ( These carbocycles and heterocycles may form a monocyclic structure, or other rings may be condensed to form a polycyclic structure.

In the formula, R ^{105 to} R ¹⁰⁸ each independently have a linking group containing a hydrogen atom, a halogen atom, an oxygen atom, a sulfur atom, a nitrogen atom or a silicon atom, and the number of substituted or unsubstituted carbon atoms 1-30 hydrocarbon groups or a polar group is represented.

  Further, the structure other than the above constituting the copolymer composition is preferably excellent in copolymerizability with the monomer, and examples thereof include maleic anhydride, citraconic anhydride, cis-1-cyclohexene-1 , 2-dicarboxylic anhydride, 3-methyl-cis-1-cyclohexene-1,2-dicarboxylic anhydride, 4-methyl-cis-1-cyclohexene-1,2-dicarboxylic anhydride and the like, acrylonitrile, Nitrile group-containing radical polymerizable monomers such as methacrylonitrile; amide bond-containing radical polymerizable monomers such as acrylamide, methacrylamide, trifluoromethanesulfonylaminoethyl (meth) acrylate; fatty acid vinyls such as vinyl acetate; Chlorine-containing radical polymerizable monomers such as vinyl and vinylidene chloride; 1,3-butadiene; Isoprene, 1,4-dimethyl butadiene and the like can be mentioned conjugated diolefin, but the present invention is not limited thereto. Of these, styrene-acrylic acid copolymers, styrene-maleic anhydride copolymers, and styrene-acrylonitrile copolymers are particularly preferred.

  In the cellulose acylate laminated film of the present invention, the compound having negative intrinsic birefringence is preferably a styrene polymer from the viewpoint of further improving the wet heat durability of optical characteristics. In addition, it is preferable that the styrenic polymer is a styrene-maleic anhydride copolymer from the viewpoint of further improving the wet heat durability of optical characteristics.

  The addition amount of the compound having negative intrinsic birefringence is preferably 0.5 to 40 parts by mass, more preferably 0.5 to 30 parts by mass with respect to 100 parts by mass of the cellulose acylate resin. Preferably, the amount is 1 to 20 parts by mass.

  In the cellulose acylate laminated film of the present invention, the mass content of the compound having negative intrinsic birefringence in the core layer with respect to cellulose acylate is the mass of the compound having negative intrinsic birefringence in the skin layer with respect to cellulose acylate. Less than the content is preferable from the viewpoint of retardation development and compatibility with the retardation developer in the core layer.

  In the cellulose acylate laminated film of the present invention, the content of the compound having negative intrinsic birefringence contained in the skin layer is 5% or more and less than 50% with respect to the cellulose acylate under wet heat conditions. It is preferable from the viewpoint of maintaining the optical property durability. The content of the compound having negative intrinsic birefringence contained in the skin layer is preferably 8% or more and less than 40%, and more preferably 13% or more and less than 30%.

  The cellulose acylate laminated film of the present invention may or may not contain a compound having negative intrinsic birefringence in the core layer, but includes a compound having negative intrinsic birefringence in the core layer. In this case, the content thereof is preferably 5% or less, more preferably less than 3%, and particularly preferably less than 2% with respect to cellulose acylate.

  When the compound having negative intrinsic birefringence is a polymer having negative intrinsic birefringence, the weight average molecular weight is preferably 500 to 100,000, and preferably 700 to 50,000. More preferred is 1,000 to 25,000.

  If the molecular weight is 500 or more, the volatility is good, and if the molecular weight is 100,000 or less, the compatibility with the cellulose acylate resin is good, so the film forming property of the cellulose acylate laminated film is also good. Is also preferable.

(Additive composition and characteristics of each layer)
The film of the present invention has a viewpoint of suppressing retardation variation caused by uneven film thickness of the core layer and skin layer by adjusting the retardation of the core layer and skin layer (in some cases, close to the expression of optical properties) More preferably, the skin B layer contains a retardation developer.

  The film of the present invention contains at least one kind of retardation Re developing agent in the in-plane direction among the retardation developing agents in at least one layer of the skin layer, thereby realizing an appropriate Nz factor and uniform optical expression. From the viewpoint of realizing the property.

(Other additives)
In the present invention, deterioration inhibitors, ultraviolet absorbers, peeling accelerators, matting agents, lubricants, the aforementioned plasticizers, and the like can be appropriately used as necessary.

(Deterioration inhibitor)
In the present invention, a known deterioration (oxidation) inhibitor such as 2,6-di-tert-butyl-4-methylphenol, 4,4'-thiobis- (6-tert-butyl-3) is added to the cellulose acylate solution. -Methylphenol), 1,1'-bis (4-hydroxyphenyl) cyclohexane, 2,2'-methylenebis (4-ethyl-6-tert-butylphenol), 2,5-di-tert-butylhydroquinone, pentaerythris A phenolic or hydroquinone antioxidant such as lithyl-tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate] can be added. Further, tris (4-methoxy-3,5-diphenyl) phosphite, tris (nonylphenyl) phosphite, tris (2,4-di-tert-butylphenyl) phosphite, bis (2,6-di-tert) It is preferable to use a phosphorus-based antioxidant such as -butyl-4-methylphenyl) pentaerythritol diphosphite and bis (2,4-di-tert-butylphenyl) pentaerythritol diphosphite. The addition amount of the deterioration inhibitor is 0.05 to 5.0 parts by mass with respect to 100 parts by mass of the cellulose resin.

(UV absorber)
In the present invention, an ultraviolet absorber is preferably used for the cellulose acylate solution from the viewpoint of preventing deterioration of the polarizing plate or the liquid crystal. As the ultraviolet absorber, those excellent in the ability to absorb ultraviolet rays having a wavelength of 370 nm or less and having little absorption of visible light having a wavelength of 400 nm or more are preferably used from the viewpoint of good liquid crystal display properties. Specific examples of ultraviolet absorbers preferably used in the present invention include, for example, hindered phenol compounds, hydroxybenzophenone compounds, benzotriazole compounds, salicylic acid ester compounds, benzophenone compounds, cyanoacrylate compounds, nickel complex compounds Etc. Examples of hindered phenol compounds include 2,6-di-tert-butyl-p-cresol, pentaerythrityl-tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate]. N, N'-hexamethylenebis (3,5-di-tert-butyl-4-hydroxy-hydrocinnamide), 1,3,5-trimethyl-2,4,6-tris (3,5-di-tert) -Butyl-4-hydroxybenzyl) benzene, tris- (3,5-di-tert-butyl-4-hydroxybenzyl) -isocyanurate and the like. Examples of benzotriazole compounds include 2- (2′-hydroxy-5′-methylphenyl) benzotriazole, 2,2-methylenebis (4- (1,1,3,3-tetramethylbutyl) -6- (2H-benzotriazol-2-yl) phenol), (2,4-bis- (n-octylthio) -6- (4-hydroxy-3,5-di-tert-butylanilino) -1,3,5- Triazine, triethylene glycol-bis [3- (3-tert-butyl-5-methyl-4-hydroxyphenyl) propionate], N, N′-hexamethylenebis (3,5-di-tert-butyl-4- Hydroxy-hydrocinnamide), 1,3,5-trimethyl-2,4,6-tris (3,5-di-tert-butyl-4-hydroxybenzyl) benzene 2- (2'-hydroxy-3 ', 5'-di-tert-butylphenyl) -5-chlorobenzotriazole, (2- (2'-hydroxy-3', 5'-di-tert-amylphenyl) -5-chlorobenzotriazole, 2,6-di-tert-butyl-p-cresol, pentaerythrityl-tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate] The addition amount of these ultraviolet light inhibitors is preferably 1 ppm to 1.0%, more preferably 10 to 1000 ppm in terms of mass ratio in the entire optical film.

(Peeling accelerator)
It is preferable that the film of the present invention contains a release accelerator from the viewpoint of more releasability. The peeling accelerator can be included at a ratio of 0.001 to 1% by mass, for example, and the addition of 0.5% by mass or less is preferable because separation of the release agent from the film hardly occurs. 005% by mass or more is preferable because a desired peeling reduction effect can be obtained. Therefore, it is preferably included at a rate of 0.005 to 0.5% by mass, and at a rate of 0.01 to 0.3% by mass. More preferably. As the peeling accelerator, known ones can be adopted, and organic and inorganic acidic compounds, surfactants, chelating agents and the like can be used. Among them, polyvalent carboxylic acids and esters thereof are effective, and in particular, ethyl esters of citric acid can be used effectively.

  The film of the present invention preferably contains a peeling accelerator in the skin B layer.

(Matting agent)
In particular, the film of the present invention is generally added with fine particles in order to prevent the film from being scratched or deteriorated in transportability. They are called matting agents, anti-blocking agents or anti-scratching agents and have been used conventionally. They are not particularly limited as long as they have the above-described functions, and may be an inorganic compound matting agent or an organic compound matting agent.

  Specific examples of the inorganic compound matting agent include silicon-containing inorganic compounds (for example, silicon dioxide, calcined calcium silicate, hydrated calcium silicate, aluminum silicate, magnesium silicate, etc.), titanium oxide, and zinc oxide. , Aluminum oxide, barium oxide, zirconium oxide, strongtium oxide, antimony oxide, tin oxide, tin oxide / antimony, calcium carbonate, talc, clay, calcined kaolin, calcium phosphate, etc., more preferably silicon-containing inorganic compounds and oxides Although it is zirconium, since the turbidity of a cellulose acylate film can be reduced, silicon dioxide is particularly preferably used. As the silicon dioxide fine particles, for example, commercially available products having trade names such as Aerosil R972, R974, R812, 200, 300, R202, OX50, TT600 (manufactured by Nippon Aerosil Co., Ltd.) can be used. As the zirconium oxide fine particles, for example, those commercially available under trade names such as Aerosil R976 and R811 (manufactured by Nippon Aerosil Co., Ltd.) can be used.

  Preferable specific examples of the organic compound matting agent include, for example, polymers such as silicone resin, fluorine resin and acrylic resin, and among them, silicone resin is preferably used. Among the silicone resins, those having a three-dimensional network structure are particularly preferable. For example, Tospearl 103, Tospearl 105, Tospearl 108, Tospearl 120, Tospearl 145, Tospearl 3120 and Tospearl 240 (manufactured by Toshiba Silicone Co., Ltd.) A commercial product having a trade name can be used.

(Explanation of dope preparation, physical properties, size, etc.)
When these matting agents are added to the cellulose acylate solution, the method is not particularly limited, and there is no problem as long as a desired cellulose acylate solution can be obtained by any method. For example, an additive may be contained at the stage of mixing cellulose acylate and a solvent, or an additive may be added after preparing a mixed solution with cellulose acylate and a solvent. Further, it may be added and mixed immediately before casting the dope, which is a so-called immediately preceding addition method, and the mixing is used by installing screw-type kneading online. Specifically, a static mixer such as an inline mixer is preferable.

  As for in-line addition, in order to eliminate density unevenness, particle aggregation, etc., Japanese Patent Application Laid-Open No. 2003-053752 adds an additive solution having a different composition to the main raw material dope in a method for producing a cellulose acylate film. There is described an invention in which the distance L between the nozzle tip and the starting end portion of the in-line mixer is 5 times or less of the main raw material pipe inner diameter d, thereby eliminating concentration unevenness, matting particles and the like. As a more preferred embodiment, the distance (L) between the tip opening of the additive liquid supply nozzle having a composition different from that of the main raw material dope and the starting end of the in-line mixer is 10 times or less the inner diameter (d) of the supply nozzle tip opening. The in-line mixer is a static non-stirring type in-tube mixer or a dynamic stirring type in-tube mixer. More specifically, it is disclosed that the flow rate ratio of the cellulose acylate film main raw material dope / in-line additive solution is 10/1 to 500/1, preferably 50/1 to 200/1. Furthermore, the additive is also added to Japanese Patent Application Laid-Open No. 2003-014933 of the invention aiming at a retardation film with little additive bleed-out, no delamination phenomenon, excellent slipperiness and excellent transparency. As a method to do this, it may be added to the melting pot, or a solution in which additives or additives are dissolved or dispersed between the melting pot and the co-casting die may be added to the dope being fed. However, in the latter case, it is described that it is preferable to provide a mixing means such as a static mixer in order to improve the mixing property.

  The film of the present invention contains a matting agent in at least one of the skin A layer and the skin B layer, and is generated when a wide film is wound long by reducing the friction coefficient of the film surface. It is preferable from the viewpoint of prevention of creaking and prevention of film breakage, and it is particularly preferable from the viewpoint of effectively reducing scratch resistance and blemishes that both the skin A layer and the skin B layer contain a matting agent.

  In the film of the present invention, when the matting agent is not added in a large amount, the haze of the film does not increase, and when actually used in an LCD, inconveniences such as a decrease in contrast and generation of bright spots are unlikely to occur. If the amount is too small, the above-mentioned creaking and scratch resistance can be realized. From these viewpoints, it is preferably included at a ratio of 0.01 to 5.0 mass%, more preferably included at a ratio of 0.03 to 3.0 mass%, and a ratio of 0.05 to 1.0 mass% It is particularly preferable to include

(Haze)
The optical film of the present invention preferably has a haze of less than 1%, more preferably less than 0.5%. By setting the haze to less than 1%, there is an advantage that the transparency of the film becomes higher and it becomes easier to use as an optical film.

(Average moisture content)
In the film of the present invention, the equilibrium water content at 25 ° C. and 60% relative humidity is preferably 4% or less, more preferably 3% or less. By setting the average moisture content to 4% or less, it is easy to cope with changes in humidity, and the optical characteristics and dimensions are more difficult to change.

(Re, Rth)
When the retardation value of the film of the present invention is used for a retardation film, Re and Rth are appropriately selected depending on the design of the liquid crystal cell and the optical film. In general, Re is 25 nm ≦ | Re | It is preferable that ≦ 100 nm and the retardation Rth in the film thickness direction is 50 nm ≦ | Rth | ≦ 250 nm. The Re is more preferably 30 nm ≦ | Re | ≦ 80 nm, and particularly preferably 35 nm ≦ | Re | ≦ 70 nm. The Rth is more preferably 70 nm ≦ | Rth | ≦ 240 nm, and particularly preferably 90 nm ≦ | Rth | ≦ 230 nm.

  Re (λ) and Rth (λ) in the present application represent in-plane retardation and retardation in the thickness direction at the wavelength λ, respectively. In the present application, the wavelength λ is 590 nm unless otherwise specified. Re (λ) is measured by making light having a wavelength of λ nm incident in the normal direction of the film in KOBRA 21ADH (manufactured by Oji Scientific Instruments). Rth (λ) is Re (λ), with the in-plane slow axis (determined by KOBRA 21ADH) as the tilt axis (rotary axis) (in the absence of the slow axis, any direction in the film plane) Is measured in 6 points from the inclined direction in 10 degree steps from the normal direction to 50 degrees on one side with respect to the normal direction of the film. KOBRA 21ADH calculates based on the retardation value, the assumed value of the average refractive index, and the input film thickness value. The retardation value is measured from any two directions with the slow axis as the tilt axis (rotation axis) (in the absence of the slow axis, the arbitrary direction in the film plane is the rotation axis), and the value Rth can also be calculated from the following formula (A) and formula (B) based on the assumed average refractive index and the input film thickness value. Here, as the assumed value of the average refractive index, values in the polymer handbook (John Wiley & Sons, Inc.) and catalogs of various optical films can be used. Those whose average refractive index is not known can be measured with an Abbe refractometer. The average refractive index values of main optical films are exemplified below: cellulose acylate (1.48), cycloolefin polymer (1.52), polycarbonate (1.59), polymethyl methacrylate (1.49), Polystyrene (1.59). The KOBRA 21ADH calculates nx, ny, and nz by inputting the assumed value of the average refractive index and the film thickness. Nz = (nx−nz) / (nx−ny) is further calculated from the calculated nx, ny, and nz.

  Here, Re (θ) represents a retardation value in a direction inclined by an angle θ from the normal direction. d represents the film thickness.

Rth = ((nx + ny) / 2−nz) × d −−− Formula (B)
At this time, an average refractive index n is required as a parameter, and a value measured by an Abbe refractometer (“Abbe refractometer 2-T” manufactured by Atago Co., Ltd.) was used.

(Nz coefficient)
In the film of the present invention, the Nz coefficient represented by the following formula (7) is appropriately selected depending on the design of the liquid crystal cell, the optical film, and the like, but is generally preferably 7 or less. More preferably, it is more preferably 4.5 or less.

Formula (7): Nz coefficient = Rth / Re + 0.5
(Film thickness)
In the film of the present invention, the average thickness of the core layer is preferably 30 to 100 μm, more preferably 30 to 80 μm, and further preferably 30 to 70 μm. By setting it to 30 μm or more, the handling property when producing a web-like film is improved, which is preferable. Moreover, by setting it as 70 micrometers or less, it is easy to respond to a humidity change and it is easy to maintain optical characteristics.

  The film of the present invention may have an average film thickness of at least one of the skin A layer or the skin B layer of 0.2% or more and less than 25% of the average film thickness of the core layer. If it is less than 25%, the optical performance of the core layer can be effectively utilized, and the laminate film can be effectively used. Is preferable from the viewpoint of obtaining sufficient optical characteristics, more preferably 0.5 to 15%, and particularly preferably 1.0 to 10%. Moreover, it is more preferable that the average film thickness of the skin A layer and the skin B layer are both 0.2% or more and less than 25% of the average core layer film thickness.

(Film width)
The film of the present invention preferably has a film width of 700 to 3000 mm, more preferably 1000 to 2800 mm, and particularly preferably 1500 to 2500 mm.

[Method for producing cellulose acylate laminated film]
The method for producing a cellulose acylate laminated film of the present invention (hereinafter also referred to as “manufacturing method according to the present invention”) comprises a dope containing cellulose acylate satisfying the formula (2) and the formula (1). A step of multi-layer casting a dope containing cellulose acylate to be filled simultaneously or sequentially on the support in this order; a step of drying the multi-layer cast dope to release from the support; and a film after release And a retardation adjusting agent is added to at least one of the core layer dope and the skin B layer dope.

(Preparation of dope)
Specifically, in the production method according to the present invention, the film of the present invention is produced using a solution (dope) obtained by dissolving cellulose acylate in an organic solvent by a solvent cast method.

  The organic solvent is selected from ethers having 3 to 12 carbon atoms, ketones having 3 to 12 carbon atoms, esters having 3 to 12 carbon atoms, and halogenated hydrocarbons having 1 to 6 carbon atoms. It is preferable to include a solvent. The ether, ketone and ester may have a cyclic structure. A compound having two or more functional groups of ether, ketone and ester (that is, —O—, —CO— and COO—) can also be used as the organic solvent. The organic solvent may have another functional group such as an alcoholic hydroxyl group (hydroxyl group). In the case of an organic solvent having two or more types of functional groups, the number of carbon atoms may be within the specified range of the compound having any functional group.

  Examples of the ether having 3 to 12 carbon atoms include diisopropyl ether, dimethoxymethane, dimethoxyethane, 1,4-dioxane, 1,3-dioxolane, tetrahydrofuran, anisole and phenetole.

  Examples of ketones having 3 to 12 carbon atoms include acetone, methyl ethyl ketone, diethyl ketone, diisobutyl ketone, cyclohexanone and methylcyclohexanone.

  Examples of the esters having 3 to 12 carbon atoms include ethyl formate, propyl formate, pentyl formate, methyl acetate, ethyl acetate and pentyl acetate.

  Examples of the organic solvent having two or more kinds of functional groups include 2-ethoxyethyl acetate, 2-methoxyethanol and 2-butoxyethanol.

  The number of carbon atoms of the halogenated hydrocarbon is preferably 1 or 2, and most preferably 1. The halogen of the halogenated hydrocarbon is preferably chlorine. The proportion of halogen atoms substituted by halogen in the halogenated hydrocarbon is preferably 25 to 75 mol%, more preferably 30 to 70 mol%, and more preferably 35 to 65 mol%. More preferably, it is most preferable that it is 40-60 mol%. Methylene chloride is a representative halogenated hydrocarbon.

  Two or more organic solvents may be mixed and used.

  A cellulose acylate solution can be prepared by a general method. A general method means processing at a temperature of 0 ° C. or higher (ordinary temperature or high temperature). The solution can be prepared by using a dope preparation method and apparatus in a normal solvent cast method. In the case of a general method, it is preferable to use a halogenated hydrocarbon (particularly, methylene chloride) as the organic solvent.

  The amount of cellulose acylate is adjusted so as to be contained in the obtained solution in an amount of 10 to 40% by mass. The amount of cellulose acylate is more preferably 10 to 30% by mass. Arbitrary additives described later may be added to the organic solvent (main solvent).

  The solution can be prepared by stirring the cellulose acylate and the organic solvent at room temperature (0 to 40 ° C.). The high concentration solution may be stirred under pressure and heating conditions. Specifically, the cellulose acylate and the organic solvent are placed in a pressure vessel and sealed, and stirred while being heated to a temperature equal to or higher than the boiling point of the solvent at normal temperature and in a range where the solvent does not boil. The heating temperature is usually 40 ° C. or higher, preferably 60 to 200 ° C., and more preferably 80 to 110 ° C.

  Each component may be coarsely mixed in advance and then placed in a container. Moreover, you may put into a container sequentially. The container needs to be configured so that it can be stirred. The container can be pressurized by injecting an inert gas such as nitrogen gas. Moreover, you may utilize the raise of the vapor pressure of the solvent by heating. Or after sealing a container, you may add each component under pressure.

  When heating, it is preferable to heat from the outside of the container. For example, a jacket type heating device can be used. The entire container can also be heated by providing a plate heater outside the container and piping to circulate the liquid.

  It is preferable to provide a stirring blade inside the container and stir using this. The stirring blade preferably has a length that reaches the vicinity of the wall of the container. A scraping blade is preferably provided at the end of the stirring blade in order to renew the liquid film on the vessel wall.

  Instruments such as a pressure gauge and a thermometer may be installed in the container. Each component is dissolved in a solvent in a container. The prepared dope is taken out of the container after cooling, or taken out and then cooled using a heat exchanger or the like.

  A solution can also be prepared by a cooling dissolution method. In the cooling dissolution method, cellulose acylate can be dissolved in an organic solvent that is difficult to dissolve by a normal dissolution method. In addition, even if it is a solvent which can melt | dissolve a cellulose acylate with a normal melt | dissolution method, there exists an effect that a uniform solution can be obtained rapidly according to a cooling melt | dissolution method.

  In the cooling dissolution method, first, cellulose acylate is gradually added to an organic solvent at room temperature while stirring. The amount of cellulose acylate is preferably adjusted so as to be contained in the mixture in an amount of 10 to 40% by mass. The amount of cellulose acylate is more preferably 10 to 30% by mass. Furthermore, you may add the arbitrary additive mentioned later in a mixture.

  The mixture is then cooled to -100 to -10 ° C (preferably -80 to -10 ° C, more preferably -50 to -20 ° C, most preferably -50 to -30 ° C). The cooling can be performed, for example, in a dry ice / methanol bath (−75 ° C.) or a cooled diethylene glycol solution (−30 to −20 ° C.). When cooled in this way, the mixture of cellulose acylate and organic solvent solidifies.

  The cooling rate is preferably 4 ° C./min or more, more preferably 8 ° C./min or more, and most preferably 12 ° C./min or more. The faster the cooling rate, the better. However, 10,000 ° C./second is the theoretical upper limit, 1000 ° C./second is the technical upper limit, and 100 ° C./second is the practical upper limit. The cooling rate is a value obtained by dividing the difference between the temperature at the start of cooling and the final cooling temperature by the time from the start of cooling to the final cooling temperature.

  Furthermore, when this is heated to 0 to 200 ° C. (preferably 0 to 150 ° C., more preferably 0 to 120 ° C., most preferably 0 to 50 ° C.), cellulose acylate dissolves in the organic solvent. The temperature can be raised by simply leaving it at room temperature or in a warm bath. The heating rate is preferably 4 ° C./min or more, more preferably 8 ° C./min or more, and most preferably 12 ° C./min or more. The higher the heating rate, the better. However, 10,000 ° C./second is the theoretical upper limit, 1000 ° C./second is the technical upper limit, and 100 ° C./second is the practical upper limit. The heating rate is a value obtained by dividing the difference between the temperature at the start of heating and the final heating temperature by the time from the start of heating until the final heating temperature is reached. .

  A uniform solution is obtained as described above. If the dissolution is insufficient, the cooling and heating operations may be repeated. Whether or not the dissolution is sufficient can be determined by merely observing the appearance of the solution with the naked eye.

  In the cooling dissolution method, it is desirable to use a sealed container in order to avoid moisture mixing due to condensation during cooling. In the cooling and heating operation, when the pressure is applied during cooling and the pressure is reduced during heating, the dissolution time can be shortened. In order to perform pressurization and decompression, it is desirable to use a pressure-resistant container.

(Co-casting)
A cellulose acylate film can be produced from the prepared two or more kinds of cellulose acylate solutions (dope) by a solvent cast method.

  The dope is cast on a drum or band and the solvent is evaporated to form a film. The concentration of the dope before casting is preferably adjusted so that the solid content is 18 to 35% by mass. The surface of the drum or band is preferably finished in a mirror state. For casting and drying methods in the solvent casting method, U.S. Pat. No. 736892, JP-B Nos. 45-4554, 49-5614, JP-A-60-176834, No. 60-203430, and No. 62-1115035.

  The dope is preferably cast on a drum or band having a surface temperature of 10 ° C. or less. After casting, it is preferable to dry it by applying air for 2 seconds or more. The obtained film can be peeled off from the drum or band and further dried with high-temperature air whose temperature is successively changed from 100 ° C. to 160 ° C. to evaporate the residual solvent. The above method is described in Japanese Patent Publication No. 5-17844. According to this method, it is possible to shorten the time from casting to stripping. In order to carry out this method, it is necessary for the dope to gel at the surface temperature of the drum or band during casting.

  In the present invention, the obtained cellulose acylate solution (dope) is formed by casting the two or more kinds of cellulose acylate solutions on a smooth band or drum as a support. There is no restriction | limiting in particular as a manufacturing method of the film of this invention other than the above, A well-known co-casting method can be used. For example, a film may be produced while casting and laminating a solution containing cellulose acylate from a plurality of casting openings provided at intervals in the traveling direction of the metal support. The methods described in JP-A Nos. 158414, 1-122419, and 11-198285 can be applied. Further, it may be formed into a film by casting a cellulose acylate solution from two casting ports. For example, JP-B-60-27562, JP-A-61-94724, JP-A-61-947245, It can be carried out by the methods described in JP-A Nos. 61-104813, 61-158413, and 6-134933. Further, a cellulose acylate film in which a flow of a high-viscosity cellulose acylate solution described in JP-A-56-162617 is wrapped with a low-viscosity cellulose acylate solution and the high- and low-viscosity cellulose acylate solutions are simultaneously extruded. A casting method may be used. Furthermore, it is also a preferred embodiment that the outer solution described in JP-A-61-94724 and JP-A-61-94725 contains a larger amount of an alcohol component which is a poor solvent than the inner solution.

  Alternatively, by using two casting ports, the film cast on the metal support is peeled off by the first casting port, and the second casting is performed on the side that is in contact with the metal support surface. Further, a film may be prepared, for example, a method described in Japanese Patent Publication No. 44-20235. The cellulose acylate solutions to be cast may be the same solution or different cellulose acylate solutions, and are not particularly limited. In order to give a function to a plurality of cellulose acylate layers, a cellulose acylate solution corresponding to the function may be extruded from each casting port. Furthermore, the cellulose acylate solution according to the present invention can be simultaneously cast with other functional layers (for example, an adhesive layer, a dye layer, an antistatic layer, an antihalation layer, a UV absorbing layer, a polarizing layer). . As a method for producing the film of the present invention, it is preferred that the film formation is simultaneous or sequential multilayer casting film formation.

  In the conventional single-layer liquid, it is necessary to extrude a high-concentration and high-viscosity cellulose acylate solution in order to obtain the required film thickness. In many cases, this causes a problem such as a fault or flatness. As a solution to this, by casting a plurality of cellulose acylate solutions from a casting port, a highly viscous solution can be extruded onto a metal support at the same time. Not only can it be produced, but also a concentrated cellulose acylate solution can be used to reduce the drying load and increase the film production speed.

  In the case of co-casting, the inner and outer thicknesses are not particularly limited, but preferably the outer side is preferably 0.2 to 50% of the total film thickness, more preferably 2 to 30%. . Here, in the case of co-casting with three or more layers, the total thickness of the layer in contact with the metal support and the layer in contact with the air side is defined as the outer thickness.

  In the case of co-casting, a cellulose acylate film having a laminated structure can be produced by co-casting cellulose acylate solutions having different additive concentrations such as the above-mentioned plasticizer, ultraviolet absorber and matting agent. For example, a cellulose acylate 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. Moreover, it is also a preferable aspect that a release agent is contained only in the skin layer on the metal support side. It is also preferable to add more alcohol, which is a poor solvent, to the skin layer than the core layer in order to cool the metal support by the cooling drum method to gel the solution. The Tg of the skin layer and the core layer may be different, and the Tg of the core layer is preferably lower than the Tg of the skin layer. Further, the viscosity of the solution containing cellulose acylate during casting may be different between the skin layer and the core layer, and the viscosity of the skin layer is preferably smaller than the viscosity of the core layer. It may be smaller than the viscosity of the layer.

  In the present invention, the multi-layer cast dope is dried and peeled from the support.

(Drying process)
A method of drying a web which has been dried on a drum or belt and peeled off will be described. The web peeled at the peeling position immediately before the drum or belt makes one round is conveyed by alternately passing through a group of rolls arranged in a staggered manner, or both ends of the peeled web are gripped by clips or the like. It is transported by a non-contact transport method. Drying is performed by a method of applying wind at a predetermined temperature to both sides of the web (film) being conveyed or a method using a heating means such as a microwave. Since rapid drying may impair the flatness of the film to be formed, it is preferable to dry at a temperature at which the solvent does not foam in the initial stage of drying, and to dry at a high temperature after the drying proceeds. In the drying process after peeling from the support, the film tends to shrink in the longitudinal direction or the width direction by evaporation of the solvent. Shrinkage increases with drying at higher temperatures. Drying while suppressing this shrinkage as much as possible is preferable for improving the flatness of the finished film. From this point, for example, as shown in Japanese Patent Laid-Open No. 62-46625, a method in which all or part of the drying process is performed while holding the width at both ends of the web with clips or pins in the width direction. (Tenter method) is preferable. It is preferable that the drying temperature in the said drying process is 100-145 degreeC. The drying temperature, the amount of drying air, and the drying time vary depending on the solvent used, but may be appropriately selected according to the type and combination of the solvents used. In the production of the film of the present invention, the web (film) peeled from the support is preferably stretched when the amount of residual solvent in the web is less than 120% by mass.

  The residual solvent amount can be expressed by the following formula.

Residual solvent amount (% by mass) = {(MN) / N} × 100
Here, M is the mass of the web at an arbitrary point in time, and N is the mass when the web of which M is measured is dried at 110 ° C. for 3 hours.

(Stretching)
The manufacturing method which concerns on this invention includes the process of extending | stretching the film after peeling after the process of drying the dope which carried out multilayer casting, and peeling from a support body.

  In the present invention, the solution cast film can be stretched without being heated to a high temperature as long as the residual solvent amount is in a specific range, but it is preferable because drying and stretching can shorten the process. . That is, the stretching process may be performed in a state where the solvent remains, or the stretching process after drying may be performed. However, if the temperature of the web is too high, the plasticizer will volatilize, so a range of 120 to 180 ° C is preferred. In addition, stretching in biaxial directions perpendicular to each other is an effective method for bringing the refractive indexes Nx, Ny, and Nz of the film within the scope of the present invention.

  For example, when stretching in the casting 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 with a width. This is sometimes seen when using, for example, the tenter method, but it is a phenomenon that occurs when the film is stretched in the width direction and contraction force is generated at the center of the film and the end is fixed. It is thought to be called the bowing phenomenon. Even in this case, by stretching in the casting direction, it is possible to suppress the bowing phenomenon and to improve the distribution of the width retardation. Furthermore, the film thickness fluctuation | variation of the film obtained by extending | stretching in the biaxial direction orthogonal to each other can be reduced. If the film thickness variation of the optical film is too large, the retardation will be uneven. 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, a method of stretching in the biaxial directions orthogonal to each other is effective, and the stretching ratios in the biaxial directions orthogonal to each other are 1.2 to 2.0 times and 0.7 to 1.0, respectively. It is preferable that the range be doubled. Here, stretching to 1.2 to 2.0 times with respect to one direction and making the other perpendicular to 0.7 to 1.0 times means that the distance between the clip or pin supporting the film is This means that the distance is 0.7 to 1.0 times the interval before stretching.

  In general, when a biaxial stretching tenter is used to stretch in the width direction so as to have an interval of 1.2 to 2.0 times, a contracting force acts in the longitudinal direction that is the perpendicular direction.

  Therefore, if the force is applied in only one direction and the stretching is continued, the width in the perpendicular direction is reduced, but this means that the amount of shrinkage is suppressed with respect to the amount that shrinks without restricting the width. This means that the interval between the clip or pin whose width is restricted is restricted to a range of 0.7 to 1.0 times that before stretching. At this time, in the longitudinal direction, a force is exerted to shrink the film by stretching in the width direction. By taking the interval between the clips or pins in the longitudinal direction, an excessive tension is not applied in the longitudinal direction. There is no particular limitation on the method of stretching the web. For example, a method in which a difference in peripheral speed is applied to a plurality of rolls, and the roll peripheral speed difference is used to stretch in the longitudinal direction, the both ends of the web are fixed with clips and pins, and the interval between the clips and pins is increased in the traveling direction. And a method of stretching in the vertical direction, a method of stretching in the horizontal direction and stretching in the horizontal direction, a method of stretching in the vertical and horizontal directions and stretching in both the vertical and horizontal directions. Of course, these methods may be used in combination. That is, the film may be stretched in the transverse direction, longitudinally, or in both directions with respect to the film forming direction, and when stretched in both directions, simultaneous stretching or sequential stretching may be used. May be. In the case of the so-called tenter method, driving the clip portion by the linear drive method is preferable because smooth stretching can be performed and the risk of breakage and the like can be reduced.

  In addition, the production method according to the present invention preferably includes a step of re-stretching the film after the stretching step, from the viewpoint of optical development properties, in particular, expansion of the optical development range by reducing the Nz factor → coefficient, and the like.

(Description of optical member)
[Polarizer]
Since the optical film of the present invention has high optical expression, it is preferably used as a retardation film as a protective film for a polarizing plate. The polarizing plate is formed by laminating and laminating a protective film on at least one surface of the polarizer. A conventionally known polarizer can be used. For example, a hydrophilic polymer film such as a polyvinyl alcohol film is treated with a dichroic dye such as iodine and stretched. The bonding of the cellulose acylate film and the polarizer is not particularly limited, but can be performed with an adhesive made of an aqueous solution of a water-soluble polymer. The water-soluble polymer adhesive is preferably a completely saponified polyvinyl alcohol aqueous solution.

  The film of the present invention is a protective film for polarizing plate / polarizer / protective film for polarizing plate / liquid crystal cell / film of the present invention / polarizer / protective film for polarizing plate, or protective film for polarizing plate / polarizer / It can use preferably by the structure of the film / liquid crystal cell of this invention / film of this invention / polarizer / protective film for polarizing plates. In particular, by bonding to a liquid crystal cell such as a TN type, a VA type, or an OCB type, it is possible to provide a display device that is further excellent in viewing angle and visibility with little coloring. In particular, a polarizing plate using the protective film for a polarizing plate according to the present invention has little deterioration under high temperature and high humidity conditions, and can maintain stable performance for a long time.

[Liquid Crystal Display]
The cellulose acylate film of the present invention and the polarizing plate using the film can be used for liquid crystal cells and liquid crystal display devices in various display modes. TN (Twisted Nematic), IPS (In-Plane Switching), FLC (Ferroelectric Liquid Crystal), AFLC (Anti-Ferroelectric Liquid Nyst) Various display modes such as HAN (Hybrid Aligned Nematic) have been proposed.

  The OCB mode liquid crystal cell is a liquid crystal display device using a bend alignment mode liquid crystal cell in which rod-like liquid crystalline molecules are aligned in a substantially opposite direction (symmetrically) between an upper portion and a lower portion of the liquid crystal cell. OCB mode liquid crystal cells are disclosed in US Pat. Nos. 4,583,825 and 5,410,422. Since the rod-like liquid crystal molecules are aligned symmetrically between the upper part and the lower part of the liquid crystal cell, the bend alignment mode liquid crystal cell has a self-optical compensation function. The bend alignment mode liquid crystal display device has an advantage of high response speed.

  In a VA mode liquid crystal cell, rod-like liquid crystalline molecules are aligned substantially vertically when no voltage is applied.

  The VA mode liquid crystal cell includes (1) a narrowly defined VA mode liquid crystal cell in which rod-like liquid crystalline molecules are aligned substantially vertically when no voltage is applied, and substantially horizontally when a voltage is applied (Japanese Patent Laid-Open No. Hei 2-). 176625 (in Japanese Patent Publication No. 176625), and (2) a liquid crystal cell (SID97, Digest of tech. Papers (Proceedings) 28 (1997) 845 in which the VA mode is converted into a multi-domain (for MVA mode) in order to enlarge the viewing angle. ), (3) a liquid crystal cell in a mode (n-ASM mode) in which rod-like liquid crystalline molecules are substantially vertically aligned when no voltage is applied and twisted multi-domain alignment is applied when a voltage is applied (Sharp Technical Report No. 80, page 11); (4) A SURVAVAL mode liquid crystal cell (Monthly Display May 14th page (1999)) is included.

  The VA mode liquid crystal display device includes a liquid crystal cell and two polarizing plates disposed on both sides thereof. The liquid crystal cell carries a liquid crystal between two electrode substrates. In one aspect of the transmission type liquid crystal display device of the present invention, the film of the present invention is disposed between the liquid crystal cell and one polarizing plate, or between the liquid crystal cell and both polarizing plates. Arrange two.

  In another aspect of the transmissive liquid crystal display device according to the present invention, an optical compensation sheet made of the film of the present invention is used as a transparent protective film for a polarizing plate disposed between a liquid crystal cell and a polarizer. The above optical compensation sheet may be used only for the protective film (between the liquid crystal cell and the polarizer) of one polarizing plate, or two (between the liquid crystal cell and the polarizer) of both polarizing plates. You may use said optical compensation sheet for a sheet of protective film. When the optical compensation sheet is used for only one polarizing plate, it is particularly preferable to use it as a protective film for the liquid crystal cell side of the backlight side polarizing plate of the liquid crystal cell. For the lamination to the liquid crystal cell, the film of the present invention is preferably on the VA cell side. The protective film may be a normal cellulose acylate film, and is preferably thinner than the film of the present invention. For example, it is preferably 40 to 80 μm, and examples thereof include, but are not limited to, commercially available KC4UY (40 μm manufactured by Konica Minolta Opto), KC5UX (60 μm manufactured by Konica Minolta Opto), TD80 (80 μm manufactured by Fujifilm), and the like.

  The features of the present invention will be described more specifically with reference to examples and comparative examples. The materials, amounts used, ratios, processing details, processing procedures, and the like shown in the following examples can be changed as appropriate without departing from the spirit of the present invention. Therefore, the scope of the present invention should not be construed as being limited by the specific examples shown below.

<Preparation of laminated film 101>
<Fine particle dispersion 1>
Fine particles (Aerosil R812V manufactured by Nippon Aerosil Co., Ltd.) 11 parts by weight Ethanol 89 parts by weight The above was stirred and mixed with a dissolver for 50 minutes, and then dispersed with Manton Gorin.

<Fine particle addition liquid 1>
The fine particle dispersion 1 was slowly added to the dissolution tank containing methylene chloride with sufficient stirring. Further, the particles were dispersed by an attritor so that the secondary particles had a predetermined particle size. This was filtered through Finemet NF manufactured by Nippon Seisen Co., Ltd. to prepare a fine particle additive solution 1.

Methylene chloride 99 parts by mass Fine particle dispersion 1 5 parts by mass A main dope solution having the following composition was prepared. First, methylene chloride and ethanol were added to the pressure dissolution tank. Cellulose esters A and B were added to a pressurized dissolution tank containing a solvent while stirring. This is completely dissolved with heating and stirring. This was designated as Azumi Filter Paper No. The main dope solution was prepared by filtration using 244.

<Composition of dope solution for core layer>
Methylene chloride 340 parts by mass Ethanol 64 parts by mass Cellulose acylate D 100 parts by mass Compound I- (2) 6.0 parts by mass Compound A-4 6.0 parts by mass UV absorber 1.0 part by mass <Dope for skin B layer Composition of liquid>
Methylene chloride 340 parts by weight Ethanol 64 parts by weight Cellulose ester B 100 parts by weight Compound 24-2 5.0 parts by weight Compound A-2 5.0 parts by weight Peeling accelerator 1.0 part by weight Fine particle additive liquid 1 part by weight <Skin Composition of dope solution for layer A>
Methylene chloride 340 parts by weight Ethanol 64 parts by weight Cellulose ester A 100 parts by weight Compound 24-2 5.0 parts by weight Compound A-7 5.0 parts by weight Particulate additive solution 1 1 part by weight Ultraviolet absorber: Product name manufactured by BASF Japan TINUVIN928
Peeling Accelerator: Partial Ethyl Ester Compound of Citric Acid The above materials were put into a sealed container and dissolved with stirring to prepare each dope solution. Next, using the co-casting die shown in FIG. 1, a laminated cellulose acylate film 101 having a three-layer structure was produced by a co-casting method using a core layer dope, a skin A layer dope, and a skin B layer dope. .

  Each dope was cast at a temperature of 35 ° C. on a stainless steel support.

  After casting, an endless belt casting apparatus was used to uniformly cast the dope solution on a stainless steel belt support at a temperature of 33 ° C. and a width of 1500 mm. The temperature of the stainless steel belt was controlled at 30 ° C.

  On the stainless steel belt support, the solvent was evaporated until the residual solvent amount in the cast (cast) film became 75%, and then peeled off from the stainless steel belt support with a peeling tension of 150 N / m.

  The peeled cellulose acylate film was stretched 36% in the width direction using a tenter while applying heat at 150 ° C. The residual solvent at the start of stretching was 10%.

  Next, drying was terminated while the drying zone was conveyed by a number of rolls. The drying temperature was 130 ° C. and the transport tension was 100 N / m.

  As described above, a laminated cellulose acylate film 101 having a dry film thickness of 60 μm was obtained.

  Hereinafter, laminated cellulose acylate films 102 to 130 were produced in substantially the same manner except that various additive types, solvent types, and film thicknesses were changed as shown in Tables 4 to 7.

<Preparation of hard coat film 1>
On the core layer of the produced laminated cellulose acylate film 109, the following hard coat layer coating composition is filtered through a polypropylene filter having a pore size of 0.4 μm to prepare a hard coat layer coating solution, and a micro gravure coater is used. applying Te, after drying at 80 ° C., using an ultraviolet lamp, irradiance 80 mW / cm ² irradiation unit to cure the coating layer the amount of irradiation as 80 mJ / cm ^2, the hard coat layer of the dry film thickness of 9 .mu.m 1 Was formed, wound up, and a roll-shaped hard coat film 1 was produced.

<Hardcoat layer coating composition>
The following materials were stirred and mixed to obtain a hard coat layer coating composition.

Thermoplastic resin, polyester urethane resin (manufactured by Toyobo Co., Ltd., trade name “Byron UR1350”, solid content concentration 33% (toluene / methyl ethyl ketone solvent = 65/35))
6.0 parts by mass (2.0 parts by mass for polyester urethane resin)
Pentaerythritol triacrylate 30 parts by mass Pentaerythritol tetraacrylate 30 parts by mass Irgacure 184 (manufactured by BASF Japan, photopolymerization initiator) 3.0 parts by mass Irgacure 907 (manufactured by BASF Japan, photopolymerization initiator) 1.0 part by mass Polyether-modified polydimethylsiloxane (BYK-UV3510, manufactured by Big Chemie Japan) 2.0 parts by mass Propylene glycol monomethyl ether 150 parts by mass Methyl ethyl ketone 150 parts by mass >
A polarizing plate 201 was prepared using one each of the hard coat film 1 and the laminated cellulose acylate film 101 as a protective film for the polarizing plate.

(A) Production of Polarizing Film What was impregnated with 10 parts by mass of glycerin and 170 parts by mass of water in 100 parts by mass of polyvinyl alcohol (hereinafter abbreviated as PVA) having a saponification degree of 99.95 mol% and a polymerization degree of 2400. After melt-kneading and defoaming, it was melt-extruded from a T-die onto a metal roll to form a film. Then, it dried and heat-processed and obtained the PVA film.

  The obtained PVA film had an average thickness of 25 μm, a moisture content of 4.4%, and a film width of 3 m. Next, the obtained PVA film was continuously treated in the order of pre-swelling, dyeing, uniaxial stretching by a wet method, fixing treatment, drying, and heat treatment to produce a polarizing film. That is, the PVA film was preliminarily swollen in water at a temperature of 30 ° C. for 30 seconds, and immersed in an aqueous solution having an iodine concentration of 0.4 g / liter and a potassium iodide concentration of 40 g / liter at a temperature of 35 ° C. for 3 minutes. Subsequently, the film was uniaxially stretched 6 times in a 50% aqueous solution with a boric acid concentration of 4% under the condition that the tension applied to the film was 700 N / m, and the potassium iodide concentration was 40 g / liter and the boric acid concentration was 40 g / liter. Then, it was immersed in an aqueous solution having a zinc chloride concentration of 10 g / liter and a temperature of 30 ° C. for 5 minutes for fixing. Thereafter, the PVA film was taken out, dried with hot air at a temperature of 40 ° C., and further heat-treated at a temperature of 100 ° C. for 5 minutes. The obtained polarizing film had an average thickness of 13 μm, a polarizing performance of a transmittance of 43.0%, a polarization degree of 99.5%, and a dichroic ratio of 40.1.

(B) Production of Polarizing Plate A polarizing plate 201 was produced by bonding the polarizing film, the cellulose acylate film 101 and the hard coat film 1 according to the following steps 1 to 4.
Process 1: The above-mentioned polarizing film was immersed for 1 to 2 seconds in the storage tank of the polyvinyl alcohol adhesive agent solution of 2 mass% of solid content.
Step 2: Excess adhesion of the hard coat film 1 in which the cellulose acylate film 101 and the hard coat layer are attached with a peelable protective film (PET) attached to the polarizing film immersed in the polyvinyl alcohol adhesive solution in Step 1 The agent was removed lightly, and the cellulose acylate film 101 and the hard coat film 1 were sandwiched between the polarizing films and laminated.
Step 3: The laminate was bonded at a speed of about 2 m / min at a pressure of ^{20 to} 30 N / cm ² with two rotating rollers. At this time, it was carried out with care to prevent bubbles from entering.
Step 4: The sample prepared in Step 3 was dried in a dryer at a temperature of 80 ° C. for 5 minutes to prepare a polarizing plate.
Step 5: A commercially available acrylic pressure-sensitive adhesive was applied to the laminated cellulose acylate film 101 of the polarizing plate prepared in Step 4 so that the thickness after drying was 25 μm, and dried in an oven at 110 ° C. for 5 minutes to adhere. A layer was formed, and a peelable protective film was attached to the adhesive layer. This polarizing plate was cut (punched) into a size of 960 × 600 mm to produce a polarizing plate 201.

<Production of Polarizing Plates 202 to 228>
In the production of the polarizing plate 201, polarizing plates 202 to 228 were produced in the same manner except that the laminated cellulose acylate film 101 was changed to the laminated cellulose acylate films 102 to 108 and 111 to 130, respectively.

<Production of Liquid Crystal Display Device 401>
The polarizing plate of the liquid crystal panel of SONY 40-type display KDL-40V5 is peeled off, and the prepared polarizing plate 201 is used as the polarizing plate on the viewing side so that the hard coat layer is on the viewing side. Was pasted. Further, on the backlight side, a polarizing plate 229 which is laminated and bonded so as to sandwich the polarizing film with the laminated cellulose acylate film 110 in the same manner as in the above procedure is liquid crystal using an acrylic adhesive having a thickness of 25 μm. The liquid crystal panel 301 was produced by bonding to cell glass. Next, the liquid crystal panel 301 was set on a liquid crystal television, and a liquid crystal display device 401 was manufactured.

<Production of Liquid Crystal Display Devices 402 to 428>
In production of the liquid crystal display device 401, except that the polarizing plate 201 is changed to the polarizing plates 202 to 228, similarly, the adhesive layer and the liquid crystal cell glass are bonded so that the hard coat layer is on the viewing side. did. Also, on the backlight side, the polarizing plate 229 laminated and bonded so as to sandwich the polarizing film with the laminated cellulose acylate film 110 in the same manner as in the above procedure was changed to polarizing plates 230 to 256, respectively. Similarly, liquid crystal panels 302 to 328 were prepared by bonding to a liquid crystal cell glass using an acrylic adhesive having a thickness of 25 μm. Next, the liquid crystal panels 302 to 328 were set on a liquid crystal television, and liquid crystal display devices 402 to 428 were manufactured.

[Evaluation]
Hereinafter, various characteristics of the laminated cellulose acylate film were measured and measured by the following methods.

(Hygroscopic expansion coefficient)
The hygroscopic expansion coefficient (cm / cm ·% RH) is represented by the following formula. In the following, L4 is the length (mm) of the film sample when it is changed to a relative humidity (RH4) of 23 ° C., L0 is the original size (mm) of the film sample in the standard state (23 ° C., 55% RH), RH0 is the standard relative humidity (% RH), and RH4 is the changed relative humidity (% RH).

β = {(L4-L0) / L0} / (RH4-RH0)
The hygroscopic expansion coefficient is a change in dimensions per 1% of relative humidity, and indicates whether the film has a large change or a small film due to a change in humidity. In the present invention, the hygroscopic expansion coefficient is preferably 8 × 10 ⁻⁵ (cm / cm ·% RH) or less, more preferably 6 × 10 ⁻⁵ (cm / cm ·% RH) or less. It is more preferable that it is below 10 < ^-5 > (cm / cm *% RH).

(Moist heat dimensional stability)
A cross-shaped mark is attached to two locations (MD direction and long direction) on the surface of the cellulose ester film sample, heat treatment (conditions: 80 ° C., 90% RH, 200 hours) is performed, and the distance between the marks is measured with a factory microscope. Was measured. The dimensional change rate was calculated by the following formula, assuming that the distance before the heat treatment is a1 and the distance after the heat treatment is a2.
Dimensional change rate (%) = (a1-a2) / a1 × 100
(Peelability)
5: Very good peelability, no optical unevenness was visible on the film after peeling 4: Good peelability, slight optical unevenness visible on the film after peeling 3: After peeling, after peeling There was no stripe-shaped film thickness unevenness in the film, but optical unevenness was visually recognized 2: the peelability was poor, and after the film was striped, the stripe-shaped film thickness unevenness was visible 1: the peelability was very poor, The film was partially stretched during peeling.

<Evaluation>
The following evaluation was performed about the polarizing plates 201-256 and the image display apparatuses 401-428.

(Polarizer)
a. Observation of deformation failure The polarizing plate subjected to the above durability test was observed from the hard coat layer side, and the state of deformation failure was observed according to the following criteria.
A: Deformation failure is not observed at all. O: Deformation failure is observed in a small part, but there is no problem in actuality. Δ: Deformation failure is partially observed. There is a problem in terms of actual damage ×: It can be seen that a partial deformation failure has occurred clearly even from a distance.

(Liquid crystal display device)
a << Evaluation of streaks >>
Each of the manufactured liquid crystal display devices 401 to 428 was treated for 300 hours at 60 ° C. in order to see deterioration due to heat, and then returned to 23 ° C. and 55% RH. Then, after turning on the power and turning on the backlight, the streak (streaks) at the time of black display 2 hours later was visually evaluated according to the following criteria.
◎: No streak ○: A weak streak exists in the center △: A weak streak exists from the center to the end ×: A strong streak exists in the entire surface .

b << Evaluation of visibility >>
About each produced said liquid crystal display device, after leaving for 100 hours on 60 degreeC and 90% RH conditions, it returned to 23 degreeC and 55% RH. Thereafter, the surface of the display device was visually observed and evaluated according to the following criteria.
A: No wavy unevenness is observed on the surface. O: A slight wavy unevenness is observed on the surface. Δ: A slight wavy unevenness is slightly observed on the surface. X: A fine wavy unevenness is observed on the surface. It is done.

The above evaluation results are shown in Tables 8 to 11 below. In Table 8, the hygroscopic expansion coefficient of the laminated film 101 is expressed as 4.82E-05, which means 4.82 × 10 ⁻⁵ (cm / cm ·% RH). . The same applies to other laminated films.

  As can be seen from the results shown in Tables 8 to 11, the laminated cellulose acylate film of the present invention has excellent performance in terms of hygroscopic expansion coefficient, wet heat dimensional stability, and peelability.

  Moreover, as can be seen from the results shown in Tables 8 to 11, the polarizing plate produced from the laminated cellulose acylate film of the present invention has no deformation failure when stored under high temperature and high humidity, and is bonded to a polarizer. Excellent in properties. In addition, when the polarizing plate is used in a liquid crystal display device, it exhibits excellent performance in both streaking and visibility (clearness).

DESCRIPTION OF SYMBOLS 10 Co-casting die 11 Base part 13, 15 Surface layer slit 14 Base layer slit 16 Metal support 17, 19 Surface layer dope 18 Base layer dope 20 Multilayer web

Claims (16)

A cellulose acylate laminated film in which a skin B layer containing cellulose acylate satisfying the following formula (1) and a core layer containing cellulose acylate satisfying the following formula (2) are laminated and formed, A cellulose acylate laminated film comprising a retardation adjusting agent in at least one of the skin B layer and the core layer.
Formula (1): 2.0 <Z ₁ <2.7
(In formula (1), Z ₁ represents the total acyl group substitution degree of the cellulose acylate of the skin layer.)
Formula (2): 2.7 <Z ₂ <3.0
(In formula (2), Z ₂ represents the total acyl group substitution degree of the cellulose acylate of the core layer.)   The cellulose acylate laminated film according to claim 1, wherein the core layer contains a retardation developer. The cellulose according to claim 1 or 2, wherein the core layer contains a compound represented by the following general formula (A) having a total average substitution degree in the range of 4.5 to 6.9. Acylate laminated film.

(Wherein R _{1 to} R ₈ each independently represents a substituted or unsubstituted alkylcarbonyl group or a substituted or unsubstituted arylcarbonyl group, and R _{1 to} R ₈ may be the same) , May be different.)   The cellulose acylate laminated film according to any one of claims 1 to 3, wherein the skin B layer contains a compound having negative intrinsic birefringence. The skin A layer containing cellulose acylate satisfying the following formula (1) is provided on a surface opposite to the surface on which the skin B layer of the laminated core layer is provided. The cellulose acylate laminated film according to any one of claims 1 to 4.
Formula (1): 2.0 <Z ₁ <2.7
(In formula (1), Z ₁ represents the total acyl group substitution degree of the cellulose acylate of the skin layer.)   The cellulose acylate laminated film according to claim 5, wherein at least one of the skin A layer and the skin B layer contains a polymer having a cyclic structure in a side chain.   The cellulose acylate laminated film according to claim 5 or 6, wherein metal fine particles are contained in at least one of the skin A layer and the skin B layer.   The average layer thickness of the core layer is in the range of 30 to 100 μm, and the average layer thickness of at least one of the skin A layer and the skin B layer is 0.2% or more and less than 25% of the average layer thickness of the core layer. The cellulose acylate laminated film according to any one of claims 5 to 7, wherein the film is a cellulose acylate laminated film.   The cellulose acylate laminated film according to any one of claims 1 to 8, wherein a film width is in a range of 700 to 3000 mm. The cellulose acylate used in the skin A layer and the skin B layer satisfies the following formulas (3) and (4): The cellulose acylate according to any one of claims 5 to 9, Laminated film.
Formula (3): 1.0 <X ₁ <2.7
(In the formula (3), X ₁ represents a degree of acetyl substitution of the cellulose acylate of the skin layer A and skin layer B.)
Formula (4): 0 ≦ Y ₁ <1.5
(In Formula (4), Y ₁ represents the total substitution degree of acyl groups having 3 or more carbon atoms in the cellulose acylate of the skin A layer and the skin B layer.) The cellulose acylate laminated film according to any one of claims 1 to 10, wherein the cellulose acylate used for the core layer satisfies the following formulas (5) and (6).
Formula (5): 1.2 <X ₂ <3.0
(In the formula (5), X ₂ represents a substitution degree of acetyl groups of the cellulose acylate of the core layer.)
Formula (6): 0 ≦ Y ₂ <1.5
(Wherein (in 6), Y ₂ represents a total substitution degree of the cellulose acylate acyl group having 3 or more carbon atoms of the core layer.)   The cellulose acylate laminated film according to any one of claims 1 to 11, wherein the cellulose acylate has an acyl group having 2 to 4 carbon atoms. The cellulose acylate laminated film according to any one of claims 1 to 12, wherein an Nz coefficient represented by the following formula (7) is 7 or less.
Formula (7): Nz coefficient = Rth / Re + 0.5   The cellulose acylate laminated film according to any one of claims 1 to 13, wherein the cellulose acylate is cellulose acetate.   A polarizing plate using at least one sheet of the cellulose acylate laminated film according to any one of claims 1 to 14.   A liquid crystal display device using at least one sheet of the cellulose acylate laminated film according to any one of claims 1 to 14.

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