JP2007108732A - Polarizing plate and liquid crystal display device - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a polarizing plate which can be manufactured with high productivity and is integrated with an optically anisotropic layer such as an optically compensation film and a brightness-improving film. <P>SOLUTION: The long-size polarizing plate has a first optically anisotropic layer, a polarizing layer, and a second optically anisotropic layer in the order, wherein any layer is continuously laminated in long length. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a polarizing plate having an optical compensation film and a liquid crystal display device. In particular, the present invention relates to a polarizing plate in which a viewing angle widening film and a brightness enhancement film are integrated in a reflective liquid crystal display device, a transflective liquid crystal display device, a transmissive liquid crystal display device, a GH-LCD, and the like.

  The λ / 4 plate has a great many applications, and is already used for a reflective LCD, a transflective LCD, a brightness enhancement film, a pickup for an optical disk, and a PS conversion element. Most of the λ / 4 plates currently used for them are retardation plates that exhibit optical anisotropy by stretching a polymer film. The optical orientation of the polymer film generally corresponds to the longitudinal or lateral direction of the sheet or roll film, and polymer films having an optical axis or slow axis in the oblique direction of the sheet or roll are very producible. It is difficult to. In many cases where a retardation plate is used, it is disposed at an angle that is neither parallel nor orthogonal to the transmission axis of the polarizing plate. In many cases, two or more retardation plates and polarizing plates are arranged at angles that are neither parallel nor orthogonal. In general, since the transmission axis of the polarizing plate is perpendicular to the roll film, in order to attach the retardation plate and the polarizing plate, cut each film at a predetermined angle and attach the resulting chip. It is necessary to match. When trying to manufacture a laminate of a retardation plate and a polarizing plate by chip bonding, an adhesive coating process, chip cutting or chip bonding process is required, and the process is complicated and the quality due to axial misalignment Decline is likely to occur, yield is reduced, cost is increased, and degradation due to contamination is likely to occur. In the polymer film, the expression of refractive index anisotropy in the three-dimensional direction is affected by various conditions such as the draw ratio, temperature, draw speed, and polymer molecular weight. Therefore, it is difficult to precisely control the optical anisotropy of the polymer film.

In order to solve such a problem, a coating liquid containing a discotic liquid crystal compound or a rod-shaped liquid crystal compound is applied to a roll-shaped film, and optical anisotropy is expressed by orienting in a predetermined direction. A phase difference plate having a slow axis at an angle that is neither parallel nor orthogonal is proposed (Patent Documents 1 and 2). In addition, there are disclosed retardation plates in which orientation is fixed so that a disc surface of discotic liquid crystal molecules is substantially perpendicular to a film surface (Patent Documents 3, 4, 5, and 6). However, in the conventional technique, since many alignment defects are generated, the yield and productivity are lowered.
JP 2001-4837 A JP 2004-53841 A Japanese Patent Laid-Open No. 9-292522 JP 2000-56310 A JP 2000-104073 A JP 2000-105316 A

  The present invention has been made in view of the above problems, and it is an object of the present invention to provide a polarizing plate integrated with an optical anisotropic layer such as an optical compensation film and a brightness enhancement film, which can be produced with high productivity. And It is another object of the present invention to provide a liquid crystal display device that can be manufactured with high productivity and has improved viewing angle characteristics and backlight efficiency.

Means for solving the above problems are as follows.
[1] A long polarizing plate having a first optically anisotropic layer, a polarizing layer, and a second optically anisotropic layer in this order, and each layer is continuously in a long state. A laminated long polarizing plate.
[2] A third optical anisotropic layer is further included, and the first optical anisotropic layer, the polarizing layer, the second optical anisotropic layer, and the third optical anisotropic layer are provided in this order. 1] polarizing plate.
[3] The polarizing plate according to [1] or [2], wherein the first and / or second optically anisotropic layer includes at least a layer formed of a composition containing a liquid crystal compound.
[4] The polarizing plate according to [3], wherein the liquid crystalline compound is a discotic liquid crystal compound or a rod-like liquid crystal compound.
[5] The polarized light according to [3] or [4], wherein in the layer, the molecules of the liquid crystalline compound are fixed in any orientation state of hybrid orientation, horizontal orientation, vertical orientation, cholesteric orientation, and tilted orientation. Board.

[6] The polarizing plate according to any one of [1] to [5], wherein the first and / or second optically anisotropic layer includes a polymer film.
[7] The polarizing plate according to [6], wherein the polymer film is a stretched polymer film that exhibits optical anisotropy by stretching.
[8] The polarizing plate according to [6] or [7], wherein the polymer film is a cellulose acylate film or a norbornene-based film.
[9] The second optically anisotropic layer has an in-plane retardation of 90 to 160 nm, and the slow axis direction is neither 90 ° nor 0 ° with respect to the longitudinal direction. 8].
[10] The second optically anisotropic layer includes at least two of an optically anisotropic layer having an in-plane retardation of 90 to 180 nm and an optically anisotropic layer having an in-plane retardation of 200 to 320 nm. The angle formed by the slow axes of each of the at least two optically anisotropic layers is neither 90 ° nor 0 °, and any of the at least two optically anisotropic layers The polarizing plate according to any one of [1] to [8], wherein the slow axis direction is neither 90 ° nor 0 ° with respect to the longitudinal direction.
[11] The polarizing plate according to any one of [2] to [10], wherein the third optically anisotropic layer is a cholesteric liquid crystal layer.
[12] A liquid crystal display device in which a polarizing film, a liquid crystal cell, a polarizing plate of any one of [1] to [11], and a light source are arranged in this order.

  ADVANTAGE OF THE INVENTION According to this invention, the polarizing plate integrated with optical anisotropic layers, such as an optical compensation film and a brightness improvement film | membrane, which can be produced with high productivity can be provided. Further, according to the present invention, it is possible to provide a liquid crystal display device that can be manufactured with high productivity and that has improved viewing angle characteristics and backlight efficiency.

BEST MODE FOR CARRYING OUT THE INVENTION

  Hereinafter, embodiments of the retardation plate, the polarizing plate, and the liquid crystal display device of the present invention will be sequentially described. In the present specification, a numerical range represented by using “to” means a range including numerical values described before and after “to” as a lower limit value and an upper limit value.

  In the present specification, “parallel” and “orthogonal” mean that the angle is within a range of strictly less than ± 10 °. In this range, an error from a strict angle is preferably less than ± 5 °, and more preferably less than ± 2 °. Further, “substantially vertical” means within a range of less than ± 20 ° from a strict vertical angle. In this range, an error from a strict angle is preferably less than ± 15 °, and more preferably less than ± 10 °. Further, the “slow axis” means a direction in which the refractive index is maximized. Further, the measurement wavelength of the refractive index is a value at λ = 550 nm in the visible light region unless otherwise specified.

  In this specification, “polarizing plate” is cut into a size to be incorporated into a long polarizing plate and a liquid crystal device unless otherwise specified (in this specification, “cutting” includes “punching” and “cutting out”. It is used in the meaning including both of the polarizing plates. In this specification, “polarizing film” and “polarizing plate” are distinguished from each other. “Polarizing plate” means a laminate having a transparent protective film for protecting the polarizing film on at least one side of the “polarizing film”. It shall be.

  In the present specification, Re and Rth respectively represent in-plane retardation and retardation in the thickness direction at a certain wavelength λ nm. Re is measured with KOBRA 21ADH (manufactured by Oji Scientific Instruments Co., Ltd.) by making light of wavelength λ nm incident in the normal direction of the film. Rth was measured by making light having a wavelength λ nm incident from a direction inclined + 40 ° with respect to the normal direction of the film with the slow axis in the plane (determined by KOBRA 21ADH) as the tilt axis (rotation axis). A retardation value and a retardation value measured by making light of wavelength λ nm incident from a direction inclined by −40 ° with respect to the film normal direction with the in-plane slow axis as the tilt axis (rotation axis). KOBRA 21ADH calculates based on the retardation value measured in the direction, the assumed value of the 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.

The present invention is a long polarizing plate having a first optically anisotropic layer, a polarizing layer, and a second optically anisotropic layer in this order, and each layer is continuous in a long state. It is related with the elongate polarizing plate laminated | stacked on. The polarizing plate of the present invention is incorporated into a liquid crystal display device as it is or after being cut into a desired size. You may use as a polarizing plate arrange | positioned in any of the display surface side and a backlight side. In the case where it is arranged on the backlight side, of the first and second optical anisotropic layers, the optical anisotropy layer arranged at a position closer to the backlight contributes to improving the luminance of the liquid crystal display device. It is preferable that the optically anisotropic layer disposed at a position closer to the liquid crystal cell has at least optical characteristics that contribute to optical compensation of the liquid crystal cell.
In addition, the order of lamination is not particularly limited, and may be the order of arrangement or vice versa. Alternatively, the polarizing plate of the present invention may be prepared by first producing a long laminate having two or more layers laminated, and then laminating another long film or the like.

  One aspect of the polarizing plate of the present invention further includes a third optical anisotropic layer, and includes a first optical anisotropic layer, a polarizing layer, a second optical anisotropic layer, and a third optical anisotropy. Have layers in this order. When the polarizing plate of this embodiment is disposed on the backlight side, it is preferable to dispose the third optically anisotropic layer so as to be closest to the backlight. Both the second and third optically anisotropic layers have at least optical characteristics that contribute to improving the luminance of the liquid crystal display device, and the first optically anisotropic layer contributes to optical compensation of the liquid crystal cell. It preferably has at least characteristics.

Hereinafter, various materials used for production of the polarizing plate of the present invention, production methods, and the like will be described in detail.
[First and second optically anisotropic layers]
The first and / or second optically anisotropic layer has optical anisotropy expressed by the orientation of molecules of the constituent material. The constituent material is not particularly limited, and a polymer film is stretched even in a layer formed from a composition containing a liquid crystal compound and exhibiting optical anisotropy expressed by the orientation of molecules of the liquid crystal compound. Even if it is a layer having optical anisotropy expressed by orienting the polymer in the film, it may have both layers. The first and / or second optically anisotropic layer preferably includes at least one layer formed from a composition containing a liquid crystal compound, or preferably includes a polymer film. More preferably. That is, the first and second optically anisotropic layers are laminates (hereinafter referred to as “optical compensation films”) of a polymer film and an optically anisotropic layer formed from a composition containing a liquid crystal compound. Preferably there is. Hereinafter, the optical compensation film that can be used as the first and / or second optically anisotropic layer in the present invention will be described in detail.

[Optical compensation film]
In the present invention, as the first and / or second optically anisotropic layer, a long shape having a support made of a polymer film and an optically anisotropic layer formed from a composition containing a liquid crystalline compound. The optical compensation film may be used.

[Optically Anisotropic Layer Containing Liquid Crystalline Compound]
There is no particular limitation on the type of liquid crystalline compound used for forming the optically anisotropic layer of the optical compensation film. For example, after forming a low molecular weight liquid crystalline compound in a nematic orientation in a liquid crystal state, an optically anisotropic layer obtained by fixing by photocrosslinking or thermal crosslinking, or after forming a polymer liquid crystalline compound in a nematic orientation in a liquid crystal state, An optically anisotropic layer obtained by fixing the orientation by cooling can also be used. In the present invention, even when a liquid crystalline compound is used for the optically anisotropic layer, the optically anisotropic layer is a layer formed by fixing the liquid crystalline compound by polymerization or the like. After that, it is no longer necessary to show liquid crystallinity. The polymerizable liquid crystal compound may be a polyfunctional polymerizable liquid crystal or a monofunctional polymerizable liquid crystal compound. The liquid crystalline compound may be a discotic liquid crystalline compound or a rod-shaped liquid crystalline compound.

In the optically anisotropic layer, the molecules of the liquid crystal compound are preferably fixed in any alignment state of vertical alignment, horizontal alignment, hybrid alignment, and tilt alignment. In order to produce a retardation plate having a symmetric viewing angle dependency, the disc surface of the discotic liquid crystalline compound is substantially perpendicular to the film surface (optically anisotropic layer surface), or a rod-like plate. It is preferable that the major axis of the liquid crystal compound is substantially horizontal with respect to the film surface (optically anisotropic layer surface). The term “substantially perpendicular to the discotic liquid crystalline compound” means that the average value of the angle formed by the film surface (optically anisotropic layer surface) and the disc surface of the discotic liquid crystalline compound is in the range of 70 ° to 90 °. Means. 80 ° to 90 ° are more preferable, and 85 ° to 90 ° are more preferable. That the rod-like liquid crystalline compound is substantially horizontal means that the angle formed by the film surface (optically anisotropic layer surface) and the director of the rod-like liquid crystalline compound is in the range of 0 ° to 20 °. 0 ° to 10 ° is more preferable, and 0 ° to 5 ° is more preferable.
In the case of producing an optical compensation film in which the viewing angle dependency is asymmetric by hybrid alignment of liquid crystal compound molecules, the average tilt angle of the director of the liquid crystal compound is preferably 5 to 85 °, and preferably 10 to 80 °. More preferably, it is more preferably 15 to 75 °. An optical compensation film including these hybrid-oriented optically anisotropic layers is preferable as a TN mode, OCB mode, ECB mode viewing angle widening film, and a retardation plate for reflection type or transflective type having those modes. Can be used.

  The optical compensation film includes an optically anisotropic layer containing a liquid crystalline compound. However, the optically anisotropic layer may consist of only one layer, or a laminate of two or more optically anisotropic layers. It may be.

  The optically anisotropic layer comprises a coating liquid containing a liquid crystalline compound such as a rod-like liquid crystalline compound or a discotic liquid crystalline compound, and, if desired, a polymerization initiator, an alignment control agent and other additives described later. It can be formed by coating on top. It is preferable to form an alignment film on a support and apply the coating solution on the surface of the alignment film.

[Discotic liquid crystalline compounds]
In the present invention, it is preferable to use a discotic liquid crystalline compound for forming the optically anisotropic layer of the optical compensation film, and it is more preferable to use triphenylene liquid crystal. Discotic liquid crystalline compounds are disclosed in various documents (C. Destrade et al., Mol. Crysr. Liq. Cryst., Vol. 71, page 111 (1981); edited by The Chemical Society of Japan, Quarterly Chemical Review, No. 22, Liquid Crystal Chemistry, Chapter 5, Chapter 10 Section 2 (1994); B. Kohne et al., Angew. Chem. Soc. Chem. Comm., Page 1794 (1985); J. Zhang et al., J Am.Chem.Soc., Vol.116, page 2655 (1994)). The polymerization of discotic liquid crystalline compounds is described in JP-A-8-27284.

The discotic liquid crystalline compound preferably has a polymerizable group so that it can be fixed by polymerization. For example, a structure in which a polymerizable group is bonded as a substituent to a discotic core of a discotic liquid crystalline compound can be considered. However, when a polymerizable group is directly connected to the discotic core, the alignment state is maintained in the polymerization reaction. It becomes difficult. Therefore, a structure having a linking group between the discotic core and the polymerizable group is preferable. That is, the discotic liquid crystalline compound having a polymerizable group is preferably a compound represented by the following formula.
D (-LP) _n
In the formula, D is a discotic core, L is a divalent linking group, P is a polymerizable group, and n is an integer of 4 to 12. Preferred specific examples of the discotic core (D), the divalent linking group (L) and the polymerizable group (P) in the above formula are (D1) to (D15) described in JP-A No. 2001-4837, respectively. ), (L1) to (L25), (P1) to (P18), and the contents described in the publication can be preferably used. In addition, the discotic nematic liquid crystal phase-solid phase transition temperature of the liquid crystalline compound is preferably 70 to 300 ° C, and more preferably 70 to 170 ° C.

  The discotic liquid crystalline compounds represented by the following formulas (DI) and (I) have low in-plane retardation wavelength dispersibility, can exhibit high in-plane retardation, and have special alignment films and additives. Even if it is not used, it is possible to achieve vertical alignment with a high average tilt angle and excellent uniformity, so that it can be used for forming the first or second optical anisotropic layer, particularly the second optical anisotropic layer. Is preferred. Furthermore, the coating liquid containing the liquid crystalline compound tends to have a relatively low viscosity, and is preferable from the viewpoint of good coating properties.

Formula (I)

In general formula (I), D is a disk-shaped core. The discotic core is located at the center of the discotic compound and constitutes the disc surface. The discotic core is a well-known concept in the molecular structure of discotic liquid crystalline molecules. Below, the example of a disk shaped core is shown. Y in each compound means the following general formula (VI). R ¹ , R ² , R ³ , R ⁴ and R ⁵ in the following general formula (VI) have the same meanings as those in the general formula (I), and preferred ranges are also the same.

Formula (VI)

The disk-shaped core (D) is particularly preferably triphenylene (Z4).
The discotic core (D) may have a substituent other than Y (the general formula (VI)). Examples of the substituent that the discotic core may have are a halogen atom (fluorine atom, chlorine atom, bromine atom, iodine atom), cyano group, hydroxyl group, amino group, carbamoyl group, sulfamoyl group, mercapto group, Ureido group, alkyl group, substituted alkyl group, alkenyl group, substituted alkenyl group, alkynyl group, substituted alkynyl group, aryl group, substituted aryl group, heterocyclic group, alkoxy group, substituted alkoxy group, aryloxy group, substituted aryloxy group , Acyl group, acyloxy group, alkoxycarbonyl group, substituted alkoxycarbonyl group, aryloxycarbonyl group, substituted aryloxycarbonyl group, substituted amino group, amide group, imide group, alkoxycarbonylamino group, substituted alkoxycarbonylamino group, aryloxy Carbonylamino , Substituted aryloxycarbonylamino group, substituted carbamoyl group, sulfonamido group, substituted sulfamoyl group, alkylthio group, substituted alkylthio group, arylthio group, substituted arylthio group, alkylsulfonyl group, substituted alkylsulfonyl group, arylsulfonyl group, substituted arylsulfonyl Group, alkylsulfinyl group, substituted alkylsulfinyl group, arylsulfinyl group, substituted arylsulfinyl group, substituted ureido group, phosphoramido group, substituted silyl group, alkoxycarbonyloxy group, substituted alkoxycarbonyloxy group, aryloxycarbonyloxy group and Contains a substituted aryloxycarbonyloxy group.

  The alkyl group may have a cyclic structure or a branched structure. The alkyl group preferably has 1 to 30 carbon atoms. The alkyl part of the substituted alkyl group has the same meaning as the alkyl group, and the preferred range is also the same. Examples of the substituent of the substituted alkyl group are the same as the examples of the substituent of the discotic core except that the alkyl group, the substituted alkyl group, the alkenyl group, the substituted alkenyl group, the alkynyl group and the substituted alkynyl group are excluded. The preferred range is also synonymous.

  The alkenyl group may have a cyclic structure or a branched structure. The alkenyl group preferably has 2 to 30 carbon atoms. The alkenyl part of the substituted alkenyl group has the same meaning as the alkenyl group, and the preferred range is also the same. Examples of the substituent of the substituted alkenyl group are the same as the examples of the substituent of the substituted alkyl group. The alkynyl group may have a cyclic structure or a branched structure. The alkynyl group preferably has 2 to 30 carbon atoms. The alkynyl part of the substituted alkynyl group is the same as the alkynyl group. The example of the substituent of a substituted alkynyl group is synonymous with the example of the substituent of a substituted alkyl group, and its preferable range is also synonymous.

  The number of carbon atoms in the aryl group is preferably 6-30. The aryl part of the substituted aryl group has the same meaning as the aryl group, and the preferred range is also the same. The example of the substituent of a substituted aryl group is synonymous with the example of the substituent of a discotic core, and its preferable range is also synonymous.

  The heterocyclic group preferably has a 5-membered or 6-membered heterocyclic ring. The heterocycle may be condensed with another heterocycle, aliphatic ring or aromatic ring. The hetero atom of the heterocyclic ring is preferably a nitrogen atom, an oxygen atom or a sulfur atom. The heterocyclic group may have a substituent. The example of the substituent of a heterocyclic group is synonymous with the example of the substituent of a discotic core, and its preferable range is also synonymous.

  The alkyl part of an alkoxy group and a substituted alkoxy group is synonymous with an alkyl group, and its preferable range is also synonymous. The example of the substituent of a substituted alkoxy group is synonymous with the example of the substituent of a substituted alkyl group, and its preferable range is also synonymous. The aryl part of the aryloxy group and the substituted aryloxy group has the same meaning as the aryl group, and the preferred range is also the same. The example of the substituent of a substituted aryloxy group is synonymous with the example of the substituent of a disk shaped core, and its preferable range is also synonymous.

The acyl group is represented by formyl or —CO—R, and R is an alkyl group, a substituted alkyl group, an alkenyl group, a substituted alkenyl group, an alkynyl group, a substituted alkynyl group, an aryl group or a substituted aryl group.
The acyloxy group is represented by formyloxy or —O—CO—R, and R is an alkyl group, a substituted alkyl group, an alkenyl group, a substituted alkenyl group, an alkynyl group, a substituted alkynyl group, an aryl group or a substituted aryl group.

The alkyl moiety of the alkoxycarbonyl group and the substituted alkoxycarbonyl group is the same as the alkyl group. The example of the substituent of a substituted alkoxycarbonyl group is synonymous with the example of the substituent of a substituted alkyl group, and its preferable range is also synonymous.
The aryl part of the aryloxycarbonyl group and the substituted aryloxycarbonyl group has the same meaning as the aryl group, and the preferred range is also the same. Examples of the substituent of the substituted aryloxycarbonyl group are synonymous with the examples of the substituent of the discotic core, and the preferred range is also synonymous.

The substituted amino group is represented by —NH—R or —N (—R) ₂ , where R is an alkyl group, a substituted alkyl group, an alkenyl group, a substituted alkenyl group, an alkynyl group, a substituted alkynyl group, an aryl group or a substituted aryl group. It is.
The amide group is represented by —NH—CO—R, and R is an alkyl group, a substituted alkyl group, an alkenyl group, a substituted alkenyl group, an alkynyl group, a substituted alkynyl group, an aryl group, or a substituted aryl group.
The imide group is represented by —N (—CO—R) ₂ , and R is an alkyl group, a substituted alkyl group, an alkenyl group, a substituted alkenyl group, an alkynyl group, a substituted alkynyl group, an aryl group or a substituted aryl group.

The alkyl moiety of the alkoxycarbonylamino group and the substituted alkoxycarbonylamino group has the same meaning as the alkyl group, and the preferred range is also the same. Examples of the substituent of the substituted alkoxycarbonylamino group are the same as the examples of the substituent of the substituted alkyl group.
The aryl part of the aryloxycarbonylamino group and the substituted aryloxycarbonylamino group has the same meaning as the aryl group, and the preferred range is also the same. Examples of the substituent of the substituted aryloxycarbonylamino group are the same as the examples of the substituent of the discotic core.

The substituted carbamoyl group is represented by —CO—NH—R or —CO—N (—R) ₂ , where R is an alkyl group, substituted alkyl group, alkenyl group, substituted alkenyl group, alkynyl group, substituted alkynyl group, aryl group. Or it is a substituted aryl group.
The sulfonamide group is represented by —NH—SO ₂ —R, and R is an alkyl group, a substituted alkyl group, an alkenyl group, a substituted alkenyl group, an alkynyl group, a substituted alkynyl group, an aryl group or a substituted aryl group. The substituted sulfamoyl group is represented by —SO ₂ —NH—R or —SO ₂ —N (—R) ₂ , where R is an alkyl group, a substituted alkyl group, an alkenyl group, a substituted alkenyl group, an alkynyl group, a substituted alkynyl group, An aryl group or a substituted aryl group.

The alkyl part of the alkylthio group and the substituted alkylthio group is the same as the alkyl group. The example of the substituent of a substituted alkylthio group is the same as the example of the substituent of a substituted alkyl group.
The aryl part of the arylthio group and the substituted arylthio group has the same meaning as the aryl group, and the preferred range is also the same. The example of the substituent of a substituted arylthio group is synonymous with the example of the substituent of a disk shaped core, and its preferable range is also synonymous.
The alkyl moiety of the alkylsulfonyl group and the substituted alkylsulfonyl group has the same meaning as the alkyl group, and the preferred range is also the same. The example of the substituent of a substituted alkylsulfonyl group is synonymous with the example of the substituent of a substituted alkyl group, and its preferable range is also synonymous.

The aryl moiety of the arylsulfonyl group and the substituted arylsulfonyl group has the same meaning as the aryl group, and the preferred range is also the same. The example of the substituent of a substituted arylsulfonyl group is synonymous with the example of the substituent of a disk shaped core, and its preferable range is also synonymous.
The alkyl part of the alkylsulfinyl group and the substituted alkylsulfinyl group has the same meaning as the alkyl group, and the preferred range is also the same. The example of the substituent of a substituted alkylsulfinyl group is synonymous with the example of the substituent of a substituted alkyl group, and its preferable range is also synonymous.
The aryl part of the alkylsulfinyl group and the substituted alkylsulfinyl group has the same meaning as the aryl group, and the preferred range is also the same. Examples of the substituent of the substituted alkylsulfinyl group are synonymous with the examples of the substituent of the discotic core, and the preferred range is also synonymous.

The substituted ureido group is represented by —NH—CO—NH—R or —NH—CO—N (—R) ₂ , where R is an alkyl group, a substituted alkyl group, an alkenyl group, a substituted alkenyl group, an alkynyl group, a substituted alkynyl group. Group, aryl group or substituted aryl group.
The phosphoric acid amide group is represented by —NH—O—P (═O) (— OH) —O—R or —NH—O—P (═O) (— O—R) ₂ , where R is an alkyl group. A substituted alkyl group, an alkenyl group, a substituted alkenyl group, an alkynyl group, a substituted alkynyl group, an aryl group or a substituted aryl group.
The substituted silyl group is represented by —SiH ₂ —R, —SiH (—R) ₂ or —Si (—R) ₃ , where R is an alkyl group, a substituted alkyl group, an alkenyl group, a substituted alkenyl group, an alkynyl group, a substituted group An alkynyl group, an aryl group or a substituted aryl group;

The alkyl moiety of the alkoxycarbonyloxy group and the substituted alkoxycarbonyloxy group is the same as the alkyl group. The example of the substituent of a substituted alkoxycarbonyloxy group is synonymous with the example of the substituent of a substituted alkyl group, and its preferable range is also synonymous.
The aryl moiety of the aryloxycarbonyloxy group and the substituted aryloxycarbonyloxy group has the same meaning as the aryl group, and the preferred range is also the same. Examples of the substituent of the substituted aryloxycarbonyloxy group are the same as the examples of the substituent of the discotic core, and the preferred range is also the same.

  In the general formula (I), n1 is an integer of 3 to 20, preferably an integer of 3 to 15, more preferably an integer of 3 to 12, and an integer of 3 to 10. More preferably, it is further preferably an integer of 4 to 8, and most preferably 6.

In the general formula (I), R ¹ , R ² , R ³ , R ⁴ and R ⁵ represent a hydrogen atom or a substituent, and examples thereof are the same as the examples of the substituent of the discotic core. Further, any two of R ¹ , R ² , R ³ , R ⁴ and R ⁵ may be bonded to form a ring, and examples thereof include an aliphatic or aromatic ring. Preferably, R ¹ , R ² , R ³ and R ⁵ are each independently a hydrogen atom, a substituted or unsubstituted alkyl group, a cyano group, a substituted or unsubstituted alkoxycarbonyl group or a halogen atom.

R ² and R ³ , R ⁴ and R ⁵ have a cis-trans positional relationship with respect to the carbonyloxy group. Cis is a state where a substituent exists in the same direction as the carbonyloxy group with respect to the cyclopropane ring surface, and trans is a state where a substituent exists in the opposite direction to the carbonyloxy group with respect to the cyclopropane ring surface. is there. This positional relationship is not particularly limited unless otherwise specified.

In general formula (I), depending on the combination of substituents R ¹ , R ² , R ³ , R ⁴ and R ⁵ , enantiomers and diastereomeric stereoisomers exist, but these are particularly limited unless otherwise specified. do not do.

  The discotic compound represented by the general formula (I) is preferably represented by the following general formula (II).

一般式（ＩＩ）において、Ｄは円盤状コアである。ｎ１は３〜２０の整数である。Ｒ¹、Ｒ²、Ｒ³及びＲ⁵は水素原子又は置換基を表し、互いに結合して環を形成していてもよい。ｍは１〜５の整数を表す。Ｒ⁶は置換基を表し、複数のＲ⁶が存在する時、それぞれ同じでも異なっていてもよく、互いに結合して環を形成していてもよい。 Formula (II)

In general formula (II), D is a disk-shaped core. n1 is an integer of 3-20. R ¹ , R ² , R ³ and R ⁵ represent a hydrogen atom or a substituent, and may be bonded to each other to form a ring. m represents an integer of 1 to 5. R ⁶ represents a substituent, and when a plurality of R ⁶ are present, they may be the same or different from each other, and may be bonded to each other to form a ring.

The ^{D, n1, R 1, R} 2, R 3 and R ^5, D defined in the general formula ^{(I), n1, R 1} , is the same as R ^2, R ³ and R ^5, the same preferable ranges It is.

In the general formula (II), R ⁶ represents a substituent, and examples thereof are the same as the examples of the substituent of the discotic core. Preferred examples of R ⁶ include halogen atom, substituted or unsubstituted alkyl group, substituted or unsubstituted alkoxy group, substituted or unsubstituted alkoxycarbonyl group, substituted or unsubstituted aryl group, substituted or unsubstituted aryloxy A group, a substituted or unsubstituted alkoxycarbonyloxy group, a substituted or unsubstituted aryloxycarbonyloxy group, or a substituted or unsubstituted acyloxy group. More preferably, at least one R ⁶ is a substituted alkyl group, a substituted alkoxy group, a substituted alkoxycarbonyl group, a substituted aryl group, a substituted aryloxy group, a substituted alkoxycarbonyloxy group, a substituted aryloxycarbonyloxy group or a substituted acyloxy group. Have a polymerizable group at the terminal of the substituent.

In general formula (II), the substitution position of R ⁶ is not particularly limited unless otherwise specified. Preferably at least one R ⁶ is in the para position.
In the general formula (II), R ⁵ has a cis-trans positional relationship with respect to the carbonyloxy group. This positional relationship is not particularly limited unless otherwise specified. Preferably it is cis.

The discotic compound of the present invention, for example, the discotic compound represented by the general formula (I) may have a polymerizable group. The discotic compound having a polymerizable group (polymerizable discotic compound) can fix the state in which the disc surface of the discotic compound is oriented by a polymerization reaction.
When the compound represented by the general formula (I) has a polymerizable group, R ⁴ is a substituted alkyl group, a substituted alkoxy group, a substituted aryl group or a substituted aryloxy group, and a polymerizable group at the end of each substituent group It is preferable to have.
The polymerizable discotic compound is further preferably represented by the following general formula (III).

General formula (III)

In general formula (III), D is a disk-shaped core. n1 represents the integer of 3-20. R ¹ , R ² , R ³ and R ⁵ each represents a hydrogen atom or a substituent, and may be bonded to each other to form a ring.
D, n1, R ^1, R ^2, R ³ and R ⁵ has the general formula (I) as defined in D, n1, a similar to R ^1, R ^2, R ³ and R ^5, the preferred range is also interchangeably is there.

In general formula (III), L is a divalent linking group selected from an oxygen atom, a sulfur atom, a carbonyl group, a substituted or unsubstituted alkylene group, a substituted or unsubstituted arylene group, and combinations thereof.
The alkylene group may have a cyclic structure or a branched structure. The alkylene group preferably has 1 to 30 carbon atoms.
The alkylene part of the substituted alkylene group is the same as the alkylene group. Examples of substituents for substituted alkylene groups include the substitution of the discotic core described in general formula (I) except that alkyl groups, substituted alkyl groups, alkenyl groups, substituted alkenyl groups, alkynyl groups and substituted alkynyl groups are excluded. The same as the group example.
The number of carbon atoms in the arylene group is preferably 1-30. The arylene group is preferably phenylene or naphthylene, more preferably phenylene, and most preferably p-phenylene.
The arylene part of the substituted arylene group is the same as the arylene group. Examples of the substituent of the substituted arylene group are the same as the examples of the substituent of the discotic core described in the general formula (I).
In the general formula (III), Q is a polymerizable group. The polymerizable group is more preferably an epoxy group or an ethylenically unsaturated group, and most preferably an ethylenically unsaturated group (eg, vinyl, 1-propenyl, isopropenyl).

  As the discotic compound of the present invention, a particularly preferable discotic compound is a triphenylene compound represented by the following general formula (IV).

Formula (IV)

In the general formula (IV), D ¹ represents triphenylene, n1 represents an integer of 3 to 6, and R ¹ , R ² , R ³ , R ^4, and R ⁵ each have 1 hydrogen atom and 1 carbon atom. -20 substituted or unsubstituted alkyl groups, substituted or unsubstituted alkenyl groups having 3 to 20 carbon atoms, substituted or unsubstituted alkoxy groups having 1 to 20 carbon atoms, 3 to 20 carbon atoms Substituted or unsubstituted alkenyloxy groups, substituted or unsubstituted aryl groups having 6 to 20 carbon atoms, substituted or unsubstituted aryloxy groups having 6 to 20 carbon atoms, and 1 to 20 carbon atoms A substituted or unsubstituted alkoxycarbonyl group. The definition and examples of each group are the same as those in formula (I), and the preferred ranges are also synonymous.

In the general formula (IV), R ¹ , R ² , R ³ and R ⁵ are each a hydrogen atom, a methyl group, an ethyl group, a methyloxy group, an ethyloxy group, a cyano group, a halogen atom or a substituted or unsubstituted alkoxy. A carbonyl group is preferred.
In the general formula (IV), R ⁴ is preferably a substituted or unsubstituted aryl group having 6 to 20 carbon atoms. In the general formula (IV), R ⁴ is preferably trans to the carbonyloxy group.

The triphenylene compound represented by the general formula (IV) can have a polymerizable group. The triphenylene compound having a polymerizable group (polymerizable triphenylene compound) can fix the state in which the disc surface made of triphenylene is oriented by a polymerization reaction.
When the triphenylene compound represented by the general formula (IV) has a polymerizable group, R ⁴ is a substituted alkyl group having 2 to 20 carbon atoms, a substituted alkoxy group having 2 to 20 carbon atoms, and having a carbon atom number. It is a substituted aryl group having 6 to 20 carbon atoms or a substituted aryloxy group having 6 to 20 carbon atoms, and preferably has a polymerizable group at the terminal of the substituent.
In the general formula (IV), since there are asymmetric carbon atoms, diastereomers and enantiomers exist, but in the present invention, these are not distinguished and are all included. That is, stereoisomers are not distinguished by the structure description method.

  Below, the example of the discotic compound represented by general formula (I) is shown. In addition, when each exemplary compound is represented, the numerical value (x) described beside the exemplary compound is referred to as exemplary compound (x).

General formula (DI)

In the general formula (DI), Y ¹¹ , Y ¹² and Y ¹³ each independently represent a methine or nitrogen atom.

When Y ¹¹ , Y ¹² and Y ¹³ are methine, the hydrogen atom of methine may be replaced with a substituent. Examples of the substituent that methine may have include an alkyl group, an alkoxy group, an aryloxy group, an acyl group, an alkoxycarbonyl group, an acyloxy group, an acylamino group, an alkoxycarbonylamino group, an alkylthio group, an arylthio group, a halogen atom, and A cyano group can be mentioned as a preferred example. Among these substituents, an alkyl group, an alkoxy group, an alkoxycarbonyl group, an acyloxy group, a halogen atom and a cyano group are more preferable, an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, and a carbon number A 2-12 alkoxycarbonyl group, a C2-C12 acyloxy group, a halogen atom, and a cyano group are more preferable.
Y ¹¹ , Y ¹² and Y ¹³ are more preferably methine, and methine is more preferably unsubstituted.

R ¹¹ , R ¹² and R ¹³ each independently represent the following general formula (DI-A), the following general formula (DI-B) or the following general formula (DI-C). In order to reduce the wavelength dispersion, the general formula (DI-A) or the general formula (DI-C) is preferable, and the general formula (DI-A) is more preferable. R ¹¹ , R ¹² and R ¹³ are preferably R ¹¹ = R ¹² = R ¹³ .

General formula (DI-A)

In the general formula (DI-A), A ¹¹ , A ¹² , A ¹³ , A ¹⁴ , A ¹⁵ and A ¹⁶ each independently represent a methine or nitrogen atom.
At least one of A ¹¹ and A ¹² is preferably a nitrogen atom, and more preferably both are nitrogen atoms.
Of A ¹³ , A ¹⁴ , A ¹⁵ and A ¹⁶ , at least three of them are preferably methine, more preferably all methine. Furthermore, methine is preferably unsubstituted.
Examples of substituents when A ¹¹ , A ¹² , A ¹³ , A ¹⁴ , A ¹⁵ or A ¹⁶ is methine include halogen atoms (fluorine atoms, chlorine atoms, bromine atoms, iodine atoms), cyano groups, nitro groups An alkyl group having 1 to 16 carbon atoms, an alkenyl group having 2 to 16 carbon atoms, an alkynyl group having 2 to 16 carbon atoms, an alkyl group substituted with a halogen having 1 to 16 carbon atoms, and 1 carbon atom -16 alkoxy group, C2-C16 acyl group, C1-C16 alkylthio group, C2-C16 acyloxy group, C2-C16 alkoxycarbonyl group, carbamoyl group, An alkyl-substituted carbamoyl group having 2 to 16 carbon atoms and an acylamino group having 2 to 16 carbon atoms are included. Among these, a halogen atom, a cyano group, an alkyl group having 1 to 6 carbon atoms, and an alkyl group substituted with a halogen having 1 to 6 carbon atoms are preferable, a halogen atom, an alkyl group having 1 to 4 carbon atoms, An alkyl group substituted with a halogen having 1 to 4 carbon atoms is more preferable, and a halogen atom, an alkyl group having 1 to 3 carbon atoms, and a trifluoromethyl group are more preferable.
X ¹ represents an oxygen atom, a sulfur atom, methylene or imino, preferably an oxygen atom.

General formula (DI-B)

In the general formula (DI-B), A ²¹ , A ²² , A ²³ , A ²⁴ , A ²⁵ and A ²⁶ each independently represents a methine or nitrogen atom.
At least one of A ²¹ and A ²² is preferably a nitrogen atom, and more preferably both are nitrogen atoms.
Of A ²³ , A ²⁴ , A ²⁵ and A ²⁶ , at least three of them are preferably methine, more preferably all methine.
Examples of substituents when A ²¹ , A ²² , A ²³ , A ²⁴ , A ²⁵ or A ²⁶ is methine include halogen atoms (fluorine atoms, chlorine atoms, bromine atoms, iodine atoms), cyano groups, nitro groups An alkyl group having 1 to 16 carbon atoms, an alkenyl group having 2 to 16 carbon atoms, an alkynyl group having 2 to 16 carbon atoms, an alkyl group substituted with a halogen having 1 to 16 carbon atoms, and 1 carbon atom -16 alkoxy group, C2-C16 acyl group, C1-C16 alkylthio group, C2-C16 acyloxy group, C2-C16 alkoxycarbonyl group, carbamoyl group, An alkyl-substituted carbamoyl group having 2 to 16 carbon atoms and an acylamino group having 2 to 16 carbon atoms are included. Among these, a halogen atom, a cyano group, an alkyl group having 1 to 6 carbon atoms, and an alkyl group substituted with a halogen having 1 to 6 carbon atoms are preferable, a halogen atom, an alkyl group having 1 to 4 carbon atoms, An alkyl group substituted with a halogen having 1 to 4 carbon atoms is more preferable, and a halogen atom, an alkyl group having 1 to 3 carbon atoms, and a trifluoromethyl group are more preferable.
X ² represents an oxygen atom, a sulfur atom, methylene or imino, preferably an oxygen atom.

General formula (DI-C)

In the general formula (DI-C), A ³¹ , A ³² , A ³³ , A ³⁴ , A ³⁵ and A ³⁶ each independently represent a methine or nitrogen atom.
At least one of A ³¹ and A ³² is preferably a nitrogen atom, and more preferably both are nitrogen atoms.
At least three of A ³³ , A ³⁴ , A ³⁵ and A ³⁶ are preferably methine, more preferably methine.
When A ³¹ , A ³² , A ³³ , A ³⁴ , A ³⁵ or A ³⁶ is methine, the methine may have a substituent. Examples of the substituent include a halogen atom (fluorine atom, chlorine atom, bromine atom, iodine atom), cyano group, nitro group, alkyl group having 1 to 16 carbon atoms, alkenyl group having 2 to 16 carbon atoms, carbon An alkynyl group having 2 to 16 atoms, an alkyl group substituted with a halogen having 1 to 16 carbon atoms, an alkoxy group having 1 to 16 carbon atoms, an acyl group having 2 to 16 carbon atoms, and 1 to 16 carbon atoms An alkylthio group having 2 to 16 carbon atoms, an alkoxycarbonyl group having 2 to 16 carbon atoms, a carbamoyl group, an alkyl-substituted carbamoyl group having 2 to 16 carbon atoms, and an acylamino group having 2 to 16 carbon atoms. included. Among these, a halogen atom, a cyano group, an alkyl group having 1 to 6 carbon atoms, and an alkyl group substituted with a halogen having 1 to 6 carbon atoms are preferable, a halogen atom, an alkyl group having 1 to 4 carbon atoms, An alkyl group substituted with a halogen having 1 to 4 carbon atoms is more preferable, and a halogen atom, an alkyl group having 1 to 3 carbon atoms, and a trifluoromethyl group are more preferable.
X ³ represents an oxygen atom, a sulfur atom, methylene or imino, preferably an oxygen atom.

L ^{11 in} the general formula (DI-A), L ^{21 in} the general formula (DI-B), and L ³¹ in the general formula (DI-C) are each independently —O—, —O—CO—. , —CO—O—, —O—CO—O—, —S—, —NH—, —SO ₂ —, —CH ₂ —, —CH═CH— or —C≡C—. Preferably, -O -, - O-CO -, - CO-O -, - O-CO-O -, - CH 2 -, - CH = CH -, - it is C≡C-, more preferably, —O—, —O—CO—, —CO—O—, —O—CO—O—, —CH ₂ —. When the above group is a group containing a hydrogen atom, the hydrogen atom may be replaced with a substituent. Examples of such a substituent include a halogen atom, a cyano group, a nitro group, an alkyl group having 1 to 6 carbon atoms, an alkyl group substituted with a halogen having 1 to 6 carbon atoms, and an alkoxy group having 1 to 6 carbon atoms. , An acyl group having 2 to 6 carbon atoms, an alkylthio group having 1 to 6 carbon atoms, an acyloxy group having 2 to 6 carbon atoms, an alkoxycarbonyl group having 2 to 6 carbon atoms, a carbamoyl group, and 2 to 2 carbon atoms Preferred examples include a carbamoyl group substituted with 6 alkyls and an acylamino group having 2 to 6 carbon atoms, and a halogen atom and an alkyl group having 1 to 6 carbon atoms are more preferred.

L ^{12 in} the general formula (DI-A), L ^{22 in} the general formula (DI-B), and L ³² in the general formula (DI-C) are each independently -O-, -S-,- It represents a divalent linking group selected from the group consisting of C (═O) —, —SO ₂ —, —NH—, —CH ₂ —, —CH═CH—, —C≡C—, and combinations thereof. Here, the hydrogen atoms of —NH—, —CH ₂ —, and —CH═CH— may be substituted with a substituent. Examples of such a substituent include a halogen atom, a cyano group, a nitro group, an alkyl group having 1 to 6 carbon atoms, an alkyl group substituted with a halogen having 1 to 6 carbon atoms, and an alkoxy group having 1 to 6 carbon atoms. , An acyl group having 2 to 6 carbon atoms, an alkylthio group having 1 to 6 carbon atoms, an acyloxy group having 2 to 6 carbon atoms, an alkoxycarbonyl group having 2 to 6 carbon atoms, a carbamoyl group, and 2 to 2 carbon atoms Preferred examples include a carbamoyl group substituted with 6 alkyls and an acylamino group having 2 to 6 carbon atoms, and a halogen atom and an alkyl group having 1 to 6 carbon atoms are more preferred.

L ¹² , L ²² and L ³² are each independently selected from the group consisting of —O—, —C (═O) —, —CH ₂ —, —CH═CH—, —C≡C—, and combinations thereof. It is preferable to be selected.

L ¹² , L ²² and L ³² each independently preferably have 1 to 20 carbon atoms, and more preferably 2 to 14 carbon atoms. The number of carbon atoms is preferably 2 to 14, more preferably 1 to 16 —CH ₂ —, and still more preferably ₂ to 12 —CH ₂ —.

L ¹² , L ²² and L ³² are each independently —O—, —S—, —C (═O) —, —SO ₂ —, —NH—, —CH ₂ —, —CH═CH— and It is preferably a divalent linking group selected from the group consisting of —C≡C— and combinations thereof, and having 1 to 20 carbon atoms. Incidentally carbon number is preferably 2 to 14 carbon atoms, -CH ₂ - and more preferably has 1 to 16, -CH ₂ - further preferred that the having 2 to 12.

Q ^{11 in} the general formula (DI-A), Q ^{21 in} the general formula (DI-B), and Q ³¹ in the general formula (DI-C) each independently represent a polymerizable group or a hydrogen atom. When the compound of the present invention is used for an optical film or the like that preferably has a phase difference that does not change due to heat, such as an optical compensation film, Q ¹¹ , Q ²¹ , and Q ³¹ are preferably a polymerizable group. . The polymerization reaction is preferably addition polymerization (including ring-opening polymerization) or condensation polymerization. That is, the polymerizable group is preferably a functional group capable of addition polymerization reaction or condensation polymerization reaction. Examples of polymerizable groups are shown below.

  Furthermore, the polymerizable group is particularly preferably a functional group capable of addition polymerization reaction. Such a polymerizable group is preferably a polymerizable ethylenically unsaturated group or a ring-opening polymerizable group.

  Examples of the polymerizable ethylenically unsaturated group include the following formulas (M-1) to (M-6).

In formulas (M-3) and (M-4), R represents a hydrogen atom or an alkyl group, preferably a hydrogen atom or a methyl group.
Among the formulas (M-1) to (M-6), (M-1) or (M-2) is preferable, and (M-1) is more preferable.

  The ring-opening polymerizable group is preferably a cyclic ether group, more preferably an epoxy group or oxetanyl group, and most preferably an epoxy group.

  Although the specific example of a compound represented by general formula (DI) below is shown, this invention is not limited to these.

[Bar-shaped liquid crystalline compound]
In the present invention, it is preferable to use a rod-like liquid crystalline compound for forming the optically anisotropic layer of the optical compensation film. Examples of rod-like liquid crystalline compounds include azomethines, azoxys, cyanobiphenyls, cyanophenyl esters, benzoic acid esters, cyclohexanecarboxylic acid phenyl esters, cyanophenylcyclohexanes, cyano-substituted phenylpyrimidines, alkoxy-substituted phenylpyrimidines. , Phenyldioxanes, tolanes and alkenylcyclohexylbenzonitriles are preferably used. Not only the above low-molecular liquid crystalline compounds but also high-molecular liquid crystalline compounds can be used. It is more preferable to fix the alignment of the rod-like liquid crystal compound by polymerization. As the liquid crystalline compound, those having a partial structure capable of causing polymerization or crosslinking reaction by actinic rays, electron beams, heat, or the like are suitably used. The number of the partial structures is preferably 1 to 6, more preferably 1 to 3. As the polymerizable rod-like liquid crystalline compound, Makromol. Chem. 190, 2255 (1989), Advanced Materials 5, 107 (1993), US Pat. No. 4,683,327, US Pat. No. 95/24455, No. 97/00600, No. 98/23580, No. 98/52905, JP-A-1-272551, No. 6-16616, No. 7-110469. 11-80081 and JP-A 2001-328773, etc. can be used.

[Vertical alignment accelerator]
In order to uniformly align the molecules of the liquid crystalline compound when forming the optically anisotropic layer, an alignment controller capable of controlling the alignment of the liquid crystalline compound vertically on the alignment film interface side and the air interface side is provided. It is preferable to use it. For this purpose, an optically anisotropic composition using a composition containing, together with a liquid crystalline compound, an alignment film having a function of vertically aligning the liquid crystalline compound by an excluded volume effect, electrostatic effect or surface energy effect. It is preferable to form a conductive layer. As for the orientation control on the air interface side, a compound that is unevenly distributed at the air interface at the time of orientation of the liquid crystalline compound, and that acts to vertically align the liquid crystalline compound by its excluded volume effect, electrostatic effect, or surface energy effect, It is preferable to form an optically anisotropic layer using a composition contained together with a liquid crystal compound. As such a compound (alignment film interface side vertical alignment agent) that promotes the vertical alignment of the molecules of the liquid crystal compound on the alignment film interface side, a pyridinium derivative is preferably used. As a compound (air interface side vertical alignment agent) that promotes the vertical alignment of the molecules of the liquid crystal compound on the air interface side, a fluoro aliphatic group that promotes the uneven distribution of the compound on the air interface side, One or more hydrophilic groups selected from the group consisting of a carboxyl group (—COOH), a sulfo group (—SO ₃ H), a phosphonoxy group {—OP (═O) (OH) ₂ }, and salts thereof. A compound is preferably used. Further, by blending these compounds, for example, when a liquid crystalline composition is prepared as a coating solution, the coating property of the coating solution is improved, and the occurrence of unevenness and repellency is suppressed. The vertical alignment agent will be described in detail below.

[Alignment film interface side vertical alignment agent]
As the alignment film interface-side vertical alignment agent that can be used in the present invention, a pyridinium derivative (pyridinium salt) represented by the following formula (I) is preferably used. By adding at least one of the pyridinium derivatives to the liquid crystalline composition, the molecules of the discotic liquid crystalline compound can be aligned substantially vertically in the vicinity of the alignment film.

In the formula (I), L ¹ represents a divalent linking group, an alkylene group and —O—, —S—, —CO—, —SO ₂ —, —NR ^a — (where R ^a is the number of carbon atoms. Is a divalent linking group having 1 to 20 carbon atoms, which is a combination of an alkenylene group, an alkynylene group or an arylene group. The alkylene group may be linear or branched.

In the formula (I), R ¹ is a hydrogen atom, an unsubstituted amino group, or a substituted amino group substituted with a substituent having 1 to 20 carbon atoms. When R ¹ is a substituted amino group, it is preferably substituted with an aliphatic group. Examples of the aliphatic group include an alkyl group, a substituted alkyl group, an alkenyl group, a substituted alkenyl group, an alkynyl group, and a substituted alkynyl group. When R ¹ is a disubstituted amino group, two aliphatic groups may be bonded to each other to form a nitrogen-containing heterocyclic ring. The nitrogen-containing heterocycle formed at this time is preferably a 5-membered ring or a 6-membered ring. R ¹ is preferably a hydrogen atom, an unsubstituted amino group or a substituted amino group having 1 to 20 carbon atoms, a hydrogen atom, an unsubstituted amino group or a substituted amino group having 2 to 12 carbon atoms. More preferably, it is more preferably a hydrogen atom, an unsubstituted amino group, or a substituted amino group having 2 to 8 carbon atoms. When R ¹ is an amino group, it is preferably substituted at the 4-position of the pyridinium ring.

  In the formula (I), X is an anion. Examples of anions include halogen anions (for example, fluorine ions, chlorine ions, bromine ions, iodine ions, etc.), sulfonate ions (for example, methanesulfonate ions, trifluoromethanesulfonate ions, methylsulfate ions, p-toluene). Sulfonate ion, p-chlorobenzenesulfonate ion, 1,3-benzenedisulfonate ion, 1,5-naphthalenedisulfonate ion, 2,6-naphthalenedisulfonate ion, sulfate ion, carbonate ion, nitrate ion, thiocyanate Examples include acid ions, perchlorate ions, tetrafluoroborate ions, picrate ions, acetate ions, formate ions, trifluoroacetate ions, phosphate ions (for example, hexafluorophosphate ions), and hydroxide ions. X is preferably a halogen anion, a sulfonate ion, or a hydroxide ion.

In the formula (I), Y ¹ is a divalent linking group having 1 to 30 carbon atoms having a 5-membered or 6-membered ring as a partial structure. The cyclic partial structure contained in Y ¹ is more preferably a cyclohexyl ring, an aromatic ring or a heterocyclic ring. Examples of the aromatic ring include a benzene ring, an indene ring, a naphthalene ring, a fluorene ring, a phenanthrene ring, an anthracene ring, a biphenyl ring, and a pyrene ring. More preferred are a benzene ring, a biphenyl ring, and a naphthalene ring. The hetero atom constituting the hetero ring is preferably a nitrogen atom, an oxygen atom or a sulfur atom. For example, a furan ring, thiophene ring, pyrrole ring, pyrroline ring, pyrrolidine ring, oxazole ring, isoxazole ring, thiazole ring, isothiazole Ring, imidazole ring, imidazoline ring, imidazolidine ring, pyrazole ring, pyrazoline ring, pyrazolidine ring, triazole ring, furazane ring, tetrazole ring, pyran ring, dioxane ring, dithiane ring, thiine ring, pyridine ring, piperidine ring, oxazine ring Morpholine ring, thiazine ring, pyridazine ring, pyrimidine ring, pyrazine ring, piperazine ring and triazine ring. The heterocycle is preferably a 6-membered ring. The divalent linking group having a 5-membered or 6-membered ring represented by Y as a partial structure may have a substituent.

In the formula (I), Z represents a halogen-substituted phenyl group, a nitro-substituted phenyl group, a cyano-substituted phenyl group, a phenyl group substituted with an alkyl group having 1 to 10 carbon atoms, or an alkoxy having 2 to 10 carbon atoms. A phenyl group substituted with a group, an alkyl group having 1 to 12 carbon atoms, an alkynyl group having 2 to 20 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, an alkoxy having 2 to 13 carbon atoms A carbonyl group, an aryloxycarbonyl group having 7 to 26 carbon atoms, an arylcarbonyloxy group having 7 to 26 carbon atoms, a cyano-substituted phenyl group, a halogen-substituted phenyl group, and an alkyl having 1 to 10 carbon atoms. Phenyl group substituted with a group, phenyl group substituted with an alkoxy group having 2 to 10 carbon atoms, aryloxycarboe having 7 to 26 carbon atoms Group or carbon atoms is preferably an aryl carbonyl group having 7 to 26.
Z may further have a substituent, and examples of the substituent include a halogen atom (a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom), a cyano group, a nitro group, and a carbon atom number of 1 to 16. An alkyl group having 1 to 16 carbon atoms, an alkynyl group having 1 to 16 carbon atoms, a halogen-substituted alkyl group having 1 to 16 carbon atoms, an alkoxy group having 1 to 16 carbon atoms, An acyl group having 2 to 16 carbon atoms, an alkylthio group having 1 to 16 carbon atoms, an acyloxy group having 2 to 16 carbon atoms, an alkoxycarbonyl group having 2 to 16 carbon atoms, a carbamoyl group, a carbon atom An alkyl-substituted carbamoyl group having 2 to 16 carbon atoms and an acylamino group having 2 to 16 carbon atoms are included.

  The pyridinium compound used in the present invention is preferably a pyridinium compound represented by the following formula (Ia).

In the formula (Ia), L ³ represents a single bond, —O—, —O—CO—, —CO—O—, —C≡C—, —CH═CH—, —CH═N—, —N═. CH—, —N═N—, —O—AL—O—, —O—AL—O—CO—, —O—AL—CO—O—, —CO—O—AL—O—, —CO—. O-AL-O-CO-, -CO-O-AL-CO-O-, -O-CO-AL-O-, -O-CO-AL-O-CO- or -O-CO-AL- CO-O-. AL is an alkylene group having 1 to 10 carbon atoms. L ³ represents a single bond, —O—, —O—AL—O—, —O—AL—O—CO—, —O—AL—CO—O—, —CO—O—AL—O—, — CO-O-AL-O-CO-, -CO-O-AL-CO-O-, -O-CO-AL-O-, -O-CO-AL-O-CO- or -O-CO- AL-CO-O- is preferable, and a single bond or -O- is more preferable.

In the formula (Ia), L ⁴ represents a single bond, —O—, —O—CO—, —CO—O—, —C≡C—, —CH═CH—, —CH═N—, —N═. CH- or -N = N-.

In the formula (Ia), R ³ is a hydrogen atom, an unsubstituted amino group, or an alkyl-substituted amino group having 2 to 20 carbon atoms. When R ³ is a dialkyl-substituted amino group, two alkyl groups may be bonded to each other to form a nitrogen-containing heterocyclic ring. The nitrogen-containing heterocycle formed at this time is preferably a 5-membered ring or a 6-membered ring. R ³ is more preferably a hydrogen atom, an unsubstituted amino group, or a dialkyl-substituted amino group having 2 to 12 carbon atoms, and most preferably a hydrogen atom, an unsubstituted amino group, or a dialkyl-substituted amino group having 2 to 8 carbon atoms. . When R ³ is an unsubstituted amino group, the 4-position of the pyridinium ring is preferably amino-substituted.

In the formula (Ia), Y ² and Y ³ are each independently a divalent group consisting of a 6-membered ring optionally having a substituent. Examples of the 6-membered ring include an aliphatic ring, an aromatic ring (benzene ring), and a heterocyclic ring. Examples of the 6-membered aliphatic ring include a cyclohexane ring, a cyclohexene ring, and a cyclohexadiene ring. Examples of 6-membered heterocycles include pyran ring, dioxane ring, dithiane ring, thiine ring, pyridine ring, piperidine ring, oxazine ring, morpholine ring, thiazine ring, pyridazine ring, pyrimidine ring, pyrazine ring, piperazine ring and triazine ring. Can be mentioned. Another 6-membered ring or 5-membered ring may be condensed to the 6-membered ring.
Examples of the substituent include a halogen atom, a cyano group, an alkyl group having 1 to 12 carbon atoms, and an alkoxy group having 1 to 12 carbon atoms. The alkyl group and the alkoxy group may be substituted with an acyl group having 2 to 12 carbon atoms or an acyloxy group having 2 to 12 carbon atoms. The definition of an acyl group and an acyloxy group will be described later.

In the formula (Ia), X ¹ is an anion. X ¹ is preferably a monovalent anion. Examples of anions include halogen anions (eg, fluorine ions, chlorine ions, bromine ions, iodine ions) and sulfonate ions (eg, methanesulfonate ions, p-toluenesulfonate ions, benzenesulfonate ions). It is.

In Formula (Ia), Z ¹ is a hydrogen atom, a cyano group, an alkyl group having 1 to 12 carbon atoms, or an alkoxy group having 1 to 12 carbon atoms, and the alkyl group and the alkoxy group are each a carbon atom. It may be substituted with an acyl group having 2 to 12 atoms or an acyloxy group having 2 to 12 carbon atoms.

In the formula (Ia), m is 1 or 2, and when m is 2, two L ⁴ and two Y ³ may be different.
When m is 2, Z ¹ is preferably a cyano group, an alkyl group having 1 to 10 carbon atoms, or an alkoxy group having 1 to 10 carbon atoms.
When m is 1, Z ¹ is an alkyl group having 7 to 12 carbon atoms, an alkoxy group having 7 to 12 carbon atoms, an acyl-substituted alkyl group having 7 to 12 carbon atoms, and 7 carbon atoms. It is preferably an acyl-substituted alkoxy group having -12, an acyloxy-substituted alkyl group having 7-12 carbon atoms, or an acyloxy-substituted alkoxy group having 7-12 carbon atoms.

  The acyl group is represented by —CO—R, the acyloxy group is represented by —O—CO—R, and R is an aliphatic group (alkyl group, substituted alkyl group, alkenyl group, substituted alkenyl group, alkynyl group, substituted alkynyl group) or aromatic. Group (aryl group, substituted aryl group). R is preferably an aliphatic group, and more preferably an alkyl group or an alkenyl group.

In formula (Ia), p is an integer of 1-10. C _p H _2p means a chain alkylene group which may have a branched structure. C _p H _2p is preferably a linear alkylene group. Further, p is more preferably 1 or 2.

  Specific examples of the compound represented by formula (I) and / or (Ia) are shown below. Here, Me represents a methyl group.

  A pyridinium derivative is generally obtained by alkylating a pyridine ring (Menstokin reaction).

  The preferred range of the content of the pyridinium derivative in the composition for forming an optically anisotropic layer varies depending on the application, but the composition (liquid crystalline composition excluding the solvent when prepared as a coating solution) In the inside, it is preferable that it is 0.005-8 mass%, and it is more preferable that it is 0.01-5 mass%.

[Air interface side vertical alignment agent]
As the air interface side vertical alignment agent usable in the present invention, a fluoro aliphatic group, a carboxyl group (—COOH), a sulfo group (—SO ₃ H), a phosphonoxy group {—OP (═O) (OH) ₂ } And one or more hydrophilic groups selected from the group consisting of the salts thereof, a fluoroaliphatic group-containing polymer (hereinafter referred to as “fluorine polymer”), or a compound represented by the general formula (III) Fluorine compounds are preferably used.

First, the fluorine polymer will be described.
Fluoropolymers that can be used in the present invention include fluoroaliphatic groups, carboxyl groups (—COOH), sulfo groups (—SO ₃ H), phosphonoxy groups {—OP (═O) (OH) ₂ }, and their It contains one or more hydrophilic groups selected from the group consisting of salts. The types of polymers are described in “Revised Chemistry of Polymer Synthesis” (written by Takayuki Otsu, published by Kagaku Dojin Co., 1968) on pages 1 to 4, for example, polyolefins, polyesters, polyamides, polyimides. , Polyurethanes, polycarbonates, polysulfones, polycarbonates, polyethers, polyacetals, polyketones, polyphenylene oxides, polyphenylene sulfides, polyarylates, polytetrafluoroethylene (PTFE), polyvinylidene fluorides And cellulose derivatives. The fluoropolymer is preferably a polyolefin.

  The fluorine-based polymer is a polymer having a fluoroaliphatic group in the side chain. The fluoroaliphatic group preferably has 1 to 12 carbon atoms, and more preferably 6 to 10 carbon atoms. The aliphatic group may be linear or cyclic, and when it is linear, it may be linear or branched. Of these, a linear fluoroaliphatic group having 6 to 10 carbon atoms is preferable. The degree of substitution with fluorine atoms is not particularly limited, but 50% or more of hydrogen atoms in the aliphatic group are preferably substituted with fluorine atoms, and more preferably 60% or more are substituted. The fluoroaliphatic group is contained in a side chain bonded to the polymer main chain via an ester bond, an amide bond, an imide bond, a urethane bond, a urea bond, an ether bond, a thioether bond, an aromatic ring, or the like. One of the fluoroaliphatic groups is derived from a fluoroaliphatic compound produced by a telomerization method (also referred to as a telomer method) or an oligomerization method (also referred to as an oligomer method). Regarding the production method of these fluoroaliphatic compounds, for example, “Synthesis and Function of Fluorine Compounds” (Supervision: Nobuo Ishikawa, Issue: CMC Co., 1987), “Chemistry of Organic Fluorines Compounds”. II "(Monograph 187, Ed by Milos Hudricky and Attila E. Pavlath, American Chemical Society 1995). The telomerization method is a method of synthesizing a telomer by radical polymerization of a fluorine-containing vinyl compound such as tetrafluoroethylene using an alkyl halide having a large chain transfer constant such as iodide as a telogen (example in Scheme-1). showed that).

  The obtained terminal iodinated telomer is usually subjected to appropriate terminal chemical modification such as [Scheme 2], and led to a fluoroaliphatic compound. These compounds are further converted into a desired monomer structure as needed, and used for the production of a fluoropolymer.

  Specific examples of monomers that can be used in the production of the fluorine-based polymer that can be used in the present invention are listed below, but the present invention is not limited to the following specific examples.

  One embodiment of a fluorine-based polymer that can be used in the present invention is represented by a repeating unit derived from a fluoroaliphatic group-containing monomer (hereinafter sometimes referred to as “fluorine-based monomer”) and the following formula (II): It is a copolymer having a repeating unit containing a hydrophilic group.

In the above formula (II), R ¹ , R ² and R ³³ each independently represents a hydrogen atom or a substituent. Q represents a carboxyl group (—COOH) or a salt thereof, a sulfo group (—SO ₃ H) or a salt thereof, or a phosphonoxy group {—OP (═O) (OH) ₂ } or a salt thereof. L represents an arbitrary group selected from the following linking group group, or a divalent linking group formed by combining two or more thereof.
(Linked group group)
Single bond, —O—, —CO—, —NR ^b — (R ^b represents a hydrogen atom, an alkyl group, an aryl group, or an aralkyl group), —S—, —SO ₂ —, —P (═O) (OR ^f ) — (R ^f represents an alkyl group, an aryl group, or an aralkyl group), an alkylene group, and an arylene group.

In formula (II), R ¹ , R ² and R ³³ each independently represent a hydrogen atom or a substituent selected from the substituent group exemplified below.
(Substituent group)
An alkyl group (preferably an alkyl group having 1 to 20 carbon atoms, more preferably 1 to 12 carbon atoms, still more preferably 1 to 8 carbon atoms, such as a methyl group, an ethyl group, an isopropyl group, a tert-butyl group, n-octyl group, n-decyl group, n-hexadecyl group, cyclopropyl group, cyclopentyl group, cyclohexyl group and the like, alkenyl group (preferably having 2 to 20 carbon atoms, more preferably 2 to 12 carbon atoms, More preferably, it is a C2-C8 alkenyl group, for example, a vinyl group, an aryl group, 2-butenyl group, 3-pentenyl group etc., an alkynyl group (preferably C2-C20, more preferably). Is an alkynyl group having 2 to 12 carbon atoms, more preferably 2 to 8 carbon atoms, such as a propargyl group or a 3-pentynyl group. An aryl group (preferably an aryl group having 6 to 30 carbon atoms, more preferably 6 to 20 carbon atoms, still more preferably 6 to 12 carbon atoms, such as a phenyl group, a p-methylphenyl group, A naphthyl group), an aralkyl group (preferably an aralkyl group having 7 to 30 carbon atoms, more preferably 7 to 20 carbon atoms, still more preferably 7 to 12 carbon atoms, such as a benzyl group, a phenethyl group, A 3-phenylpropyl group), a substituted or unsubstituted amino group (preferably an amino group having 0 to 20 carbon atoms, more preferably 0 to 10 carbon atoms, still more preferably 0 to 6 carbon atoms, For example, an unsubstituted amino group, a methylamino group, a dimethylamino group, a diethylamino group, an anilino group, etc.)

An alkoxy group (preferably an alkoxy group having 1 to 20 carbon atoms, more preferably 1 to 16 carbon atoms, still more preferably 1 to 10 carbon atoms, and examples thereof include a methoxy group, an ethoxy group, and a butoxy group); An alkoxycarbonyl group (preferably an alkoxycarbonyl group having 2 to 20 carbon atoms, more preferably 2 to 16 carbon atoms, still more preferably 2 to 10 carbon atoms such as a methoxycarbonyl group and an ethoxycarbonyl group), acyloxy A group (preferably an acyloxy group having 2 to 20 carbon atoms, more preferably 2 to 16 carbon atoms, still more preferably 2 to 10 carbon atoms such as an acetoxy group and a benzoyloxy group), an acylamino group (preferably 2-20 carbon atoms, more preferably 2-16 carbon atoms, still more preferably 2 carbon atoms 10 acylamino groups such as acetylamino group and benzoylamino group), alkoxycarbonylamino groups (preferably having 2 to 20 carbon atoms, more preferably 2 to 16 carbon atoms, still more preferably 2 to 2 carbon atoms). 12 alkoxycarbonylamino groups, for example, a methoxycarbonylamino group and the like, and aryloxycarbonylamino groups (preferably having 7 to 20 carbon atoms, more preferably 7 to 16 carbon atoms, still more preferably 7 carbon atoms). To 12 aryloxycarbonylamino groups, such as phenyloxycarbonylamino group, and sulfonylamino groups (preferably having 1 to 20 carbon atoms, more preferably 1 to 16 carbon atoms, and still more preferably carbon atoms). 1 to 12 sulfonylamino groups, for example, Sulfonylamino groups, benzenesulfonylamino groups, etc.), sulfamoyl groups (preferably 0-20 carbon atoms, more preferably 0-16 carbon atoms, still more preferably 0-12 carbon atoms sulfamoyl groups, , Sulfamoyl group, methylsulfamoyl group, dimethylsulfamoyl group, phenylsulfamoyl group and the like), carbamoyl group (preferably having 1 to 20 carbon atoms, more preferably 1 to 16 carbon atoms, still more preferably A carbamoyl group having 1 to 12 carbon atoms, and examples thereof include an unsubstituted carbamoyl group, a methylcarbamoyl group, a diethylcarbamoyl group, and a phenylcarbamoyl group).

An alkylthio group (preferably an alkylthio group having 1 to 20 carbon atoms, more preferably 1 to 16 carbon atoms, still more preferably 1 to 12 carbon atoms, such as a methylthio group and an ethylthio group), an arylthio group ( Preferably it is a C6-C20, More preferably, it is a C6-C16, More preferably, it is a C6-C12 arylthio group, For example, a phenylthio group etc. are mentioned, A sulfonyl group (preferably C1-C1). 20, more preferably a sulfonyl group having 1 to 16 carbon atoms, still more preferably 1 to 12 carbon atoms, and examples thereof include a mesyl group and a tosyl group), a sulfinyl group (preferably having a carbon number of 1 to 20, and more. A sulfinyl group having 1 to 16 carbon atoms, more preferably 1 to 12 carbon atoms, is preferable. A ureido group (preferably a benzenesulfinyl group), a ureido group (preferably a ureido group having 1 to 20 carbon atoms, more preferably 1 to 16 carbon atoms, and still more preferably 1 to 12 carbon atoms. Ureido group, methylureido group, phenylureido group, etc.), phosphoric acid amide group (preferably having 1 to 20 carbon atoms, more preferably having 1 to 16 carbon atoms, and further preferably having 1 to 12 carbon atoms) Group such as diethyl phosphoramide group and phenylphosphoric acid amide group), hydroxy group, mercapto group, halogen atom (eg fluorine atom, chlorine atom, bromine atom, iodine atom), cyano group, sulfo group Group, carboxyl group, nitro group, hydroxamic acid group, sulfino group, hydrazino group, imino group, heterocyclic group (preferably A heterocyclic group having 1 to 30 carbon atoms, more preferably 1 to 12 carbon atoms, such as a heterocyclic group having a hetero atom such as a nitrogen atom, an oxygen atom, or a sulfur atom, such as an imidazolyl group, a pyridyl group, or a quinolyl group; Group, furyl group, piperidyl group, morpholino group, benzoxazolyl group, benzimidazolyl group, benzthiazolyl group and the like), silyl group (preferably having 3 to 40 carbon atoms, more preferably 3 to 30 carbon atoms, More preferably, it is a silyl group having 3 to 24 carbon atoms, and examples thereof include a trimethylsilyl group and a triphenylsilyl group. 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.

R ¹ , R ² and R ³³ are each independently a hydrogen atom, an alkyl group, a halogen atom (for example, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, etc.), or a group represented by -LQ described later. It is preferably a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, a chlorine atom, or a group represented by -LQ, more preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. Particularly preferred are a hydrogen atom and an alkyl group having 1 to 2 carbon atoms. Specific examples of the alkyl group include methyl group, ethyl group, n-propyl group, n-butyl group, sec-butyl group and the like. The alkyl group may have a suitable substituent. Examples of the substituent include a halogen atom, aryl group, heterocyclic group, alkoxyl group, aryloxy group, alkylthio group, arylthio group, acyl group, hydroxyl group, acyloxy group, amino group, alkoxycarbonyl group, acylamino group, oxycarbonyl Group, carbamoyl group, sulfonyl group, sulfamoyl group, sulfonamido group, sulfolyl group, carboxyl group and the like. The carbon number of the alkyl group does not include the carbon atom of the substituent. The same applies to the carbon number of other groups.

L represents a divalent linking group selected from the above linking group group, or a divalent linking group formed by combining two or more thereof. In the linking group group, R ^{b in} —NR ^b — represents a hydrogen atom, an alkyl group, an aryl group or an aralkyl group, and preferably a hydrogen atom or an alkyl group. R ^f in —PO (OR ^f ) — represents an alkyl group, an aryl group or an aralkyl group, and preferably an alkyl group. When R ^b and R ^f represent an alkyl group, an aryl group, or an aralkyl group, the carbon number is the same as that described in the “substituent group”. L preferably contains a single bond, —O—, —CO—, —NR ^b —, —S—, —SO ₂ —, an alkylene group or an arylene group, and —CO—, —O—, —NR ^b- , an alkylene group or an arylene group is particularly preferred. When L contains an alkylene group, the alkylene group preferably has 1 to 10 carbon atoms, more preferably 1 to 8 carbon atoms, and still more preferably 1 to 6 carbon atoms. Specific examples of particularly preferable alkylene groups include a methylene group, an ethylene group, a trimethylene group, a tetrabutylene group, and a hexamethylene group. When L contains an arylene group, the carbon number of the arylene group is preferably 6 to 24, more preferably 6 to 18, and still more preferably 6 to 12. Specific examples of particularly preferred arylene groups include phenylene groups and naphthalene groups. When L contains a divalent linking group (that is, an aralkylene group) obtained by combining an alkylene group and an arylene group, the carbon number of the aralkylene group is preferably 7 to 34, more preferably 7 to 26, and still more preferably. 7-16. Specific examples of particularly preferred aralkylene groups include a phenylenemethylene group, a phenyleneethylene group, and a methylenephenylene group. The group listed as L may have a suitable substituent. Examples of such a substituent include the same substituents as those described above as the substituents for R ¹ , R ² and R ³³ .
The specific structure of L is illustrated below.

  In the formula (II), Q is a carboxyl group, a salt of a carboxyl group (for example, lithium salt, sodium salt, potassium salt, ammonium salt (for example, ammonium, tetramethylammonium, trimethyl-2-hydroxyethylammonium, tetrabutylammonium, Trimethylbenzylammonium, dimethylphenylammonium, etc.), pyridinium salts, etc.), sulfo groups, salts of sulfo groups (examples of cations forming the salts are the same as those described above for carboxyl groups), phosphonoxy groups, salts of phosphonoxy groups ( Examples of the cation forming the salt are the same as those described for the carboxyl group). A carboxyl group, a sulfo group, and a phospho group are more preferable, and a carboxyl group or a sulfo group is particularly preferable.

  The fluoropolymer may contain one type of repeating unit represented by the formula (II) or two or more types. Moreover, the said fluorine-type polymer may have 1 type (s) or 2 or more types of repeating units other than said each repeating unit. The other repeating units are not particularly limited, and preferred examples thereof include repeating units derived from ordinary radical polymerizable monomers. Hereinafter, specific examples of monomers for deriving other repeating units will be given. The fluoropolymer may contain a repeating unit derived from one or more monomers selected from the following monomer group.

Monomer group (1) Alkenes ethylene, propylene, 1-butene, isobutene, 1-hexene, 1-dodecene, 1-octadecene, 1-eicosene, hexafluoropropene, vinylidene fluoride, chlorotrifluoroethylene, 3, 3, 3-trifluoropropylene, tetrafluoroethylene, vinyl chloride, vinylidene chloride, etc .;
(2) Dienes 1,3-butadiene, isoprene, 1,3-pentadiene, 2-ethyl-1,3-butadiene, 2-n-propyl-1,3-butadiene, 2,3-dimethyl-1,3 -Butadiene, 2-methyl-1,3-pentadiene, 1-phenyl-1,3-butadiene, 1-α-naphthyl-1,3-butadiene, 1-β-naphthyl-1,3-butadiene, 2-chloro -1,3-butadiene, 1-bromo-1,3-butadiene, 1-chlorobutadiene, 2-fluoro-1,3-butadiene, 2,3-dichloro-1,3-butadiene, 1,1,2- Trichloro-1,3-butadiene and 2-cyano-1,3-butadiene, 1,4-divinylcyclohexane and the like;

(3) Derivatives of α, β-unsaturated carboxylic acid (3a) Alkyl acrylates Methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, sec-butyl acrylate, tert-butyl acrylate , Amyl acrylate, n-hexyl acrylate, cyclohexyl acrylate, 2-ethylhexyl acrylate, n-octyl acrylate, tert-octyl acrylate, dodecyl acrylate, phenyl acrylate, benzyl acrylate, 2-chloroethyl acrylate, 2-bromoethyl acrylate, 4-chlorobutyl acrylate, 2-cyanoethyl acrylate, 2-acetoxyethyl acrylate, methoxybenzyl Chryrate, 2-chlorocyclohexyl acrylate, furfuryl acrylate, tetrahydrofurfuryl acrylate, 2-methoxyethyl acrylate, ω-methoxypolyethylene glycol acrylate (number of added polyoxyethylene: n = 2 to 100), 3-methoxy Butyl acrylate, 2-ethoxyethyl acrylate, 2-butoxyethyl acrylate, 2- (2-butoxyethoxy) ethyl acrylate, 1-bromo-2-methoxyethyl acrylate, 1,1-dichloro-2-ethoxyethyl acrylate, glycidyl acrylate Such);

(3b) Alkyl methacrylates Methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, sec-butyl methacrylate, tert-butyl methacrylate, amyl methacrylate, n-hexyl methacrylate, cyclohexyl methacrylate, 2 -Ethylhexyl methacrylate, n-octyl methacrylate, stearyl methacrylate, benzyl methacrylate, phenyl methacrylate, allyl methacrylate, furfuryl methacrylate, tetrahydrofurfuryl methacrylate, cresyl methacrylate, naphthyl methacrylate, 2-methoxyethyl methacrylate, 3-methoxybutyl methacrylate, ω Methoxypolyethylene glycol methacrylate (number of added polyoxyethylene: n = 2 to 100), 2-acetoxyethyl methacrylate, 2-ethoxyethyl methacrylate, 2-butoxyethyl methacrylate, 2- (2-butoxyethoxy) ethyl methacrylate Glycidyl methacrylate, 3-trimethoxysilylpropyl methacrylate, allyl methacrylate, 2-isocyanatoethyl methacrylate, etc .;

(3c) Diesters of unsaturated polycarboxylic acids Dimethyl maleate, dibutyl maleate, dimethyl itaconate, dibutyl taconate, dibutyl crotonate, dihexyl crotonate, diethyl fumarate, dimethyl fumarate, etc .;

(3d) Amides of α, β-unsaturated carboxylic acids N, N-dimethylacrylamide, N, N-diethylacrylamide, Nn-propylacrylamide, N-tertbutylacrylamide, N-tertoctylmethacrylamide, N- Cyclohexylacrylamide, N-phenylacrylamide, N- (2-acetoacetoxyethyl) acrylamide, N-benzylacrylamide, N-acryloylmorpholine, diacetone acrylamide, N-methylmaleimide and the like;

(4) Unsaturated nitriles Acrylonitrile, methacrylonitrile, etc .;
(5) Styrene and its derivatives Styrene, vinyl toluene, ethyl styrene, p-tert butyl styrene, methyl p-vinyl benzoate, α-methyl styrene, p-chloromethyl styrene, vinyl naphthalene, p-methoxy styrene, p-hydroxy Methyl styrene, p-acetoxy styrene, etc .;
(6) Vinyl esters Vinyl acetate, vinyl propionate, vinyl butyrate, vinyl isobutyrate, vinyl benzoate, vinyl salicylate, vinyl chloroacetate, vinyl methoxyacetate, vinyl vinyl acetate, etc .;

(7) Vinyl ethers Methyl vinyl ether, ethyl vinyl ether, n-propyl vinyl ether, isopropyl vinyl ether, n-butyl vinyl ether, isobutyl vinyl ether, tert-butyl vinyl ether, n-pentyl vinyl ether, n-hexyl vinyl ether, n-octyl vinyl ether, n-dodecyl Vinyl ether, n-eicosyl vinyl ether, 2-ethylhexyl vinyl ether, cyclohexyl vinyl ether, fluorobutyl vinyl ether, fluorobutoxyethyl vinyl ether, etc .; and (8) other polymerizable monomers N-vinyl pyrrolidone, methyl vinyl ketone, phenyl vinyl ketone, Methoxyethyl vinyl ketone, 2-vinyl oxazoline, 2-isopropenyl oxazoline, etc.

  In the fluoropolymer, the amount of the fluoroaliphatic group-containing monomer is preferably 5% by mass or more, more preferably 10% by mass or more, and more preferably 30% by mass or more of the total amount of constituent monomers of the polymer. Is more preferable. In the fluoropolymer, the amount of the repeating unit represented by the formula (II) is preferably 0.5% by mass or more of the total amount of constituent monomers of the fluoropolymer, and is 1 to 20% by mass. More preferably, it is 1 to 10% by mass. Since the above-mentioned mass percentage easily varies in a preferable range depending on the molecular weight of the monomer used, the content of the repeating unit represented by the formula (II) is expressed by the number of functional group moles per unit mass of the polymer. Can be defined accurately. When this notation is used, the preferred amount of the hydrophilic group (Q in the formula (II)) contained in the fluoropolymer is 0.1 mmol / g to 10 mmol / g, and the more preferred amount is 0. .2 mmol / g to 8 mmol / g.

  The fluoropolymer used in the present invention has a mass average molecular weight of preferably 1,000,000 or less, more preferably 500,000 or less, and even more preferably 100,000 or less. The mass average molecular weight can be measured as a value in terms of polystyrene (PS) using gel permeation chromatography (GPC).

  The polymerization method of the fluorine-based polymer is not particularly limited. For example, a polymerization method such as cation polymerization, radical polymerization, or anion polymerization using a vinyl group can be employed. Polymerization is particularly preferred in that it can be used for general purposes. As the polymerization initiator for radical polymerization, known compounds such as radical thermal polymerization initiators and radical photopolymerization initiators can be used, and it is particularly preferable to use radical thermal polymerization initiators. Here, the radical thermal polymerization initiator is a compound that generates radicals by heating to a decomposition temperature or higher. Examples of such radical thermal polymerization initiators include diacyl peroxide (acetyl peroxide, benzoyl peroxide, etc.), ketone peroxide (methyl ethyl ketone peroxide, cyclohexanone peroxide, etc.), hydroperoxide (hydrogen peroxide, tert. -Butyl hydroperoxide, cumene hydroperoxide, etc.), dialkyl peroxides (di-tert-butyl peroxide, dicumyl peroxide, dilauroyl peroxide, etc.), peroxyesters (tert-butyl peroxyacetate, tert -Butyl peroxypivalate, etc.), azo compounds (azobisisobutyronitrile, azobisisovaleronitrile, etc.), persulfates (ammonium persulfate, sodium persulfate) Beam, such as potassium sulphate). Such radical thermal polymerization initiators can be used alone or in combination of two or more.

  The radical polymerization method is not particularly limited, and an emulsion polymerization method, a suspension polymerization method, a bulk polymerization method, a solution polymerization method, and the like can be adopted. The solution polymerization, which is a typical radical polymerization method, will be described more specifically. The outlines of other polymerization methods are the same, and details thereof are described, for example, in “Polymer Science Experimental Method” edited by Polymer Society (Tokyo Kagaku Dojin, 1981).

  An organic solvent is used for solution polymerization. These organic solvents can be arbitrarily selected as long as the objects and effects of the present invention are not impaired. These organic solvents are usually organic compounds having boiling points under atmospheric pressure in the range of 50 to 200 ° C., and organic compounds that uniformly dissolve each component are preferred. Examples of preferred organic solvents are: alcohols such as isopropanol and butanol; ethers such as dibutyl ether, ethylene glycol dimethyl ether, tetrahydrofuran and dioxane; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone; ethyl acetate and acetic acid And esters such as butyl, amyl acetate, and γ-butyrolactone; and aromatic hydrocarbons such as benzene, toluene, and xylene. In addition, these organic solvents can be used individually by 1 type or in combination of 2 or more types. Furthermore, a water-mixed organic solvent in which water is used in combination with the above organic solvent is also applicable from the viewpoint of the solubility of the monomer and the polymer to be produced.

  Also, the solution polymerization conditions are not particularly limited, but for example, it is preferable to heat within a temperature range of 50 to 200 ° C. for 10 minutes to 30 hours. Furthermore, in order not to deactivate the generated radicals, it is preferable to perform an inert gas purge not only during solution polymerization but also before the start of solution polymerization. Usually, nitrogen gas is suitably used as the inert gas.

  In order to obtain the fluoropolymer in a preferable molecular weight range, a radical polymerization method using a chain transfer agent is particularly effective. As chain transfer agents, mercaptans (for example, octyl mercaptan, decyl mercaptan, dodecyl mercaptan, tert-dodecyl mercaptan, octadecyl mercaptan, thiophenol, p-nonylthiophenol, etc.), polyhalogenated alkyls (for example, carbon tetrachloride, Chloroform, 1,1,1-trichloroethane, 1,1,1-tribromooctane, etc.) and low-activity monomers (α-methylstyrene, α-methylstyrene dimer, etc.) can be used, but preferably It is a mercaptan having 4 to 16 carbon atoms. The amount of these chain transfer agents to be used is remarkably influenced by the activity of the chain transfer agent, the combination of the monomers, the polymerization conditions, and the like, and must be precisely controlled. It is about 01 mol% to 50 mol%, more preferably 0.05 mol% to 30 mol%, still more preferably 0.08 mol% to 25 mol%. These chain transfer agents may be present in the system simultaneously with the target monomer whose degree of polymerization is to be controlled in the polymerization process, and the addition method is not particularly limited. It may be added after being dissolved in the monomer, or may be added separately from the monomer.

  In addition, what has a polymeric group as a substituent in order for the fluorine-type polymer of this invention to fix the orientation state of a discotic liquid crystalline compound is also preferable.

  Specific examples that can be preferably used in the present invention as fluorine-based polymers are shown below, but the present invention is not limited to these specific examples. Here, the numerical values (numerical values such as a, b, c, and d) in the formula are mass percentages indicating the composition ratio of each monomer, and Mw is the mass average molecular weight in terms of PEO measured by GPC.

  The fluoropolymer used in the present invention can be produced by a publicly known and commonly used method. For example, it can be produced by adding a general-purpose radical polymerization initiator to an organic solvent containing the above-mentioned fluorine-based monomer, a monomer having a hydrogen bonding group, and the like, and polymerizing it. Further, in some cases, other addition-polymerizable unsaturated compounds can be further added and produced by the same method as described above. Depending on the polymerizability of each monomer, a dropping polymerization method in which a monomer and an initiator are added dropwise to a reaction vessel is also effective for obtaining a polymer having a uniform composition.

  The preferred range of the content of the fluoropolymer in the composition for forming an optically anisotropic layer (a liquid crystalline composition excluding a solvent when prepared as a coating liquid) varies depending on the use, but the composition In the product (composition excluding the solvent in the case of a coating solution), the content is preferably 0.005 to 8% by mass, more preferably 0.01 to 5% by mass, and 0.05 to 1% by mass. % Is more preferable. If the addition amount of the fluorine-based polymer is less than 0.005% by mass, the effect is insufficient, and if it exceeds 8% by mass, the coating film cannot be sufficiently dried, or the performance as an optical film (for example, letter Adversely affects the uniformity of the foundation.

Next, the fluorine-containing compound represented by the formula (III) that can be similarly used as the air interface side vertical alignment agent will be described.
Formula (III)
(R ⁰ ) _mo −L ⁰ − (W) _no
In the formula, R ⁰ represents an alkyl group, an alkyl group having a CF ₃ group at the terminal, or an alkyl group having a CF ₂ H group at the terminal, and mo represents an integer of 1 or more. A plurality of R ⁰ may be the same or different, but at least one represents an alkyl group having a CF ₃ group or a CF ₂ H group at the terminal. L ⁰ represents a (mo + no) -valent linking group, W represents a carboxyl group (—COOH) or a salt thereof, a sulfo group (—SO ₃ H) or a salt thereof, or phosphonoxy {—OP (═O) (OH) ₂ } Or a salt thereof, and no represents an integer of 1 or more.

In the formula (III), R ⁰ functions as a hydrophobic group of the fluorine-containing compound. The alkyl group represented by R ⁰ is a substituted or unsubstituted alkyl group, which may be linear or branched, preferably an alkyl group having 1 to 20 carbon atoms, more preferably Is an alkyl group of 4 to 16, particularly preferably an alkyl group of 6 to 16. As the substituent, any of the substituents exemplified as the substituent group D described later can be applied.

The alkyl group having a CF ₃ group at the terminal represented by R ⁰ preferably has 1 to 20 carbon atoms, more preferably 4 to 16 and even more preferably 4 to 8. The alkyl group having a CF ₃ group at the terminal is an alkyl group in which part or all of the hydrogen atoms contained in the alkyl group are substituted with fluorine atoms. 50% or more of hydrogen atoms in the alkyl group are preferably substituted with fluorine atoms, more preferably 60% or more are substituted, and particularly preferably 70% or more are substituted. The remaining hydrogen atoms may be further substituted with the substituents exemplified as the substituent group D described later. The alkyl group having a CF ₂ H group at the terminal represented by R ⁰ preferably has 1 to 20 carbon atoms, more preferably 4 to 16 and even more preferably 4 to 8. The alkyl group having a CF ₂ H group at the terminal is an alkyl group in which some or all of the hydrogen atoms contained in the alkyl group are substituted with fluorine atoms. 50% or more of the hydrogen atoms in the alkyl group are preferably substituted with fluorine atoms, more preferably 60% or more are substituted, and even more preferably 70% or more are substituted. The remaining hydrogen atoms may be further substituted with a substituent exemplified as the substituent group D described later. Examples of an alkyl group having a CF ₃ group at the terminal represented by R ⁰ or an alkyl group having a CF ₂ H group at the terminal are shown below.

R1: n-C ₈ F _{17-
R2: n-C 6 F 13} -
_{R3: n-C 4 F 9} -
_{R4: n-C 8 F 17} - (CH 2) 2 -
_{R5: n-C 6 F 13} - (CH 2) 2 -
_{R6: n-C 4 F 9} - (CH 2) 2 -
_{R7: H- (CF 2) 8} -
_{R8: H- (CF 2) 6} -
_{R9: H- (CF 2) 4} -
_{R10: H- (CF 2) 8} - (CH 2) -
R11: H— (CF ₂ ) ₆ — (CH ₂ ) —
_{R12: H- (CF 2) 4} - (CH 2) -

In the formula (III), the (mo + no) -valent linking group represented by L ⁰ is an alkylene group, an alkenylene group, an aromatic group, a heterocyclic group, —CO—, —NR ^d — (R ^d is the number of carbon atoms) Is a linking group in which at least two groups selected from the group consisting of —O—, —S—, —SO—, and —SO ₂ — are combined.

In the formula (III), W represents a carboxyl group (—COOH) or a salt thereof, a sulfo group (—SO ₃ H) or a salt thereof, or a phosphonoxy group {—OP (═O) (OH) ₂ } or a salt thereof. . The preferred range of W is the same as Q in formula (II).

  Among the fluorine-containing compounds represented by the formula (III), compounds represented by the following formula (III) -a or formula (III) -b are preferable.

In formula (III) -a, R ⁴ and R ⁵ each represents an alkyl group, an alkyl group having a CF ₃ group at the terminal, or an alkyl group having a CF ₂ H group at the terminal, and R ⁴ and R ⁵ are simultaneously It is not an alkyl group. W ¹ and W ² are each a hydrogen atom, a carboxyl group (—COOH) or a salt thereof, a sulfo group (—SO ₃ H) or a salt thereof, phosphonoxy {—OP (═O) (OH) ₂ } or a salt thereof, or An alkyl group, an alkoxy group or an alkylamino group having a carboxyl group, a sulfo group or a phosphonoxy group as a substituent is represented, but W ¹ and W ² are not simultaneously hydrogen atoms.

Formula (III) -b
_{^{(R 6 -L 2 -) m2}} (Ar 1) -W 3
In formula (III) -b, R ⁶ represents an alkyl group, an alkyl group having a CF ₃ group at the terminal, or an alkyl group having a CF ₂ H group at the terminal, m2 represents an integer of 1 or more, R ⁶ may be the same or different, but at least one represents an alkyl group having a CF ₃ group or a CF ₂ H group at the terminal. L ² represents an alkylene group, an aromatic group, —CO—, —NR′— (R ′ is an alkyl group having 1 to 5 carbon atoms or a hydrogen atom), —O—, —S—, —SO—, It represents a divalent linking group selected from the group consisting of —SO ₂ — and combinations thereof, and a plurality of L ² may be the same or different. Ar ¹ represents an aromatic hydrocarbon ring or an aromatic heterocycle, W ³ represents a carboxyl group (—COOH) or a salt thereof, a sulfo group (—SO ₃ H) or a salt thereof, a phosphonoxy group {—OP (═O) (OH) ₂ } or a salt thereof, or an alkyl group, an alkoxy group or an alkylamino group having a carboxyl group, a sulfo group or a phosphonoxy group as a substituent.

First, the formula (III) -a will be described.
R ⁴ and R ⁵ are synonymous with R ⁰ in the formula (III), and their preferred ranges are also the same. The carboxyl group (—COOH) or a salt thereof represented by W ¹ and W ² , a sulfo group (—SO ₃ H) or a salt thereof, a phosphonoxy group {—OP (═O) (OH) ₂ } or a salt thereof is It is synonymous with W in Formula (III), and its preferable range is also the same. The alkyl group having a carboxyl group, a sulfo group or a phosphonoxy group as a substituent represented by W ^{1 or} W ² may be linear or branched, and preferably has 1 to 20 carbon atoms. It is an alkyl group, More preferably, it is a 1-8 alkyl group, Most preferably, it is a 1-3 alkyl group. The alkyl group having a carboxyl group, a sulfo group, or a phosphonoxy group as the substituent only needs to have at least one carboxyl group, sulfo group, or phosphonoxy group. It is synonymous with the carboxyl group, sulfo group and phosphonoxy group represented by W in formula (III), and the preferred range is also the same. The alkyl group having a carboxyl group, a sulfo group, or a phosphonoxy group as the substituent may be substituted with any other substituent, and the substituent is any of the substituents exemplified as the substituent group D described later. Can be applied. The alkoxy group having a carboxyl group, a sulfo group or a phosphonoxy group as a substituent represented by W ¹ and W ² may be linear or branched, and preferably has 1 to 20 carbon atoms. An alkoxy group, more preferably an alkoxy group of 1 to 8, and particularly preferably an alkoxy group of 1 to 4. The alkoxy group having a carboxyl group, a sulfo group, or a phosphonoxy group as the substituent only needs to have at least one carboxyl group, a sulfo group, or a phosphonoxy group. It is synonymous with the carboxyl group, sulfo group and phosphonoxy group represented by W in formula (III), and the preferred range is also the same. The alkoxy group having a carboxyl group, a sulfo group, or a phosphonoxy group may be substituted with other substituents, and any of the substituents exemplified as the substituent group D described later can be applied as the substituent. . The alkylamino group having a carboxyl group, a sulfo group or a phosphonoxy group as a substituent represented by W ^{1 or} W ² may be linear or branched, and preferably has 1 to 20 carbon atoms. More preferably 1 to 8 alkylamino groups, and still more preferably 1 to 4 alkylamino groups. The alkylamino group having a carboxyl group, a sulfo group, or a phosphonoxy group may have at least one carboxyl group, a sulfo group, or a phosphonoxy group. Examples of the carboxyl group, the sulfo group, and the phosphonoxy group include the above-described formula ( It is synonymous with the carboxyl group, sulfo group and phosphonoxy group represented by W in III), and the preferred range is also the same. The alkylamino group having a carboxyl group, a sulfo group, or a phosphonoxy group may be substituted with other substituents, and any of the substituents exemplified as Substituent Group D described later is applied as the substituent. it can.

W ¹ and W ² are particularly preferably each a hydrogen atom or — (CH ₂ ) _n SO ₃ M (n represents 0 or 1). M represents a cation, but M may not be present when the charge is 0 in the molecule. As the cation represented by M, for example, protonium ion, alkali metal ion (lithium ion, sodium ion, potassium ion, etc.), alkaline earth metal ion (barium ion, calcium ion, etc.), ammonium ion, etc. are preferably applied. . Of these, proton ions, lithium ions, sodium ions, potassium ions, and ammonium ions are particularly preferable.

Next, the formula (III) -b will be described.
R ⁶ has the same meaning as R ⁰ in formula (III), and the preferred range thereof is also the same. L ² is preferably an alkylene group having 1 to 12 carbon atoms, an aromatic group having 6 to 12 carbon atoms, —CO—, —NR—, —O—, —S—, —SO—, —SO ₂ — and Represents a linking group having a total carbon number of 0 to 40 consisting of a combination thereof, more preferably an alkylene group having 1 to 8 carbon atoms, a phenyl group, —CO—, —NR—, —O—, —S—, —SO. ₂ represents a linking group having 0 to 20 carbon atoms and a combination thereof. Ar ¹ preferably represents an aromatic hydrocarbon ring having 6 to 12 carbon atoms, more preferably a benzene ring or a naphthalene ring. As a carboxyl group (—COOH) represented by W ³ or a salt thereof, a sulfo group (—SO ₃ H) or a salt thereof, a phosphonoxy group {—OP (═O) (OH) ₂ } or a salt thereof, or a substituent The alkyl group, alkoxy group, or alkylamino group having a carboxyl group, a sulfo group or a phosphonoxy group is a carboxyl group (—COOH) represented by W ¹ and W ² in the above formula (III) -a or a salt thereof, sulfo Group (—SO ₃ H) or a salt thereof, phosphonoxy {—OP (═O) (OH) ₂ } or a salt thereof, or an alkyl group, an alkoxy group, or an alkyl having a carboxyl group, a sulfo group, or a phosphonoxy group as a substituent. It is synonymous with an amino group and its preferable range is also the same.

W ³ is preferably a carboxyl group (—COOH) or a salt thereof, a sulfo group (—SO ₃ H) or a salt thereof, or a carboxyl group (—COOH) or a salt thereof or a sulfo group (—SO ₃ H) as a substituent. Alternatively, it is an alkylamino group having a salt thereof, and particularly preferably SO ₃ M or CO ₂ M. M represents a cation, but M may not be present when the charge is 0 in the molecule. As the cation represented by M, for example, protonium ion, alkali metal ion (lithium ion, sodium ion, potassium ion, etc.), alkaline earth metal ion (barium ion, calcium ion, etc.), ammonium ion, etc. are preferably applied. . Of these, proton ions, lithium ions, sodium ions, potassium ions, and ammonium ions are particularly preferable.

  In the present specification, the substituent group D includes an alkyl group (preferably an alkyl group having 1 to 20 carbon atoms, more preferably 1 to 12 carbon atoms, and particularly preferably 1 to 8 carbon atoms, such as a methyl 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 having 2 carbon atoms) -20, more preferably an alkenyl group having 2 to 12 carbon atoms, more preferably 2 to 8 carbon atoms, and examples thereof include a vinyl group, an allyl group, a 2-butenyl group, and a 3-pentenyl group), alkynyl A group (preferably an alkynyl group having 2 to 20 carbon atoms, more preferably 2 to 12 carbon atoms, still more preferably 2 to 8 carbon atoms, Argyl group, 3-pentynyl group and the like), an aryl group (preferably an aryl group having 6 to 30 carbon atoms, more preferably 6 to 20 carbon atoms, and further preferably 6 to 12 carbon atoms). Group, p-methylphenyl group, naphthyl group and the like), substituted or unsubstituted amino group (preferably having 0 to 20 carbon atoms, more preferably 0 to 10 carbon atoms, and further preferably 0 to 6 carbon atoms). An amino group, for example, an unsubstituted amino group, a methylamino group, a dimethylamino group, a diethylamino group, a dibenzylamino group and the like),

An alkoxy group (preferably an alkoxy group having 1 to 20 carbon atoms, more preferably 1 to 12 carbon atoms, still more preferably 1 to 8 carbon atoms, and examples thereof include a methoxy group, an ethoxy group, and a butoxy group). An aryloxy group (preferably an aryloxy group having 6 to 20 carbon atoms, more preferably 6 to 16 carbon atoms, still more preferably 6 to 12 carbon atoms, and examples thereof include a phenyloxy group and a 2-naphthyloxy group. An acyl group (preferably an acyl group having 1 to 20 carbon atoms, more preferably 1 to 16 carbon atoms, and still more preferably 1 to 12 carbon atoms, such as an acetyl group, a benzoyl group, a formyl group, and a pivaloyl group. Etc.), an alkoxycarbonyl group (preferably having 2 to 20 carbon atoms, more preferably 2 to 16 carbon atoms, still more preferably A C2-C12 alkoxycarbonyl group, for example, a methoxycarbonyl group, an ethoxycarbonyl group, and the like; an aryloxycarbonyl group (preferably having a carbon number of 7-20, more preferably having a carbon number of 7-16, even more preferably Is an aryloxycarbonyl group having 7 to 10 carbon atoms, such as a phenyloxycarbonyl group, and an acyloxy group (preferably having 2 to 20 carbon atoms, more preferably 2 to 16 carbon atoms, and still more preferably carbon atoms). An acyloxy group having a number of 2 to 10, and examples thereof include an acetoxy group and a benzoyloxy group).

  An acylamino group (preferably an acylamino group having 2 to 20 carbon atoms, more preferably 2 to 16 carbon atoms, still more preferably 2 to 10 carbon atoms, such as an acetylamino group and a benzoylamino group), alkoxycarbonyl An amino group (preferably an alkoxycarbonylamino group having 2 to 20 carbon atoms, more preferably 2 to 16 carbon atoms, still more preferably 2 to 12 carbon atoms, such as a methoxycarbonylamino group), aryloxy Carbonylamino group (preferably an aryloxycarbonylamino group having 7 to 20 carbon atoms, more preferably 7 to 16 carbon atoms, still more preferably 7 to 12 carbon atoms, such as a phenyloxycarbonylamino group) A sulfonylamino group (preferably having 1 to 20 carbon atoms) Preferably it is a C1-C16, More preferably, it is a C1-C12 sulfonylamino group, for example, a methanesulfonylamino group, a benzenesulfonylamino group, etc.), a sulfamoyl group (preferably C0-20). More preferably, it is a sulfamoyl group having 0 to 16 carbon atoms, more preferably 0 to 12 carbon atoms, and examples thereof include a sulfamoyl group, a methylsulfamoyl group, a dimethylsulfamoyl group, and a phenylsulfamoyl group. ), A carbamoyl group (preferably a carbamoyl group having 1 to 20 carbon atoms, more preferably 1 to 16 carbon atoms, and still more preferably 1 to 12 carbon atoms, such as an unsubstituted carbamoyl group, a methylcarbamoyl group, or a diethylcarbamoyl group. Group, phenylcarbamoyl group, etc.),

An alkylthio group (preferably an alkylthio group having 1 to 20 carbon atoms, more preferably 1 to 16 carbon atoms, still more preferably 1 to 12 carbon atoms, such as a methylthio group and an ethylthio group), an arylthio group ( Preferably it is a C6-C20, More preferably, it is a C6-C16, More preferably, it is a C6-C12 arylthio group, For example, a phenylthio group etc. are mentioned, A sulfonyl group (preferably C1-C1). 20, more preferably a sulfonyl group having 1 to 16 carbon atoms, still more preferably 1 to 12 carbon atoms, and examples thereof include a mesyl group and a tosyl group), a sulfinyl group (preferably having a carbon number of 1 to 20, and more. A sulfinyl group having 1 to 16 carbon atoms, more preferably 1 to 12 carbon atoms, is preferable. A ureido group (preferably a benzenesulfinyl group), a ureido group (preferably a ureido group having 1 to 20 carbon atoms, more preferably 1 to 16 carbon atoms, and still more preferably 1 to 12 carbon atoms. Ureido group, methylureido group, phenylureido group, etc.), phosphoric acid amide group (preferably having 1 to 20 carbon atoms, more preferably having 1 to 16 carbon atoms, and further preferably having 1 to 12 carbon atoms) Group such as diethyl phosphoramide group and phenylphosphoric acid amide group), hydroxy group, mercapto group, halogen atom (eg fluorine atom, chlorine atom, bromine atom, iodine atom), cyano group, sulfo group Group, carboxyl group, nitro group, hydroxamic acid group, sulfino group, hydrazino group, imino group, heterocyclic group (preferably A heterocyclic group having 1 to 30 carbon atoms, more preferably 1 to 12 carbon atoms, such as a heterocyclic group having a hetero atom such as a nitrogen atom, an oxygen atom, or a sulfur atom, such as an imidazolyl group, a pyridyl group, or a quinolyl group; Group, furyl group, piperidyl group, morpholino group, benzoxazolyl group, benzimidazolyl group, benzthiazolyl group and the like), silyl group (preferably having 3 to 40 carbon atoms, more preferably 3 to 30 carbon atoms, More preferably, it is a silyl group having 3 to 24 carbon atoms, and examples thereof include a trimethylsilyl group and a triphenylsilyl group. These substituents may be further substituted with these substituents. Further, when two or more substituents are present, they may be the same or different. If possible, they may be bonded to each other to form a ring.

  The fluorine-containing compound of the present invention preferably has a polymerizable group as a substituent in order to fix the alignment state of the discotic liquid crystalline compound.

  Specific examples of the fluorine-containing compound represented by the formula (III) that can be used in the present invention are shown below, but the fluorine-containing compound used in the present invention is not limited thereto.

  The preferable range of the content of the fluorine-containing compound in the composition for forming an optically anisotropic layer varies depending on the use, but 0 in the composition (a composition excluding the solvent in the case of a coating solution). 0.005 to 8% by mass is preferable, 0.01 to 5% by mass is more preferable, and 0.05 to 1% by mass is even more preferable.

[Polymerization initiator]
The aligned (preferably vertically aligned) liquid crystal compound is fixed while maintaining the alignment state. The immobilization is preferably performed by a polymerization reaction of the polymerizable group (P) introduced into the liquid crystal compound. The polymerization reaction includes a thermal polymerization reaction using a thermal polymerization initiator and a photopolymerization reaction using a photopolymerization initiator. A photopolymerization reaction is preferred. Examples of the photopolymerization initiator include α-carbonyl compounds (described in US Pat. Nos. 2,367,661 and 2,367,670), acyloin ether (described in US Pat. No. 2,448,828), α-hydrocarbon substituted aromatic acyloin. Compound (described in US Pat. No. 2,722,512), polynuclear quinone compound (described in US Pat. Nos. 3,046,127 and 2,951,758), a combination of triarylimidazole dimer and p-aminophenyl ketone (US Pat. No. 3,549,367) Description), acridine and phenazine compounds (JP-A-60-105667, U.S. Pat. No. 4,239,850) and oxadiazole compounds (U.S. Pat. No. 4,212,970).

It is preferable that the usage-amount of a photoinitiator is 0.01-20 mass% of solid content of a coating liquid, and it is more preferable that it is 0.5-5 mass%. Light irradiation for polymerization of discotic liquid crystalline molecules is preferably performed using ultraviolet rays. The irradiation energy is preferably ^{20mJ / cm 2 ~50J / cm 2} , further preferably 100 to 800 mJ / cm ^2. In order to accelerate the photopolymerization reaction, light irradiation may be performed under heating conditions. The thickness of the retardation layer is preferably 0.1 to 10 μm, more preferably 0.5 to 5 μm, and most preferably 1 to 5 μm.

[Other additives for optically anisotropic layer]
Along with the liquid crystal compound, a plasticizer, a surfactant, a polymerizable monomer, and the like can be used in combination to improve the uniformity of the coating film, the strength of the film, the orientation of the liquid crystal compound, and the like. These materials are preferably compatible with the liquid crystal compound and do not inhibit the alignment.

  Examples of the polymerizable monomer include radically polymerizable or cationically polymerizable compounds. Preferably, it is a polyfunctional radically polymerizable monomer and is preferably copolymerizable with the above-described polymerizable group-containing liquid crystal compound. Examples thereof include those described in paragraph numbers [0018] to [0020] in JP-A No. 2002-296423. The amount of the compound added is generally in the range of 1 to 50% by mass and preferably in the range of 5 to 30% by mass with respect to the discotic liquid crystalline molecules.

  Examples of the surfactant include conventionally known compounds, and fluorine compounds are particularly preferable. Specifically, for example, compounds described in paragraphs [0028] to [0056] in JP-A No. 2001-330725, and paragraphs [0069] to [0126] in Japanese Patent Application No. 2003-295212 are described. The compound of this is mentioned.

The polymer used together with the liquid crystal compound is preferably capable of thickening the coating solution. A cellulose ester can be mentioned as an example of a polymer. Preferable examples of the cellulose ester include those described in paragraph [0178] of JP-A No. 2000-155216. The addition amount of the polymer is preferably in the range of 0.1 to 10% by mass, and in the range of 0.1 to 8% by mass with respect to the liquid crystal molecules so as not to inhibit the alignment of the liquid crystal compound. It is more preferable.
The discotic nematic liquid crystal phase-solid phase transition temperature of the liquid crystal compound is preferably 70 to 300 ° C, more preferably 70 to 170 ° C.

[Coating solvent]
As the solvent used for preparing the coating solution, an organic solvent is preferably used. Examples of organic solvents include amides (eg, N, N-dimethylformamide), sulfoxides (eg, dimethyl sulfoxide), heterocyclic compounds (eg, pyridine), hydrocarbons (eg, benzene, hexane), alkyl halides (eg, , Chloroform, dichloromethane), esters (eg, methyl acetate, butyl acetate), ketones (eg, acetone, methyl ethyl ketone), ethers (eg, tetrahydrofuran, 1,2-dimethoxyethane). Alkyl halides and ketones are preferred. Two or more organic solvents may be used in combination.

[Coating method]
The coating liquid can be applied by a known method (eg, wire bar coating method, extrusion coating method, direct gravure coating method, reverse gravure coating method, die coating method). Especially, when forming the said optically anisotropic layer, it is preferable to apply | coat using a wire bar coating method, and it is preferable that the rotation speed of a wire bar satisfy | fills a following formula.
0.6 <(W × (R + 2r) × π) / V <1.4
[W: Number of revolutions of wire bar (rpm), R: Diameter of bar core (m), r: Diameter of wire (m), V: Conveying speed of support (m / min)]
The range of (W × (R + 2r) × π) / V is more preferably 0.7 to 1.3, and still more preferably 0.8 to 1.2.

  For forming the optically anisotropic layer, a die coating method is preferably used, and a coating method using a slide coater or a slot die coater is particularly preferable.

  FIG. 1 is a schematic view of a slot coater that can be used in the present invention. The coater 10 applies the coating liquid 14 from the slot die 13 as a bead 14a to a web 12 (for example, a transparent film that serves as a support for the optically anisotropic layer) supported by the backup roll 11 and continuously running. Thereby, the coating film 14 b is formed on the web 12.

  The slot die 13 has a pocket 15 and a slot 16 formed therein. The pocket 15 has a curved cross section and a straight line. For example, a substantially circular shape as shown in FIG. 1 or a semicircular shape may be used. The pocket 15 is a space extended with the same cross-sectional shape in the width direction of the slot die 13 (in FIG. 1, the direction perpendicular to the paper surface, the same applies hereinafter), and is used to store the coating liquid. Used. The effective length of the extension in the width direction is generally equal to or slightly longer than the coating width (for example, the width of the transparent film). The application liquid 14 is supplied to the pocket 15 from the side surface of the slot die 13 or from the center of the surface opposite to the slot, for example, by a supply pump (not shown) capable of controlling the supply amount. The pocket 15 may be provided with a stopper for preventing the coating liquid 14 from leaking out.

  Similarly to the pocket 15, the slot 16 is a space extended with the same cross-sectional shape in the width direction of the slot die 13, and is a flow path of the coating liquid 14 from the pocket 15 to the web 12. The opening 16a located on the web side is generally adjusted to have a width that is substantially the same as the coating width by using a width regulating plate (not shown) or the like. The angle between the slot 16 and the tangent in the web traveling direction of the backup roll 11 at the slot tip is generally preferably 30 ° or more and 90 ° or less, but is not limited to this range.

  The tip lip 17 of the slot die 13 where the opening 16a of the slot 16 is located is tapered, and the tip is a flat portion 17a called a land. In this flat portion 17 a, the upstream side of the web 12 in the traveling direction of the web 12 with respect to the slot 16 is hereinafter referred to as an upstream lip land 18 and the downstream side is referred to as a downstream lip land 19.

  The length ILO in the web traveling direction of the downstream lip land 19 is preferably 30 μm to 500 μm, more preferably 30 μm to 100 μm, and still more preferably 30 μm to 60 μm. Further, the length IUP of the upstream lip land 18 in the web traveling direction is not particularly limited, but is preferably used in the range of 500 μm to 1 mm.

  FIG. 2 is a schematic view (A) of the cross-sectional shape of the slot die 13 and a schematic view (B) of the cross-sectional shape of another slot die 30. In the slot die 30 shown in FIG. 2B, the land length ILO of the downstream lip land 31 is the same as the length IUP of the upstream lip land. Reference numeral 32 denotes a pocket, and 33 denotes a slot. On the other hand, in the slot die 13 shown in FIG. 2A, the downstream lip land length ILO is shorter than the upstream lip land length IUP. In the present invention, any shape of the slot die can be used. However, when coating with a film thickness of 20 μm or less, it is more preferable to use a slot die having a shape with an ILO shorter than IUP, like the slot die 13. This is preferable because a uniform film thickness can be applied with high accuracy. Furthermore, when the land length ILO of the downstream lip land 19 is in the range of 30 μm to 100 μm, a lip land with good dimensional accuracy can be formed, which is more preferable.

  Further, in order to make the film thickness of the coating film uniform with high accuracy, it is preferable that the fluctuation width in the width direction of the slot die 13 of the land length ILO of the downstream lip land 19 is within 20 μm. If the fluctuation range is within the above range, the beads can be formed more stably, and even if a disturbance or the like occurs, the beads can be prevented from becoming unstable, and the suitability for manufacturing can be maintained.

The material of the slot die is not particularly limited, but from the viewpoint of improving the strength and surface condition of the tip lip 17 including the opening a of the slot 16, the material of the slot die including at least this portion is made of a carbide material. Is preferred. By using a super hard material, the homogeneity of the surface shape can be improved, and wear of the tip lip due to the coating liquid that is always discharged can be prevented. This is particularly effective when applying a magnetic liquid containing an abrasive as the coating liquid. An example of the super hard material is a material mainly composed of WC. For example, a material prepared by bonding a WC carbide crystal with a bonding metal such as Co can be used. The bonding metal is not limited to Co, and various metals including Ti, Ta, and Nb can also be used. The average particle size of the WC crystal is not particularly limited, but the average particle size is preferably small and is preferably within 5 μm.

Furthermore, in order to maintain the coating thickness of the thin layer uniformly with high accuracy, not only the dimensional accuracy at the tip of the slot die 10 but also the accuracy of the straightness of the backup roll 13 is important. Therefore, in addition to maintaining the dimensional accuracy in the application width direction of the land length ILO of the downstream lip land 19, it is preferable that the straightness accuracy of both the tip lip 17 of the slot die 13 and the backup roll 11 is high. The straightness can be determined with sufficient accuracy practically by the following formula (1). However, even a slot die coater that does not satisfy the following formula (1) can be used in the present invention. Here, Po is the pressure outside the bead meniscus on the traveling direction side of the web 12, Pp is the internal pressure of the pocket 15, σ is the surface tension of the coating solution 14, μ is the viscosity of the coating solution 14a, U is the coating speed, and h is the film. Thickness, d is the length of the gap between the downstream lip land 19 and the web 12, L is the length of the slot 16 of the slot die 13, and D is the slot gap of the slot die 13. Then, the differential pressure Po-Pp between the internal pressure Pp of the pocket 15 of the slot die 13 and the pressure Po outside the bead meniscus on the web traveling direction side is made constant in the width direction of the slot die 13 and the following equation (1) is used: Find the required straightness. This is because the differential pressure between the pocket 15 of the slot die 13 and the outside of the bead meniscus is constant even if the length d of the gap between the tip of the slot die 13 and the backup roll 11 changes. This is because the flow in the width direction of the die 13 is generated in the pocket 15 and becomes a flow distribution.
Po−Pp = 1.34σ / h · (μU / σ) 2/3 + 12 μUILO (d / 2-h) / d3-12 μhUL / D3 (1)

When coating is performed with a slot die coater under the conditions satisfying the above formula (1), in a coating system used for general industrial production, the coating film thickness distribution is 2% with a straightness in the die block width direction of about 5 μm. Degree (which may differ strictly depending on conditions). Therefore, it can be considered that this limit is the limit when high-precision thin film coating is performed. Thereby, when the slot die 13 is set at the coating position, the straightness of the tip lip and the backup roll is set so that the fluctuation width in the slot die width direction of the gap between the tip lip and the web is within 5 μm. Is preferably maintained.
In the present invention, when a plurality of optically anisotropic layers are applied simultaneously, it is also preferable to apply using a slide coater.

[Alignment film]
In the present invention, it is preferable to align the molecules of the liquid crystal compound by applying the composition to the surface of the alignment film. Since the alignment film has a function of defining the alignment direction of the liquid crystalline compound, it is preferably used for realizing a preferred embodiment of the present invention. However, if the alignment state is fixed after aligning the liquid crystalline compound, the alignment film plays the role, and thus is not necessarily an essential component of the present invention. That is, it is also possible to produce the polarizing plate of the present invention by transferring only the optically anisotropic layer on the alignment film in which the alignment state is fixed onto the polarizing layer or the support.
The alignment film is an organic compound (eg, ω-tricosanoic acid) formed by rubbing treatment of an organic compound (preferably a polymer), oblique deposition of an inorganic compound, formation of a layer having a microgroove, or Langmuir-Blodgett method (LB film). , Dioctadecylmethylammonium chloride, methyl stearylate). Furthermore, an alignment film in which an alignment function is generated by application of an electric field, application of a magnetic field, or light irradiation is also known.
The alignment film is preferably formed by polymer rubbing treatment.

  Examples of the polymer include methacrylate copolymer, styrene copolymer, polyolefin, polyvinyl alcohol, modified polyvinyl alcohol, poly (N-methylol) described in paragraph No. [0022] of JP-A-8-338913. Acrylamide), polyester, polyimide, vinyl acetate copolymer, carboxymethylcellulose, polycarbonate and the like. Silane coupling agents can be used as the polymer. Water-soluble polymers (eg, poly (N-methylolacrylamide), carboxymethylcellulose, gelatin, polyvinyl alcohol, modified polyvinyl alcohol) are preferred, gelatin, polyvinyl alcohol and modified polyvinyl alcohol are more preferred, and polyvinyl alcohol and modified polyvinyl alcohol are most preferred. .

  The saponification degree of polyvinyl alcohol is preferably 70 to 100%, more preferably 80 to 100%. The polymerization degree of polyvinyl alcohol is preferably 100 to 5000.

In the alignment film, a side chain having a crosslinkable functional group (eg, a double bond) is bonded to the main chain, or a crosslinkable functional group having a function of aligning liquid crystal molecules is introduced into the side chain. Is preferred. As the polymer used for the alignment film, either a polymer that can be crosslinked by itself or a polymer that is crosslinked by a crosslinking agent can be used, and a plurality of combinations thereof can be used.
When a side chain having a crosslinkable functional group is bonded to the main chain of the alignment film polymer or a crosslinkable functional group is introduced into a side chain having a function of aligning liquid crystalline molecules, the alignment film polymer and the optically anisotropic film The polyfunctional monomer contained in the conductive layer can be copolymerized. As a result, not only between the polyfunctional monomer and the polyfunctional monomer, but also between the alignment film polymer and the alignment film polymer and between the polyfunctional monomer and the alignment film polymer is firmly bonded by a covalent bond. Therefore, the strength of the optical compensation sheet can be remarkably improved by introducing the crosslinkable functional group into the alignment film polymer.
The crosslinkable functional group of the alignment film polymer preferably contains a polymerizable group in the same manner as the polyfunctional monomer. Specifically, for example, those described in paragraphs [0080] to [0100] of JP-A No. 2000-155216, and the like can be mentioned.

  Apart from the crosslinkable functional group, the alignment film polymer can also be crosslinked using a crosslinking agent. Examples of the crosslinking agent include aldehydes, N-methylol compounds, dioxane derivatives, compounds that act by activating carboxyl groups, active vinyl compounds, active halogen compounds, isoxazole and dialdehyde starch. Two or more kinds of crosslinking agents may be used in combination. Specific examples include compounds described in paragraphs [0023] to [0024] in JP-A-2002-62426. Aldehydes having high reaction activity, particularly glutaraldehyde are preferred.

  0.1-20 mass% is preferable with respect to a polymer, and, as for the addition amount of a crosslinking agent, 0.5-15 mass% is more preferable. The amount of the unreacted crosslinking agent remaining in the alignment film is preferably 1.0% by mass or less, and more preferably 0.5% by mass or less. By adjusting in this way, even if the alignment film is used for a long time in a liquid crystal display device or left in a high temperature and high humidity atmosphere for a long time, sufficient durability without reticulation can be obtained.

  The alignment film is basically formed by applying a solution containing the polymer, the cross-linking agent, and the additive, which is an alignment film forming material, onto a transparent support, followed by heat drying (cross-linking) and rubbing treatment. be able to. As described above, the crosslinking reaction may be performed at an arbitrary time after coating on the transparent support. When a water-soluble polymer such as polyvinyl alcohol is used as the alignment film forming material, the coating solution is preferably a mixed solvent of an organic solvent (eg, methanol) having a defoaming action and water. The ratio of water: methanol is preferably 0: 100 to 99: 1, and more preferably 0: 100 to 91: 9. Thereby, generation | occurrence | production of a bubble is suppressed and the defect of the layer surface of an orientation film and also an optically anisotropic layer reduces remarkably.

  The coating method used for forming the alignment film is preferably a spin coating method, a dip coating method, a curtain coating method, an extrusion coating method, a rod coating method or a roll coating method. A rod coating method is particularly preferable. The film thickness after drying is preferably 0.1 to 10 μm. Heating and drying can be performed at 20 ° C to 110 ° C. In order to form sufficient cross-linking, 60 ° C to 100 ° C is preferable, and 80 ° C to 100 ° C is particularly preferable. The drying time can be 1 minute to 36 hours, preferably 1 minute to 30 minutes. The pH is preferably set to an optimum value for the crosslinking agent to be used. When glutaraldehyde is used, the pH is 4.5 to 5.5, and 5 is particularly preferable.

  The alignment film is preferably provided on the transparent support. The alignment film can be obtained by rubbing the surface after crosslinking the polymer layer as described above.

  For the rubbing treatment, a treatment method widely adopted as a liquid crystal alignment treatment process of LCD can be applied. That is, a method of obtaining the orientation by rubbing the surface of the orientation film in a certain direction using paper, gauze, felt, rubber, nylon, polyester fiber or the like can be used. In general, it is carried out by rubbing several times using a cloth in which fibers having a uniform length and thickness are flocked on average.

The said composition is apply | coated to the rubbing process surface of alignment film, and the molecule | numerator of a liquid crystalline compound is aligned. Thereafter, if necessary, the alignment film polymer and the polyfunctional monomer contained in the optically anisotropic layer are reacted, or the alignment film polymer is crosslinked using a crosslinking agent, thereby the optically anisotropic layer. Can be formed.
The thickness of the alignment film is preferably in the range of 0.1 to 10 μm.

[Support]
The optical compensation film used as the first and second optically anisotropic layers has a support made of a polymer film that supports the optically anisotropic layer formed from a composition containing a liquid crystal compound. A polymer film having small optical anisotropy may be used, or a polymer film exhibiting optical anisotropy by stretching treatment or the like may be used. The support preferably has a light transmittance of 80% or more.

  The in-plane retardation (Re) of the support is preferably from 0 to 200 nm, more preferably from 0 to 150 nm, and most preferably from 0 to 100 nm. The retardation (Rth) in the thickness direction of the support is preferably −1000 nm to 300 nm, more preferably −500 nm to 250 nm, and most preferably −300 nm to 200 nm.

  Examples of the polymer include cellulose ester, polycarbonate, polysulfone, polyethersulfone, polyacrylate, polymethacrylate and cyclic polyolefin. Cellulose esters are preferred, acetyl cellulose is more preferred, and triacetyl cellulose is most preferred. As the cyclic polyolefin, a polymer obtained by hydrogenation reaction of a ring-opening polymer of tetracyclododecene or a ring-opening copolymer of tetracyclododecene and norbornene described in JP-B-2-9619 Can be used from the series of Arton (manufactured by JSR), Zeonex, and Zeonore (manufactured by Nippon Zeon). The polymer film is preferably formed by a solvent cast method.

  The polymer film is preferably formed by a solvent cast method. The thickness of the transparent support is preferably 20 to 500 μm, and more preferably 50 to 200 μm. In order to improve adhesion between the transparent support and the layer (adhesive layer, vertical alignment film or retardation layer) provided thereon, surface treatment (eg, glow discharge treatment, corona discharge treatment, ultraviolet light (UV) ) Treatment, flame treatment). An adhesive layer (undercoat layer) may be provided on the transparent support. Moreover, the average particle diameter is 10 to 100 nm in order to provide the transparent support or the long transparent support with slipperiness in the conveying process or to prevent the back surface and the surface from sticking after winding. It is preferable to use what formed the polymer layer which mixed the inorganic particle of about 5%-40% by solid content weight ratio by the application | coating or co-casting with the support body on the one side of the support body.

  In the above description, the example in which the optical compensation film having a laminate structure is used as the first and / or second optically anisotropic layer has been described in detail. However, the present invention is not limited to this embodiment. Of course, the first and / or second optically anisotropic layer may be composed of a stretched polymer film alone or only a liquid crystal film formed from a composition containing a liquid crystalline compound. Preferred examples of the stretched polymer film are the same as the preferred examples of the support that the optical compensation film has. Moreover, the preferable example of a liquid crystal film is the same as the preferable example of the optically anisotropic layer which the said optical compensation film has.

  One of the optical compensation films used as the first and second optically anisotropic layers has an optically anisotropic layer whose slow axis is neither parallel nor orthogonal to the longitudinal direction. Is preferred. The other may have an optically anisotropic layer whose slow axis is parallel or orthogonal to the longitudinal direction, or an optically anisotropic layer whose slow axis is neither parallel nor orthogonal You may have. When the polarizing plate of the present invention is disposed on the backlight side, at least the optical compensation film used as the optically anisotropic layer disposed at a position closer to the backlight has a slow axis parallel to the longitudinal direction. It is preferable to have an optically anisotropic layer in a direction that is not orthogonal. The angle of the slow axis of the optically anisotropic layer can be adjusted by the rubbing angle. By making the slow axis of the optically anisotropic layer not parallel or orthogonal to the longitudinal direction of the long support (for example, by forming an alignment film on the support, the surface of the alignment film In the direction of 2 to 88 ° with respect to the longitudinal direction), in the production of an elliptically polarizing plate to be described later, it becomes possible to bond with a long polarizing film and roll-to-roll. An elliptical polarizing plate with high axial angle accuracy and high productivity can be manufactured.

When the polarizing plate of the present invention is disposed on the backlight side and the second optical anisotropic layer is disposed closer to the backlight, the second optical anisotropic layer has a quarter wavelength. It preferably has a function as a plate, and the in-plane retardation is preferably 90 to 160 nm. The slow axis direction of at least one layer included in the second optically anisotropic layer is preferably neither 90 ° nor 0 ° with respect to the longitudinal direction. The direction of the slow axis of the optically anisotropic layer can be detected by measuring the retardation from the normal direction of the film using KOBRA 21ADH (manufactured by Oji Scientific Instruments). Specifically, the angle formed by the direction of the slow axis of at least one layer included in the second optically anisotropic layer and the longitudinal direction is 2 to 88 °, and is 5 to 85 °. More preferably.
When the second optically anisotropic layer includes an optically anisotropic layer in which the discotic liquid crystal compound is vertically aligned, or an optically anisotropic layer in which the rod-like liquid crystal compound is horizontally aligned, It can be suitably used as a phase difference plate such as a four-wavelength plate. When used as a half-wave plate, the in-plane retardation of the optically anisotropic layer is preferably 200 to 320 nm, more preferably 220 to 300 nm. When used as a quarter-wave plate, the in-plane retardation of the optically anisotropic layer is preferably 90 to 180 nm, and more preferably 100 to 170 nm. Further, the half-wave plate and the quarter-wave plate may be laminated so as to intersect with each other so that the slow axes thereof are not orthogonal or parallel to each other to form a broadband quarter-wave plate.
In order to control the refractive index in the thickness direction of the optically anisotropic layer, in addition to the optically anisotropic layer, an optically anisotropic layer in which a rod-like liquid crystal compound is vertically aligned and a discotic liquid crystal compound are horizontally aligned The optically anisotropic layer may be laminated, or an optically anisotropic layer formed by mixing a discotic liquid crystal compound and a rod-like liquid crystal compound may be included. Further, it may be controlled using a support having optical anisotropy.
When used as a retardation plate such as a half-wave plate or a quarter-wave plate, Nz is preferably −5 to 2 when Nz is defined by the following formula, −4.5 to 1 0.5 is more preferable, and -4 to 1.2 is most preferable.
Nz = 0.5 + Rth / Re
(Here, Re is the in-plane retardation value, Rth is the retardation value in the thickness direction)
It is preferable that the second optically anisotropic layer has such an optical characteristic because it improves the use efficiency of the booklight and contributes to the improvement in luminance.

The polarizing plate of the present invention may further have a third optically anisotropic layer, and the first optically anisotropic layer, the polarizing layer, the second optically anisotropic layer, and the third optically anisotropic layer. It is preferable to have the isotropic layer in this order. The third optically anisotropic layer preferably includes an optically anisotropic layer containing a liquid crystal compound, and the layer including the liquid crystal compound is more preferably a cholesrelic liquid crystal layer. Examples of the cholesteric liquid crystal layer include one that reflects either left-handed or right-handed circularly polarized light and transmits other light. The cholesteric liquid crystal layer can be formed by a polymerized layer of a liquid crystal polymer alignment product or a liquid crystal monomer alignment product. The cholesteric liquid crystal layer can also be formed of these composite layers. Details of the method for producing a long cholesteric liquid crystal film are described in paragraphs [0162] to [0163] and [0164] of Japanese Patent Application Laid-Open No. 2003-337221 and can also be used in the present invention.
The embodiment having the third optically anisotropic layer is preferably used as a polarizing plate on the backlight side, and in particular, disposed so that the third optically anisotropic layer is closest to the backlight. It is preferable to do this.

[Polarizing layer]
The polarizing plate of the present invention has a long polarizing layer. As the polarizing layer, any of an iodine polarizing film, a dye polarizing film using a dichroic dye, and a polyene polarizing film may be used. The iodine polarizing film and the dye polarizing film are generally produced using a polyvinyl alcohol film. The absorption axis of the polarizing film corresponds to the stretching direction of the film. Accordingly, the polarizing film stretched in the longitudinal direction (transport direction) has an absorption axis parallel to the longitudinal direction, and the polarizing film stretched in the lateral direction (perpendicular to the transport direction) is perpendicular to the longitudinal direction. Has an absorption axis.

  The preferable manufacturing method of the polarizing plate of this invention includes the process in which the 1st optically anisotropic layer, the polarizing layer, and the 2nd optically anisotropic layer are each laminated | stacked continuously in a elongate state. The long polarizing plate is cut according to the screen size of the liquid crystal display device used.

  If a linear polarizing film is used as the polarizing film and is configured as an elliptically polarizing plate in combination with a phase difference plate, the polarizing film can be easily incorporated into a reflective or transflective liquid crystal display device. It can also be used as an antireflection film for organic EL display devices. In addition, since a long cholesteric liquid crystal film prepared separately can be further laminated on the long elliptical polarizing plate, it is easy to manufacture a highly productive brightness enhancement film.

  The polarizing film generally has a protective film. In the present invention, as the first and / or second optically anisotropic layer, an optical having the optical compensation film, that is, a support made of a polymer film, and an optically anisotropic layer containing a liquid crystal compound. When a compensation film is used, the transparent support can function as a protective film for the polarizing layer. When a protective film for the polarizing layer is laminated separately from the support, it is preferable to use a cellulose ester film having high optical isotropy as the protective film.

[Liquid Crystal Display]
The liquid crystal display device of the present invention is not particularly limited as long as it has at least the polarizing plate. Any of a reflective type, a transflective type, a transmissive liquid crystal display device, and the like may be used. A liquid crystal display device generally includes a polarizing plate, a liquid crystal cell, and a retardation plate, a reflection layer, a light diffusion layer, a backlight, a front light, a light control film, a light guide plate, a prism sheet, a color filter, and the like as necessary. Although comprised from a member, in this invention, there is no restriction | limiting in particular except the point which makes it essential to use for the polarizing plate display surface side and / or backlight side of this invention. Moreover, there is no restriction | limiting in particular about the use position of the polarizing plate of this invention, Moreover, one place or multiple places may be sufficient. The liquid crystal cell is not particularly limited, and a general liquid crystal cell such as a liquid crystal layer sandwiched between a pair of transparent substrates provided with electrodes can be used. The transparent substrate constituting the liquid crystal cell is not particularly limited as long as the liquid crystal material constituting the liquid crystal layer is aligned in a specific alignment direction. Specifically, a transparent substrate in which the substrate itself has a property of orienting liquid crystals, a transparent substrate in which an alignment film having the property of orienting liquid crystals is provided, but the substrate itself lacks the alignment ability. Either can be used. Moreover, a well-known thing can be used for the electrode of a liquid crystal cell. Usually, it can be provided on the surface of the transparent substrate in contact with the liquid crystal layer, and when a substrate having an alignment film is used, it can be provided between the substrate and the alignment film. The material exhibiting liquid crystallinity for forming the liquid crystal layer is not particularly limited, and examples thereof include various ordinary low-molecular liquid crystalline compounds, high-molecular liquid crystalline compounds, and mixtures thereof that can constitute various liquid crystal cells. Moreover, a pigment | dye, a chiral agent, a non-liquid crystalline compound, etc. can also be added to these in the range which does not impair liquid crystallinity.

  In addition to the electrode substrate and the liquid crystal layer, the liquid crystal cell may include various components necessary for forming various types of liquid crystal cells described later. As the liquid crystal cell system, a TN (Twisted Nematic) system, a STN (Super Twisted Nematic) system, an ECB (Electrically Controlled Birefringence) system, an IPS (In-Plane Switching) system, a VA (In-Plane Switching) system, a VA (In-Plane Switching) system, a VA (In-Plane Switching) system, a VA (In-Plane Switching) system, Alignment), PVA (Patterned Vertical Alignment), OCB (Optically Compensated Birefringence), HAN (Hybrid Aligned Nematic), ASM crocell) method, halftone gray scale method, domain division method, or display method using ferroelectric liquid crystal or antiferroelectric liquid crystal. The driving method of the liquid crystal cell is not particularly limited, and a passive matrix method used for STN-LCD and the like, and an active matrix method using an active electrode such as a TFT (Thin Film Transistor) electrode and a TFD (Thin Film Diode) electrode, Any driving method such as a plasma addressing method may be used. A field sequential method that does not use a color filter may be used.

  The polarizing plate in the present invention is preferably used for a reflective, transflective, and transmissive liquid crystal display device. Moreover, the polarizing plate in this invention is preferably used also as a brightness improvement film | membrane by combining with a cholesteric liquid crystal film (for example, 3rd optically anisotropic layer). The reflective liquid crystal display device has a configuration in which a reflector, a liquid crystal cell, and a polarizing plate are laminated in this order. The retardation plate is disposed between the reflecting plate and the polarizing film (between the reflecting plate and the liquid crystal cell or between the liquid crystal cell and the polarizing film). The reflector may share the liquid crystal cell and the substrate. The transflective liquid crystal display device includes an electro-liquid crystal cell, a polarizing plate disposed closer to the viewer than the liquid crystal cell, and at least one retardation plate disposed between the polarizing plate and the liquid crystal cell. And at least a transflective layer disposed behind the liquid crystal layer as viewed from the viewer, and at least one retardation plate and a polarizing plate behind the transflective layer as viewed from the viewer. Have In this type of liquid crystal display device, it is possible to use both a reflection mode and a transmission mode by installing a backlight.

The liquid crystal cell is preferably in VA mode, OCB mode, IPS mode, or TN mode.
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) (2) Liquid crystal cell (SID97, Digest of tech. Papers (Preliminary Proceed) 28 (1997) 845 in which the VA mode is converted into a multi-domain (MVA mode) for widening 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 (Preliminary collections 58-59 of the Japan Liquid Crystal Society) (1998)) and (4) SURVAVAL mode liquid crystal cells (announced at LCD International 98).
The OCB mode liquid crystal cell is 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. Liquid crystal display devices using a bend alignment mode liquid crystal cell are disclosed in US Pat. Nos. 4,583,825 and 5,410,422. Since the rod-like liquid crystal molecules are symmetrically aligned at the upper and lower portions of the liquid crystal cell, the bend alignment mode liquid crystal cell has a self-optical compensation function. For this reason, this liquid crystal mode is also called an OCB (Optically Compensatory Bend) liquid crystal mode. The bend alignment mode liquid crystal display device has an advantage of high response speed.
In an IPS mode liquid crystal cell, rod-like liquid crystal molecules are aligned substantially parallel to the substrate, and the liquid crystal molecules respond in a planar manner when an electric field parallel to the substrate surface is applied. In the IPS mode, black is displayed when no electric field is applied, and the transmission axes of the pair of upper and lower polarizing plates are orthogonal. JP-A-10-54982, JP-A-11-202323, and JP-A-9-292522 are methods for reducing leakage light at the time of black display in an oblique direction and improving a viewing angle using an optical compensation sheet. No. 11-133408, No. 11-305217, No. 10-307291, and the like.
In a TN mode liquid crystal cell, rod-like liquid crystalline molecules are substantially horizontally aligned when no voltage is applied, and are twisted and aligned at 60 to 120 °. The TN mode liquid crystal cell is most frequently used as a color TFT liquid crystal display device, and is described in many documents.

  The first and / or second optically anisotropic layer preferably has a function as a viewing angle compensation layer of the liquid crystal display device. As the optically anisotropic layer, a layer that exhibits optical anisotropy by stretching a polymer film or orienting a liquid crystal compound can be used. The optically anisotropic layer preferably controls the refractive index anisotropy in the three-dimensional direction according to the mode of the liquid crystal display device used and the position where it is disposed. The refractive index anisotropy in the three-dimensional direction may be controlled by the molecular shape or orientation state of the liquid crystalline compound contained in the optically anisotropic layer, or may be a polymer film having optical anisotropy used as a support. It may be controlled, or may be controlled in combination.

One preferred embodiment of the first and / or second optically anisotropic layer includes a liquid crystal compound, and a discotic liquid crystal compound or a rod-like liquid crystal compound is preferably used. The alignment state of the liquid crystalline compound is preferably any of vertical alignment, horizontal alignment, hybrid alignment, tilt alignment, twist alignment, and helical alignment.
The vertical alignment of the discotic liquid crystalline compound means that the disc surface of the discotic liquid crystalline compound is substantially perpendicular to the film plane (the molecular symmetry axis is substantially parallel to the film plane). . The average inclination angle of the disc surface with respect to the film plane is preferably 70 to 90 °, more preferably 75 to 90 °, and most preferably 80 to 90 °.
The horizontal alignment of the discotic liquid crystalline compound means that the disc surface of the discotic liquid crystalline compound is substantially parallel to the film plane (the molecular symmetry axis is substantially perpendicular to the film plane). . The average inclination angle of the disc surface with respect to the film plane is preferably 0 to 20 °, more preferably 0 to 15 °, and most preferably 0 to 10 °.
The vertical alignment of the rod-like liquid crystalline compound means that the major axis (molecular symmetry axis) of the rod-like liquid crystalline compound is substantially perpendicular to the film plane. The average inclination angle of the major axis with respect to the film plane is preferably 70 to 90 °, more preferably 75 to 90 °, and most preferably 80 to 90 °.
The horizontal alignment of the rod-like liquid crystalline compound means that the long axis (molecular symmetry axis) of the rod-like liquid crystalline compound is substantially horizontal with respect to the film plane. The average inclination angle of the major axis with respect to the film plane is preferably 0 to 20 °, more preferably 0 to 15 °, and most preferably 0 to 10 °.

When the optically anisotropic layer contains a vertically aligned discotic liquid crystalline compound or a vertically aligned rod-like liquid crystalline compound, the optically anisotropic layer is suitable as a viewing angle compensation film for liquid crystal display devices such as IPS mode. Can be used.
When used as a viewing angle compensation film for an IPS mode liquid crystal display device, the in-plane retardation of the optically anisotropic layer in which the discotic liquid crystalline compound is vertically aligned is preferably 50 to 200 nm, and preferably 60 to 180 nm. More preferably, it is most preferable that it is 70-160 nm. Further, the retardation in the thickness direction of the optically anisotropic layer is preferably −100 to −25 nm, more preferably −90 to −30 nm, and most preferably −80 to −35 nm. preferable. A transparent support may also be included. The in-plane retardation of the support is preferably 0 to 20 nm, more preferably 0 to 10 nm, and most preferably 0 to 5 nm. Furthermore, the retardation in the thickness direction of the support is preferably 20 to 120 nm, and more preferably 40 to 100 nm.
When used as a viewing angle compensation film for an IPS mode liquid crystal display device, the in-plane retardation of the optically anisotropic layer in which the rod-like liquid crystalline compound is vertically aligned is preferably 0 to 10 nm, and preferably 0 to 5 nm. Is more preferable, and most preferably 0 to 3 nm. Furthermore, the retardation in the thickness direction of the optically anisotropic layer is preferably −400 to −80 nm, more preferably −360 to −100 nm, and most preferably −320 to −120 nm. preferable. A transparent support may also be included. The in-plane retardation of the support is preferably 20 to 150 nm, more preferably 30 to 130 nm, and most preferably 40 to 110 nm. Furthermore, the retardation in the thickness direction of the support is preferably from 100 to 300 nm, more preferably from 120 to 280 nm, and most preferably from 140 nm to 260 nm.

When the optically anisotropic layer contains a horizontally aligned discotic liquid crystalline compound or a horizontally aligned rod-shaped liquid crystalline compound, the optically anisotropic layer is a viewing angle compensation film for a liquid crystal display device such as a VA mode. Can be suitably used.
When used as a viewing angle compensation film for a VA mode liquid crystal display device, the in-plane retardation of the optically anisotropic layer in which the discotic liquid crystalline compound is horizontally aligned is preferably 0 to 10 nm, and preferably 0 to 5 nm. It is more preferable. Furthermore, the retardation in the thickness direction of the optically anisotropic layer is preferably 30 to 300 nm, and more preferably 40 to 200 nm. A transparent support may also be included. The in-plane retardation of the support is preferably 0 to 40 nm, and more preferably 0 to 20 nm. Furthermore, the retardation in the thickness direction of the support is preferably from 0 to 200 nm, and more preferably from 20 to 150 nm.
When used as a viewing angle compensation film for a VA mode liquid crystal display device, the in-plane retardation of the optically anisotropic layer in which the rod-like liquid crystalline compound is horizontally aligned is preferably 60 to 140 nm, and preferably 80 to 120 nm. Is more preferable. Furthermore, the retardation in the thickness direction of the optically anisotropic layer is preferably 30 to 70 nm, and more preferably 40 to 60 nm. A transparent support may also be included. The in-plane retardation of the support is preferably 0 to 20 nm, and more preferably 0 to 10 nm. Furthermore, the retardation in the thickness direction of the support is preferably from -30 to 30 nm, and more preferably from -20 nm to 20 nm.

When the optically anisotropic layer contains a discotic liquid crystalline compound and the disc surface of the discotic liquid crystalline compound is oriented with an inclination with respect to the film plane, the optically anisotropic layer has a TN mode and an OCB mode. It can be suitably used as a viewing angle compensation film for liquid crystal display devices such as ECB mode and HAN mode. In the thickness direction of the optically anisotropic layer, the discotic liquid crystalline compound may be tilted at a substantially uniform angle, or may be hybrid aligned at different tilt angles. Is more preferable.
When used as a viewing angle compensation film for liquid crystal display devices such as TN mode, OCB mode, ECB mode, and HAN mode, the in-plane retardation of the optically anisotropic layer containing the discotic liquid crystalline compound is 0 to 50 nm. It is preferably 15 to 45 nm, more preferably 20 to 40 nm. A transparent support may also be included. The in-plane retardation of the support is preferably 0 to 60 nm, and more preferably 0 to 50 nm. Furthermore, the thickness direction retardation of the support is preferably 40 to 300 nm, more preferably 60 nm to 200 nm.

  In the liquid crystal display device, the polarizing plate of the present invention functions as an elliptically polarizing plate or a circularly polarizing plate.

  The polarizing plate of the present invention is not limited to the above uses, and can be used for various other uses. For example, it can be used for an antireflection film such as a host-guest type liquid crystal display device, a touch panel, an electroluminescence (EL) element, a reflection type polarizing plate, 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.

[Example 1]
<Preparation of Second Optical Anisotropic Layer (Optical Compensation Film R1)>
<< Production of Cellulose Acetate Film (T1) >>
(Preparation of cellulose acetate solution)
The following composition was put into a mixing tank and stirred to dissolve each component to prepare a cellulose acetate solution A.
Composition of cellulose acetate solution A ――――――――――――――――――――――――――――――――――――
Cellulose acetate with an acetyl substitution degree of 2.94 100.0 parts by mass Methylene chloride (first solvent) 402.0 parts by mass Methanol (second solvent) 60.0 parts by mass ――――――――――――― ――――――――――――――――――――――

(Preparation of matting agent solution)
20 parts by mass of silica particles having an average particle diameter of 16 nm (AEROSIL R972, manufactured by Nippon Aerosil Co., Ltd.) and 80 parts by mass of methanol were mixed well for 30 minutes to obtain a silica particle dispersion. This dispersion was put into a disperser together with the following composition, and further stirred for 30 minutes or more to dissolve each component to prepare a matting agent solution.
Matting agent solution composition ――――――――――――――――――――――――――――――――――
Silica particle dispersion with an average particle size of 16 nm 10.0 parts by weight Methylene chloride (first solvent) 76.3 parts by weight Methanol (second solvent) 3.4 parts by weight Cellulose acetate solution A 10.3 parts by weight ―――――――――――――――――――――――――――――

(Preparation of additive solution)
The following composition was put into a mixing tank and stirred while heating to dissolve each component to prepare a cellulose acetate solution.
Additive solution composition ――――――――――――――――――――――――――――――
The following optical anisotropy reducing agent 49.3 parts by mass The following wavelength dispersion adjusting agent 4.9 parts by mass Methylene chloride (first solvent) 58.4 parts by mass Methanol (second solvent) 8.7 parts by mass Cellulose acetate Solution A 12.8 parts by mass ――――――――――――――――――――――――――――――

Optical anisotropy reducing agent

Chromatic dispersion modifier

94.6 parts by mass of the cellulose acetate solution A, 1.3 parts by mass of the matting agent solution, and 4.1 parts by mass of the additive solution were mixed after filtration, and cast using a band casting machine. The mass ratio of the compound that reduces optical anisotropy and the wavelength dispersion adjusting agent to cellulose acetate in the above composition was 12% and 1.2%, respectively. The film was peeled from the band with a residual solvent amount of 30% and dried at 140 ° C. for 40 minutes to produce a long cellulose acetate film T1 having a thickness of 80 μm.
The in-plane retardation (Re) of the obtained film was 1 nm (the slow axis was a direction perpendicular to the film longitudinal direction), and the thickness direction retardation (Rth) was −1 nm.

<< Production of optically anisotropic layer >>
After saponifying the surface of the produced long cellulose acetate film T1, an alignment film coating solution having the following composition was continuously applied with a # 14 wire bar. The film was formed by drying with warm air of 60 ° C. for 60 seconds and further with warm air of 100 ° C. for 120 seconds. Next, the formed film was continuously rubbed in a direction of 45 ° with respect to the longitudinal direction of the film to form an alignment film.
Composition of alignment film coating solution ――――――――――――――――――――――――――
The following modified polyvinyl alcohol 10 parts by weight Water 371 parts by weight Methanol 119 parts by weight Glutaraldehyde 0.5 parts by weight ――――――――――――――――――――――――――――

Modified polyvinyl alcohol

A coating solution containing a discotic liquid crystal compound having the following composition was continuously applied to the prepared alignment film with a # 4.0 wire bar. The conveyance speed (V) of the film was 20 m / min. In order to dry the solvent of the coating solution and to mature the orientation of the discotic liquid crystal compound, the coating liquid was heated with warm air of 100 ° C. for 30 seconds and further with warm air of 130 ° C. for 60 seconds. Subsequently, the alignment of the liquid crystal compound was fixed by UV irradiation to form an optically anisotropic layer.
Composition of coating solution for optically anisotropic layer ―――――――――――――――――――――――――――――――――
91 parts by mass of ethylene oxide-modified trimethylolpropane triacrylate (V # 360, manufactured by Osaka Organic Chemical Co., Ltd.) 9 parts by mass of a photopolymerization initiator (Irgacure 907, manufactured by Ciba Geigy) 3 parts by mass of the following discotic liquid crystalline compound Sensitizer (Kayacure DETX, manufactured by Nippon Kayaku Co., Ltd.) 1 part by mass The following pyridinium salt 0.5 part by mass The following fluoropolymer (A) 0.4 part by mass Methanol 30 parts by mass Methyl ethyl ketone 165 parts by mass ―――――――――――――――――――――――――――――――

Discotic liquid crystalline compounds

Fluoropolymer (A)

Pyridinium salt

Subsequently, the surface of the cellulose acetate film T1 opposite to the surface on which the optically anisotropic layer was formed was continuously saponified to produce an optical compensation film R1.
Using an automatic birefringence meter (KOBRA-21ADH, manufactured by Oji Scientific Instruments Co., Ltd.), Re (0), Re (40) and Re (−40) at 589 nm of the optical compensation film R1 were measured. They were 121.6 nm, 113.8 nm, and 113.7 nm, respectively. From these results, the average inclination angle of the disc surface of the discotic liquid crystalline molecules with respect to the film surface was 90 °, and it was confirmed that the discotic liquid crystal was aligned perpendicular to the film surface. The direction of the slow axis was parallel to the rubbing direction of the alignment film, and the angle formed with the longitudinal direction of the support was 45 °.
The produced long optical compensation film R1 was used as the second optically anisotropic layer.

<Production of third optically anisotropic layer>
A long cholesteric liquid crystal film was prepared and used as the third optically anisotropic layer (C1) in the same manner as described in Examples of JP-A-2003-337221.

<Preparation of first optical anisotropic layer (optical compensation film F1)>
<< Production of Cellulose Acetate Film (T2) >>
The following composition was put into a mixing tank and stirred while heating to dissolve each component to prepare a cellulose acetate solution.
(Cellulose acetate solution composition)
Cellulose acetate having an acetylation degree of 60.7 to 61.1% 100 parts by weight Triphenyl phosphate (plasticizer) 7.8 parts by weight Biphenyl diphenyl phosphate (plasticizer) 3.9 parts by weight Methylene chloride (first solvent) 336 parts by weight Methanol (second solvent) 29 parts by mass 1-butanol (third solvent) 11 parts by mass

  In another mixing tank, 16 parts by mass of the following retardation increasing agent (A), 92 parts by mass of methylene chloride and 8 parts by mass of methanol were added and stirred while heating to prepare a retardation increasing agent solution. A dope was prepared by mixing 474 parts by mass of the cellulose acetate solution with 25 parts by mass of the retardation increasing agent solution and stirring sufficiently. The addition amount of the retardation increasing agent was 6.0 parts by mass with respect to 100 parts by mass of cellulose acetate.

Retardation increasing agent (A)

  The obtained dope was cast using a band stretching machine. After the film surface temperature on the band reaches 40 ° C., the film is dried with warm air of 70 ° C. for 1 minute, and the film is dried from the band with 140 ° C. of drying air for 10 minutes. A cellulose acetate film T2 was prepared.

  The obtained cellulose acetate film T2 had a width of 1340 mm and a thickness of 80 μm. The in-plane retardation (Re) was 8 nm and the thickness direction retardation (Rth) was 78 nm.

<< Formation of optically anisotropic layer containing discotic liquid crystal compound >>
The surface of the cellulose acetate film T2 was saponified in the same manner as in the formation of the alignment film in the production of the second optically anisotropic layer, and then the alignment film was formed. The alignment film surface was continuously rubbed so that the angle formed by the longitudinal direction of the film and the rotation axis of the rubbing roller was at right angles.

A coating solution containing a discotic liquid crystal compound having the following composition was continuously applied to the prepared alignment film with a wire bar of # 3.6. The conveyance speed of the film was 20 m / min. In order to dry the solvent of the coating solution and to mature the orientation of the discotic liquid crystal compound, the coating liquid was heated with warm air at 100 ° C. for 30 seconds and further with warm air at 130 ° C. for 120 seconds. Subsequently, the alignment of the liquid crystal compound was fixed by UV irradiation to form an optically anisotropic layer.
Composition of coating solution for optically anisotropic layer ―――――――――――――――――――――――――――――――――――
91 parts by mass of the above discotic liquid crystalline compound, ethylene oxide-modified trimethylolpropane triacrylate (V # 360, manufactured by Osaka Organic Chemical Co., Ltd.) 9 parts by mass of a photopolymerization initiator (Irgacure 907, manufactured by Ciba Geigy) 3 parts by mass Sensitizer (Kayacure DETX, manufactured by Nippon Kayaku Co., Ltd.) 1 part by weight cellulose acetate butyrate (CAB551-0.2, manufactured by Eastman Chemical Co., Ltd.) 2.0 parts by weight cellulose acetate butyrate (CAB531-1, yeast) Man Chemical Co., Ltd.) 0.5 parts by mass of fluoroaliphatic group-containing copolymer (Megafac F780, manufactured by Dainippon Ink & Co., Ltd.) 1.3 parts by mass of methyl ethyl ketone 207 parts by mass ―――――――――――――――――――――――――

Subsequently, the surface of the cellulose acetate film opposite to the surface on which the optically anisotropic layer was formed was continuously saponified to produce an optical compensation film F1.
In the produced optically anisotropic layer, the discotic liquid crystalline compound has an angle (tilt angle) formed by the disc surface and the transparent protective film increasing from the alignment film toward the air interface, and an average tilt angle of 37 °. Hybrid orientation. The optically anisotropic layer was a uniform film free from defects such as schlieren. The tilt angle is measured using an automatic birefringence meter (MKOBRA 21ADH, manufactured by Oji Scientific Instruments), the retardation is measured by changing the observation angle, and is assumed to be a refractive index ellipsoid model. It was calculated by the method described in “Birrefringence Compensation Films SID98 DIGEST”. Furthermore, when only the optically anisotropic layer was peeled from the sample and the average direction of the molecular symmetry axis of the optically anisotropic layer was measured, it was 90 ° with respect to the longitudinal direction of the film.
The produced long optical compensation film F1 was used as the first optical anisotropic layer.

<Preparation of polarizing plate>
A roll-shaped polyvinyl alcohol film having a thickness of 80 μm continuously dyed in an aqueous iodine solution was stretched 5 times in the transport direction and dried to obtain a long polarizing film. The surface on which the optically anisotropic layer containing the discotic liquid crystal compound of the prepared second optically anisotropic layer (R1) is not formed on one surface of the polarizing film is formed on the other surface. The surface of the first optically anisotropic layer (F1) on which the optically anisotropic layer containing the discotic liquid crystal compound is not formed is continuously bonded using a polyvinyl alcohol-based adhesive, and the first optically anisotropic layer is bonded. A long polarizing plate was produced in which an isotropic layer, a polarizing film, and a second optically anisotropic layer were laminated in this order. The absorption axis of the polarizing film is parallel to the longitudinal direction of the film, the slow axis of the first optically anisotropic layer F1 is orthogonal to the polarizing plate absorption axis, and the second optically anisotropic layer R1 The angle formed between the slow axis and the polarizing plate absorption axis was 45 °. Subsequently, the polarizing plate and the produced long third optically anisotropic layer (C1) were continuously bonded in a long state. At this time, the third optically anisotropic layer (C1) was bonded so as to be on the second optically anisotropic layer (R1) side. In this way, the first optical anisotropic layer (F1), the polarizing film, the second optical anisotropic layer (R1), and the third optical anisotropic layer (C1) were laminated in this order. A long polarizing plate (P1) was produced.

[Example 2]
<Production of first optical anisotropic layer (optical compensation film F2)>
<< Production of Cellulose Acetate Film (T3) >>
The following composition was put into a mixing tank and stirred while heating to dissolve each component to prepare a cellulose acetate solution.
<Cellulose acetate solution composition>
Cellulose acetate having an acetylation degree of 60.9% 100 parts by weight Triphenyl phosphate (plasticizer) 7.8 parts by weight Biphenyl diphenyl phosphate (plasticizer) 3.9 parts by weight Methylene chloride (first solvent) 300 parts by weight Methanol (second solvent) 45 parts by weight Dye (360FP, manufactured by Sumika Finechem Co., Ltd.) 0.0009 parts by weight

In another mixing tank, 16 parts by mass of the following retardation increasing agent, 80 parts by mass of methylene chloride and 20 parts by mass of methanol were added and stirred while heating to prepare a retardation increasing agent solution.
To 464 parts by mass of the cellulose acetate solution having the above composition, 36 parts by mass of the retardation increasing agent (B) solution and 1.1 parts by mass of silica fine particles (R972, manufactured by Irosil) were mixed, and thoroughly stirred to prepare a dope. . The addition amount of the retardation increasing agent was 5.0 parts by mass with respect to 100 parts by mass of cellulose acetate. Moreover, the addition amount of silica fine particles was 0.15 mass part with respect to 100 mass parts of cellulose acetate.

Retardation increasing agent (B)

The obtained dope was cast using a casting machine having a band having a width of 2 m and a length of 65 m. After the film surface temperature on the band reached 40 ° C., it was dried for 1 minute, peeled off, and then stretched 28% in the width direction using a tenter with a drying air of 140 ° C. Then, it dried for 20 minutes with 135 degreeC dry air, and produced the cellulose acetate film T3 whose residual solvent amount is 0.3 mass%.
The obtained cellulose acetate film T3 had a width of 1340 mm and a thickness of 92 μm. The in-plane retardation (Re) was 38 nm and the thickness direction retardation (Rth) was 175 nm.

<< Formation of optically anisotropic layer containing discotic liquid crystal compound >>
The surface of the cellulose acetate film T3 was saponified in the same manner as in the formation of the alignment film in the production of the second optically anisotropic layer of Example 1, and then the alignment film was formed. The alignment film surface was continuously rubbed so that the angle formed by the longitudinal direction of the film and the rotation axis of the rubbing roller was 45 °.

A coating solution containing a discotic liquid crystal compound having the following composition was continuously applied onto the prepared alignment film with a wire bar of # 3.2. The conveyance speed of the film was 20 m / min. In order to dry the solvent of the coating solution and to mature the orientation of the discotic liquid crystal compound, the coating liquid was heated with warm air at 100 ° C. for 30 seconds and further with warm air at 130 ° C. for 120 seconds. Subsequently, the alignment of the liquid crystal compound was fixed by UV irradiation to form an optically anisotropic layer.
Composition of coating solution for optically anisotropic layer ―――――――――――――――――――――――――――――――――――
91 parts by mass of the above discotic liquid crystalline compound, ethylene oxide-modified trimethylolpropane triacrylate (V # 360, manufactured by Osaka Organic Chemical Co., Ltd.) 9 parts by mass of a photopolymerization initiator (Irgacure 907, manufactured by Ciba Geigy) 3 parts by mass Sensitizer (Kayacure DETX, manufactured by Nippon Kayaku Co., Ltd.) 1 part by weight Cellulose acetate butyrate (CAB531-1, manufactured by Eastman Chemical Co.) 1 part by weight fluoroaliphatic group-containing copolymer (Megafac F780, large (Made by Nippon Ink Co., Ltd.) 1.3 parts by mass methyl ethyl ketone 227 parts by mass ―――――――――――――――――――――――――――――――――― -

Subsequently, the surface of the cellulose acetate film opposite to the surface on which the optically anisotropic layer was formed was continuously saponified to produce an optical compensation film F2.
In the produced optically anisotropic layer, the discotic liquid crystalline compound has an angle (tilt angle) between the disc surface and the transparent protective film increasing from the alignment film toward the air interface, and an average tilt angle of 32 °. Hybrid orientation. Furthermore, when only the optically anisotropic layer was peeled from the sample and the average direction of the molecular symmetry axis of the optically anisotropic layer was measured, it was 45 ° with respect to the longitudinal direction of the film.
The produced long optical compensation film F2 was used as the first optical anisotropic layer.

<Preparation of polarizing plate>
In the same manner as in Example 1, a long second optically anisotropic layer (optical compensation film R1) and a third optically anisotropic layer (cholesteric liquid crystal film C3) were produced. In preparation of the polarizing plate of Example 1, instead of using F1 as the first optical anisotropic layer, a long polarizing plate (P2) was prepared using F2. In this way, the first optical anisotropic layer (F2), the polarizing film, the second optical anisotropic layer (R1), and the third optical anisotropic layer (C1) were laminated in this order. A long polarizing plate (P2) was produced.

[Example 3]
<Preparation of first optically anisotropic layer (optical compensation film F3)>
<< Production of Cellulose Acylate Film (T4) >>
The following composition was put into a mixing tank and stirred while heating to dissolve each component to prepare a cellulose acetate solution.

──────────────────────────────────
Cellulose acetate solution composition ──────────────────────────────────
Cellulose acetate having an acetylation degree of 60.9% (degree of polymerization: 300, Mn / Mw = 1.5) 100 parts by weight Triphenyl phosphate (plasticizer) 7.8 parts by weight Biphenyl diphenyl phosphate (plasticizer) 3.9 parts by weight Methylene chloride (first solvent) 300 parts by weight Methanol (second solvent) 54 parts by weight 1-butanol (third solvent) 11 parts by weight ──────────────────── ──────────────

  In another mixing tank, 16 parts by mass of the above-mentioned retardation increasing agent B, 8 parts by mass of the following retardation increasing agent C, 0.28 parts by mass of silicon dioxide fine particles (average particle size: 0.1 μm), methylene chloride 80 parts by mass and 20 parts by mass of methanol were added and stirred while heating to prepare a retardation increasing agent solution (and a fine particle dispersion). The dope was prepared by mixing 45 parts by mass of the retardation increasing agent solution with 474 parts by mass of the cellulose acetate solution and stirring sufficiently.

Retardation raising agent C

The obtained dope was cast using a casting machine having a band having a width of 2 m and a length of 65 m. A film having a residual solvent amount of 15% by mass was stretched transversely at a stretch ratio of 20% using a tenter under the conditions of 130 ° C., held at 50 ° C. for 30 seconds with the stretched width, and then clipped to remove cellulose. An acetate film was prepared. The residual solvent amount at the end of stretching was 5% by mass, and further dried to prepare a cellulose acetate film (T4) with the residual solvent amount being less than 0.1% by mass. In addition, Tg of the used cellulose acylate is 140 degreeC.
The obtained cellulose acetate film T4 had a width of 1340 mm and a thickness of 88 μm. The in-plane retardation (Re) was 70 nm, and the thickness direction retardation (Rth) was 210 nm.

<< Formation of optically anisotropic layer containing rod-like liquid crystal compound >>
The surface of the cellulose acetate film T4 was saponified in the same manner as in the formation of the alignment film in the production of the second optically anisotropic layer of Example 1, and then the alignment film was formed. However, the rubbing process was not performed.

  A coating solution containing a rod-like liquid crystal compound having the following composition was continuously applied onto the prepared alignment film with a # 5.0 wire bar. The conveyance speed of the film was 20 m / min. The solvent was dried in the step of continuously heating from room temperature to 90 ° C., and then heated in a 90 ° C. drying zone for 90 seconds to align the rod-like liquid crystal compound. Subsequently, the alignment of the liquid crystal compound was fixed by UV irradiation to form an optically anisotropic layer.

――――――――――――――――――――――――――――――――――――
Composition of coating liquid containing rod-shaped liquid crystal compound ――――――――――――――――――――――――――――――――――――
The following rod-like liquid crystalline compound 100 parts by mass Photopolymerization initiator (Irgacure 907, manufactured by Ciba Geigy) 3 parts by mass Sensitizer (Kayacure DETX, manufactured by Nippon Kayaku Co., Ltd.) 1 part by mass The following fluoropolymer 0. 4 parts by weight The following pyridinium salts 1 part by weight Methyl ethyl ketone 198 parts by weight ――――――――――――――――――――――――――――――――――――

Rod-like liquid crystalline compound

Fluoropolymer

Pyridinium salt

Subsequently, the surface of the cellulose acetate film opposite to the surface on which the optically anisotropic layer was formed was continuously saponified to produce an optical compensation film F3.
Only the optically anisotropic layer containing the rod-like liquid crystalline compound was peeled from the produced optical compensation film F3, and the optical characteristics were measured. Re of only the optically anisotropic layer measured at a wavelength of 550 nm was 0 nm, and Rth was −280 nm. It was also confirmed that an optically anisotropic layer in which rod-like liquid crystal molecules were aligned substantially perpendicular to the film surface was formed.
The produced long optical compensation film F3 was used as the first optically anisotropic layer.

<Preparation of polarizing plate>
In the same manner as in Example 1, a long second optical anisotropic layer (optical compensation film R1) and a third optical anisotropic layer (cholesteric liquid crystal film C3) were produced. In the production of the polarizing plate of Example 1, a long polarizing plate (P3) was produced using F3 instead of using F1 as the first optical anisotropic layer. In this way, the first optical anisotropic layer (F3), the polarizing film, the second optical anisotropic layer (R1), and the third optical anisotropic layer (C1) were laminated in this order. A long polarizing plate (P3) was produced.

[Example 4]
<Production of first optical anisotropic layer (optical compensation film F4)>
In the same manner as in Example 3, a cellulose acylate film (T4) was produced. The obtained cellulose acetate film T4 had a width of 1340 mm and a thickness of 88 μm. The in-plane retardation (Re) was 70 nm, and the thickness direction retardation (Rth) was 210 nm.
Both surfaces of this film were saponified to produce a long optical compensation film (first optical anisotropic layer) F4.

<Preparation of polarizing plate>
In the same manner as in Example 1, a long second optically anisotropic layer (optical compensation film R1) and a third optically anisotropic layer (cholesteric liquid crystal film C3) were produced. In the production of the polarizing plate of Example 1, a long polarizing plate (P4) was produced using F4 instead of using F1 as the first optical anisotropic layer. In this way, the first optical anisotropic layer (F4), the polarizing film, the second optical anisotropic layer (R1), and the third optical anisotropic layer (C1) were laminated in this order. A long polarizing plate (P4) was produced.

[Example 5]
<Preparation of second optical anisotropic layer (optical compensation film R2)>
<< Formation of optically anisotropic layer A >>
A cellulose acylate film (T1) was produced in the same manner as in Example 1, and after the surface was saponified, a diluted solution of an alignment film (polymer having the following structural formula) was continuously applied to one side of the transparent support to obtain a thickness. An alignment film of 0.5 μm was formed. Subsequently, the rubbing process was continuously performed in a direction of 15 ° with respect to the longitudinal direction of the transparent support.

Polymer for alignment film

On the formed alignment film, a coating solution having the following composition is continuously applied using a bar coater, dried and heated (alignment aging), and further irradiated with ultraviolet rays to a thickness of 2.4 μm.
The optically anisotropic layer A was formed. The optically anisotropic layer A had a slow axis in the direction of 75 ° with respect to the longitudinal direction of the transparent support. The retardation value at 550 nm was 264 nm.
Composition of coating solution for optically anisotropic layer ――――――――――――――――――――――――――――――――――――
100 parts by mass of the above rod-like liquid crystalline compound Photopolymerization initiator (Irgacure 907, manufactured by Ciba Geigy) 3 parts by mass Sensitizer (Kayacure DETX, manufactured by Nippon Kayaku Co., Ltd.) 1 part by mass The following polymer 3 parts by mass Methyl ethyl ketone 197 parts by mass ――――――――――――――――――――――――――――――――――――

polymer

<< Formation of optically anisotropic layer B >>
The surface of the optically anisotropic layer A thus formed was rubbed. At this time, the rubbing treatment was performed so as to be 60 ° with respect to the slow axis of the optically anisotropic layer A and 15 ° with respect to the longitudinal direction of the support. Next, a coating liquid having the following composition was continuously applied using a bar coater, dried and heated (alignment aging), and further irradiated with ultraviolet rays to form an optically anisotropic layer B having a thickness of 1.2 μm. . The slow axis direction of the optically anisotropic layer B was parallel to the rubbing direction (15 ° with respect to the longitudinal direction), and the retardation value at 550 nm was 132 nm.
Composition of coating solution for optically anisotropic layer ――――――――――――――――――――――――――――――――――――
100 parts by mass of the above rod-like liquid crystalline compound Photopolymerization initiator (Irgacure 907, manufactured by Ciba Geigy) 3 parts by mass Sensitizer (Kayacure DETX, manufactured by Nippon Kayaku Co., Ltd.) 1 part by mass The above polymer 1 part by mass of fluoro Aliphatic group-containing copolymer (Megafac F780, manufactured by Dainippon Ink Co., Ltd.) 1.3 parts by weight Methyl ethyl ketone 197 parts by weight ――――――――――――――――――――― ―――――――――――――――

  Subsequently, the surface of the cellulose acetate film T1 opposite to the surface on which the optically anisotropic layer was formed was continuously saponified to produce an optical compensation film R2. This long optical compensation film R2 was used as the second optical anisotropic layer.

<Preparation of polarizing plate>
In the same manner as in Example 1, a long first optically anisotropic layer (optical compensation film F1) and a third optically anisotropic layer (cholesteric liquid crystal film C3) were produced. In the production of the polarizing plate of Example 1, instead of using R1 as the second optically anisotropic layer, a long polarizing plate (P5) was produced using R2. In this way, the first optical anisotropic layer (F1), the polarizing film, the second optical anisotropic layer (R2), and the third optical anisotropic layer (C1) were laminated in this order. A long polarizing plate (P5) was produced.

[Example 6]
<Production of Second Optically Anisotropic Layer (Optical Compensation Film R3)>
<< Production of optically anisotropic layer >>
(Synthesis of discotic liquid crystal compound DLB-1)
Synthesized according to the following scheme.

(Synthesis of DLB-1A)
2.5 g of 3-cyanobenzoic acid chloride was dissolved in 20 mL of tetrahydrofuran (THF), 1.3 mL of 5-chloro-1-pentanol and 3.0 mL of diisopropylethylamine (DIPEA) were added, and the mixture was stirred at room temperature for 1 hour. Water was added to the reaction mixture, and the mixture was extracted with ethyl acetate. The organic layer was concentrated under reduced pressure. The residue was dissolved in 100 mL of methanol (MeOH), and 2.8 mL of 50% hydroxylamine solution was added, followed by stirring at 40 ° for 1 hour. After cooling, water was added to the reaction solution, and the precipitated crystals were separated by filtration and dried to obtain 3.4 g of DLB-1A.

(Synthesis of DLB-1B)
DLB-1A (3.4 g) was dissolved in dimethylacetamide (DMAc) (10 mL), pyridine (1.2 mL) and trimesic acid chloride (1.2 g) were added, and the mixture was stirred at 120 ° for 1 hour. After cooling, methanol was added, and the precipitated crystals were collected by filtration and dried to obtain 3.9 g of DLB-1B.

(Synthesis of DLB-1)
DLB-1B 3.9g was dissolved in dimethylacetamide 50mL, potassium carbonate 3.7g, sodium iodide 2.0g, and acrylic acid 1.9mL were added, and it stirred at 100 degrees for 3 hours. Water was added to the reaction solution, and the precipitated crystals were collected by filtration. Purification was performed by column chromatography to obtain 3.0 g of DLB-1. The NMR spectrum of the obtained DLB-1 is as follows.

¹ H-NMR (solvent: CDCl ₃ , standard: tetramethylsilane) δ (ppm): 1.60 (6H, m), 1.80-1.90 (12H, m), 4.25 (6H, t ), 4.45 (6H, t), 5.80 (3H, dd), 6.15 (3H, dd), 6.40 (3H, dd), 7.65 (3H, t), 8.25. (3H, d), 8.45 (3H, d), 8.90 (3H, s), 9.30 (3H, s).

  When the phase transition temperature of the obtained DLB-1 was measured by texture observation with a polarizing microscope, the temperature was increased and the crystal phase changed to a discotic nematic liquid crystal phase around 86 ° C. It turned into a phase. That is, it was found that DLB-1 exhibits a discotic nematic liquid crystal phase between 86 ° C. and 142 ° C.

  After the surface of the long cellulose acetate film T1 produced in Example 1 was saponified, a modified polyvinyl alcohol alignment film was formed in the same manner as in Example 1. Next, the formed film was continuously rubbed in a direction of 45 ° with respect to the longitudinal direction of the film.

A coating solution containing a discotic liquid crystal compound DLB-1 having the following composition was continuously applied onto the prepared alignment film with a # 3.0 wire bar. The conveyance speed (V) of the film was 20 m / min. In order to dry the solvent of the coating solution and to mature the orientation of the discotic liquid crystal compound, the coating liquid was heated with warm air at 100 ° C. for 30 seconds and further with warm air at 120 ° C. for 60 seconds. Subsequently, UV irradiation was performed at 90 ° C. to fix the orientation of the liquid crystal compound and form an optically anisotropic layer.
Composition of coating solution for optically anisotropic layer ―――――――――――――――――――――――――――――――――
Discotic liquid crystal compound DLB-1 100 parts by mass Photopolymerization initiator (Irgacure 907, manufactured by Ciba Geigy) 3 parts by mass sensitizer (Kayacure DETX, manufactured by Nippon Kayaku Co., Ltd.) 1 part by mass Used in Example 3 Pyridinium salt 0.5 parts by mass The following fluoropolymer (B) 0.4 parts by mass Methanol 30 parts by mass Methyl ethyl ketone 280 parts by mass ――――――――――――――――――――― ―――――――――――

Fluoropolymer (B)

Subsequently, the surface of the cellulose acetate film T1 opposite to the surface on which the optically anisotropic layer was formed was continuously saponified to produce an optical compensation film R3.
Using an automatic birefringence meter (KOBRA-21ADH, manufactured by Oji Scientific Instruments), Re (0), Re (40) and Re (-40) at 589 nm of the optical compensation film R3 were measured. They were 122.5 nm, 114.0 nm, and 114.1 nm, respectively. From these results, the average inclination angle of the disc surface of the discotic liquid crystalline molecules with respect to the film surface was 90 °, and it was confirmed that the discotic liquid crystal was aligned perpendicular to the film surface. The direction of the slow axis was parallel to the rubbing direction of the alignment film, and the angle formed with the longitudinal direction of the support was 45 °.
The produced long optical compensation film R3 was used as the second optically anisotropic layer.

<Preparation of polarizing plate>
In the same manner as in Example 1, a long first optically anisotropic layer (optical compensation film F1) and a third optically anisotropic layer (cholesteric liquid crystal film C3) were produced. In preparation of the polarizing plate of Example 1, instead of using optical compensation film R1 as a 2nd optically anisotropic layer, the elongate polarizing plate (P6) was produced using optical compensation film R3. In this way, the first optical anisotropic layer (F1), the polarizing film, the second optical anisotropic layer (R3), and the third optical anisotropic layer (C1) were laminated in this order. A long polarizing plate (P6) was produced.

[Comparative example]
<Preparation of second optically anisotropic layer>
A long polycarbonate film was longitudinally uniaxially stretched in the longitudinal direction to produce a stretched film RH1 having a thickness of 60 μm. Re (0), Re (40) and Re (-40) at 589 nm of the second optically anisotropic layer (RH1) were measured and found to be 138.0 nm, 152.6 nm and 152.5 nm, respectively. . The direction of the slow axis of the second optically anisotropic layer (RH1) was parallel to the longitudinal direction.
The produced elongated stretched film RH1 was cut into a size of 20 inches and then used as a second optical anisotropic layer.

<Production of third optically anisotropic layer>
A cholesteric liquid crystal film C3 was produced in the same manner as in Example 1. The produced long cholesteric liquid crystal film C3 was cut in a size of 20 inches parallel to the longitudinal direction, and then used as a third optical anisotropic layer.

<Preparation of polarizing plate>
In the same manner as in Example 1, a long polarizing film was prepared, a long optical compensation film F1 (first optical anisotropic layer) was formed on one side, and a cellulose triacetate film was saponified on the other side. (Fujitack TD80UL, manufactured by Fuji Photo Film Co., Ltd.) was continuously bonded using a polyvinyl alcohol adhesive to produce a polarizing plate. This polarizing plate was cut into a size of 20 inches at an angle of 45 ° with respect to the longitudinal direction.
The cut second optically anisotropic layer (RH1) is bonded to the surface of the cut polarizing plate on the Fujitac side, and the separately cut third optically anisotropic layer (C3) is secondly cut. A polarizing plate (PH1) having a size of 20 inches was produced by bonding to the optically anisotropic layer (RH1) side.

  In the production of the polarizing plate (PH1), polarizing plates PH2, PH3, and PH4 are respectively used in the same manner as in the comparative example, except that F1, F3, and F4 are used instead of F1 as the first optically anisotropic layer. Was made.

  Twenty long polarizing plates (P1 to P6) of Examples 1 to 6 were cut to a size of 20 inches. In all of the polarizing plates (P1 to P6) of the examples, the variation in the angle between the polarization axis and the slow axis of each optically anisotropic layer is different from that of the 20 polarizing plates (PH1 to PH4) prepared in the comparative example. It was very small. In addition, in the manufacturing process of the polarizing plate of the comparative example, cutting loss was large and foreign matter was mixed in, whereas in the polarizing plate of the example, there was no cutting loss and foreign matter mixed, resulting in a very high yield. It was.

[Example 7]
<Production of TN mode liquid crystal display device>
<Preparation of counter polarizing plate>
A roll-shaped polyvinyl alcohol film having a thickness of 80 μm continuously dyed in an aqueous iodine solution was stretched 5 times in the transport direction and dried to obtain a long polarizing film. A saponified commercial cellulose acetate film (Fujitac TD80UL, manufactured by Fuji Photo Film Co., Ltd.) was applied to one surface of the polarizing film, and the first optically anisotropic layer (F1) prepared above was formed on the other surface. The surface on which the optically anisotropic layer containing the discotic liquid crystal compound is not formed is continuously bonded using a polyvinyl alcohol-based adhesive, and used as a counter polarizing plate (PT1) for the polarizing plate (P1). Was made.

(Production of liquid crystal display device)
The liquid crystal cell has a cell gap (d) of 5 μm, a liquid crystal material having a positive dielectric constant anisotropic layer is sealed between the substrates by drop injection, and Δnd is 420 nm (Δn is the refractive index anisotropy of the liquid crystal material) . In addition, the twisted angle of the liquid crystal cell liquid crystal layer is 90 °, and the prepared polarizing plates (P1 and PT1) are interposed via an adhesive so that the polarizing plate absorption axis is aligned with the upper and lower substrate rubbing directions of the liquid crystal cell. And pasted together. At this time, P1 was arranged on the polarizing plate on the backlight side, and PT1 was arranged on the viewer side. Note that both P1 and PT1 were bonded so that the first optical anisotropic layer was on the cell side.

  A rectangular wave voltage of 60 Hz was applied to the liquid crystal display device thus manufactured. A normally white mode with a white display of 1.5 V and a black display of 5.6 V was set. Display characteristics were evaluated using a measuring machine (EZ-Contrast 160D, manufactured by ELDIM).

[Example 8]
<Production of bend alignment mode liquid crystal display device>
(Preparation of counter polarizing plate)
In the production of the counter polarizing plate of Example 1, instead of using F1 as the first optical anisotropic layer, a long polarizing plate (PT2) using F2 as the counter polarizing plate of the polarizing plate (P2) is used. ) Was produced.

(Production of liquid crystal display device)
A polyimide film was provided as an alignment film on a glass substrate with an ITO electrode, and the alignment film was rubbed. The obtained two glass substrates were faced to each other so that the rubbing directions were parallel to each other, and the cell gap was set to 4.5 μm. A bend-aligned liquid crystal cell was prepared by injecting a liquid crystal compound (ZLI1132, manufactured by Merck & Co., Inc.) having a Δn of 0.1396 into the cell gap.
The produced polarizing plates (P2 and PT2) were attached via an adhesive so as to sandwich the produced bend alignment cell. At this time, both P2 and PT2 are bonded so that the first optically anisotropic layer is on the cell side, and the rubbing direction when forming the optically anisotropic layer containing the discotic liquid crystal and the rubbing direction of the liquid crystal cell And are arranged so as to be antiparallel. Further, P2 was arranged on the polarizing plate on the backlight side, and PT2 was arranged on the viewer side.

  A rectangular wave voltage of 55 Hz was applied to the manufactured liquid crystal cell. A normally white mode with a white display of 2V and a black display of 5V was adopted. Display characteristics were evaluated using a measuring machine (EZ-Contrast 160D, manufactured by ELDIM).

[Example 9]
<Production of IPS mode liquid crystal display device>
(Preparation of counter polarizing plate)
A roll-shaped polyvinyl alcohol film having a thickness of 80 μm continuously dyed in an aqueous iodine solution was stretched 5 times in the transport direction and dried to obtain a long polarizing film. One surface of this polarizing film was saponified on cellulose acetate film T1 of Example 1, and the other surface was saponified on a commercially available cellulose acetate film (Fujitac TD80UL, manufactured by Fuji Photo Film Co., Ltd.) with a polyvinyl alcohol system. The polarizing plate (PT3) used as an opposing polarizing plate of the said polarizing plate (P3) was continuously bonded together using the adhesive agent.

(Production of liquid crystal display device)
On one glass substrate, electrodes were arranged so that the distance between adjacent electrodes was 20 μm, and a polyimide film was provided as an alignment film thereon, and a rubbing treatment was performed. A polyimide film was provided on one surface of a separately prepared glass substrate, and a rubbing treatment was performed to obtain an alignment film. The two glass substrates were laminated and bonded so that the alignment films were opposed to each other, the cell gap (d) was 3.9 μm, and the rubbing directions of the two glass substrates were parallel. Next, a nematic liquid crystal composition having a refractive index anisotropy (Δn) of 0.0769 and a dielectric anisotropy (Δε) of 4.5 was sealed to produce a horizontally aligned liquid crystal cell. The value of Δn · d of the liquid crystal layer was 300 nm.

Polarizing plates (P3 and PT3) were bonded to the upper and lower glass substrates of the horizontal alignment cell using an adhesive. At this time, P3 is disposed on the polarizing plate on the backlight side, PT3 is disposed on the viewer side, and the first optical anisotropic layer (F3) included in the polarizing plate (P3) is the glass substrate on the backlight side. Further, the cellulose acetate film (T1) contained in the polarizing plate (PT3) was bonded so as to be in contact with the glass substrate on the viewer side. In addition, the absorption axis of the polarizing plate (P3) and the rubbing direction of the liquid crystal cell were orthogonal to each other, and the absorption axes of the polarizing plate (P3) and the polarizing plate (PT3) were orthogonal to each other.
A rectangular wave voltage of 55 Hz was applied to the manufactured liquid crystal cell. A normally black mode with 5 V white display and 0 V black display was set. Display characteristics were evaluated using a measuring machine (EZ-Contrast 160D, manufactured by ELDIM).

[Example 10]
<Production of VA mode liquid crystal display device>
(Preparation of counter polarizing plate)
A roll-shaped polyvinyl alcohol film having a thickness of 80 μm continuously dyed in an aqueous iodine solution was stretched 5 times in the transport direction and dried to obtain a long polarizing film. One surface of this polarizing film was saponified on cellulose acetate film T1 of Example 1, and the other surface was saponified on a commercially available cellulose acetate film (Fujitac TD80UL, manufactured by Fuji Photo Film Co., Ltd.) with a polyvinyl alcohol system. A polarizing plate (PT4) used as an opposing polarizing plate of the polarizing plate (P4) was prepared by continuously bonding using an adhesive.

(Production of liquid crystal display device)
The liquid crystal cell has a cell gap between the substrates of 3.6 μm, and a liquid crystal material having a negative dielectric anisotropy (MLC6608, manufactured by Merck & Co., Inc.) is dropped and sealed between the substrates, and a liquid crystal layer is interposed between the substrates. Formed. The retardation of the liquid crystal layer (that is, the product Δn · d of the thickness d (μm) of the liquid crystal layer and the refractive index anisotropy Δn) was set to 300 nm. The liquid crystal material was aligned so as to be vertically aligned.

  Polarizing plates (P4 and PT4) were bonded to the upper and lower glass substrates of the vertical alignment cell using an adhesive. At this time, P4 is disposed on the polarizing plate on the backlight side, PT4 is disposed on the viewer side, and the first optical anisotropic layer (F4) included in the polarizing plate (P4) is disposed on the backlight side. The cellulose acetate film (T1) contained in the polarizing plate (PT4) was bonded so as to be in contact with the glass substrate on the viewer side. Further, a crossed Nicol arrangement was adopted so that the absorption axis of the polarizing plate (PT4) on the viewer side is in the horizontal direction of the panel and the absorption axis of the polarizing plate (P4) on the backlight side is in the vertical direction.

  A rectangular wave voltage of 55 Hz was applied to the manufactured liquid crystal cell. A normally black mode with 5 V white display and 0 V black display was set. Display characteristics were evaluated using a measuring machine (EZ-Contrast 160D, manufactured by ELDIM).

[Example 11]
In the production of the TN mode liquid crystal display device of Example 7, a TN mode liquid crystal display device was produced using P5 instead of P1 as a polarizing plate disposed on the backlight side, and the display characteristics were evaluated.

[Example 12]
In the production of the TN mode liquid crystal display device of Example 7, a TN mode liquid crystal display device was produced using P6 instead of P1 as the polarizing plate disposed on the backlight side, and the display characteristics were evaluated.

  The liquid crystal display device of any mode produced above had high front luminance and excellent viewing angle characteristics.

It is the schematic of the slot coater which can be utilized for this invention. FIG. 2 is a schematic diagram (A) of a cross-sectional shape of a slot die 13 in FIG. 1 and a schematic diagram (B) of a cross-sectional shape of another slot die 30.

Explanation of symbols

10 Coater
11 Backup roll 12 Web 13, 30 Slot die 14 Coating liquid 15, 32 Pocket 16, 33 Slot 17 Tip lip 18 Upstream lip land 19 Downstream lip land

Claims (12)

A long polarizing plate having a first optically anisotropic layer, a polarizing layer, and a second optically anisotropic layer in this order, and each layer is continuously laminated in a long state Long polarizing plate. Further comprising a third optically anisotropic layer, comprising the first optically anisotropic layer, the polarizing layer, the second optically anisotropic layer, and the third optically anisotropic layer in this order. The polarizing plate as described. The polarizing plate according to claim 1 or 2, wherein the first and / or second optically anisotropic layer includes at least a layer formed from a composition containing a liquid crystal compound. The polarizing plate according to claim 3, wherein the liquid crystal compound is a discotic liquid crystal compound or a rod-like liquid crystal compound. In the layer formed from the composition containing the liquid crystal compound, the molecules of the liquid crystal compound are fixed in any alignment state of hybrid alignment, horizontal alignment, vertical alignment, cholesteric alignment, and tilted alignment. Item 5. The polarizing plate according to item 3 or 4. The polarizing plate according to claim 1, wherein the first and / or second optically anisotropic layer includes a polymer film. The polarizing plate according to claim 6, wherein the polymer film is a stretched polymer film that exhibits optical anisotropy by stretching. The polarizing plate according to claim 6 or 7, wherein the polymer film is a cellulose acylate film or a norbornene-based film. The second optically anisotropic layer has an in-plane retardation of 90 to 160 nm and a slow axis direction of neither 90 ° nor 0 ° with respect to the longitudinal direction. 2. The polarizing plate according to item 1. The second optically anisotropic layer includes at least two layers of an optically anisotropic layer having an in-plane retardation of 90 to 180 nm and an optically anisotropic layer having an in-plane retardation of 200 to 320 nm. The angle formed by the slow axes of each of the at least two optically anisotropic layers is not 90 ° or 0 °, and any slow phase of the at least two optically anisotropic layers is a laminate. The polarizing plate according to any one of claims 1 to 8, wherein the direction of the axis is neither 90 ° nor 0 ° with respect to the longitudinal direction. The polarizing plate according to claim 1, wherein the third optically anisotropic layer is a cholesteric liquid crystal layer. A liquid crystal display device in which a polarizing film, a liquid crystal cell, the polarizing plate according to any one of claims 1 to 11 and a light source are arranged in this order.

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